JPWO2020179394A1 - Polycarbonate resin composition - Google Patents

Abstract

The present invention provides a polycarbonate resin composition having excellent thermal conductivity and electrical insulation.
The resin composition of the present invention comprises (C) a styrene-based thermoplastic elastomer (component C) 1 with respect to a total of 100 parts by weight of (A) polycarbonate-based resin (component A) and (B) polyolefin-based resin (component B). It is characterized by containing ~ 30 parts by weight and (D) 1 to 100 parts by weight of heat-expanded graphite (component D).

Description

The present invention relates to a polycarbonate resin composition having excellent thermal conductivity and electrical insulation.

Polycarbonate-based resins have excellent heat resistance and impact resistance, and are widely used in electronic devices, machines, automobiles, and the like. Particularly in recent years, in LED lighting applications, heat dissipation measures for efficiently dissipating generated heat to the outside have become a very important issue in order to suppress a decrease in LED life and a decrease in brightness. Normally, in order to diffuse the heat of LED lighting, a method of using a metal or ceramic material with good thermal conductivity, or a method of dissipating heat from a heat source using a metal heat sink or a heat dissipation fan is used. There is. However, metal heat-dissipating members have problems such as heavy specific gravity and high manufacturing cost, and in order to further develop the LED lighting market, there is a great demand for an injection-moldable thermally conductive resin composition. high.

On the other hand, when polycarbonate resin is used for various purposes such as housings for personal computers and displays, electronic device materials, interior and exterior of automobiles, and next-generation lighting such as LEDs, polycarbonate resin is used as an inorganic substance such as metal or ceramic material. In comparison, the heat conductivity is low, so it may be difficult to dissipate the generated heat, which may be a problem.

Therefore, a thermally conductive polymer material in which a polymer material is filled with a carbon-based material having high thermal conductivity has been proposed. For example, a method of adding graphitized carbon fibers to a polymer material (Patent Document 1), a method of blending carbon fiber powder obtained by heat-treating polymer fibers into graphite (Patent Document 2), and a resin. A method of mixing expanded graphite powder (Patent Document 3) has been proposed. However, when improving the thermal conductivity of a resin composition by adding a conductive thermal conductive filler such as carbon fiber in this way, a resin is used. Since the composition exhibits conductivity, its use is restricted in applications requiring electrical insulation such as electronic device materials.

On the other hand, a method of filling a large amount of an insulating thermal conductive filler in order to achieve both electrical insulation and thermal conductivity (Patent Documents 4 to 6) has been proposed, but the insulating thermal conductive filler is compared with a resin. Due to the high density, the density of the obtained resin molded body is also high, and it is difficult to meet the demand for weight reduction of portable electronic devices and lighting equipment members, and there is a problem that the thermal conductivity is not improved so much. be.

JP-A-2002-88250 JP-A-2002-339171 Japanese Unexamined Patent Publication No. 2001-31880 Japanese Unexamined Patent Publication No. 2016-29142 Japanese Unexamined Patent Publication No. 2013-209508 Japanese Unexamined Patent Publication No. 2016-53188

In view of the above, an object of the present invention is to provide a polycarbonate resin composition having excellent thermal conductivity and electrical insulation.

As a result of diligent studies to solve the above problems, the present inventor has added heat-expanded graphite and styrene-based thermoplastic elastomer to the resin component composed of polycarbonate-based resin and polyolefin-based resin to conduct heat conduction. It has been found that a polycarbonate resin composition having excellent properties and electrical insulating properties can be obtained. According to the present invention, the above problem is to solve the above problem with respect to 100 parts by weight of the total of (A) polycarbonate resin (A component) and (B) polyolefin resin (B component), and (C) styrene-based thermoplastic elastomer (C component). ) 1 to 30 parts by weight and (D) 1 to 100 parts by weight of the heat-expanded graphite (component D).

Since the resin composition of the present invention has excellent thermal conductivity and electrical insulation, it is extremely useful for various industrial applications such as the field of OA equipment and the field of electrical and electronic equipment, and housings and housings for OA equipment and electrical and electronic equipment. It satisfies the good characteristics corresponding to the housing molded product. In particular, it is useful for molded products of products having a heat source such as LSIs, CPUs, LED lamps, and laser printer fusers. Specifically, desktop personal computers, laptop computers, game machines (household game machines, commercial game machines, pachinko, slot machines, etc.), display devices (CRT, liquid crystal, plasma, projector, organic EL, etc.), and printers. Suitable for housing and chassis moldings such as copiers, scanners and fax machines (including multifunction devices thereof). Further, the resin composition of the present invention is useful for a wide range of other uses, for example, a mobile information terminal (so-called PDA), a mobile phone, a mobile book (dictionaries, etc.), an electronic book, a mobile television, a recording medium (CD, Drives for MDs, DVDs, next-generation high-density disks, hard disks, etc., readers for recording media (IC cards, smart media, memory sticks, etc.), optical cameras, digital cameras, parabolic antennas, power tools, VTRs, irons, hair dryers. , Rice cookers, microwave ovens, acoustic equipment, lighting equipment (LED lighting, etc.), refrigerators, air conditioners, air purifiers, negative ion generators, typewriters, etc. A resin product formed from the resin composition of the present invention can be used. Examples of other resin products include vehicle parts such as lamp reflectors, lamp housings, instrumental panels, center console panels, deflector parts, car navigation parts, car audio visual parts, and auto mobile computer parts. As is clear from the above, the industrial effect of the present invention is extremely large.

Hereinafter, the present invention will be specifically described.
(Component A: Polycarbonate resin)
The polycarbonate resin used as the component A in the present invention is obtained by reacting a divalent phenol with a carbonate precursor. Examples of the reaction method include an interfacial polymerization method, a molten transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

Typical examples of the dihydric phenol used here are hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl). ) Propane (commonly known as 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) Pentan, 4,4'-(p-phenylenediisopropyridene) diphenol, 4,4'-(m-phenylenediisopropylidene) 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) ketone Hydroxyphenyl) esters, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, etc. Be done. A preferable divalent phenol is a bis (4-hydroxyphenyl) alkane, and among them, bisphenol A is particularly preferable from the viewpoint of impact resistance, and is widely used.

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

For example, 4,4'-(m-phenylenediisopropyridene) diphenol (hereinafter sometimes abbreviated as "BPM"), 1,1-bis (4-hydroxy) as a part or all of the divalent phenol component. Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as "Bis-TMC"), 9,9-bis (4-hydroxyphenyl) Polycarbonates (homopolymers or copolymers) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as "BCF") have dimensions due to water absorption. Suitable for applications with particularly stringent requirements for change and morphological stability. It is preferable to use these divalent phenols other than BPA in an amount of 5 mol% or more, particularly 10 mol% or more, of the total divalent phenol components 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 the following copolymerized polycarbonates (1) to (3). be.
(1) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, further preferably 45 to 65 mol%) and BCF in 100 mol% of the divalent phenol component constituting the polycarbonate. Copolymerized polycarbonate having a content of 20 to 80 mol% (more preferably 25 to 60 mol%, still more preferably 35 to 55 mol%).
(2) BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, further preferably 60 to 85 mol%) and BCF in 100 mol% of the divalent phenol component constituting the polycarbonate. Polycarbonate having a content of 5 to 90 mol% (more preferably 10 to 50 mol%, still more preferably 15 to 40 mol%).
(3) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, further preferably 45 to 65 mol%) and Bis in 100 mol% of the divalent phenol component constituting the polycarbonate. -A copolymerized polycarbonate having a TMC of 20-80 mol% (more preferably 25-60 mol%, even more preferably 35-55 mol%).

