JP7505937B2 - Polycarbonate resin composition - Google Patents

Description

The present invention relates to a polycarbonate resin composition. More specifically, the present invention relates to a polycarbonate resin composition having improved mechanical properties, chemical resistance, and thermal stability.

Polycarbonate resins have excellent mechanical and thermal properties and are therefore widely used in a variety of fields, including office equipment, electronic and electrical equipment, and the automotive industry. However, polycarbonate resins have poor processability due to their high melt viscosity, and because they are amorphous resins, they have problems with chemical resistance. For this reason, it is known to add polyolefin resins to compensate for these shortcomings (see Patent Documents 1 and 2).

For components that require rigidity, it is known to mix inorganic fillers such as glass fiber, mica, talc, wollastonite, and potassium titanate into the resin composition, and a resin composition consisting of a polycarbonate resin, a polypropylene resin, a styrene-based thermoplastic elastomer, and an inorganic filler has been disclosed (see Patent Document 3). However, these compositions have the problem that the molded product may have poor appearance such as silver, and furthermore, the molecular weight of the polycarbonate resin is significantly reduced, making it impossible to obtain the desired resin composition.

On the other hand, polycarbonate resins and polyolefin resins have low compatibility, and therefore there is a problem that delamination occurs when molded products are made by injection molding or the like. However, it has been disclosed that a resin composition in which delamination is suppressed can be obtained by adding a polyolefin resin modified with an epoxy group (see Patent Documents 4 and 5). However, when an inorganic filler is mixed into such a resin composition for the purpose of imparting rigidity, there is a problem that the rigidity at high temperatures is significantly reduced.

JP 2014-181323 A JP 2015-203098 A JP 2016-125025 A Japanese Patent Application Laid-Open No. 7-258530 JP 2012-41415 A

In view of the above, an object of the present invention is to provide a polycarbonate resin composition having improved mechanical properties, chemical resistance and thermal stability.

As a result of intensive research conducted by the inventors to solve the above problems, they discovered that by adding a compound that contains at least one functional group selected from the group consisting of an epoxy group, a carboxy group, and an acid anhydride group, and does not contain an olefin component, to a component consisting of a polycarbonate resin, a polypropylene resin, a styrene-based thermoplastic elastomer, and an inorganic filler, it is possible to obtain a resin composition that suppresses poor appearance such as silver and a decrease in the molecular weight of the polycarbonate resin, and also has excellent chemical resistance and high-temperature rigidity, and thus completed the present invention.

According to the present invention, the above object is achieved by a polycarbonate resin composition containing 100 parts by weight of components consisting of (A) 40 to 90 parts by weight of polycarbonate resin (component A) and (B) 60 to 10 parts by weight of polypropylene resin (component B), 1 to 20 parts by weight of (C) styrene-based thermoplastic elastomer (component C), 5 to 100 parts by weight of (D) inorganic filler (component D), and 0.3 to 10 parts by weight of (E) a compound (component E) that contains at least one functional group selected from the group consisting of epoxy groups, carboxy groups, and acid anhydride groups and does not contain an olefin component.

The details of the present invention are described below.

<Component A: Polycarbonate Resin>
The polycarbonate resin used in the present invention is obtained by reacting a dihydric phenol with a carbonate precursor. Examples of the reaction method include an interfacial polymerization method, a melt transesterification method, a solid-phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

Representative examples of the dihydric phenols used herein include 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)pentane, 4,4'-(p-phenylene) Examples of the dihydric phenol include 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)ester, bis(4-hydroxy-3-methylphenyl)sulfide, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. The preferred dihydric phenols are bis(4-hydroxyphenyl)alkanes, and among them, bisphenol A is particularly preferred from the viewpoint of impact resistance and is widely used.

In the present invention, in addition to the general-purpose polycarbonate bisphenol A polycarbonate, it is possible to use special polycarbonates produced using other dihydric phenols as component A.

For example, polycarbonates (homopolymers or copolymers) using 4,4'-(m-phenylenediisopropylidene)diphenol (hereinafter sometimes abbreviated as "BPM"), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as "Bis-TMC"), 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter sometimes abbreviated as "BCF") as part or all of the dihydric phenol components are suitable for applications where dimensional changes due to water absorption and dimensional stability are particularly demanding. These dihydric phenols other than BPA are preferably used in an amount of 5 mol % or more, particularly 10 mol % or more, of the total dihydric 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 a copolymer polycarbonate of the following (1) to (3).
(1) A copolymer polycarbonate in which, relative to 100 mol % of the dihydric phenol component constituting the polycarbonate, BPM is 20 to 80 mol % (more preferably 40 to 75 mol %, and even more preferably 45 to 65 mol %) and BCF is 20 to 80 mol % (more preferably 25 to 60 mol %, and even more preferably 35 to 55 mol %).
(2) A copolymer polycarbonate in which, relative to 100 mol % of the dihydric phenol component constituting the polycarbonate, BPA is 10 to 95 mol % (more preferably 50 to 90 mol %, even more preferably 60 to 85 mol %) and BCF is 5 to 90 mol % (more preferably 10 to 50 mol %, even more preferably 15 to 40 mol %).
(3) A copolymer polycarbonate in which, relative to 100 mol % of the dihydric phenol component constituting the polycarbonate, BPM is 20 to 80 mol % (more preferably 40 to 75 mol %, and even more preferably 45 to 65 mol %) and Bis-TMC is 20 to 80 mol % (more preferably 25 to 60 mol %, and even more preferably 35 to 55 mol %).

These special polycarbonates may be used alone or in a suitable mixture of two or more. They may also be used in a mixture with the commonly used bisphenol A polycarbonate.

The manufacturing methods and properties of these special polycarbonates are described in detail, for example, in JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580.

Among the various polycarbonates mentioned above, those in which the copolymer composition and the like are adjusted to bring the water absorption rate and Tg (glass transition temperature) into the ranges described below have good hydrolysis resistance of the polymer itself and are also remarkably excellent in terms of low warpage after molding, and are therefore particularly suitable in fields where dimensional stability is required.
(i) A polycarbonate having a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.13%, and a Tg of 120 to 180°C, or (ii) a polycarbonate having a Tg of 160 to 250°C, preferably 170 to 230°C, and a water absorption of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

The water absorption rate of polycarbonate is measured by measuring the moisture content after immersing a disk-shaped test piece with a diameter of 45 mm and a thickness of 3.0 mm in water at 23°C for 24 hours in accordance with ISO 62-1980. The glass transition temperature (Tg) is a value determined by differential scanning calorimetry (DSC) measurement in accordance with JIS K7121.

Carbonate precursors include carbonyl halides, carbonic acid diesters, or haloformates, such as phosgene, diphenyl carbonate, or dihaloformates of dihydric phenols.

When producing an aromatic polycarbonate resin by the interfacial polymerization method of the dihydric phenol and the carbonate precursor, a catalyst, a terminal terminator, an antioxidant for preventing oxidation of the dihydric phenol, etc. may be used as necessary. The aromatic polycarbonate resin of the present invention also includes a branched polycarbonate resin copolymerized with a polyfunctional aromatic compound having three or more functionalities, a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, a copolymerized polycarbonate resin copolymerized with a bifunctional alcohol (including alicyclic), and a polyester carbonate resin copolymerized with such a bifunctional carboxylic acid and a bifunctional alcohol. It may also be a mixture of two or more of the obtained aromatic polycarbonate resins.

The branched polycarbonate resin can impart drip prevention properties and the like to the resin composition of the present invention. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucine, phloroglucide, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-{4-[1,1-bis(4- Examples include trisphenols such as {4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof, among which 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, with 1,1,1-tris(4-hydroxyphenyl)ethane being particularly preferred.

In the branched polycarbonate, the constituent units derived from the polyfunctional aromatic compound preferably account for 0.01 to 1 mol %, more preferably 0.05 to 0.9 mol %, and even more preferably 0.05 to 0.8 mol %, of the total 100 mol % of the constituent units derived from the dihydric phenol and the constituent units derived from the polyfunctional aromatic compound.

In particular, in the case of the melt transesterification method, branched structural units may be generated as a side reaction, and the amount of such branched structural units is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and even more preferably 0.01 to 0.8 mol% relative to the total of 100 mol% including the structural units derived from the dihydric phenol. The proportion of such branched structures can be calculated by ^1H -NMR measurement.

The aliphatic bifunctional carboxylic acid is preferably an 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 icosane diacid, as well as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.

The reaction formats for producing the polycarbonate resin of the present invention, such as the interfacial polymerization method, the melt transesterification method, the carbonate prepolymer solid-phase transesterification method, and the ring-opening polymerization method of cyclic carbonate compounds, are well known in various literature and patent publications.

In producing the resin composition of the present invention, the viscosity average molecular weight (M) of the polycarbonate resin is not particularly limited, but is preferably 1.8×10 ⁴ to 4.0×10 ⁴ , more preferably 2.0×10 ⁴ to 3.5×10 ⁴ , and even more preferably 2.2×10 ⁴ to 3.0×10 ^4. With a polycarbonate resin having a viscosity average molecular weight of less than 1.8×10 ⁴ , good mechanical properties may not be obtained. On the other hand, a resin composition obtained from a polycarbonate resin having a viscosity average molecular weight of more than 4.0×10 ⁴ is inferior in versatility in that it has poor fluidity during injection molding.

