TW202006064A - Polycarbonate resin composition - Google Patents

Abstract

Provided is a polycarbonate resin composition having excellent mechanical properties, chemical resistance, anti-fouling properties, and outward appearance. The polycarbonate resin composition is characterized by comprising, per 100 parts by weight of the total of (A) a polycarbonate-polydiorganosiloxane copolymer resin (A component) and (B) a polyester resin (B component), (C) 3-15 parts by weight of a graft copolymer (C component) having a core-shell structure in which at least one unit selected from the group consisting of aromatic alkenyl compound monomer units and alkyl (meth)acrylate compound monomer units is graft polymerized to a compositerubber comprising a component which includes a polyorganosiloxane rubber and an alkyl (meth) acrylate rubber, and (D) 0.5-6 parts by weight of an anti-fouling adhesive (D component).

Description

Polycarbonate resin composition

The present invention relates to a polycarbonate resin composition and its molded product. More specifically, the present invention relates to a composite rubber formed from polycarbonate-based resins and polyester-based resins having components containing polyorganosiloxane rubber and alkyl (meth)acrylate rubber, It has a core-shell structure obtained by graft polymerization of at least one unit selected from the group consisting of an aromatic alkenyl compound monomer unit and an alkyl (meth)acrylate compound monomer unit Graft copolymers, and polycarbonate resin compositions that can improve mechanical properties, chemical resistance, stain resistance, and appearance when added with stain resistance imparting agents. In addition to the mechanical properties, chemical resistance, stain resistance, and appearance, the present invention also relates to a flame retardant polycarbonate resin composition that can improve flame resistance and thermal stability.

Aromatic polycarbonate resins are widely used in industry because of their excellent mechanical properties and thermal properties. However, since the aromatic polycarbonate resin is an amorphous resin, it has a disadvantage of poor resistance. Therefore, there are studies on alloying with various polymers, among which, alloying with polyester resins represented by polyethylene terephthalate resin or polybutylene terephthalate resin Method (Patent Document 1), which improves the resistance of the aromatic polycarbonate resin to shortcomings, and based on its excellent balance characteristics, not only in the automotive field, electrical and electronic equipment field, but also in the field of residential equipment or infrastructure, etc. All have begun research.

So far, these inventions have reported, for example, the use of Si copolymerized PC (Patent Document 2) or the use of Si-based rubber (Patent Documents 3 and 4) for the purpose of changing the impact strength at low temperatures. In addition, for the purpose of changing the flow or even improving the drug resistance, there have also been reports of examples of adding silicone compounds such as polysiloxane oils or dialkyl polysiloxanes (Patent Documents 5, 6, and 7).

In addition, in applications such as electrical and electronic equipment, the requirements for flame retardancy are increasing, and various flame retardant resin compositions have been proposed. For example, in a polycarbonate resin and a polyester resin, a method of using a halogen-based flame retardant and an antimony compound in combination (Patent Document 8), but due to the catalyst effect caused by the antimony compound, the thermal stability is significantly reduced. In addition, methods such as a boron compound using a flame retardant (Patent Document 9), red phosphorus (Patent Document 10), and phosphate ester (Patent Document 11) have also been proposed. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2012-36323 [Patent Document 2] Japanese Patent Laid-Open No. 2-43255 [Patent Document 3] Japanese Patent Laid-Open No. 1-261454 [Patent Literature 4] JP 2008-88334 [Patent Literature 5] JP 2004-162014 [Patent Document 6] Japanese Patent Laid-Open No. 1-272661 [Patent Document 7] JP 2005-133087 [Patent Document 8] JP 2015-081327 [Patent Document 9] JP 2000-001610 [Patent Document 10] JP 2000-136297 [Patent Document 11] Japanese Patent Application Publication No. 08-012864

[Problems to be solved by the invention]

In recent years, the purpose of "outdoor or waterways (bathrooms, toilets, kitchens, etc.) is mainly to use products comfortably in environments where products are easily stained, and gradually require higher resistance to resins. Medicinal and antifouling properties. However, previous reports did not focus on stain resistance, so in the current situation, it is not possible to provide a polycarbonate resin composition with mechanical properties, chemical resistance, stain resistance and appearance that can meet market demand.

In view of the above circumstances, an object of the present invention is to provide a polycarbonate resin composition that can highly satisfy mechanical properties, chemical resistance, stain resistance, and appearance. [Method of solving the problem]

The inventor of the present invention, after intensive research on solving the above problems, found that in a polycarbonate resin composition having a polycarbonate-polydiorganosiloxane copolymer resin and a polyester resin, and an antifouling imparting agent, and then The above problems can be solved when the graft copolymer having a core-shell structure obtained by grafting a specific monomer unit on a specific composite rubber.

(式中，X₁ 及X₂ 為相同或相異之下述通式(I)所表示之經芳香族取代的烷基)。

(式中，AL為碳數1～5之分支狀或直鏈狀之脂肪族烴基，Ar為苯基、萘基或蒽基，n表示1～3之整數，Ar可鍵結於AL之任意碳原子)。 ＜態樣3＞ 如態樣1或2記載之聚碳酸酯樹脂組成物，其中，B成份之含量，於A成份與B成份的合計100重量份中，為20重量份～70重量份。 ＜態樣4＞ 如態樣1～3之任一項記載的聚碳酸酯樹脂組成物，其中，B成份為含有聚乙烯對苯二甲酸酯樹脂及聚丁烯對苯二甲酸酯樹脂中之至少一者。 ＜態樣5＞ 如態樣1～4之任一項記載的聚碳酸酯樹脂組成物，其中，D成份為分子量10萬以上的聚矽氧膠體。 ＜態樣6＞ 如態樣1～5之任一項記載的聚碳酸酯樹脂組成物，其中，D成份為聚有機矽氧烷接枝聚烯烴樹脂。 ＜態樣7＞ 如態樣1～6之任一項記載的聚碳酸酯樹脂組成物，其中，C成份之複合橡膠中的聚有機矽氧烷橡膠成份之比例，為15%以上。 ＜態樣8＞ 如態樣1～7之任一項記載的聚碳酸酯樹脂組成物，其中，相對於A成份與B成份合計100重量份，(G)抗垂涎劑(G成份)為含有0.05重量份～2重量份。 ＜態樣9＞ 如態樣8記載的聚碳酸酯樹脂組成物，其中，G成份為具有纖絲形成能力的含氟聚合物。 [發明之效果]That is, the inventor of the present invention found that the above-mentioned object can be achieved based on the polycarbonate resin composition described below. <Aspect 1> A polycarbonate resin composition characterized by containing: (A) polycarbonate-polydiorganosiloxane copolymer resin (component A) and (B) polyester resin (component B) ) For a total of 100 parts by weight, (C) a composite rubber formed from components containing polyorganosiloxane rubber and alkyl (meth)acrylate rubber, having a monomer unit consisting of an aromatic alkenyl compound and a (meth ) A core-shell structured graft copolymer (component C) obtained by graft polymerization of at least one unit selected from the group consisting of alkyl acrylate compound monomer units is 3 to 15 parts by weight, and (D) The antifouling imparting agent (component D) is 0.5 to 6 parts by weight. <Aspect 2> The polycarbonate resin composition described in Aspect 1, which further contains (E) a halogen-based flame retardant (component E) 5 to 35 parts by weight, and (F) has the following formula ( 1) The phosphorus-based flame retardant (component F) of the structure shown is 0.5 to 5 parts by weight.

(In the formula, X ₁ and X ₂ are the same or different alkyl groups substituted with aromatic 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 phenyl, naphthyl or anthracenyl, n represents an integer of 1 to 3, and Ar may be bonded to any of AL carbon atom). <Aspect 3> The polycarbonate resin composition according to aspect 1 or 2, wherein the content of the component B is 20 parts by weight to 70 parts by weight in the total 100 parts by weight of the component A and the component B. <Aspect 4> The polycarbonate resin composition according to any one of Aspects 1 to 3, wherein component B contains polyethylene terephthalate resin and polybutylene terephthalate resin At least one of them. <Aspect 5> The polycarbonate resin composition according to any one of Aspects 1 to 4, wherein the component D is a polysiloxane colloid 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 grafted polyolefin resin. <Aspect 7> The polycarbonate resin composition according to any one of Aspects 1 to 6, wherein the proportion of the polyorganosiloxane rubber component in the C component compound rubber is 15% or more. <Aspect 8> The polycarbonate resin composition as described in any one of Aspects 1 to 7, wherein (G) an anti-salivation agent (G component) is contained relative to 100 parts by weight of the A component and the B component in total 0.05 parts by weight to 2 parts by weight. <Aspect 9> The polycarbonate resin composition according to Aspect 8, wherein the G component is a fluoropolymer having filament forming ability. [Effect of invention]

Since the polycarbonate resin composition of the present invention can satisfy higher levels of mechanical properties, chemical resistance, stain resistance, and appearance, it can be widely used not only in outdoor/indoor, but also in residential equipment, Uses in building materials, uses for living materials, uses for infrastructure equipment, uses for automobiles, uses for OA and EE, uses for outdoor equipment, and various other fields. Therefore, the present invention can achieve great industrial effects.

[Forms for carrying out the invention]

Hereinafter, the content of the invention will be described in detail.

＜＜Polycarbonate resin composition＞＞ The polycarbonate resin composition of the present invention contains: (A) Polycarbonate-polydiorganosiloxane copolymer resin (component A) and (B) polyester resin (component B); and 100 parts by weight relative to the total of component A and component B, (C) The composite rubber formed from components containing polyorganosiloxane rubber and alkyl (meth)acrylate rubber has an aromatic alkenyl compound monomer unit and alkyl (meth)acrylate compound monomer The core-shell structured graft copolymer (component C) obtained by graft polymerization of at least one unit selected from the group of units is 3 parts by weight to 15 parts by weight, and (D) The antifouling imparting agent (component D) is 0.5 to 6 parts by weight.

In addition to mechanical properties, chemical resistance and appearance, the resin composition of the present invention can also obtain excellent properties in terms of stain resistance. The mechanism for obtaining these effects is not clear, but it is supposed to be the following mechanism: that is, but not limited to theory, it is supposed to be (A) polycarbonate-polydiorganosiloxane copolymer resin (A) Component) the polydiorganosiloxane produced on the surface of the resin, and the organosiloxane rubber component produced from the surface of the copolymer in the (C) graft copolymer (component C), and (D ) Antifouling imparting agent (component D) At the same time, the effect of improving the antifouling by its siloxane part.

In addition, the composition of the present invention uses (B) a polyester resin (component B) in addition to (A) polycarbonate-polydiorganosiloxane copolymer resin (component A), so in addition to mechanical properties, In addition to stain resistance and appearance, excellent properties can be obtained in drug resistance.

(Component A: polycarbonate-polydiorganosiloxane copolymer resin) In the resin composition of the present invention, component A is a polycarbonate-polydiorganosiloxane copolymer resin.

When the polycarbonate resin that does not contain polydiorganosiloxane is used as the component A, impact resistance, stain resistance, and chemical resistance cannot be improved.

The polycarbonate-polydiorganosiloxane copolymer resin (component A) used in the present invention is represented by the polycarbonate block represented by the following general formula (2) and the following general formula (4) The copolymer resin composed of polydiorganosiloxane blocks is preferred.

[(上述通式(2)中，R¹ 及R² 各別獨立表示由氫原子、鹵素原子、碳原子數1～18之烷基、碳原子數1～18之烷氧基、碳原子數6～20之環烷基、碳原子數6～20之環烷氧基、碳原子數2～10之烯基、碳原子數6～14之芳基、碳原子數6～14之芳基氧基、碳原子數7～20之芳烷基、碳原子數7～20之芳烷基氧基、硝基、醛基、氰基及羧基所成之群所選出之基；其各別為複數時，該些可相同亦可、相異亦可，e及f各別為1～4之整數，W為單鍵或由下述通式(3)所表示之基所成之群所選出的至少一個之基)。

[(In the above general formula (2), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and the number of carbon atoms Cycloalkyl groups of 6-20, cycloalkoxy groups of 6-20 carbon atoms, alkenyl groups of 2-10 carbon atoms, aryl groups of 6-14 carbon atoms, aryloxy groups of 6-14 carbon atoms Group selected from the group consisting of a group, 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; , These may be the same or different, e and f are each an integer of 1-4, W is a single bond or selected by the group represented by the group represented by the following general formula (3) At least one basis).

[上述通式(3)中，R¹¹ 、R¹² 、R¹³ 、R¹⁴ 、R¹⁵ 、R¹⁶ 、R¹⁷ 及R¹⁸ 各別獨立表示由氫原子、碳原子數1～18之烷基、碳原子數6～14之芳基及碳原子數7～20之芳烷基所成之群所選出之基；R¹⁹ 及R²⁰ 各別獨立表示由氫原子、鹵素原子、碳原子數1～18之烷基、碳原子數1～10之烷氧基、碳原子數6～20之環烷基、碳原子數6～20之環烷氧基、碳原子數2～10之烯基、碳原子數6～14之芳基、碳原子數6～10之芳基氧基、碳原子數7～20之芳烷基、碳原子數7～20之芳烷基氧基、硝基、醛基、氰基及羧基所成之群所選出之基；其複數時，該些可相同亦可、相異亦可，g為1～10之整數、h為4～7之整數]。

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

[上述通式(4)中，R³ 、R⁴ 、R⁵ 、R⁶ 、R⁷ 及R⁸ ，各別獨立為氫原子、碳數1～12之烷基或碳數6～12之取代或無取代之芳基；R⁹ 及R¹⁰ 各別為獨立之氫原子、鹵素原子、碳原子數1～10之烷基、碳原子數1～10之烷氧基；p為自然數，q為0或自然數，p＋q為10～300之自然數。X為碳數2～8之二價脂肪族基]。

[In the above general formula (4), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 are} each independently a hydrogen atom, a C 1-12 alkyl group or a C 6-12 substitution Or unsubstituted aryl groups; R ⁹ and R ^{10 are} each independently hydrogen atom, halogen atom, C 1-10 alkyl group, C 1-10 alkoxy group; p is a natural number, q It is 0 or a natural number, and p+q is a natural number ranging from 10 to 300. X is a divalent aliphatic group having 2 to 8 carbons].

The polycarbonate-polydiorganosiloxane copolymer resin (component A) used in the present invention preferably represents the divalent phenol represented by the following general formula (5) and the following general formula (6) The hydroxyaryl terminal polydiorganosiloxane is prepared by copolymerization.

[(上述通式(5)中，R¹ 及R² 各別獨立表示由氫原子、鹵素原子、碳原子數1～18之烷基、碳原子數1～18之烷氧基、碳原子數6～20之環烷基、碳原子數6～20之環烷氧基、碳原子數2～10之烯基、碳原子數6～14之芳基、碳原子數6～14之芳基氧基、碳原子數7～20之芳烷基、碳原子數7～20之芳烷基氧基、硝基、醛基、氰基及羧基所成之群所選出之基；其各別為複數時，該些可相同亦可、相異亦可，e及f各別為1～4之整數，W為單鍵或由上述通式(3)所表示之基所成之群所選出的至少一個之基)。

[(In the above general formula (5), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and the number of carbon atoms Cycloalkyl groups of 6-20, cycloalkoxy groups of 6-20 carbon atoms, alkenyl groups of 2-10 carbon atoms, aryl groups of 6-14 carbon atoms, aryloxy groups of 6-14 carbon atoms Group selected from the group consisting of a group, 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; At the time, these may be the same or different, e and f are each an integer of 1-4, W is a single bond or selected from the group represented by the group represented by the above general formula (3) One basis).

[上述通式(6)中，R³ 、R⁴ 、R⁵ 、R⁶ 、R⁷ 及R⁸ ，各別獨立為氫原子、碳數1～12之烷基或碳數6～12之取代或無取代之芳基，R⁹ 及R¹⁰ 各別為獨立為氫原子、鹵素原子、碳原子數1～10之烷基、碳原子數1～10之烷氧基，p為自然數，q為0或自然數，p＋q為10～300之自然數。X為碳數2～8的二價脂肪族基]。

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

The divalent phenol (I) represented by the general formula (5) may be exemplified by: 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl) ) Ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3- Methylphenyl) propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3'-biphenyl ) Propane, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis( 4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3, 5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl) Cyclohexane, bis(4-hydroxyphenyl)diphenylmethane, 9,9-bis(4-hydroxyphenyl) stilbene, 9,9-bis(4-hydroxy-3-methylphenyl) stilbene, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy -3,3'-dimethyldiphenyl ether, 4,4'-sulfonol, 4,4'-dihydroxydiphenylsulfonate, 4,4'-dihydroxydiphenylsulfide, 2,2'-Dimethyl-4,4'-sulfadiol, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfonate, 4,4'-dihydroxy- 3,3'-Dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfadiol, 4,4'-dihydroxy-3,3'-diphenyl di Phenylsulfonate, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1, 4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1. 0 ^2,6 ]decane, 4,4'-(1,3-adamantanediyl) diphenol, 1,3-bis (4-hydroxyphenyl)-5,7-dimethyladamantane, etc.

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'-sulfadiol, 2,2'-dimethyl-4,4'-sulfadiol, 9,9-bis(4-hydroxy-3-methylphenyl) stilbene, 1,3 -Bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, preferably 2,2-bis(4- Hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4'-sulfadiol, 9,9-bis(4-hydroxy-3-methylbenzene Base) Fu is better. Among them, in view of having excellent strength and good durability, 2,2-bis(4-hydroxyphenyl)propane is the best. Moreover, these can be used individually or in combination of 2 or more types.

The hydroxyaryl terminal polydiorganosiloxane represented by the above general formula (6) is preferably, for example, a compound shown below.

