CN114630859A

CN114630859A - Polycarbonate resin composition and molded article thereof

Info

Publication number: CN114630859A
Application number: CN202080076197.0A
Authority: CN
Inventors: 矶江晋辅
Original assignee: Teijin Ltd
Current assignee: Teijin Ltd
Priority date: 2019-10-31
Filing date: 2020-10-26
Publication date: 2022-06-14
Also published as: JPWO2021085384A1; WO2021085384A1

Abstract

The invention provides a polycarbonate resin composition having excellent continuous antistatic property and thermal stability, and a molded body thereof. The resin composition of the present invention is characterized in that: comprising (A) an aromatic polycarbonate resin (component A) and 0.3 to 5 parts by weight of (B) an ion pair compound (component B) per 100 parts by weight of the aromatic polycarbonate resin; the melting point of the ion pair compound is 80 ℃ or lower, the 5% weight loss temperature measured by TG-TDA is 350 ℃ or higher, and the following formula (1) R is satisfied₁＞R_D-20 (1) (wherein R is₁Being ion pair compoundsA contact angle (. degree.) of a water droplet of the above resin composition in an amount of 2 parts by weight, R_DThe contact angle (°)) of a water droplet of the aromatic polycarbonate resin.

Description

Polycarbonate resin composition and molded article thereof

Technical Field

The present invention relates to a polycarbonate resin composition. More particularly, the present invention relates to a polycarbonate resin composition to which good antistatic properties and thermal stability are imparted.

Background

Polycarbonate resins are used in a variety of applications such as machine parts, automobile parts, electric and electronic parts, office equipment parts, and the like because of their excellent properties such as mechanical strength, dimensional stability, and flame retardancy. On the other hand, since it has a property of high surface resistivity, when static electricity is generated on the surface of a molded article of polycarbonate resin, dust adheres to the surface and is not easily removed, and there is a risk of causing problems such as failure when the molded article is produced into an electrical device part. Therefore, a large number of techniques relating to polycarbonate resin compositions imparted with antistatic properties have been studied, and the use of sulfonic acids has been proposed

A method using a salt (see patent document 1) and a method using a surfactant such as a glycerin fatty acid ester (see patent document 2).

However, the polycarbonate resin compositions described in patent documents 1 and 2 have a drawback that the antistatic property is poor in durability such that the effect is significantly reduced by one-time washing with water. On the other hand, as a method for imparting a continuous antistatic property, a method using polyether ester amide has been proposed (see patent document 3), but the following disadvantages are present: a disadvantage of deteriorated thermal stability during melt kneading and injection molding, a disadvantage of lowered heat resistance (deflection temperature under load), and a disadvantage of difficulty in achieving good transparency at the same time.

Documents of the prior art

Patent document

Patent document 1 Japanese patent No. 4606762

Patent document 2 Japanese patent No. 6215717

Patent document 3 Japanese laid-open patent publication No. 2002-129026

Disclosure of Invention

The invention aims to provide a polycarbonate resin composition with excellent continuous antistatic property and thermal stability and a formed body thereof.

The present inventors have made intensive studies and as a result have found that the above problems can be solved by using a polycarbonate resin composition containing a specific ion-pair compound. That is, the present inventors have found that the above-mentioned problems can be achieved by the following polycarbonate resin composition and a molded article thereof.

1. A resin composition comprising (A) an aromatic polycarbonate resin (component A) and 0.3 to 5 parts by weight of (B) an ion-pair compound (component B) per 100 parts by weight of the aromatic polycarbonate resin;

the melting point of the ion pair compound is 80 ℃ or lower,

a 5% weight loss temperature of 350 ℃ or higher as measured by TG-TDA (thermogravimetric differential thermal analysis), and

satisfies the following formula (1) R₁＞R_D-20 (1) (wherein R is₁The contact angle (DEG), R, of a water droplet of the resin composition containing 2 parts by weight of an ion-pairing compound_DThe contact angle (°)) of a water droplet of the aromatic polycarbonate resin.

2. The resin composition according to the above item 1, which satisfies the following formula (2).

R₁＞R_D-15 (2) (wherein R is₁The contact angle (DEG), R, of a water droplet of the resin composition containing 2 parts by weight of an ion-pairing compound_DIs a contact angle (. degree.) of a water droplet of an aromatic polycarbonate resin

3. The resin composition according to the aforementioned item 1 or 2, characterized in that the ion pair compound is a compound represented by the following formula (I).

[(R₁)₃R₂P]⁺·M^- (I)

[ wherein, R₁Represents an alkyl group having 6 to 12 carbon atoms, R₂Represents an alkyl group having 10 to 20 carbon atoms, M^-Represents any anion.]

4. The resin composition according to the preceding item 3, wherein M is^-Is represented by the following formula (II).

(R₃SO₂)(R₄SO₂)N^- (II)

[ in the formula, R₃、R₄Each having 1 to c atoms4 perfluoroalkyl group, R₃、R₄May be the same or different.]

5. The resin composition according to the preceding item 3 or 4, wherein R is₁Is straight-chain alkyl with 6-8 carbon atoms, R₂Is a C12-C16 linear alkyl group, R₃、R₄Each of which is a perfluoroalkyl group having 1 to 4 carbon atoms.

6. The resin composition according to the preceding item 3 or 4, wherein R is₁Is a linear alkyl group having 6 carbon atoms, R₂Is a linear alkyl group of 14 carbon atoms, R₃、R₄Each is trifluoromethyl.

7. The resin composition as described in any of the above items 1 to 6, wherein the phosphorus-based heat stabilizer (C component) is contained in an amount of 0.001 to 0.5 part by weight based on 100 parts by weight of the A component.

8. A molded article obtained by molding the resin composition according to any one of items 1 to 7.

The polycarbonate resin composition of the present invention is excellent in long-lasting antistatic properties and thermal stability, and therefore, is useful in the information field such as a transport tray for semiconductor parts, which is highly required to suppress dust adsorption. Further, the present invention is also useful in the optical field of lenses used in vehicle cameras, smart phones, and the like, which are further required to have transparency. The resin material has a disadvantage that dust is easily attached to the resin material, which causes a reduction in image quality and a reduction in sensor function. Further, the antistatic coating composition is also useful in the field of automobiles requiring continuous antistatic properties (interior parts requiring good appearance, etc.). Therefore, the present invention provides a great industrial effect.

Detailed Description

(component A: aromatic polycarbonate resin)

The aromatic polycarbonate resin used as component A 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 molten transesterification method, a solid-phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

Representative examples of the dihydric phenol used herein include hydroquinone, resorcinol, 4 '-biphenol, 1-bis (4-hydroxyphenyl) ethane, 2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A), 2-bis (4-hydroxy-3-methylphenyl) propane, 2-bis (4-hydroxyphenyl) butane, 1-bis (4-hydroxyphenyl) -1-phenylethane, 1-bis (4-hydroxyphenyl) cyclohexane, 1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane, 2-bis (4-hydroxyphenyl) pentane, 4' - (p-phenylenediisopropylidene) diphenol, 4 '-diphenylene, 4' -bis (4-hydroxyphenyl) propane, 1, 2-bis (4-hydroxyphenyl) propane, 1-bis (4-hydroxyphenyl) propane, 1,3, 5-trimethylcyclohexane, and the like, 4,4' - (m-phenylenediisopropylidene) diphenol, 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-bis (4-hydroxyphenyl) fluorene, 9-bis (4-hydroxy-3-methylphenyl) fluorene and the like. The preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, of which bisphenol A is particularly preferred from the viewpoint of impact resistance, and is commonly used.

In the present invention, in addition to bisphenol A type polycarbonate which is a general-purpose polycarbonate, a specific polycarbonate produced from other 2-membered phenols may be used as the component A.

For example, a polycarbonate (homopolymer or copolymer) using 4,4' - (m-phenylenediisopropylidene) diphenol (hereinafter, abbreviated as "BPM"), 1-Bis (4-hydroxyphenyl) cyclohexane, 1-Bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane (hereinafter, abbreviated as "Bis-TMC"), 9-Bis (4-hydroxyphenyl) fluorene and 9, 9-Bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter, abbreviated as "BCF") as a part or all of the 2-membered phenol component is suitable for use in applications where the requirements for dimensional change and morphological stability due to water absorption are particularly strict. The 2-membered phenol other than BPA is preferably used in an amount of 5 mol% or more, particularly preferably 10 mol% or more, based on the whole 2-membered phenol component constituting the polycarbonate.

Particularly when high rigidity and further good hydrolysis resistance are required, the copolycarbonates of the following (1) to (3) are particularly preferable as the component A constituting the resin composition.

(1) A copolycarbonate wherein BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, and still more preferably 45 to 65 mol%) and BCF is 20 to 80 mol% (more preferably 25 to 60 mol%, and still more preferably 35 to 55 mol%) based on 100 mol% of a 2-membered phenol component constituting the polycarbonate.

(2) A copolycarbonate wherein BPA accounts for 10 to 95 mol% (more preferably 50 to 90 mol%, and still more preferably 60 to 85 mol%) and BCF accounts for 5 to 90 mol% (more preferably 10 to 50 mol%, and still more preferably 15 to 40 mol%) in 100 mol% of a 2-membered phenol component constituting the polycarbonate.

(3) A copolycarbonate wherein BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, and still more preferably 45 to 65 mol%) and Bis-TMC is 20 to 80 mol% (more preferably 25 to 60 mol%, and still more preferably 35 to 55 mol%) based on 100 mol% of a 2-membered phenol component constituting the polycarbonate.

These specific polycarbonates may be used alone or in combination of 2 or more kinds thereof. Further, they may be used in combination with a general bisphenol A type polycarbonate.

The production method and properties of these specific polycarbonates are described in detail in, for example, Japanese patent application laid-open Nos. 6-172508, 8-27370, 2001-55435, 2002-117580, and the like.

Among the above-mentioned various polycarbonates, the adjustment of the copolymerization composition and the like so that the water absorption rate and Tg (glass transition temperature) are within the range of (i) or (ii) described below is particularly preferable in the field where morphological stability is required, because the hydrolysis resistance of the polymer itself is good and the low warpage property after molding is also excellent.