The polycarbonate resin may be a mixture of polycarbonate resins having a viscosity average molecular weight outside the above range. In particular, polycarbonate resins having a viscosity average molecular weight exceeding the above range (5×10 ⁴ ) have improved entropy elasticity. As a result, they exhibit good moldability in gas-assisted molding and foam molding, which are sometimes used when molding reinforced resin materials into structural members. Such improvement in moldability is even better than that of the branched polycarbonate. In a more preferred embodiment, component A is composed of a polycarbonate resin (component A-1-1) having a viscosity average molecular weight of 7×10 ⁴ to 3×10 ⁵ , and an aromatic polycarbonate resin (component A-1-2) having a viscosity average molecular weight of 1×10 ⁴ to 3×10 ⁴ , and a polycarbonate resin (component A-1) having a viscosity average molecular weight of 1.6×10 ⁴ to 3.5×10 ⁴ (hereinafter sometimes referred to as a “polycarbonate resin containing a high molecular weight component”) can also be used.

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

The polycarbonate resin containing high molecular weight components (A-1 component) can be obtained by mixing the A-1-1 and A-1-2 components in various ratios and adjusting to satisfy a specified molecular weight range. Preferably, the A-1-1 component is 2 to 40% by weight out of 100% by weight of the A-1 component, more preferably 3 to 30% by weight, even more preferably 4 to 20% by weight, and particularly preferably 5 to 20% by weight of the A-1-1 component.

Methods for preparing component A-1 include (1) a method of independently polymerizing components A-1-1 and A-1-2 and mixing them together, (2) a method of producing an aromatic polycarbonate resin that exhibits multiple polymer peaks in a molecular weight distribution chart obtained by GPC in the same system, as typified by the method shown in JP-A-5-306336, and producing such an aromatic polycarbonate resin so as to satisfy the conditions for component A-1 of the present invention, and (3) a method of mixing the aromatic polycarbonate resin obtained by such a production method (production method (2)) with components A-1-1 and/or A-1-2 that have been produced separately.

The viscosity average molecular weight in the present invention is determined by first determining the specific viscosity (η _SP ) calculated by the following formula using an Ostwald viscometer from a solution in which 0.7 g of polycarbonate is dissolved in 100 ml of methylene chloride at 20° C.:
Specific viscosity (η _SP )=(t−t ₀ )/t ₀
[ _t0 is the number of seconds that methylene chloride falls, and t is the number of seconds that the sample solution falls]
The viscosity average molecular weight M is calculated from the specific viscosity (η _SP ) thus determined according to the following formula.
η _SP /c = [η] + 0.45 × [η] ² c (where [η] is the intrinsic viscosity)
[η] = 1.23 × 10 ⁻⁴ M ^0.83
c=0.7

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

[In the above general formula (1), R ¹ and R ² each independently represent a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 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 carboxy group, and when there are a plurality of each, they may be the same or different, e and f each represent an integer of 1 to 4, and W represents a single bond or at least one group selected from the group consisting of groups 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 each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms and an aralkyl group having 7 to 20 carbon atoms; R ¹⁹ and R ²⁰ each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, 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 carboxy group, and when there are a plurality of such groups, they may be the same or different, g is an integer from 1 to 10, and h is an integer from 4 to 7.]

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

Examples of the dihydric phenol (I) represented by the general formula (1) include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3'-biphenyl)propane, 2,2-bis(4-hydroxy-3-isopropylphenyl)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'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'-di Hydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4,4'-(1,3-adamantanediyl)diphenol, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, and the like.

Among these, 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, and 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene are preferred, and 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4'-sulfonyldiphenol, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are particularly preferred. Among these, 2,2-bis(4-hydroxyphenyl)propane, which has excellent strength and good durability, is the most suitable. These may be used alone or in combination of two or more.

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

Hydroxyaryl-terminated polydiorganosiloxane (II) is easily produced by subjecting a phenol having an olefinic unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol, to a polysiloxane chain end having a predetermined degree of polymerization through a hydrosilylation reaction. Among these, (2-allylphenol)-terminated polydiorganosiloxane and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxane are preferred, and (2-allylphenol)-terminated polydimethylsiloxane and (2-methoxy-4-allylphenol)-terminated polydimethylsiloxane are particularly preferred. Hydroxyaryl-terminated polydiorganosiloxane (II) preferably has a molecular weight distribution (Mw/Mn) of 3 or less. In order to achieve even better low outgassing properties during high-temperature molding and low-temperature impact properties, the molecular weight distribution (Mw/Mn) is more preferably 2.5 or less, and even more preferably 2 or less. If the upper limit of this preferred range is exceeded, the amount of outgassing during high-temperature molding may be large, and low-temperature impact resistance may be poor.

In order to achieve a high level of impact resistance, the diorganosiloxane polymerization degree (p+q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is preferably 10 to 300. The diorganosiloxane polymerization degree (p+q) is preferably 10 to 200, more preferably 12 to 150, and even more preferably 14 to 100. Below the lower limit of this preferred range, the impact resistance that is a characteristic of the polycarbonate-polydiorganosiloxane copolymer is not effectively expressed, and above the upper limit of this preferred range, poor appearance appears.

The polydiorganosiloxane content of the total weight of the polycarbonate-polydiorganosiloxane copolymer resin used in component A is preferably 0.1 to 50% by weight. The polydiorganosiloxane content is more preferably 0.5 to 30% by weight, and even more preferably 1 to 20% by weight. At or above the lower limit of this preferred range, excellent impact resistance and flame retardancy are obtained, while at or below the upper limit of this preferred range, a stable appearance that is less susceptible to the effects of molding conditions is likely to be obtained. The polydiorganosiloxane polymerization degree and polydiorganosiloxane content 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.

In addition, other comonomers than the dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) may be used in an amount of 10% by weight or less based on the total weight of the copolymer, provided that the use of these comonomers does not interfere with the performance of the present invention.

In the present invention, a mixed solution containing an oligomer having a terminal chloroformate group is prepared in advance by reacting a dihydric phenol (I) with a carbonate ester-forming compound in a mixed solution of a water-insoluble organic solvent and an aqueous alkaline solution.

When producing an oligomer of dihydric phenol (I), the entire amount of dihydric phenol (I) used in the method of the present invention may be converted into an oligomer at once, or a part of it may be added as a post-added monomer as a reaction raw material to the subsequent interfacial polycondensation reaction. A post-added monomer is added to facilitate the subsequent polycondensation reaction, and there is no need to add it if it is not necessary.

The method for this oligomer formation reaction is not particularly limited, but it is usually preferable to carry out the reaction in a solvent in the presence of an acid binder.

The proportion of the carbonate ester-forming compound used may be adjusted appropriately, taking into consideration the stoichiometric ratio (equivalents) of the reaction. When using a gaseous carbonate ester-forming compound such as phosgene, it is preferable to blow this into the reaction system.

As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkali metal carbonate such as sodium carbonate or potassium carbonate, an organic base such as pyridine, or a mixture of these may be used. Similarly to the above, the proportion of the acid binder used may be appropriately determined taking into account the stoichiometric ratio (equivalents) of the reaction. Specifically, it is preferable to use 2 equivalents or a slightly excess amount of the acid binder relative to the number of moles of the dihydric phenol (I) used to form the oligomer (usually 1 mole corresponds to 2 equivalents).

As the solvent, a solvent inert to various reactions, such as those used in the production of known polycarbonates, may be used alone or as a mixture of solvents. Representative examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. In particular, halogenated hydrocarbon solvents such as methylene chloride are preferably used.

There are no particular restrictions on the reaction pressure for oligomer formation, and it may be normal pressure, elevated pressure, 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 since heat is generated during polymerization in many cases, it is desirable to cool the reaction with water or ice. The reaction time depends on other conditions and cannot be specified in general, but is usually carried out for 0.2 to 10 hours. The pH range for the oligomer formation reaction is the same as known interfacial reaction conditions, and the pH is always adjusted to 10 or higher.

In this way, the present invention obtains a mixed solution containing an oligomer of dihydric phenol (I) having terminal chloroformate groups, and then adds hydroxyaryl-terminated polydiorganosiloxane (II) represented by general formula (3) that has been highly refined to a molecular weight distribution (Mw/Mn) of 3 or less to the dihydric phenol (I) while stirring the mixed solution, and obtains a polycarbonate-polydiorganosiloxane copolymer by interfacially polycondensing the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer.

(In the above general formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms; R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; p is a natural number; q is 0 or a natural number; and p+q is a natural number from 10 to 300; and 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 appropriately in consideration of the stoichiometric ratio (equivalents) of the reaction. Examples of acid binders include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Specifically, when the hydroxyaryl-terminated polydiorganosiloxane (II) used or a portion of the dihydric phenol (I) as described above is added to this reaction stage as a post-added monomer, it is preferable to use 2 equivalents or an excess amount of alkali relative to the total moles of the post-added dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).

The polycondensation by interfacial polycondensation reaction between the oligomer of dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the above mixture.