Hydroxyaryl terminal polydiorganosiloxane (II) is a phenol having an olefinic unsaturated carbon-carbon bond. Preferred examples are vinyl phenol, 2-allyl phenol, isopropenol, 2-methyl The oxy-4-allylphenol is easily prepared at the end of a polysiloxane chain with a specific degree of polymerization through a hydrosilylation reaction. Among them, (2-allylphenol) terminal polydiorganosiloxane and (2-methoxy-4-allylphenol) terminal polydiorganosiloxane are preferred, especially (2-allyl Phenol) terminal polydimethylsiloxane and (2-methoxy-4-allylphenol) terminal polydimethylsiloxane. The hydroxyaryl terminal polydiorganosiloxane (II) has a molecular weight distribution (Mw/Mn) of preferably 3 or less. In addition, it is preferable to reduce the leakage gas property and the low-temperature impact property during high-temperature forming. The molecular weight distribution (Mw/Mn) is more preferably 2.5 or less, and particularly preferably 2 or less. Within this preferred range, the amount of outgas generated during high-temperature forming can be suppressed, and it has excellent low-temperature impactability.

From the viewpoint of achieving high impact resistance, the degree of polymerization (p+q) of the diorganosiloxane (p+q) of the hydroxyaryl terminal polydiorganosiloxane (II) is appropriately 10 to 300. The degree of polymerization (p+q) of the diorganosiloxane is preferably 10 to 200, more preferably 12 to 150, and particularly preferably 14 to 100. In this preferred range, when the degree of polymerization (p+q) is maximum, the impact resistance of the polycarbonate-polydiorganosiloxane copolymer can be effectively exerted without causing the degree of polymerization (p+q) to be too large, so It still has a good appearance.

For the total weight of the polycarbonate-polydiorganosiloxane copolymer resin used in component A, the content of polydiorganosiloxane is preferably 0.1% to 50% by weight. The content of the polydiorganosiloxane component is more preferably 0.5% by weight to 30% by weight, and particularly preferably 1% by weight to 20% by weight. When it is above the lower limit of the preferred range, it can have excellent impact resistance or flame retardancy. When it is below the upper limit of the preferred range, it is not easily affected by molding conditions, and a stable appearance is easily obtained. The degree of polymerization of polydiorganosiloxane and the content of polydiorganosiloxane can be calculated by ¹ H-NMR measurement.

In the present invention, only one kind of hydroxyaryl terminal polydiorganosiloxane (II) may be used, or two or more kinds may be used.

In addition, as long as the scope of the present invention is not hindered, the divalent phenol (I) and the hydroxyaryl terminal polydiorganosiloxane (II) may be used in combination within the range of 10% by weight or less of the total weight of the copolymer ) Other than comonomers.

In the present invention, first, a mixture of an organic solvent insoluble in water and an aqueous alkali solution is reacted with a divalent phenol (I) and a compound capable of forming a carbonate to obtain a terminal chloroformate group. The mixed solution of oligomers.

After the oligomer of divalent phenol (I) is formed, the entire amount of divalent phenol (I) used in the method of the present invention may be used as an oligomer at a time, or a part of it may be used as a post-addition monomer, and in the subsequent stage In the interfacial polycondensation reaction, it can be added as a reaction raw material. After the monomer is added, it is added for the purpose of accelerating the polycondensation reaction in the subsequent stage, and it may not be added when it is unnecessary.

The method of the oligomer formation reaction is not particularly limited, but it is generally preferred to proceed in the presence of an acid bonding agent in a solvent.

The use ratio of the carbonate-forming compound can be appropriately adjusted after considering the stoichiometric ratio (equivalent) of the reaction. In addition, when a gaseous compound such as phosgene that can form a carbonate is used, it is preferably added to the reaction system using a blowing method.

As the acid-bonding agent, 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 can be used. The use ratio of the acid bonding agent is also the same as the above, and the appropriate determination can be made after considering the chemical quantity ratio (equivalent) of the reaction. Specifically, the number of moles of the divalent phenol (I) used when forming the oligomer (usually 1 mole is equivalent to 2 equivalents) to use 2 equivalents or slightly more of the acid bonding agent Better.

As the above-mentioned solvent, one kind of solvent which is inert to various reactions when manufacturing a well-known polycarbonate, or a mixed solvent of these may be used alone. Representative examples include various halogenated hydrocarbon solvents starting from hydrocarbon solvents such as xylene, dichloromethane, and chlorobenzene. In particular, halogenated hydrocarbon solvents such as methylene chloride are preferred users.

The reaction pressure at the time of generating the oligomer is not particularly limited, and may be any of normal pressure, pressurization, and reduced pressure, and it is usually advantageous to perform the reaction under normal pressure. The reaction temperature can be selected in the range of -20°C to 50°C. In most cases, the polymerization is accompanied by heat generation, so it is preferably carried out under water cooling or ice cooling. The reaction time is generalized due to the influence of other conditions, but it is usually 0.2 to 10 hours. The pH range of the oligomer formation reaction is the same as the well-known interface reaction conditions, and it is usually carried out in an environment of pH 10 or higher.

In the present invention, as described above, after preparing a mixed solution containing an oligomer of a divalent phenol (I) having a terminal chloroformate group, the mixed solution is stirred, and the above general formula (6) ) Represents a hydroxyaryl terminal polydiorganosiloxane (II) added to the mixed solution to highly purify the molecular weight distribution (Mw/Mn) to below 3, and by making the hydroxyaryl terminal polydiorganosiloxane (II) The result of interfacial polycondensation with the oligomer to produce a polycarbonate-polydiorganosiloxane copolymer.

In carrying out the interfacial polycondensation reaction, an acid-bonding agent can be added appropriately in consideration of the stoichiometric ratio (equivalent) of the reaction. As the acid-bonding agent, 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, or mixtures thereof can be used. Specifically, when the hydroxyaryl terminal polydiorganosiloxane (II) used is added, or as described above, part of the divalent phenol (I) is added as the post-addition monomer in this reaction stage, Use 2 equivalents or more based on the total number of moles (usually 1 mole is equivalent to 2 equivalents) of the total amount of divalent phenol (I) and hydroxyaryl terminal polydiorganosiloxane (II) added later The amount of alkali is better.

The polycondensation method of the interfacial polycondensation reaction between the oligomer of divalent phenol (I) and the hydroxyaryl terminal polydiorganosiloxane (II) can be carried out by vigorously stirring the above mixed liquid.

In this polymerization reaction, a chain stopper or a molecular weight regulator is usually used. Examples of the chain stopper include compounds having a monovalent phenolic hydroxyl group, etc.; in addition to ordinary phenols, p-tert-butanol, p-cumene, tribromophenol, etc., such as long-chain alkanols, aliphatic Carboxylic acid chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxyphenyl alkanoate, alkyl ether phenol, etc. The amount used is 100 moles to 0.5 moles, preferably 50 moles to 2 moles, relative to 100 moles of all the divalent phenolic compounds used. Of course, two or more compounds may be combined use.

From the viewpoint of promoting the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may also be added.

The reaction time of this polymerization reaction is preferably 30 minutes or more, and particularly preferably 50 minutes or more. It can be added with a small amount of antioxidants such as sodium sulfite and hydrosulfide in accordance with the intended purpose.

The disproportionating agent can be used in combination with the above-mentioned divalent phenolic compound to produce disproportionated polycarbonate-polydiorganosiloxane. The trifunctional or more polyfunctional aromatic compounds used in the branched polycarbonate-polydiorganosiloxane copolymer resin may be exemplified by resorcinol, phloroglucine, or 4,6-dimethyl Yl-2,4,6-tris(4-hydroxydiphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1 ,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4- Hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-cresol, 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl ]Benzene}-α,α-dimethylbenzylphenol and other triphenols, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl) ketone, 1,4-bis(4,4 -Dihydroxytrityl)benzene, or trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, and acid chlorides of these; among them, 1,1,1-tri(4 -Hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane; preferably 1,1,1-tris(4-hydroxybenzene) Radical) ethane is preferred. In the branched polycarbonate-polydiorganosiloxane copolymer resin, the ratio of the multifunctional compound is preferably 0.001 mol% to 1 mol% in the total amount of the aromatic polycarbonate-polydiorganosiloxane copolymer resin. Ear%, more preferably 0.005 mole% to 0.9 mole%, particularly preferably 0.01 mole% to 0.8 mole%, most preferably 0.05 mole% to 0.4 mole%. In addition, the amount of the branch structure can be calculated using ¹ H-NMR measurement.

The reaction pressure may be any of reduced pressure, normal pressure, and increased pressure, and it is usually carried out under normal pressure or within the pressure range of the reaction system itself. The reaction temperature can be appropriately selected within the range of -20°C to 50°C. In most cases, the polymerization is accompanied by heat generation, so it is preferably carried out under water cooling or ice cooling. The reaction time varies depending on other conditions such as the reaction temperature and cannot be generalized, but it is usually carried out within 0.5 hours to 10 hours.

Depending on the situation, the resulting polycarbonate-polydiorganosiloxane copolymer resin can be subjected to appropriate physical treatment (mixing, separation, etc.) and/or chemical treatment (polymer reaction, crosslinking treatment, partial Decomposition treatment, etc.) to produce polycarbonate-polydiorganosiloxane copolymer resin with the expected reduced viscosity [η _SP /c].

After the obtained reaction product (crude product) is subjected to various post-treatments such as a well-known separation and purification method, it can be recovered in a polycarbonate-polydiorganosiloxane copolymer resin of a desired purity (purity).

In the polycarbonate-polydiorganosiloxane copolymer resin molded product, the average size (average area size) of the polydiorganosiloxane region is preferably in the range of 1 nm to 40 nm. The average size is more preferably 1 nm to 30 nm, and particularly preferably 5 nm to 25 nm. In this preferred range, since the average area size is extremely large, the impact resistance or flame retardancy can be fully exhibited, and because the average area size is not too large, the impact resistance can be stably exhibited. Therefore, in particular, a polycarbonate resin composition having excellent impact resistance and appearance can be provided.

In the present invention, the average area size of the polydiorganosiloxane area of the polycarbonate-polydiorganosiloxane copolymer resin molded product can be given using the Small Angle X-ray Scattering (SAXS) method Assessment. The small-angle X-ray scattering method is a method of measuring diffusive scattering/diffraction generated in a small-angle region with a scattering angle (2θ)<10°. Using this small-angle X-ray scattering method, when a substance has a region with a different electron density of about 1 nm to 100 nm, the diffuse scattering of X-rays can be measured through the difference in electron density. Based on the scattering angle and scattering intensity, the particle size of the object to be measured is obtained. If the polydiorganosiloxane region in the matrix of the polycarbonate polymer is a polycarbonate-polydiorganosiloxane copolymer resin with a dispersed and condensed structure, the polycarbonate matrix can be combined with the polydiorganosiloxane The electron density of the alkane region is poor, and diffuse scattering of X-rays occurs. The scattering intensity I at each scattering angle (2θ) with a scattering angle (2θ) less than 10° can be measured first, and then the appearance of small-angle X-ray scattering can be measured, and the polydiorganosiloxane area can be set as a spherical area The particle size distribution exists in a random distribution mode, and then through a standard experiment on the particle size and particle size distribution model, after using a commercially available analysis software to perform a simulation experiment, the average size of the polydiorganosiloxane region is obtained. By using the small angle X-ray scattering method, the polydiorganic dispersed in the polycarbonate polymer matrix, which can not be accurately measured by the transmission electron microscope observation, can be measured in a more accurate, simple and reproducible manner. The average size of the silicone area. The average area size refers to the mean of the size of each area.

The term "average area size" used in connection with the present invention refers to the measurement value obtained by measuring the thickness of 1.0 mm of a three-step type plate produced by the method described in the examples by the small-angle X-ray scattering method. In addition, it is based on independent particle samples that do not consider the interaction between particles (interparticle interference).

The viscosity-average molecular weight (M) of the polycarbonate-polydiorganosiloxane copolymer resin is not particularly limited, but it is generally preferably 1.8×10 ⁴ to 4.0×10 ⁴ , and more preferably 2.0×10 ⁴ to 3.5 ×10 ⁴ , particularly preferably 2.2×10 ⁴ to 3.0×10 ⁴ . Polycarbonate-polydiorganosiloxane copolymer resin with viscosity average molecular weight of 1.8×10 ⁴ or more can obtain good mechanical properties, and can ensure sufficient melt viscosity difference with polyolefin resin, so it can have good The appearance and tape peeling resistance. On the other hand, the resin composition obtained from a polycarbonate-polydiorganosiloxane copolymer resin having an average viscosity molecular weight of 4.0×10 ⁴ or less has excellent fluidity during injection molding, and therefore has excellent versatility .

In addition, the polycarbonate-polydiorganosiloxane copolymer resin may be obtained by mixing with a resin having a viscosity average molecular weight outside the aforementioned range. In particular, when a polycarbonate-polydiorganosiloxane copolymer resin having a viscosity average molecular weight exceeding the aforementioned range (5×10 ⁴ ), the entropy elasticity of the resin can be improved. As a result, it is possible to provide good molding processability in gas molding and foam molding in which a reinforced resin material is used to form a structural member. In a more suitable aspect, a polycarbonate-polydiorganosiloxane copolymer resin (component A-1-1-1) with an average viscosity of 7×10 ⁴ ～3×10 ⁵ and an average viscosity Polycarbonate-polydiorganosiloxane copolymer resin (component A-1-1-2) with a molecular weight of 1×10 ⁴ ～3×10 ⁴ has a viscosity average molecular weight of 1.6×10 ⁴ ～3.5×10 ⁴ Carbonate-polydiorganosiloxane copolymer resin (component A-1-1) (hereinafter, also referred to as "polycarbonate-polydiorganosiloxane copolymer resin containing high molecular weight components").

In the polycarbonate-polydiorganosiloxane copolymer resin (component A-1-1) containing a high molecular weight component, the molecular weight of the component A-1-1-1 is preferably 7×10 ⁴ ～2×10 ⁵ , More preferably 8×10 ⁴ to 2×10 ⁵ , particularly preferably 1×10 ⁵ to 2×10 ⁵ , and most preferably 1×10 ⁵ to 1.6×10 ⁵ . In addition, the molecular weight of the component A-1-1-2 is preferably from 1×10 ⁴ to 2.5×10 ⁴ , more preferably from 1.1×10 ⁴ to 2.4×10 ⁴ , and particularly preferably from 1.2×10 ⁴ to 2.4×10 ⁴ , The best is 1.2 × 10 ⁴ ~ 2.3 × 10 ⁴ .

Polycarbonate-polydiorganosiloxane copolymer resin containing high molecular weight components (component A-1-1), the aforementioned components A-1-1-1 and A-1-1-2 can be mixed in various proportions , Adjusted to meet a specific molecular weight range. Preferably, in the case of 100% by weight of the A-1-1 component, 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 to 30%. % By weight, particularly preferably A-1-1-1 component is 4%-20% by weight, and most preferably A-1-1-1 component is 5%-20% by weight.

In addition, the manufacturing method of the A-1-1 component can be listed as follows: (1) The A-1-1-1 component and the A-1-1-2 component are independently polymerized, and the method of mixing these, (2) In the molecular weight distribution curve of the GPC method represented by the method shown in Japanese Patent Laid-Open No. 5-306336, an aromatic polycarbonate resin having a plurality of polymer peaks is produced in the same reaction system Method, a method of preparing the aromatic polycarbonate resin to satisfy the conditions of the A-1-1 component of the present invention, and (3) The aromatic polycarbonate resin produced by the production method (the production method of (2)) and the A-1-1-1 component and/or A-1-1 produced by other methods -2 Method of mixing ingredients, etc.

The viscosity-average molecular weight in the present invention is first a solution obtained by dissolving 0.7 g of polycarbonate-polydiorganosiloxane copolymer resin in 100 ml of dichloromethane using an Ostwald viscometer and calculating it according to the following formula Specific viscosity (η _SP ) at 20°C, specific viscosity (η _SP ) = (tt ₀ )/t ₀ [t ₀ is the number of seconds of dichloromethane drop, t is the number of seconds of sample solution drop] The specific viscosity (η _SP ) obtained was calculated as the viscosity average molecular weight M according to the following mathematical formula. η _SP /c=[η]+0.45×[η] ² c (however, [η] is the critical viscosity) [η]=1.23×10-4M ^0.83 c=0.7

In the polycarbonate resin composition of the present invention, the viscosity average molecular weight of the polycarbonate-polydiorganosiloxane copolymer resin is calculated according to the following points. That is, the composition is mixed with 20 to 30 times the weight of methylene chloride to re-dissolve soluble components in the composition. The soluble ingredients were collected using celite filtration. Subsequently, the solvent in the resulting solution is removed. The solid after removing the solvent was sufficiently dried to prepare a solid dissolved in methylene chloride. Then, a solution obtained by dissolving 0.7 g of the solid in 100 ml of dichloromethane was obtained, and the specific viscosity at 20° C. was calculated according to the same method as above, and the viscosity average molecular weight M was calculated from the specific viscosity according to the same method as above.

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

The aromatic dicarboxylic acid referred to herein is preferably terephthalic acid, isophthalic acid, phthalic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 4, 4'-biphenyl dicarboxylic acid, 4,4'-biphenyl ether dicarboxylic acid, 4,4'-biphenyl methane dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 4,4'- Biphenyl isopropylidene dicarboxylic acid, 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4'-p-biphenylene dicarboxylic acid, 2,5-pyridinedicarboxylic acid and other aromatic dicarboxylic acids, diphenylmethane dicarboxylic acid, diphenyl ether dicarboxylic acid, and β -Hydroxyethoxybenzoic acid is preferred. In particular, terephthalic acid and 2,6-naphthalene dicarboxylic acid are preferred users. The aromatic dicarboxylic acids may be used in combination of two or more. In addition, if it is a small amount, the dicarboxylic acid may also be combined with aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, and the like, and cycloaliphatic dicarboxylic acids, etc. One or more of dicarboxylic acids are mixed for use.

