JP6976438B2 - Polycarbonate resin composition - Google Patents

Description

The present disclosure relates to a polycarbonate resin composition and a molded product thereof. More specifically, the present disclosure describes a composite rubber composed of a polycarbonate resin and a polyester resin containing a polyorganosiloxane rubber and an alkyl (meth) acrylicate rubber, and an aromatic alkenyl compound monomer unit and an alkyl (meth). ) Mechanical properties and chemical resistance by adding a graft copolymer having a core-shell structure in which at least one unit selected from the group consisting of acrylate compound monomer units is graft-polymerized, and an antifouling agent. It relates to a polycarbonate resin composition having improved antifouling property and appearance. The present disclosure further relates to flame-retardant polycarbonate resin compositions with improved flame retardancy and thermal stability, as well as mechanical properties, chemical resistance, stain resistance and appearance.

Aromatic polycarbonate resins are widely used industrially because they have excellent mechanical and thermal properties. However, since the aromatic polycarbonate resin is an amorphous resin, it has a drawback of inferior chemical resistance. Therefore, studies have been conducted on alloying with various polymers. Among them, aromatic polycarbonate is alloyed with polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin (see Patent Document 1). Due to the improved chemical resistance, which is a weak point of resin, and its well-balanced characteristics, it is being considered for use not only in the fields of automobiles and electrical and electronic equipment, but also in the fields of housing equipment and infrastructure. ..

So far, there have been reports of an example in which a Si copolymerized PC is applied (see Patent Document 2) and an example in which a Si-based rubber is applied (see Patent Documents 3 and 4) in order to modify the impact strength particularly at a low temperature. ing. Further, an example (see Patent Documents 5, 6 and 7) in which a siloxane compound such as silicone oil or dialkyl silicone is added for the purpose of fluid modification and further improvement of chemical resistance has been reported.

Further, there is an increasing demand for flame retardancy in applications such as electrical and electronic equipment, and various flame retardant resin compositions have been proposed. For example, there is a method in which a halogen-based flame retardant and an antimony compound are used in combination with a polycarbonate resin and a polyester-based resin (see Patent Document 8), but the thermal stability is significantly lowered by the catalytic action of the antimony compound. Further, as a flame retardant, there is a method of applying a boron compound (see Patent Document 9), red phosphorus (see Patent Document 10), and a phosphoric acid ester (see Patent Document 11).

Japanese Unexamined Patent Publication No. 2012-36323 Japanese Unexamined Patent Publication No. 2-433255 Japanese Unexamined Patent Publication No. 1-261454 Japanese Unexamined Patent Publication No. 2008-88334 Japanese Unexamined Patent Publication No. 2004-162014 Japanese Unexamined Patent Publication No. 1-272661 Japanese Unexamined Patent Publication No. 2005-133087 Japanese Unexamined Patent Publication No. 2015-081327 Japanese Unexamined Patent Publication No. 2000-001610 Japanese Unexamined Patent Publication No. 2000-136297 Japanese Unexamined Patent Publication No. 08-012864

In recent years, in order to make it possible to use the product comfortably even in an environment where the product is easily soiled, such as for outdoor and water-related applications (bathrooms, toilets, kitchens, etc.), high chemical resistance and protection against resins have been achieved. Dirtyness is being required. However, conventional reports have not focused on antifouling properties, and at present, it has been possible to provide a polycarbonate resin composition having mechanical properties, chemical resistance, antifouling properties and appearance that can meet the demands of the market. Not in.

In view of the above, an object of the present disclosure is to provide a polycarbonate resin composition that satisfies mechanical properties, chemical resistance, stain resistance, and appearance at a high level.

As a result of diligent studies to solve the above problems, the present inventor has made a polycarbonate resin composition having a polycarbonate-polydiorganosiloxane copolymer resin and a polyester-based resin an antifouling agent and a specific composite rubber. It has been found that the above-mentioned problems are solved by further having a graft copolymer having a core-shell structure grafted with a specific monomer unit.

（式中、Ｘ_１およびＸ_２は、同一もしくは異なり、下記一般式（Ｉ）で表される芳香族置換アルキル基である。）

（式中、ＡＬは炭素数１〜５の分岐状または直鎖状の脂肪族炭化水素基であり、Ａｒはフェニル基、ナフチル基またはアントリル基であり、ｎは１〜３の整数を示し、ＡｒはＡＬの任意の炭素原子に結合することができる。）
〈態様３〉
Ｂ成分の含有量が、Ａ成分とＢ成分との合計１００重量部中、２０重量部〜７０重量部であることを特徴とする、態様１又は２に記載のポリカーボネート樹脂組成物。
〈態様４〉
Ｂ成分が、ポリエチレンテレフタレート樹脂およびポリブチレンテレフタレート樹脂のうち少なくとも一方を含むことを特徴とする、態様１〜３のいずれかに記載のポリカーボネート樹脂組成物。
〈態様５〉
Ｄ成分が、分子量１０万以上のシリコーンガムであることを特徴とする、態様１〜４のいずれかに記載のポリカーボネート樹脂組成物。
〈態様６〉
Ｄ成分が、ポリオルガノシロキサングラフトポリオレフィン樹脂であることを特徴とする、態様１〜５のいずれかに記載のポリカーボネート樹脂組成物。
〈態様７〉
Ｃ成分の複合ゴム中のポリオルガノシロキサンゴム成分の割合が、１５％以上であることを特徴とする、態様１〜６のいずれかに記載のポリカーボネート樹脂組成物。
〈態様８〉
Ａ成分とＢ成分との合計１００重量部に対し、（Ｇ）ドリップ防止剤（Ｇ成分）０．０５重量部〜２重量部を含むことを特徴とする、態様１〜７のいずれかに記載のポリカーボネート樹脂組成物。
〈態様９〉
Ｇ成分が、フィブリル形成能を有する含フッ素ポリマーであることを特徴とする、態様８に記載のポリカーボネート樹脂組成物。That is, the present inventor has found that the above-mentioned problems are achieved by the following polycarbonate resin composition.
<Aspect 1>
For a total of 100 parts by weight of (A) polycarbonate-polydiorganosiloxane copolymer resin (component A) and (B) polyester resin (component B).
(C) At least selected from the group consisting of an aromatic alkenyl compound monomer unit and an alkyl (meth) acrylate compound monomer unit in a composite rubber composed of a component containing a polyorganosiloxane rubber and an alkyl (meth) acrylic rubber. 3 parts by weight to 15 parts by weight of a graft copolymer (C component) having a core-shell structure in which one unit is graft-polymerized, and (D) 0.5 parts by weight to 6 parts by weight of an antifouling agent (D component). A polycarbonate resin composition comprising a moiety.
<Aspect 2>
(E) 5 parts by weight to 35 parts by weight of the halogen-based flame retardant (E component), and (F) 0.5 parts by weight to 5 parts of the phosphorus-based flame retardant (F component) having a structure represented by the following formula (1). Weight part,
The polycarbonate resin composition according to aspect 1, wherein the polycarbonate resin composition further comprises.

(In the formula, X ₁ and X ₂ are the same or different, and are aromatic substituted alkyl groups represented by the following general formula (I).)

(In the formula, AL is a branched or linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, Ar is a phenyl group, a naphthyl group or an anthryl group, and n is an integer of 1 to 3; Ar can be bonded to any carbon atom of AL.)
<Aspect 3>
The polycarbonate resin composition according to aspect 1 or 2, wherein the content of the B component is 20 parts by weight to 70 parts by weight in a total of 100 parts by weight of the A component and the B component.
<Aspect 4>
The polycarbonate resin composition according to any one of aspects 1 to 3, wherein the component B contains at least one of a polyethylene terephthalate resin and a polybutylene terephthalate resin.
<Aspect 5>
The polycarbonate resin composition according to any one of aspects 1 to 4, wherein the component D is a silicone gum having a molecular weight of 100,000 or more.
<Aspect 6>
The polycarbonate resin composition according to any one of aspects 1 to 5, wherein the component D is a polyorganosiloxane graft polyolefin resin.
<Aspect 7>
The polycarbonate resin composition according to any one of aspects 1 to 6, wherein the ratio of the polyorganosiloxane rubber component in the composite rubber of the C component is 15% or more.
<Aspect 8>
1. Polycarbonate resin composition.
<Aspect 9>
The polycarbonate resin composition according to aspect 8, wherein the G component is a fluoropolymer having a fibril-forming ability.

Since the polycarbonate resin composition of the present disclosure satisfies mechanical properties, chemical resistance, stain resistance, and appearance at a high level, it is not limited to outdoor / indoor use, but also for housing equipment, building materials, and living materials. It is widely useful in various fields such as infrastructure equipment applications, automobile applications, OA / EE applications, outdoor equipment applications, and so on. Therefore, the industrial effect of the invention according to the present disclosure is extremely large.

Hereinafter, the details of the invention according to the present disclosure will be described.

≪Polycarbonate resin composition≫
The polycarbonate resin composition according to the present disclosure is
It contains (A) polycarbonate-polydiorganosiloxane copolymer resin (component A) and (B) polyester resin (component B).
And for a total of 100 parts by weight of A component and B component
(C) At least selected from the group consisting of an aromatic alkenyl compound monomer unit and an alkyl (meth) acrylate compound monomer unit in a composite rubber composed of a component containing a polyorganosiloxane rubber and an alkyl (meth) acrylic rubber. 3 parts by weight to 15 parts by weight of a graft copolymer (C component) having a core-shell structure in which one unit is graft-polymerized, and (D) 0.5 parts by weight to 6 parts by weight of an antifouling agent (D component). Includes part.

According to the resin composition of the present application, excellent properties are obtained not only in mechanical properties, chemical resistance and appearance, but also in antifouling property. The mechanism by which such an effect is obtained is not always clear, but the following mechanism is conceivable: (A) Polycarbonate-polydiorganosiloxane copolymer resin (component A), although not intended to be limited by theory. In (C) the graft copolymer (C component), the organosiloxane rubber component exposed on the surface of the copolymer is (D) an antifouling agent. It is considered that the antifouling property is improved by the siloxane portion together with (D component).

Further, according to the composition of the present disclosure, by using (B) a polyester resin (component B) in addition to (A) a polycarbonate-polydiorganosiloxane copolymer resin (component A), mechanical properties and antifouling properties are obtained. In addition to its properties and appearance, it is believed to provide excellent chemical resistance.

(Component A: Polycarbonate-polydiorganosiloxane copolymer resin)
The resin composition of the present disclosure contains a polycarbonate-polydiorganosiloxane copolymer resin as the component A.

When a polycarbonate resin containing no polydiorganosiloxane as the component A is used, the impact resistance, stain resistance and chemical resistance are not improved.

The polycarbonate-polydiorganosiloxane copolymer resin (component A) used in the present disclosure is composed of a polycarbonate block represented by the following general formula (2) and a polydiorganosiloxane block represented by the following general formula (4). It is preferable that the copolymerized resin is used.

［（上記一般式（２）において、Ｒ^１及びＲ^２は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１８のアルキル基、炭素原子数１〜１８のアルコキシ基、炭素原子数６〜２０のシクロアルキル基、炭素原子数６〜２０のシクロアルコキシ基、炭素原子数２〜１０のアルケニル基、炭素原子数６〜１４のアリール基、炭素原子数６〜１４のアリールオキシ基、炭素原子数７〜２０のアラルキル基、炭素原子数７〜２０のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシル基からなる群から選ばれる基を表し、それぞれ複数ある場合はそれらは同一でも異なっていても良く、ｅ及びｆは夫々１〜４の整数であり、Ｗは単結合もしくは下記一般式（３）で表される基からなる群より選ばれる少なくとも一つの基である。）

[(In the above general formula (2), R ¹ and R ² are independent hydrogen atoms, halogen atoms, alkyl groups having 1 to 18 carbon atoms, alkoxy groups having 1 to 18 carbon atoms, and 6 carbon atoms, respectively. ~ 20 cycloalkyl groups, 6-20 carbon atoms cycloalkoxy groups, 2-10 carbon atoms alkenyl groups, 6-14 carbon atoms aryl groups, 6-14 carbon atoms aryloxy groups, carbon Represents a group selected from the group consisting of an alkoxy group having 7 to 20 atoms, an alkoxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group, and if there are a plurality of each, they may be the same. It may be different, e and f are each an integer of 1 to 4, and W is at least one group selected from the group consisting of a single bond or a group represented by the following general formula (3).)

［上記一般式（３）においてＲ^１１，Ｒ^１２，Ｒ^１３，Ｒ^１４，Ｒ^１５，Ｒ^１６，Ｒ^１７及びＲ^１８は夫々独立して水素原子、炭素原子数１〜１８のアルキル基、炭素原子数６〜１４のアリール基及び炭素原子数７〜２０のアラルキル基からなる群から選ばれる基を表し、Ｒ^１９及びＲ^２０は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１８のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数６〜２０のシクロアルキル基、炭素原子数６〜２０のシクロアルコキシ基、炭素原子数２〜１０のアルケニル基、炭素原子数６〜１４のアリール基、炭素原子数６〜１０のアリールオキシ基、炭素原子数７〜２０のアラルキル基、炭素原子数７〜２０のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシル基からなる群から選ばれる基を表し、複数ある場合はそれらは同一でも異なっていても良く、ｇは１〜１０の整数、ｈは４〜７の整数である。］

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

［上記一般式（４）において、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、各々独立に水素原子、炭素数１〜１２のアルキル基又は炭素数６〜１２の置換若しくは無置換のアリール基であり、Ｒ^９及びＲ^１０は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基であり、ｐは自然数であり、ｑは０又は自然数であり、ｐ＋ｑは１０〜３００の自然数である。Ｘは炭素数２〜８の二価脂肪族基である。］

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

The polycarbonate-polydiorganosiloxane copolymer resin (component A) used in the present disclosure is preferably a dihydric phenol represented by the following general formula (5) and a hydroxyaryl terminal represented by the following general formula (6). It can be prepared by copolymerizing a polydiorganosiloxane.

［（上記一般式（５）において、Ｒ^１及びＲ^２は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１８のアルキル基、炭素原子数１〜１８のアルコキシ基、炭素原子数６〜２０のシクロアルキル基、炭素原子数６〜２０のシクロアルコキシ基、炭素原子数２〜１０のアルケニル基、炭素原子数６〜１４のアリール基、炭素原子数６〜１４のアリールオキシ基、炭素原子数７〜２０のアラルキル基、炭素原子数７〜２０のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシル基からなる群から選ばれる基を表し、それぞれ複数ある場合はそれらは同一でも異なっていても良く、ｅ及びｆは夫々１〜４の整数であり、Ｗは単結合もしくは上記一般式（３）で表される基からなる群より選ばれる少なくとも一つの基である。）

[(In the above general formula (5), R ¹ and R ² are independent hydrogen atoms, halogen atoms, alkyl groups having 1 to 18 carbon atoms, alkoxy groups having 1 to 18 carbon atoms, and 6 carbon atoms, respectively. ~ 20 cycloalkyl groups, 6-20 carbon atoms cycloalkoxy groups, 2-10 carbon atoms alkenyl groups, 6-14 carbon atoms aryl groups, 6-14 carbon atoms aryloxy groups, carbon Represents a group selected from the group consisting of an alkoxy group having 7 to 20 atoms, an alkoxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group, and if there are a plurality of each, they may be the same. It may be different, and e and f are integers of 1 to 4 respectively, and W is at least one group selected from the group consisting of a single bond or a group represented by the above general formula (3).)