In such polymerization reactions, a terminal terminator or a molecular weight regulator is usually used. Examples of terminal terminators include compounds having a monovalent phenolic hydroxyl group, such as ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, and the like, as well as long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, hydroxybenzoic acid alkyl esters, hydroxyphenyl alkyl acid esters, and alkyl ether phenols. The amount of the agent used is in the range of 100 to 0.5 moles, preferably 50 to 2 moles, per 100 moles of all dihydric phenol compounds used, and it is of course possible to use two or more compounds in combination.

To accelerate the polycondensation reaction, a catalyst such as a tertiary amine like triethylamine or a quaternary ammonium salt may be added.

The reaction time for such a polymerization reaction is preferably 30 minutes or more, more preferably 50 minutes or more. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.

A branching agent can be used in combination with the above dihydric phenol compound to produce a branched polycarbonate-polydiorganosiloxane. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate-polydiorganosiloxane copolymer resins include phloroglucine, phloroglucide, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-{4-[1 [0113] Examples of the hydroxyphenyl group include trisphenols such as {1,1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof. Among these, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred. 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 mol %, still more preferably 0.01 to 0.8 mol %, and particularly preferably 0.05 to 0.4 mol %, based on the total amount of the polycarbonate-polydiorganosiloxane copolymer resin. The amount of branched structures can be calculated by ¹ H-NMR measurement.

The reaction pressure can be reduced, normal, or increased, but is usually suitable for carrying out the reaction at normal pressure or the reaction system's own pressure. The reaction temperature is selected from the range of -20 to 50°C, and since the polymerization often generates heat, it is desirable to cool the reaction with water or ice. The reaction time varies depending on other conditions such as the reaction temperature and cannot be specified in general, but is usually carried out for 0.5 to 10 hours.

In some cases, the obtained polycarbonate-polydiorganosiloxane copolymer resin can be appropriately subjected to a physical treatment (mixing, fractionation, etc.) and/or a chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a polycarbonate-polydiorganosiloxane copolymer resin having a desired reduced viscosity [η _SP /c].

The resulting reaction product (crude product) can be subjected to various post-treatments, such as known separation and purification methods, to recover a polycarbonate-polydiorganosiloxane copolymer resin of the desired purity (degree of purification).

The average size of the polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molded product is preferably in the range of 1 to 40 nm. Such an average size is more preferably 1 to 30 nm, and even more preferably 5 to 25 nm. Below the lower limit of this preferred range, impact resistance and flame retardancy may not be fully exhibited, and above the upper limit of this preferred range, impact resistance may not be stably exhibited. This provides a polycarbonate resin composition with excellent impact resistance and appearance.

The average domain size of the polydiorganosiloxane domains of the polycarbonate-polydiorganosiloxane copolymer resin molded product of the present invention was evaluated by small angle X-ray scattering (SAXS). Small angle X-ray scattering is a method for measuring diffuse scattering and diffraction occurring in a small angle region within a scattering angle (2θ) of <10°. In this small angle X-ray scattering method, if there are regions in a substance with different electron densities of about 1 to 100 nm in size, the diffuse scattering of X-rays is measured based on the electron density difference. The particle size of the measurement object is determined based on the scattering angle and scattering intensity. In the case of a polycarbonate-polydiorganosiloxane copolymer resin having an aggregate structure in which polydiorganosiloxane domains are dispersed in a polycarbonate polymer matrix, the difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domains causes diffuse scattering of X-rays. The scattering intensity I at each scattering angle (2θ) in the range of scattering angles (2θ) less than 10° is measured to measure a small-angle X-ray scattering profile, and assuming that the polydiorganosiloxane domains are spherical domains and that there is variation in particle size distribution, a simulation is performed using commercially available analysis software from a tentative particle size and a tentative particle size distribution model to determine the average size of the polydiorganosiloxane domains. The small-angle X-ray scattering method allows the average size of the polydiorganosiloxane domains dispersed in the polycarbonate polymer matrix, which cannot be accurately measured by observation using a transmission electron microscope, to be measured accurately, easily, and with good reproducibility. The average domain size means the number average of the individual domain sizes.

The term "average domain size" used in connection with the present invention refers to a measurement value obtained by measuring a 1.0 mm thick portion of a three-tiered plate prepared by the method described in the Examples using the small angle X-ray scattering method. In addition, the analysis was performed using an isolated particle model that does not take into account interparticle interactions (interparticle interference).

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

In the present invention, one or more of the above-mentioned homopolypropylene resins, block polypropylenes, and random polypropylenes may be used as the polypropylene-based resin, with homopolypropylene and block polypropylene being preferred.

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-butene, 1-heptene, and 3-methyl-1-hexene.

The content of ethylene in the polypropylene copolymer is preferably 5% by mass or less of all monomers. The content of α-olefins having 4 to 10 carbon atoms in the polypropylene copolymer is preferably 20% by mass or less of all monomers. The polypropylene copolymer is preferably a copolymer of propylene and ethylene, or a copolymer of propylene and 1-butene, and a copolymer of propylene and ethylene is particularly preferred.

The content of component B is 10 to 60 parts by weight, preferably 15 to 50 parts by weight, and more preferably 20 to 40 parts by weight, out of 100 parts by weight of the total of components A and B. If the content of component B is less than 10 parts by weight, chemical resistance will deteriorate, and if it exceeds 60 parts by weight, rigidity will decrease.

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

Specific examples include styrene-ethylene-butylene-styrene copolymer, styrene-ethylene-propylene-styrene copolymer, styrene-ethylene-ethylene-propylene-styrene copolymer, styrene-butadiene-butene-styrene copolymer, styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-hydrogenated butadiene diblock copolymer, styrene-hydrogenated isoprene diblock copolymer, styrene-butadiene diblock copolymer, styrene-isoprene diblock copolymer, etc., of which styrene-ethylene-butylene-styrene copolymer, styrene-ethylene-propylene-styrene copolymer, styrene-ethylene-ethylene-propylene-styrene copolymer, and styrene-butadiene-butene-styrene copolymer are the most suitable.

The content of the X component in the block copolymer is desirably 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 between the A component and the B component decreases, and the mechanical properties and chemical resistance of the resin composition may decrease. Also, if it exceeds 80% by weight, the compatibility effect may decrease and the mechanical properties may decrease, so neither is 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 moldability may decrease and the dispersibility in the polycarbonate resin composition may also deteriorate. There is no particular limit to the lower limit of the weight average molecular weight, but it 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 using a gel permeation chromatograph, and the weight average molecular weight was calculated.

The content of component C is 1 to 20 parts by weight, preferably 2 to 17 parts by weight, and more preferably 3 to 15 parts by weight, per 100 parts by weight of components A and B. If the content of component C is less than 1 part by weight, the mechanical properties will not improve, and if it exceeds 20 parts by weight, the rigidity will decrease.

<Component D: Inorganic filler>
The resin composition of the present invention contains an inorganic filler as component D. The inorganic filler may be any of various commonly known fillers such as glass fiber, flat glass fiber, milled fiber, carbon fiber, glass flake, wollastonite, kaolin clay, mica, talc, fibrous magnesium sulfate, and various whiskers (potassium titanate whisker, aluminum borate whisker, etc.). The shape of the inorganic filler may be freely selected from fibrous, flaky, spherical, and hollow, and fibrous and plate-shaped fillers are particularly suitable for improving the strength and impact resistance of the resin composition. In addition, glass-based inorganic fillers such as glass fiber and glass flake have the problem that they tend to wear out the mold during molding, so silicate minerals are more preferably used as component D. The silicate mineral used as component D of the present invention is a mineral consisting of at least a metal oxide component and a _SiO2 component, and orthosilicate, disilicate, cyclic silicate, and chain silicate are suitable. Silicate minerals are in a crystalline state, and the crystals can take various shapes such as fibers or plates.

The silicate mineral may be any of the compounds of a composite oxide, an oxyacid salt (composed of an ion lattice), and a solid solution, and the composite oxide may be any of a combination of two or more single oxides, and a combination of two or more single oxides and oxyacid salts, and the solid solution may be any of a solid solution of two or more metal oxides, and a solid solution of two or more oxyacid salts. The silicate mineral may be a hydrate. The form of the water of crystallization in the hydrate may be any of the forms of hydrogen silicate ions as Si-OH, ions as hydroxide ions ( ^OH- ) for metal cations, and _H2O molecules in the gaps of the structure.

Silicate minerals can also be artificially synthesized products that correspond to natural products. As artificially synthesized products, silicate minerals obtained by various synthetic methods using various conventionally known methods, such as solid-state reactions, hydrothermal reactions, and ultra-high pressure reactions, can be used.

Specific examples of silicate minerals in each metal oxide component (MO) include the following. The notation in parentheses here is the name of the mineral, etc. that contains such a silicate mineral as the main component, and means that the compound in parentheses can be used as the exemplified metal salt.

Examples of materials that contain K ₂ O as a component include K ₂ O.SiO ₂ , K ₂ O.4SiO _{2.H 2 O} , K ₂ O.Al ₂ O _{3.2SiO 2} (kalsilite), K ₂ O.Al ₂ O _{3.4SiO 2} (leucite), and K ₂ O.Al ₂ O _{3.6SiO 2} (orthoclase).