(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 ℃.

(ii) A polycarbonate having a Tg of 160 to 250 ℃, preferably 170 to 230 ℃ 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 of the polycarbonate is measured by using a disk-shaped test piece having a diameter of 45mm and a thickness of 3.0mm, and measuring the water absorption after immersion in water at 23 ℃ for 24 hours in accordance with ISO 62-1980. The Tg (glass transition temperature) is a value determined by measurement with a Differential Scanning Calorimeter (DSC) according to JIS K7121.

As the carbonate precursor, a carbonyl halide, a carbonic diester, a haloformate, or the like can be used, and specifically, phosgene, diphenyl carbonate, a dihaloformate of a dihydric phenol, or the like can be mentioned.

When the above-mentioned dihydric phenol and the carbonate precursor are subjected to an interfacial polymerization method to produce a polycarbonate resin, a catalyst, a terminal terminator, an antioxidant for preventing oxidation of the dihydric phenol, and the like may be used as necessary. Further, the polycarbonate resin of the present invention comprises: a branched polycarbonate resin obtained by copolymerizing a polyfunctional aromatic compound having three or more functions, a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic (alicyclic group-containing) bifunctional carboxylic acid, a copolycarbonate resin obtained by copolymerizing a bifunctional alcohol (alicyclic group-containing) and a polyester carbonate resin obtained by copolymerizing the bifunctional carboxylic acid and the bifunctional alcohol at the same time. Further, a mixture of 2 or more kinds of the obtained polycarbonate resins may be used.

The branched polycarbonate resin may impart drip-proof properties to the resin composition of the present invention. Examples of the polyfunctional aromatic compound having three or more functions used for the branched polycarbonate resin include phloroglucinol, or 4, 6-dimethyl-2, 4, 6-tris (4-hydroxyphenyl) heptene-2, 4, 6-trimethyl-2, 4, 6-tris (4-hydroxyphenyl) heptane, 1,3, 5-tris (4-hydroxyphenyl) benzene, 1,1, 1-tris (4-hydroxyphenyl) ethane, 1,1, 1-tris (3, 5-dimethyl-4-hydroxyphenyl) ethane, 2, 6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [1, 1-bis (4-hydroxyphenyl) ethyl ] benzene } -alpha, triphenols such as α -dimethylbenzylphenol, tetrakis (4-hydroxyphenyl) methane, bis (2, 4-dihydroxyphenyl) ketone, 1, 4-bis (4, 4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, and acid chlorides thereof, and 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 constituent unit derived from a polyfunctional aromatic compound in the branched polycarbonate is preferably 0.01 to 1 mol%, more preferably 0.05 to 0.9 mol%, and still more preferably 0.05 to 0.8 mol% of the total 100 mol% of the constituent unit derived from a 2-membered phenol and the constituent unit derived from the polyfunctional aromatic compound.

In particular, in the case of the melt transesterification method, when a branched structural unit is generated as a side reaction, the amount of the branched structural unit is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and further preferably 0.01 to 0.8 mol% of the total 100 mol% of the constituent units derived from 2-membered phenol. The ratio of the branched structure may be determined by¹H-NMR measurement was carried out.

The aliphatic difunctional carboxylic acids are preferably alpha, omega-dicarboxylic acids. Examples of the aliphatic difunctional carboxylic acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid and eicosanedioic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. The bifunctional alcohol is more preferably an alicyclic diol, and examples thereof include cyclohexanedimethanol, cyclohexanediol, tricyclodecanedimethanol, and the like.

The reaction forms of the interfacial polymerization method, the melt transesterification method, the carbonate prepolymer solid-phase transesterification method, the ring-opening polymerization method of a cyclic carbonate compound, and the like, which are the methods for producing an aromatic polycarbonate resin of the present invention, may be known from various documents, patent publications, and the like.

The melt index (300 ℃ C., 1.2kg load) of the aromatic polycarbonate resin in the present invention is not particularly limited, but is preferably 1 to 60cm³A/10 min, more preferably 3-30 cm³A concentration of 10min, preferably 5 to 20cm³And/10 min. From a melt index of less than 1cm³10min aromatic polycarbonateThe resin composition obtained from the ester resin may have poor flowability in injection molding, and in this respect, the general-purpose property may be poor. On the other hand, if the melt index is more than 60cm³The polycarbonate-based resin of/10 min may not have good mechanical properties. It should be noted that the melt index, also referred to as "MVR", can be determined in accordance with ISO 1133.

As the aromatic polycarbonate resin (component A) of the present invention, a polycarbonate-polydiorganosiloxane copolymer resin can be used. 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), R¹And R²Each independently represents a group selected from 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 aralkoxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group, and may be the same or different when the number of the groups is plural, e and f are each an integer of 1 to 4, and W is a single bond or at least one group selected from the group represented by the following general formula (2).]

[ in the above general formula (2), R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷And R¹⁸Each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 20 carbon atomsRadical of (II), R¹⁹And R²⁰Each 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 carboxyl group, and when there are a plurality of them, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7.]

[ in the above general formula (3), R³、R⁴、R⁵、R⁶、R⁷And R⁸Each independently represents a group selected from a hydrogen atom, an alkyl group having 1 to 12 carbon atoms and a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, R⁹And R¹⁰Each independently represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms and 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 of 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-bis (4-hydroxyphenyl) ethane, 1-bis (4-hydroxyphenyl) -1-phenylethane, 2-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3-methylphenyl) propane, 1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane, 2-bis (4-hydroxy-3, 3' -biphenyl) propane, 2-bis (4-hydroxy-3-isopropylphenyl) propane, 2-bis (3-tert-butyl-4-hydroxyphenyl) propane, and the like, 2, 2-bis (4-hydroxyphenyl) butane, 2-bis (4-hydroxyphenyl) octane, 2-bis (3-bromo-4-hydroxyphenyl) propane, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, 2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 9-bis (4-hydroxyphenyl) fluorene, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 1-bis (4-hydroxyphenyl) cyclohexane, 1-bis (4-hydroxyphenyl) cyclopentane, 1-bis (4-hydroxyphenyl) cyclopentane, 2-bis (4-hydroxyphenyl) octane, 2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 9-bis (4-hydroxyphenyl) fluorene, 4,4' -dihydroxydiphenyl ether, 4' -dihydroxy-3, 3' -dimethyldiphenyl ether, 4' -sulfonyldiphenol, 4' -dihydroxydiphenyl sulfoxide, 4' -dihydroxydiphenyl sulfide, 2' -dimethyl-4, 4' -sulfonyldiphenol, 4' -dihydroxy-3, 3' -dimethyldiphenyl sulfoxide, 4' -dihydroxy-3, 3' -dimethyldiphenyl sulfide, 2' -diphenyl-4, 4' -sulfonyldiphenol, 4' -dihydroxy-3, 3' -diphenyldiphenyl sulfoxide, 4' -dihydroxy-3, 3' -diphenylsulfide, 4' -dihydroxydiphenyl sulfide, 4' -dimethyldiphenyl sulfide, 4' -dihydroxydiphenyl sulfide, 4' -dihydroxydiphenyl-3, 4' -sulfonyldiphenol, 4' -dimethyldiphenyl sulfide, 4' -dihydroxydiphenyl, 4' -diphenyl, 4' -dihydroxydiphenyl, 4' -diphenyl, 4,3, 4,3' -diphenyl, 3, or a mixture of a, 1, 3-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' - (1, 3-adamantanediyl) diphenol, 1, 3-bis (4-hydroxyphenyl) -5, 7-dimethyladamantane, and the like.

Among them, preferred are 1, 1-bis (4-hydroxyphenyl) -1-phenylethane, 2-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3-methylphenyl) propane, 1-bis (4-hydroxyphenyl) cyclohexane, 1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane, 4' -sulfonyldiphenol, 2' -dimethyl-4, 4' -sulfonyldiphenol, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 1, 3-bis {2- (4-hydroxyphenyl) propyl } benzene, 1, 4-bis {2- (4-hydroxyphenyl) propyl } benzene, particularly preferred are 2, 2-bis (4-hydroxyphenyl) propane, 1-bis (4-hydroxyphenyl) cyclohexane (BPZ), 4' -sulfonyldiphenol, and 9, 9-bis (4-hydroxy-3-methylphenyl) fluorene. Among them, 2-bis (4-hydroxyphenyl) propane, which is excellent in strength and has good durability, is most preferable. 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 following compounds can be preferably used.

The hydroxyaryl-terminated polydiorganosiloxane (II) can be easily produced by subjecting a phenol having an olefinic unsaturated carbon-carbon bond and the end of a polysiloxane chain having a predetermined degree of polymerization to a hydrosilylation reaction, and the phenol is preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol. Among them, a (2-allylphenol) -terminated polydiorganosiloxane and a (2-methoxy-4-allylphenol) -terminated polydiorganosiloxane are preferable, and a (2-allylphenol) -terminated polydimethylsiloxane and a (2-methoxy-4-allylphenol) -terminated polydimethylsiloxane are particularly preferable. The molecular weight distribution (Mw/Mn) of the hydroxyaryl-terminated polydiorganosiloxane (II) is preferably 3 or less. Further, in order to exhibit excellent low outgassing property and low temperature impact property at the time of high temperature molding, the molecular weight distribution (Mw/Mn) is more preferably 2.5 or less, and still more preferably 2 or less. If the content is more than the upper limit of the preferable range, the amount of outgas generated during high-temperature molding may be large, and the low-temperature impact property may be poor.

In addition, in order to achieve high impact resistance, the polymerization degree (p + q) of diorganosiloxane of hydroxyaryl-terminated polydiorganosiloxane (II) is preferably 10 to 300. The polymerization degree (p + q) of the diorganosiloxane is preferably 10 to 200, more preferably 12 to 150, and still more preferably 14 to 100. If the lower limit of the preferred range is less than the lower limit of the preferred range, the impact resistance, which is a characteristic of the polycarbonate-polydiorganosiloxane copolymer, cannot be effectively exhibited, and if the upper limit of the preferred range is more than the lower limit of the preferred range, appearance defects may occur.