These special polycarbonates may be used alone or in admixture of two or more. Further, these can also be used by mixing them with a widely used bisphenol A type polycarbonate.

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, JP-A-2002-117580 and the like. ing.

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

Here, the water absorption rate of polycarbonate is a value obtained by measuring the water content after immersing in water at 23 ° C. for 24 hours in accordance with ISO62-1980 using a disk-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. be. The Tg (glass transition temperature) is a value obtained by differential scanning calorimetry (DSC) measurement based on JIS K7121.

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

In producing a polycarbonate resin by interfacial polymerization of the divalent phenol and the carbonate precursor, a catalyst, a terminal terminator, an antioxidant for preventing the dihydric phenol from being oxidized, etc. are used as necessary. You may use it. The polycarbonate resin of the present invention is a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher functional aromatic compound, or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid. , A copolymerized polycarbonate resin obtained by copolymerizing a bifunctional alcohol (including an alicyclic type), and a polyester carbonate resin obtained by copolymerizing both the bifunctional carboxylic acid and the bifunctional alcohol. Further, it may be a mixture of two or more of the obtained polycarbonate resins.

The branched polycarbonate resin can impart drip prevention performance and the like to the resin composition of the present invention. Examples of the trifunctional or higher polyfunctional aromatic compound used in such a branched polycarbonate resin include fluoroglucolcin, fluorogluside, or 4,6-dimethyl-2,4,6-tris (4-hydrokidiphenyl) hepten-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) Etan, 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, trisphenol such as α-dimethylbenzylphenol, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1, Examples thereof include 4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and their acid chlorides, among which 1,1,1-tris (4-hydroxy) Phenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable.

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 to 1 mol%, more preferably 0.05 to 0.9 mol%, still more preferably 0.05 to 0.8 mol%.

Further, particularly in the case of the molten ester exchange method, a branched structural unit may be generated as a side reaction, and the amount of the branched structural unit is preferably 100 mol% in total including the structural unit derived from the divalent phenol. It is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, still more preferably 0.01 to 0.8 mol%. The ratio of such a branched structure ^{can be calculated by 1 1} H-NMR measurement.

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

Reaction formats such as the interfacial polymerization method, the melt transesterification method, the carbonate prepolymer solid phase ester exchange method, and the ring-opening polymerization method of the cyclic carbonate compound, which are the methods for producing the polycarbonate resin of the present invention, are described in various documents and patent publications. This is a well-known method.

Melt volume rate of the polycarbonate resin in the present invention (300 ° C., 1.2 kg load) is not particularly limited, preferably 1~60cm ³ / 10min, more preferably 3~30cm ³ / 10min, more preferably 5~20cm is a ³ / 10min. Resin composition melt volume rate is obtained from the polycarbonate resin is less than 1 cm 3 ^/ 10min may be inferior in versatility in that poor flowability during injection molding. Meanwhile, in the polycarbonate resin melt volume rate exceeds the 60cm ³ / 10min, there is the case where no good mechanical properties are obtained. The melt volume rate is also called "MVR" and is measured according to ISO1133.

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

[In the above general formula (1), R ¹ and R ² are independently hydrogen atom, halogen atom, alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, and 6 to 6 carbon atoms, respectively. 20 cycloalkyl groups, 6 to 20 carbon atoms cycloalkoxy groups, 2 to 10 carbon atoms alkenyl groups, 6 to 14 carbon atoms aryl groups, 6 to 14 carbon atoms aryloxy groups, carbon atoms Represents a group selected from the group consisting of an alkoxy group having a number of 7 to 20 and an alkoxy group having a carbon atom number of 7 to 20, 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 at least one group selected from the group consisting of a single bond or a group represented by the following general formula (2). ]

[In the above general formula (2), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are independently hydrogen atoms, alkyl groups having 1 to 18 carbon atoms, and carbon. Represents a group selected from the group consisting of an aryl group having 6 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ are independent hydrogen atoms, halogen atoms, and carbon atoms 1 to 18 respectively. Alkyl group, alkoxy group with 1 to 10 carbon atoms, cycloalkyl group with 6 to 20 carbon atoms, cycloalkoxy group with 6 to 20 carbon atoms, alkenyl group with 2 to 10 carbon atoms, 6 carbon atoms From an aryl group of ~ 14, an aryloxy group having 6 to 10 carbon atoms, 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. Represents a group selected from the group, and if there are a plurality of groups, they may be the same or different, and g is an integer of 1 to 10 and h is an integer of 4 to 7. ]

[In the above general formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently substituted with a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or 6 to 12 carbon atoms, respectively. Alternatively, it is an unsubstituted aryl group, and R ⁹ and R ¹⁰ are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 10 carbon atoms, and alkoxy groups 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 divalent aliphatic group having 2 to 8 carbon atoms. ]
Examples of the divalent phenol (I) represented by the general formula (1) include 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and the like. 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-t-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-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'-dimethyldiphenylether,4,4'-sulfonyldiphenol,4,4'-dihydroxydiphenylsulfoxide,4,4'-dihydroxydiphenylsulfide,2,2'-dimethyl-4,4'-sulfonyldiphenol,4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide,4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide,2,2'-diphenyl-4,4' -Sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenylsulfide, 1,3-bis {2- (4-hydroxyphenyl) ) Propyl} benzene, 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis (4-hydro) Xyphenyl) cyclohexane, 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4,4'-(1, 3-adamantaneyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane and the like can be mentioned.

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'-. Sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is preferred. Of these, 2,2-bis (4-hydroxyphenyl) propane, which has excellent strength and good durability, is most preferable. Moreover, these may be used 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) prescribes phenols having an olefinic unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, and 2-methoxy-4-allylphenol. It is easily produced by subjecting the terminal of a polysiloxane chain having the degree of polymerization of the above to a hydrosilylation reaction. Of these, (2-allylphenol) -terminal polydiorganosiloxane and (2-methoxy-4-allylphenol) -terminal polydiorganosiloxane are preferable, and (2-allylphenol) -terminal polydimethylsiloxane and (2-methoxy-4) are particularly preferable. -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, still more preferably 2 or less, in order to exhibit more excellent low outgassing property and low temperature impact property during high temperature molding. If 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 resistance may be inferior.

Further, in order to realize high impact resistance, the degree of polymerization (p + q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is preferably 10 to 300. The degree of polymerization of diorganosiloxane (p + q) is preferably 10 to 200, more preferably 12 to 150, and even more preferably 14 to 100. Below the lower limit of the suitable range, the impact resistance characteristic of the polycarbonate-polydiorganosiloxane copolymer is not effectively exhibited, and when the upper limit of the suitable range is exceeded, poor appearance appears.

The content of polydiorganosiloxane in the total weight of the polycarbonate-polydiorganosiloxane copolymer used in component A is preferably 0.1 to 50% by weight. The content of the polydiorganosiloxane component is more preferably 0.5 to 30% by weight, still more preferably 1 to 20% by weight. Above the lower limit of the suitable range, impact resistance and flame retardancy are excellent, and below the upper limit of the suitable range, a stable appearance that is not easily affected by molding conditions can be easily obtained. The degree of polymerization of polydiorganosiloxane and the content of polydiorganosiloxane ^{can be calculated by 1} H-NMR measurement.

In the present invention, only one type of hydroxyaryl-terminated polydiorganosiloxane (II) may be used, or two or more types may be used.

Further, as long as it does not interfere with the present invention, a comonomer other than the above divalent phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) may be added in 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 the reaction of a divalent phenol (I) and a carbonic acid ester-forming compound in a mixed solution of an organic solvent insoluble in water and an alkaline aqueous solution. do.