Examples of minerals that contain _{Na2O as} a component _{include Na2O.SiO2 and} its hydrates, _Na2O.2SiO2 , _{2Na2O.SiO2 , Na2O.4SiO2 , Na2O.3SiO2.3H2O , Na2O.Al2O3.2SiO2 , Na2O.Al2O3.4SiO2 ( jadeite ) , 2Na2O.3CaO.5SiO2 , 3Na2O.2CaO.5SiO2 , and Na2O.Al2O3.6SiO2} ( _{albite ) .}

Examples of materials containing _{Li2O as a} component _{include Li2O.SiO2} , _{2Li2O.SiO2 , Li2O.SiO2.H2O , 3Li2O.2SiO2 , Li2O.Al2O3.4SiO2} ( _{petalite ) , Li2O.Al2O3.2SiO2 ( eucryptite )} , and _{Li2O.Al2O3.4SiO2} ( _{spodumene )} .

Examples of materials containing BaO as a component include BaO.SiO ₂ , 2BaO.SiO ₂ , BaO.Al ₂ O _{3.2SiO 2} (celsian), and BaO.TiO _{2.3SiO 2} (bentite).

Examples of minerals that contain CaO include 3CaO.SiO ₂ (alite, a cement clinker mineral), 2CaO.SiO ₂ (belite, a cement clinker mineral), 2CaO.MgO.2SiO ₂ (akermanite), 2CaO.Al ₂ O _{3.SiO 2} (gehlenite), a solid solution of akermanite and gehlenite (melilite), CaO.SiO ₂ (wollastonite (including both α-type and β-type)), CaO.MgO.2SiO ₂ (diopside), CaO.MgO.SiO ₂ (magnesium olivine), 3CaO.MgO.2SiO ₂ (merwinite), CaO.Al ₂ O _{3.2SiO 2} (anorthite), and 5CaO.6SiO _{2.5H 2} . Tobermorite group hydrates such as 2CaO.SiO 2.H 2 O (tobermorite, 5CaO.6SiO _{2.9H 2} O, etc.), wollastonite group hydrates such as 2CaO.SiO _{2.H 2} O (hillebrandite), xonotlite group hydrates such as 6CaO.6SiO 2.H ₂ O (xonotlite), gyrolite group hydrates such as 2CaO.SiO _{2.2H 2} O (gyrolite), CaO.Al 2 O 3.2SiO 2.H ₂ O (lawsonite), CaO.FeO.2SiO 2 (hedengite), 3CaO.2SiO 2 (chilcoanite), 3CaO.Al ₂ O 3.3SiO 2 (grossula), 3CaO.Fe 2 O 3.3SiO ₂ (silicate), 3CaO.Al ₂ O 3.3SiO ₂ (silicate ...Al 2 O 3.3SiO _{2 (silicate), 3CaO.Al 2 O 3.3SiO 2} (silicate), 3CaO.Al 2 O 3.3SiO ₂ (silicate), 3CaO.Al ₂ O 3.3SiO ₂ (silicate), 3CaO.Al 2 O 3.3SiO ₂ (silicate), 3CaO.Al ₂ O 3.3SiO ₂ (silicate), ₃ (andradite), 6CaO.4Al ₂ O _{3.FeO.SiO 2} (pleochroite), as well as clinozoisite, pomegranate, allanite, vesuvianite, onosite, scotite, and augite.

Furthermore, Portland cement can be mentioned as an example of a silicate mineral that contains CaO as a component. There are no particular limitations on the type of Portland cement, and any type can be used, such as normal, early strength, extra early strength, medium heat, sulfate resistant, and white. Furthermore, various types of mixed cements, such as blast furnace cement, silica cement, and fly ash cement, can also be used as component D.

Other silicate minerals that contain CaO include blast furnace slag and ferrite.

Examples of materials containing ZnO as a component include ZnO.SiO ₂ , 2ZnO.SiO ₂ (troostite), and 4ZnO.2SiO _{2.H 2} O (hemimorphite).

Examples of materials containing MnO as a component include MnO.SiO ₂ , 2MnO.SiO ₂ , CaO.4MnO.5SiO ₂ (rhodonite) and coesrite.

Examples of materials containing FeO as a component include FeO.SiO ₂ (ferrosilite), 2FeO.SiO ₂ (ferroolitic olivine), 3FeO.Al ₂ O _{3.3SiO 2} (almandine), and 2CaO.5FeO.8SiO 2.H _{2 O} (tetractinocene).

Examples of materials containing CoO as a component include _CoO.SiO2 and _2CoO.SiO2 .

Examples of minerals that contain MgO include _MgO.SiO2 (steatite, enstatite), _2MgO.SiO2 ( _{forsterite ) , 3MgO.Al2O3.3SiO2} (byropes), 2MgO.2Al2O3.5SiO2 (cordierite ₎ , _{2MgO.3SiO2.5H2O , 3MgO.4SiO2.H2O (} talc), _{5MgO.8SiO2.9H2O} (attapulgite _{) ,} 4MgO.6SiO2.7H2O ₍ sepiolite), _{3MgO.2SiO2.2H2O (} chrysolite ₎ , _{5MgO.2CaO.8SiO2.H2O} (tremelite), _{5MgO.Al2O3.3SiO2} (calcite), _{5MgO . 2.4H 2} O (chlorite), K ₂ O.6MgO.Al ₂ O _{3.6SiO 2.2H 2} O (phlogovite), Na ₂ O.3MgO.3Al ₂ O _{3.8SiO 2.H 2} O (lanthanite), as well as magnesium tourmaline, orthoclase, cummingtonite, vermiculite, and smectite.

_Examples of _{materials that} contain _Fe2O3 as a component include _Fe2O3.SiO2 .

Examples of _refractories that contain _ZrO2 as a component include _ZrO2.SiO2 (zircon) and AZS refractories.

Examples of materials that contain Al ₂ O ₃ include Al ₂ O _{3.SiO 2} (sillimanite, andalusite, kyanite), 2Al ₂ O 3.SiO ₂ , Al ₂ O 3.3SiO ₂ , 3Al ₂ O _{3.2SiO 2} (mullite), Al ₂ O 3.2SiO _{2.2H 2} O (kaolinite), Al ₂ O 3.4SiO _{2.H 2} O (pyrophyllite ₎ , Al ₂ O _{3.4SiO 2.H 2} O _{(bentonite), K 2 O.3Na 2 O.4Al 2 O 3.8SiO 2 (nepheline), K 2 O.3Al 2 O 3.6SiO 2.2H 2 O ( muscovite , sericite ) ,} K ₂ O.6MgO.Al ₂ O _{3.6SiO 2.2H 2} O (phlogovite), as well as various zeolites, fluorphlogopite, and biotite.

Among the above silicate minerals, mica, talc, and wollastonite are particularly suitable, and more preferably one or more silicate minerals including talc.

(talc)
The talc in the present invention is a hydrous magnesium silicate in terms of chemical composition, generally represented by the chemical formula _{4SiO2.3MgO.2H2O} , and is a scaly particle having a layered structure, and is composed of 56-65% by weight of _SiO2 , 28-35% by weight of MgO, and about 5% by weight of _H2O . Other minor components include _{0.03-1.2 %} by weight of _Fe2O3 , 0.05-1.5% by weight _{of Al2O3} , 0.05-1.2% by weight of CaO, 0.2% by weight or less of _K2O , and 0.2% by weight or less of _Na2O . The particle size of the talc is preferably in the range of 0.1-15 μm (more preferably 0.2-12 μm, even more preferably 0.3-10 μm, and particularly preferably 0.5-5 μm) in terms of average particle size measured by a sedimentation method. Furthermore, it is particularly preferable to use talc having a bulk density of 0.5 (g/ ^cm3 ) or more as the raw material. The average particle size of talc refers to D50 (median size of particle size distribution) measured by X-ray transmission method, which is one of the liquid phase precipitation methods. A specific example of an apparatus for performing such a measurement is Sedigraph 5100 manufactured by Micromeritics.

There is no particular restriction on the method for crushing talc from raw stones, and axial flow milling, annular milling, roll milling, ball milling, jet milling, and container rotation compression shear milling can be used. Furthermore, the crushed talc is preferably classified by various classifiers to obtain a uniform particle size distribution. There is no particular restriction on the classifier, and examples include impactor-type inertial force classifiers (variable impactor, etc.), Coanda effect-based inertial force classifiers (elbow jet, etc.), and centrifugal field classifiers (multi-stage cyclone, microplex, dispersion separator, Accucut, turbo classifier, turboplex, micron separator, and super separator, etc.). Furthermore, talc is preferably in an agglomerated state in terms of its handling properties, and examples of such methods include a method using deaeration compression and a method using a bundling agent for compression. In particular, the degassing and compression method is preferred because it is simple and does not mix unnecessary sizing agent resin components into the resin composition of the present invention.