The content of the polydiorganosiloxane in the total weight of the polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.1 to 50 wt%. The polydiorganosiloxane component is more preferably contained in an amount of 0.5 to 30 wt%, and still more preferably 1 to 20 wt%. When the lower limit of the preferable range is not less than the upper limit of the preferable range, the impact resistance and flame retardancy are excellent, and when the upper limit of the preferable range is not more than the lower limit of the preferable range, the stable appearance which is not easily affected by molding conditions can be easily obtained. The polymerization degree and the content of the polydiorganosiloxane can be adjusted¹H-NMR measurement was carried out.

In the present invention, the hydroxyaryl-terminated polydiorganosiloxane (II) may be used alone or in combination of 1 or more.

In addition, other comonomers than the dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) may be used in combination within a range of 10 wt% or less based on the total weight of the copolymer within a range not to impair the present invention.

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

In the case of producing the oligomer of the dihydric phenol (I), the total amount of the dihydric phenol (I) used in the method of the present invention may be once formed into an oligomer, or a part thereof may be added as a monomer to be added later and may be added as a reaction raw material in the interfacial polycondensation reaction in the later stage. The post-addition monomer is a monomer added for rapidly advancing the polycondensation reaction in the subsequent stage, and when not necessary, it is not necessary to add it.

The mode of the oligomer formation reaction is not particularly limited, and is preferably a mode in which the reaction is carried out in a solvent in the presence of an acid-binding agent.

The proportion of the carbonate-forming compound to be used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. When a gaseous carbonate-forming compound such as phosgene is used, it is preferable to employ a method of blowing the gaseous carbonate-forming compound into the reaction system.

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

As the solvent, a solvent which is inactive in various reactions, such as a solvent used in the production of a known polycarbonate, can be used, and 1 kind of solvent can be used alone or as a mixed solvent. Typical examples thereof include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. In particular, a halogenated hydrocarbon solvent such as methylene chloride is preferably used.

The reaction pressure for forming the oligomer is not particularly limited, and may be any of normal pressure, elevated pressure and reduced pressure, and it is usually advantageous to carry out the reaction under normal pressure. The reaction temperature is selected from the range of-20 to 50 ℃ and, in most cases, heat generation is caused by polymerization, and therefore, water cooling or ice cooling is desirable. The reaction time is not generally specified depending on other conditions, but is usually within 0.2 to 10 hours. The pH of the oligomer formation reaction is usually 10 or more, as in the case of the known interfacial reaction conditions.

The present invention has been made in this manner, and a polycarbonate-polydiorganosiloxane copolymer is obtained by obtaining a mixed solution containing an oligomer of a dihydric phenol (I) having a terminal chloroformate group, stirring the mixed solution, and simultaneously adding a hydroxyaryl-terminated polydiorganosiloxane (II) highly purified to have a molecular weight distribution (Mw/Mn) of 3 or less, represented by general formula (3), to the dihydric phenol (I), and subjecting the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer to interfacial polycondensation.

(in the above general formula (3), R³、R⁴、R⁵、R⁶、R⁷And R⁸Each independently represents a group selected from 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, R⁹And R¹⁰Each independently represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and 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 of 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms. )

In the interfacial polycondensation reaction, an acid-binding agent may be added appropriately in consideration of the stoichiometric ratio (equivalent) of the reaction. Examples of the acid-binding agent 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 a part of the hydroxyaryl-terminated polydiorganosiloxane (II) or the above-mentioned dihydric phenol (I) is added as a post-addition monomer to the reaction stage, it is preferable to use 2 equivalents or an excess amount of the base relative to the total mole number (usually 1 mole corresponds to 2 equivalents) of the dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) in the post-addition part.

The polycondensation by the interfacial polycondensation reaction of the oligomer of the dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) can be performed by vigorously stirring the above-described mixed liquid.

In the polymerization reaction, a terminal terminator or a molecular weight regulator is generally used. Examples of the terminal terminator include compounds having a monovalent phenolic hydroxyl group, and examples thereof include long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, alkyl hydroxybenzoates, hydroxyphenyl alkyl esters, and alkyl ether phenols, in addition to ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, and the like. The amount of the compound to be used is 100 to 0.5 mol, preferably 50 to 2mol, based on 100 mol of all the diphenol compounds to be used, but two or more compounds may be used 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 of the polymerization reaction is preferably 30 minutes or more, and more preferably 50 minutes or more. Antioxidants such as sodium sulfite and hydrosulfide may be added in a small amount as desired.

The branching agent may be used in combination with the above-mentioned dihydric phenol compound to prepare a branched polycarbonate-polydiorganosiloxane. Examples of the polyfunctional aromatic compound having three or more functions used in the branched polycarbonate-polydiorganosiloxane copolymer resin include phloroglucinol, 4, 6-dimethyl-2, 4, 6-tris (4-hydroxyphenyl) heptene-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, triphenols such as 1-bis (4-hydroxyphenyl) ethyl ] benzene } -alpha, alpha-dimethylbenzylphenol, tetrakis (4-hydroxyphenyl) methane, bis (2, 4-dihydroxyphenyl) ketone, 1, 4-bis (4, 4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, and acid chlorides thereof, among which 1,1, 1-tris (4-hydroxyphenyl) ethane and 1,1, 1-tris (3, 5-dimethyl-4-hydroxyphenyl) ethane are 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%, even 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 the branched structure may be determined by¹H-NMR measurement was carried out.

The reaction pressure may be any of reduced pressure, normal pressure and increased pressure, and it is generally preferred to carry out the reaction at normal pressure or at the autogenous pressure level of the reaction system. The reaction temperature is selected from the range of-20 to 50 ℃ and, in most cases, heat generation is caused by polymerization, and therefore, water cooling or ice cooling is desirable. The reaction time varies depending on other conditions such as the reaction temperature, and therefore, cannot be defined in general, but is usually carried out within 0.5 to 10 hours.

In some cases, the obtained polycarbonate-polydiorganosiloxane copolymer resin can be obtained as a polycarbonate-polydiorganosiloxane copolymer resin having a desired reduced viscosity [. eta.SP/c ] by subjecting the polycarbonate-polydiorganosiloxane copolymer resin to appropriate physical treatment (mixing, classification, etc.) and/or chemical treatment (polymerization reaction, crosslinking treatment, partial decomposition treatment, etc.).

The obtained reaction product (crude product) can be subjected to various post-treatments such as a known separation and purification method, and recovered as a polycarbonate-polydiorganosiloxane copolymer resin having a desired purity (degree of purification).

The average size of the polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molded article is preferably in the range of 1 to 40 nm. The average size is more preferably 1 to 30nm, and still more preferably 5 to 25 nm. If the content is less than the lower limit of the preferred range, impact resistance and flame retardancy cannot be sufficiently exhibited, and if the content is more than the upper limit of the preferred range, impact resistance may not be stably exhibited. Thus, a resin composition excellent in impact resistance and appearance can be provided.

The average domain size of the polydiorganosiloxane domains of the polycarbonate-polydiorganosiloxane copolymer resin molded article of the invention was evaluated by Small Angle X-ray Scattering (SAXS). The small angle X-ray scattering method is a method for measuring diffuse scattering and diffraction generated in a small angle region having a scattering angle (2 θ) < 10 °. In the small angle X-ray scattering method, if there are regions having different electron densities of about 1 to 100nm in a substance, the diffuse scattering of X-rays can be measured from the difference in electron density. The particle size of the object to be measured is determined based on the scattering angle and the scattering intensity. In the case of a polycarbonate-polydiorganosiloxane copolymer resin in which polydiorganosiloxane domains are dispersed in a matrix of a polycarbonate polymer to form an agglomerated structure, diffuse scattering of X-rays occurs due to the difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domains. The scattering intensity I at each scattering angle (2 θ) in the range of less than 10 ° of the scattering angle (2 θ) was measured, the small angle X-ray scattering profile was measured, and the average size of the polydiorganosiloxane domains was determined by performing a simulation using commercially available analytical software from the assumed particle diameter and the assumed particle diameter distribution model, assuming that the polydiorganosiloxane domains are spherical domains and there is unevenness in particle diameter distribution. The average size of the polydiorganosiloxane domains dispersed in the matrix of the polycarbonate polymer, which cannot be accurately measured by observation with a transmission electron microscope, can be measured with high accuracy, simplicity, and good reproducibility by the small angle X-ray scattering method. The average domain size refers to the number average of the individual domain sizes.

The term "average domain size" used in connection with the present invention means a measured value obtained by measuring a 1.0mm portion of the thickness of a 3-segment plate produced by the method described in the examples by the small angle X-ray scattering method. In addition, analysis was performed using an isolated particle model without considering the interaction between particles (inter-particle interference).

(component B: ion pair Compound)

The ion pair compound used in the present invention is used as an antistatic agent, has a melting point of 80 ℃ or lower, a 5% weight loss temperature measured by TG-TDA of 350 ℃ or higher, and satisfies the following formula (1)

R₁＞R_D-20 (1)

(wherein R is₁The contact angle (DEG), R, of a water droplet of the resin composition containing 2 parts by weight of an ion-pairing compound_DThe contact angle (°)) of a water droplet of the aromatic polycarbonate resin. As the antistatic agent other than the ion pair compound, a surfactant such as glycerin fatty acid ester is used, but the resin composition using these surfactants is inferior in the antistatic property and thermal stability. Further, as an antistatic agent which is not an ion-pairing compound, there are also polymer materials such as polyether, but a resin composition using these materials has a disadvantage of not causing transparency and a disadvantage of being inferior in thermal stability and deflection temperature under load.

Hereinafter, the necessity of the melting point of the ion pair compound being 80 ℃ or lower will be explained. It is known that an ion-pair compound has a low melting point, and particularly, a resin composition has antistatic properties by adding an ion-pair compound which is liquid at ordinary temperature to a resin. The reason for this is considered to be: since the ion pair compound having a low melting point has an organic compound site having a large size to some extent, the ion pair compound exhibits antistatic properties by being appropriately dispersed in the resin composition because of a weak coulomb force of the positive charge and the negative charge and a high affinity with the matrix resin. In particular, when considering the addition to a polycarbonate resin, an ion pair compound having a melting point of 80 ℃ or lower is preferable for imparting good antistatic properties. On the other hand, the ion-pairing compound having a melting point of more than 80 ℃ has a strong coulombic force, or has a small organic compound site and a low affinity with the resin, and therefore, is not easily dispersed in the aromatic polycarbonate resin, and cannot exhibit a good antistatic property. The melting point of the ion pair compound is preferably 30 ℃ or lower, and more preferably 0 ℃ or lower.