In producing the oligomer of divalent phenol (I), the entire amount of divalent phenol (I) used in the method of the present invention may be an oligomer at a time, or a part of the oligomer may be used as a post-added monomer at the subsequent interface. It may be added as a reaction raw material to the polycondensation reaction. The post-added monomer is added to allow the polycondensation reaction in the subsequent stage to proceed rapidly, and it is not necessary to dare to add it when it is not necessary.

The method of this oligomer-forming reaction is not particularly limited, but a method performed in a solvent in the presence of an acid binder is usually preferable.

The ratio of the carbonic acid ester-forming compound used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. Further, when a gaseous carbonic acid ester-forming compound such as phosgene is used, a method of blowing it into the reaction system can be preferably adopted.

As the acid binder, for example, 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 are used. Similarly to the above, the ratio of the acid binder used may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, it is preferable to use 2 equivalents or a slightly excess amount of the acid binder with respect to the number of moles of divalent phenol (I) used for forming the oligomer (usually 1 mol corresponds to 2 equivalents). ..

As the solvent, a solvent inert to various reactions such as those used for producing a known polycarbonate may be used alone or as a mixed solvent. Typical examples include hydrocarbon solvents such as xylene and 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 forming the oligomer is not particularly limited and may be normal pressure, pressurization, or reduced pressure, 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 during polymerization, so it is desirable to cool with water or ice. The reaction time depends on other conditions and cannot be unconditionally defined, but is usually 0.2 to 10 hours. The pH range of the oligomer-forming 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 divalent phenol (I) having a terminal chloroformate group, the molecular weight distribution (Mw / Mn) is up to 3 or less while stirring the mixed solution. The highly purified hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula (3) is added to the divalent phenol (I), and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are polycondensed. Thereby, a polycarbonate-polydiorganosiloxane copolymer is obtained.

(In the above general formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently substituted with a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or 6 to 12 carbon atoms, respectively. Alternatively, it is an unsubstituted aryl group, and R ⁹ and R ¹⁰ are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 10 carbon atoms, and alkoxy groups 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 carrying out the interfacial polycondensation reaction, an acid binder may be added as appropriate in consideration of the stoichiometric ratio (equivalent) of the reaction. As the acid binder, for example, 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 are used. Specifically, when the hydroxyaryl-terminated polydiorganosiloxane (II) to be used or a part of the divalent phenol (I) as described above is added as a post-addition monomer to this reaction step, the post-addition amount is two. It is preferable to use 2 equivalents or an excess amount of alkali with respect to the total number of moles of the valent phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mol corresponds to 2 equivalents).

Polycondensation by the interfacial polycondensation reaction between the oligomer of divalent phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the above mixed solution.

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 monovalent phenolic hydroxyl group, and in addition to ordinary phenols, p-tert-butylphenols, p-cumylphenols, tribromophenols, etc., long-chain alkylphenols and aliphatic carboxylic acids Examples thereof include chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxyphenyl alkyl acid ester, and alkyl ether phenol. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, with respect to 100 mol of all the divalent phenolic compounds used, and it is naturally possible to use two or more kinds of compounds in combination. be.

A catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added to promote the polycondensation reaction.

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 divalent phenolic compound to obtain a branched polycarbonate-polydiorganosiloxane. Examples of the trifunctional or higher polyfunctional aromatic compound used in such a branched polycarbonate-polydiorganosiloxane copolymer resin include fluoroglusin, fluorogluside, or 4,6-dimethyl-2,4,6-tris (4-hydrokidiphenyl). ) Hepten-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, trisphenol such as α-dimethylbenzylphenol, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxy) Examples thereof include phenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and their acid chlorides, among which 1,1,1 -Tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable. .. The proportion of the polyfunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9, based on the total amount of the polycarbonate-polydiorganosiloxane copolymer resin. It is mol%, more preferably 0.01 to 0.8 mol%, and particularly preferably 0.05 to 0.4 mol%. The amount of the branched structure ^{can be calculated by 1 1} H-NMR measurement.

The reaction pressure can be reduced pressure, normal pressure, or pressurization, but usually, normal pressure or the self-pressure of the reaction system can be preferably used. The reaction temperature is selected from the range of -20 to 50 ° C., and in many cases, heat is generated during polymerization, so it is desirable to cool with water or ice. The reaction time varies depending on other conditions such as the reaction temperature and cannot be unconditionally specified, but is usually 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, cross-linking treatment, partial decomposition treatment, etc.) to reduce the desired amount. 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 (purification degree) by subjecting 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 product 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, impact resistance and flame retardancy may not be sufficiently exhibited, and if it exceeds the upper limit of such a suitable range, impact resistance may not be stably exhibited. This provides a resin composition having excellent impact resistance and appearance.

The average domain size of the polydiorganosiloxane domain of the polycarbonate-polydiorganosiloxane copolymer resin molded product in the present invention was evaluated by the Small Angle X-ray Scattering method (SAXS). The small-angle X-ray scattering method is a method for measuring diffuse scattering / diffraction occurring in a small-angle region within a scattering angle (2θ) <10 °. In this small-angle X-ray scattering method, when a substance has regions having different electron densities having a size of about 1 to 100 nm, diffuse scattering of X-rays is measured by the difference in electron densities. The particle size of the object to be measured is determined based on the scattering angle and the scattering intensity. In the case of a polycarbonate-polydiorganosiloxane copolymer resin having an aggregated structure in which polydiorganosiloxane domains are dispersed in a matrix of a polycarbonate polymer, diffuse scattering of X-rays 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. From the tentative particle size and the tentative particle size distribution model, a simulation is performed using commercially available analysis software to obtain the average size of the polydiorganosiloxane domain. According to the small-angle X-ray scattering method, the average size of polydiorganosiloxane domains dispersed in a matrix of polycarbonate polymers, which cannot be measured accurately by observation with a transmission electron microscope, can be measured accurately, easily, and with good reproducibility. can. The average domain size means the number average of individual domain sizes.

The term "average domain size" used in connection with the present invention is a measured value obtained by measuring a 1.0 mm thick portion of a three-stage plate produced by the method described in Examples by such a small angle X-ray scattering method. show. In addition, the analysis was performed using an isolated particle model that does not consider the interaction between particles (interference between particles).
(B component: polyolefin resin)
The resin composition of the present invention contains a polyolefin-based resin as the B component. The polyolefin-based resin is a synthetic resin obtained by polymerizing or copolymerizing an olefin-based monomer having a radically polymerizable double bond. The olefin-based monomer is not particularly limited, and for example, α- such as ethylene, propylene, 1-butane, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene and the like. Examples thereof include olefins and conjugated dienes such as butadiene and isoprene. The olefin-based monomer may be used alone or in combination of two or more. The polyolefin-based resin is not particularly limited, and for example, a homopolymer of ethylene, a copolymer of ethylene and α-olefin other than ethylene, a homopolymer of propylene, and a copolymer of propylene and α-olefin other than propylene. Examples thereof include polymers, homopolymers of butene, homopolymers or copolymers of conjugated diene such as butadiene and isoprene, and homopolymers of propylene and copolymers of propylene and α-olefins other than propylene are preferable. .. More preferably, it is a homopolymer of propylene. The polyolefin-based resin may be used alone or in combination of two or more.

In the present invention, polypropylene-based resins are more preferably used from the viewpoint of versatility and rigidity. The polypropylene-based resin is a polymer of propylene, but in the present invention, it also includes a copolymer with another monomer. Examples of the polypropylene resin of the present invention include homopolypropylene resin, block copolymer of propylene and ethylene and α-olefin having 4 to 10 carbon atoms (also referred to as “block polypropylene”), propylene and ethylene and 4 to 4 carbon atoms. A random copolymer with 10 α-olefins (also referred to as “random polypropylene”) is included. The combination of "block polypropylene" and "random polypropylene" is also 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-based resin, and among them, homopolypropylene and block polypropylene are preferable.