(Mica)
The mica preferably has an average particle size of 10 to 100 μm as measured by a microtrack laser diffraction method. More preferably, the average particle size is 20 to 50 μm. If the average particle size of the mica is less than 10 μm, the effect of improving the rigidity may not be sufficient, and if it exceeds 100 μm, the improvement in rigidity may not be sufficient and the mechanical strength such as impact properties may be significantly reduced, which is not preferable. The mica preferably has a thickness of 0.01 to 1 μm as measured by observation with an electron microscope. More preferably, the thickness is 0.03 to 0.3 μm. The aspect ratio is preferably 5 to 200, more preferably 10 to 100. The mica used is preferably muscovite mica, and its Mohs hardness is about 3. Muscovite mica can achieve higher rigidity and higher strength than other micas such as phlogovite, and solves the problem of the present invention at a better level. The mica may be produced by either a dry grinding method or a wet grinding method. The dry grinding method is more common and has a lower cost, whereas the wet grinding method is effective for grinding the mica more thinly and finely, which results in a greater effect of improving the rigidity of the resin composition.

(Wallastonite)
The fiber diameter of wollastonite is preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, and even more preferably 0.1 to 3 μm. The aspect ratio (average fiber length/average fiber diameter) is preferably 3 or more. The upper limit of the aspect ratio is 30 or less. Here, the fiber diameter is measured by observing the reinforcing filler with an electron microscope, determining the individual fiber diameters, and calculating the number average fiber diameter from the measured values. The electron microscope is used because it is difficult to accurately measure the size of the target level with an optical microscope. The fiber diameter is measured by randomly extracting the filler to be measured for the image obtained by observation with the electron microscope, measuring the fiber diameter near the center, and calculating the number average fiber diameter from the measured values. The magnification of the observation is about 1000 times, and the number of measured fibers is 500 or more (600 or less is suitable for work). On the other hand, the average fiber length is measured by observing the filler with an optical microscope, determining the individual lengths, and calculating the number average fiber length from the measured values. Observation with an optical microscope begins with preparing a sample in which the fillers are dispersed so that they do not overlap too much. Observation is performed under conditions of a 20x objective lens, and the observed image is captured as image data by a CCD camera with approximately 250,000 pixels. The obtained image data is used in an image analyzer to calculate the fiber length using a program that determines the maximum distance between two points on the image data. Under these conditions, the size per pixel corresponds to a length of 1.25 μm, and the number of fibers measured is 500 or more (600 or less is preferable for operational reasons).

In order to fully reflect the inherent whiteness of the wollastonite of the present invention in the resin composition, it is preferable to remove as much iron as possible from the raw ore and from the equipment wear during the crushing of the raw ore using a magnetic separator. The iron content in the wollastonite after the magnetic separator treatment is preferably _0.5 % by weight or less, calculated as _Fe2O3 .

The silicate mineral (more preferably, mica, talc, or wollastonite) is preferably not surface-treated, but may be surface-treated with various surface treatment agents such as silane coupling agents, higher fatty acid esters, and waxes. It may also be granulated into granules using bundling agents such as various resins, higher fatty acid esters, and waxes.

The content of component D is 5 to 100 parts by weight, preferably 10 to 90 parts by weight, and more preferably 15 to 80 parts by weight, per 100 parts by weight of the components A and B. If the content of component D is less than 5 parts by weight, sufficient rigidity cannot be obtained, and if it exceeds 100 parts by weight, a decrease in impact resistance and poor appearance such as silveriness will occur.

<Component E: Compound containing at least one functional group selected from the group consisting of an epoxy group, a carboxy group, and an acid anhydride group, and not containing an olefin component>
The resin composition of the present invention contains a compound containing at least one functional group selected from the group consisting of an epoxy group, a carboxy group, and an acid anhydride group, and not containing an olefin component, as component E. If component E contains an olefin component, the rigidity decreases.

Examples of compounds that contain epoxy groups and do not contain olefin components include phenoxy resins and epoxy resins.

Examples of phenoxy resins include those represented by the following general formula (4):

(In the formula, X is at least one group selected from the group consisting of groups represented by the following general formula (5), Y is a residue of a compound that reacts with a hydrogen atom or a hydroxyl group, and n is an integer of 0 or more.)

（式中、Ｐｈはフェニル基を示す。）

(In the formula, Ph represents a phenyl group.)

Examples of epoxy resins include those represented by the following general formula (6):

（式中、Ｘ及びｎは一般式（４）と同じである。）

(In the formula, X and n are the same as in general formula (4).)

In the above general formula (4), examples of compounds that react with hydroxyl groups include esters, carbonates, compounds having epoxy groups, carboxylic anhydrides, acid halides, compounds having isocyanate groups, etc., and as esters, intramolecular esters are particularly preferred, such as caprolactone. In the phenoxy resin represented by the above general formula (4), a compound in which Y is a hydrogen atom can be easily produced from divalent phenols and epichlorohydrin. In addition, a compound in which Y is a residue of a compound that reacts with hydroxyl groups can be easily produced by mixing a phenoxy resin produced from divalent phenols and epichlorohydrin with the above compound that reacts with hydroxyl groups under heating.

The epoxy resin represented by the above general formula (6) can be easily produced from a dihydric phenol and epichlorohydrin. As the dihydric phenol, 2,2-bis(4-hydroxyphenyl)propane [bisphenol A], 1,1-bis(4-hydroxyphenyl)ethane, 4,4'-dihydroxybiphenyl, etc. can be used.

Commercially available phenoxy resins and epoxy resins can also be used. Commercially available phenoxy resins (bisphenol A type) include PKHB (InChem, Mw = 13,700), PKHH (InChem, Mw = 29,000), PKFE (InChem, Mw = 36,800), and YP-50 (Tohto Kasei, Mw = 43,500).

Commercially available epoxy resins (bisphenol A type) include EPICLON HM-101 (manufactured by Dainippon Ink and Chemicals, Mw = 48,000) and jER1256 (manufactured by Mitsubishi Chemical Corporation, Mw = 26,600).

Other specific examples include glycidyl methacrylate, glycidyl methacrylate-styrene copolymer, glycidyl methacrylate-styrene-acrylonitrile copolymer, glycidyl methacrylate-styrene-methyl methacrylate copolymer, and copolymers in which glycidyl methacrylate-styrene-acrylonitrile copolymer is graft-polymerized onto polycarbonate.

As the compound containing a carboxy group and not containing an olefin component, aromatic polyester resins such as polybutylene terephthalate, polyethylene terephthalate and polyarylate are preferred.

The aromatic polybutylene terephthalate resins and aromatic polyethylene terephthalate resins preferably used in the present invention are aromatic polybutylene terephthalate resins and aromatic polyethylene terephthalate resins in which, of the dicarboxylic acid components and diol components that form the polyester, 70 mol % or more of 100 mol % of the dicarboxylic acid components are aromatic dicarboxylic acids, more preferably 90 mol % or more, and most preferably 99 mol % or more. Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, adipic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbene dicarboxylic acid, 4,4-biphenyl dicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis(p-carboxyphenyl)methane, anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, 4,4-diphenoxyethane dicarboxylic acid, 5-Na sulfoisophthalic acid, and ethylene-bis-p-benzoic acid. These dicarboxylic acids can be used alone or in combination of two or more. In addition to the aromatic dicarboxylic acids, the aromatic polybutylene terephthalate resin and aromatic polyethylene terephthalate resin of the present invention can be copolymerized with less than 30 mol% of an aliphatic dicarboxylic acid component. Specific examples thereof include adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Examples of the diol component of the present invention include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans- or cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, and tetrabromobisphenol A-bis(2-hydroxyethyl ether). These can be used alone or in combination of two or more. Furthermore, it is preferable that the dihydric phenol content in the diol component is 30 mol% or less.

The aromatic polybutylene terephthalate resin and aromatic polyethylene terephthalate resin used in the present invention are produced by polymerizing a dicarboxylic acid component and the diol component while heating in the presence of a polycondensation catalyst containing titanium, germanium, antimony, or the like, and discharging the by-product water or lower alcohol from the system. For example, germanium-based polymerization catalysts include germanium oxides, hydroxides, halides, alcoholates, and phenolates, and more specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, and tetramethoxygermanium. In the present invention, compounds such as manganese, zinc, calcium, and magnesium used in the transesterification reaction, which is a step prior to polycondensation, can be used in combination, and after the transesterification reaction, such catalysts can be deactivated with a phosphoric acid or phosphorous acid compound to carry out polycondensation. Furthermore, the production method of aromatic polybutylene terephthalate resin and aromatic polyethylene terephthalate resin can be either a batch method or a continuous polymerization method.

The molecular weight of the aromatic polybutylene terephthalate resin and aromatic polyethylene terephthalate resin of the present invention is not particularly limited, but the intrinsic viscosity measured at 25°C using o-chlorophenol as a solvent is preferably 0.4 to 1.5, and particularly preferably 0.5 to 1.2.

In addition, the amount of terminal carboxyl groups in the aromatic polybutylene terephthalate resin and aromatic polyethylene terephthalate resin used in the present invention is preferably 5 to 75 eq/ton, more preferably 5 to 70 eq/ton, and even more preferably 7 to 65 eq/ton.

The aromatic polyarylate resin preferably used in the present invention is obtained from an aromatic dicarboxylic acid or its derivative and a dihydric phenol or its derivative. The aromatic dicarboxylic acid used in the preparation of the aromatic polyarylate resin may be any one that reacts with a dihydric phenol to give a satisfactory polymer, and may be used alone or in a mixture of two or more kinds.