In addition, as the diol of the polyester resin component of the present invention, for example, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, pentamethyldiol, hexamethylene glycol, and nonamethyl glycol can be cited. , Aliphatic diols such as 2-methyl-1,3-propanediol, diethylene glycol, triethylene glycol, etc., cycloaliphatic diols such as 1,4-cyclohexanedimethanol, etc., 2,2- Aromatic ring-containing diols such as bis(β-hydroxyethoxyphenyl)propane and the like and mixtures thereof. In addition, when it is a small amount, it may be copolymerized with one or more types of long-chain diols having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propanediol, polytetramethylene glycol, and the like.

In addition, the polyester-based resin of the present invention may be introduced into a branched form with a small amount of disproportionating agent. The type of disproportionating agent is not particularly limited. Generally, for example, trimethanesulfonic acid, trimesic acid, trimethylolethane, trimethylolpropane, pentaerythritol, etc.

Specifically, polyester resins include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), and polyhexene. Terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene-1,2-bis(phenoxy)ethane-4,4'-dicarboxylate, Other than this, there are copolymerized polyester resins such as polyethylene isophthalate/terephthalate, polybutylene terephthalate/isophthalate, etc. Among these, when the balance of mechanical properties and the like can be achieved, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and these The mixture is better.

In addition, the terminal group structure of the obtained polyester resin is not particularly limited, except that the ratio of the hydroxyl group to the carboxyl group in the terminal group is almost the same amount, or the ratio of one of them may be large. In addition, the terminal group may be blocked with the terminal group by reacting with a compound reactive with the terminal group.

The production method of the polyester resin can be carried out according to the usual method, in the presence of a polymerization catalyst containing titanium, germanium, antimony, etc., under heating, the dicarboxylic acid component and the aforementioned diol component are polymerized, and the auxiliary The product water or lower alcohol is discharged outside the reaction system. For example, the germanium-based polymerization catalyst may be oxides, hydroxides, halides, alcoholates, phenols, etc. of germanium, more specifically, for example, germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxy Germanium, etc.

Among the polymerization catalysts of organic titanium compounds, preferred specific examples are, for example: titanium tetrabutoxide, titanium isopropoxide, titanium oxalate, titanium acetate, titanium benzoate, titanium trimellitate, tetrabutyl titanate and The reactants of trimellitic anhydride, etc. Moreover, since it is manufactured using a specific titanium-based catalyst other than the above, a polyester resin with more excellent thermal stability can be obtained, so it is more suitable for use.

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

The titanium compound component (A) is a titanium compound (1) represented by the following general formula (I) and an aromatic polyvalent carboxylic acid represented by the titanium compound (1) and the following general formula (II) or anhydrous At least one type of titanium compound component selected from the group of titanium compounds (2) obtained by reacting the compounds.

[其中，式(I)中，R¹ 、R² 、R³ 及R⁴ ，各別獨立表示具有2～10個碳原子之烷基；k表示1～3之整數，且，k為2或3時，2個或3個的R² 及R³ ，可互相為相同亦可，或相異亦可]。

[Wherein, in formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group having 2 to 10 carbon atoms; k represents an integer of 1 to 3, and k is 2 or At 3 o'clock, 2 or 3 R ² and R ³ may be the same or different from each other].

[其中，式(II)中，m表示2～4之整數]。

[Wherein, in formula (II), m represents an integer of 2 to 4]

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

[其中，式(III)中，R⁵ 表示無取代或有取代的具有6～20個碳原子之芳基，或具有1～20個碳原子之烷基]。

[Wherein, in formula (III), R ⁵ represents an unsubstituted or substituted aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms].

The polyester resin obtained by using the above-mentioned specific titanium catalyst shows better thermal stability and moisture resistance when compared with the case of using germanium, antimony, and other titanium catalysts. When using the above-mentioned specific titanium catalyst, compared with the case of using other catalysts, stable quality can be obtained even if the amount of additives such as hue stabilizers or heat stabilizers at the time of manufacture is reduced. It can reduce the decomposition of additives in hot environment or hot and humid environment, so it has excellent thermal stability and heat and humidity resistance.

In the reaction product of the titanium compound component (A) and the phosphorus compound component (B), the titanium compound component (A) has a titanium atom conversion molar amount (mTi), and the phosphorus compound component (B) has a phosphorus atom conversion molar amount The reaction molar ratio (mTi/mP) of (mP) is preferably in the range of 1/3 to 1/1, preferably in the range of 1/2 to 1/1.

The molar amount of titanium atoms of the titanium compound component (A) is the sum of 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 1 molecule of the titanium compound, The molar amount of phosphorus atom conversion of the phosphorus compound component (B) is the sum of the product of the molar amount of each phosphorus compound contained in the phosphorus compound component (B) and the number of phosphorus atoms contained in one molecule of the phosphorus compound. Among them, the phosphorus compound represented by the formula (III) is one containing one phosphorus atom per molecule, so the molar amount of the phosphorus compound converted to the phosphorus atom 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 excessive, the polyester resin obtained by using the obtained catalyst has a good color tone (no This causes the b value to be too high), and can make it heat resistant. In addition, 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 resulting catalyst can still have sufficient contact with the polyester formation reaction Media activity.

The titanium compound (1) represented by the aforementioned general formula (I) used for the titanium compound component (A) includes, for example, titanium tetrabutoxide, titanium tetraisopropoxide, titanium tetrapropoxide, titanium tetraethoxide, etc. Titanium tetraoxanes, and octyl trititanates, hexyl dititanates, etc. alkyl titanates, etc., among these, it has good reactivity with the phosphorus compound component used in the present invention The tetraoxane titanium oxides are preferred, and the use of tetrabutyl titanium oxide is particularly preferred.

The titanium compound (2) used for 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 its anhydrous. The aromatic polyvalent carboxylic acid and its anhydrous of the general formula (II) above are composed of phthalic acid, trimellitic acid, hemicellitic acid, pyromellitic acid and these anhydrous The one selected by the group is better. In particular, it is preferred to use trimellitic anhydride having excellent reactivity with the titanium compound (1) and having high affinity with the polyester of the polycondensation catalyst obtained.

The reaction of the titanium compound (1) with the aromatic polyvalent carboxylic acid or its anhydrous of the general formula (II) is to mix the aromatic polyvalent carboxylic acid or its anhydrous in a solvent, and make it partially or All are dissolved in the solvent, the titanium compound (1) is dropped into the mixed solution, and the heating is carried out at a temperature of 0°C to 200°C for 30 minutes or more, preferably at a temperature of 30°C to 150°C for 40 minutes to 90 minutes Way. There is no particular restriction on the reaction pressure at this time, and it is generally sufficient under normal pressure. In addition, the aforementioned solvent can be appropriately selected and used from a part or all of the solvent that can dissolve the required amount of the compound of formula (II) or its anhydrous, preferably selected from ethanol, ethylene glycol, and trimethyl glycol , Tetramethylene glycol, benzene and xylene.

The molar ratio of the reaction between the titanium compound (1) and the compound represented by the formula (II) or its anhydrous is not particularly limited. However, if the proportion of the titanium compound (1) is not too high, the color tone of the obtained polyester resin can be improved, and the softening point can be prevented from lowering. Conversely, when the ratio of the titanium compound (1) is not too low, the polycondensation reaction can proceed well. Therefore, the molar ratio of the reaction between the titanium compound (1) and the compound of formula (II) or its anhydrous is preferably controlled within the range of 2/1 to 2/5. The reaction product obtained by this reaction can be immediately supplied to the aforementioned reaction with the phosphorus compound (3) or the solvent formed with acetone, methanol and/or ethyl acetate, etc. after recrystallization and purification, and then It can react with the phosphorus compound (3).

In the phosphorus compound (3) of the aforementioned general formula (III) used in the phosphorus compound component (B), an aryl group having 6 to 20 carbon atoms represented by R ⁵ or an alkyl group having 1 to 20 carbon atoms , May be unsubstituted or substituted by more than one substituent. The substituent includes, for example, a carboxyl group, an alkyl group, a hydroxyl group, an amine group, and the like.

The phosphorus compound (3) of the aforementioned general formula (III) includes, for example, monomethyl phosphate, monoethyl phosphate, monotrimethyl phosphate, mono-n-butyl phosphate, monohexyl phosphate, mono Heptyl phosphate, monooctyl phosphate, monononyl phosphate, 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-ethylphenyl) phosphate, Mono(4-propylphenyl) phosphate, mono(4-dodecylphenyl) phosphate, monotolyl phosphate, monoxylyl phosphate, monobiphenyl phosphate, mononaphthyl phosphate , And monoalkyl phosphates and monoaryl phosphates such as monoanthryl phosphates, these can be used alone or in a mixture of two or more, such as monoalkyl phosphate and monoaryl It can also be used as a mixture of basic phosphates. Among them, when the above phosphorus compound is a mixture of two or more kinds, the proportion of monoalkyl phosphate is preferably 50% or more, preferably 90% or more, and more preferably 100%.

A method for manufacturing a catalyst from a titanium compound component (A) and a phosphorus compound component (B), for example: mixing a phosphorus compound component (B) formed from at least one phosphorus compound (3) of formula (III) with a solvent, A part or all of the phosphorus compound component (B) is dissolved in a solvent, and the titanium compound component (A) is dropped into the mixed solution, usually the reaction system is preferably at 50°C to 200°C, more preferably 70 At a temperature of ℃ to 150°C, the heating is preferably performed for 1 minute to 4 hours, more preferably for 30 minutes to 2 hours. In this reaction, the reaction pressure is not particularly limited, and it can be carried out under any of pressurization (0.1 MPa to 0.5 MPa), normal pressure, or under reduced pressure (0.001 MPa to 0.1 MPa), usually Under normal pressure.

In addition, the solvent of the phosphorus compound component (B) of the formula (III) used in the above catalyst production reaction is not particularly limited as long as it can be dissolved in at least a part of the phosphorus compound component (B). It is preferable to use at least one selected solvent such as ethanol, ethylene glycol, trimethyl glycol, tetramethyl glycol, benzene, and xylene. In particular, it is preferable to use a compound having the same diol component as the polyester constituting the final product as the solvent user.

The reaction product of the titanium compound component (A) and the phosphorus compound component (B) can be separated from the reaction system by centrifugal precipitation treatment or filtration, and can be manufactured as a polyester resin without purification treatment The catalyst may be used, or the separated reaction product may be recrystallized and purified using a recrystallization agent such as acetone, methanol, and/or water, and the resulting purified product may be used as a catalyst. In addition, the aforementioned reaction product may not need to be separated by the reaction system, and the reaction mixture containing the reaction product may then be used as a catalyst-containing mixture.

The titanium-based catalyst is composed of the titanium compound component (A) formed of at least one titanium compound (1) of the aforementioned formula (I) (wherein k represents 1), that is, a titanium tetraalkanate, and the aforementioned formula (1) III) The reaction product of the phosphorus compound component (B) formed by at least one phosphorus compound is preferably used as a catalyst. In addition, the titanium-based catalyst is preferably a compound represented by the following general formula (IV).

[上述式中，R⁶ 及R⁷ ，各別獨立表示具有2～12個碳原子之烷基，或具有6～12個碳原子之芳基]

[In the above formula, R ⁶ and R ⁷ 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 formula (IV) has high catalyst activity, so the polyester resin obtained using it has a good hue (low b-value). In practical use, It is a cyclic terpolymer with extremely low content of acetaldehyde, residual metals, and esters of aromatic dicarboxylic acids and alkanediols, and has sufficient polymer properties in practical use.

In the titanium-based catalyst, the titanium/phosphorus compound of the general formula (IV) is preferably 50% by weight or more, and preferably 70% by weight or more.

The amount of titanium catalyst used, the amount of titanium atoms converted to millimoles, relative to the total millimoles of the aromatic dicarboxylic acid components contained in the polymerization starting material, is 2 to 40 mill% Preferably, 5% to 35% is more preferred, and 10% to 30% is particularly preferred. When it is 2 mM or more, the polycondensation reaction of the polymerization starting material can sufficiently have the effect of promoting the catalyst, and the polyester production efficiency can be excellent, and the polyester system having the desired degree of polymerization can be obtained Resin. Moreover, when it is 40 milli% or less, the color tone (b value) of the obtained polyester resin can be made favorable, the generation of a yellow color can be suppressed, and its practicability can be ensured.

The method for producing the alkylene glycol ester of aromatic dicarboxylic acid and/or its oligomer is not particularly limited. Generally, it is an aromatic dicarboxylic acid or its esterified derivative, and the alkylene glycol or Its esterified derivatives are prepared by heating reaction. For example, ethylene glycol terephthalate and/or its oligomers used as raw materials for polyethylene terephthalate are directly esterified with terephthalic acid and ethylene glycol, or will be The lower alkyl ester of phthalic acid can be prepared by transesterification with ethylene glycol, or by adding ethylene oxide to terephthalic acid. In addition, among the above alkylene glycol esters of aromatic dicarboxylic acids and/or their oligomers, other dicarboxylic acid esters copolymerizable therewith can be used as additional components within a range that does not substantially impair the effect of the method of the present invention The amount, specifically, when the total molar amount of the acid component is used as a reference, it may contain 10 mol% or less, preferably 5 mol% or less, as the addition amount.

The aforementioned additional components that can be copolymerized, and preferred acid components include aliphatic and alicyclic dicarboxylic acids such as adipic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, and hydroxycarboxylic acid An acid, for example, one or more kinds selected from β-hydroxyethoxybenzoic acid, p-oxybenzoic acid, etc., and as a diol component, for example: an alkanediol having 1, 2 or more carbon atoms constituting the structure, 1,4 -Esters or esters formed from one or more of aliphatic, alicyclic, aromatic diol compounds such as cyclohexanedimethanol, neopentyl glycol, bisphenol A, bisphenol S, and polyoxyalkylene glycol Anhydrous. The ester of the above additional components may be used alone, or two or more of these components may be used in combination. However, the copolymerization amount is preferably within the above range.

In addition, when terephthalic acid or dimethyl terephthalate is used as the starting material, it can be obtained by recovering dimethyl terephthalate obtained by depolymerizing polyalkyl terephthalate or hydrolyzing it. The recovered terephthalic acid is 70% by weight or more relative to the weight basis of the total acid component constituting polyester. In this case, the target polyalkyl terephthalate is preferably polyethylene terephthalate, especially recycled PET bottles, recycled fiber products, recycled polyester film products, or even these products When used as a raw material source for polyester production, the polymer scraps and the like generated in the manufacturing process of the present invention are preferably from the viewpoint of effectively utilizing resources.

However, the method of depolymerizing the recovered polyalkyl terephthalate to obtain dimethyl terephthalate is not particularly limited, and any conventionally known method can be used. For example, after depolymerization of the recovered polyalkylene terephthalate using ethylene glycol, the depolymerized product is subjected to a transesterification reaction using a lower alcohol, such as methanol, etc., after the reaction mixture is purified, the recovered The lower alkyl ester of phthalic acid is then transesterified using an alkylene glycol, and then the resulting phthalic acid/alkylene glycol ester is subjected to a polycondensation reaction to obtain a polyester resin. In addition, the method for recovering terephthalic acid from the recovered dimethyl terephthalate is not particularly limited, and any conventional method can be used. For example, in the reaction mixture obtained by transesterification, dimethyl terephthalate is recovered by recrystallization and/or distillation, and then heated and hydrolyzed with water at high temperature and high pressure to recover terephthalic acid . Among the impurities contained in terephthalic acid obtained by this method, the content of 4-carboxybenzaldehyde, p-toluic acid, benzoic acid, and dimethyl hydroxyterephthalate is preferably 1 ppm or less in total. The content of monomethyl terephthalate is preferably in the range of 1 ppm to 5000 ppm. The terephthalic acid recovered by the above method is directly esterified with an alkylene glycol, and then the obtained ester is subjected to a polycondensation reaction to obtain a polyester resin.

In the polyester resin used in the present invention, the time when the catalyst is added to the polymerization starting material may be any before the time when the polyalkylene aromatic dicarboxylate and/or its oligomer starts to undergo the polycondensation reaction In addition, there is no particular restriction on the method of addition. For example: manufacturing aromatic dicarboxylic acid alkyl glycol esters, then adding a catalyst solution or slurry to the reaction system, and then starting the polycondensation reaction, or in manufacturing the aforementioned aromatic dicarboxylic acid alkyl glycol esters At the same time, it can be added to the reaction system at the same time as the starting materials or after adding the starting materials.

The reaction conditions for producing polyester resins used in the present invention are also not particularly limited. The general polycondensation reaction is conducted at a temperature between 230°C and 320°C under normal pressure or reduced pressure (0.1 Pa to 0.1 MPa) or a combination of these conditions for 15 minutes to 300 minutes. Condensers are better.

In the reaction system, the polyester resin used in the present invention may be added with a reaction stabilizer, such as trimethyl phosphate, at any stage in the production of the polyester resin, if necessary, and, if necessary, In the reaction system, one or more kinds of antioxidants, ultraviolet absorbers, flame retardants, fluorescent whitening agents, anticancer agents, coloring agents, antifoaming agents, and other additives are added. In particular, in the polyester resin, an antioxidant containing at least one hindered phenol compound is preferred, and its content is preferably 1% by weight or less relative to the weight of the polyester resin. When the content is 1% by weight or less, the quality of the resulting product can be ensured through the thermal degradation resistance of the antioxidant itself.

