JP5056354B2 - Method for producing antistatic polycarbonate resin molded product and molded product - Google Patents

Description

  The present invention relates to a method for producing an antistatic polycarbonate resin molded article and a molded article. More specifically, even when melt-kneaded, molded, and used under high temperatures for extended periods of time, coloring to yellow and brown is suppressed, improving fluidity without significantly reducing mechanical strength and transparency. The present invention relates to a method for producing an antistatic polycarbonate resin molded article having good heat resistance and a molded article.

  Polycarbonate resins are widely used in the fields of various parts of electrical / electronic / OA equipment, automobile parts, building materials, medical uses, miscellaneous goods, etc. as resins having excellent mechanical strength, heat resistance, transparency and the like. However, since polycarbonate resin has a high surface resistivity, static electricity generated by contact and friction is difficult to disappear, dust and dust adhere to the surface of the molded product, and the appearance and transparency are impaired. Furthermore, due to electric shock to the human body There are problems such as discomfort, generation of noise and malfunction of equipment. For this reason, there is a strong demand to provide an antistatic polycarbonate resin molded product obtained by melt-molding a polycarbonate resin composition having a reduced surface resistivity and imparted antistatic properties without impairing the original properties of the polycarbonate resin. Yes.

  Conventionally, as a polycarbonate resin composition having antistatic properties, a resin composition in which a sulfonic acid phosphonium salt, a phosphite ester and a caprolactone polymer are blended with a polycarbonate resin (Patent Document 1), a phosphonium salt with a polycarbonate resin, etc. A resin composition (Patent Document 2) containing an antistatic agent and polycaprolactone has been proposed. However, the resin compositions according to these patent documents have a large variation in fluidity, making stable molding difficult, causing coloration from yellow to brown during melt-kneading and molding, and mechanical strength and charging. There was a problem that the preventive property was lowered. This is probably because the melt viscosity of the polycarbonate resin is high, so that the melt kneading temperature and the melt molding temperature of the resin composition are high, and as a result, the thermal decomposition of the resin composition becomes remarkable.

  Patent Document 3 proposes an optical molded product of polycarbonate resin obtained by blending 1 to 60% by weight of a polycarbonate oligomer with a polycarbonate resin. Patent Document 4 discloses at least a polycarbonate oligomer having a molecular weight of 2000 to 5000 in a polycarbonate resin. Resins containing 10% by weight have been proposed. However, these documents only describe that in the case of an optical molded product, blending an oligomer affects the fluidity.

  Furthermore, in Patent Document 5, in a method of molding a molded product from a polycarbonate resin composition containing an antistatic agent, the resin temperature of the molding machine at the time of molding is 290 to 330 ° C., and the mold temperature is 60 to 90 ° C. Although a method for molding an antistatic polycarbonate resin composition characterized by molding under the conditions described above has been proposed, the effect of improving the antistatic property is limited, and yellow or brown coloring or burnt dust is likely to occur. There was a drawback.

JP-A-9-194711 JP 2006-257177 A JP 61-123658 A JP-A-9-208684 JP 2002-144393 A

  The object of the present invention is to suppress yellowing and browning even during melt-kneading, molding, and in an environment used at high temperatures for a long time, without significantly reducing mechanical strength and transparency. It is an object to provide an antistatic polycarbonate resin molded article having improved performance and particularly good performance with a comprehensive balance including heat resistance.