Preferred aromatic dicarboxylic acid components include terephthalic acid and isophthalic acid. Mixtures of these may also be used.

Specific examples of dihydric phenol components include 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenylmethane, 2,2'-bis(4-hydroxy-3,5-dimethylphenyl)propane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxydiphenyl, and hydroquinone. These dihydric phenol components are para-substituted, but other isomers may be used, and further, the dihydric phenol components may be used in combination with ethylene glycol, propylene glycol, neopentyl glycol, and the like.

Among the above, preferred aromatic polyarylate resins include those in which the aromatic dicarboxylic acid component is made of terephthalic acid and isophthalic acid, and the dihydric phenol component is made of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A). The ratio of terephthalic acid to isophthalic acid is preferably terephthalic acid/isophthalic acid = 9/1 to 1/9 (molar ratio), and particularly from the standpoint of melt processability and performance balance, 7/3 to 3/7 is desirable.

Other representative aromatic polyarylate resins include those in which the aromatic dicarboxylic acid component is terephthalic acid and the dihydric phenol component is bisphenol A and hydroquinone. The ratio of bisphenol A to hydroquinone is preferably bisphenol A/hydroquinone = 50/50 to 70/30 (molar ratio), more preferably 55/45 to 70/30, and even more preferably 60/40 to 70/30.

In the present invention, the aromatic polyarylate resin preferably has a viscosity average molecular weight in the range of about 7,000 to 100,000 in terms of physical properties and extrusion processability. In addition, the aromatic polyarylate resin can be produced by either the interfacial polycondensation method or the ester exchange reaction method.

Examples of compounds that contain an acid anhydride group but do not contain an olefin component include styrene-maleic anhydride copolymers.

The content of component E is 0.3 to 10 parts by weight, preferably 0.5 to 8 parts by weight, and more preferably 1 to 6 parts by weight, per 100 parts by weight of components A and B. If the content of component E is less than 0.3 parts by weight, the silver suppression effect and the thermal stability improvement effect will be insufficient, resulting in poor appearance of the molded product and reduced impact resistance. On the other hand, a sufficient effect is exhibited at 10 parts by weight or less, so if it exceeds 10 parts by weight, it will lead to increased costs.

<Other ingredients>
The resin composition of the present invention may also contain phosphorus-based stabilizers, hindered phenol-based antioxidants, release agents, ultraviolet absorbers, impact modifiers, dyes and pigments (carbon black, titanium oxide, etc.), and the like.

(i) Phosphorus-based stabilizers, phenol-based stabilizers, and other heat stabilizers It is preferable that various heat stabilizers are blended in the resin composition of the present invention. Phosphorus-based stabilizers are suitable as such heat stabilizers. Examples of phosphorus-based stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof, as well as tertiary phosphines. Such phosphorus-based stabilizers can be used alone or in combination of two or more. Examples of phosphite compounds include trialkyl phosphites such as tridecyl phosphite, dialkyl monoaryl phosphites such as didecyl monophenyl phosphite, monoalkyl diaryl phosphites such as monobutyl diphenyl phosphite, triaryl phosphites such as triphenyl phosphite and tris(2,4-di-tert-butylphenyl)phosphite, distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol, and the like. Examples of the phosphate compound include pentaerythritol phosphites such as 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite and 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite. Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenylmonoorthoxenyl phosphate, tributoxyethyl phosphate, and diisopropyl phosphate, with triphenyl phosphate and trimethyl phosphate being preferred. Preferred examples of the phosphonite compound include tetrakis(di-tert-butylphenyl)-biphenylene diphosphonite and bis(di-tert-butylphenyl)-phenyl-phenyl phosphonite, and more preferred are tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenyl phosphonite. Such phosphonite compounds can be used in combination with the above-mentioned phosphite compounds having an aryl group substituted with two or more alkyl groups, and are therefore preferred. Examples of the phosphonate compounds include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. Examples of the tertiary phosphine include triphenylphosphine.

The content of such phosphorus-based stabilizer is preferably 0.001 to 3.0 parts by weight, more preferably 0.01 to 2.0 parts by weight, and even more preferably 0.05 to 1.0 parts by weight, per 100 parts by weight of the components A and B.

As the hindered phenol compound, various compounds that are usually blended in resins can be used, such as α-tocopherol, butyl hydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxybenzyl phosphonic acid, etc. 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-butylphenyl)propionyloxy]-1,1-dimethylethyl nol), 4,4'-tri-thiobis(2,6-di-tert-butylphenol), 2,2-thiodiethylene bis-[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'-hexamethylene bis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] pionyl]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-tris-2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acetate, 3,9-bis[2-{3-(3-t Examples of the tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acetyloxy]-2,4,8,10-tetraoxaspiro[5,5]undecane, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, 1,3,5-trimethyl-2,4,6-tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)benzene, and tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)isocyanurate are mentioned. Among the above compounds, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane are preferably used in the present invention. In particular, 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane is preferred. The above hindered phenol-based antioxidants can be used alone or in combination of two or more kinds.

The content of the hindered phenol-based antioxidant is preferably 0.001 to 3.0 parts by weight, more preferably 0.01 to 2.0 parts by weight, and even more preferably 0.05 to 1.0 parts by weight, per 100 parts by weight of the components A and B.

The resin composition of the present invention may also contain other heat stabilizers other than the phosphorus-based stabilizer and phenol-based stabilizer. Such other heat stabilizers are preferably used in combination with either one of these stabilizers and antioxidants, and particularly preferably used in combination with both. Suitable examples of such other heat stabilizers include lactone-based stabilizers such as the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (details of such stabilizers are described in JP-A-7-233160). Such compounds are commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and such compounds can be used. Furthermore, stabilizers in which such compounds are mixed with various phosphite compounds and hindered phenol compounds are commercially available. Suitable examples include Irganox HP-2921 manufactured by the above company. Such premixed stabilizers can also be used in the present invention. The amount of lactone stabilizer to be added is preferably 0.0005 to 0.05 parts by weight, and more preferably 0.001 to 0.03 parts by weight, per 100 parts by weight of the components A and B.

Other examples of stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Such stabilizers are particularly effective when the resin composition is applied to rotational molding. The amount of such sulfur-containing stabilizers is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, per 100 parts by weight of the components consisting of components A and B.

(ii) Mold release agent The resin composition of the present invention may contain a mold release agent for the purpose of improving the productivity during molding and reducing distortion of the molded product, within a range that does not impede the effects of the present invention. Known mold release agents can be used. For example, saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes (polyethylene wax, 1-alkene polymers, etc., those modified with functional group-containing compounds such as acid modification can also be used), silicone compounds, fluorine compounds (fluorine oils represented by polyfluoroalkyl ethers, etc.), paraffin wax, beeswax, etc. can be mentioned. Among them, fatty acid esters can be mentioned as a preferred mold release agent. Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. Such aliphatic alcohols may be monohydric alcohols or polyhydric alcohols having dihydric or higher valences. 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 triacontanol. 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, polyhydric alcohols are more preferred. On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably has 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include saturated aliphatic carboxylic acids such as decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, 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 cetoleic acid. Among the above, the aliphatic carboxylic acid is preferably one having 14 to 20 carbon atoms. Among them, saturated aliphatic carboxylic acids are preferred. Stearic acid and palmitic acid are particularly preferred. The above aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from natural oils and fats such as animal oils and fats such as beef tallow and lard, and vegetable oils and fats such as palm oil and sunflower oil, and therefore these aliphatic carboxylic acids are usually mixtures containing other carboxylic acid components with different numbers of carbon atoms. Therefore, in the production of the fatty acid ester of the present invention, aliphatic carboxylic acids produced from such natural oils and fats 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 full ester (full ester). However, partial esters usually have a high hydroxyl value and are prone to inducing decomposition of the resin at high temperatures, so full esters are more preferred. The acid value of the fatty acid ester of the present invention is preferably 20 or less, more preferably in the range of 4 to 20, and even more preferably in the range of 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. The iodine value is preferably 10 or less. The iodine value can be substantially 0. These properties 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, and even more preferably 0.1 to 2.5 parts by weight, per 100 parts by weight of the components A and B.

(iii) UV absorber The resin composition of the present invention may contain a UV absorber. Benzophenone-based examples include 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-sulfoxytrihydridorate 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)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. Benzotriazoles include, 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-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 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, Examples of the polymer include polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton, such as azole, 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-benzoxazin-4-one), and 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, as well as copolymers of 2-(2'-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole and a vinyl monomer copolymerizable with the monomer, and copolymers of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole and a vinyl monomer copolymerizable with the monomer. Examples of hydroxyphenyltriazines include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-ethyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-propyloxyphenol, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-butyloxyphenol. Further examples include compounds in which the phenyl group of the above-mentioned compounds is replaced with a 2,4-dimethylphenyl group, such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol. Examples of cyclic imino esters include 2,2'-p-phenylenebis(3,1-benzoxazin-4-one), 2,2'-(4,4'-diphenylene)bis(3,1-benzoxazin-4-one), and 2,2'-(2,6-naphthalene)bis(3,1-benzoxazin-4-one).

Examples of cyanoacrylates include 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene.