Examples of α-olefins having 4 to 10 carbon atoms used in polypropylene copolymers include 1-butene, 1-pentene, isobutylene, 3-methyl-1-butene, 1-hexene, 3,4-dimethyl-1. Includes -butene, 1-heptene and 3-methyl-1-hexene.

The content of ethylene in the polypropylene copolymer is preferably 5% by mass or less in all the 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 the total monomer.

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 load) of the polyolefin resin in the present invention is preferably 1 g / 10 min or more, more preferably 10 g / 10 min or more, and 40 g / 10 min or more. More preferred. If the melt flow rate of the polypropylene resin is less than 1 g / min, the fluidity and electrical insulation may be inferior. The upper limit of the melt flow rate is not particularly limited, but is preferably 300 g / min or less from the viewpoint of mechanical properties. The melt flow rate is also called "MFR" and is measured according to ISO1133.

The present invention also includes an example in which the modified polyolefin resin is used alone as the polyolefin resin, or the polyolefin resin and the modified polyolefin resin are used in combination. The modified polyolefin resin is a polyolefin-based resin that is modified and has a polar group, and the modified polar groups include acid groups such as epoxy groups, glycidyl groups, and carboxyl groups, and acids such as acid anhydride groups. It is at least one functional group selected from the group consisting of derivatives. Specifically, a resin obtained by copolymerizing the above-mentioned polyolefin resin with a monomer containing a polar group such as an epoxy group, a carboxyl group, and an acid anhydride group can be preferably used, and further, graft copolymerization can be used. The one that has been 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, and N- (4- (2,3-epoxy) -3,5-dimethyl). Acrylamide and the like are preferably mentioned. Examples of the monomer containing a carboxyl group include acrylic acid, methacrylic acid, maleic acid and the like. 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 content of the B component is preferably 5 to 80 parts by weight, more preferably 10 to 70 parts by weight, and 30 to 50 parts by weight out of a total of 100 parts by weight of the A component and the B component. Is even more preferable. If the content of component B is less than 5 parts by weight, the electrical insulation may be insufficient, and if it exceeds 80 parts by weight, the extrudability may be significantly reduced.

In the resin composition of the present invention, the ratio of MVR of component A at 300 ° C. and 1.2 kg load to MFR of component B at 230 ° C. and 2.16 kg load (MVR of component A / MFR of component B) was 0. It is preferably 1 to 30, more preferably 0.1 to 20, and even more preferably 0.1 to 10. If the ratio is less than 0.1, the extrudability may be significantly reduced, and if it exceeds 30, the electrical insulation may be insufficient.
(C component: styrene-based thermoplastic elastomer)
The resin composition of the present invention contains a styrene-based thermoplastic elastomer as the C component. The styrene-based thermoplastic elastomer used in the present invention is preferably a block copolymer represented by the following formula (I) or (II).
X- (YX) 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. In addition, Y is a butadiene polymer block, an isoprene polymer block, a butadiene / isoprene copolymer block, a hydrogenated butadiene polymer block, a hydrogenated isoprene polymer block, and a hydrogenated butadiene / isoprene co-weight. It is at least one selected from a coalesced block, a partially hydrogenated butadiene polymer block, a partially hydrogenated isoprene polymer block and a partially hydrogenated butadiene / isoprene copolymer block. Further, n is an integer of 1 or more.

Specific examples include a styrene-ethylene / butylene-styrene copolymer, a styrene-ethylene / propylene-styrene copolymer, a styrene-ethylene / ethylene / propylene-styrene copolymer, and a styrene-butadiene-butene-styrene copolymer. , Styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-hydrogenated butadiene diblock copolymer, styrene-hydrogenated isoprene block copolymer, styrene-butadiene diblock copolymer, Examples thereof include styrene-isopregen block copolymers, among which styrene-ethylene / butylene-styrene copolymers, styrene-ethylene / propylene-styrene copolymers, styrene-ethylene / ethylene / propylene-styrene copolymers, etc. The styrene-butadiene-butene-styrene copolymer is most suitable.

The content of the X component in the block copolymer is preferably in the range of 40 to 80% by weight, preferably 45 to 75% by weight, and more preferably 50 to 70% by weight. If this amount is less than 40% by weight, the compatibility effect of the components A and B may decrease, and the mechanical properties and chemical resistance of the resin composition may decrease. Further, even if it exceeds 80% by weight, the compatibility effect may be similarly lowered and the mechanical properties may be lowered, which is not preferable.

The weight average molecular weight of the styrene-based thermoplastic elastomer is preferably 250,000 or less, more preferably 200,000 or less, and even more preferably 150,000 or less. If the weight average molecular weight exceeds 250,000, the molding processability may be lowered and the dispersibility in the resin composition may be deteriorated. The lower limit of the weight average molecular weight is not particularly limited, but is preferably 40,000 or more, and more preferably 50,000 or more. The weight average molecular weight was measured by the following method. That is, the molecular weight was measured in terms of polystyrene by a gel permeation chromatograph, and the weight average molecular weight was calculated.

The content of the C component is 1 to 30 parts by weight, preferably 3 to 28 parts by weight, and more preferably 5 to 25 parts by weight with respect to 100 parts by weight of the total of the A component and the B component. By adding the C component, the extrudability is improved, but the characteristics are not exhibited when the amount is less than 1 part by weight, and the electrical insulating property is lowered when the amount exceeds 30 parts by weight.

Further, in the present invention, the styrene-based elastomer of the C component may be modified in the same manner as the B component.
(D component: graphite subjected to thermal expansion treatment)
The resin composition of the present invention contains graphite that has been subjected to a thermal expansion treatment as a D component. The heat-expanded graphite used in the present invention is obtained by heat-treating naturally produced natural graphite, petroleum coke, petroleum pitch, amorphous carbon, etc. as minerals at 2000 ° C. or higher, and the orientation of irregularly arranged micrographite crystals. Artificial graphite artificially subjected to It is graphite that is rapidly heated at 800 to 1000 ° C. and expanded in the C-axis direction of the raw material graphite. When graphite that has not been subjected to thermal expansion treatment is used, the dispersibility in the resin is poor and the thermal conductivity is significantly lowered. Natural graphite is particularly preferable as the graphite to be subjected to the thermal expansion treatment.

It is desirable that the graphite subjected to this thermal expansion treatment is graphite prepared by subjecting the above thermal expansion treatment and then pulverizing. Further, the expanded graphite subjected to the thermal expansion treatment has a cocoon-like expanded shape, and its specific volume is generally 100 cc / g or more. However, it is more preferable to press-compress the expanded graphite expanded into a cocoon shape using a roll, a press or the like to form a sheet, which is then crushed by various known crushers.

The graphite subjected to this thermal expansion treatment is classified and used as necessary, and further washed with water and dried as necessary to reduce the residual acid component. The average particle size is preferably 0.1 to 1000 μm, more preferably 25 to 1000 μm. If the average particle size is less than 0.1 μm, the extrusion stability during production of the resin composition may be poor and the productivity may be lowered. If the average particle size exceeds 1000 μm, the appearance of the surface of the molded product may deteriorate.

The surface of the heat-expanded graphite in the present invention is treated with a surface treatment such as epoxy treatment, urethane treatment, or silane in order to increase the affinity with the aromatic polycarbonate resin as long as the characteristics of the composition of the present invention are not impaired. Coupling treatment, oxidation treatment and the like may be performed. Further, the apparent bulk specific gravity of the heat-expanded graphite of the present invention is preferably 0.01 to 0.50 g / cc, more preferably 0.05 to 0.30 g / cc, and 0.10 to 0.25 g / cc. cc is more preferred. When the apparent bulk specific gravity exceeds 0.50 g / cc, the expansion coefficient of expanded graphite is low, so that the thermal conductivity and flame retardancy may be inferior. If the apparent bulk specific gravity is less than 0.01 g / cc, the extrusion stability during the production of the resin composition may be poor and the productivity may be lowered.