［上記一般式（６）において、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、各々独立に水素原子、炭素数１〜１２のアルキル基又は炭素数６〜１２の置換若しくは無置換のアリール基であり、Ｒ^９及びＲ^１０は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基であり、ｐは自然数であり、ｑは０又は自然数であり、ｐ＋ｑは１０〜３００の自然数である。Ｘは炭素数２〜８の二価脂肪族基である。］

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

Examples of the divalent phenol (I) represented by the general formula (5) include 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and the like. 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1 -Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3'-biphenyl) propane, 2,2-bis (4-hydroxy-3-isopropyl) Phenyl) propane, 2,2-bis (3-t-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2 , 2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) Propane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy) -3-Methylphenyl) Fluolen, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 4,4'-dihydroxydiphenylether, 4,4' -Dihydroxy-3,3'-dimethyldiphenylether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfide, 2,2'-dimethyl-4, 4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide, 2,2'-diphenyl-4,4' -Sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenylsulfide, 1,3-bis {2- (4-hydroxyphenyl) ) Propyl} benzene, 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis (4-hydro) Xiphenyl) cyclohexane, 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4,4'-(1, Examples thereof include 3-adamantandiyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane and the like.

Among them, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl- 4,4'-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis { 2- (4-Hydroxyphenyl) propyl} benzene is preferred, especially 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane (BPZ), 4,4'-. Sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is preferred. Of these, 2,2-bis (4-hydroxyphenyl) propane, which has excellent strength and good durability, is most suitable. Moreover, these may be used individually or in combination of 2 or more types.

As the hydroxyaryl-terminated polydiorganosiloxane represented by the general formula (6), for example, the compounds shown below are preferably used.

The hydroxyaryl-terminated polydiorganosiloxane (II) is preferably a phenol having an olefinic unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol. It is easily produced by subjecting the terminal of a polysiloxane chain having the degree of polymerization of the above to a hydrosyllation reaction. Among them, (2-allylphenol) -terminated polydiorganosiloxane and (2-methoxy-4-allylphenol) -terminated polydiorganosiloxane are preferable, and (2-allylphenol) -terminated polydimethylsiloxane and (2-methoxy-4) are particularly preferable. -Allylphenol) -terminated polydimethylsiloxane is preferred. The hydroxyaryl-terminated polydiorganosiloxane (II) preferably has a molecular weight distribution (Mw / Mn) of 3 or less. The molecular weight distribution (Mw / Mn) is more preferably 2.5 or less, still more preferably 2 or less, in order to exhibit more excellent low outgassing property and low temperature impact resistance during high temperature molding. Within such a suitable range, the amount of outgas generated during high-temperature molding may be suppressed and the low-temperature impact resistance may be excellent.

Further, in order to realize high impact resistance, the degree of polymerization (p + q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is preferably 10 to 300. The degree of polymerization of diorganosiloxane (p + q) is preferably 10 to 200, more preferably 12 to 150, and even more preferably 14 to 100. In such a suitable range, the degree of polymerization (p + q) is sufficiently large, so that the impact resistance characteristic of the polycarbonate-polydiorganosiloxane copolymer is effectively exhibited, and the degree of polymerization (p + q) is not too large. , Brings a good appearance.

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

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

Further, to the extent that it does not interfere with the invention according to the present disclosure, 10% by weight of other comonomer other than the above divalent phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) is added to the total weight of the copolymer. It can also be used in combination within the following range.

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

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

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

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

As the acid binder, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof are used. Similarly to the above, the ratio of the acid binder used may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, it is preferable to use 2 equivalents or a slightly excess amount of the acid binder with respect to the number of moles of the dihydric phenol (I) used for forming the oligomer (usually 1 mol corresponds to 2 equivalents). ..

As the solvent, a solvent inert to various reactions such as those used for producing a known polycarbonate may be used alone or as a mixed solvent. Typical examples include hydrocarbon solvents such as xylene, halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene, and the like. In particular, a halogenated hydrocarbon solvent such as methylene chloride is preferably used.

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

In the present disclosure, after obtaining a mixed solution containing an oligomer of divalent phenol (I) having a terminal chloroformate group in this way, the molecular weight distribution (Mw / Mn) is 3 while stirring the mixed solution. The hydroxyaryl-terminated polydiorganosiloxane (II) represented by the above general formula (6), which has been highly purified to the following, is added to the mixed solution, and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation. Thereby, a polycarbonate-polydiorganosiloxane copolymer is obtained.

In carrying out the interfacial polycondensation reaction, an acid binder may be added as appropriate in consideration of the stoichiometric ratio (equivalent) of the reaction. As the acid binder, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof are used. Specifically, when a part of the hydroxyaryl-terminated polydiorganosiloxane (II) to be used or a divalent phenol (I) as described above is added as a post-addition monomer to this reaction step, the post-addition amount is two. It is preferable to use 2 equivalents or an excess amount of alkali with respect to the total number of moles of the valent phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mol corresponds to 2 equivalents).

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

In such a polymerization reaction, a terminal terminator or a molecular weight modifier is usually used. Examples of the terminal terminator include compounds having a monovalent phenolic hydroxyl group, and in addition to ordinary phenols, p-tert-butylphenols, p-cumylphenols, tribromophenols, etc., long-chain alkylphenols and aliphatic carboxylic acids Examples thereof include chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxyphenyl alkyl acid ester, and alkyl ether phenol. The amount used is in the range of 100 mol to 0.5 mol, preferably 50 mol to 2 mol, with respect to 100 mol of all the dihydric phenolic compounds used, and it is natural that two or more kinds of compounds may be used in combination. It is possible.

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

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

The branching agent can be used in combination with the above-mentioned divalent phenolic compound to obtain a branched polycarbonate-polydiorganosiloxane. Examples of the trifunctional or higher polyfunctional aromatic compound used in such a branched polycarbonate-polydiorganosiloxane copolymer include fluoroglucolcin, fluorogluside, or 4,6-dimethyl-2,4,6-tris (4-hydrochidiphenyl). ) Hepten-2, 2,4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-Hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, trisphenol such as α-dimethylbenzylphenol, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxy) Phenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and their acid chlorides, among others, 1,1,1 -Tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable. .. The proportion of the polyfunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 mol% to 1 mol%, more preferably 0.005, based on the total amount of the aromatic polycarbonate-polydiorganosiloxane copolymer resin. It is mol% to 0.9 mol%, more preferably 0.01 mol% to 0.8 mol%, and particularly preferably 0.05 mol% to 0.4 mol%. The amount of the branched structure ^{can be calculated by 1} H-NMR measurement.

The reaction pressure can be reduced pressure, normal pressure, or pressurization, but usually, normal pressure or the self-pressure of the reaction system can be preferably used. The reaction temperature is selected from the range of −20 ° C. to 50 ° C., and in many cases, heat is generated with the polymerization, so it is desirable to cool the reaction with water or ice. Since the reaction time varies depending on other conditions such as the reaction temperature, it cannot be unconditionally specified, but it is usually carried out in 0.5 hours to 10 hours.

In some cases, the obtained polycarbonate-polydiorganosiloxane copolymer resin is appropriately subjected to physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, cross-linking treatment, partial decomposition treatment, etc.) to achieve the desired reduction. It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin having a viscosity [η _{SP / c].}

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

The average size (average domain size) of the polydiorganosiloxane domain in the polycarbonate-polydiorganosiloxane copolymer resin molded product is preferably in the range of 1 nm to 40 nm. The average size is more preferably 1 nm to 30 nm, still more preferably 5 nm to 25 nm. In such a suitable range, if the average domain size is sufficiently large, impact resistance and flame retardancy may be sufficiently exhibited, and if the average domain size is not too large, the impact resistance is stable. May be demonstrated. This provides a polycarbonate resin composition having particularly excellent impact resistance and appearance.

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

The term "average domain size" used in connection with the present disclosure refers to a measured value obtained by measuring a 1.0 mm thick portion of a three-stage plate produced by the method described in the examples by such a small angle X-ray scattering method. show. In addition, the analysis was performed using an isolated particle model that does not consider the interaction between particles (interference between particles).

The viscosity average molecular weight (M) of the polycarbonate-polydiorganosiloxane copolymer resin is not particularly limited, but is preferably 1.8 × 10 ^{4 to} 4.0 × 10 ⁴ , and more preferably 2.0 × 10 ⁴ to. It is 3.5 × 10 ⁴ , more preferably 2.2 × 10 ^{4 to} 3.0 × 10 ⁴ . The viscosity-average molecular weight of 1.8 × 10 ⁴ or more polycarbonate - the polydiorganosiloxane copolymer resin, may good mechanical properties are obtained, and since a sufficient melt viscosity difference between the polyolefin resin can be ensured , Appearance and tape peeling resistance may be good. On the other hand, viscosity-average molecular weight of 4.0 × 10 ⁴ or less of the polycarbonate - resin composition obtained from polydiorganosiloxane copolymer resin may excellent versatility in terms of excellent fluidity during injection molding.

The polycarbonate-polydiorganosiloxane copolymer resin may be obtained by mixing those having a viscosity average molecular weight outside the above range. In particular, the polycarbonate-polydiorganosiloxane copolymer resin having a viscosity average molecular weight exceeding the above range (5 × 10 ^{4) improves the entropy elasticity of the resin.} As a result, good molding processability is exhibited in gas-assisted molding and foam molding, which may be used when molding a reinforced resin material into a structural member. More preferred embodiments include a polycarbonate-polydiorganosiloxane copolymer resin (A-1-1-1 component) having a viscosity average molecular weight of 7 × 10 ^{4 to} 3 × 10 ^{5 and a viscosity average molecular weight of 1 × 10 4 to} 3 ×. A polycarbonate-polyorganosiloxane copolymer consisting of 10 ⁴ polycarbonate-polydiorganosiloxane copolymer resin (A-1-1-2 component) having a viscosity average molecular weight of 1.6 × 10 ^{4 to} 3.5 × 10 ⁴ A polymer resin (A-1-1 component) (hereinafter, may be referred to as "polycarbonate-polydiorganosiloxane copolymer resin containing a high molecular weight component") can also be used.

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

The high molecular weight component-containing polycarbonate-polydiorganosiloxane copolymer resin (A-1-1 component) is obtained by mixing the A-1-1-1 component and the A-1-1-2 component in various ratios and having a predetermined molecular weight. It can be adjusted and obtained to satisfy the range. It is preferable that the A-1-1-1 component is 2% by weight to 40% by weight, and more preferably the A-1-1-1 component is 3% by weight in 100% by weight of the A-1-1 component. It is ~ 30% by weight, more preferably 4% by weight to 20% by weight of the A-1-1-1 component, and particularly preferably 5% by weight to 20% by weight of the A-1-1-1 component. ..

In addition, as a method for preparing the A-1-1 component,
(1) A method of independently polymerizing the A-1-1-1 component and the A-1-1-2 component and mixing them.
(2) Using a method for producing an aromatic polycarbonate resin showing a plurality of polymer peaks in a molecular weight distribution chart by the GPC method represented by the method shown in JP-A-5-306336, such aromatics are used. A method for producing a polycarbonate resin so as to satisfy the conditions of the A-1-1 component of the present disclosure, and (3) an aromatic polycarbonate resin obtained by such a production method (the production method of (2)) are separately produced. Examples thereof include a method of mixing the A-1-1-1 component and / or the A-1-1-2 component.

The viscosity average molecular weight referred to in the present disclosure is the Ostwald viscosity from a solution in which 0.7 g of a polycarbonate-polydiorganosiloxane copolymer resin is dissolved in 100 ml of methylene chloride _{at a specific viscosity (η SP) calculated by the following formula at 20 ° C.} Obtained using a meter,
Specific viscosity (η _SP ) = (t-t ₀ ) / t ₀
[T ₀ is the number of seconds for methylene chloride to fall, and t is the number of seconds for the sample solution to fall]
From the obtained specific viscosity (η _SP ), the viscosity average molecular weight M is calculated by the following formula.
η _SP / c = [η] +0.45 × ^{[η] 2} c (however, [η] is the ultimate viscosity)
[Η] = 1.23 × 10-4M ^0.83
c = 0.7

The viscosity average molecular weight of the polycarbonate-polydiorganosiloxane copolymer resin in the polycarbonate resin composition of the present disclosure is calculated as follows. That is, the composition is mixed with 20 to 30 times the weight of methylene chloride to dissolve the soluble component in the composition. Such soluble matter is collected by cerite filtration. The solvent in the resulting solution is then removed. The solid after removing the solvent is sufficiently dried to obtain a solid having a component that dissolves in methylene chloride. From a solution of 0.7 g of such a solid in 100 ml of methylene chloride, the specific viscosity at 20 ° C. is obtained in the same manner as above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as above.

(B component: polyester resin)
The polyester resin used as the component B of the present disclosure is a polymer or copolymer obtained by a condensation reaction containing an aromatic dicarboxylic acid or a reactive derivative thereof and a diol or an ester derivative thereof as main components.

The aromatic dicarboxylic acid referred to here is terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-biphenyl ether. Dicarboxylic acid, 4,4'-biphenylmethane dicarboxylic acid, 4,4'-biphenylsulfonate dicarboxylic acid, 4,4'-biphenylisopropyridene dicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid Aromatic dicarboxylic acids such as acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4'-p-terphenylenedicarboxylic acid, 2,5-pyridinedicarboxylic acid, diphenylmethanedicarboxylic acid, diphenyl ether Those selected from dicarboxylic acid and β-hydroxyethoxybenzoic acid are preferably used, and terephthalic acid and 2,6-naphthalenedicarboxylic acid are particularly preferable. Two or more kinds of aromatic dicarboxylic acids may be mixed and used. If the amount is small, it is also possible to mix and use one or more aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecandic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid together with the dicarboxylic acid. ..

The diols that are the components of the polyester resin of the present disclosure include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, 2-methyl-1, Contains an aliphatic diol such as 3-propanediol, diethylene glycol, triethylene glycol, an alicyclic diol such as 1,4-cyclohexanedimethanol, and an aromatic ring such as 2,2-bis (β-hydroxyethoxyphenyl) propane. Examples thereof include diols and the like and mixtures thereof. In a smaller amount, one or more long chain diols having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, or the like may be copolymerized.

Further, the polyester resin of the present disclosure can be branched by introducing a small amount of branching agent. The type of branching agent is not limited, and examples thereof include trimesic acid, trimesic acid, trimethylolethane, trimethylolpropane, and pentaerythritol.

Specific polyester-based resins include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), and polyethylene-1,2. -In addition to bis (phenoxy) ethane-4,4'-dicarboxylate, etc., copolymerized polyester-based resins such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, etc. may be mentioned. Of these, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and mixtures thereof, which have a good balance of mechanical properties and the like, can be preferably used.

Further, the terminal group structure of the obtained polyester resin is not particularly limited, and may be a case where the ratio of the hydroxyl group and the carboxyl group in the terminal group is not substantially the same but a case where one of them is large. Further, those terminal groups may be sealed by reacting with a compound having reactivity with such terminal groups.

Regarding the method for producing such a polyester resin, according to a conventional method, the dicarboxylic acid component and the diol component are polymerized while heating in the presence of a polymerization catalyst containing titanium, germanium, antimony, etc., and water or by-produced water or This is done by discharging the lower alcohol out of the system. For example, examples of the germanium-based polymerization catalyst include germanium oxides, hydroxides, halides, alcoholates, and phenolates, and more specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium, and the like. Can be exemplified.