Hereinafter, the necessity of the 5% weight loss temperature measured by TG-TDA being 350 ℃ or more will be described. When the temperature is low, the resin compound is exposed to a high temperature environment such as melt kneading and injection molding, so that the ion pair compound is likely to be thermally decomposed, and the compound generated by the thermal decomposition contributes to the thermal decomposition of the resin polymer, thereby causing problems such as a decrease in molecular weight. In particular, in the case of polycarbonate resins, the processing temperature in melt kneading, injection molding, and the like is often 300 to 350 ℃, and therefore, 350 ℃ or higher is suitable. The 5% weight loss temperature of the ion pair compound as measured by TG-TDA is preferably 355 ℃ or higher, more preferably 360 ℃ or higher.

Hereinafter, the reason why the formula (1) should be satisfied will be described. The more hydrophobic the ion-pairing compound is, the more elution of the ion-pairing compound into water can be suppressed when the resin composition containing the ion-pairing compound is contacted with water, and therefore, the longer antistatic property is improved. The degree of hydrophobicity of the ion-pairing compound can be defined by the contact angle of a water droplet of the resin composition to which the ion-pairing compound is added. If the formula (1) is not satisfied, it means that the ion pair compound exhibits more hydrophilicity, and therefore, the elution of the ion pair compound into water when the resin composition is brought into contact with water increases, and it is difficult to ensure continuous antistatic properties. Further, in order to ensure more excellent and continuous antistatic properties, the following formula (2) is preferably satisfied, and the following formula (3) is more preferably satisfied.

R₁＞R_D-15 (2)

R₁≥R_D-10 (3)

(wherein R is₁The contact angle (DEG), R, of a water droplet of the resin composition containing 2 parts by weight of an ion-pairing compound_DContact Angle of Water drop (. degree.) of thermoplastic resin

The ion pair compound having a melting point of 80 ℃ or lower, a 5% weight loss temperature measured by TG-TDA of 350 ℃ or higher and satisfying the formula (1) is preferably one satisfying the following formula (I)

And (3) salt.

[(R₁)₃R₂P]⁺·M^- (I)

(in the formula, R₁Represents an alkyl group having 6 to 12 carbon atoms, R₂M represents an alkyl group having 10 to 20 carbon atoms^-Represents any anion. )

Further, M in the above formula (I)^-The following formula (II) is preferred.

(R₃SO₂)(R₄SO₂)N^- (II)

(in the formula, R₃、R₄Each represents a C1-4 perfluoroalkyl group, R₃、R₄May be the same or different. )

In the formula (I), R is preferably R₁Is a linear alkyl group of 6-8 carbon atoms, R₂Is a C12-C16 linear alkyl group, R₃、R₄Each is a perfluoroalkyl group having 1 to 4 carbon atoms; more preferably R₁Is a linear alkyl group of 6 carbon atoms, R₂Is a linear alkyl group of 14 carbon atoms, R₃、R₄Each is trifluoromethyl.

The content of the component B is 0.3 to 5 parts by weight, preferably 0.4 to 4 parts by weight, and more preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the component A. If the content of the component B is less than 0.3 part by weight, good antistatic property is not exhibited, and if it exceeds 5 parts by weight, the resin viscosity is lowered and the processability is unstable.

(component C: phosphorus-based Heat stabilizer)

The polycarbonate resin composition of the present invention is preferably blended with a phosphorus-based heat stabilizer to such an extent that the hydrolysis is not promoted. The phosphorus-based heat stabilizer improves the thermal stability during production or molding, and improves the mechanical properties, hue, and molding stability. Examples of the phosphorus-based heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, esters thereof, and tertiary phosphine.

Specific examples of the phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecylmonophenyl phosphite, dioctylmonophenyl phosphite, diisopropylmonophenyl phosphite, monobutyldiphenyl phosphite, monodecyl diphenyl phosphite, monooctyldiphenyl phosphite, 2-methylenebis (4, 6-di-t-butylphenyl) octyl phosphite, tris (diethylphenyl) phosphite, tris (diisopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2, 4-di-t-butylphenyl) phosphite, tris (2, 6-di-t-butylphenyl) phosphite, distearylpentaerythritol diphosphite, distearyl phosphite, and the like, Bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2, 6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenyl bisphenol a pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite and the like.

Further, as the other phosphite compound, a compound having a cyclic structure which reacts with a dihydric phenol can be used. Examples thereof include 2,2 '-methylenebis (4, 6-di-tert-butylphenyl) (2, 4-di-tert-butylphenyl) phosphite, 2' -methylenebis (4, 6-di-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2 '-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, and 2,2' -ethylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite.

Examples of the phosphate ester compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenylmonoanthidyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, and the like, and triphenyl phosphate and trimethyl phosphate are preferable.

The phosphonite compounds include tetrakis (2, 4-di-tert-butylphenyl) -4,4 '-biphenylene diphosphonite, tetrakis (2, 4-di-tert-butylphenyl) -4,3' -biphenylene diphosphonite, tetrakis (2, 4-di-tert-butylphenyl) -3,3 '-biphenylene diphosphonite, tetrakis (2, 6-di-tert-butylphenyl) -4,4' -biphenylene diphosphonite, tetrakis (2, 6-di-tert-butylphenyl) -4,3 '-biphenylene diphosphonite, tetrakis (2, 6-di-tert-butylphenyl) -3,3' -biphenylene diphosphonite, bis (2, 4-di-tert-butylphenyl) -4-phenyl phosphonite, and mixtures thereof, Bis (2, 4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2, 6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2, 6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2, 6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite and the like, preferably tetrakis (di-tert-butylphenyl) -biphenylene diphosphonite, bis (di-tert-butylphenyl) -phenyl-phenylphosphonite, more preferably tetrakis (2, 4-di-tert-butylphenyl) -biphenylene diphosphonite, bis (2, 4-di-tert-butylphenyl) -phenyl-phenylphosphonite. The phosphite compound may be used in combination with the above-mentioned phosphite compound having an aryl group substituted with 2 or more alkyl groups, and is preferable.

Examples of the phosphonate compound include dimethyl phenylphosphonate, diethyl phenylphosphonate, dipropyl phenylphosphonate, and the like. Examples of the tertiary phosphine include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, tripentylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolylphosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine. The phosphorus-based stabilizer is not limited to 1 type, and may be used by mixing 2 or more types.

Among the phosphorus-based stabilizers, an alkyl phosphate compound represented by trimethyl phosphate is preferably blended. Further, the combination of the alkyl phosphate compound, the phosphite compound and/or the phosphonite compound is also a preferable mode. The content of the phosphorus-based heat stabilizer is preferably 0.001 to 0.5 part by weight, more preferably 0.005 to 0.3 part by weight, and still more preferably 0.01 to 0.2 part by weight based on 100 parts by weight of the component A.

(other additives)

In order to improve the polycarbonate resin composition of the present invention, its thermal stability and design properties, additives useful for these improvements may be advantageously used. These additives will be specifically described below.

(I) Heat stabilizer other than phosphorus-based heat stabilizer

(i) Hindered phenol-based stabilizer

The polycarbonate resin composition of the present invention may contain a hindered phenol stabilizer. This combination can exhibit an effect of, for example, suppressing deterioration of the hue at the time of molding processing and deterioration of the hue in long-term use. Examples of the hindered phenol-based stabilizer include α -tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, N-octadecyl- β - (4 '-hydroxy-3', 5 '-di-t-butylphenyl) propionate, 2-t-butyl-6- (3' -t-butyl-5 '-methyl-2' -hydroxybenzyl) -4-methylphenyl acrylate, 2, 6-di-t-butyl-4- (N, N-dimethylaminomethyl) phenol, diethyl 3, 5-di-t-butyl-4-hydroxybenzylphosphonate, 2 '-methylenebis (4-methyl-6-t-butylphenol), 2' -methylenebis (4-ethyl-6-t-butylphenol), 4,4 '-methylenebis (2, 6-di-tert-butylphenol), 2' -methylenebis (4-methyl-6-cyclohexylphenol), 2 '-dimethylene-bis (6-. alpha. -methyl-benzyl-p-cresol) 2,2' -ethylene-bis (4, 6-di-tert-butylphenol), 2 '-butylidene-bis (4-methyl-6-tert-butylphenol), 4' -butylidene-bis (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' -thiobis (6-tert-butyl-m-cresol), 4' -thiobis (3-methyl-6-tert-butylphenol), 2' -thiobis (4-methyl-6-tert-butylphenol), Bis (3, 5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4' -dithiobis (2, 6-di-tert-butylphenol), 4' -trithiobis (2, 6-di-tert-butylphenol), 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 ' -hexamethylenebis- (3, 5-di-tert-butyl-4-hydroxyhydrocinnamide), N ' -bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine, N ' -bis (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine, 1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3, 5-di-tert-butyl-4-hydroxyphenyl) isocyanurate, tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanurate, 1,3, 5-tris 2[3(3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy ] ethyl isocyanurate and tetrakis [ methylene-3- (3',5' -di-t-butyl-4-hydroxyphenyl) propionate ] methane, and the like. These are readily available. The hindered phenol-based stabilizer may be used alone or in combination of 2 or more. The content of the hindered phenol stabilizer is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.5 part by weight, based on 100 parts by weight of the component A.

(ii) Heat stabilizers other than the above

The polycarbonate resin composition of the present invention may contain a heat stabilizer other than the phosphorus stabilizer and the hindered phenol stabilizer. Examples of the other heat stabilizer include lactone-based stabilizers typified by a reaction product of 3-hydroxy-5, 7-di-tert-butyl-furan-2-one and o-xylene. The details of the stabilizer are described in Japanese patent application laid-open No. 7-233160. This compound is commercially available as Irganox HP-136 (trade name, manufactured by CIBA SPECIALTY CHEMICALS Co.), and can be used. Further, stabilizers obtained by mixing the compound with various phosphite compounds and hindered phenol compounds are also commercially available. For example, IrganoxHP-2921 manufactured by the above-mentioned company is preferably used. The content of the lactone-based stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, based on 100 parts by weight of the component A.