The content of the D component is 1 to 100 parts by weight, preferably 5 to 80 parts by weight, and more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the total of the A component and the B component. If the content of the D component is less than 1 part by weight, it is difficult to obtain a sufficient effect of thermal conductivity, and if it exceeds 100 parts by weight, the extrudability is remarkably lowered.
(Component E: Inorganic filler)
In the resin composition of the present invention, various inorganic fillers known as reinforcing fillers can be blended in order to obtain a resin composition having good rigidity. Examples of the inorganic filler include fibrous fillers such as glass fiber (chopped strand), wallastnite, zonotrite, potassium titanate whiskers, aluminum borate whisker, and basic magnesium sulfate whiskers, talc, mica, glass flakes, and boron nitride. Plate-like fillers such as, glass short fibers (milled fibers), irregular cross-section glass fibers, glass beads, glass balloons, silica particles, titania particles, alumina particles, kaolin, clay, calcium carbonate, titanium oxide and other particulate fillers. Can be mentioned.

The content of the E component is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the total of the A component and the B component. If the content is less than 1 part by weight, sufficient rigidity may not be obtained, and if it exceeds 100 parts by weight, the physical properties of the composition may be deteriorated.
(Other additives)
In addition, a heat stabilizer, a mold release agent, an ultraviolet absorber, an impact modifier, and the like can be added to the resin composition of the present invention.
(I) Heat Stabilizer Various known stabilizers can be added to the resin composition of the present invention. Examples of the stabilizer include a phosphorus-based stabilizer and a hindered phenol-based antioxidant.
(Ii) Phosphorus Stabilizer The resin composition of the present invention improves thermal stability during manufacturing or molding to the extent that it does not promote hydrolyzability, and has mechanical properties, hue, and molding stability. It is preferable that a phosphorus-based stabilizer is blended for the purpose of improving the above. Examples of phosphorus-based stabilizers include phosphoric acid, phosphorous acid, phosphorous acid, phosphonic acid and esters thereof, and tertiary phosphine.

Specifically, as phosphate stabilizers, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, etc. Examples thereof include dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate and the like.

Examples of phosphite stabilizers include triphenylphosphite, tris (nonylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, dioctylmonophenylphosphite, and diisopropyl. Monophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, tris (diethylphenyl) phos Fight, Tris (di-iso-propylphenyl) phosphite, Tris (di-n-butylphenyl) phosphite, Tris (2,4-di-tert-butylphenyl) phosphite, Tris (2,6-di-) tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methyl) Phenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite , Dicyclohexylpentaerythritol diphosphite and the like.

Further, as another phosphite-based stabilizer, one that reacts with divalent phenols and has a cyclic structure can also 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-). Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2'-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite , 2,2'-Etilidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and the like.

Phosphonite stabilizers include tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite and tetrakis (2,4-di-tert-butylphenyl) -4,3'-. Biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenedi Phosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite , 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-butyl) Examples thereof include phenyl) -3-phenyl-phenylphosphonite, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite are preferable. 2,4-Di-tert-butylphenyl) -biphenylenediphosphonite and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite are more preferred. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which the alkyl group is substituted by 2 or more. Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

Examples of the tertiary phosphine stabilizer include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, and tri-. Examples thereof include p-tolylphosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine stabilizer is triphenylphosphine. The phosphorus-based stabilizer can be used not only by one type but also by mixing two or more types.
(I-ii) Hindered Phenol Stabilizer The resin composition of the present invention may be further blended with a hindered phenol stabilizer. Such a formulation has an effect of suppressing deterioration of hue during molding processing and deterioration of hue during long-term use, for example. Examples of the hindered phenol-based stabilizer include α-tocopherol, butylhydroxytoluene, cinapyl alcohol, vitamin E, n-octadecyl-β- (4'-hydroxy-3', 5'-di-tert-butylfel). Propionate, 2-tert-butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N) , N-dimethylaminomethyl) 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-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-butylpheno) , 2,2-thiodiethylenebis- [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) isocyanurate, 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, and tetrakis [methylene-3- (3', 3',) 5'-di-tert-butyl-4-hydroxyphenyl) propionate] methane and the like are exemplified. All of these are readily available. The above hindered phenolic stabilizers can be used alone or in combination of two or more. The blending amount of the phosphorus-based stabilizer and the hindered phenol-based stabilizer is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.5 parts, based on 100 parts by weight of the total of the A component and the B component, respectively. It is by weight, more preferably 0.005 to 0.3 parts by weight. If the amount of stabilizer is too small, it is difficult to obtain a good stabilizing effect, and if the amount exceeds the above range, the physical properties of the composition may be deteriorated.
(I-iii) Heat Stabilizers Other Than The Phosphorus Stabilizers and Hindered Phenol Stabilizers Other than the Phosphorus Stabilizers and Hindered Phenol Stabilizers can be added to the resin composition of the present invention. As such other heat stabilizers, for example, lactone-based stabilizers typified by the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene are preferably exemplified. Will be done. Details of such stabilizers are described in JP-A-7-233160. Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and the compound can be used. Further, stabilizers obtained by mixing the compound with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the above-mentioned company is preferably exemplified. The blending amount of the lactone-based stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, based on 100 parts by weight of the resin component. Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Illustrated. The blending amount of the sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, based on 100 parts by weight of the total of the components A and B. An epoxy compound can be added to the resin composition of the present invention, if necessary. Such an epoxy compound is blended for the purpose of suppressing mold corrosion, and basically all compounds having an epoxy functional group can be applied. Specific examples of preferable epoxy compounds include 3,4-epoxycyclohexylmethyl-3', 4-'-epoxycyclohexylcarboxylate, and 1,2-epoxy-4-butanol of 2,2-bis (hydroxymethyl) -1-butanol. Examples thereof include a (2-oxylanyl) cyclosexane adduct, a copolymer of methyl methacrylate and glycidyl methacrylate, a copolymer of styrene and glycidyl methacrylate, and the like. The amount of the epoxy compound added is preferably 0.003 to 0.2 parts by weight, more preferably 0.004 to 0.15 parts by weight, based on 100 parts by weight of the total of the A component and the B component. It is preferably 0.005 to 0.1 parts by weight.
(Ii) Release Agent A mold release agent can be further added to the resin composition of the present invention for the purpose of improving productivity at the time of molding and reducing distortion of the molded product. As such a mold release agent, a known one can be used. For example, saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes (polyethylene wax, 1-alkene polymer, etc., which are modified with functional group-containing compounds such as acid modification can also be used), silicone compounds, fluorine compounds ( Fluorooil represented by polyfluoroalkyl ether), paraffin wax, beeswax and the like can be mentioned. Among them, a fatty acid ester is mentioned as a preferable release agent. Such fatty acid esters are esters of fatty alcohols and aliphatic carboxylic acids. Such an aliphatic alcohol may be a monohydric alcohol or a divalent or higher polyhydric alcohol. The carbon number of the alcohol is in the range of 3 to 32, more preferably in the range of 5 to 30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, and triacanthanol. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. In the fatty acid ester of the present invention, a polyhydric alcohol is more preferable. On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, bechenic acid, and the like. Saturated aliphatic carboxylic acids such as icosanoic acid and docosanoic acid, and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and sethalic acid can be mentioned. .. Among the above, the aliphatic carboxylic acid preferably has 14 to 20 carbon atoms. Of these, saturated aliphatic carboxylic acids are preferable. Particularly stearic acid and palmitic acid are preferred. The above-mentioned aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from animal fats and oils such as beef fat and pork fat and natural fats and oils such as palm oil and sunflower oil. Therefore, these aliphatic carboxylic acids are usually mixtures containing other carboxylic acid components having different carbon atom numbers. Therefore, also in the production of the fatty acid ester of the present invention, an aliphatic carboxylic acid produced from such natural fats and oils and in the form of a mixture containing other carboxylic acid components, particularly stearic acid and palmitic acid are preferably used. The fatty acid ester may be either a partial ester or a total ester (full ester). However, a partial ester usually has a high hydroxyl value and easily induces decomposition of the resin at a high temperature, so that it is more preferably a full ester. The acid value of the fatty acid ester of the present invention is preferably 20 or less, more preferably 4 to 20, and even more preferably 4 to 12 from the viewpoint of thermal stability. The acid value can be substantially 0. The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1 to 30. Further, the iodine value is preferably 10 or less. The iodine value can be substantially 0. These characteristics can be determined by the method specified in JIS K 0070.