Preferred specific examples of the polymerization catalyst of the organic titanium compound include titanium tetrabutoxide, titanium isopropoxide, titanium oxalate, titanium acetate, titanium benzoate, titanium trimellitic acid, and a reaction product of tetrabutyl titanate and trimellitic anhydride. Can be mentioned. Further, when it is manufactured using a specific titanium-based catalyst other than the above, a polyester-based resin having more excellent thermal stability can be obtained, so that it is more preferably used.

The above-mentioned specific titanium-based catalyst contains a reaction product of the following titanium compound component (A) and a phosphorus compound component (B).

The titanium compound component (A) is a titanium compound (1) represented by the following general formula (I), an aromatic polyvalent carboxylic acid represented by the titanium compound (1) and the following general formula (II), or an anhydride thereof. It is at least one titanium compound component selected from the group consisting of the titanium compound (2) obtained by reacting with a substance.

〔但し、式（Ｉ）中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、それぞれ互いに独立に２〜１０個の炭素原子を有するアルキル基を表し、ｋは１〜３の整数を表し、かつｋが２又は３の場合、２個又は３個のＲ^２及びＲ^３は、それぞれ互いに同一であってもよく、或いは異なっていてもよい。〕

[However, in formula (I), R ¹ , R ² , R ³ and R ⁴ each represent an alkyl group having 2 to 10 carbon atoms independently of each other, and k represents an integer of 1 to 3. and when k is 2 or 3, two or three R ² and R ³ may each be the same as each other, or may be different. ]

〔但し、式（ＩＩ）中、ｍは２〜４の整数を表す。〕

[However, in equation (II), m represents an integer of 2 to 4. ]

The phosphorus compound component (B) is a phosphorus compound component composed of at least one of the phosphorus compounds (3) represented by the following general formula (III).

〔但し、式（ＩＩＩ）中、Ｒ^５は、未置換の又は置換された、６〜２０個の炭素原子を有するアリール基、又は１〜２０個の炭素原子を有するアルキル基を表す。〕

[In the formula (III), ^{R 5} is, was unsubstituted or substituted, an aryl group, or a 1-20 alkyl group having a carbon atom having 6 to 20 carbon atoms. ]

The polyester-based resin produced by using the above-mentioned specific titanium-based catalyst is excellent in thermal stability and moisture resistance as compared with the case of using germanium, antimony and other titanium-based catalysts. When the above specific titanium-based catalyst is used, the quality is stable even if the amount of additives such as hue stabilizer and heat stabilizer added at the time of manufacture is smaller than when other catalysts are used. Since the decomposition of additives in a hot environment or a moist heat environment is reduced, it is presumed that the heat stability and the moist heat resistance are excellent.

In the reaction product of the titanium compound component (A) and the phosphorus compound component (B), the titanium atomic equivalent molar amount (mTi) of the titanium compound component (A) and the phosphorus atomic equivalent molar amount of the phosphorus compound component (B). The reaction molar ratio (mTi / mP) with (mP) is preferably in the range of 1/3 to 1/1, and more preferably in the range of 1/2 to 1/1.

The titanium atom equivalent molar amount of the titanium compound component (A) is the product of the molar amount of each titanium compound contained in the titanium compound component (A) and the number of titanium atoms contained in one molecule of the titanium compound. It is a total value, and the phosphorus atom equivalent molar amount of the phosphorus compound component (B) is the molar amount of each phosphorus compound contained in the phosphorus compound component (B) and the phosphorus atom contained in one molecule of the phosphorus compound. It is the total value of the product with the number. However, since the phosphorus compound represented by the formula (III) contains one phosphorus atom per molecule, the phosphorus atom equivalent molar amount of the phosphorus compound is equal to the molar amount of the phosphorus compound.

When the reaction molar ratio (mTi / mP) is 1/1 or less, that is, when the amount of the titanium compound component (A) is not too large, the polyester resin obtained by using the obtained catalyst is good. The color tone (b value is not too high) may be obtained, and the heat resistance thereof may be good. Further, when the reaction molar ratio (mTi / mP) is 1/3 or more, that is, when the amount of the titanium compound component (A) is not too small, the catalytic activity of the obtained catalyst for the polyester production reaction is high. It may be enough.

Examples of the titanium compound (1) represented by the general formula (I) used for the titanium compound component (A) include titanium such as titanium tetrabutoxide, titanium tetraisopropoxide, titanium tetrapropoxide, and titanium tetraethoxyoxide. Examples thereof include tetraalkoxides and alkyl titanates such as octaalkyl trititanates and hexaalkyl dititanates, and among these, titanium having good reactivity with the phosphorus compound component used in the present disclosure. It is preferable to use tetraalkoxides, and it is more preferable to use titanium tetrabutoxide.

The titanium compound (2) used as the titanium compound component (A) is obtained by reacting the titanium compound (1) with the aromatic polyvalent carboxylic acid represented by the general formula (II) or an anhydride thereof. The aromatic polyvalent carboxylic acid of the general formula (II) and its anhydride are preferably selected from the group consisting of phthalic acid, trimellitic acid, hemmellitic acid, pyromellitic acid and their anhydrides. In particular, it is more preferable to use trimellitic acid anhydride, which has good reactivity with the titanium compound (1) and has a high affinity with the polyester of the obtained polycondensation catalyst.

The reaction between the titanium compound (1) and the aromatic polyvalent carboxylic acid of the general formula (II) or its anhydride thereof is a part or all of the aromatic polyvalent carboxylic acid or its anhydride mixed with a solvent. Is dissolved in a solvent, the titanium compound (1) is added dropwise to this mixed solution, and the mixture is heated at a temperature of 0 ° C to 200 ° C for 30 minutes or longer, preferably at a temperature of 30 ° C to 150 ° C for 40 minutes to 90 minutes. It is done by. The reaction pressure at this time is not particularly limited, and normal pressure is sufficient. The catalyst can be appropriately selected from those capable of dissolving a part or all of the required amount of the compound of the formula (II) or its anhydride, but ethanol, ethylene glycol and trimethylene are preferable. It is selected from glycol, tetramethylene glycol, benzene, xylene and the like.

The reaction molar ratio between the titanium compound (1) and the compound represented by the formula (II) or its anhydride is not limited. However, if the proportion of the titanium compound (1) is not too high, the color tone of the obtained polyester-based resin becomes good, and a decrease in the softening point can be prevented. On the contrary, when the ratio of the titanium compound (1) is not too low, the polycondensation reaction can proceed satisfactorily. Therefore, the reaction molar ratio between the titanium compound (1) and the compound of the formula (II) or its anhydride is preferably controlled within the range of 2/1 to 2/5. The reaction product obtained by this reaction may be directly subjected to the reaction with the above-mentioned phosphorus compound (3), or this may be recrystallized using a solvent consisting of acetone, methyl alcohol and / or ethyl acetate. After purification, this may be reacted with the phosphorus compound (3).

Phosphorus compounds of the phosphorus compound component (B) in the general formula used (III) in (3), an aryl group having 6 to 20 carbon atoms represented by ^{R 5,} or 1 to 20 carbon atoms The alkyl group contained may be unsubstituted or substituted with one or more substituents. This substituent includes, for example, a carboxyl group, an alkyl group, a hydroxyl group, an amino group and the like.

The phosphorus compound (3) of the general formula (III) is, for example, monomethyl phosphate, monoethyl phosphate, monotrimethyl phosphate, mono-n-butyl phosphate, monohexyl phosphate, monoheptyl phosphate, monooctyl phosphate, monononyl phosphate, and the like. Monodecyl phosphate, monododecyl phosphate, monolauryl phosphate, monooleyl phosphate, monotetradecyl phosphate, monophenyl phosphate, monobenzyl phosphate, mono (4-dodecyl) phenyl phosphate, mono (4-methylphenyl) phosphate, mono (4) -Monoalkyl such as ethylphenyl) phosphate, mono (4-propylphenyl) phosphate, mono (4-dodecylphenyl) phosphate, monotril phosphate, monoxylyl phosphate, monobiphenyl phosphate, mononaphthyl phosphate, and monoanthryl phosphate. It includes phosphates and monoaryl phosphates, which may be used alone or as a mixture of two or more, for example a mixture of monoalkyl phosphate and monoaryl phosphate. However, when the above phosphorus compound is used as a mixture of two or more kinds, the ratio of monoalkyl phosphate preferably occupies 50% or more, more preferably 90% or more, and particularly occupies 100%. It is more preferable to have.

In order to prepare a catalyst from the titanium compound component (A) and the phosphorus compound component (B), for example, a phosphorus compound component (B) composed of at least one phosphorus compound (3) of the formula (III) and a solvent are used. By mixing, a part or all of the phosphorus compound component (B) is dissolved in a solvent, and the titanium compound component (A) is added dropwise to this mixed solution, and the reaction system is usually heated at preferably 50 ° C to 200 ° C, more preferably. Is carried out by heating at a temperature of 70 ° C. to 150 ° C., preferably for 1 minute to 4 hours, more preferably 30 minutes to 2 hours. In this reaction, the reaction pressure is not particularly limited and may be under pressure (0.1 MPa to 0.5 MPa), normal pressure, or reduced pressure (0.001 MPa to 0.1 MPa). It is usually performed under normal pressure.

The solvent for the phosphorus compound component (B) of the formula (III) used in the catalyst preparation reaction is not particularly limited as long as it can dissolve at least a part of the phosphorus compound component (B), but for example, ethanol and ethylene. A solvent consisting of at least one selected from glycol, trimethylene glycol, tetramethylene glycol, benzene, xylene and the like is preferably used. In particular, it is preferable to use as a solvent the same compound as the glycol component constituting the polyester to be finally obtained.

The reaction product of the titanium compound component (A) and the phosphorus compound component (B) is separated from the reaction system by means such as centrifugation or filtration, and then is polyester-based without purification. It may be used as a catalyst for resin production, or the separated reaction product is recrystallized and purified with a recrystallization agent such as acetone, methyl alcohol and / or water, and the resulting purification is obtained. A substance may be used as a catalyst. Further, the reaction product-containing reaction mixture may be used as it is as the catalyst-containing mixture without separating the reaction product from the reaction system.

As the titanium-based catalyst, a titanium compound component (A) composed of at least one titanium compound (1) of the above formula (I) (where k represents 1), that is, titanium tetraalkoxide, and the above formula (III). It is preferable that the reaction product with the phosphorus compound component (B) composed of at least one phosphorus compound of the above is used as a catalyst.
Further, a compound represented by the following general formula (IV) is preferably used as the titanium-based catalyst.

〔上記式中Ｒ^６及びＲ^７は、それぞれ互いに独立に、２〜１２個の炭素原子を有するアルキル基、又は６〜１２個の炭素原子を有するアリール基を表す〕

[In the above formula, R ⁶ and R ⁷ each independently represent an alkyl group having 2 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms].

The catalyst containing the titanium / phosphorus compound represented by the formula (IV) has a high catalytic activity, and the polyester resin produced by using the catalyst has a good color tone (low b value) and is practically used. It has a sufficiently low content of a cyclic trimer of acetaldehyde, a residual metal and an ester of an aromatic dicarboxylic acid and an alkylene glycol, and has sufficient polymer performance for practical use.

The titanium-based catalyst preferably contains the titanium / phosphorus compound of the general formula (IV) in an amount of 50% by weight or more, and more preferably 70% by weight or more.

The amount of the titanium-based catalyst used is preferably such that the titanium atomic equivalent mmol amount is 2 mm% to 40 mm% with respect to the total millimole amount of the aromatic dicarboxylic acid component contained in the polymerization starting material. It is even more preferably 5 milli% to 35 milli%, and even more preferably 10 milli% to 30 milli%. When it is 2 mm% or more, the effect of accelerating the catalyst on the polycondensation reaction of the polymerization starting material is sufficient, the polyester production efficiency is sufficient, and a polyester resin having a desired degree of polymerization can be obtained. In some cases. Further, when it is 40 mm% or less, the color tone (b value) of the obtained polyester resin becomes good, yellowing is suppressed, and its practicality can be ensured.

There are no restrictions on the method for producing an alkylene glycol ester of an aromatic dicarboxylic acid and / or a low polymer thereof, but usually, an aromatic dicarboxylic acid or an ester-forming derivative thereof and an alkylene glycol or an ester-forming derivative thereof are heated. Manufactured by reacting. For example, an ethylene glycol ester of terephthalic acid and / or a low polymer thereof used as a raw material for polyethylene terephthalate can directly transesterify terephthalic acid and ethylene glycol, or a lower alkyl ester of terephthalic acid and ethylene glycol. It is produced by a method of transesterification reaction or addition reaction of ethylene oxide to terephthalic acid. In addition, in the above-mentioned alkylene glycol ester of aromatic dicarboxylic acid and / or a low polymer thereof, another dicarboxylic acid ester copolymerizable therewith is added as an additional component, and the effect of the method of the present disclosure is substantially impaired. It may be contained in an amount not within the range, specifically, in an amount of 10 mol% or less, preferably 5 mol% or less based on the total molar amount of the acid component.

The copolymerizable additional component is preferably an acid component such as an aliphatic and alicyclic dicarboxylic acid such as adipic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, and a hydroxycarboxylic acid, for example. One or more of β-hydroxyethoxybenzoic acid, p-oxybenzoic acid and the like, and as glycol components, for example, alkylene glycol having two or more constituent carbon atoms, 1,4-cyclohexanedimethanol, neopentylglycol, bisphenol A , Bisphenol S and other aliphatic, alicyclic, aromatic diol compounds and polyoxyalkylene glycols, selected from esters or anhydrides thereof. The above-mentioned additional component ester may be used alone or in combination of two or more thereof. However, the copolymerization amount is preferably within the above range.

When terephthalic acid and / or dimethyl terephthalate are used as starting materials, polyester is used as the recovered dimethyl terephthalate obtained by depolymerizing polyalkylene terephthalate or the recovered terephthalic acid obtained by hydrolyzing the recovered terephthalic acid. It can also be used in an amount of 70% by weight or more based on the weight of all the constituent acid components. In this case, the target polyalkylene terephthalate is preferably polyethylene terephthalate, particularly recovered PET bottles, recovered textile products, recovered polyester film products, polymer scraps generated in the manufacturing process of these products, and the like. Is preferable from the viewpoint of effective utilization of resources.

Here, the method for obtaining dimethyl terephthalate by depolymerizing the recovered polyalkylene terephthalate is not particularly limited, and any conventionally known method can be adopted. For example, after depolymerizing the recovered polyalkylene terephthalate with ethylene glycol, the depolymerization product is subjected to a transesterification reaction with a lower alcohol, for example, methanol, and the reaction mixture is purified to recover the lower alkyl ester of terephthalic acid. Then, this is subjected to a transesterification reaction with alkylene glycol, and the obtained phthalic acid / alkylene glycol ester is subjected to transesterification to obtain a polyester resin. Further, the method for recovering terephthalic acid from the recovered dimethyl terephthalate is not particularly limited, and any of the conventional methods may be used. For example, dimethyl terephthalate can be recovered from the reaction mixture obtained by the transesterification reaction by a recrystallization method and / or a distillation method, and then hydrolyzed by heating with water under high temperature and high pressure to recover terephthalic acid. Among the impurities contained in the terephthalic acid obtained by this method, the total content of 4-carboxybenzaldehyde, paratorylic acid, benzoic acid and dimethyl hydroxyterephthalate is preferably 1 ppm or less. Further, the content of monomethyl terephthalate is preferably in the range of 1 ppm to 5000 ppm. A polyester resin can be produced by directly subjecting the terephthalic acid recovered by the above method to an alkylene glycol in an esterification reaction and polycondensing the obtained ester.