Examples of the other stabilizer include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate) and glycerol-3-stearylthiopropionate. The content of the sulfur-containing stabilizer is preferably 0.001 to 0.1 part by weight, more preferably 0.01 to 0.08 part by weight, based on 100 parts by weight of the component A.

The polycarbonate resin composition of the present invention may contain an epoxy compound as needed. The epoxy compound is compounded for the purpose of suppressing corrosion of a mold, and basically, all compounds having an epoxy functional group can be used. Specific examples of the preferable epoxy compound include 3, 4-epoxycyclohexylmethyl-3 ',4' -epoxycyclohexylcarboxylate, 1, 2-epoxy-4- (2-oxirane) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol, a copolymer of methyl methacrylate and glycidyl methacrylate, and a copolymer of styrene and glycidyl methacrylate. The content of the epoxy compound is preferably 0.003 to 0.2 part by weight, more preferably 0.004 to 0.15 part by weight, and further preferably 0.005 to 0.1 part by weight based on 100 parts by weight of the component A.

(II) flame retardant

The polycarbonate resin composition of the present invention may contain a flame retardant. The incorporation of such a compound can improve flame retardancy, and in addition, can improve antistatic properties, fluidity, rigidity, and thermal stability, for example, depending on the properties of each compound. Examples of the flame retardant include (i) an organic metal salt flame retardant (e.g., an organic sulfonic acid alkali (alkaline earth) metal salt, an organic borate metal salt flame retardant, and an organic tin metal salt flame retardant), (ii) an organic phosphorus flame retardant (e.g., an organic group-containing monophosphate compound, a phosphate oligomer compound, a phosphonate oligomer compound, a phosphazene oligomer compound, and a phosphonic acid amide compound), (iii) a silicone flame retardant composed of a silicone compound, and (iv) fibrillated PTFE, and among them, an organic metal salt flame retardant and an organic phosphorus flame retardant are preferable. They may be used singly or in combination.

(i) Organic metal salt flame retardant

The organic metal salt compound is an alkali (alkaline earth) metal salt of an organic acid having 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms, and is preferably an alkali (alkaline earth) metal salt of an organic sulfonic acid. In the organic sulfonic acid alkali (alkaline earth) metal salt, comprising: a metal salt of a fluorine-substituted alkylsulfonic acid such as a metal salt of a perfluoroalkylsulfonic acid having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, and an alkali metal or alkaline earth metal, and a metal salt of an aromatic sulfonic acid having 7 to 50 carbon atoms, preferably 7 to 40 carbon atoms, and an alkali metal or alkaline earth metal. Examples of the alkali metal constituting the metal salt include lithium, sodium, potassium, rubidium, and cesium, and examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium, and barium. More preferably an alkali metal. Among the alkali metals, rubidium and cesium having a larger ionic radius are preferable in the case where the demand for transparency is higher, and on the other hand, they are not versatile and difficult to purify, and therefore, as a result, there is a disadvantage in terms of cost. On the other hand, metals having a smaller ionic radius such as lithium and sodium may have a disadvantage in flame retardancy. In view of this, although the alkali metal of the alkali metal sulfonate may be used individually, the potassium sulfonate is most preferable because it is excellent in balance of properties at any point. Alkali metal salts of sulfonic acids formed from the potassium salt and other alkali metals may also be used in combination.

Specific examples of the alkali metal salt of a perfluoroalkylsulfonic acid include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, sodium perfluorobutanesulfonate, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, cesium perfluorooctanesulfonate, cesium perfluorohexanesulfonate, rubidium perfluorobutanesulfonate and rubidium perfluorohexanesulfonate, and 1 kind or 2 or more kinds of them may be used in combination. The number of carbon atoms of the perfluoroalkyl group is preferably in the range of 1 to 18, more preferably in the range of 1 to 10, and still more preferably in the range of 1 to 8.

Among these, potassium perfluorobutane sulfonate is particularly preferable. In the alkali (alkaline earth) metal salt of a perfluoroalkylsulfonic acid formed of an alkali metal, at least fluoride ion (F-) is usually incorporated. The presence of the fluoride ion may be an important factor for reducing the flame retardancy, and therefore, it is preferable to reduce the amount as much as possible. The proportion of fluoride ions can be determined by ion chromatography. The content of fluoride ions is preferably 100ppm or less, more preferably 40ppm or less, and particularly preferably 10ppm or less. In addition, it is preferably 0.2ppm or more from the viewpoint of efficient production. For the alkali (alkaline earth) metal salt of a perfluoroalkylsulfonic acid in which the amount of fluoride ions is reduced, a known production method can be used and the amount of fluoride ions contained in the raw materials for producing a fluorine-containing organic metal salt can be reduced; a method of removing hydrogen fluoride and the like obtained by the reaction by heating the gas generated during the reaction; and a method of reducing the amount of fluoride ions by using a purification method such as recrystallization and reprecipitation in the production of a fluorine-containing organic metal salt. In particular, the organic metal salt-based flame retardant is relatively easily soluble in water, and therefore, is preferably produced by the following steps: ion-exchanged water, particularly water having a resistance value of 18 M.OMEGA.cm or more, that is, a conductivity of about 0.55. mu.S/cm or less, is used, and the solution is dissolved at a temperature higher than the room temperature, washed, and then cooled to recrystallize.

Specific examples of the alkali (alkaline earth) metal salts of aromatic sulfonic acids include disodium diphenylsulfide-4, 4 '-disulfonate, dipotassium diphenylsulfide-4, 4' -disulfonate, potassium 5-sulfoisophthalate, sodium poly (ethylene-poly (styrene-co-terephthalate)), calcium 1-methoxynaphthyl-4-sulfonate, disodium 4-dodecylphenylether disulfonate, poly (2, 6-dimethylphenylene ether) poly (sodium sulfonate), poly (1, 3-phenylene ether) poly (sodium sulfonate), poly (1, 4-phenylene ether) poly (sodium sulfonate), poly (2, 6-diphenylphenylene ether) poly (potassium sulfonate), poly (2-fluoro-6-butylphenylene ether) poly (lithium sulfonate), potassium sulfonate of benzenesulfonate, sodium sulfonate, Strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium terephthalamide, dipotassium naphthyl-2, 6-disulfonate, calcium biphenyl-3, 3' -disulfonate, sodium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-sulfonate, dipotassium diphenylsulfone-3, 3' -disulfonate, dipotassium diphenylsulfone-3, 4' -disulfonate, alpha, the alpha is the sum of the alpha and the alpha, alpha-trifluoroacetophenone-4-sodium sulfonate, benzophenone-3, 3' -dipotassium disulfonate, thiophene-2, 5-disodium disulfonate, thiophene-2, 5-dipotassium disulfonate, thiophene-2, 5-calcium disulfonate, sodium benzothiophene sulfonate, potassium diphenylsulfoxide-4-sulfonate, formalin condensate of sodium naphthylsulfonate, formalin condensate of sodium anthracenesulfonate, and the like. Among these alkali (alkaline earth) metal salts of aromatic sulfonic acids, potassium salt is particularly preferable. Among these aromatic sulfonic acid alkali (alkaline earth) metal salts, potassium diphenylsulfone-3-sulfonate and dipotassium diphenylsulfone-3, 3' -disulfonate are preferable, and a mixture thereof is particularly preferable (the weight ratio of the former to the latter is 15/85 to 30/70).

As the organic metal salt other than the sulfonic acid alkali (alkaline earth) metal salt, alkali (alkaline earth) metal salts of sulfuric acid esters, alkali (alkaline earth) metal salts of aromatic sulfonamides, and the like can be preferably exemplified. The alkali (alkaline earth) metal salt of a sulfuric acid ester includes, in particular, alkali (alkaline earth) metal salts of sulfuric acid esters of monohydric and/or polyhydric alcohols, and examples of the sulfuric acid esters of monohydric and/or polyhydric alcohols include methyl sulfate, ethyl sulfate, lauryl sulfate, cetyl sulfate, sulfuric acid esters of polyoxyethylene alkylphenyl ethers, mono-, di-, tri-, tetra-sulfuric acid esters of pentaerythritol, sulfuric acid esters of lauric acid monoglycerides, sulfuric acid esters of palmitic acid monoglycerides, and sulfuric acid esters of stearic acid monoglycerides. As the alkali (alkaline earth) metal salt of these sulfuric acid esters, alkali (alkaline earth) metal salts of lauryl sulfuric acid ester can be preferably mentioned. Examples of the alkali (alkaline earth) metal salt of the aromatic sulfonamide include alkali (alkaline earth) metal salts of saccharin, N- (p-tolylsulfonyl) p-toluenesulfonimide, N- (N' -benzylaminocarbonyl) sulfanylimide, and N- (phenylcarboxy) sulfanylimide. The content of the organic metal salt-based flame retardant is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, still more preferably 0.01 to 0.3 part by weight, and particularly preferably 0.03 to 0.15 part by weight, based on 100 parts by weight of the component A.

(ii) Organic phosphorus flame retardant

As the organic phosphorus flame retardant, an aryl phosphate compound or a phosphazene compound is preferably used. These organic phosphorus flame retardants have a plasticizing effect and are therefore advantageous in improving moldability. As the aryl phosphate ester compound, known various phosphate ester compounds can be used as conventional flame retardants, but 1 or 2 or more kinds of phosphate ester compounds represented by the following general formula (4) are particularly preferable.

(wherein M in the above formula represents a divalent organic group derived from a dihydric phenol, Ar¹、Ar²、Ar³And Ar⁴Each represents a monovalent organic group derived from a monohydric phenol. a. b, c and d each independently represent 0 or 1, m is an integer of 0 to 5, and in the case of a mixture of phosphoric esters having different polymerization degrees m, m represents an average value thereof and is a value of 0 to 5. )

The phosphate ester compound of the above formula may be a mixture of compounds having different m numbers, and in the case of the mixture, the average m number is preferably in the range of 0.5 to 1.5, more preferably 0.8 to 1.2, further preferably 0.95 to 1.15, and particularly preferably 1 to 1.14.