In the polyester resin used in the present invention, the hindered phenol compound used for the antioxidant may be pentaerythritol-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate], 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethane Radical}-2,4,8,10-tetraoxaspiro[5,5]undecane, etc., or these hindered phenolic antioxidants and sulfide secondary antioxidants can also be used in combination, also for Preferred embodiment. The method of adding the hindered phenol-based antioxidant to the polyester-based resin is not particularly limited, and it is generally preferable to add it at any stage between the transesterification reaction, or the end of the esterification reaction and the end of the polymerization reaction.

In addition, when adjusting the color tone of the obtained polyester resin, in the production stage of the polyester resin, azo, triphenylmethane, quinoline, anthraquinone, phthalocyanine, etc. A color modifier formed by one or more of the organic blue pigment and the inorganic blue pigment is added to the reaction system. In addition, in the production method of the present invention, of course, it is not necessary to use an inorganic blue pigment containing cobalt or the like, which will reduce the melting heat stability of the polyester-based resin, as a color modifier. Therefore, the polyester resin used in the present invention does not substantially contain cobalt.

The polyester resin used in the present invention preferably contains 0.001 ppm to 100 ppm of titanium element produced by the above catalyst. The content is preferably 0.001 ppm to 50 ppm, and more preferably 1 ppm to 50 ppm. When the content of titanium is more than 100 ppm, it may cause deterioration of thermal stability or resistance to moisture and heat. When using a polyester resin less than 0.001 ppm, the amount of catalyst residue will be greatly reduced, which will cause manufacturing The degree of difficulty of polyester resins may not be able to obtain good mechanical strength, thermal stability or damp heat stability of this composition feature.

Of the polyester resins used in the present invention, the L value measured using a Hunter-type color difference meter is usually 80.0 or more and the b value is in the range of -2.0 to 5.0. When the L value of the polyester-based resin is less than 80.0, the whiteness of the obtained polyester-based resin is too low, and a high-whiteness molded article that can be used practically cannot be obtained. In addition, when the b value is less than -2.0, the yellow tone of the resulting polyester-based resin is reduced, and the cyan color tone is increased. Also, when the b value exceeds 5.0, the yellow tone of the obtained polyester-based resin is increased, so it cannot be used for manufacturing. Actually used moldings. The L value of the polyester resin obtained by the method of the present invention is more preferably 82 or more, particularly preferably 83 or more, and the b value is more preferably in the range of -1.0 to 4.5, particularly preferably 0.0 to 4.0.

The critical viscosity of the polyester resin prepared by the invention is preferably 0.4-1.5. The preferred range of the aforementioned critical viscosity is 0.45 to 1.4, and more preferably 0.50 to 1.3. When the critical viscosity of the polyester resin is 0.4 or more, it can have sufficient impact characteristics and chemical resistance. When it is 1.5 or less, the fluidity during injection molding can be ensured, and appearance defects such as flow marks or poor coloring can be prevented. Happen. The critical viscosity of the polyester resin can be measured by dissolving the polyester resin in o-chlorophenol at a temperature of 35°C. In addition, the polyester resin obtained by solid-phase polycondensation can be used for general bottles, etc. Therefore, the polyester resin has a critical viscosity of 0.70 to 0.90. The content of the cyclic trimer of the ester of aromatic dicarboxylic acid and alkanediol is 0.5 wt% or less, and the content of acetaldehyde is preferably 5 ppm or less. The aforementioned cyclic terpolymers include: alkyl terephthalate, such as ethyl terephthalate, trimethyl terephthalate, tetramethyl terephthalate, and hexamethylene terephthalate Esters, etc., and alkyl naphthyl esters, such as ethyl naphthalene, trimethyl naphthalene, tetramethyl naphthalene, hexamethyl naphthalene, etc.

In addition, in the present invention, compounds of manganese, zinc, calcium, magnesium and the like used in the previous transesterification reaction in the conventionally known polycondensation reaction and compounds of phosphoric acid or phosphorous acid after the completion of the transesterification reaction can be used in combination. To make the catalyst polycondensation with passivation.

For the production method of the polyester resin, either batch method or continuous polymerization method can be used.

The content of component B is preferably 20 to 70 parts by weight, preferably 30 to 70 parts by weight, more preferably 35 to 65 parts by weight, and more preferably 40 to 100 parts by weight of component A and B. 60 parts by weight is particularly preferred. When the content of the component B is too low, drug resistance will not easily occur, and if the content of the component B is too large, it may cause a decrease in good mechanical properties, flame retardancy and stain resistance.

(Component C: a compound rubber formed from a component containing polyorganosiloxane rubber and alkyl (meth)acrylate rubber, having a monomer unit of an aromatic alkenyl compound and a monomer of alkyl (meth)acrylate compound (Graft copolymers of core-shell structure obtained by graft polymerization of at least one kind of units selected from the group of body units) In the resin composition of the present invention, component C contains: in a composite rubber formed from components containing polyorganosiloxane rubber and alkyl (meth)acrylate rubber, it has a monomer unit composed of an aromatic alkenyl compound and A graft copolymer of a core-shell structure obtained by graft polymerization of at least one unit selected from the group consisting of monomer units of alkyl (meth)acrylate compounds.

The rubber component of component C is a compound rubber component formed by components containing polyorganosiloxane rubber and alkyl (meth)acrylate rubber. Compound rubber refers to the rubber obtained by copolymerization of two kinds of rubber components, or the rubber that can not be separated to form a polymerized IPN structure in a complex manner. Also, from the viewpoint of antifouling properties, the proportion of polyorganosiloxane rubber in the rubber component is preferably 10% or more, and preferably 15% or more. The upper limit of the proportion of polyorganosiloxane rubber in the rubber component is not particularly limited, but it is generally 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, preferably 0.1 μm to 0.6 μm, and more preferably 0.15 μm to 0.5 μm in the weight average particle size good. When it is in the range of 0.05 μm to 0.8 μm, better impact resistance can be achieved, which is better.

The aromatic alkenyl compound graft-polymerized with the shell of the core-shell type graft polymer may be exemplified by styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, halogenated benzene Ethylene etc. The alkyl (meth)acrylate compound includes, for example, acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, and octyl acrylate, or methyl methacrylate and methacrylic acid. Alkyl methacrylate such as ethyl ester, butyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, etc.

From the viewpoint of affinity with aromatic polycarbonate resins, at least one unit selected from the group consisting of aromatic alkenyl compound monomer units and alkyl (meth)acrylate compound monomer units is combined with As a result of the graft polymerization of rubber, the good impact resistance possessed by the aromatic polycarbonate resin can be more effectively exerted, and as a result, the impact resistance of the resin composition can be improved.

Elastic polymer containing composite rubber formed from components containing polyorganosiloxane rubber and alkyl (meth)acrylate rubber, any of the polymerization methods of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization can be used It can be manufactured, wherein the copolymerization method can also be one-stage graft polymerization or multiple-stage graft polymerization. In addition, the by-products at the time of manufacture may also be a mixture of copolymers of graft components. In addition to the general emulsification polymerization method, the polymerization method may be a soap-free polymerization method using a starter such as potassium persulfate, a seed polymerization method, a two-stage swelling polymerization method, and the like. In addition, in the suspension polymerization method, the water phase and the monomer phase can be stored separately, and the two can be correctly supplied to the continuous disperser. The particle size can be controlled by the method of controlling the number of revolutions of the disperser. In the continuous manufacturing method, in an aqueous liquid having a dispersing ability, the monomer phase is passed through a small diameter orifice with a diameter of several to several tens of μm or a porous filter to control the particle size. . In the case of a core-shell type graft polymer, the core and the shell can be simultaneously supplied to the reaction in a one-stage or multi-stage manner.

Since this polymer is commercially available, it can be easily obtained. For example, Metablen S-2501 or S-2030, SX-005 whose core component is polysilicone-acrylate composite rubber and whose shell component is methyl methacrylate are the main components. The shell component is a trader of SRK-200A or SX-200R with acrylonitrile and styrene as the main components, etc.

The component C was not found to have chemical resistance and stain resistance when using graft copolymers other than the above graft copolymers.

The content of the component C is 3 to 15 parts by weight, preferably 4 to 12 parts by weight, and more preferably 5 to 10 parts by weight relative to 100 parts by weight of the components A and B in total. When the C component is added, the impact resistance, drug resistance and stain resistance can be further improved. When it is 15 parts by weight or less, a good appearance can be ensured.

(Component D: antifouling agent) The D component of the resin composition of the present invention contains an antifouling imparting agent. Specific examples of the antifouling imparting agent of the present invention include polysiloxane oil, polysiloxane colloid, polysiloxane resin fine particles, polyolefin, polysiloxane-modified polyolefin, wax, etc. Among them, it is effective In addition, the viewpoint of continuous stain resistance can be produced, and the use of polysiloxane colloid and polysiloxane modified polyolefin is particularly preferred.

The polysiloxane colloid used in the present invention is preferably a colloidal polyorganosiloxane with a molecular weight of more than 100,000. Polyorganosiloxane is a high molecular material with an organic group added to the structure where silicon atoms are bonded to other silicon atoms through oxygen atoms. The skeleton of the polyorganosiloxane may be linear, branched, or cyclic, or may be a mixture of these.

The structure of polyorganosiloxane can be exemplified by: polydimethylsiloxane, polymethylphenylsiloxane, polymethylhydrogenated silicone, aralkyl modified polydimethylsiloxane, poly Ether modified polydimethylsiloxane, alkyl modified polydimethylsiloxane, higher fatty acid modified polydimethylsiloxane, fluoroalkyl modified polydimethylsiloxane, amino modified polydimethyl Siloxane, epoxy modified polydimethylsiloxane, methanol modified polydimethylsiloxane, carboxy modified polydimethylsiloxane, phenol modified polydimethylsiloxane, silanol modified Polydimethylsiloxane, etc. These may be used alone or in combination of two or more. Among these, from the viewpoint of the balance between performance and cost, it is best to use polydimethylsiloxane.

When the molecular weight is above 100,000, extremely high viscosity will be formed. Therefore, from the viewpoint of improving handleability, it is better to use a masterbatch diluted with a thermoplastic resin. This substrate is a commercially available product, so it is easy to obtain. Examples include: MB50-315 of polycarbonate 50% matrix made by Toray Dow Corporation, BY27-001 of polypropylene 50% matrix, BY27-009 of polyester elastomer 50% matrix, etc. Market sellers.

In addition, in the present invention, polysiloxane-modified polyolefin can also be used. The polysiloxane-modified polyolefin is one in which a polyolefin-based resin and polyorganosiloxane form a chemical bond. Examples of polysiloxane-modified polyolefins include polyorganosiloxane grafted polyolefin resins. The polyolefin resin is a synthetic resin obtained by polymerizing or copolymerizing an olefin monomer having a radically polymerizable double bond. The olefin-based monomer is not particularly limited, and examples thereof include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 4-methyl- Α-olefins such as 1-pentene, or conjugated dienes such as butadiene and isoprene. The olefin-based monomer may be used alone or in combination of two or more. Polyolefin resins are not particularly limited, and examples include homopolymers of ethylene, copolymers of α-olefins other than ethylene and ethylene, homopolymers of propylene, and copolymerizations of α-olefins other than propylene and propylene Materials, homopolymers of butene, homopolymers or copolymers of conjugated dienes such as butadiene and isoprene, etc., and copolymerized with homopolymers of propylene and α-olefins other than propylene and propylene Good is better. Tejia is a homopolymer of propylene. The polyolefin resin may be used alone, or two or more kinds may be used in combination. In the present invention, from the viewpoint of versatility and rigidity, it is more preferable to use a polypropylene-based resin.

In addition, the skeleton of the polyorganosiloxane may be linear, branched, or cyclic, or a mixture of these. The structure of polyorganosiloxane can be exemplified by: polydimethylsiloxane, polymethylphenylsiloxane, polymethylhydrogenated silicone, aralkyl modified polydimethylsiloxane, poly Ether modified polydimethylsiloxane, alkyl modified polydimethylsiloxane, higher fatty acid modified polydimethylsiloxane, fluoroalkyl modified polydimethylsiloxane, amino modified polydimethyl Siloxane, epoxy modified polydimethylsiloxane, methanol modified polydimethylsiloxane, carboxy modified polydimethylsiloxane, phenol modified polydimethylsiloxane, silanol modified Polydimethylsiloxane, etc. These may be used alone or in combination of two or more. Among these, in terms of the balance between performance and cost, polydimethylsiloxane is the best user. Since this polymer is commercially available, it is easy to obtain. For example, the commercial names of BY27-201 or BY27-201C of polyorganosiloxane grafted polypropylene made by Toray Dow Co., Ltd. are available on the market.

The content of the component D is 0.5 parts by weight to 6.0 parts by weight, preferably 1.0 parts by weight to 5.0 parts by weight, and more preferably 1.5 parts by weight to 4.0 parts by weight with respect to a total of 100 parts by weight of the parts A and B. When the D component is 0.5 parts by weight or more, stain resistance can be produced. In addition, when the content of the D component is 4.0 parts by weight or less, the appearance defect caused by bleeding does not occur. In addition, when the above substrate is used, the content of the component D indicates the amount of the antifouling-imparting agent contained in the substrate.

(式中，X₁ 及X₂ 為相同或相異之下述通式(I)所表示之經芳香族取代的烷基)。

(式中，AL為碳數1～5之分支狀或直鏈狀之脂肪族烴基，Ar為苯基、萘基或蒽基，n表示1～3之整數，Ar可鍵結於AL之任意碳原子)。<<flame retardant polycarbonate resin composition>> In one embodiment of the present invention, the polycarbonate resin composition further contains the following flame retardant: (E) halogen flame retardant (component E), And (F) a phosphorus-based flame retardant (component F) having a structure represented by the following formula (1)

(In the formula, X ₁ and X ₂ are the same or different alkyl groups substituted with aromatic 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 phenyl, naphthyl or anthracenyl, n represents an integer of 1 to 3, and Ar may be bonded to any of AL carbon atom).

In applications such as electrical and electronic equipment, requirements for flame retardancy are increasing, and various flame retardant resin compositions have been proposed. However, at present, regardless of any proposal, in the current situation, it is still impossible to provide a flame-retardant polycarbonate resin composition that has mechanical properties, appearance, flame resistance, chemical resistance, stain resistance, and thermal stability.

The polycarbonate resin composition of the above embodiment of the present invention contains the above-mentioned components E and F as a flame retardant, so in addition to excellent mechanical properties, chemical resistance, stain resistance, and appearance, it is acceptable Meet a higher level of flame retardancy and thermal stability. Therefore, it can be widely used not only in outdoor/indoor, but also in residential equipment, building materials, living materials, infrastructure equipment, automotive, OA, EE, outdoor equipment, and other fields. use.

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

In formula (7), X is a bromine atom, and R is a C 1-4 alkylene group, a C 1-4 alkylene group, or -SO ₂ -. In addition, in the formula (7), R preferably represents methylidene, ethylidene, isopropylidene, and -SO ₂ -, and particularly preferably isopropylidene.

The brominated polycarbonate preferably has fewer residual chloroformate groups and has a terminal chlorine content of 0.3 ppm or less, and more preferably 0.2 ppm or less. The amount of terminal chlorine is to dissolve the sample in dichloromethane, then add 4-(p-nitrobenzyl)pyridine to react with terminal chlorine (terminal chloroformate), and then use an ultraviolet-visible spectrophotometer (U-3200 manufactured by Hitachi, Ltd.) Observed and measured. When the amount of terminal chlorine is 0.3 ppm or less, the thermal stability of the polycarbonate resin composition can be improved, and high-temperature molding can be performed. As a result, a resin composition having more excellent moldability can be provided.

In addition, the brominated polycarbonate is preferably the one with fewer residual hydroxyl ends. More specifically, the amount of terminal hydroxyl groups is preferably 0.0005 moles or less, and more preferably 0.0003 moles or less, relative to 1 mole of the structural unit of brominated polycarbonate. The amount of terminal hydroxyl groups can be obtained by dissolving the sample in heavy chloroform and then measuring by ¹ H-NMR method. This amount of terminal hydroxyl groups can make the thermal stability of the polycarbonate resin composition more upward, which is better.

The specific viscosity of the brominated polycarbonate is preferably in the range of 0.015 to 0.1, and more preferably in the range of 0.015 to 0.08. The specific viscosity of the brominated polycarbonate is calculated by the above-mentioned specific viscosity calculation formula used when calculating the viscosity average molecular weight of the polycarbonate resin of the component A of the present invention as described above.

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

In addition, the halogen-based flame retardant is generally used in combination with an antimony oxide compound to increase the flame retardancy of the resin composition. However, in the present invention, the thermal stability is significantly reduced, so it is not recommended.

(F component: phosphorus flame retardant) The phosphorus-based flame retardant of the present invention 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 alkyl groups substituted with aromatic groups 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. Specifically, AL is preferably an alkyl group represented by the following formula (8). In addition, Ar is phenyl, naphthyl or anthracenyl, and among them, phenyl is preferred. n is an integer of 1 to 3, and preferably 1 or 2. Ar can be bonded to any carbon atom of AL.

The organic phosphorus flame retardant represented by the above formula (1) has an excellent flame retardant effect on aromatic polyester resins. The organic phosphorus-based flame retardant, among the compounds represented by the aforementioned general formula (1), the most representative compound is at least one compound selected from the group consisting of the following formulas (Ba) to (Bd) . One type of these compounds may be used, or two or more types may be used.