In the polyester resin used in the present disclosure, the time to add the catalyst to the polymerization starting material may be any stage before the start time of the polycondensation reaction of the aromatic dicarboxylic acid alkylene glycol ester and / or its low polymer. Furthermore, there are no restrictions on the method of addition thereof. For example, an aromatic dicarboxylic acid alkylene glycol ester may be prepared and a catalyst solution or slurry may be added to the reaction system to initiate a polycondensation reaction, or the aromatic dicarboxylic acid alkylene glycol ester may be used. A catalyst solution or slurry may be added to the reaction system with the starting material at the time of preparation or after the preparation thereof.

There are no particular restrictions on the production reaction conditions of the polyester resin used in the present disclosure. Generally, the polycondensation reaction is carried out at a temperature of 230 ° C. to 320 ° C. under normal pressure or reduced pressure (0.1 Pa to 0.1 MPa), or by combining these conditions, and polycondensation is carried out for 15 minutes to 300 minutes. Is preferable.

In the polyester resin used in the present disclosure, a reaction stabilizer, for example, trimethyl phosphate may be added to the reaction system at any stage in the production of the polyester resin, if necessary, and if necessary, antioxidant is added to the reaction system. One or more of agents, ultraviolet absorbers, flame retardants, fluorescent whitening agents, matting agents, color matching agents, defoaming agents, and other additives may be blended. In particular, the polyester resin preferably contains an antioxidant containing at least one hindered phenol compound, but the content thereof is 1% by weight or less based on the weight of the polyester resin. Is preferable. When the content is 1% by weight or less, the quality of the obtained product can be ensured by preventing the thermal deterioration of the antioxidant itself.

The hindered phenol compounds for antioxidants used in the polyester resins used in the present disclosure are pentaerythritol-tetra extract [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3, 9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5] , 5] It is also preferably used in combination with these hindered phenolic antioxidants and thioether-based secondary antioxidants, which are selected from undecane and the like. The method of adding the above hindered phenolic antioxidant to the polyester resin is not particularly limited, but preferably any step after the completion of the transesterification reaction or the esterification reaction until the polymerization reaction is completed. Is added at.

Further, in order to finely adjust the color tone of the obtained polyester-based resin, organic blue pigments such as azo-based, triphenylmethane-based, quinoline-based, anthraquinone-based, and phthalocyanine-based pigments are included in the reaction system at the production stage of the polyester resin. And a color matching agent consisting of one or more kinds of inorganic blue pigments can be added. As a matter of course, in the production method of the present disclosure, it is not necessary to use an inorganic blue pigment containing cobalt or the like, which lowers the thermal stability of the polyester resin, as the color modifier. Therefore, the polyester-based resin used in the present disclosure does not substantially contain cobalt.

The polyester resin used in the present disclosure preferably contains 0.001 ppm to 100 ppm of the titanium element derived from the catalyst. The content is more preferably 0.001 ppm to 50 ppm, further preferably 1 ppm to 50 ppm. If the amount of titanium element contained is more than 100 ppm, thermal stability and moisture resistance may be deteriorated, and if it is less than 0.001 ppm, the remaining amount of the catalyst of the polyester resin used is significantly less than that of the polyester resin. However, it may not be possible to obtain the good mechanical strength / thermal stability and wet thermal stability that are the characteristics of this composition.

In the polyester resin used in the present disclosure, it is usually preferable that the L value obtained from the hunter type color difference meter is 80.0 or more and the b value is in the range of −2.0 to 5.0. If the L value of the polyester resin is less than 80.0, the whiteness of the obtained polyester resin becomes low, so that it may not be possible to obtain a high whiteness molded product that can be put into practical use. Further, when the b value is less than -2.0, the yellowness of the obtained polyester resin is small, but the bluish color increases, and when the b value exceeds 5.0, the yellowness of the obtained polyester resin is increased. May not be available for the production of practically useful molded products. The L value of the polyester resin obtained by the method of the present disclosure is more preferably 82 or more, particularly preferably 83 or more, and the more preferable range of the b value is -1.0 to 4.5, particularly preferably 0. It is .0 to 4.0.

The intrinsic viscosity of the polyester resin obtained by the present disclosure is preferably 0.4 to 1.5. A more preferable range of the intrinsic viscosity is 0.45 to 1.4, and more preferably 0.50 to 1.3. When the intrinsic viscosity of the polyester resin is 0.4 or more, sufficient impact characteristics and chemical resistance may be obtained, and when it is 1.5 or less, the fluidity during injection molding is ensured. Therefore, the occurrence of appearance defects such as flow marks and coloring defects can be prevented. The intrinsic viscosity of the polyester resin is measured at a temperature of 35 ° C. by dissolving the polyester resin in orthochlorophenol. The polyester resin obtained by solid phase polycondensation is often used for general bottles and the like, and is therefore contained in the polyester resin and has an intrinsic viscosity of 0.70 to 0.90. It is preferable that the content of the cyclic trimer of the ester of the aromatic dicarboxylic acid and the alkylene glycol is 0.5 wt% or less, and the content of acetaldehyde is 5 ppm or less. The cyclic trimer includes alkylene terephthalates such as ethylene terephthalate, trimethylene terephthalate, tetramethylene terephthalate, and hexamethylene terephthalate, and alkylene naphthalates such as ethylene naphthalate, trimethylene naphthalate, tetramethylene naphthalate and hexa. Includes methylene naphthalate and the like.

Further, in the present disclosure, compounds such as manganese, zinc, calcium and magnesium used in the ester exchange reaction which is the pre-stage of the conventionally known polycondensation can be used together, and phosphoric acid or subphosphoric acid or subphosphoric acid can be used after the ester exchange reaction is completed. It is also possible to inactivate such a catalyst and carry out polycondensation with an acid compound or the like.

As the method for producing the polyester resin, either a batch method or a continuous polymerization method can be adopted.

The content of the B component is preferably 20 to 70 parts by weight, more preferably 30 to 70 parts by weight, and 35 to 65 parts by weight out of 100 parts by weight of the total of the A component and the B component. It is more preferably 40 to 60 parts by weight, and particularly preferably 40 to 60 parts by weight. If the content of component B is too low, chemical resistance may not be exhibited, and if the content of component B is too high, good mechanical properties, flame retardancy and antifouling property may be deteriorated. There is.

(C component: A composite rubber composed of a component containing a polyorganosiloxane rubber and an alkyl (meth) acrylic rubber, selected from the group consisting of an aromatic alkenyl compound monomer unit and an alkyl (meth) acrylate compound monomer unit. A graft copolymer having a core-shell structure in which at least one unit is graft-polymerized)
The resin composition of the present disclosure comprises a composite rubber composed of a polyorganosiloxane rubber and an alkyl (meth) acrylicate rubber as a C component, an aromatic alkenyl compound monomer unit and an alkyl (meth) acrylate compound single amount. At least one selected from the group consisting of body units also contains a graft copolymer having a core-shell structure in which the units are graft-polymerized.

The rubber component of the C component is a composite rubber component composed of a component containing a polyorganosiloxane rubber and an alkyl (meth) acrylic rubber. The composite rubber refers to a rubber obtained by copolymerizing two kinds of rubber components or a rubber polymerized so as to have an IPN structure in which they are intertwined with each other so as not to be separated. Further, from the viewpoint of antifouling property, the ratio of the polyorganosiloxane rubber in the rubber component is preferably 10% or more, and more preferably 15% or more. The upper limit of the ratio of the polyorganosiloxane rubber in the rubber component is not particularly limited, but is preferably 95% or less, 90% or less, 80% or less, or 70% or less. In the core-shell type graft polymer, the particle size of the core is preferably 0.05 μm to 0.8 μm, more preferably 0.1 μm to 0.6 μm, still more preferably 0.15 μm to 0.5 μm in terms of weight average particle size. A range of 0.05 μm to 0.8 μm is preferable because better impact resistance may be achieved.

Examples of the aromatic alkenyl compound to be graft-polymerized on the shell of the core-shell type graft polymer include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, halogenated styrene and the like. Examples of the alkyl (meth) acrylate compound include acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, and octyl acrylate, and methyl methacrylate, ethyl methacrylate, butyl methacrylate, and methacrylic acid. Examples thereof include methacrylic acid esters such as cyclohexyl and octyl methacrylate.

From the viewpoint of compatibility with the aromatic polycarbonate resin, at least one unit selected from the group consisting of the aromatic alkenyl compound monomer unit and the alkyl (meth) acrylate compound monomer unit is graft-polymerized on the composite rubber. As a result, the good impact resistance of the aromatic polycarbonate resin is more effectively exhibited, and as a result, the impact resistance of the resin composition is improved.

The elastic polymer containing a composite rubber composed of a component containing polyorganosiloxane rubber and an alkyl (meth) acrylic rubber was produced by any of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. The copolymerization method may be either a one-step graft or a multi-step graft. Further, it may be a mixture with a copolymer containing only a graft component produced as a by-product during production. Further, as the polymerization method, in addition to the general emulsion polymerization method, a soap-free polymerization method using an initiator such as potassium persulfate, a seed polymerization method, a two-step swelling polymerization method and the like can be mentioned. Further, in the suspension polymerization method, a method in which the aqueous phase and the monomer phase are individually held and both are accurately supplied to a continuous disperser, and the particle size is controlled by the rotation speed of the disperser, and continuous manufacturing. In the method, a method of supplying a monomer phase into an aqueous liquid having a dispersibility through a small diameter orifice having a diameter of several to several tens of μm or a porous filter to control the particle size may be used. In the case of a core-shell type graft polymer, the reaction may be one-stage or multi-stage for both the core and the shell.

Such polymers are commercially available and easily available. For example, Mitsubishi Chemical Corporation's Metabrene S-2501, S-2030, SX-005, which has a core component of silicone-acrylic composite rubber and a shell component of methyl methacrylate as the main component, or acrylonitrile and styrene as shell components. Examples thereof include those commercially available under the trade names of SRK-200A and SX-200R, which are the main components.

When a graft copolymer other than the above-mentioned graft copolymer is used as the C component, chemical resistance and antifouling property are not exhibited.

The content of the C component is 3 parts by weight to 15 parts by weight, preferably 4 parts by weight to 12 parts by weight, and more preferably 5 parts by weight to 10 parts by weight with respect to 100 parts by weight of the total of the A component and the B component. It is a department. The addition of the C component further improves impact resistance, chemical resistance, and stain resistance. When it is 15 parts by weight or less, a good appearance is ensured.

(D component: antifouling agent)
The resin composition of the present disclosure contains an antifouling agent as a component D. Specific examples of the antifouling agent of the present disclosure include silicone oil, silicone gum, silicone resin fine particles, polyolefin, silicone-modified polyolefin, wax, and the like, among which effective and continuous antifouling property is exhibited. From this point of view, silicone gum and silicone-modified polyolefin are particularly desirable.

The silicone gum used in the present disclosure is preferably a polyorganosiloxane having a molecular weight of 100,000 or more in the form of a gum. Polyorganosiloxane is a polymer substance in which an organic group is added to a structure in which a silicon atom is bonded to another silicon atom via an oxygen atom. The skeleton of the polyorganosiloxane may be linear, branched, cyclic, or a mixture thereof.

The structure of polyorganosiloxane includes polydimethylsiloxane, polymethylphenylsiloxane, polymethylhydrogensiloxane, aralkyl-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, alkyl-modified polydimethylsiloxane, higher fatty acid-modified polydimethylsiloxane, and fluoro. Examples thereof include alkyl-modified polydimethylsiloxane, amino-modified polydimethylsiloxane, epoxy-modified polydimethylsiloxane, carbinol-modified polydimethylsiloxane, carboxyl-modified polydimethylsiloxane, phenol-modified polydimethylsiloxane, and silanol-modified polydimethylsiloxane. These may be used alone or in combination of two or more. Of these, polydimethylsiloxane is most preferably used because of the balance between performance and cost.

When the molecular weight is 100,000 or more, the viscosity can be very high. From the viewpoint of improving handleability, a masterbatch product diluted with a thermoplastic resin is preferably used. Such a masterbatch product is commercially available and can be easily obtained. For example, MB50-315, which is a 50% polycarbonate masterbatch product manufactured by Toray Dow Corning Co., Ltd., BY27-001, which is a 50% polypropylene masterbatch product, and BY27-009, which is a 50% polyester elastomer masterbatch product. Examples are those on the market.

Silicone-modified polyolefins can also be used in the present disclosure. The silicone-modified polyolefin is a polyolefin-based resin chemically bonded with polyorganosiloxane. Examples of the silicone-modified polyolefin include polyorganosiloxane grafted polyolefin resins. The polyolefin-based resin is a synthetic resin obtained by polymerizing or copolymerizing an olefin-based monomer having a radically polymerizable double bond. The olefin-based monomer is not particularly limited, and for example, α- such as ethylene, propylene, 1-butane, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene and the like. Examples thereof include olefins and conjugated dienes such as butadiene and isoprene. The olefin-based monomer may be used alone or in combination of two or more. The polyolefin-based resin is not particularly limited, and is not particularly limited, for example, a homopolymer of ethylene, a copolymer of ethylene and an α-olefin other than ethylene, a homopolymer of propylene, and a copolymer of propylene and an α-olefin other than propylene. Examples thereof include polymers, homopolymers of butene, homopolymers or copolymers of conjugated diene such as butadiene and isoprene, and homopolymers of propylene and copolymers of propylene and α-olefins other than propylene are preferable. .. More preferably, it is a homopolymer of propylene. The polyolefin-based resin may be used alone or in combination of two or more. In the present disclosure, polypropylene-based resins are more preferably used from the viewpoint of versatility and rigidity.

Further, the skeleton of the polyorganosiloxane may be linear, branched, cyclic, or a mixture thereof. The structure of polyorganosiloxane includes polydimethylsiloxane, polymethylphenylsiloxane, polymethylhydrogensiloxane, aralkyl-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, alkyl-modified polydimethylsiloxane, higher fatty acid-modified polydimethylsiloxane, and fluoro. Examples thereof include alkyl-modified polydimethylsiloxane, amino-modified polydimethylsiloxane, epoxy-modified polydimethylsiloxane, carbinol-modified polydimethylsiloxane, carboxyl-modified polydimethylsiloxane, phenol-modified polydimethylsiloxane, and silanol-modified polydimethylsiloxane. These may be used alone or in combination of two or more. Of these, polydimethylsiloxane is most preferably used because of the balance between performance and cost. Such polymers are commercially available and easily available. For example, the polyorganosiloxane graft polypropylenes manufactured by Toray Dow Corning Co., Ltd., which are commercially available under the trade names BY27-201 and BY27-201C, can be mentioned.

The content of the D component is 0.5 parts by weight to 6.0 parts by weight, preferably 1.0 part by weight to 5.0 parts by weight, based on 100 parts by weight of the total of the A component and the B component. It is preferably 1.5 parts by weight to 4.0 parts by weight. When the D component is 0.5 parts by weight or more, antifouling property is exhibited. When the content of the D component is 4.0 parts by weight or less, appearance defects such as bleed-out do not occur. When the above masterbatch product is used, the content of the D component indicates the amount of the antifouling agent contained in the masterbatch product.