Preferred specific examples of the dihydric phenol from which M is derived include hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxybiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone and bis (4-hydroxyphenyl) sulfide, and among these, resorcinol, bisphenol A and dihydroxybiphenyl are preferred.

As a derivative of the above-mentioned Ar¹、Ar²、Ar³And Ar⁴As preferable specific examples of the monohydric phenol of (a), phenol, cresol, xylenol, isopropylphenol, butylphenol and p-cumylphenol can be cited, and among them, phenol and 2, 6-dimethylphenol are preferable.

The monophenol may be substituted with a halogen atom, and specific examples of the phosphate ester compound having a group derived from the monophenol include tris (2,4, 6-tribromophenyl) phosphate, tris (2, 4-dibromophenyl) phosphate, tris (4-bromophenyl) phosphate, and the like.

On the other hand, specific examples of the phosphate ester compound not substituted with a halogen atom are preferably a monophosphate ester compound such as triphenyl phosphate or tris (2, 6-xylyl) phosphate, and a phosphate ester oligomer mainly composed of resorcinol bis (2, 6-xylyl) phosphate, a phosphate ester oligomer mainly composed of 4, 4-dihydroxydiphenyl bis (diphenyl phosphate), and a phosphate ester oligomer mainly composed of bisphenol a bis (diphenyl phosphate) (here, expressed mainly as … …, other components having different degrees of polymerization may be contained in a small amount, more preferably 80% by weight or more of the component having m ═ 1 in the above formula (4), still more preferably 85% by weight or more, and still more preferably 90% by weight or more).

Phosphazene compound as a conventional flame retardant, various known phosphazene compounds can be used, but phosphazene compounds represented by the following general formulae (5) and (6) are preferable.

(in the formula, X¹、X²、X³、X⁴Represents hydrogen, hydroxyl, amino, or an organic group containing no halogen atom. In addition, r represents an integer of 3 to 10. )

In the above formulae (5) and (6), X is¹、X²、X³、X⁴Examples of the organic group not containing a halogen atom include an alkoxy group, a phenyl group, an amino group, and an allyl group. Among them, the cyclic phosphazene compound represented by the formula (5) is preferable, and further, X in the formula (5) is particularly preferable¹、X²A cyclic phenoxyphosphazene which is a phenoxy group.

The content of the organic phosphorus flame retardant is preferably 1 to 50 parts by weight, more preferably 2 to 30 parts by weight, and still more preferably 5 to 20 parts by weight, based on 100 parts by weight of the component A. If the amount of the organic phosphorus flame retardant is less than 1 part by weight, the effect of flame retardancy is difficult to obtain, and if it exceeds 50 parts by weight, there is a problem that breakage, surging, or the like occurs during kneading and extrusion, and productivity is deteriorated.

(iii) Silicone-based flame retardant

The silicone compound used as the silicone flame retardant improves flame retardancy by a chemical reaction during combustion. As the compound, various compounds proposed as flame retardants for conventional aromatic polycarbonate resins can be used. It is considered that the silicone compound forms a structure by bonding to itself or to a component derived from a resin upon combustion thereof, or by a reduction reaction upon formation of the structure, and thereby, particularly in the case of using a polycarbonate resin, can impart a high flame retardant effect.

Therefore, it is preferable to include a group having high activity in the reaction, specifically, at least 1 group of an alkoxy group and hydrogen (i.e., Si — H group) in a predetermined amount. The content ratio of the group (alkoxy group, Si-H group) is preferably in the range of 0.1 to 1.2mol/100g, more preferably in the range of 0.12 to 1mol/100g, and still more preferably in the range of 0.15 to 0.6mol/100 g. This ratio can be determined by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound by an alkali decomposition method. The alkoxy group is an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group.

In general, the structure of the silicone compound can be constituted by arbitrarily combining 4 kinds of siloxane units shown below. Namely, the M unit: (CH)₃)₃SiO_1/2、H(CH₃)₂SiO_1/2、H₂(CH₃)SiO_1/2、(CH₃)₂(CH₂＝CH)SiO_1/2、(CH₃)₂(C₆H₅)SiO_1/2、(CH₃)(C₆H₅)(CH₂＝CH)SiO_1/2Etc. 1 functional siloxane units, D units: (CH)₃)₂SiO、H(CH₃)SiO、H₂SiO、H(C₆H₅)SiO、(CH₃)(CH₂＝CH)SiO、(C₆H₅)₂2-functional siloxane units such as SiO, T units: (CH)₃)SiO_3/2、(C₃H₇)SiO_3/2、HSiO_3/2、(CH₂＝CH)SiO_3/2、(C₆H₅)SiO_3/2Etc. 3 functional siloxane units, Q units: SiO 2₂4 functional siloxane units as indicated.

Specific examples of the structure of the silicone compound used in the silicone flame retardant include Dn, Tp, MmDn, MmTp, mmpqq, MmDnTp, MmDnQq, MmTpQq, MmDnTpQq, DnTp, DnQq, and DnTpQq. Among them, preferred silicone compounds have structures of MmDn, MmTp, MmDnTp, and MmDnQq, and more preferred structures are MmDn and MmDnTp.

Here, the coefficients m, n, p, and q in the above exemplary formulae are integers of 1 or more representing the degree of polymerization of each siloxane unit, and the sum of the coefficients in the exemplary formulae represents the average degree of polymerization of the silicone compound. The average polymerization degree is preferably in the range of 3 to 150, more preferably in the range of 3 to 80, further preferably in the range of 3 to 60, and particularly preferably in the range of 4 to 40. The more preferable range is, the more excellent flame retardancy is. As described later, a silicone compound containing an aromatic group in a predetermined amount is excellent in transparency and color. As a result, good reflected light can be obtained. When any one of m, n, p, and q is a numerical value of 2 or more, the siloxane unit having such a coefficient may be 2 or more siloxane units having different bonded hydrogen atoms and organic residues.

The silicone compound may be linear or branched. The organic residue bonded to the silicon atom is preferably an organic residue having 1 to 30 carbon atoms, more preferably an organic residue having 1 to 20 carbon atoms. Specific examples of the organic residue include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a decyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, and an aralkyl group such as a tolyl group. Further, an alkyl group, an alkenyl group or an aryl group having 1 to 8 carbon atoms is preferable. The alkyl group is particularly preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group. Further, the silicone compound used as the silicone flame retardant preferably contains an aryl group. On the other hand, the silane compound and siloxane compound as the organic surface treating agent for titanium dioxide pigment can be clearly distinguished from the silicone-based flame retardant in its preferred embodiment in that a desired effect can be obtained when the silane compound and siloxane compound do not contain an aryl group. The silicone compound used as the silicone flame retardant may contain a reactive group in addition to the Si — H group and the alkoxy group, and examples of the reactive group include an amino group, a carboxyl group, an epoxy group, a vinyl group, a mercapto group, and a methacryloxy group.

The content of the silicone flame retardant is preferably 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and still more preferably 1 to 5 parts by weight, based on 100 parts by weight of the component A.

(iv) Polytetrafluoroethylene (fibrillated PTFE) having fibril forming ability

The fibrillated PTFE may be fibrillated PTFE alone or in a mixed form, that is, a polytetrafluoroethylene-based mixture composed of fibrillated PTFE particles and an organic polymer. Fibrillated PTFE has an extremely high molecular weight and shows a tendency to bond PTFE to each other into a fibrous form by an external action such as a shearing force. The number average molecular weight is in the range of 150 to tens of millions. The lower limit is more preferably 300 ten thousand. The number average molecular weight can be calculated based on the melt viscosity of polytetrafluoroethylene at 380 ℃ as disclosed in, for example, Japanese patent application laid-open No. 6-145520. That is, the melt viscosity of fibrillated PTFE at 380 ℃ measured by the method described in the above publication is 10⁷～10¹³Poise range, preferably 10⁸～10¹²The range of poise. The PTFE can be used in the form of an aqueous dispersion, in addition to a solid form. In addition, in order to improve the dispersibility of the fibrillated PTFE in a resin and to obtain good flame retardancy and mechanical properties, a PTFE mixture in a mixed form with another resin may be used.

As disclosed in Japanese patent application laid-open No. 6-145520, it is preferable to use a material having a structure in which the fibrillated PTFE is used as a core and a low molecular weight polytetrafluoroethylene is used as a shell.

Commercially available products of this fibrillated PTFE include, for example, Mitsui DuPont Fluorochemical Co., Ltd., Teflon (registered trademark) 6J of Ltd., Polyflon MPA FA500 of Daikin Chemical Industry Co., Ltd., F-201L, and the like.

As the fibrillated PTFE in the mixed form, fibrillated PTFE obtained by: (1) a method in which an aqueous dispersion of fibrillated PTFE is mixed with an aqueous dispersion or solution of an organic polymer and coprecipitated to obtain a co-coagulated mixture (methods described in, for example, Japanese patent application laid-open Nos. 60-258263 and 63-154744); (2) a method of mixing an aqueous dispersion of fibrillated PTFE with dried organic polymer particles (a method described in japanese unexamined patent publication No. 4-272957); (3) a method of uniformly mixing an aqueous dispersion of fibrillated PTFE with a solution of organic polymer particles and simultaneously removing each medium from the mixture (methods described in japanese patent application laid-open nos. h 06-220210 and 08-188653); (4) a method of polymerizing a monomer forming an organic polymer in an aqueous dispersion of fibrillated PTFE (a method described in japanese unexamined patent publication No. 9-95583); and (5) a method in which an aqueous dispersion of PTFE and an organic polymer dispersion are uniformly mixed, and then a vinyl monomer is polymerized in the mixed dispersion, thereby obtaining a mixture (a method described in japanese unexamined patent application publication No. 11-29679, etc.).