Furthermore, the ultraviolet absorber may be a polymer type ultraviolet absorber in which such an ultraviolet absorbing monomer and/or a light stable monomer having a hindered amine structure is copolymerized with a monomer such as an alkyl (meth)acrylate by adopting a structure of a monomer compound capable of radical polymerization. Suitable examples of the ultraviolet absorbing monomer include compounds 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.

The content of the ultraviolet absorber is preferably 0.01 to 2.0 parts by weight, more preferably 0.02 to 1.5 parts by weight, and even more preferably 0.03 to 1.0 parts by weight, per 100 parts by weight of the components A and B.

(iv) Core-shell type graft polymer The resin composition of the present invention may contain a core-shell type graft polymer. The core-shell type graft polymer is a graft copolymer obtained by copolymerizing a rubber component having a glass transition temperature of 10° C. or less as a core and one or more monomers selected from aromatic vinyl, vinyl cyanide, acrylic acid ester, methacrylic acid ester, and vinyl compounds copolymerizable therewith 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, ethylene-propylene rubber, nitrile rubber, ethylene-acrylic rubber, silicone rubber, epichlorohydrin rubber, fluororubber, and those with hydrogen added to the unsaturated bonds of these. However, rubber components that do not contain halogen atoms are preferable in terms of environmental impact, in view of concerns about the generation of harmful substances during combustion. The glass transition temperature of the rubber component is preferably -10°C or lower, more preferably -30°C or lower, and butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, and acrylic-silicone composite rubber are particularly preferable as rubber components. Composite rubber refers to rubber in which two types of rubber components are copolymerized, or rubber polymerized to form an IPN structure in which the components are intertwined with each other so that they cannot be separated. In the core-shell graft polymer, the core preferably has a weight average particle diameter of 0.05 to 0.8 μm, more preferably 0.1 to 0.6 μm, and even more preferably 0.15 to 0.5 μm. If the particle diameter is in the range of 0.05 to 0.8 μm, better impact resistance is achieved.

Examples of aromatic vinyls in the vinyl compounds copolymerized as the shell of the core-shell graft polymer with the rubber component include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, and halogenated styrene. Examples of acrylic acid esters include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, and octyl acrylate. Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, and octyl methacrylate, with methyl methacrylate being particularly preferred. Among these, it is particularly preferred to contain methacrylic acid esters such as methyl methacrylate as an essential component. This is because the core-shell graft polymer has excellent affinity with the aromatic polycarbonate resin, so that more rubber components are present in the resin, and the excellent impact resistance of the aromatic polycarbonate resin is more effectively exerted, resulting in good impact resistance of the resin composition. More specifically, the methacrylic acid ester is preferably contained in 100% by weight of the graft component (100% by weight of the shell in the case of a core-shell polymer), preferably 10% by weight or more, more preferably 15% by weight or more. The elastic polymer containing a rubber component having a glass transition temperature of 10° C. or less may be produced by any of the polymerization methods of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method may be either one-stage grafting or multi-stage grafting. It may also be a mixture with a copolymer of only the graft component that is a by-product during production. In addition to the general emulsion polymerization method, examples of the polymerization method include a soap-free polymerization method using an initiator such as potassium persulfate, a seed polymerization method, and a two-stage swelling polymerization method. In addition, in the suspension polymerization method, the aqueous phase and the monomer phase are held separately and both are accurately supplied to a continuous disperser, and the particle size is controlled by the rotation speed of the disperser, and in the continuous production method, a method in which the monomer phase is supplied to an aqueous liquid having dispersibility by passing it through a fine orifice or a porous filter having a diameter of several to several tens of μm to control the particle size may be performed. 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, those that have butadiene rubber as the main component as a rubber component include Kane Ace M series manufactured by Kaneka Corporation (e.g. M-711, whose shell component is mainly methyl methacrylate, and M-701, whose shell component is mainly methyl methacrylate and styrene), Metablen C series manufactured by Mitsubishi Rayon Co., Ltd. (e.g. C-223A, whose shell component is mainly methyl methacrylate and styrene), E series (e.g. E-870A, whose shell component is mainly methyl methacrylate and styrene), and Paraloid EXL series manufactured by Dow Chemical Co., Ltd. (e.g. EXL-2690, whose shell component is mainly methyl methacrylate). Examples of rubbers that are mainly made of acrylic rubber or butadiene-acrylic composite rubber include the W series (for example, W-600A, whose shell component is mainly made of methyl methacrylate), and the Paraloid EXL series from Dow Chemical Co., Ltd. (for example, EXL-2390, whose shell component is mainly made of methyl methacrylate), and examples of rubbers that are mainly made of acrylic-silicone composite rubber include Mitsubishi Rayon Co., Ltd.'s Metablen S-2501, whose shell component is mainly made of methyl methacrylate, and SX-200R, whose shell component is mainly made of acrylonitrile-styrene, both of which are commercially available.

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, and further preferably 2 to 7 parts by weight, based on 100 parts by weight of the components consisting of the A component and the B component.

(v) Other Resins/Elastomers The resin composition of the present invention may contain other resins or elastomers in small proportions within the range in which the effects of the present invention are exhibited. Examples of such other resins include AS resins, ABS resins, AES resins, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polymethacrylate resins, phenolic resins, and fluororesins. Examples of elastomers include isobutylene/isoprene rubber, ethylene/propylene rubber, acrylic elastomers, polyester elastomers, and polyamide elastomers.

(vi) Dyes and Pigments The resin composition of the present invention further contains various dyes and pigments, and can provide molded products that exhibit a variety of designs. By blending a fluorescent whitening agent or other fluorescent dyes that emit light, it is possible to impart even better design effects that make use of the emitted color. It is also possible to provide polycarbonate resin compositions that are colored with extremely small amounts of dyes and pigments and have vivid color development.

Fluorescent dyes (including fluorescent whitening agents) used in the present invention include, for example, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, perylene-based fluorescent dyes, anthraquinone-based fluorescent dyes, thioindigo-based fluorescent dyes, xanthene-based fluorescent dyes, xanthone-based fluorescent dyes, thioxanthene-based fluorescent dyes, thioxanthone-based fluorescent dyes, thiazine-based fluorescent dyes, and diaminostilbene-based fluorescent dyes. Among these, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes are preferred because they have good heat resistance and are less susceptible to deterioration during molding of polycarbonate resin.

Dyes other than the above bluing agents and fluorescent dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as Prussian blue, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the resin composition of the present invention can be blended with a metallic pigment to obtain better metallic colors. As metallic pigments, those having a metal coating or a metal oxide coating on various plate-like fillers are suitable.

The content of the dye or pigment is preferably 0.00001 to 1 part by weight, and more preferably 0.00005 to 0.5 parts by weight, per 100 parts by weight of the components A and B.

(vii) Flame retardant Various compounds that are conventionally known as flame retardants for thermoplastic resins, particularly polycarbonate-based resins, can be applied to the resin composition of the present invention, but more preferably, (i) halogen-based flame retardants (e.g., brominated polycarbonate compounds, etc.), (ii) phosphorus-based flame retardants (e.g., monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, and phosphazene compounds, etc.), (iii) metal salt-based flame retardants (e.g., organic sulfonic acid alkali (earth) metal salts, boric acid metal salt-based flame retardants, and stannic acid metal salt-based flame retardants, etc.), and (iv) silicone-based flame retardants made of silicone compounds. Note that the incorporation of the compounds used as flame retardants not only improves flame retardancy, but also improves, for example, antistatic properties, 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, and even more preferably 0.08 to 25 parts by weight, per 100 parts by weight of the components consisting of components A and B. 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, there may be a significant decrease in mechanical properties.

(viii) Highly light-reflective white pigment A highly light-reflective white pigment can be blended into the resin composition of the present invention to impart a light-reflecting effect. Examples of such white pigments include zinc sulfide, zinc oxide, barium sulfate, calcium carbonate, and calcined kaolin. The content of such highly light-reflective white pigment is preferably 1 to 30 parts by weight, and more preferably 3 to 25 parts by weight, per 100 parts by weight of the components consisting of component A and component B. Two or more types of highly light-reflective white pigments can be used in combination.

(ix) Other additives In addition, the resin composition of the present invention may contain small amounts of additives known per se to impart various functions to the molded product or improve its characteristics. These additives are used in normal amounts as long as they do not impair the object of the present invention. Examples of such additives include sliding agents (e.g., PTFE particles), colorants (e.g., pigments such as carbon black, dyes), light diffusing agents (e.g., acrylic crosslinked particles, silicon crosslinked particles, ultrathin glass flakes, calcium carbonate particles), fluorescent dyes, inorganic phosphors (e.g., phosphors with aluminate as the parent crystal), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (e.g., fine titanium oxide particles, fine zinc oxide particles), radical generators, infrared absorbing agents (heat ray absorbing agents), and photochromic agents.

<Method for preparing thermoplastic resin composition>
The resin composition of the present invention is prepared by mixing the above-mentioned components simultaneously or in any order using a mixer such as a tumbler, V-type blender, Nauter mixer, Banbury mixer, kneading roll, or extruder. As a mixer, melt kneading using a twin-screw extruder is preferred, and if necessary, any component is preferably fed into the other melt-mixed components from a second feed port using a side feeder or the like. The resin extruded as described above is directly cut and pelletized, or is pelletized by cutting the strands with a pelletizer after forming them. When it is necessary to reduce the influence of external dust during pelletization, it is preferable to purify the atmosphere around the extruder. The shape of the obtained pellets can be a general shape such as a cylinder, a rectangular column, or a sphere, but is more preferably a cylinder. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and even more preferably 2 to 3.5 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and even more preferably 2.5 to 4 mm.