（式中、Ｘ_１およびＸ_２は、同一もしくは異なり、下記一般式（Ｉ）で表される芳香族置換アルキル基である。）

（式中、ＡＬは炭素数１〜５の分岐状または直鎖状の脂肪族炭化水素基であり、Ａｒはフェニル基、ナフチル基またはアントリル基であり、ｎは１〜３の整数を示し、ＡｒはＡＬの任意の炭素原子に結合することができる。）。≪Flame-retardant polycarbonate resin composition≫
In one embodiment of the present disclosure, the polycarbonate resin composition further comprises the following flame retardants:
(E) Halogen-based flame retardant (E component), and (F) Phosphorus-based flame retardant (F component) having a structure represented by the following formula (1).

(In the formula, X ₁ and X ₂ are the same or different, and are aromatic substituted alkyl groups represented by the following general formula (I).)

(In the formula, AL is a branched or linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, Ar is a phenyl group, a naphthyl group or an anthryl group, and n is an integer of 1 to 3; Ar can be attached to any carbon atom of AL.).

In applications such as electrical and electronic equipment, the demand for flame retardancy is increasing, and various flame retardant resin compositions have been proposed. However, none of these proposals has yet provided a flame-retardant polycarbonate resin composition having mechanical properties, appearance, flame retardancy, chemical resistance, stain resistance, and thermal stability.

The polycarbonate resin composition according to the above-described embodiment of the present disclosure further contains the above-mentioned E component and F component as a flame retardant, in addition to excellent mechanical properties, chemical resistance, antifouling property, and appearance. It meets flame retardancy and thermal stability at a high level. Therefore, it is particularly widely useful not only in outdoor / indoor use but also in housing equipment use, building material use, living material use, infrastructure equipment use, automobile use, OA / EE use, outdoor equipment use, and various other fields.

(E component: halogen-based flame retardant)
The resin composition according to one embodiment of the present disclosure contains a halogen-based flame retardant as the E component. As the halogen-based flame retardant, brominated polycarbonate (including an oligomer) is particularly suitable. Brominated polycarbonate has excellent heat resistance and can greatly improve flame retardancy. In the brominated polycarbonate used in the present disclosure, the structural unit represented by the following formula (7) is preferably at least 60 mol%, more preferably at least 80 mol%, and particularly preferably substantially the following. It is a brominated polycarbonate compound composed of a structural unit represented by the formula (7).

In the formula (7), X is a bromine atom, R is an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 1 to 4 carbon atoms, or −SO ₂ −.
Further, in such formula (7), preferably R is a methylene group, an ethylene group, an isopropylidene group, -SO 2 - shows a _particularly preferably isopropylidene group.

The brominated polycarbonate has a small amount of residual chlorohomate group terminals, and the amount of terminal chlorine is preferably 0.3 ppm or less, more preferably 0.2 ppm or less. To determine the amount of terminal chlorine, dissolve the sample in methylene chloride, add 4- (p-nitrobenzyl) pyridine to react with terminal chlorine (terminal chlorohomet), and use this as an ultraviolet-visible spectrophotometer (U, manufactured by Hitachi, Ltd.). It can be measured and obtained by -3200). When the amount of terminal chlorine is 0.3 ppm or less, the thermal stability of the polycarbonate resin composition becomes better, and molding at a higher temperature becomes possible, and as a result, a resin composition having better molding processability is provided.

Further, it is preferable that the brominated polycarbonate has few remaining hydroxyl group ends. More specifically, the amount of terminal hydroxyl groups is preferably 0.0005 mol or less, and more preferably 0.0003 mol or less, with respect to 1 mol of the constituent unit of the brominated polycarbonate. The amount of terminal hydroxyl groups can be determined by dissolving the sample in deuterated chloroform and ^{measuring by 1 1} H-NMR method. Such an amount of terminal hydroxyl groups is preferable because the thermal stability of the polycarbonate resin composition is further improved.

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

The content of the E component is 5 parts by weight to 35 parts by weight, preferably 8 parts by weight to 30 parts by weight, and more preferably 10 parts by weight to 25 parts by weight with respect to 100 parts by weight of the total of the A component and the B component. Is. When the content of the E component is 5 parts by weight or more, flame retardancy may be exhibited, and when it is 35 parts by weight or less, good mechanical properties, appearance and chemical resistance may be ensured.

Further, the halogen-based flame retardant can generally further enhance the flame retardancy of the resin composition by using it in combination with the antimony oxide compound, but in the present disclosure, it is not desirable because the thermal stability is significantly lowered.

(F component: phosphorus-based flame retardant)
The phosphorus-based flame retardant of the present disclosure is an organic phosphorus compound represented by the following general formula (1).

In the above formula (1), X ₁ and X ₂ are the same or different, and represent an aromatic substituted alkyl group represented by the following general formula (I).

In the above formula (I), AL is a branched or linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, preferably 1 or 2 carbon atoms. Specifically, AL is preferably an alkyl group represented by the following formula (8). Further, Ar is a phenyl group, a naphthyl group or an anthryl group, of which a phenyl group is preferable. n represents an integer of 1 to 3, but is preferably 1 or 2. Ar can be attached to any carbon of AL.

The organophosphorus flame retardant represented by the above formula (1) exhibits an extremely excellent flame retardant effect on the aromatic polyester resin.
The organophosphorus flame retardant is represented by the above general formula (1), and the most preferable representative compound is at least one compound selected from the group consisting of the following formulas (B-a) to (Bd). be. These compounds may be used alone or in combination of two or more.

Of these formulas (B-a) to (B-d), the B-a component represented by the formula (B-a) or the B-c component represented by the formula (B-c) has a flame-retardant effect or It is suitable in terms of ease of synthesis and the like. When a phosphorus-based flame retardant other than the phosphorus-based flame retardant is used, flame retardancy does not develop at an amount added within the range of the present disclosure.

The method for synthesizing the organophosphorus flame retardant in the present disclosure may be synthesized by a known method and manufactured by a method other than the method described below.

The organic phosphorus flame retardant can be obtained, for example, by reacting pentaerythritol with phosphorus trichloride, then treating the oxidized reaction product with an alkali metal compound such as sodium methoxydo, and then reacting with aralkylhalide. It can also be obtained by a method of reacting pentaerythritol with aralkylphosphonate dichloride, or a method of reacting pentaerythritol with phosphorus trichloride to react with aralkyl alcohol and then performing Arbuzov transfer at high temperature. .. The latter reaction is disclosed in, for example, US Pat. No. 3,141,032, Japanese Patent Application Laid-Open No. 54-157156, and Japanese Patent Application Laid-Open No. 53-39698.

The specific synthetic method will be described below, but this synthetic method is for illustration purposes only, and the organophosphorus flame retardants used in the present disclosure are not limited to these synthetic methods, but are modified and other synthetic methods thereof. It may be synthesized. A more specific synthetic method will be described in Preparation Example 1 described later.
(I) The organic phosphorus compound of (B) above;
It can be obtained by reacting pentaerythritol with phosphorus trichloride and then treating the reaction product oxidized with tertiary butanol with sodium methoxide and reacting with benzyl bromide.
(Ii) The organic phosphorus compound of (B) above;
It can be obtained by reacting pentaerythritol with phosphorus trichloride, and then treating the reaction product oxidized with tertiary butanol with sodium methoxide and reacting with 1-bromoethylbenzene.
(Iii) The organic phosphorus compound of the above (B-c);
It can be obtained by reacting pentaerythritol with phosphorus trichloride, and then treating the reaction product oxidized with tertiary butanol with sodium methoxide and reacting with 2-bromoethylbenzene.
(Iv) The organic phosphorus compound of the above (Bd);
It can be obtained by reacting pentaerythritol with diphenylmethylphosphonic acid dichloride.

The acid value of the organophosphorus flame retardant is preferably 0.7 mgKOH / g or less, more preferably 0.5 mgKOH / g or less. By using an organic phosphorus-based flame retardant having an acid value in this range, the polyester resin is less likely to be decomposed and the thermal stability is improved, so that the composition has good processability. The organic phosphorus flame retardant most preferably has an acid value of 0.4 mgKOH / g or less. Here, the acid value means the amount (mg) of KOH required to neutralize the acid component in 1 g of the sample. When the acid value is 0.7 mgKOH / g or less, good thermal stability is ensured and processability may be excellent, which is preferable.

Further, as the organophosphorus flame retardant, one having an HPLC purity of preferably 90% or more, more preferably 95% or more is used. Such high-purity products are preferable because they are excellent in flame retardancy and hue of molded products. Here, the HPLC purity of the F component can be effectively measured by using the following method. The column used was Develosil ODS-7 300 mm × 4 mmφ manufactured by Nomura Chemical Co., Ltd., and the column temperature was set to 40 ° C. As a solvent, a mixed solution of acetonitrile and water in a ratio of 6: 4 (volume ratio) was used, and 5 μl was injected. The detector used was UV-260 nm. The method for removing impurities in the F component is not particularly limited, but the method of performing repulp washing (washing with a solvent and repeating filtration several times) with a solvent such as water or methanol is the most effective. Moreover, it is advantageous in terms of cost.

The content of the F component is 0.5 parts by weight to 5 parts by weight, preferably 0.8 parts by weight to 4 parts by weight, and more preferably 1 part by weight with respect to 100 parts by weight of the total of the A component and the B component. It is in the range of 3 parts to 3 parts by weight. When the content of the F component is 0.5 parts by weight or more, flame retardancy develops, and when the content is 5 parts by weight or less, good mechanical properties, appearance, and chemical resistance may be ensured. be.

(G component: anti-drip agent)
The resin composition of the present disclosure can contain a drip inhibitor as the G component. By containing this drip inhibitor, good flame retardancy can be achieved without impairing the physical properties of the molded product.

Examples of the G component drip inhibitor include a fluoropolymer having a fibril-forming ability, and examples of such a polymer include polytetrafluoroethylene and a tetrafluoroethylene-based copolymer (for example, tetrafluoroethylene / hexafluoropropylene). Polymers, etc.), partially fluorinated polymers as shown in US Pat. No. 4,379,910, polycarbonate resins made from fluorinated diphenols, and the like. Of these, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferable.

The molecular weight of PTFE having a fibril-forming ability has an extremely high molecular weight, and exhibits a tendency to bond PTFE to each other to form a fibrous form due to an external action such as a shearing force. The molecular weight is 1 million to 10 million, more preferably 2 million to 9 million in the number average molecular weight obtained from the standard specific gravity. As the PTFE, not only a solid form but also an aqueous dispersion form can be used. Further, the PTFE having such a fibril-forming ability improves the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with another resin in order to obtain better flame retardancy and mechanical properties. be.

Examples of commercially available PTFE products having such a fibril-forming ability include Teflon (registered trademark) 6J of Mitsui-DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500 and F-201L of Daikin Industries, Ltd. and the like. Commercially available aqueous dispersions of PTFE include Fluon AD-1, AD-936 manufactured by Asahi Icy Fluoropolymers Co., Ltd., Fluon D-1 and D-2 manufactured by Daikin Industries, Ltd., and Mitsui DuPont Fluoro. Teflon (registered trademark) 30J manufactured by Chemical Co., Ltd. can be mentioned as a representative.

As a mixed form of PTFE,
(1) A method for obtaining a coaggregating mixture by mixing an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer and co-precipitating them (Japanese Patent Laid-Open No. 60-258263, JP-A-63-154744). Method described in the gazette etc.),
(2) A method of mixing an aqueous dispersion of PTFE and dried organic polymer particles (method described in JP-A-4-272957).
(3) A method of uniformly mixing an aqueous dispersion of PTFE and an organic polymer particle solution and simultaneously removing each medium from such a mixture (Japanese Patent Laid-Open No. 06-220210, Japanese Patent Application Laid-Open No. 08-188653, etc.). The way it was done),
(4) A method of polymerizing a monomer forming an organic polymer in an aqueous dispersion of PTFE (method described in JP-A-9-95583), and (5) an aqueous dispersion of PTFE and an organic weight. The product obtained by a method of uniformly mixing the combined dispersion, further polymerizing a vinyl-based monomer in the mixed dispersion, and then obtaining a mixture (method described in JP-A-11-29679) is used. Can be used.
Examples of commercially available products of these mixed forms of PTFE include "Metabrene A3800" (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and "BLENDEX B449" (trade name) manufactured by GE Specialty Chemicals.

The proportion of PTFE in the mixed form is preferably 1% by weight to 60% by weight, more preferably 5% by weight to 55% by weight, based on 100% by weight of the PTFE mixture. When the proportion of PTFE is in such a range, good dispersibility of PTFE can be achieved. The ratio of the G component indicates the amount of the net anti-drip agent, and in the case of the mixed form of PTFE, it indicates the net amount of PTFE.

The content of the G component is preferably 0.05 parts by weight to 2 parts by weight, more preferably 0.1 parts by weight to 1.5 parts by weight, and further, with respect to 100 parts by weight of the total of the A component and the B component. It is preferably 0.2 parts by weight to 1 part by weight. If the amount of drip inhibitor exceeds the above range and is too small, the flame retardancy may be insufficient. On the other hand, if the amount of the drip inhibitor exceeds the above range and is too large, PTFE may precipitate on the surface of the molded product and the appearance may be poor, which leads to an increase in the cost of the resin composition, which is not preferable.

The styrene-based monomer used in the organic polymer used in the polytetrafluoroethylene-based mixture of the present disclosure includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen. Styrene which may be substituted with one or more groups selected from the group consisting of, for example, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, dimethylstyrene, ethyl-styrene, para-tert-butylstyrene. , Methoxystyrene, fluorostyrene, monobromostyrene, dibromostyrene, and tribromostyrene, vinylxylene, vinylnaphthalene, but are not limited thereto. The styrene-based monomer can be used alone or in combination of two or more types.

The acrylic monomer used in the organic polymer used in the polytetrafluoroethylene-based mixture of the present disclosure contains a (meth) acrylate derivative which may be substituted. Specifically, the acrylic monomer is substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, and a glycidyl group. May be (meth) acrylate derivatives such as (meth) acrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth). Acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate and glycidyl (meth) acrylate, Maleimides which may be substituted with an alkyl group having 1 to 6 carbon atoms or an aryl group, for example, maleimide, N-methyl-maleimide and N-phenyl-maleimide, maleic acid, phthalic acid and itaconic acid are exemplified. Not limited to these. The acrylic monomer can be used alone or in combination of two or more types. Of these, (meth) acrylonitrile is preferred.

The amount of the acrylic monomer-derived unit contained in the organic polymer used for the coating layer is preferably 8 parts by weight to 11 parts by weight, more preferably 8 parts by weight, based on 100 parts by weight of the styrene-based monomer-derived unit. 10 parts by weight, more preferably 8 parts by weight to 9 parts by weight. When the unit derived from the acrylic monomer is 8 parts by weight or more, the coating strength may be ensured, and when it is 11 parts by weight or less, a good surface appearance of the molded product can be ensured.

The polytetrafluoroethylene-based mixture of the present disclosure preferably has a residual water content of 0.5% by weight or less, more preferably 0.2% by weight to 0.4% by weight, still more preferably 0.1% by weight. % To 0.3% by weight. When the residual water content is 0.5% by weight or less, adverse effects on flame retardancy can be avoided.