Among 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) is more preferable from the viewpoint of the flame retardant effect or the ease of synthesis. In addition, when using a phosphorus-based flame retardant other than the phosphorus-based flame retardant, the amount added within the scope of the present invention does not cause flame retardancy.

In the present invention, the synthesis method of the organic phosphorus-based flame retardant may be synthesized using a known method, or may be prepared using a method other than the method described below.

Organophosphorus flame retardants, for example: can react pentaerythritol with phosphorus trichloride, then treat the oxidized reactants with alkali metal compounds such as sodium methoxide, and then react with aralkyl halide to prepare Get. Alternatively, a method of reacting pentaerythritol with aralkylphosphonic acid dichloride, or a compound obtained by reacting pentaerythritol with phosphorus trichloride, and then reacting with aralkyl alcohol, followed by high temperature Arbuzov transfer and other methods. The content of the latter reaction is disclosed in, for example, U.S. Patent No. 3,141,032, JP-A-S 54-157156, and JP-S-53-39698.

The specific synthesis method will be described as follows, but it is only for explaining the synthesis method. The organophosphorus flame retardant used in the present invention is not limited to these synthesis methods, and it can be changed or other synthesis methods can be used. Any method for synthesis can be used. A more specific synthesis method will be described in Production Example 1 described later. (i) The organophosphorus compound of (B-a) above; The pentaerythritol is reacted with phosphorus trichloride, and then the reactant obtained by oxidation of tri-butanol is treated with sodium methoxide and then reacted with benzyl bromide. (ii) The organophosphorus compound of (B-b) above; Pentaerythritol is reacted with phosphorus trichloride, and then the reactant obtained by oxidation of tri-butanol is treated with sodium methoxide and then reacted with 1-bromoethylbenzene. (iii) the organophosphorus compound of (B-c) above; The pentaerythritol is reacted with phosphorus trichloride, and then the reactant obtained by oxidation of tri-butanol is treated with sodium methoxide and then reacted with 2-bromoethylbenzene. (iv) the organophosphorus compound of (B-d) above; It is prepared by reacting pentaerythritol with benzhydrylphosphonate dichloride.

The acid value of the organic phosphorus-based flame retardant is preferably 0.7 mgKOH/g or less, and more preferably 0.5 mgKOH/g or less. When an organic phosphorus-based flame retardant having an acid value in this range is used, it is hard to cause decomposition of the polyester resin and has good thermal stability, so it is a composition with good processability. The organic phosphorus-based flame retardant is preferably the one having an acid value of 0.4 mgKOH/g or less. The acid value here means the amount (mg) of KOH that must be used to neutralize the acid component in 1 g of the sample. When the acid value is 0.7 mgKOH/g or less, it is better because it can ensure good thermal stability and has excellent processability.

In addition, the purity of HPLC of the organic phosphorus flame retardant is preferably 90% or more, and more preferably 95% or more. Those with high purity can make the shaped products have excellent flame retardancy or hue. Among them, the HPLC purity measurement of the F component can be effectively measured using the following method. The column was made by Nomura Chemical Co., Ltd. Develosil ODS-7 300mm×4mmφ, and the column temperature was set to 40°C. The solvent is a 6:4 (volume ratio) mixed solution using acetonitrile and water, and 5 μl is injected. The detector uses UV-260nm. The method of removing impurities in the F component is not particularly limited. Generally, the method of repulping and washing using solvents such as water and methanol (repeatedly using a solvent to wash and filter several times) is the most suitable method. It has an effect and is also advantageous in terms of cost.

The content of the component F 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 to 3 parts by weight with respect to the total 100 parts by weight of the parts A and B. . When the content of the F component is 0.5 parts by weight or more, flame retardancy is produced, and when the content is 5 parts by weight or less, good mechanical properties, appearance, and drug resistance can be ensured.

(G ingredient: anti-salivation agent) The resin composition of the present invention may contain an anti-salivating agent as a G component. When this anti-salivation agent is contained, good flame retardancy can be achieved without damaging the physical properties of the molded product.

The anti-salivation agent of the G component may be exemplified by a fluoropolymer having the ability to form filaments. The polymer may be, for example, polytetrafluoroethylene or a tetrafluoroethylene copolymer (e.g. tetrafluoroethylene/hexafluoropropylene) Copolymers, etc.), partially fluorinated polymers disclosed in US Patent No. 4379910, polycarbonate resins prepared from fluorinated diphenols, and the like. Among them, polytetrafluoroethylene (hereinafter, also referred to as PTFE) is preferred.

The molecular weight of PTFE having the ability to form fibrils is extremely high molecular weight, and tends to bond PTFE to each other to form a fibrous shape due to external action such as shearing force. The molecular weight is a number average molecular weight calculated from the standard specific gravity of 1 million to 10 million, more preferably 2 million to 9 million. In addition to the solid shape, the PTFE may be in the form of an aqueous dispersion. In addition, PTFE having the ability to form filaments can improve the dispersibility in the resin, and has good flame retardancy and mechanical properties. It is also possible to use a PTFE mixture in a mixed form with other resins.

The commercially available products of PTFE having the ability to form filaments include, for example, Teflon (registered trademark) 6J of Mitsui DuPont Fluorochemicals Co., Ltd., and Teflon MPA FA500 and F-201L of Daikin Industries Co., Ltd., etc. Commercial products of PTFE aqueous dispersions, such as Asahi ICI Fluoropolymer Co., Ltd. Fruon AD-1, AD-936, Daikin Industries Co., Ltd. Fruon D-1 and D-2, Mitsui Dupont Teflon (registered trademark) 30J manufactured by Fluorochemicals Co., Ltd. is the representative.

PTFE in mixed form can be obtained by the following method, for example: (1) A method of preparing a co-agglomeration mixture by mixing an aqueous dispersion of PTFE with an aqueous dispersion or solution of an organic polymer and performing co-precipitation (Japanese Patent Laid-Open No. 60-258263, Japanese Patent Laid-Open No. 63-154744) The method described in the bulletin), (2) A method of mixing an aqueous dispersion of PTFE with dried organic polymer particles (method described in Japanese Patent Laid-Open No. 4-272957), (3) A method of uniformly mixing an aqueous dispersion of PTFE and an organic polymer particle solution, and simultaneously removing individual solvents from the mixture (methods described in JP-A 06-220210, JP-A 08-188653, etc.) ), (4) A method for polymerizing an organic polymer-forming monomer in an aqueous dispersion of PTFE (method described in Japanese Patent Laid-Open No. 9-95583), and (5) After uniformly mixing the aqueous dispersion of PTFE and the organic polymer dispersion, and then polymerizing vinyl monomers in the mixed dispersion, a method of preparing a mixture (the method described in JP-A-11-29679 etc.) ). The commercially available products of these mixed forms of PTFE include, for example, "Metablen A3800" (trade name) of Mitsubishi Rayon Co., Ltd., and "BLENDEX B449" (trade name) manufactured by GE Special Chemicals.

The proportion of PTFE in the mixed form is preferably 100% by weight to 60% by weight of PTFE in 100% by weight of the PTFE mixture, and more preferably 5% to 55% by weight. When the ratio of PTFE is within this range, PTFE can achieve good dispersibility. In addition, the ratio of the above-mentioned G component is the amount of the anti-salivating agent actually used, and in the case of the mixed form of PTFE, it is the actual amount of PTFE.

The content of the G component is preferably 0.05 to 2 parts by weight, more preferably 0.1 to 1.5 parts by weight, and particularly preferably 0.2 to 1 part by weight relative to 100 parts by weight of the total of the A and B components. . When the anti-salivation agent is slightly outside the above range, the flame retardancy may be insufficient. On the other hand, if the anti-salivation agent greatly exceeds the above range, not only does PTFE precipitate on the surface of the molded product and causes a poor appearance, but it also increases the cost of the resin composition, which is not good.

In addition, in the organic polymer used in the polytetrafluoroethylene-based mixture of the present invention, the styrene-based monomer used is an alkyloxy group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. The styrene substituted by one or more groups selected from the group consisting of a group and a halogen can be exemplified by o-methylstyrene, m-methylstyrene, p-methylstyrene, dimethyl Styrene, ethyl-styrene, p-tert-butylstyrene, methoxystyrene, fluorostyrene, monobromostyrene, dibromostyrene, and tribromostyrene, ethylene xylene, ethylene naphthalene Etc., but not limited to these ingredients. The aforementioned styrene-based monomers may be used alone or in combination of two or more kinds.

In the organic polymer used in the polytetrafluoroethylene-based mixture of the present invention, the acrylic monomer used includes a (meth)acrylate derivative that may be substituted. Specifically, the aforementioned acrylic monomers include, for example, those selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, aryl groups, and glycidyl groups. (Meth)acrylate derivatives substituted with more than one group, for example: (meth)acrylonitrile, meth (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate , Butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth) Octyl acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate and glycidyl (meth) acrylate; alkyl groups with 1 to 6 carbon atoms, Or aryl substituted maleimide, such as: maleimide, N-methyl-maleimide and N-phenyl-maleimide, maleic acid, phthalic acid Formic acid and itaconic acid are not limited to these contents. The aforementioned acrylic monomers may be used alone or in combination of two or more kinds. Among these, (meth)acrylonitrile is preferred.

In the organic polymer used in the coating layer, the amount of the unit derived from the acrylic monomer is preferably 8 to 11 parts by weight relative to 100 parts by weight of the unit derived from the styrene monomer. More preferably, it is 8 to 10 parts by weight, and particularly preferably 8 to 9 parts by weight. When the unit of the acrylic monomer is 8 parts by weight or more, the coating strength can be ensured, and when it is 11 parts by weight or less, the molded article can have a good surface appearance.

The polytetrafluoroethylene-based mixture of the present invention preferably has a residual moisture content of 0.5% by weight or less, more preferably 0.2% by weight to 0.4% by weight, and particularly 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 production step of the polytetrafluoroethylene-based mixture of the present invention, in the presence of an initiator, one or more monomers selected from the group consisting of styrene-based monomers and acrylic monomers are included The step of forming the coating layer of the body on the outside of the branched Teflon. In addition, after the coating layer forming step is included, the residual moisture content is 0.5% by weight or less, preferably 0.2% by weight to 0.4% by weight, more preferably 0.1% by weight to 0.3% by weight. The steps are better. For the drying step, for example, a hot air drying method or a vacuum drying method can be used, and the method is well-known in the industry.

The initiator used in the polytetrafluoroethylene-based mixture of the present invention is not particularly limited as long as it is used by the user during the polymerization reaction of styrene-based and/or acrylic-based monomers. Examples of the aforementioned initiator include cumene hydroperoxide, di-tert-butyl peroxide, benzoyl peroxide, hydrogen peroxide, and potassium peroxide, but are not limited to these. content. In the polytetrafluoroethylene-based mixture of the present invention, one or more of the aforementioned initiators can be used in accordance with the reaction conditions. The amount of the aforementioned initiator can be freely selected within the usable range after considering the amount of polytetrafluoroethylene and the type/quantity of the monomer. Generally, when the amount of the entire composition is used as the basis, 0.15 weight is used Parts to 0.25 parts by weight is preferred.

The polytetrafluoroethylene-based mixture of the present invention can be produced in the following order using the suspension polymerization method.

First, after dispersing water and branched polytetrafluoroethylene (solid concentration: 60%, polytetrafluoroethylene particle size: 0.15 to 0.3 μm) into the reactor, add acrylic monomer, styrene monomer and Cumene hydroperoxide as a water-soluble starter was reacted at 80°C to 90°C for 9 hours. After the reaction, centrifugal separation was carried out using a centrifuge for 30 minutes, and the water was removed to obtain a paste-like product. Subsequently, the paste product was dried for 8 hours using a hot air dryer at 80°C to 100°C. Subsequently, the dried product is pulverized to obtain the polytetrafluoroethylene-based mixture of the present invention.

Since this suspension polymerization method does not need to perform the polymerization step using emulsion dispersion in the emulsion polymerization method exemplified in Patent No. 3469391, etc., there is no need to use an emulsifier and electrolyte salts that solidify and precipitate the latex after polymerization. In addition, in the conventional polytetrafluoroethylene mixture manufactured by the emulsion polymerization method, since the mixture is easily mixed with emulsifiers and electrolyte salts and is not easily removed, it is difficult to reduce the sodium metal produced by the emulsifiers, electrolyte salts, etc. Ions, potassium metal ions, etc. However, when the polytetrafluoroethylene mixture used in the present invention is produced by the suspension polymerization method, since the emulsifier and electrolyte salt are not used, sodium metal ions and potassium metal ions in the mixture can be reduced, and can be increased Thermal stability and hydrolysis resistance.

In addition, in the present invention, coated branched PTFE as an anti-salivating agent may also be used. The coated branched PTFE is a polytetrafluoroethylene-based mixture formed of branched polytetrafluoroethylene particles and an organic polymer, and has an organic polymer outside the branched polytetrafluoroethylene, preferably containing A coating layer formed of a polymer produced by a styrene-based monomer and/or an acrylic monomer-based unit. The aforementioned coating layer is formed on the surface of the branched polytetrafluoroethylene. In addition, the coating layer is preferably a copolymer containing a styrene monomer and an acrylic monomer.

The polytetrafluoroethylene contained in the coated branched PTFE is branched polytetrafluoroethylene. When the contained polytetrafluoroethylene is not branched polytetrafluoroethylene, if the polytetrafluoroethylene is added too little, the effect of preventing dripping will be insufficient. The branched polytetrafluoroethylene is in the form of particles, preferably 0.1 μm to 0.6 μm, more preferably 0.3 μm to 0.5 μm, and particularly preferably 0.3 μm to 0.4 μm. When the particle size is less than 0.1 μm, although the molded article can have an excellent surface appearance, it is difficult to obtain polytetrafluoroethylene having a particle size of less than 0.1 μm commercially. In addition, when the particle size is 0.6 μm or less, a good surface appearance of the molded product can be ensured. The number average molecular weight of the polytetrafluoroethylene used in the present invention is preferably from 1×10 ⁴ to 1×10 ⁷ , more preferably from 2×10 ⁶ to 9×10 ^6. Generally speaking, high molecular weight polytetrafluoroethylene is used In the case of vinyl fluoride, the stability point of view is better. It can be in any form of powder or dispersion.

The content of branched polytetrafluoroethylene in the coated branched PTFE is preferably from 20 parts by weight to 60 parts by weight, more preferably from 40 parts by weight to 55 parts by weight relative to the total weight of the coated branched PTFE by 100 parts by weight, particularly preferably It is 47 parts by weight to 53 parts by weight, most 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 branched polytetrafluoroethylene is within this range, the branched polytetrafluoroethylene can achieve good dispersibility.

(Other additives) (i) Phosphorus stabilizer Phosphorus-based stabilizers include, for example, phosphorous acid, phosphoric acid, hypophosphorous acid, phosphonic acid, and esters thereof, and tertiary phosphine.

Specific examples of the phosphite compound include triphenyl phosphite, tri(nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, and tri-octadecane Phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl di Phenyl phosphite, monooctyl diphenyl phosphite, tri(diethylphenyl) phosphite, tri(di-iso-propylphenyl) phosphite, tri(di-n-butyl Phenyl)phosphite, tri(2,4-di-tert-butylphenyl)phosphite, tri(2,6-di-tert-butylphenyl)phosphite, distearyl Pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite Phosphate, bis(2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis{2,4-bis(1-methyl-1-phenylethyl)benzene }Pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite, etc.

In addition, for other phosphite compounds, those having a cyclic structure obtained by reaction with divalent phenols can also be used. Examples include: 2,2'-methylidene bis(4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2'- Methylidene bis(4,6-di-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, and 2,2-methylidene bis(4,6 -Di-tert-butylphenyl)octyl phosphite and the like.

Phosphate compounds, such as: tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresol Phosphate, diphenyl monophosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, etc., preferably triphenyl phosphate, tris Methyl phosphate.

Phosphonate compounds, such as: tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonate, tetrakis(2,4-di-tert-butyl Phenyl)-4,3'-biphenylene diphosphonate, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonate, tetra (2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphonate, tetrakis(2,6-di-tert-butylphenyl)-4,3'- Biphenyl bisphosphonate, tetrakis(2,6-di-tert-butylphenyl)-3,3'-bibiphenyl bisphosphonate, bis(2,4-di-tert-butyl Phenyl)-4-phenyl-phenylphosphonate, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonate, bis(2,6-di -n-butylphenyl)-3-phenyl-phenylphosphonate, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonate, bis(2 ,6-di-tert-butylphenyl)-3-phenyl-phenylphosphonate, etc., and tetra(di-tert-butylphenyl)-biphenyl bisphosphonate, bis( Di-tert-butylphenyl)-phenyl-phenylphosphonate is preferred, tetra(2,4-di-tert-butylphenyl)-biphenylene diphosphonate, bis(2, 4-Di-tert-butylphenyl)-phenyl-phenylphosphonate is preferred. This phosphonate compound is preferably used in combination with the above phosphite compound having two or more alkyl substituted aryl groups.

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

Tertiary phosphines, such as: triethyl phosphine, tripropyl phosphine, tributyl phosphine, trioctyl phosphine, tripentyl phosphine, dimethyl phenyl phosphine, dibutyl Phenyl phosphin, diphenylmethyl phosphin, diphenyloctyl phosphin, triphenyl phosphin, tri-p-tolyl phosphin, trinaphthyl phosphin, diphenyl benzyl phosphin, etc. . A particularly preferred tertiary phosphin, such as triphenyl phosphin.

The phosphorus-based stabilizer can be used alone or in combination of two or more. Among the phosphorus-based stabilizers, a phosphonate compound or a phosphite compound represented by the following general formula (9) is preferred.