<Regarding molded articles made of resin compositions obtained by the production method of the present invention>
The resin composition obtained by the manufacturing method of the present invention can be used to manufacture various products by injection molding the pellets obtained by the above-mentioned method. In such injection molding, molded products can be obtained using not only ordinary molding methods but also injection molding methods such as injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including injection of supercritical fluid), insert molding, 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, depending on the purpose. The advantages of these various molding methods are already widely known. In addition, molding can be performed using either a cold runner method or a hot runner method.

The polycarbonate resin composition of the present invention is excellent in mechanical properties, chemical resistance and thermal stability, and is therefore useful not only for indoor/outdoor use, but also for a wide range of applications including housing equipment, building materials, daily necessities, infrastructure equipment, automobiles, office automation/energy, outdoor equipment and other fields. Therefore, the industrial effects of the present invention are extremely great.

The form of the invention that the inventors currently consider to be the best is a combination of the preferred ranges of each of the above requirements, and representative examples are described in the examples below. Of course, the present invention is not limited to these forms.

The present invention will be further described below with reference to examples, which were evaluated by the following methods.
(i) Appearance of Molded Article The appearance of the ISO tensile test specimens prepared by the following method was visually evaluated according to the following criteria.
○: No appearance defect observed ×: Appearance defect such as silver occurred (ii) Thermal stability The viscosity average molecular weight of the melt-kneaded pellets obtained by the following method was measured by the method described in the present text. On the other hand, the viscosity average molecular weight of the polycarbonate powder before melt-kneading was also measured in the same manner. The value obtained by subtracting the molecular weight after melt-kneading from the molecular weight before melt-kneading was evaluated as ΔMv. It can be said that the smaller the ΔMv, the better the thermal stability.
(iii) Flexural Modulus Using an ISO flexural test piece obtained by the following method, the flexural modulus was measured in an atmosphere at a temperature of 80° C. according to ISO 178. The resin composition of the present invention needs to have a flexural modulus of 2,000 MPa or more.
(iv) Charpy impact strength Using an ISO bending test piece obtained by the following method, the notched Charpy impact strength was measured according to ISO179 under an atmosphere of 23°C and 50% RH. The resin composition of the present invention needs to have a Charpy impact strength of 3 J/ ^m2 or more. (v) Chemical resistance Using an ISO tensile test piece obtained by the following method, a 1% strain was applied by a three-point bending test method, and then a cloth impregnated with Magiclean (manufactured by Kao Corporation) was placed over the test piece, and the test piece was left at 23°C for 96 hours, after which the presence or absence of any change in appearance was confirmed. The evaluation was performed according to the following criteria.
◯: No change in appearance was observed △: Fine cracks were observed ×: Large cracks that could lead to breakage were observed

[Examples 1 to 25, Comparative Examples 1 to 8]
A mixture consisting of the components listed in Tables 1 and 2, excluding the polypropylene resin of component B and the inorganic filler of component D, was supplied from the first supply port of the extruder. This mixture was obtained by mixing with a V-type blender. The polypropylene resin of component B and the inorganic filler of component D were each supplied from the second supply port using a side feeder. Extrusion was performed using a vented twin-screw extruder (TEX30α-38.5BW-3V, Japan Steel Works, Ltd.) with a diameter of 30 mmφ, with a screw rotation speed of 230 rpm, a discharge rate of 25 kg/h, and a vent vacuum of 3 kPa to obtain pellets. The extrusion temperature was 260°C from the first supply port to the die portion. The obtained pellets were dried in a hot air circulation dryer at 100°C for 6 hours, and then molded into ISO bending test pieces and ISO tensile test pieces for evaluation using an injection molding machine (cylinder temperature 260°C, mold temperature 60°C).

The following raw materials were used:
(Component A)
A-1: Aromatic polycarbonate resin (polycarbonate resin powder having a viscosity average molecular weight of 19,800, produced by a conventional method from bisphenol A and phosgene, manufactured by Teijin Limited, Panlite L-1225WX (product name))
A-2: Aromatic polycarbonate resin (polycarbonate resin powder having a viscosity average molecular weight of 25,100, produced by a conventional method from bisphenol A and phosgene, manufactured by Teijin Limited, Panlite L-1250WQ (product name))
A-3: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight 19,800, PDMS content 8.4%, PDMS polymerization degree 37)

(Component B)
B-1: Polypropylene resin (homopolymer, MFR: 2g/10min, SanAllomer PL400A (product name) manufactured by SanAllomer Co., Ltd.)
B-2: Polypropylene resin (homopolymer, MFR: 70 g/10 min, Sanallomer PLB00A (product name) manufactured by Sanallomer Co., Ltd.)
B-3: Polypropylene resin (block polymer, MFR: 1.5 g/10 min, Sanallomer VB370BA (product name) manufactured by Sanallomer Co., Ltd.)

(Component C)
C-1: Styrene-ethylene propylene-styrene block copolymer (styrene content: 65 wt%, MFR: 0.4 g/10 min, Septon 2104 (product name) manufactured by Kuraray Co., Ltd.)
C-2: Styrene-butadiene-butylene-styrene block copolymer (styrene content: 67 wt%, MFR: 28 g/10 min, Asahi Kasei Chemicals Corporation, Tuftec P2000 (product name))

(Component D)
D-1: Wollastonite (average particle size 3 μm, Kinsei Matec Co., Ltd. SH-1800 (product name))
D-2: Wollastonite (average particle size 5 μm, Kinsei Matec Co., Ltd. SH-1250 (product name))
D-3: Mica (GM-6 (product name) manufactured by Kinsei Matec Co., Ltd.)
D-4: Talc (manufactured by Shokozan Mining Co., Ltd.: Victorilite TK-RC (product name))

(Component E)
E-1: Bisphenol A type epoxy resin (product name jER1256 manufactured by Mitsubishi Chemical Corporation)
E-2: A copolymer obtained by graft-polymerizing a glycidyl methacrylate-styrene-acrylonitrile copolymer onto polycarbonate (product name: Modiper CL430-G, manufactured by NOF Corporation)
E-3: Polybutylene terephthalate resin (BASF Japan Ltd., product name B2550)
E-4: Styrene-maleic anhydride copolymer (XIBOND140 (product name) manufactured by POLYSCOPE POLYMERS B.V.)
E-5: Ethylene-glycidyl methacrylate copolymer (product name: Bondfast-E, manufactured by Sumitomo Chemical Co., Ltd.)

(Other ingredients)
F-1: Phosphorus-based stabilizer (trimethyl phosphate, TMP (product name) manufactured by Daihachi Chemical Industry Co., Ltd.)
F-2: Phenol-based heat stabilizer (octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, molecular weight 531, Irganox 1076 (product name) manufactured by BASF Japan Ltd.)
F-3: Butadiene-based core-shell type graft polymer (a graft copolymer having a core-shell structure in which the core is 70 wt% butadiene rubber as the main component and the shell is 30 wt% methyl methacrylate and styrene as the main components, manufactured by Kaneka Corporation, Kane Ace M-701 (product name))
F-4: Carbon black (manufactured by Koshigaya Chemical Industries, Ltd.: ROYAL BLACK RB90003S (product name))

From the above table, it can be seen that by adding a compound that contains at least one functional group selected from the group consisting of epoxy groups, carboxy groups, and acid anhydride groups and does not contain an olefin component to a component consisting of a polycarbonate resin, a polypropylene resin, a styrene-based thermoplastic elastomer, and an inorganic filler, it is possible to obtain a polycarbonate resin composition with improved mechanical properties, chemical resistance, and thermal stability.

Claims (5)

A polycarbonate resin composition comprising 100 parts by weight of a component consisting of 40 to 90 parts by weight of (A) a polycarbonate-based resin (component A) and 60 to 10 parts by weight of (B) a polypropylene-based resin (component B), and containing 1 to 20 parts by weight of (C) a styrene-based thermoplastic elastomer (component C), 5 to 100 parts by weight of (D) an inorganic filler ( component D), and 0.3 to 10 parts by weight of (E) at least one compound (component E) selected from the group consisting of bisphenol A type epoxy resin, a styrene-maleic anhydride copolymer, and a glycidyl methacrylate copolymer not containing an olefin component . The polycarbonate resin composition according to claim 1, characterized in that component D is a silicate mineral. The polycarbonate resin composition according to claim 1 or 2, characterized in that the styrene content of component C is 40 to 80% by weight. The polycarbonate resin composition according to any one of claims 1 to 3, characterized in that component C is a block copolymer in which the hydrogenated polydiene units are hydrogenated butadiene units and which has ethylene-butylene block units. The polycarbonate resin composition according to any one of claims 1 to 3, characterized in that component C is a block copolymer in which the hydrogenated polydiene units are partially hydrogenated butadiene units and which has butadiene-butylene block units.