In the process of producing the polytetrafluoroethylene-based mixture of the present disclosure, a coating layer containing one or more monomers selected from the group consisting of styrene-based monomers and acrylic monomers in the presence of an initiator is used. Includes the step of forming outside the branched polytetrafluoroethylene. Further, after the step of forming the coating layer, the residual water content is 0.5% by weight or less, preferably 0.2% by weight to 0.4% by weight, and more preferably 0.1% by weight to 0.3% by weight. It is preferable to include a step of drying. The drying step can be performed using methods known in the art, such as hot air drying or vacuum drying methods.

The initiator used in the polytetrafluoroethylene-based mixture of the present disclosure may be used without limitation as long as it is used for the polymerization reaction of styrene-based and / or acrylic-based monomers. Examples of the initiator include, but are not limited to, cumyl hydroperoxide, di-tert-butyl peroxide, benzoyl peroxide, hydrogen peroxide, and potassium peroxide. In the polytetrafluoroethylene-based mixture of the present disclosure, one or more of the initiators can be used depending on the reaction conditions. The amount of the initiator is freely selected within the range used in consideration of the amount of polytetrafluoroethylene and the type / amount of the monomer, and is from 0.15 part by weight based on the amount of the total composition. It is preferable to use 0.25 parts by weight.

The polytetrafluoroethylene-based mixture of the present disclosure was produced by the suspension polymerization method according to the following procedure.

First, water and branched polytetrafluoroethylene dispersion (solid concentration: 60%, polytetrafluoroethylene particle size: 0.15 to 0.3 μm) are placed in the reactor, and then the acrylic monomer and styrene are stirred while stirring. Kumen hydroperoxide was added as a monomer and a water-soluble initiator, and the reaction was carried out at 80 ° C. to 90 ° C. for 9 hours. After completion of the reaction, water was removed by centrifuging with a centrifuge for 30 minutes to obtain a paste-like product. Then, the paste of the product was dried in a hot air dryer at 80 ° C. to 100 ° C. for 8 hours. Then, the dried product was pulverized to obtain a polytetrafluoroethylene-based mixture of the present disclosure.

Since such a suspension polymerization method does not require a polymerization step by emulsification dispersion in the emulsion polymerization method exemplified in Japanese Patent No. 3469391, it does not require an emulsifier and electrolyte salts for coagulating and precipitating the latex after polymerization. Further, in the polytetrafluoroethylene mixture produced by the emulsion polymerization method, the emulsifier and the electrolyte salts in the mixture are easily mixed and difficult to remove, so that the emulsifier, the sodium metal ion derived from the electrolyte salt and the potassium metal ion are reduced. That is difficult. Since the polytetrafluoroethylene-based mixture used in the present disclosure is produced by a suspension polymerization method, sodium metal ions and potassium metal ions in the mixture are reduced because such emulsifiers and electrolyte salts are not used. It is possible to improve thermal stability and hydrolysis resistance.

Further, in the present disclosure, coated branched PTFE can be used as a drip inhibitor. The coated branched PTFE is a polytetrafluoroethylene-based mixture composed of branched polytetrafluoroethylene particles and an organic polymer, and is derived from an organic polymer, preferably a styrene-based monomer, on the outside of the branched polytetrafluoroethylene. It has a coating layer made of a polymer containing a unit and / or a unit derived from an acrylic monomer. The coating layer is formed on the surface of branched polytetrafluoroethylene. Further, it is preferable that the coating layer contains a copolymer of a styrene-based monomer and an acrylic-based monomer.

The polytetrafluoroethylene contained in the coated branched PTFE is branched polytetrafluoroethylene. When the contained polytetrafluoroethylene is not branched polytetrafluoroethylene, the effect of preventing dropping is insufficient when the addition of polytetrafluoroethylene is small. The branched polytetrafluoroethylene is in the form of particles and has a particle size of preferably 0.1 μm to 0.6 μm, more preferably 0.3 μm to 0.5 μm, still more preferably 0.3 μm to 0.4 μm. When the particle size is smaller than 0.1 μm, the surface appearance of the molded product is excellent, but it is difficult to commercially obtain polytetrafluoroethylene having a particle size smaller than 0.1 μm. Further, when the particle size is 0.6 μm or less, a good surface appearance of the molded product may be ensured. The number average molecular weight of the polytetrafluoroethylene used in the present disclosure ^{is preferably 1 × 10 4} to 1 × 10 ⁷ , more preferably 2 × 10 ^{6 to} 9 × 10 ⁶ , and generally has a high molecular weight of polytetra. Fluoroethylene is more preferred in terms of stability. Either powder or dispersion can be used.

The content of the branched polytetrafluoroethylene in the coated branched PTFE is preferably 20 parts by weight to 60 parts by weight, more preferably 40 parts by weight to 55 parts by weight, and further, with respect to 100 parts by weight of the total weight of the coated branched PTFE. It is preferably 47 parts by weight to 53 parts by weight, particularly preferably 48 parts by weight to 52 parts by weight, and most preferably 49 parts by weight to 51 parts by weight. When the ratio of the branched polytetrafluoroethylene is in such a range, good dispersibility of the branched polytetrafluoroethylene can be achieved.

(Other additives)
(I) Phosphorus Stabilizer Examples of the phosphorus stabilizer include phosphoric acid, phosphoric acid, subphosphonic acid, phosphoric acid and esters thereof, and tertiary phosphine.

Specifically, examples of the phosphite compound include triphenylphosphite, tris (nonylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, and dioctylmonophenyl. Phenylphosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-iso-propylphenyl) -N-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert) -Butyl-4-ethylphenyl) pentaerythritol diphosphite, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis ( Nonylphenyl) pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite and the like.

Further, as another phosphite compound, a compound that reacts with divalent phenols and has a cyclic structure can also be used. For example, 2,2'-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2'-methylenebis (4,6-di-tert-). Examples thereof include butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, and 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite.

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

Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite and tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite , Tetrakiss (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di) -N-Butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) Examples thereof include -3-phenyl-phenylphosphonite, tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (di-tert-butylphenyl) -phenyl-phenylphosphonite, and tetrakis (2, 4-Di-tert-butylphenyl) -biphenylenediphosphonite and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite are more preferred. Such a phosphonite compound can be used in combination with a phosphite compound having an aryl group in which the above alkyl group is substituted by 2 or more, and is preferable.

Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate and the like.

Examples of tertiary phosphine include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, and tri-p-tolyl. Examples thereof include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

The phosphorus-based stabilizer can be used not only by one type but also by mixing two or more types. Among the phosphorus-based stabilizers, a phosphonite compound or a phosphite compound represented by the following general formula (9) is preferable.

（式（９）中、ＲおよびＲ’は炭素数６〜３０のアルキル基または炭素数６〜３０のアリール基を表し、互いに同一であっても異なっていてもよい。）

(In the formula (9), R and R'represent an alkyl group having 6 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be the same as or different from each other.)

As described above, the phosphonite compound is preferably tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, and the stabilizer containing the phosphonite as a main component is Sandostab P-EPQ (trademark, manufactured by Clariant). ) And Irgafos P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS), both of which can be used.

Further, more suitable phosphite compounds in the above formula (9) are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and bis (2,6-di). -Tert-Butyl-4-methylphenyl) pentaerythritol diphosphite, and bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite.

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

The phosphorus-based stabilizer can be used alone or in combination of two or more. The content of the phosphorus-based stabilizer is preferably 0.01 part by weight to 1.0 part by weight, more preferably 0.03 part by weight to 0, based on 100 parts by weight of the total of the A component and the B component. It is 8.8 parts by weight, more preferably 0.05 parts by weight to 0.5 parts by weight. When the content is 0.01 parts by weight or more, the effect of suppressing thermal decomposition during processing may be exhibited and good mechanical properties may be ensured, and even when the content is 1.0 parts by weight or less. Good mechanical properties may be ensured.

(Ii) Phenolic Stabilizer The resin composition of the present disclosure may contain a phenol stabilizer. Examples of the phenol-based stabilizer generally include hindered phenol, semi-hindered phenol, and less hindered phenol compound, but the hindered phenol compound is particularly preferable from the viewpoint of applying a heat-stabilizing formulation to the polypropylene-based resin. Used for. Examples of such hindered phenol compounds include α-tocopherol, butyl hydroxytoluene, cinapyl alcohol, vitamin E, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and 2-tert. -Butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylamino) Methyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl) -6-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-dimethylene- Bis (6-α-methyl-benzyl-p-cresol), 2,2'-ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-) tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate , 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert-butyl) -5-Methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1,- Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-thiobis (3-methyl) -6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'- Di-thiobis (2,6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-tert-butylpheno) Le), 2,2-thiodiethylenebis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy) -3,5-di-tert-butylanilino) -1,3,5-triazine, N, N'-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) Butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxy) Phenyl) isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) Isocyanurate, 1,3,5-tris2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3,5-di-tert) -Butyl-4-hydroxyphenyl) propionate] methane, triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, triethylene glycol-N-bis-3- (3-tert-Butyl-4-hydroxy-5-methylphenyl) acetate, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) acetyloxy} -1 , 1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane , 1,3,5-trimethyl-2,4,6-tris (3-tert-butyl-4-hydroxy-5-methylbenzyl) benzene, and tris (3-tert-butyl-4-hydroxy-5-methyl). Benzyl) isocyanurate and the like are exemplified. Among the above compounds, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate is preferably used, and is represented by the following formula (10) (3,3', 3'', 5,5', 5 as an excellent substance for suppressing deterioration of mechanical properties due to thermal decomposition during processing. '' -Hexa-tert-butyl-a, a', a''-(methitylen-2,4,6-triyl) tri-p-cresol, and 1,3,5 represented by the following formula (11). -Tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trion is more preferably used.

The above-mentioned phenolic stabilizer can be used alone or in combination of two or more. The content of the phenolic stabilizer is preferably 0.05 parts by weight to 1.0 part by weight, more preferably 0.07 parts by weight to 0, based on 100 parts by weight of the total of the A component and the B component. It is 8.8 parts by weight, more preferably 0.1 parts by weight to 0.5 parts by weight. When the content is 0.05 parts by weight or more, the effect of suppressing thermal decomposition during processing may be exhibited and good mechanical properties may be ensured, and even when the content is 1.0 parts by weight or less. Good mechanical properties may be ensured.

It is preferable that either a phosphorus-based stabilizer or a phenol-based stabilizer is blended, and the combined use of these is even more preferable. In the case of combined use, 0.01 parts by weight to 0.5 parts by weight of phosphorus-based stabilizer and 0.01 parts by weight to 0.5 parts by weight of phenol-based stabilizer are used for a total of 100 parts by weight of A component and B component. It is preferable that the agent is blended.

(Iii) Ultraviolet absorber The polycarbonate resin composition of the present disclosure can contain an ultraviolet absorber. Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, and 2-. Hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxitrihydride benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2', 4,4' -Tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis (5-benzoyl-4-) Hydroxy-2-methoxyphenyl) methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like are exemplified.

In the benzotriazole system, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazol, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-Dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [4- (1,1,3) , 3-Tetramethylbutyl) -6- (2H-benzotriazole-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazol, 2- (2- (2-) Hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5) -Tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'- Methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis (1,3-benzoxazine-4-one), and 2- [2-hydroxy-3- (3,4) 5,6-Tetrahydrophthalimidemethyl) -5-methylphenyl] benzotriazol, and 2- (2'-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and vinyl-based monomers copolymerizable with the monomer. 2-Hydroxyphenyl-2H, such as a copolymer with and a copolymer of 2- (2'-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and a vinyl-based monomer copolymerizable with the monomer. -A polymer having a benzotriazole skeleton is exemplified.

In the hydroxyphenyltriazine system, for example, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-hexyloxyphenol, 2- (4,6-diphenyl-1,3,5) -Triazine-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-ethyloxyphenol, 2- (4,6-diphenyl) -1,3,5-triazine-2-yl) -5-propyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-butyloxyphenol, etc. Illustrated. Further, the phenyl group of the above-exemplified compound such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. A compound that has become a phenyl group is exemplified.

In the cyclic iminoester system, for example, 2,2'-p-phenylenebis (3,1-benzoxazine-4-one), 2,2'-m-phenylenebis (3,1-benzoxazine-4-one). , And 2,2'-p, p'-diphenylenebis (3,1-benzoxazine-4-one) and the like.

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

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

Among the above compounds, the compounds represented by any of the following formulas (12), (13) and (14) are more preferably used in the present disclosure.

The above-mentioned ultraviolet absorber may be used alone or in combination of two or more.
The content of the ultraviolet absorber is preferably 0.1 part by weight to 2 parts by weight, more preferably 0.12 parts by weight to 1.5 parts by weight, based on 100 parts by weight of the total of the A component and the B component. Parts, more preferably 0.15 parts by weight to 1 part by weight. When the content of the ultraviolet absorber is 0.1 parts by weight or more, sufficient light resistance may be exhibited, and when it is 2 parts by weight or less, the appearance may be poor or the physical properties may be deteriorated due to gas generation. It is preferable because it can be avoided.

(Iv) Hindered Amine-based Light Stabilizer The polycarbonate resin composition of the present disclosure can contain a hindered amine-based light stabilizer. Hindered amine-based light stabilizers are generally called HALS (Hindered Amine Light Stabilizer) and are compounds having a 2,2,6,6-tetramethylpiperidine skeleton in their structure, for example, 4-acetoxy-2,2,6. , 6-Tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2, 2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2, 2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2, 2,6,6-tetramethylpiperidine, 4- (ethylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (Phenylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetra Methyl-4-piperidyl) oxalate, bis (2,2,6,6-tetramethyl-4-piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2) 2,6,6-tetramethyl-4-piperidyl) adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, bis (1,2,2,6,6-pentamethyl-4-) Piperidine) carbonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) oxalate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) malonate, bis (1,2, 2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) adipate, bis (1,2,2,6,6-pentamethyl-4-) Piperidine) terephthalate, N, N'-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxyamide, 1,2-bis (2,2,6,6-tetra) Methyl-4-pi Peridyloxy) ethane, α, α'-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6-tetramethyl-4-piperidyltrilen) -2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2,6,6-tetramethyl-4) -Piperidyl) -benzene-1,3,5-tricarboxylate, N, N', N'', N'''-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2)) , 6,6-tetramethylpiperidine-4-yl) amino) -triazine-2-yl) -4,7-diazadecan-1,10-diamine, dibutylamine, 1,3,5-triazine, N, N' Polycondensate of −bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine , Poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-diyl} Piperidine) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3 , 4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tris (2,2,6,6- Tetramethyl-4-piperidyl) -benzene-1,3,4-tricarboxylate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl]- With 4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] 2,2,6,6-tetramethylpiperidine, and 1,2,3,4-butanetetracarboxylic acid 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β', β'-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5)) Undecane] Condensations with diethanol and the like can be mentioned.

Hindered amine-based photostabilizers are broadly divided according to the binding partner of the nitrogen atom in the piperidine skeleton, NH type (hydrogen is bonded to the nitrogen atom), NR type (alkyl group (R) is bonded to the nitrogen atom), There are three types, N-OR type (alkoxy group (OR) bonded to nitrogen atom), but when applied to polycarbonate resin, N-R is low basic from the viewpoint of basicity of hindered amine-based photostabilizer. It is more preferable to use a mold and an N-OR type.

Among the above compounds, the compounds represented by the following formulas (15) and (16) are more preferably used in the present disclosure.