The content of the release agent is preferably 0.01 to 4.0 parts by weight, more preferably 0.05 to 3.0 parts by weight, still more preferably 0, based on 100 parts by weight of the total of the A component and the B component. .1 to 2.5 parts by weight.
(Iii) Ultraviolet absorber The resin composition of the present invention can contain an ultraviolet absorber. In the benzophenone system, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy- 5-Sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxitrihydride benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2 , 2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) ) Methan, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like are exemplified. In the benzotriazole system, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-Dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [4- (1,1,3) , 3-Tetramethylbutyl) -6- (2H-benzotriazole-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazol, 2- (2- (2-) Hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5) -Tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'- Methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis (1,3-benzoxazine-4-one), and 2- [2-hydroxy-3- (3,4) 5,6-Tetrahydrophthalimidemethyl) -5-methylphenyl] benzotriazole, and 2- (2'-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and vinyl-based monomers copolymerizable with the monomer. 2-Hydroxyphenyl-2H, such as a copolymer of 2- (2'-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and a vinyl-based monomer copolymerizable with the monomer. -A polymer having a benzotriazole skeleton is exemplified. In the hydroxyphenyltriazine system, for example, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-hexyloxyphenol, 2- (4,6-diphenyl-1,3,5) -Triazine-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-ethyloxyphenol, 2- (4,6-diphenyl) -1,3,5-triazine-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-butyloxyphenol, etc. Illustrated. Further, the phenyl group of the above-exemplified compound such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. A compound that has become a phenyl group is exemplified. In the cyclic iminoester system, for example, 2,2'-p-phenylene bis (3,1-benzoxazine-4-one), 2,2'-(4,4'-diphenylene) bis (3,1-benzoxazine) -4-one), 2,2'-(2,6-naphthalene) bis (3,1-benzoxazine-4-one) and the like are exemplified.

In the cyanoacrylate system, for example, 1,3-bis-[(2'-cyano-3', 3'-diphenylacryloyl) oxy] -2,2-bis [(2-cyano-3,3-diphenylacryloyl) oxy] ] Methyl) propane, 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene and the like are exemplified.

Further, the above-mentioned ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, whereby a photostable monomer having such an ultraviolet-absorbing monomer and / or a hindered amine structure and an alkyl (meth) acrylate are used. It may be a polymer type ultraviolet absorber copolymerized with a monomer such as. As the ultraviolet-absorbing monomer, a compound containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of the (meth) acrylic acid ester is preferably exemplified. NS.

The content of the ultraviolet absorber is preferably 0.1 to 2.0 parts by weight, more preferably 0.2 to 1.5 parts by weight, still more preferably 0, based on 100 parts by weight of the total of the A component and the B component. .3 to 1.0 parts by weight. If the content of the ultraviolet absorber is less than 0.1 parts by weight, sufficient light resistance may not be exhibited, and if it is more than 2 parts by weight, the appearance may be poor or the physical properties may be deteriorated due to gas generation, which is not preferable.
(Iv) Core-shell type graft polymer The resin composition of the present invention can contain a core-shell type graft polymer. The core-shell type graft polymer is a monomer selected from aromatic vinyl, vinyl cyanide, acrylic acid ester, methacrylic acid ester, and a vinyl compound copolymerizable with the rubber component having a glass transition temperature of 10 ° C. or less as a core. It is a graft copolymer copolymerized with one or more kinds as a shell.

The rubber components of the core-shell graft polymer include butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, acrylic-silicone composite rubber, isobutylene-silicone composite rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, and ethylene-propylene rubber. Styrene rubber, ethylene-acrylic rubber, silicone rubber, epichlorohydrin rubber, fluororubber, and those in which hydrogen is added to these unsaturated bond portions can be mentioned, but from the viewpoint of concern about the generation of harmful substances during combustion. , A rubber component containing no halogen atom is preferable in terms of environmental load. The glass transition temperature of the rubber component is preferably −10 ° C. or lower, more preferably −30 ° C. or lower, and the rubber component is particularly preferably butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, or acrylic-silicone composite rubber. The composite rubber refers to a rubber obtained by copolymerizing two kinds of rubber components or a rubber polymerized so as to have an IPN structure in which they are intertwined with each other so as not to be separated. In the core-shell type graft polymer, the particle size of the core is preferably 0.05 to 0.8 μm, more preferably 0.1 to 0.6 μm, still more preferably 0.15 to 0.5 μm in terms of weight average particle size. Better impact resistance is achieved in the range of 0.05 to 0.8 μm.

Examples of aromatic vinyl in the vinyl compound copolymerized with the rubber component as the shell of the core-shell type graft polymer include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, and halogenated styrene. Examples of the acrylate ester include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, and octyl acrylate, and examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, and butyl methacrylate. , Cyclohexyl methacrylate, octyl methacrylate and the like, and methyl methacrylate is particularly preferable. Among these, it is particularly preferable to contain a methacrylate ester such as methyl methacrylate as an essential component. This is because the core-shell type graft polymer has an excellent affinity with the aromatic polycarbonate resin, so that more rubber components are present in the resin, and the good impact resistance of the aromatic polycarbonate resin is further improved. This is because it is effectively exhibited, and as a result, the impact resistance of the resin composition is improved. More specifically, the methacrylic acid ester is contained in 100% by weight of the graft component (in the case of the core-shell type polymer, in 100% by weight of the shell), preferably 10% by weight or more, and more preferably 15% by weight or more. Is preferable. The elastic polymer containing a rubber component having a glass transition temperature of 10 ° C. or lower may be produced by any of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method is as follows. It does not matter whether it is a one-stage graft or a multi-stage graft. Further, it may be a mixture with a copolymer containing only a graft component produced as a by-product during production. Further, as the polymerization method, in addition to the general emulsion polymerization method, a soap-free polymerization method using an initiator such as potassium persulfate, a seed polymerization method, a two-step swelling polymerization method and the like can be mentioned. Further, in the suspension polymerization method, a method in which the aqueous phase and the monomer phase are individually held and both are accurately supplied to a continuous disperser, and the particle size is controlled by the rotation speed of the disperser, and continuous production. In the method, a method of controlling the particle size by supplying the monomer phase into an aqueous liquid having dispersibility by passing it through a small-diameter orifice or a porous filter having a diameter of several to several tens of μm may be used. In the case of a core-shell type graft polymer, the reaction may be one-stage or multi-stage for both the core and the shell.