(式(9)中，R及R’表示碳數6～30之烷基或碳數6～30之芳基，其可相互為相同亦可、相異亦可)。

(In 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, which may be the same or different from each other).

As mentioned above, the phosphonate compound is preferably tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphonate. The stabilizer as a main component can be used Any one of commercially available Sandostab P-EPQ (trademark, manufactured by Clariant) and Irgafos P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS).

In addition, in the above formula (9), preferred phosphite compounds include, for example, distearyl pentaerythritol diphosphite and bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite Ester, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and bis{2,4-bis(1-methyl-1-phenylethyl)benzene Radical} pentaerythritol diphosphite.

Distearyl pentaerythritol diphosphite can be any of the commercially available ADEKASTAB PEP-8 (trademark, manufactured by Asahi Kasei Chemical Industry Co., Ltd.) and JPP681S (trademark, manufactured by Seongbuk Chemical Industry Co., Ltd.). Bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, ADEKASTAB PEP-24G (trademark, manufactured by Asahi Kasei Chemical Industry Co., Ltd.), Alkanox P-24 (trademark, manufactured by Great Lakes) ), Ultranox P626 (trademark, manufactured by GE Specialty Chemicals), Doverphos S-9432 (trademark, manufactured by Dover Chemical), and Irgaofos126 and 126FF (trademark, manufactured by CIBA SPECIALTY CHEMICALS), etc. Bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is sold under the name of ADEKASTAB PEP-36 (trademark, manufactured by Asahi Kasei Chemical Industry Co., Ltd.) and is easy to use. In addition, for bis{2,4-bis(1-methyl-1-phenylethyl)phenyl}pentaerythritol diphosphite, ADEKASTAB PEP-45 (trademark, manufactured by Asahi Kasei Chemical Industry Co., Ltd.), and Doverphos S-9228 (trademark, manufactured by Dover Chemical) is any commercially available product.

The phosphorus-based stabilizer can be used alone or in combination of two or more. The content of the phosphorus-based stabilizer is 0.01 parts by weight to 1.0 parts by weight, more preferably 0.03 parts by weight to 0.8 parts by weight, and particularly preferably 0.05 parts by weight to 0.5 parts by weight with respect to 100 parts by weight of the components A and B in total. Copies. When the content is 0.01 parts by weight or more, a thermal decomposition suppression effect is produced during processing, and good mechanical properties are ensured, and when it is 1.0 parts by weight or less, good mechanical properties are ensured.

、N,N’-伸六甲基雙-(3,5-二-tert-丁基-4-羥基氫化苯丙醛)、N,N’-雙[3-(3,5-二-tert-丁基-4-羥基苯基)丙醯基]肼、1,1,3-三(2-甲基-4-羥基-5-tert-丁基苯基)丁烷、1,3,5-三甲基-2,4,6-三(3,5-二-tert-丁基-4-羥基苄基)苯、三(3,5-二-tert-丁基-4-羥基苯基)異三聚氰酸酯、三(3,5-二-tert-丁基-4-羥基苄基)異三聚氰酸酯、1,3,5-三(4-tert-丁基-3-羥基-2,6-二甲基苄基)異三聚氰酸酯、1,3,5-三2[3(3,5-二-tert-丁基-4-羥基苯基)丙醯氧基]乙基異三聚氰酸酯、四[伸甲基-3-(3,5-二-tert-丁基-4-羥基苯基)丙酸酯]甲烷、三乙二醇-N-雙-3-(3-tert-丁基-4-羥基-5-甲基苯基)丙酸酯、三乙二醇-N-雙-3-(3-tert-丁基-4-羥基-5-甲基苯基)乙酸酯、3,9-雙[2-{3-(3-tert-丁基-4-羥基-5-甲基苯基)乙醯氧基}-1,1-二甲基乙基]-2,4,8,10-四氧雜螺[5,5]十一烷、四[伸甲基-3-(3-tert-丁基-4-羥基-5-甲基苯基)丙酸酯]甲烷、1,3,5-三甲基-2,4,6-三(3-tert-丁基-4-羥基-5-甲基苄基)苯，及三(3-tert-丁基-4-羥基-5-甲基苄基)異三聚氰酸酯等。上述化合物之中，又以四[伸甲基-3-(3-tert-丁基-4-羥基-5-甲基苯基)丙酸酯]甲烷、十八烷基-3-(3,5-二-tert-丁基-4-羥基苯基)丙酸酯為較佳使用者，又，具有可抑制加工時的熱分解所造成的機械特性降低之觀點，又以使用下述式(10)所表示之(3,3’,3’’,5,5’,5’’-六-tert-丁基-a,a’,a’’-(三甲苯-2,4,6-三基)三-p-甲酚，及下述式(11)所表示之1,3,5-三-(3,5-二-tert-丁基-4-羥基苄基)-1,3,5-三

-2,4,6(1H,3H,5H)-三酮為更佳。(ii) Phenol-based stabilizer The resin composition of the present invention may contain a phenol-based stabilizer. Phenolic stabilizers generally include, for example, hindered phenol, semi hindered phenol, and less hindered phenol compounds. For polypropylene-based resins, heat can be applied. From the viewpoint of stability, hindered phenol compounds are more suitable for use. Examples of the hindered phenol compound include: α-tocopherol, butylhydroxytoluene, erucyl alcohol, vitamin E, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) Propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di -tert-butyl-4-(N,N-dimethylaminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-extrin Methyl bis (4-methyl-6-tert-butanol), 2,2'-methyl bis (4-ethyl-6-tert-butanol), 4,4'-methyl bis ( 2,6-di-tert-butanol), 2,2'-methylidene bis(4-methyl-6-cyclohexanol), 2,2'-dimethylene-bis(6-α- Methyl-benzyl-p-cresol), 2,2'-ethylene-bis (4,6-di-tert-butanol), 2,2'-butylene-bis (4-methyl- 6-tert-butanol), 4,4'-butylene bis(3-methyl-6-tert-butanol), 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-tetraoxy Heterospiro[5,5]undecane, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert -Butanol), 2,2'-thiobis(4-methyl-6-tert-butanol), bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4 ,4'-di-thiobis (2,6-di-tert-butanol), 4,4'-tri-thiobis (2,6-di-tert-butanol), 2,2-sulfur Substituted ethylidene bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis(n-octylthio)-6-( 4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-tri

, N,N'-hexahexamethylbis-(3,5-di-tert-butyl-4-hydroxyhydrophenylpropionaldehyde), N,N'-bis[3-(3,5-di-tert -Butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5 -Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl) ) Isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(4-tert-butyl-3 -Hydroxy-2,6-dimethylbenzyl)isocyanurate, 1,3,5-tris 2(3(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide Oxy]ethyl isocyanurate, tetra[methylidene-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)acetoxy}-1, 1-Dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, tetrakis[methyl-3-(3-tert-butyl-4-hydroxy- 5-methylphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)benzene , And tris(3-tert-butyl-4-hydroxy-5-methylbenzyl) isocyanurate, etc. Among the above compounds, tetra[methyl-3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, octadecyl-3-(3, 5-Di-tert-butyl-4-hydroxyphenyl) propionate is a preferred user, and has the viewpoint of suppressing the degradation of mechanical properties caused by thermal decomposition during processing, and uses the following formula ( 10) represented by (3,3',3'',5,5',5''-hexa-tert-butyl-a,a',a''-(trimethylbenzene-2,4,6- Triyl) tri-p-cresol, and 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3 represented by the following formula (11) ,5-three

-2,4,6(1H,3H,5H)-trione is better.

The above phenolic stabilizers can be used alone or in combination of two or more. The content of the phenolic stabilizer is 0.05 parts by weight to 1.0 parts by weight, more preferably 0.07 parts by weight to 0.8 parts by weight, and particularly preferably 0.1 parts by weight to 0.5 parts by weight relative to 100 parts by weight of the components A and B in total. Copies. When the content is 0.05 parts by weight or more, it can have an effect of suppressing thermal decomposition during processing, and can ensure good mechanical properties, and when it is 1.0 parts by weight or less, it can also ensure good mechanical properties.

The phosphorus-based stabilizer and the phenol-based stabilizer are preferably added either, and it is more preferable to use these in combination. When used in combination, it is preferred to use 0.01 parts by weight to 0.5 parts by weight of a phosphorus stabilizer and 0.01 parts by weight to 0.5 parts by weight of a phenolic stabilizer relative to 100 parts by weight of the components A and B in total.

(iii) UV absorber The polycarbonate resin composition of the present invention may contain an ultraviolet absorber. Ultraviolet absorbers, such as benzophenone series, include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxy Benzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonylbenzophenone, 2-hydroxy-4-methoxy-5 -Sulfonyl trihydride 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 sulfonyl benzophenone, bis(5 -Benzyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2' -Carboxybenzophenone, etc.

-4-酮)，及2-[2-羥基-3-(3,4,5,6-四氫呋喃基醯亞胺甲基)-5-甲基苯基]苯併三唑，及2-(2’-羥基-5-甲基丙烯醯氧基乙基苯基)-2H-苯併三唑，與可與該單體共聚的乙烯系單體之共聚物，或2-(2’―羥基-5-丙烯醯氧基乙基苯基)―2H―苯併三唑，與可與該單體共聚的乙烯系單體之共聚物等的具有2-羥基苯基-2H-苯併三唑骨架之聚合物等。Examples of the benzotriazole system include 2-(2-hydroxy-5-methylphenyl)benzotriazole and 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'-methylidene bis(4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl) Phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5 -Chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-pentylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzene Pentatriazole, 2-(2-hydroxy-5-tert-butylphenyl) benzotriazole, 2-(2-hydroxy-4-octyloxyphenyl) benzotriazole, 2,2'- Phenylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzox

-4-one), and 2-[2-hydroxy-3-(3,4,5,6-tetrahydrofuranylimidemethyl)-5-methylphenyl]benzotriazole, and 2-( 2'-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole, copolymer with vinyl monomer copolymerizable with this monomer, or 2-(2'-hydroxyl -5-Acryloyloxyethylphenyl)-2H-benzotriazole, copolymer with ethylene monomer copolymerizable with this monomer, etc. with 2-hydroxyphenyl-2H-benzotriazole Skeleton polymer, etc.

系中，可列舉如：2-(4,6-二苯基-1,3,5-三

-2-基)-5-己氧基酚、2-(4,6-二苯基-1,3,5-三

-2-基)-5-甲基氧酚、2-(4,6-二苯基-1,3,5-三

-2-基)-5-乙基氧酚、2-(4,6-二苯基-1,3,5-三

-2-基)-5-丙基氧酚，及2-(4,6-二苯基-1,3,5-三

-2-基)-5-丁基氧酚等。又如2-(4,6-雙(2,4-二甲基苯基)-1,3,5-三

-2-基)-5-己氧基酚等上述例示化合物中之苯基為2,4-二甲基苯基之化合物等。Hydroxyphenyl tri

In the system, for example: 2-(4,6-diphenyl-1,3,5-tri

-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5-tri

-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-tri

-2-yl)-5-ethyloxyphenol, 2-(4,6-diphenyl-1,3,5-tri

-2-yl)-5-propyloxyphenol, and 2-(4,6-diphenyl-1,3,5-tri

-2-yl)-5-butyloxyphenol etc. Another example is 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-tri

-2-yl)-5-hexyloxyphenol, etc. Among the compounds exemplified above, the phenyl group is a compound such as 2,4-dimethylphenyl.

-4-酮)、2,2’-m-伸苯基雙(3,1-苯併噁

-4-酮)，及2,2’-p,p’-二伸苯基雙(3,1-苯併噁

-4-酮)等。Cyclic imine (acid) esters, for example: 2,2'-p-phenylene bis(3,1-benzox

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

-4-one), and 2,2'-p,p'-biphenylene bis(3,1-benzox

-4-one) etc.

In the cyanoacrylate system, for example: 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano -3,3-diphenylpropenyl)oxy]methyl)propane, and 1,3-bis-[(2-cyano-3,3-diphenylpropenyl)oxy]benzene, etc.

骨架、環狀亞胺酯骨架，及氰基丙烯酸酯骨架之化合物為較佳之例示。In addition, since the above-mentioned ultraviolet absorber has a structure of a monomer compound capable of undergoing radical polymerization, it may also be the ultraviolet-absorbing monomer and/or the light-stabilizing monomer, and monomers such as alkyl (meth)acrylate Polymer-type ultraviolet absorber obtained by copolymerization. The aforementioned ultraviolet absorbing monomer contains a benzotriazole skeleton, a benzophenone skeleton, and a

Compounds of skeleton, cyclic imide skeleton, and cyanoacrylate skeleton are preferred examples.

Among the above compounds, the compound represented by any one of the following formulas (12), (13), and (14) of the present invention is more suitable for users.

The above ultraviolet absorbers may be used alone or in combination of two or more. The content of the ultraviolet absorber is preferably 0.1 to 2 parts by weight, more preferably 0.12 to 1.5 parts by weight, and particularly preferably 0.15 to 1 part by weight with respect to 100 parts by weight of the components A and B in total. . When the content of the ultraviolet absorber is 0.1 parts by weight or more, sufficient light resistance can be produced, and when it is 2 parts by weight or less, phenomena such as poor appearance or deterioration of physical properties due to gas generation can be avoided, which is preferable.

-2-基)-4,7-二氮雜癸烷-1,10-二胺、二丁胺・1,3,5-三

・N,N’-雙(2,2,6,6-四甲基-4-哌啶基)-1,6-伸六甲基二胺與N-(2,2,6,6-四甲基-4-哌啶基)丁胺之聚縮合物、聚[{6-(1,1,3,3-四甲基丁基)胺基-1,3,5-三

-2,4-二基}{(2,2,6,6-四甲基-4-哌啶基)亞胺}伸六甲基{(2,2,6,6-四甲基-4-哌啶基)亞胺}]、四(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯、四(1,2,2,6,6-五甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯、三(2,2,6,6-四甲基-4-哌啶基)-苯-1,3,4-三羧酸酯、1-[2-{3-(3,5-二-t-丁基-4-羥基苯基)丙醯氧基}丁基]-4-[3-(3,5-二-t-丁基-4-羥基苯基)丙醯氧基]2,2,6,6-四甲基哌啶，及1,2,3,4-丁烷四羧酸與1,2,2,6,6-五甲基-4-哌啶醇與β,β,β’,β’-四甲基-3,9-[2,4,8,10-四氧雜螺(5,5)十一烷]二乙醇之縮合物等。(iv) Hindered amine light stabilizers The polycarbonate resin composition of the present invention may contain a hindered amine light stabilizers. Hindered amine light stabilizers, generally known as HALS (Hindered Amine Light Stabilizer), compounds with 2,2,6,6-tetramethylpiperidine skeleton in the structure, which can be exemplified by: 4-acetoxy- 2,2,6,6-tetramethylpiperidine, 4-stearyl-2,2,6,6-tetramethylpiperidine, 4-propenyloxy-2,2,6,6-tetra Methylpiperidine, 4-(phenylacetoxy)-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine Pyridine, 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-tetramethyl Piperidine, 4-(ethylaminemethyloxy)-2,2,6,6-tetramethylpiperidine, 4-(cyclohexylaminemethyloxy)-2,2,6,6-tetra Methylpiperidine, 4-(anilinemethyloxy)-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidinyl)carbonate Ester, bis(2,2,6,6-tetramethyl-4-piperidinyl) oxide, bis(2,2,6,6-tetramethyl-4-piperidinyl) malonate, Bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl) adipate, Bis(2,2,6,6-tetramethyl-4-piperidinyl) terephthalate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)carbonate Ester, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) oxide, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)propane Diester, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-pipe Pyridyl) adipate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) terephthalate, N,N'-bis-2,2,6, 6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxyamide, 1,2-bis(2,2,6,6-tetramethyl-4-piperidinyloxy)ethane, α,α'-bis(2,2,6,6-tetramethyl-4-piperidinyloxy)-p-xylene, bis(2,2,6,6-tetramethyl-4-piperidine Tolyl-2,4-diamine formate, bis(2,2,6,6-tetramethyl-4-piperidinyl)-hexamethylene-1,6-diamine formate, Tris(2,2,6,6-tetramethyl-4-piperidinyl)-benzene-1,3,5-tricarboxylic acid ester, N,N',N'',N'''-tetra- (4,6-bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-tri

-2-yl)-4,7-diazadecane-1,10-diamine, dibutylamine, 1,3,5-tri

・N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexahexamethylenediamine and N-(2,2,6,6-tetra Methyl-4-piperidinyl)butylamine polycondensate, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-tri

-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imine}hexamethylene{(2,2,6,6-tetramethyl-4 -Piperidinyl)imine}), tetra(2,2,6,6-tetramethyl-4-piperidinyl)-1,2,3,4-butane tetracarboxylate, tetra(1, 2,2,6,6-pentamethyl-4-piperidinyl)-1,2,3,4-butane tetracarboxylate, tri(2,2,6,6-tetramethyl-4- Piperidinyl)-benzene-1,3,4-tricarboxylic acid ester, 1-[2-{3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoyloxy}butane Group]-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy] 2,2,6,6-tetramethylpiperidine, and 1,2, 3,4-butane tetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and β,β,β',β'-tetramethyl-3,9-[2 , 4,8,10-tetraoxaspiro(5,5)undecane] diethanol condensate, etc.

Hindered amine light stabilizers can be divided into NH type (nitrogen atom bonded hydrogen), NR type (nitrogen atom bonded alkyl (R)), N- OR type (nitrogen-bonded alkoxy group (OR)) and other three forms. When polycarbonate resin is generally used, from the viewpoint of the basicity of the hindered amine light stabilizer, use the low basicity NR type, N -OR type is better.