The hindered amine-based light stabilizer can be used alone or in combination of two or more. The content of the hindered amine-based light stabilizer is preferably 0 parts by weight to 1 part by weight, more preferably 0.05 parts by weight to 1 part by weight, based on 100 parts by weight of the total of the A component and the B component. It is more preferably 0.08 parts by weight to 0.7 parts by weight, and particularly preferably 0.1 parts by weight to 0.5 parts by weight. When the content of the hindered amine-based light stabilizer is 1 part by weight or less, poor appearance due to gas generation and deterioration of physical properties due to decomposition of the polycarbonate resin may be avoided, which is preferable. Further, when it is 0.05 parts by weight or more, sufficient light resistance may be exhibited.

(V) Release Agent It is preferable to further add a mold release agent to the polycarbonate resin composition of the present disclosure for the purpose of improving productivity at the time of molding and reducing distortion of the molded product. As such a mold release agent, a known one can be used. For example, saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes (polyethylene wax, 1-alkene polymer, etc. those modified with functional group-containing compounds such as acid modification can also be used), silicone compounds, fluorine compounds ( Fluorooil represented by polyfluoroalkyl ether), paraffin wax, beeswax and the like can be mentioned. Among them, a fatty acid ester is mentioned as a preferable release agent. Such fatty acid esters are esters of fatty alcohols and aliphatic carboxylic acids. The aliphatic alcohol may be a monohydric alcohol or a divalent or higher polyhydric alcohol. The carbon number of the alcohol is in the range of 3 to 32, more preferably in the range of 5 to 30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, triacanthanol and the like. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. Polyhydric alcohols are more preferred in the fatty acid esters of the present disclosure.

On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid and bechenic acid. Saturated aliphatic carboxylic acids such as icosanoic acid and docosanoic acid, and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and setreic acid can be mentioned. .. Among the above, the aliphatic carboxylic acid preferably has 14 to 20 carbon atoms. Of these, saturated aliphatic carboxylic acids are preferable. Particularly stearic acid and palmitic acid are preferred.

The above-mentioned aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from animal fats and oils such as beef tallow and pork fat and natural fats and oils such as palm oil and sunflower oil. Therefore, these aliphatic carboxylic acids are usually mixtures containing other carboxylic acid components having different carbon atoms. Therefore, also in the production of the fatty acid ester of the present disclosure, an aliphatic carboxylic acid, particularly stearic acid or palmitic acid, which is produced from such natural fats and oils and is in the form of a mixture containing other carboxylic acid components, is preferably used.

The fatty acid ester of the present disclosure may be either a partial ester or a total ester (full ester). However, a partial ester usually has a high hydroxyl value and easily induces decomposition of the resin at high temperatures, so that it is more preferably a full ester. The acid value of the fatty acid ester of the present disclosure is preferably 20 or less, more preferably 4 to 20, and even more preferably 4 to 12 from the viewpoint of thermal stability. The acid value can be substantially 0. The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1 to 30. Further, the iodine value is preferably 10 or less. The iodine value can be substantially 0. These characteristics can be obtained by the method specified in JIS K 0070.

The content of the release agent is preferably 0.005 parts by weight to 2 parts by weight, more preferably 0.01 parts by weight to 1 part by weight, still more preferably, based on 100 parts by weight of the total of the components A and B. Is from 0.05 parts by weight to 0.5 parts by weight. In such a range, the polycarbonate resin composition has good releasability and releasability. In particular, such an amount of fatty acid ester provides a polycarbonate resin composition having good releasability and releasability without impairing good hue.

(Vi) Dyeing Pigment The polycarbonate resin composition of the present disclosure can further provide a molded product containing various dyeing pigments and exhibiting various designs. By blending a fluorescent whitening agent or a fluorescent dye that emits light other than that, a better design effect that makes the best use of the emitted color can be imparted. Further, it is also possible to provide a polycarbonate resin composition which is colored with a very small amount of dye and has a vivid color-developing property.

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

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

The content of the dyeing pigment is preferably 0.00001 parts by weight to 1 part by weight, more preferably 0.00005 parts by weight to 0.5 parts by weight, based on 100 parts by weight of the total of the A component and the B component. ..

(Vii) Other heat stabilizers The polycarbonate resin composition of the present disclosure may contain other heat stabilizers other than the above-mentioned phosphorus-based stabilizers and phenol-based stabilizers. Such other heat stabilizers are preferably used in combination with either of these stabilizers and antioxidants, and particularly preferably in combination with both. Examples of such other heat stabilizers include lactone-based stabilizers represented by reaction products of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (such stabilizers). The details of the above are described in Japanese Patent Application Laid-Open No. 7-233160). Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and the compound can be used. Further, stabilizers obtained by mixing the compound with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the above-mentioned company is preferably exemplified. Also in the present disclosure, such premixed stabilizers can be utilized. The blending amount of the lactone-based stabilizer is preferably 0.0005 parts by weight to 0.05 parts by weight, more preferably 0.001 parts by weight to 0.03 parts by weight, based on 100 parts by weight of the total of the A component and the B component. It is a department.

Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Illustrated. Such stabilizers are particularly effective when the resin composition is applied to rotary molding. The blending amount of the sulfur-containing stabilizer is preferably 0.001 part by weight to 0.1 part by weight, more preferably 0.01 part by weight to 0 part by weight, based on 100 parts by weight of the total of the A component and the B component. It is 08 parts by weight.

(Viii) Filler In the polycarbonate resin composition of the present disclosure, various fillers can be blended as a reinforcing filler within the range in which the effect of the present disclosure is exhibited. For example, calcium carbonate, glass fiber, glass bead, glass balloon, glass milled fiber, glass flake, carbon fiber, carbon flake, carbon bead, carbon milled fiber, graphite, gas phase growth method ultrafine carbon fiber (fiber diameter 0.1 μm) Less than), carbon nanotubes (fiber diameter less than 0.1 μm, hollow), fullerene, metal flakes, metal fibers, metal coated glass fibers, metal coated carbon fibers, metal coated glass flakes, silica, metal oxide particles, Examples thereof include metal oxide fibers, metal oxide balloons, and various whiskers (potassium titanate whiskers, aluminum borate whiskers, basic magnesium sulfate, and the like). These reinforcing fillers may be contained alone or in combination of two or more. The content of these fillers is preferably 0.1 parts by weight to 60 parts by weight, more preferably 0.5 parts by weight to 50 parts by weight, based on 100 parts by weight of the total of the components A and B.

(Ix) White Pigment for High Light Reflection The polycarbonate resin composition of the present disclosure may be blended with a white pigment for high light reflection to impart a light reflection effect. Examples of such white pigments include titanium oxide, zinc sulfide, zinc oxide, barium sulfate, calcium carbonate, calcined kaolin and the like, and titanium oxide is publicly used. As the titanium oxide used, titanium oxide having an average particle size of 0.1 to 5.0 μm surface-treated with an organic substance is preferable. (In this disclosure, the titanium oxide component of the titanium oxide pigment _{is referred to as "TIM 2} ", and the entire pigment containing the surface treatment agent is referred to as "titanium oxide".) The _{crystal form of TIO 2} is anatase type or rutile type. Any of these may be used, and they may be mixed and used as required. The rutile type is more preferable in terms of initial mechanical properties and long-term weather resistance. It should be noted that the rutile-type crystal may contain anatase-type crystals. Further, as _{the method for producing TiO 2} , a product produced by a sulfuric acid method, a chlorine method, or various other methods can be used, but the chlorine method is more preferable. Further, the titanium oxide of the present disclosure is not particularly limited in shape, but is more preferably in the form of particles. Titanium oxide is usually used for various coloring applications, and the average particle size of titanium oxide used as the white pigment of the present disclosure is preferably 0.10 μm to 5.0 μm, preferably 0.15 μm to 2. 0 μm is more preferable, and 0.18 μm to 1.5 μm is even more preferable. When the average particle size is 0.10 μm or more, poor appearance such as silver may be avoided even when highly filled, and when it is 5.0 μm or less, good appearance may be avoided. And mechanical properties may be ensured. The average particle size is calculated by measuring each single particle size from electron microscope observation and averaging the numbers.

The titanium oxide used in the present disclosure is preferably surface-treated with an organic compound. When titanium oxide that has not been organically treated is used, the appearance deteriorates due to yellowing, the reflectance of the molded product is significantly reduced, and sufficient solar reflectance may not be obtained. Therefore, it is used outdoors. May not be suitable for. As such a surface treatment agent, various treatment agents such as polyol-based, amine-based, and silicone-based can be used. Examples of the polyol-based surface treatment agent include pentaerythritol, trimethylolethane, and trimethylolpropane, and examples of the amine-based surface treatment agent include an acetate of triethanolamine and an acetate of trimethylolamine. Examples of the silicone-based surface treatment agent include alkylchlorosilane (trimethylchlorosilane and the like), alkylalkoxysilane (methyltrimethoxysilane and the like), and hydrogenpolysiloxane. Examples of the hydrogen polysiloxane include alkylhydrogenpolysiloxane and alkylphenylhydrogenpolysiloxane. As such an alkyl group, a methyl group and an ethyl group are suitable. Titanium oxide surface-treated with such alkylalkoxysilanes and / or hydrogenpolysiloxanes provides better light reflectivity with the resin compositions of the present disclosure. The amount of the organic compound used for the surface treatment is preferably 0.05 parts by weight to 5 parts by weight, more preferably 0.5 parts by weight to 3 parts by weight, still more preferably 1.5 parts by weight, per 100 parts by weight of titanium oxide. The range is from parts by weight to 2.5 parts by weight. When the surface treatment amount is 0.05 parts by weight or more, sufficient thermal stability may be obtained, and when it is 5 parts by weight or less, molding defects such as silver can be avoided, which is preferable. .. The surface treatment agent for the organic compound is preferably titanium oxide (more preferably, titanium oxide coated with another metal oxide) in advance. However, a method may be used in which the surface treatment agent is separately added when the raw material of the resin composition is melt-kneaded, and the surface treatment of titanium oxide is performed in the melt-kneading step.

The content of the white pigment for high light reflection is preferably 0.1 part by weight to 10 parts by weight, preferably 0.15 parts by weight to 7.5 parts by weight, based on 100 parts by weight of the total of the A component and the B component. The portion is more preferable, and more preferably 0.15 parts by weight to 5 parts by weight. When the content of the white pigment for high light reflection is 0.1 parts by weight or more, a sufficient white appearance and light-shielding property may be obtained, and when it is 10 parts by weight or less, molding of silver or the like may be obtained. It is preferable because defects and significant deterioration of physical properties can be avoided. Two or more kinds of white pigments for high light reflection can be used in combination.

(X) Other Resins and Elastomers In the resin compositions of the present disclosure, graft polymers other than other resins and the D component can be used in a small proportion as long as the effects of the present disclosure are exhibited.

Examples of such other resins include styrene resins such as ABS, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polymethacrylate resins, and phenol resins. Examples thereof include resins such as epoxy resins.

Examples of the elastomer include isobutylene / isoprene rubber, ethylene / propylene rubber, styrene-based elastomer, acrylic-based elastomer, polyester-based elastomer, and polyamide-based elastomer.

(Xi) Polycarbonate resin other than component A In the resin composition of the present disclosure, a polycarbonate resin other than the component A may be used in a small amount as long as the effect of the present disclosure is exhibited.

Polycarbonate-based resins other than the polycarbonate-polydiorganosiloxane copolymer resin (component A) used in the present disclosure are generally obtained by reacting a dihydric phenol with a carbonate precursor. Examples of the reaction method include an interfacial polymerization method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

Typical examples of the dihydric phenol used here are hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl). ) Propane (commonly known as bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl)- 1-Phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) Pentan, 4,4'-(p-phenylenediisopropyridene) diphenol, 4,4'-(m-phenylenediisopropyriden) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane , Bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ketone Hydroxyphenyl) esters, bis (4-hydroxy-3-methylphenyl) sulfides, 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, etc. Will be. The preferred divalent phenol is bis (4-hydroxyphenyl) alkane, and among them, bisphenol A is particularly preferable from the viewpoint of impact resistance, and is widely used.

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

For example, 4,4'-(m-phenylenediisopropyridene) diphenol (hereinafter sometimes abbreviated as "BPM"), 1,1-bis (4-hydroxy) as a part or all of the divalent phenol component. Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as "Bis-TMC"), 9,9-bis (4-hydroxyphenyl) Polycarbonates (homogeneous polymers or copolymers) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as "BCF") have dimensions due to water absorption. Suitable for applications where changes and morphological stability requirements are particularly stringent. It is preferable to use these divalent phenols other than BPA in an amount of 5 mol% or more, particularly 10 mol% or more, of the total divalent phenol component constituting the polycarbonate.

In particular, when high rigidity and better hydrolysis resistance are required, a polycarbonate resin other than the component A constituting the resin composition is copolymerized with any of the following (1) to (3). Polycarbonate is particularly preferred:
(1) BPM is 20 mol% to 80 mol% (more preferably 40 mol% to 75 mol%, more preferably 45 mol% to 65 mol%) in 100 mol% of the divalent phenol component constituting the polycarbonate. ) And the BCF is 20 mol% to 80 mol% (more preferably 25 mol% to 60 mol%, still more preferably 35 mol% to 55 mol%). BPA is 10 mol% to 95 mol% (more preferably 50 mol% to 90 mol%, more preferably 60 mol% to 85 mol%) and BCF in 100 mol% of the constituent divalent phenol components. Is 5 mol% to 90 mol% (more preferably 10 mol% to 50 mol%, more preferably 15 mol% to 40 mol%), a copolymerized polycarbonate (3) a divalent phenol component constituting the polycarbonate. In 100 mol%, BPM is 20 mol% to 80 mol% (more preferably 40 mol% to 75 mol%, still more preferably 45 mol% to 65 mol%), and Bis-TMC is 20 mol%. Copolymerized polycarbonate in an amount of up to 80 mol% (more preferably 25 mol% to 60 mol%, more preferably 35 mol% to 55 mol%).

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

The production method and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, JP-A-2002-117580 and the like. ing.

Among the various polycarbonates described above, those having a water absorption rate and Tg (glass transition temperature) within the following ranges by adjusting the copolymerization composition and the like have good hydrolysis resistance of the polymer itself and. Since it is remarkably excellent in low warpage after molding, it is particularly suitable in fields where morphological stability is required.
(I) Polycarbonate having a water absorption rate of 0.05% to 0.15%, preferably 0.06% to 0.13% and a Tg of 120% to 180 ° C., or (ii) Tg of 160 ° C. ~ 250 ° C., preferably 170 ° C. to 230 ° C., and the water absorption rate is 0.10% to 0.30%, preferably 0.13% to 0.30%, more preferably 0.14% to 0. Polycarbonate which is 27%.

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

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

In producing an aromatic polycarbonate resin by interfacial polymerization of the divalent phenol and the carbonate precursor, if necessary, a catalyst, a terminal terminator, and an antioxidant for preventing the dihydric phenol from oxidizing are prevented. Etc. may be used. The aromatic polycarbonate resin of the present disclosure is a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a polyester obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid. It contains a carbonate resin, a copolymerized polycarbonate resin obtained by copolymerizing a bifunctional alcohol (including an alicyclic type), and a polyester carbonate resin obtained by copolymerizing the bifunctional carboxylic acid and the bifunctional alcohol together. Further, it may be a mixture of two or more of the obtained aromatic polycarbonate resins.