Such polymers are commercially available and easily available. For example, as a rubber component, those containing butadiene rubber as the main component are Kaneace M series manufactured by Kaneka Co., Ltd. (for example, the shell component is M-711 containing methyl methacrylate as the main component, and the shell component is mainly composed of methyl methacrylate and styrene. M-701, etc.), Metabrene C series manufactured by Mitsubishi Chemical Co., Ltd. (for example, C-223A whose shell component is mainly methyl methacrylate / styrene), E series (for example, shell component is methyl methacrylate / styrene) E-870A as the main component), Paraloid EXL series of DOWN Chemical Co., Ltd. (for example, EXL-2690 whose shell component is methyl methacrylate as the main component) can be mentioned, and acrylic rubber or butadiene-acrylic composite rubber is the main component. W series (for example, W-600A whose shell component is mainly composed of methyl methacrylate) and DOWN Chemical Co., Ltd.'s Pararoid EXL series (for example, EXL-2390 whose shell component is mainly composed of methyl methacrylate). Etc.), and as a rubber component containing acrylic-silicone composite rubber as the main component, the shell component manufactured by Mitsubishi Chemical Co., Ltd. is Metabrene S-2501 containing methyl methacrylate as the main component, or the shell component is acrylonitrile-styrene. An example of which is commercially available under the trade name of SX-200R whose main component is SX-200R.

The content of the core-shell type graft polymer is preferably 1 to 10 parts by weight, more preferably 1 to 8 parts by weight, still more preferably 2 to 7 parts by weight, based on 100 parts by weight of the total of the components A and B. Is.
(V) Other Resins / Elastomers In the resin composition of the present invention, other resins or elastomers other than the C component can be used in a small proportion as long as the effects of the present invention are exhibited. Examples of such other resins include polyester resin, AS resin, ABS resin, AES resin, polyamide resin, polyimide resin, polyetherimide resin, polyurethane resin, silicone resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, and polymethacrylate. Examples thereof include resins such as resins, phenol resins, and epoxy resins. Examples of the elastomer include isobutylene / isoprene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, and polyamide elastomer.
(Vi) Dyeing Pigment The resin composition of the present invention can further provide a molded product containing various dyeing pigments and exhibiting various design properties. By blending a fluorescent whitening agent or a fluorescent dye that emits light other than that, it is possible to impart a better design effect that makes the best use of the emitted color. It is also possible to provide a resin composition which is colored with a very small amount of dyeing pigment and has a vivid color development property.

Examples of the fluorescent dye (including the fluorescent whitening agent) used in the present invention include a coumarin-based fluorescent dye, a benzopyran-based fluorescent dye, a perylene-based fluorescent dye, an anthracinone-based fluorescent dye, a thioindigo-based fluorescent dye, and a xanthene-based fluorescent dye. , Xantone-based fluorescent dye, thioxanthene-based fluorescent dye, thioxanthone-based fluorescent dye, thiazine-based fluorescent dye, diaminostilben-based fluorescent dye and the like. Among these, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes, which have good heat resistance and little deterioration during molding of the polycarbonate resin, are preferable.

Examples of dyes other than the above brewing agents and fluorescent dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthracinone dyes, thioxanthone dyes, ferrocyanides such as navy blue, perinone dyes, quinoline dyes, and quinacridones. Examples thereof include dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Further, the resin composition of the present invention can also be blended with a metallic pigment to obtain a better metallic color. As the metallic pigment, those having a metal film or a metal oxide film on various plate-shaped fillers are preferable.

The content of the dyeing pigment is preferably 0.00001 to 1 part by weight, more preferably 0.00005 to 0.5 part by weight, based on 100 parts by weight of the total of the A component and the B component.
(Vii) Flame Retardant Various compounds known as flame retardants of thermoplastic resins, particularly polycarbonate-based resins, can be applied to the resin composition of the present invention, but more preferably halogen-based flame retardants (for example, bromine). Phosphorescent polycarbonate compounds, etc.), phosphorus flame retardants (eg, monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, and phosphazene compounds, etc.), metal salt flame retardants (eg, organic sulfonic acids). It is a silicone-based flame retardant composed of an alkali (earth) metal salt, a borate metal salt-based flame retardant, a tin acid metal salt-based flame retardant, etc.) and a silicone compound. The compounding of the compound used as the flame retardant not only improves the flame retardancy, but also improves, for example, antistatic property, fluidity, rigidity, and thermal stability based on the properties of each compound.

The content of the flame retardant is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 28 parts by weight, still more preferably 0.08 to 0.08 parts by weight, based on 100 parts by weight of the total of the A component and the B component. 25 parts by weight. If the content of the flame retardant is less than 0.01 parts by weight, sufficient flame retardancy may not be obtained, and if it exceeds 30 parts by weight, the mechanical properties may be significantly deteriorated.
(Xiii) Other Additives In addition, the resin composition of the present invention may contain a small proportion of additives known per se in order to impart various functions and improve properties to the molded product. These additives are in the usual blending amount as long as the object of the present invention is not impaired. Examples of such additives include sliding agents (for example, PTFE particles), colorants (for example, pigments and dyes such as carbon black), and light diffusing agents (for example, acrylic crosslinked particles, silicone crosslinked particles, ultrathin glass flakes, calcium carbonate particles). , Fluorescent dye, inorganic phosphor (for example, a phosphor whose mother crystal is an aluminate), antistatic agent, crystal nucleating agent, inorganic and organic antibacterial agent, photocatalytic antifouling agent (for example, fine particle titanium oxide, fine particle oxidation) Zinc), radical generators, infrared absorbers (heat ray absorbers), photochromic agents and the like.
(Manufacturing of resin composition)
Any method is adopted for producing the resin composition of the present invention. For example, components A to D and optionally other additives are sufficiently mixed using a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical device, and an extrusion mixer, and then extruded granulation as necessary. Examples thereof include a method in which the premix is granulated by a vessel or a briquetting machine, then melt-kneaded by a melt-kneader typified by a bent twin-screw extruder, and then pelletized by a pelletizer.

In addition, each component is independently supplied to a melt kneader represented by a bent twin-screw extruder, or a part of each component is premixed and then supplied to the melt kneader independently of the remaining components. There is also a way to do it. Examples of the method of premixing a part of each component include a method of premixing a component other than the component A in advance and then mixing the polycarbonate resin of the component A or directly supplying the component to the extruder.

As a method of premixing, for example, when a component A having a powder form is included, a masterbatch of the additive diluted with the powder is produced by blending a part of the powder and the additive to be blended. One method is to use a masterbatch. Further, there is also a method of independently supplying one component from the middle of the melt extruder. If some of the components to be blended are in liquid form, a so-called liquid injection device or liquid addition device can be used to supply the melt extruder.

As the extruder, one having a vent capable of degassing the moisture in the raw material and the volatile gas generated from the melt-kneaded resin can be preferably used. A vacuum pump is preferably installed from the vent to efficiently discharge the generated water and volatile gas to the outside of the extruder. It is also possible to install a screen for removing foreign substances and the like mixed in the extruded raw material in the zone in front of the die portion of the extruder to remove the foreign substances from the resin composition. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (disc filter, etc.) and the like.

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

The resin extruded as described above is directly cut and pelletized, or the strands are cut with a pelletizer after forming the strands and pelletized. When it is necessary to reduce the influence of external dust and the like during pelletization, it is preferable to clean the atmosphere around the extruder. Furthermore, in the production of such pellets, various methods already proposed for polycarbonate resins for optical discs are used to narrow the shape distribution of pellets, reduce miscuts, and reduce fine powder generated during transportation or transportation. , And bubbles (vacuum bubbles) generated inside the strands and pellets can be appropriately reduced. With these formulations, it is possible to increase the cycle of molding and reduce the rate of defects such as silver. The shape of the pellet can be a general shape such as a cylinder, a prism, and a sphere, but a cylinder is more preferable. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, 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, still more preferably 2.5 to 3.5 mm.
(About a molded product made of the resin composition of the present invention)
In the resin composition of the present invention, various products can be produced by injection molding pellets obtained by the above-mentioned method. In such injection molding, not only ordinary molding methods, but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including those by injection of supercritical fluid), insert molding, and insert molding, depending on the intended purpose. Molded products can be obtained using injection molding methods such as in-mold coating molding, heat insulating mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding. The advantages of these various molding methods are already widely known. Further, either a cold runner method or a hot runner method can be selected for molding.