Examples of commercially available products of fibrillated PTFE in a mixed form include "Metablen A3000" (trade name) "Metablen A3700" (trade name) "of MITSUBISHI RAYON CO., LTD.," Metablen A3800 "(trade name)" Metablen A series, SN3300B7 (trade name) of Shine Polymer, and "BLENDEX B449" (trade name) manufactured by GE Specialty Chemicals Company.

The proportion of fibrillated PTFE in the mixed form is preferably 1 to 95 wt%, more preferably 10 to 90 wt%, and most preferably 20 to 80 wt% of the mixture 100 wt%.

When the proportion of the fibrillated PTFE in the mixed form is in this range, good dispersibility of the fibrillated PTFE can be achieved. The content of the fibrillated PTFE is preferably 0.001 to 0.5 part by weight, more preferably 0.01 to 0.5 part by weight, and still more preferably 0.1 to 0.5 part by weight, based on 100 parts by weight of the component A.

(III) dye pigments

The polycarbonate resin composition of the present invention can further contain various dyes and pigments,provided is a molded article exhibiting various designability. Examples of the dye pigment used in the present invention include ferrocyanide such as perylene dye, coumarin dye, thioindigo dye, anthraquinone dye, thioxanthone dye and cyanoazurin, pyrene dye, quinoline dye, quinacridone dye and diclazine dye

Oxazine dyes, isoindolinone dyes, phthalocyanine dyes, and the like. Further, the polycarbonate resin composition of the present invention can obtain a more favorable metallic color by blending a metallic pigment. The metal pigment is preferably aluminum powder. Further, by blending a fluorescent whitening agent and a fluorescent dye emitting light in addition to the fluorescent whitening agent, a more favorable design effect can be imparted to the luminous color.

(IV) fluorescent whitening agent

The fluorescent whitening agent in the polycarbonate resin composition of the present invention is not particularly limited as long as it is used for improving the color tone of a resin or the like to white or bluish white, and examples thereof include stilbene-based, benzimidazole-based, and benzo

Azole series, naphthalimide series, rhodamine series, coumarin series,

And oxazine compounds. Specifically, for example, CI Fluorescent Brightener 219: 1. EASTOBRITE OB-1 manufactured by Eastman Chemical Company, "Hakkol PSR" manufactured by Showa Chemical Company, and the like. Here, the fluorescent whitening agent has a function of absorbing energy of ultraviolet light of light and emitting the energy to a visible part. The content of the fluorescent whitening agent is preferably 0.001 to 0.1 part by weight, more preferably 0.001 to 0.05 part by weight, based on 100 parts by weight of the component A. If it exceeds 0.1 part by weight, the effect of improving the hue of the composition is small.

(V) Compound having Heat ray absorbing ability

The polycarbonate resin composition of the present invention may contain a compound having a heat ray absorbing ability. As the compound, various metal compounds excellent in near infrared absorbing ability such as phthalocyanine-based near infrared absorbing agent, ATO, ITO, iridium oxide, ruthenium oxide, ammonium oxide, titanium oxide, and the like, lanthanum boride, cerium boride, tungsten boride, and the like, tungsten oxide-based near infrared absorbing agent, and carbon filler can be preferably exemplified. The phthalocyanine-based near-infrared absorber is easily available, for example, as commercially available MIR-362 available from Mitsui chemical Co., Ltd. Examples of the carbon filler include carbon black, graphite (including both natural and artificial materials), fullerene, and the like, and carbon black and graphite are preferable. These can be used alone, or in combination of 2 or more. The content of the phthalocyanine-based near-infrared absorber is preferably 0.0005 to 0.2 part by weight, more preferably 0.0008 to 0.1 part by weight, and still more preferably 0.001 to 0.07 part by weight, based on 100 parts by weight of the component A. In the polycarbonate resin composition of the present invention, the content of the metal oxide-based near infrared ray absorber, the metal boride-based near infrared ray absorber and the carbon filler is preferably in the range of 0.1 to 200ppm (weight ratio), and more preferably in the range of 0.5 to 100 ppm.

(VI) light diffusing agent

The polycarbonate resin composition of the present invention may contain a light diffusing agent to impart a light diffusing effect. Examples of the light diffusing agent include polymer fine particles, low refractive index inorganic fine particles such as calcium carbonate, and a composite thereof. The polymer fine particles are fine particles known as a light diffusing agent for polycarbonate resins. More preferably, acrylic crosslinked particles having a particle diameter of several μm, silicone crosslinked particles typified by polyorganosilsesquioxane, and the like are exemplified. Examples of the shape of the light diffusing agent include a spherical shape, a disc shape, a columnar shape, an amorphous shape, and the like. The spherical shape need not be a perfect sphere but also encompasses a deformed sphere, the cylindrical shape encompassing a cube. The light diffusing agent is preferably spherical, and the more uniform the particle diameter, the more preferable it is. The content of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and still more preferably 0.01 to 3 parts by weight based on 100 parts by weight of the component A. The light diffusing agent may be used in combination of 2 or more.

(VII) white pigment for high light reflection

The polycarbonate resin composition of the present invention can be blended with a white pigment for high light reflection to impart a light reflection effect. As the white pigment, a titanium dioxide (particularly, a titanium dioxide treated with an organic surface treatment agent such as silicone) pigment is particularly preferable. The content of the white pigment for high light reflection is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight, based on 100 parts by weight of the component A. The white pigment for high light reflection may be used in combination of 2 or more.

(VIII) ultraviolet absorber

The polycarbonate resin composition of the present invention may be blended with an ultraviolet absorber to impart weather resistance. Specific examples of the ultraviolet absorber include benzophenone-based ones, such as 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxideylbenzophenone, 2' -dihydroxy-4-methoxybenzophenone, 2',4,4' -tetrahydroxybenzophenone, 2' -dihydroxy-4, 4' -dimethoxybenzophenone, 2' -dihydroxy-4, 4' -dimethoxy-5-sodiosulideylbenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, and the like, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2' -carboxybenzophenone, and the like.

Specific examples of the ultraviolet absorber include benzotriazole-based ones such as 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, and 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-pentylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octyloxyphenyl) benzotriazole, 2' -methylenebis (4-cumyl-6-benzene)Benzotriazolyl), 2' -p-phenylene bis (1, 3-benzo)

Oxazin-4-one) and 2- [ 2-hydroxy-3- (3,4,5, 6-tetrahydrophthalimidomethyl) -5-methylphenyl]And polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton such as a copolymer of 2- (2 '-hydroxy-5-methacryloyloxyethylphenyl) -2H-benzotriazole and a vinyl monomer copolymerizable with the above monomer, a copolymer of 2- (2' -hydroxy-5-acryloyloxyethylphenyl) -2H-benzotriazole and a vinyl monomer copolymerizable with the above monomer, and the like.

Specifically, when the ultraviolet absorber is a hydroxyphenyltriazine-based ultraviolet absorber, examples thereof 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, compounds in which the phenyl group of the above exemplified compounds is a 2, 4-dimethylphenyl group, such as 2- (4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazin-2-yl) -5-hexyloxyphenol, can be exemplified.

As the ultraviolet absorber, specifically, if cyclic imino ester, for example, can be cited 2,2' -p phenylene two (3, 1-benzene and benzene)

Oxazin-4-one), 2' -m-phenylene bis (3, 1-benzo

Oxazin-4-ones) and 2,2'-p, p' -diphenylenebis (3, 1-benzo

Oxazin-4-one).

Specific examples of the ultraviolet absorber include cyanoacrylates, such as 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.

Further, the ultraviolet absorber may be a polymer type ultraviolet absorber, that is, a polymer type ultraviolet absorber obtained by copolymerizing the ultraviolet absorbing monomer and/or the light stabilizing monomer with a monomer such as alkyl (meth) acrylate by adopting a structure of a monomer compound capable of radical polymerization. As the ultraviolet absorbing monomer, a compound containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in an ester substituent of a (meth) acrylate is preferably exemplified.

Among the above ultraviolet absorbers, benzotriazole-based and hydroxyphenyltriazine-based are preferable in terms of ultraviolet absorbability, and cyclic imino ester-based and cyanoacrylate-based are preferable in terms of heat resistance and hue. Specifically, for example, Chemipro Kasei co., ltd. "Chemisorb 79", BASF Japan Corporation "Chinubin 234", and the like. The ultraviolet absorber may be used alone or in combination of 2 or more.

The content of the ultraviolet absorber is preferably 0.01 to 3 parts by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the component A. More preferably 0.05 to 1 part by weight, and particularly preferably 0.05 to 0.5 part by weight.

(IX) Filler Material

In the polycarbonate resin composition of the present invention, various known fillers can be blended as reinforcing fillers other than fibrous fillers. Examples of the filler include various plate-like fillers and particulate fillers. Here, the plate-like filler is a filler having a plate-like shape (including a case where the plate has irregularities on the surface and a bend). The particulate filler material is a filler material containing irregular shapes other than these.

Examples of the plate-like filler include glass flakes, talc, mica, kaolin, metal flakes, carbon flakes, graphite, and plate-like fillers obtained by coating the surface of a different material such as a metal or a metal oxide with these fillers. The particle size is preferably in the range of 0.1 to 300 μm. The particle size in the region of about 10 μm is the median particle size (D50) of the particle size distribution measured by the X-ray transmission method, which is one of the liquid phase sedimentation methods, in the region of 10 to 50 μm is the median particle size (D50) of the particle size distribution measured by the laser diffraction/scattering method, and in the region of 50 to 300 μm is the value of the vibration type sieving method. The particle diameter is the particle diameter in the resin composition. The plate-like filler may be surface-treated with various coupling agents such as silane-based, titanate-based, aluminate-based, and zirconate-based ones, or may be a granulated product obtained by bundling or compressing various resins such as olefin-based resins, styrene-based resins, acrylic resins, polyester-based resins, epoxy-based resins, and urethane-based resins, higher fatty acid esters, and the like.