The branched polycarbonate resin can impart drip prevention performance and the like to the resin composition of the present disclosure. Examples of the trifunctional or higher polyfunctional aromatic compound used in such a branched polycarbonate resin include fluoroglucolcin, fluoroglucolside, or 4,6-dimethyl-2,4,6-tris (4-hydrochidiphenyl) heptene-2, 2. , 4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) Etan, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [ 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, trisphenol such as α-dimethylbenzylphenol, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1, Examples thereof include 4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and acid chlorides thereof, among which 1,1,1-tris (4-hydroxy). Phenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable.

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

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

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

Various literatures and patent publications describe reaction formats such as a surface polymerization method, a melt transesterification method, a carbonate prepolymer solid phase ester exchange method, and a ring-opening polymerization method of a cyclic carbonate compound, which are methods for producing a polycarbonate resin of the present disclosure. This is a well-known method.

(Xi) Other Additives In addition, the polycarbonate resin composition of the present disclosure may contain a small proportion of additives known per se in order to impart various functions and improve properties to the molded product. These additives are in the usual blending amount as long as the object of the present disclosure is not impaired.

Examples of such additives include sliding agents (for example, PTFE particles), colorants (for example, pigments and dyes such as carbon black), and light diffusing agents (for example, acrylic crosslinked particles, silicon crosslinked particles, ultrathin glass flakes, calcium carbonate particles). , Fluorescent dyes, inorganic fluorescent materials (for example, fluorescent materials having aluminate as a parent crystal), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (for example, fine particle titanium oxide, fine particle oxidation) Zinc), radical generators, infrared absorbers (heat ray absorbers), photochromic agents and the like.

(Manufacturing of Polycarbonate Resin Composition)
Any method is adopted for producing the polycarbonate resin composition of the present disclosure. For example, A component to D component or A component to F component excluding B component, and optionally other additives can be sufficiently mixed by using a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical device, and an extrusion mixer. After mixing in, if necessary, granulate the premixed mixture with an extruder or briquetting machine, and then melt and knead with a melt kneader represented by a bent twin-screw extruder, and then a pelletizer. There is a method of pelletizing by.

In addition, each component is independently supplied to a melt kneader represented by a bent twin-screw extruder, or a part of each component is premixed and then independently supplied to the melt kneader with the remaining components. There is also a way to do it. As a method of premixing a part of each component, for example, a method of premixing components other than the component A and the component B in advance and then mixing the thermoplastic resin of the component A or directly supplying the component to the extruder can be mentioned.

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

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

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

The resin extruded as described above is either directly cut and pelletized, or the strands are cut and pelletized with a pelletizer after forming the strands. When it is necessary to reduce the influence of external dust and the like during pelletization, it is preferable to clean the atmosphere around the extruder. Furthermore, in the production of such pellets, various methods already proposed for polycarbonate resins for optical discs are used to narrow the shape distribution of pellets, reduce miscuts, and reduce fine powder generated during transportation or transportation. , And bubbles (vacuum bubbles) generated inside the strands and pellets can be appropriately reduced. With these formulations, it is possible to increase the cycle of molding and reduce the rate of defects such as silver. The shape of the pellet can be a general shape such as a cylinder, a prism, and a sphere, but is more preferably a cylinder. The diameter of the cylinder is preferably 1 mm to 5 mm, more preferably 1.5 mm to 4 mm, still more preferably 2 mm to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 mm to 30 mm, more preferably 2 mm to 5 mm, and further preferably 2.5 mm to 3.5 mm.

(About a molded product made of the resin composition of the present disclosure)
As the resin composition in the present disclosure, various products can be produced by injection molding the pellets obtained by the above-mentioned method. In such injection molding, not only ordinary molding methods, but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including those by injecting supercritical fluid), insert molding, and insert molding, depending on the intended purpose. Molded products can be obtained using injection molding methods such as in-mold coating molding, heat insulating mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding. The advantages of these various molding methods are already widely known. In addition, either a cold runner method or a hot runner method can be selected for molding.

Further, the resin composition in the present disclosure can also be used in the form of various deformed extruded products, sheets, films and the like by extrusion molding. Inflation method, calendar method, casting method, etc. can also be used for forming sheets and films. Further, it can be molded as a heat-shrinkable tube by applying a specific stretching operation. Further, the resin composition of the present disclosure can be made into a molded product by rotary molding, blow molding or the like.

Specific examples of the molded product in which the resin composition of the present disclosure is used are suitable for application to living materials, housing equipment materials, building materials, interior goods, OA equipment, internal parts of home appliances, housings, and the like. .. These products include, for example, personal computers, laptop computers, CRT displays, printers, mobile terminals, mobile phones, copiers, fax machines, recording medium (CD, CD-ROM, DVD, PD, FDD, etc.) drives, parabolic antennas, electric motors. Tools, VTRs, TVs, irons, hair dryers, rice cookers, microwave ovens, audio equipment, audio equipment such as audio / laser discs (registered trademarks) / compact discs, lighting equipment, refrigerators, air conditioners, typewriters, word processors, suitcases And living materials such as cleaning tools, housing equipment materials such as bathrooms, toiletries, and vanities, and various parts such as these housings are made of resin products formed from the polycarbonate resin composition of the present disclosure. Can be used. Examples of other resin products include vehicle parts such as deflector parts, car navigation parts, and car stereo parts.

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

Hereinafter, the invention according to the present disclosure will be further described with reference to examples. Unless otherwise specified, the parts in the examples are parts by weight, and% is by weight%. The evaluation was carried out by the following method.

(Evaluation of Polycarbonate Resin Composition)
(I) Charpy impact strength Using the ISO bending test piece obtained by the following method, the Charpy impact strength with a notch was measured according to ISO 179.
(Ii) Flame retardancy A V test was carried out according to UL94 using UL test pieces obtained by the following method. The case where the determination could not meet any of the criteria of V-0, V-1, and V-2 was indicated as "notV".
(Iii) Chemical resistance Using the ISO tensile test piece obtained by the following method, after applying 1% strain by the 3-point bending test method, magic phosphorus, bath magic phosphorus and toilet magic phosphorus (all, A cloth impregnated with Kao Corporation) was applied, and the mixture was left at 23 ° C. for 96 hours, and then the presence or absence of a change in appearance was confirmed. The evaluation was carried out according to the following criteria.
◯: No change in appearance △: Fine cracks are observed ×: Large cracks such as breakage are observed (iv) Antifouling property (contact angle with water)
The contact angle with water on the surface of the sample plate (three-stage plate with holes) obtained by the following method was measured using a contact angle measuring machine GI-1000 (manufactured by Elma Co., Ltd.). The evaluation was carried out as "◯" when the contact angle with water was 100 ° or more and "x" when it was less than 100 °.
(V) Thermal stability Calculate the amount of decrease in viscosity average molecular weight between the test piece and the pellet obtained by allowing it to stay in the cylinder for 10 minutes under the same conditions as the following method, ΔMv, based on the following formula. did.
Amount of decrease in viscosity average molecular weight ΔMv = (viscosity average molecular weight of pellets)-(viscosity average molecular weight of molded product after residence for 10 minutes)
The evaluation was carried out according to the following criteria.
◯: ΔMv <3,000
Δ: 3,000 ≦ ΔMv <5,000
×: 5,000 ≦ ΔMv
(Vi) Appearance The appearance of the sample plate (three-stage plate with holes) produced by the following method was visually evaluated. The evaluation was carried out according to the following criteria.
○: No noticeable appearance defects near the gate ×: Large flow marks or peeling occurred near the gate

[Examples 1-33, Comparative Examples 1-11]
A mixture having the composition shown in Tables 1 to 3 and composed of the components excluding the polyester resin of the component B was supplied from the first supply port of the extruder. The contents of the D component in Examples 1 to 13, 15 to 29 and 31 to 33, and Comparative Examples 1 to 4, 6, 7, 10 and 11 are D-1 to D-3 shown in parentheses. The amount of the antifouling agent contained in (the numbers in parentheses represent the amount of D-1 to D-3, which is a masterbatch having a concentration of 50%). Such a mixture was obtained by mixing with a V-type blender. The polyester resin of component B was supplied from the second supply port using a side feeder. For extrusion, a vent type twin-screw extruder (TEX30α-38.5BW-3V, Japan Steel Works, Ltd.) with a diameter of 30 mmφ is used, and melt-kneaded at a screw rotation speed of 230 rpm, a discharge rate of 25 kg / h, and a vacuum degree of vent of 3 kPa. Pellets were obtained. The extrusion temperature was 260 ° C. from the first supply port to the die portion. A part of the obtained pellets was dried at 80 ° C. for 6 hours in a hot air circulation type dryer, and then a test piece for evaluation was used at a cylinder temperature of 260 ° C. and a mold temperature of 60 ° C. using an injection molding machine. ISO tensile test piece (ISO527-1 and ISO527-2 compliant), ISO bending test piece (ISO178, ISO179, ISO75-1 and ISO75-2 compliant)), UL test piece (width 13 mm x length 125 mm x thickness 1. 5 mm) and a sample plate (three-stage plate with holes)) were prepared.

Each component of the symbol notation in Tables 1 to 3 is as follows.

(Component A)
A: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight 25,000, PDMS amount 8.4%, PDMS degree of polymerization 37, Teijin Limited Panlite W-0111)

(B component)
B-1: Polybutylene terephthalate resin (1100-211MD (product name) manufactured by Choharu Artificial Resin Co., Ltd., intrinsic viscosity: 0.965 dl / g)
B-2: Polybutylene terephthalate resin (1100-211XG (product name) manufactured by Choharu Artificial Resin Co., Ltd., intrinsic viscosity: 1.26 dl / g)
B-3: Polyethylene terephthalate resin (TRN-8550FF (product name) manufactured by Teijin Limited, intrinsic viscosity: 0.77 dl / g)

(C component)
C-1: Silicone-based core-shell type graft polymer (a graft copolymer having a core-shell structure in which the core is mainly composed of acrylic-silicone composite rubber and the shell is mainly composed of methyl methacrylate, Metablene S-2030 manufactured by Mitsubishi Rayon Co., Ltd. (product name))
C-2: Butadiene-based core-shell type graft polymer (Kaneka M-711 (product name) manufactured by Kaneka Corporation, a graft copolymer having a core-shell structure in which the core is mainly composed of butadiene rubber and the shell is mainly composed of methyl methacrylate. )
C-3: Acrylic core-shell type graft polymer (a graft copolymer having a core-shell structure in which the core is mainly composed of butyl acrylate and the shell is mainly composed of methyl methacrylate, Metablen W-600A manufactured by Mitsubishi Rayon Co., Ltd. (product name) )))

(D component)
D-1: Silicone gum PC master (ultra-high molecular weight polydimethylsiloxane 50% polycarbonate masterbatch product, MB50-315 (product name) manufactured by Toray Dow Corning Co., Ltd.)
D-2: Silicone gum PEst master (50% masterbatch of polyester elastomer of ultra-high molecular weight polydimethylsiloxane, BY27-009 (product name) manufactured by Toray Dow Corning Co., Ltd.)
D-3: Silicone gum PP master (polypropylene 50% masterbatch product of ultra-high molecular weight polydimethylsiloxane, BY27-001 (product name) manufactured by Toray Dow Corning Co., Ltd.)
D-4: Silicone-modified polypropylene (Polymer obtained by graft-polymerizing polyorganosiloxane on polypropylene, BY27-201 (product name) manufactured by Toray Dow Corning Co., Ltd.)

(E component)
E: Brominated flame retardant (bromineed carbonate oligomer having bisphenol A skeleton, FG-8500 (product name) manufactured by Teijin Limited)

(F component)
F-1: Phosphorus flame retardant (2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-dibenzyl-3,9-dioxide, FCX manufactured by Teijin Limited -210 (product name))

(G component)
G-1: Coated PTFE (polytetrafluoroethylene coated with a styrene-acrylonitrile copolymer (polytetrafluoroethylene content 50% by weight), SN3307PF manufactured by Shine polymer (trade name))
G-2: Coated PTFE (polytetrafluoroethylene coated with a copolymer of methyl methacrylate and butyl acrylate (polytetrafluoroethylene content 50% by weight), Metablen A3750 (trade name) manufactured by Mitsubishi Rayon Co., Ltd.)

(Other ingredients)
PC: Aromatic polycarbonate resin (polycarbonate resin powder with a viscosity average molecular weight of 25,100 made from bisphenol A and phosgene, Panlite L-1250WQ (product name) manufactured by Teijin Limited)
STB-1: Phenolic heat stabilizer (octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, molecular weight 531 and Irganox 1330 (product name) manufactured by BASF Japan Ltd.)
STB-2: Phosphorus-based heat stabilizer (Tris (2,4-di-tert-butylphenyl) phosphite, Irgafos 168 (product name) manufactured by BASF Japan Ltd.)
STB-3: Phosphorus-based heat stabilizer (trimethyl phosphate, TMP (product name) manufactured by Daihachi Chemical Industry Co., Ltd.)

Claims (11)

For a total of 100 parts by weight of (A) polycarbonate-polydiorganosiloxane copolymer resin (component A) and (B) polyester resin (component B).
(C) At least selected from the group consisting of an aromatic alkenyl compound monomer unit and an alkyl (meth) acrylate compound monomer unit in a composite rubber composed of a component containing a polyorganosiloxane rubber and an alkyl (meth) acrylic rubber. 3 parts by weight to 15 parts by weight of a graft copolymer (C component) having a core-shell structure in which one unit is graft-polymerized, and (D) 0.5 parts by weight to 6 parts by weight of an antifouling agent (D component). part only contains,
A polycarbonate resin composition, wherein the component D is silicone oil, silicone gum, silicone resin fine particles, or silicone-modified polyolefin. The polycarbonate resin composition according to claim 1, wherein the component D is a silicone gum or a silicone-modified polyolefin. The polycarbonate resin composition according to claim 2, wherein the silicone-modified polyolefin is a silicone-modified polypropylene. The polycarbonate resin composition according to claim 1, wherein the D component is a silicone gum having a molecular weight of 100,000 or more. The polycarbonate resin composition according to claim 1, wherein the component D is a polyorganosiloxane graft polyolefin resin. (E) 5 parts by weight to 35 parts by weight of the halogen-based flame retardant (E component), and (F) 0.5 parts by weight to 5 parts of the phosphorus-based flame retardant (F component) having a structure represented by the following formula (1). The polycarbonate resin composition according to any one of claims 1 to 5, further comprising a part by weight.

(In the formula, X ₁ and X ₂ are the same or different, and are aromatic substituted alkyl groups represented by the following general formula (I).)

(In the formula, AL is a branched or linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, Ar is a phenyl group, a naphthyl group or an anthryl group, and n is an integer of 1 to 3; Ar can be bonded to any carbon atom of AL.) The polycarbonate resin according to any one of claims 1 to 6, wherein the content of the B component is 20 parts by weight to 70 parts by weight in a total of 100 parts by weight of the A component and the B component. Composition. The polycarbonate resin composition according to any one of claims 1 to 7 , wherein the component B contains at least one of a polyethylene terephthalate resin and a polybutylene terephthalate resin. The polycarbonate resin composition according to any one of claims 1 to 8 , wherein the ratio of the polyorganosiloxane rubber component in the composite rubber of the C component is 15% or more. Any one of claims 1 to 9 , wherein 0.05 parts by weight to 2 parts by weight of the (G) drip inhibitor (G component) is contained in a total of 100 parts by weight of the A component and the B component. polycarbonate resin composition according to item. The polycarbonate resin composition according to claim 10 , wherein the G component is a fluoropolymer having a fibril-forming ability.