The volume resistivity of the molded product obtained by the above method ^{is preferably 1 × 10 11} Ωcm or more, more preferably 1 × 10 ¹² Ωcm or more, and ^{further preferably 1 × 10 13} Ωcm or more.

The thermal conductivity of the molded product obtained by the above method is preferably 1 W / mK or more, more preferably 2 to 15 W / mK, and even more preferably 3 to 15 W / mK.

The embodiment for carrying out the present invention is a collection of preferable ranges of the above-mentioned requirements. For example, a representative example thereof will be described in the following examples. Of course, the present invention is not limited to these forms.

Hereinafter, the present invention will be described in more detail with reference to Examples. Unless otherwise specified, parts in the examples are parts by weight, and% is% by weight. The evaluation was performed according to the following method.
(I) Volume resistivity A flat plate having a thickness of 2 mm was formed under the following conditions, 500 V was applied between the electrodes according to JIS K6911, and the resistivity after 1 minute was measured.
(Ii) Thermal conductivity A square plate (50 mm × 100 mm × 4 mmt) was formed under the following conditions, and the thermal conductivity in the flow direction of the sample was measured by a laser flash method.
(Iii) Extrudability The takeability of the strands when extruded under the following conditions and the state of the strands during the strand cutting were evaluated according to the following criteria.
◯: Extrusion was possible without any problem.
X: Difficult to pick up, or the strand was broken during the strand cut.

The following raw materials were used.
(Component A)
A-1: aromatic polycarbonate resin ^(MVR made by a conventional method from bisphenol A and phosgene: Polycarbonate resin powder 11cm 3 / 10min)
A-2: aromatic polycarbonate resin ^(MVR made by a conventional method from bisphenol A and phosgene: 54cm 3 / 10min for polycarbonate resin powder)
A-3: aromatic polycarbonate resin ^(MVR made by a conventional method from bisphenol A and phosgene: Polycarbonate resin powder 2.8 cm 3 / 10min)
A-4: Polycarbonate - polydiorganosiloxane copolymer resin ^{(MVR: 5.5cm 3 / 10min,} PDMS content 8.4%, PDMS polymerization degree 37)
(B component)
B-1: Polypropylene resin (homopolymer, MFR: 70 g / 10 min, manufactured by SunAllomer Ltd .: SunAllomer PLB00A (product name))
B-2: Polypropylene resin (homopolymer, MFR: 2g / 10min, manufactured by SunAllomer Ltd .: SunAllomer PL400A (product name))
B-3: Polypropylene resin (homopolymer, MFR: 0.5 g / 10 min, manufactured by Japan Polypropylene Corporation: Novatec EA9 (product name))
(C component)
C-1: Styrene-ethylene / propylene-styrene block copolymer (SEPS, manufactured by Kuraray Co., Ltd .: Septon 2104 (product name))
C-2: Styrene-ethylene / butylene-styrene block copolymer (SEBS, manufactured by Asahi Kasei Corporation: Tuftec H1043 (product name))
C-3: Styrene-butadiene-butylene-styrene block copolymer (SBBS, manufactured by Asahi Kasei Corporation: Tuftec P2000 (product name))
(D component)
D-1: Expanded graphite subjected to thermal expansion treatment (manufactured by Nishimura Graphite Co., Ltd .: EN-250HT (product name))
D-2: Expanded graphite subjected to thermal expansion treatment (manufactured by Marutoyo Casting Co., Ltd .: CSF400R (product name))
D-3: Synthetic graphite (manufactured by Imerys GC Japan Co., Ltd .: SFG44 (product name))
(E component)
E-1: Glass filler (chopped strand) (manufactured by Nitto Boseki Co., Ltd .: CS-3PE-455FB (product name))
(Other ingredients)
Stabilizer: Phosphate stabilizer (manufactured by Daihachi Chemical Industry Co., Ltd .: trimethyl phosphate (TMP))
Release agent: Fatty acid ester (manufactured by Riken Vitamin Co., Ltd .: EW-400 (product name))
[Examples 1 to 18 and Comparative Examples 1 to 6]
Of the components listed in the table, component A and other components are mixed with a V-type blender to prepare a mixture, and together with component B, which can be supplied independently, a vent type twin-screw extruder with a screw diameter of 30 mm [(Co., Ltd.) ) Japan Steel Works TEX30α-38.5BW-3V], supply from the first supply port at the rear end using a measuring instrument at a predetermined ratio, and use a vacuum pump under a vacuum of 3 kPa. It was melt-extruded at a cylinder temperature of 260 ° C. and pelletized. The obtained pellets are dried at 100 ° C. for 6 hours in a hot air circulation type dryer, and then a flat plate and a square plate for evaluation are molded using an injection molding machine (cylinder temperature 260 ° C., mold temperature 70 ° C.). bottom. The table shows the results of various evaluations.

From the above table, a resin composition having excellent thermal conductivity and electrical insulation can be obtained by blending a heat-expanding treated graphite and a styrene-based thermoplastic elastomer with a resin component composed of a polycarbonate-based resin and a polyolefin-based resin. You can see that you can do it.

Claims (11)

1 to 30 parts by weight of (C) styrene-based thermoplastic elastomer (C component) and (D) with respect to a total of 100 parts by weight of (A) polycarbonate-based resin (A component) and (B) polyolefin-based resin (B component). A polycarbonate resin composition containing 1 to 100 parts by weight of heat-expanded graphite (component D). Group C consisting of styrene-ethylene / propylene-styrene block copolymer (SEPS), styrene-ethylene / butylene-styrene block copolymer (SEBS) and styrene-butadiene / butylene-styrene block copolymer (SBBS) The polycarbonate resin composition according to claim 1, wherein the polymer is at least one kind of styrene-based thermoplastic polymer selected from the above. The polycarbonate resin composition according to claim 1 or 2, wherein the component D is expanded graphite crushed after compression treatment of expanded graphite. The ratio of MVR of component A at 300 ° C. and 1.2 kg load to MFR of component B at 230 ° C. and 2.16 kg load (MVR of component A / MFR of component B) is 0.1 to 10. The polycarbonate resin composition according to any one of claims 1 to 3. The polycarbonate resin composition according to any one of claims 1 to 4, wherein 1 to 100 parts by weight of (E) an inorganic filler (component E) is contained with respect to 100 parts by weight of the total of the components A and B. .. The polycarbonate resin composition according to claim 5, wherein the component E is glass fiber. The polycarbonate resin composition according to any one of claims 1 to 6, wherein the MFR of the component B at 230 ° C. and a load of 2.16 kg is 40 g / 10 min or more. The polycarbonate resin composition according to any one of claims 1 to 7, wherein the component B is a polypropylene-based resin. The polycarbonate resin composition according to any one of claims 1 to 8, wherein the ratio (weight ratio) of the component A to the component B (component A / component B) is 95/5 to 20/80. A molded product comprising the polycarbonate resin composition according to any one of claims 1 to 9, wherein the volume resistivity is 1 × 10 ¹¹ Ωcm or more. A molded product comprising the polycarbonate resin composition according to any one of claims 1 to 9, wherein the molded product has a thermal conductivity of 1 W / mK or more.