(X) other resins, elastomers

In the polycarbonate resin composition of the present invention, other resins and elastomers may be used in a small proportion in place of part of the resin components within the range in which the effects of the present invention are exhibited, within the range in which the effects of the present invention are not impaired. The amount of the other resin or elastomer is preferably 50 parts by weight or less, and more preferably 30 parts by weight or less, based on 100 parts by weight of the component composed of the component a and the component B. Examples of the other resin include resins such as polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polymethacrylate resins, phenol resins, and epoxy resins. Examples of the elastomer include isobutylene/isoprene rubber, styrene/butadiene rubber, ethylene/propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, MBS (methyl methacrylate/styrene/butadiene) rubber, MB (methyl methacrylate/butadiene) rubber, MAS (methyl methacrylate/acrylonitrile/styrene) rubber, and the like, which are core-shell elastomers.

(XI) other additives

The polycarbonate resin composition of the present invention may contain other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, photocatalyst-based antifouling agents, photochromic agents, and the like.

< production of resin composition >

The polycarbonate resin composition of the present invention can be melt-kneaded and pelletized using an extruder such as a single-screw extruder or a twin-screw extruder. The above-mentioned various reinforcing fillers and additives may be blended in the production of the pellets. The reinforced polycarbonate resin composition of the present invention can be generally produced into various products by injection molding the pellets produced as described above. Further, the resin melt-kneaded in the extruder may be directly formed into a sheet, a film, a profile extrusion molded article, a direct blow molded article, and an injection molded article without being subjected to pellets. In this injection molding, not only a usual molding method but also an injection molding method such as injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including a case of injection using a supercritical fluid), insert molding, in-mold coating molding, heat-insulating mold molding, rapid-heating cooling mold molding, two-color molding, sandwich molding, and ultrahigh-speed injection molding can be used depending on the purpose to obtain a molded article. The advantages of these various molding processes are well known. In addition, the molding may be performed by either a cold runner method or a hot runner method. The resin composition of the present invention can be used in various shapes such as extrusion molded articles, sheets, and films by extrusion molding. In addition, in the molding of a sheet or film, an inflation method, a rolling method, a casting method, or the like may be used. The heat shrinkable tape can be molded by further applying a specific stretching operation. The resin composition of the present invention may be molded into a molded article by spin molding, blow molding, or the like.

< production of molded article >

The resin molded article formed from the polycarbonate resin composition of the present invention can be usually obtained by injection molding the pellets. In the injection molding, not only a molding method of a general cold runner system but also a hot runner capable of realizing no runner can be used for manufacturing. In addition, in the injection molding, not only a usual molding method but also a gas-assisted injection molding, an injection compression molding, an ultra high-speed injection molding, an injection press molding, a two-color molding, a sandwich molding, an in-mold coating molding, an insert molding, a foam molding (including a case of using injection of a supercritical fluid), a rapid-heating cooling mold molding, a heat insulating mold molding, an in-mold remelting molding, a molding method using a combination thereof, or the like can be used.

Examples

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "part" is based on the weight.

Based on the components and compounding amounts shown in table 2, various compounding ingredients were mixed using a tumbler, and melt-kneaded at a cylinder temperature of 280 ℃ using a twin-screw extruder (HYPER KTX30XHT, manufactured by shenko corporation) to obtain various pellets.

The components used are as follows.

(A component)

A-1: panlite L-1225WX manufactured by Dijingyi corporation (viscosity average molecular weight: 19700)

A-2: panlite L-1225WP (viscosity average molecular weight: 22400) manufactured by Diren corporation

(component B)

B-1: trihexyl (tetradecyl)

Bis (trifluoromethylsulfonyl) imide salt (manufactured by Kanto chemical Co., Ltd.)

B-2 (comparative): methylethylbis (trifluoromethylsulfonyl) imide (P12N 111 manufactured by Mitsubishi Materials Corporation)

B-3 (comparative): potassium perfluorobutane sulfonate (Megafac F-114P, Dainippon ink chemical Co., Ltd.)

B-4 (comparative): dodecyl benzene sulfonic acid tetrabutyl

Salt (DBS-P) (bamboo oil Co., Ltd.)

(component C)

C-1: phosphorus heat stabilizer (Adekastab 2112 manufactured by ADEKA K.K.)

(other Components)

D: phenol heat stabilizer (Adekastab A Oo-50, manufactured by ADEKA K.K.)

E: fatty acid ester-based mold release agent (Riken Vitamin Co., Ltd. RIKEMAL SL900 manufactured by Ltd.)

F: surfactant type antistatic agent (nonionic Pair) (Riken Vitamin Co., Ltd., Poem DL-100. manufactured)

The pellets thus obtained were dried at 120 ℃ for 5 hours in a hot air circulation dryer, and then a test piece for evaluation was molded using an injection molding machine (cylinder temperature 300 ℃ C., mold temperature 80 ℃ C.), to carry out the following evaluation.

[ evaluation of resin composition ]

1. Antistatic (before water wiping): surface resistivity

A flat test piece of 90 mm. times.50 mm. times.2 mm was prepared by injection molding under the above conditions, and the measurement was carried out under the following conditions. That is, the surface resistivity of the flat test piece was measured under the condition of measuring voltage 1000V by using a resistivity meter (high resistance resistivity meter MCP-HT450 manufactured by Mitsubishi Chemical Analyc Co., Ltd.) after adjusting the state for 48 hours or more under the condition of 23 ℃ and 50% relative humidity. The surface resistivity is less than 1 x 10¹⁴Omega/□ is set to O, 1X 10¹⁴Omega/□ is set to be X.

2. Antistatic (after water wiping): surface resistivity

A500 g cylindrical hammer was wrapped with a water-wet kimtopael Paper towel (made by Nippon Paper Crecia co., ltd.), and then placed on the above flat test piece, and slid 10 times to wipe the surface with water. Next, to wipe off the water droplets, the surface was lightly wiped 3 times with a dry Kimwipe paper towel. Thereafter, the surface resistivity was evaluated by the same method as in 1. The evaluation results were evaluated to be good when the surface resistivity was equivalent to the initial value in 1.

3. Thermal stability: viscosity average molecular weight

In the injection molding, after 10 minutes from the termination of the molding, the viscosity average molecular weight (M) of the molded article after the molding was measured by the method described in the specification₁) And the viscosity average molecular weight (M) of the particles₀). Will satisfy M₀-M₁The value of < 2000 is good, and the value of unsatisfied is X.

[ evaluation of ion-pairing Compound ]

1.5% weight loss temperature

The measurement was carried out using a TG-DTA analyzer (Thermo plus EVO2, Rigaku corporation) under an air atmosphere at a temperature increase rate of 20 ℃ per minute.

2. Contact angle of water drop

A contact angle (R) of a water droplet with respect to the polycarbonate resin (A-1) was measured under a condition of 23 ℃ C.. times.50% using a contact angle measuring apparatus (Elma Sales Co., Ltd., G-I-1000 manufactured by Ltd.)_D) And a contact angle (R) of a water droplet of a resin composition containing 2 parts by weight of each ion pair compound per 100 parts by weight of the polycarbonate resin₁) Using these resins, water droplets were dropped onto a flat test piece obtained by injection molding under the above conditions to perform measurement.

The melting points, 5% weight loss temperatures and contact angles of water droplets of B-1 to B-4 are shown in Table 1. The contact angle (R) of a water droplet of the polycarbonate resin_D) Was 88(°).

[ Table 1]

Examples 1 to 7 and comparative examples 1 to 6

The evaluation results are shown in table 2. Examples 1 to 7 all showed good results. Comparative example 1 did not contain component B and did not exhibit antistatic properties. Comparative example 2 and comparative example 3 each containing an ion pair compound (B-2, B-3) having a melting point of more than 80 ℃ and water wipingThe former had high surface resistivity and exhibited no antistatic property. Comparative example 4 has a 5% weight loss temperature of less than 350 ℃ and contains R_D-20 ratio R₁The large ion pair compound (B-4) has poor antistatic properties. Further, the viscosity average molecular weight of the molded article after retention in injection molding is greatly reduced, and the thermal stability is poor. Comparative example 5, which contains the surfactant type antistatic agent (F), is poor in sustained antistatic property and thermal stability. In comparative example 6, since the content of the component B is more than 5 parts by weight, the metering is unstable due to the influence of the decrease in the viscosity of the pellets, and a molded article suitable for evaluation cannot be obtained.

Claims

1. A resin composition characterized by comprising (A) an aromatic polycarbonate resin as component A, and

0.3 to 5 parts by weight of (B) an ion pair compound (component B) per 100 parts by weight of the aromatic polycarbonate resin;

the melting point of the ion pair compound is 80 ℃ or lower, the 5% weight loss temperature measured by TG-TDA is 350 ℃ or higher, and the following formula (1) is satisfied,

R₁＞R_D-20 (1)

in the formula, R₁Is a contact angle (°) of a water droplet of the resin composition containing 2 parts by weight of an ion-pairing compound_DThe contact angle (°) of a water droplet of the aromatic polycarbonate resin.

2. The resin composition according to claim 1, wherein the following formula (2) is satisfied,

R₁＞R_D-15 (2)

3. The resin composition according to claim 1 or 2, wherein the ion pair compound is a compound represented by the following formula (I),

[(R₁)₃R₂P]⁺·M^- (I)

in the formula, R₁Represents an alkyl group having 6 to 12 carbon atoms, R₂M represents an alkyl group having 10 to 20 carbon atoms^-Represents any anion.

4. Resin composition according to claim 3, characterized in that M^-Is represented by the following formula (II),

(R₃SO₂)(R₄SO₂)N^- (II)

in the formula, R₃、R₄Each being a perfluoroalkyl group of 1 to 4 carbon atoms, R₃、R₄May be the same or different.

5. Resin composition according to claim 3 or 4, characterized in that R₁Is a linear alkyl group of 6-8 carbon atoms, R₂Is a C12-C16 linear alkyl group, R₃、R₄Each of which is a perfluoroalkyl group having 1 to 4 carbon atoms.

6. The resin composition according to claim 3 or 4, wherein R is₁Is a linear alkyl group of 6 carbon atoms, R₂Is a straight-chain alkyl group of 14 carbon atoms, R₃、R₄Each is trifluoromethyl.

7. The resin composition according to any one of claims 1 to 6, wherein the component (C) is a phosphorus-based heat stabilizer and is contained in an amount of 0.001 to 0.5 part by weight based on 100 parts by weight of the component (A).

8. A molded article obtained by molding the resin composition according to any one of claims 1 to 7.