Among the above compounds, in the present invention, compounds represented by the following formulas (15) and (16) are more suitable for use.

The hindered amine light stabilizer can be used alone or in combination of two or more. The content of the hindered amine light stabilizer is relative to 100 parts by weight of component A and component B in total, preferably 0 parts by weight to 1 part by weight, preferably 0.05 parts by weight to 1 part by weight, more preferably 0.08 parts by weight ~0.7 parts by weight, 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, it is preferable because it can avoid appearance defects due to gas generation or deterioration of physical properties due to decomposition of the polycarbonate resin. Moreover, when it is 0.05 weight part or more, sufficient light resistance can be obtained.

(v) Release agent In the polycarbonate resin composition of the present invention, it is preferable to add a release agent for the purpose of improving productivity during molding or reducing deformation of molded products. Well-known ingredients can be used for this release agent. Examples include: saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes (polyethylene wax, 1-olefin polymers, etc. those modified by compounds containing functional groups such as acid denaturation), poly Silicone compounds, fluorine compounds (fluorine oil representing polyfluoroalkane, etc.), paraffin, beeswax, etc. Among them, preferred release agents are, for example, fatty acid esters. The fatty acid ester is an ester formed of an aliphatic alcohol and an aliphatic carboxylic acid. The aliphatic alcohol may be a monohydric alcohol or a polyhydric alcohol having a valence of two or more. In addition, the carbon number of the alcohol is in the range of 3 to 32, more preferably in the range of 5 to 30. The monohydric alcohol is exemplified by, for example, dodecanol, myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosanol, tetracosyl alcohol, hexacosanol, and tricosyl alcohol. . Examples of the polyol include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), di-trimethylolpropane, xylitol, sorbitol, and mannitol. Among the fatty acid esters of the present invention, polyhydric alcohols are preferred.

On the other hand, the aliphatic carboxylic acid is preferably 3 to 32 carbon atoms, and particularly preferably the aliphatic carboxylic acid having 10 to 22 carbon atoms. The aliphatic carboxylic acid, for example: capric acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid) ), nineteen acid, behenic acid, icosene acid, and icosene acid, saturated fatty carboxylic acids such as palmitic acid, oleic acid, linolenic acid, linolenic acid, eicosenoic acid, Unsaturated aliphatic carboxylic acids such as hexadecenoic acid and cetenoic acid. Among the above, the aliphatic carboxylic acid is preferably 14 to 20 carbon atoms. Among them, saturated aliphatic carboxylic acids are preferred. In particular, stearic acid and palmitic acid are preferred.

The above-mentioned aliphatic carboxylic acids such as stearic acid or palmitic acid are usually produced from natural fats such as animal fats and oils represented by tallow or porpoise fat, and vegetable fats and oils represented by palm oil or sunflower oil, but these fats Group carboxylic acids are usually mixtures containing other carboxylic acid components with different numbers of carbon atoms. Therefore, in the production of the fatty acid ester of the present invention, the aliphatic carboxylic acid formed in the form of a mixture containing other carboxylic acid components prepared from the natural oils and fats is usually used, especially stearic acid or palm Acid is better.

The fatty acid ester of the present invention may be either a partial ester or a full ester. However, partial esters usually have a higher hydroxyl value, and are liable to induce decomposition of resins at high temperatures, so it is more preferable to use full esters. From the viewpoint of thermal stability, the acid value in the fatty acid ester of the present invention is preferably 20 or less, more preferably in the range of 4-20, and particularly preferably in the range of 4-12. Moreover, the acid value may be substantially zero. In addition, the hydroxyl value of the fatty acid ester is preferably in the range of 0.1 to 30. In addition, the iodine value is preferably 10 or less. In addition, the iodine value may be substantially zero. These characteristics can be obtained according to 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, and particularly preferably 0.05 parts by weight to 0.5 parts by weight relative to 100 parts by weight of the total of the components A and B. Copies. Within this range, the polycarbonate resin composition can have good mold release properties and roll release properties. In particular, the fatty acid ester in this amount can provide a polycarbonate resin composition having good mold releasability and roll releasability without damaging good hue.

(vi) Dyes The polycarbonate resin composition of the present invention can also provide molded articles containing various dyes that can produce various new styles. By adding a fluorescent whitening agent or other fluorescent dye that can produce other luminescence, it can give the effect of producing a good new style with luminous color. In addition, a polycarbonate resin composition that can be colored with a very small amount of dye and has a vivid color development property can be provided.

系螢光染料、硫

系螢光染料、氧硫

系螢光染料、噻

系螢光染料，及二胺基二苯基乙烯系螢光染料等。該些之中，又以使用具有良好的耐熱性，且於聚碳酸酯樹脂成形加工時，可降低劣化的香豆素系螢光染料、苯併吡喃系螢光染料，及苝系螢光染料為佳。The fluorescent dyes (including fluorescent whitening agents) used in the present invention include, for example, coumarin fluorescent dyes, benzopyran fluorescent dyes, perylene fluorescent dyes, and anthraquinone fluorescent dyes. , Thioindigo fluorescent dyes, dibenzopiperan fluorescent dyes,

Department of fluorescent dyes, sulfur

Department of fluorescent dyes, oxygen sulfur

Department of fluorescent dyes, thio

Fluorescent dyes, and diaminodiphenylethylene fluorescent dyes, etc. Among these, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes, which have good heat resistance and can reduce the deterioration during the molding process of polycarbonate resin Dye is better.

系染料、紺青等的亞鐵氰化物、Perinone系染料、喹啉系染料、喹吖啶酮系染料、二噁

系染料、異吲哚二酮(indolinone)系染料，及酞菁系染料等。此外，本發明的樹脂組成物亦可添加金屬顏料，而得到良好的金屬色彩。金屬顏料，又以各種板狀填料中，具有金屬被膜或金屬氧化物被膜者為佳。Examples of dyes other than the bluing agent and fluorescent dye include perylene-based dyes, coumarin-based dyes, thioindigo-based dyes, anthraquinone-based dyes, and oxysulfur

Ferrocyanide based dyes, cyanine, etc., Perinone based dyes, quinoline based dyes, quinacridone based dyes, dioxins

Dyes, indolinone dyes, and phthalocyanine dyes. In addition, the resin composition of the present invention may also be added with metallic pigments to obtain a good metallic color. Metallic pigments, and various plate-like fillers, preferably have a metal coating or a metal oxide coating.

The content of the above-mentioned dye is preferably 0.00001 parts by weight to 1 part by weight, and preferably 0.00005 parts by weight to 0.5 parts by weight relative to 100 parts by weight of the total of the A component and the B component.

(vii) Other thermal stabilizers In the polycarbonate resin composition of the present invention, other thermal stabilizers other than the phosphorus-based stabilizer and phenol-based stabilizer may be added. The other thermal stabilizer is preferably used in combination with any one of these stabilizers and antioxidants, and particularly preferably in combination with both users. The other thermal stabilizer, for example: a lactone-based stabilizer represented by the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (the stabilizer The details are as exemplified in Japanese Patent Laid-Open No. 7-233160). This compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), so this compound can be used. In addition, stabilizers obtained by mixing this compound with various phosphite compounds and hindered phenol compounds are also commercially available. For example, Irganox HP-2921 manufactured by the aforementioned company is a preferred example. In the present invention, the pre-mixed stabilizer can also be used. The added amount of the lactone-based stabilizer is preferably 0.0005 parts by weight to 0.05 parts by weight, and more preferably 0.001 parts by weight to 0.03 parts by weight with respect to 100 parts by weight of the A component and the B component in total.

In addition, other stabilizers include, for example, pentaerythritol tetrakis(3-hydrothiopropionate), pentaerythritol tetrakis(3-lauryl thiopropionate), and glycerol-3-stearyl thiopropionic acid Sulfur-containing stabilizers such as esters. This stabilizer is particularly effective when the resin composition is subjected to rotational molding. The added amount of the sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, and more preferably 0.01 to 0.08 parts by weight relative to 100 parts by weight of the total of the components A and B.

(viii) filler In the polycarbonate resin composition of the present invention, various fillers as reinforcing fillers can be added to the extent that the effects of the present invention can be exerted. Examples include: calcium carbonate, glass fibers, glass particles, glass bubbles, glass grinding fibers, glass flakes, carbon fibers, carbon flakes, carbon particles, carbon grinding fibers, graphite, and vapor phase growth ultrafine carbon fibers (fiber diameter less than 0.1 μm ), carbon nanotube (fiber diameter less than 0.1μm, hollow), fullerene, metal foil, metal fiber, metal-coated glass fiber, metal-coated carbon fiber, metal-coated glass flake, silicon dioxide, metal oxide Examples are particles, metal oxide fibers, metal oxide bubbles, and various whiskers (potassium titanate whiskers, aluminum borate whiskers, and basic magnesium sulfate, etc.). It is also possible to contain one kind of these reinforcing fillers or to combine two or more kinds of users. The content of these fillers is preferably 0.1 to 60 parts by weight, and more preferably 0.5 to 50 parts by weight relative to 100 parts by weight of the total of the components A and B.

(ix) White pigment highly reflecting light The polycarbonate resin composition of the present invention may be added with a white pigment highly reflecting light to impart a light reflecting effect. Examples of the white pigment include titanium oxide, zinc sulfide, zinc oxide, barium sulfate, calcium carbonate, and sintered kaolin. Especially titanium oxide is suitable for public use. The titanium oxide used is preferably titanium oxide having an average particle diameter of 0.1 to 5.0 μm after surface treatment with an organic substance. (In addition, in the present invention, the titanium oxide component of the titanium oxide pigment is labeled as "TiO ₂ ", and the entire pigment containing the surface treatment agent is labeled as "titanium oxide"). The crystal form of TiO ₂ may be any of anatase type and rutile type, and if necessary, these may be mixed and used. From the viewpoint of initial mechanical properties or long-term weather resistance, rutile type is preferred. In addition, there may be an anatase crystal in the rutile crystal. In addition, for TiO _2, for example, sulfuric acid method, chlorine method, or other methods can be used, and the chlorine method is more preferable. In addition, the titanium oxide of the present invention is not limited in its shape, and it is more preferably in the form of particles. Titanium oxide can generally be used for various coloring applications. The average particle diameter of titanium oxide used as a white pigment in the present invention is preferably 0.10 μm to 5.0 μm, preferably 0.15 μm to 2.0 μm, and preferably 0.18 μm to 1.5μm is better. When the average particle size is 0.10 μm or more, even in the case of high filling, it is possible to avoid the occurrence of appearance defects such as silver-like, and when it is 5.0 μm or less, good appearance and mechanical characteristics can be ensured. In addition, this average particle diameter is observed using an electron microscope, each single particle diameter is measured, and the number average thereof is calculated.

The titanium oxide used in the present invention is preferably a surface-treated organic compound. When titanium oxide without organic treatment is used, yellowing easily occurs, which deteriorates the appearance, and significantly reduces the reflectance of the molded body, and because it cannot obtain sufficient solar reflectance, it may not be suitable for outdoor use. situation. As the surface treatment agent, various treatment agents such as polyalcohol-based, amine-based, and polysiloxane-based can be used. Polyol-based surface treatment agents, for example: pentaerythritol, trimethylolethane, and trimethylolpropane; amine-based surface treatment agents, for example: acetate of triethanolamine, and acetate of trimethylolamine; Polysiloxane-based surface treatment agents, for example: alkyl chloride silane (trimethyl chloride silane, etc.), alkyl alkoxy silane (methyl trimethoxy silane, etc.), hydrogenated polysiloxane, etc. Examples of hydrogenated polysiloxanes include alkyl hydrogenated polysiloxanes and alkylphenyl hydrogenated polysiloxanes. The alkyl group is preferably methyl and ethyl. Titanium oxide surface-treated with the alkylalkoxysilane and/or hydrogenated polysiloxane can give the resin composition of the present invention better light reflectivity. The amount of the organic compound used for the surface treatment is generally 0.05 parts by weight to 5 parts by weight relative to 100 parts by weight of titanium oxide, more preferably 0.5 parts by weight to 3 parts by weight, and particularly preferably 1.5 parts by weight. ~2.5 parts by weight. When the amount of surface treatment is 0.05 parts by weight or more, sufficient thermal stability can be obtained, and when it is 5 parts by weight or less, it is more preferable to avoid forming defects such as silver-like formation. The surface treatment agent of the organic compound is preferably pre-treated with titanium oxide (more preferably titanium oxide coated with other metal oxides). In addition, it is also possible to use a method in which the surface treatment agent is additionally added when melt-kneading the raw materials of the resin composition, and titanium oxide is used for surface treatment in the melt-kneading step.

The content of the white pigment that can highly reflect light is 0.1 parts by weight to 10 parts by weight, more preferably 0.15 parts by weight to 7.5 parts by weight, and more preferably 0.15 parts by weight with respect to 100 parts by weight of the components A and B in total. Parts ~ 5 parts by weight. When the content of the highly reflective light white pigment is 0.1 parts by weight or more, sufficient white appearance or light-shielding property can be obtained, and when it is 10 parts by weight or less, it can avoid molding defects such as silver-like and significantly reduce physical properties, etc., which is better. In addition, the highly reflective white pigments can be used in combination of two or more.

(x) Other resins or elastomers In the resin composition of the present invention, other resins or graft polymers other than the D component can be used in a small proportion within the range where the effects of the present invention can be effectively exhibited.

The other resins include, for example, styrene resins such as ABS, polyimide resins, polyimide resins, polyether amide imide resins, polyurethane resins, polysiloxane resins, and polyphenylene ether resins , Polyphenylene sulfide resin, polyphenol resin, polymethacrylate resin, phenol resin, epoxy resin and other resins.

In addition, elastomers include, for example, isobutylene/isoprene rubber, ethylene/propylene rubber, styrene elastomers, acrylic elastomers, polyester elastomers, and polyamide elastomers.

(xi) Polycarbonate resin other than A component In the resin composition of the present invention, a polycarbonate-based resin other than the component A can be used in a small amount within the range where the effect of the present invention can be effectively exhibited.

Polycarbonate resins other than the polycarbonate-polydiorganosiloxane copolymer resin (component A) used in the present invention are generally obtained by reacting a divalent phenol and a carbonate precursor. An example of the reaction method includes, for example, the interfacial polymerization method, the melt transesterification method, the solid phase transesterification method of the carbonate prepolymer, and the ring-opening polymerization method of the cyclic carbonate compound.

Among them, representative examples of the divalent phenol used include hydroquinone, resorcinol, 4,4′-bisphenol, 1,1-bis(4-hydroxyphenyl)ethane, 2,2 -Bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane , 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)- 3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)pentane, 4,4'-(p-phenylene diisopropylidene) diphenol, 4, 4'-(m-phenylene diisopropylidene) diphenol, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, bis(4-hydroxyphenyl) oxide , Bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfonate, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxybenzene) Group) ester, bis(4-hydroxy-3-methylphenyl) sulfide, 9,9-bis(4-hydroxyphenyl) stilbene and 9,9-bis(4-hydroxy-3-methylphenyl) ) Wait. A preferred divalent phenol is bis(4-hydroxyphenyl)alkane. Among them, bisphenol A is particularly preferred from the viewpoint of impact resistance, and is widely used.

In the present invention, in addition to the bisphenol A-based polycarbonates which are widely used polycarbonates, special polycarbonates prepared from other divalent phenols can also be used as the A component.

For example: using some or all of the components of divalent phenol is using 4,4'-(m-phenylene diisopropylidene) diphenol (hereinafter, also referred to as "BPM"), 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter, also referred to as "Bis-TMC"), 9 , 9-bis (4-hydroxyphenyl) stilbene and 9,9-bis (4-hydroxy-3-methylphenyl) stilbene (hereinafter, also referred to as "BCF") polycarbonate (homopolymer or (Copolymer), suitable for applications that have particularly strict requirements for dimensional changes or morphological stability after absorbing moisture. The use amount of these divalent phenols other than BPA is preferably 5 mol% or more, particularly 10 mol% or more, which constitutes the entire divalent phenol component of the polycarbonate.

Especially in the case where high rigidity and better hydrolysis resistance are required, polycarbonate resins other than the A component constituting the resin composition, polycarbonate copolymerized with any of the following (1) to (3) For the best: (1) Of 100 mol% of the divalent phenol component constituting the polycarbonate, BPM is 20 mol% to 80 mol% (preferably 40 mol% to 75 mol%, more preferably 45 mol %～65mol%), and BCF is 20mol%～80mol% (preferably 25mol%～60mol%, more preferably 35mol%～55mol%) Polycarbonate (2) Of 100 mol% of the divalent phenol component constituting the polycarbonate, BPA is 10 mol% to 95 mol% (preferably 50 mol% to 90 mol%, more preferably 60 mol %～85mol%), and BCF is 5mol%～90mol% (preferably 10mol%～50mol%, more preferably 15mol%～40mol%) Polycarbonate (3) Of 100 mol% of the divalent phenol component constituting the polycarbonate, BPM is 20 mol% to 80 mol% (preferably 40 mol% to 75 mol%, more preferably 45 mol % To 65 mol%), and Bis-TMC is 20 mol% to 80 mol% (preferably 25 mol% to 60 mol%, more preferably 35 mol% to 55 mol%) Copolymerized polycarbonate.

These special polycarbonates may be used alone, or two or more kinds may be appropriately mixed and used. It can also be used in combination with these widely used bisphenol A polycarbonates.

The manufacturing methods and characteristics of these special polycarbonates are detailed in, for example, Japanese Patent Laid-Open No. 6-172508, Japanese Patent Laid-Open No. 8-27370, Japanese Patent Laid-Open No. 2001-55435, Japanese Patent Laid-Open No. 2002-117580, etc. Record.

In addition, among the above-mentioned various polycarbonates, the composition of the copolymer can be adjusted, and when the water absorption rate and Tg (glass transition temperature) are within the following ranges, the polymer itself can have good hydrolysis resistance, and after molding The warpage resistance is also excellent, so it is especially suitable for the technical field that requires morphological stability. (i) polycarbonate with a water absorption of 0.05% to 0.15%, preferably 0.06% to 0.13%, and a Tg of 120°C to 180°C, or (ii) Polycarbonate with a Tg of 160°C to 250°C, preferably 170°C to 230°C, and a water absorption rate of 0.10% to 0.30%, preferably 0.13% to 0.30%, more preferably 0.14% to 0.27% ester.

Among them, the water absorption rate of polycarbonate is obtained by using a disc-shaped test piece with a diameter of 45 mm and a thickness of 3.0 mm, which is immersed in water at 23° C. according to ISO62-1980 for 24 hours, and the moisture content is measured Value. In addition, Tg (glass transition temperature) is a value obtained by measuring using a differential scanning calorimeter (DSC) based on JIS K7121.

As the carbonate precursor, carbonyl halides, carbonate diesters, or halogenated formates can be used. Specifically, for example, phosgene, diphenyl carbonate, or dihalogenated formates of divalent phenols.

When using the interfacial polymerization method to produce the aromatic polycarbonate resin using the divalent phenol and the carbonate precursor, a catalyst, a chain stopper, an antioxidant that prevents oxidation of the divalent phenol, and the like can be used as necessary. Furthermore, the aromatic polycarbonate resin of the present invention is a branched polycarbonate resin obtained by copolymerization of a polyfunctional aromatic compound having more than three functions, and an aromatic or aliphatic (including alicyclic) difunctional carboxyl Copolymerized polycarbonate resin obtained by copolymerizing polyester carbonate resin and difunctional alcohol (including alicyclic) obtained by copolymerization of acid, and copolymerizing the difunctional carboxylic acid and difunctional alcohol together The resulting polyester carbonate resin. Moreover, it may be a mixture obtained by mixing two or more types of aromatic polycarbonate resins obtained.

Branched polycarbonate resins, in the resin composition of the present invention, can impart resistance to salivation and the like. The trifunctional or more polyfunctional aromatic compounds used in the branched polycarbonate resin may be exemplified by resorcinol, phloroglucine, or 4,6-dimethyl-2,4,6- Tris(4-hydroxydiphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4 -Hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2 ,6-bis(2-hydroxy-5-methylbenzyl)-4-cresol, 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α- Triphenol such as dimethylbenzylphenol, tetrakis(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl) ketone, 1,4-bis(4,4-dihydroxytrityl) Benzene, or trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, and acid chlorides of these. Among them, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, especially 1,1,1-tris(4-hydroxyphenyl)ethane is preferred.

In the branched polycarbonate, the structural unit derived from the polyfunctional aromatic compound is more than 100 mole% of the structural unit derived from the divalent phenol and the structural unit derived from the polyfunctional aromatic compound. It is preferably 0.01 mol% to 1 mol%, more preferably 0.05 mol% to 0.9 mol%, and particularly preferably 0.05 mol% to 0.8 mol%.

In addition, especially when the melt transesterification method is used, when a branch structure unit occurs in a side reaction, the amount of the branch structure unit is 100 mole% of the total structural units derived from divalent phenol, preferably 0.001 mole Ear% to 1 mole%, more preferably 0.005 mole% to 0.9 mole%, particularly preferably 0.01 mole% to 0.8 mole%. In addition, the ratio of the branch structure can be calculated by ¹ H-NMR measurement.

The aliphatic difunctional carboxylic acid is preferably α,ω-dicarboxylic acid. Aliphatic difunctional carboxylic acid, for example: linear saturation with sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, eicosanedioic acid, etc. Aliphatic dicarboxylic acids, cycloaliphatic dicarboxylic acids and other alicyclic dicarboxylic acids are preferred. The bifunctional alcohol is preferably an alicyclic diol, such as cyclohexane dimethanol, cyclohexane diol, and tricyclodecane dimethanol.

The reaction methods of the production method of the polycarbonate resin of the present invention include the interfacial polymerization method, the melt transesterification method, the carbonate prepolymer solid-phase transesterification method, and the ring-opening polymerization method of the cyclic carbonate compound. It can be fully understood by various documents and patent bulletins.

(xi) Other additives In addition, in the polycarbonate resin composition of the present invention, additives with known characteristics can be added in small amounts for the purpose of imparting various functions to the molded article or improving characteristics. These additives can be added in an ordinary amount within a range that does not impair the object of the present invention.

Examples of the additives include: fold agents (such as PTFE particles), colorants (such as pigments and dyes such as carbon black), and light diffusing agents (such as acrylic cross-linked particles, silicon cross-linked particles, extremely thin glass flakes, and carbonic acid) Calcium particles), fluorescent dyes, inorganic phosphors (e.g. phosphors with aluminate as the mother crystal), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalyst antifouling agents (e.g. microparticles) Titanium oxide, particulate zinc oxide), free radical generators, infrared absorbers (heat ray absorbers), and photochromic agents.

(Manufacture of polycarbonate resin composition) When manufacturing the polycarbonate resin composition of the present invention, any method can be used. For example: use A-D components or A-F components that do not contain component B, and any other additives, using V-type blender, Henschel Mixer, mechanochemical device, extrusion mixer After the pre-mixing method is fully mixed, if necessary, the pre-mixing granulation is performed using an extrusion granulator or briquetting machine, and then a melt-kneading machine represented by an exhaust type two-axis extruder is used. A method of melt-kneading and then granulating it using a granulator.

Others, such as a method of supplying each component independently to a melt-kneading machine represented by an exhaust type two-shaft extruder, or after pre-mixing a part of each component, the remaining part is independently supplied to The method of melt kneading machine, etc. A method of pre-mixing a part of each component, for example, after pre-mixing components other than component A and component B, and then mixing with the thermoplastic resin of component A, or directly supplying it to the extruder.

The method of pre-mixing, for example: when component A contains a powder form, part of the powder can be blended with the blended additive, and then diluted with the powder to prepare an additive matrix (master batch), and the method of using the matrix . In addition, such as the method of taking out one of the components independently and then adding it in the process of melt extruder. In addition, when the added component contains a liquid component, a liquid injection device or a liquid addition device can be used when it is supplied to the melt extruder.

For the extruder, it is preferable to use an exhaust valve which can discharge the moisture in the raw material or can discharge the volatile gas generated by the melt-kneading resin. In order to make the exhaust valve efficiently discharge the generated water or volatile gas outside the extruder, it is better to install a vacuum pump. In addition, for the purpose of removing foreign materials mixed into the extrusion raw material, a filter may be provided in the area in front of the mold portion of the extruder to remove foreign materials from the resin composition. As the filter, a metal mesh, a filter replacement machine, a sintered metal plate (dish filter, etc.) can be used.

The melt-kneading machine, in addition to the two-axis extruder, for example: Banbury kneading machine, kneading drum, single-axis extruder, multi-axis extruder with more than 3 axes, etc.

As described above, the extruded resin can be directly cut and pelletized, or after forming a strand, the strand is cut and pelletized using a pelletizer. When granulating, if it is necessary to reduce the influence of external dust, it is better to clean the environment around the extruder. In addition, in the production of the particles, various methods for polycarbonate resins for optical discs proposed in the past can be used to appropriately narrow the distribution of particle shapes, reduce false cuts, and reduce fine powder that occurs during transportation or transportation. And reduce bubbles (vacuum bubbles) that occur inside strands or particles. These methods can increase the frequency of molding and reduce the occurrence rate of silver-like defects. In addition, the shape of the particles may be a general shape such as a cylinder, a prism, and a sphere, and it is preferably a cylinder. The diameter of the cylinder is preferably 1 mm to 5 mm, more preferably 1.5 mm to 4 mm, and particularly 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 particularly preferably 2.5 mm to 3.5 mm.

(Molded product formed by the resin composition of the present invention) In the resin composition of the present invention, granules produced according to the above-mentioned general method can be injection molded to produce various products. This injection molding is not only a general molding method, but can also be used for appropriate purposes, such as injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including those formed by supercritical fluid injection), and insert molding , In-mold coating molding, heat insulation mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high-speed injection molding and other injection molding methods to produce molded products. The advantages of these various forming methods are widely known. In addition, the forming method can select either cold pouring method or hot pouring method.

In addition, the resin composition in the present invention can be used in various shapes such as extruded products, sheets, films, etc. of various shapes obtained by extrusion molding. In addition, blow molding, curtain molding, mold molding, etc. can be used for forming sheets and films. In addition, it can be formed into a heat-shrinkable tube or the like through a specific stretching operation. In addition, the resin composition of the present invention may be a molded product obtained by rotary molding, blow molding, or the like.

Specific examples of molded products that can utilize the resin composition of the present invention are, for example, suitable for applications such as living materials, housing equipment materials, construction materials, indoor articles, OA equipment, and interior parts of home appliances or houses. These products can be exemplified by: personal computers, notebook personal computers, CRT monitors, printers, laptop computers, mobile phones, photocopiers, fax machines, recording media (CD, CD-ROM, DVD, PD, FDD, etc.) ) Drive device, dish antenna, power tool, VTR, TV, iron, hair dryer, electric pot, microwave oven, audio equipment, stereo, optical disc drive (registered trademark), portable optical disc and other audio, lighting equipment, refrigerator, air conditioner , Living materials such as typewriters, word processors, luggage or cleaning appliances, residential equipment materials such as bathrooms, toilets, face dressers, etc., and various parts such as the outer frame can use the polycarbonate of the present invention A resin product formed of an ester resin composition. In addition, other resin products include vehicle parts such as guide parts, car navigation parts, and car audio parts.

The form of the invention for carrying out the present invention is a summary of the above-mentioned requirements, and a representative example will be described in the following examples. Of course, the present invention is not limited by these forms. [Example]

The present invention will be described in more detail with examples below. In addition, unless otherwise specified, "parts" in the examples refer to parts by weight, and% means% by weight. In addition, the evaluation was performed according to the following method.

(Evaluation of polycarbonate resin composition) (i) Charpy impact strength The ISO bending test piece obtained by the following method was used, and the Charpy impact strength with a scale was measured in accordance with ISO 179. (ii) Flame retardancy Using the UL test piece obtained by the following method, the V test was carried out in accordance with UL94. In addition, if the determination method is that there is no case that meets any of the criteria of V-0, V-1, and V-2, it is marked as "notV". (iii) Drug resistance Use the ISO tensile test piece obtained according to the following method, apply a 1% deformation according to the 3-point bending test method, and cover it and immerse it in the magic spirit, bathroom magic spirit and toilet magic spirit (all made by Kao Corporation) ) Cloth, after leaving it at 23°C for 96 hours, check whether the appearance has changed. In addition, the evaluation was performed according to the following criteria. ○: No change in appearance was observed △: Fine cracking phenomenon was observed ×: Observation of finer cracks into larger cracks (iv) Stain resistance (contact angle to water) A contact angle measuring machine G-I-1000 (manufactured by ERMA Co., Ltd.) was used to measure the water contact angle of the surface of the sample plate (three-step plate with holes) obtained by the following method. When the contact angle to water is 100° or more, the mark is “○”, and when it is less than 100°, it is evaluated as “×”. (v) Thermal stability Under the same conditions as the following method, the amount of decrease in the average molecular weight of the viscosity between the test piece and the pellet obtained by forming the test piece after being left in the cylinder for 10 minutes was calculated according to the following formula ΔMv. Viscosity average molecular weight reduction ΔMv = (particle viscosity average molecular weight)-(viscosity average molecular weight of the molded product after 10 minutes of residence) In addition, the evaluation method is based on the following criteria. ○: ΔMv<3,000 △: 3,000≦ΔMv<5,000 ×: 5,000≦ΔMv (vi) Appearance The appearance of the sample plate (three-stage plate with holes) prepared by the following method was visually evaluated. In addition, the evaluation is performed according to the following criteria. ○: No obvious appearance defect was observed near the frame ×: Large marks or peeling occurs near the frame

[Examples 1 to 33, Comparative Examples 1 to 11] According to the composition shown in Tables 1 to 3, the mixture formed by the components of the polyester resin that does not contain the component B is fed from the first feed port of the extruder. In addition, in Examples 1 to 13, 15 to 29, and 31 to 33, and Comparative Examples 1 to 4, 6, 7, 10, and 11, the content of the D component is shown in parentheses D-1 to D- 3 The amount of the antifouling-imparting agent (the number outside the parentheses indicates the amount of D-1 to D-3 of the masterbatch at a concentration of 50%). This mixture was mixed using a V-type blender. The polyester resin of component B is fed from the side feeding port of the second feeding port. The extrusion method is an exhaust type two-shaft extruder with a diameter of 30 mmφ ((Co) Japan Steel Works TEX30α-38.5BW-3V), according to the number of screw rotations 230 rpm, discharge volume 25 kg/h, and the vacuum degree of the exhaust port 3 kPa The conditions were melt-kneaded to obtain granules. In addition, the extrusion temperature was 260°C from the first feed port to the pellet portion. A part of the obtained pellets were dried using a hot air circulation dryer at 80°C for 6 hours, and then an injection molding machine was used to prepare test pieces for evaluation according to the conditions of the cylinder temperature of 260°C and the mold temperature of 60°C ( ISO tensile test specimens (ISO527-1 and ISO527-2 standards), ISO bending test specimens (ISO178, ISO179, ISO75-1 and ISO75-2 standards)), UL test specimens (width 13mm × length 125mm × thickness 1.5mm) , And sample plates (three sections of plates with holes)).

In addition, the components indicated by the symbols in Tables 1 to 3 are as follows.

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

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

(Component C) C-1: Polysilicone core-shell graft polymer (core is a core-shell structure with acrylic-polysiloxane composite rubber as the main component, and shell is methyl methacrylate as the main component (Branch copolymer, Metablen S-2030 (product name) manufactured by Mitsubishi Rayon Co., Ltd.) C-2: Butadiene core-shell graft polymer (core is a graft copolymer with core-shell structure mainly composed of butadiene rubber and shell mainly composed of methyl methacrylate , (Shares) Kaneas M-711 (product name) made by Kaneka) C-3: Acrylic core-shell graft polymer (core is a core-shell graft copolymer with butyl acrylate as the main component and shell is methyl methacrylate as the main component, Mitsubishi Rei (Metablen W-600A (product name))

(Component D) D-1: Polysiloxane colloidal PC matrix (Ultra-high molecular weight polydimethylsiloxane polycarbonate 50% matrix, manufactured by Toray Dow Co., Ltd. MB50-315 (product name)) D-2: Polysilicone colloid PEst matrix (Ultra high molecular weight polydimethylsiloxane polyester elastomer 50% matrix, manufactured by Toray Dow Co., Ltd. BY27-009 (product name)) D-3: Polysilicone colloidal PP matrix (Ultra high molecular weight polydimethylsiloxane polypropylene 50% matrix, manufactured by Toray Dow Co., Ltd. BY27-001 (product name)) D-4: Polysiloxane modified polypropylene (polymer obtained by graft polymerization of polypropylene and polyorganosiloxane, manufactured by Toray Dow (stock) BY27-201 (product name))

(E component) E: Bromine-based flame retardant (brominated carbonate oligomer with bisphenol A skeleton, Teijin Co., Ltd. product FG-8500 (product name))

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

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

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

Claims (9)

A polycarbonate resin composition characterized by containing: 100 parts by weight relative to the total of (A) polycarbonate-polydiorganosiloxane copolymer resin (component A) and (B) polyester resin (component B), (C) The composite rubber formed from components containing polyorganosiloxane rubber and alkyl (meth)acrylate rubber has an aromatic alkenyl compound monomer unit and alkyl (meth)acrylate compound monomer The core-shell structured graft copolymer (component C) obtained by graft polymerization of at least one unit selected from the group of units is 3 parts by weight to 15 parts by weight, and (D) The antifouling imparting agent (component D) is 0.5 to 6 parts by weight. The polycarbonate resin composition according to claim 1, which further contains: (E) 5 parts by weight to 35 parts by weight of halogen-based flame retardant (component E), and (F) has the following formula (1) Structure of phosphorus flame retardant (component F) 0.5 parts by weight to 5 parts by weight;

(In the formula, X ₁ and X ₂ are the same or different alkyl groups substituted with aromatic 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 phenyl, naphthyl or anthracenyl, n represents an integer of 1 to 3, and Ar may be bonded to any of AL carbon atom). The polycarbonate resin composition according to claim 1 or 2, wherein the content of the component B is 20 to 70 parts by weight in a total of 100 parts by weight of the component A and the component B. The polycarbonate resin composition according to any one of claims 1 to 3, wherein the component B contains at least one of polyethylene terephthalate resin and polybutylene terephthalate resin. The polycarbonate resin composition according to any one of claims 1 to 4, wherein the component D is a polysiloxane colloid having a molecular weight of 100,000 or more. The polycarbonate resin composition according to any one of claims 1 to 5, wherein the component D is a polyorganosiloxane grafted polyolefin resin. The polycarbonate resin composition according to any one of claims 1 to 6, wherein the proportion of the polyorganosiloxane rubber component in the compound rubber of component C is 15% or more. The polycarbonate resin composition according to any one of claims 1 to 7, wherein (G) the anti-salivation agent (component G) contains 0.05 parts by weight to 2 parts by weight with respect to the total of 100 parts by weight of the components A and B Copies. The polycarbonate resin composition according to claim 8, wherein the G component is a fluoropolymer having filament forming ability.