（一般式（１）中、Ｒ ^１ は炭素数１〜４０のアルキル基又はアリール基であり、置換基を有していても良く、Ｒ ^２ 〜Ｒ ^５ は、各々独立して水素原子、炭素数１〜１０のアルキル基又はアリール基であり、これらは同じでも異なっていてもよい。）
を配合したポリカーボネート樹脂組成物（Ｊ）から成形機の樹脂温度２７０〜３２０℃、金型温度４０〜１２０℃で成形品を射出成形する際、ゲート通過時の樹脂組成物（Ｊ）の最大せん断速度を１５００〜１００００／ｓｅｃとすることを特徴とする帯電防止性ポリカーボネート樹脂成形品の製造方法、
（ロ） 上記ポリカーボネート樹脂組成物（Ｊ）が、ポリカーボネート樹脂（Ａ）１００重量部に対し、
[Means for solving problems]
As a result of intensive studies to achieve the above-mentioned object, the inventors of the present invention have suppressed the coloring to yellow and brown by injection molding the antistatic polycarbonate resin composition under specific conditions, such as a flow mark. The present invention was completed by finding that a molded article having a stable antistatic property can be molded without causing any poor appearance and without significantly reducing the mechanical strength and transparency. That is, the gist of the present invention is as follows.
(B) to polycarbonate resin (A) 100 parts by weight of, 0.1 to 5.0 parts by weight of a sulfonic acid phosphonium salt (b) represented by the following general formula (1) as the antistatic agent (B)

(In General Formula (1), R ¹ is an alkyl group having 1 to 40 carbon atoms or an aryl group, and may have a substituent, and R ^{2 to} R ⁵ are each independently a hydrogen atom or carbon. (It is an alkyl group or an aryl group of formulas 1 to 10, and these may be the same or different.)
When a molded product is injection-molded from a polycarbonate resin composition (J) blended with resin at a molding machine resin temperature of 270 to 320 ° C. and a mold temperature of 40 to 120 ° C., the maximum shear of the resin composition (J) when passing through the gate A method for producing an antistatic polycarbonate resin molded article, wherein the speed is 1500 to 10,000 / sec,
(B) The polycarbonate resin composition (J) is 100 parts by weight of the polycarbonate resin (A) .

Kaoru aromatic polycarbonate oligomer (C) 0.1 to 10 parts by weight, and, in (a) above, wherein the caprolactone-based polymer (D) is obtained by compounding 0.01 to 8 parts by weight Production method of antistatic polycarbonate resin molded product,
(C) The polycarbonate resin composition (J) is a total amount [(C + D)] of the aromatic polycarbonate oligomer (C) and the caprolactone polymer (D) with respect to 100 parts by weight of the polycarbonate resin (A). The method for producing an antistatic polycarbonate resin molded article according to (a) or (b) above, wherein 0.11 to 18 parts by weight is blended,
(D) The polycarbonate resin composition (J) is characterized by blending 0.01 to 1.0 part by weight of a phosphorus stabilizer (E) with respect to 100 parts by weight of the polycarbonate resin (A). A method for producing an antistatic polycarbonate resin molded article according to any one of (a) to (c) above,
(E) The polycarbonate resin composition (J) is a phenolic antioxidant (F) having a structure represented by the following general formula (2) in the molecule with respect to 100 parts by weight of the polycarbonate resin (A). The method for producing an antistatic polycarbonate resin molded article according to any one of the above (a) to (d), wherein 01 to 1.0 part by weight is blended,

（一般式（２）中、Ｒ^６〜Ｒ^８は、各々独立して水素原子、又は炭素数１〜３のアルキル基を示し、ｔ−Ｂｕは、ｔｅｒｔ−ブチル基を示す。）
（ヘ） 上記ポリカーボネート樹脂組成物（Ｊ）が、ポリカーボネート樹脂（Ａ）１００重量部に対し、耐候性改良剤（Ｇ）を０．０１〜３．０重量部配合したものであることを特徴とする上記（イ）〜（ホ）のいずれかに記載の帯電防止性ポリカーボネート樹脂成形品の製造方法、及び
（ト） 上記（イ）〜（ヘ）のいずれかに記載の製造方法によって得られた帯電防止性ポリカーボネート樹脂成形品に存する。

(In General Formula (2), R ^{6 to} R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and t-Bu represents a tert-butyl group.)
(F) The polycarbonate resin composition (J) is characterized by blending 0.01 to 3.0 parts by weight of the weather resistance improver (G) with respect to 100 parts by weight of the polycarbonate resin (A). Obtained by the production method of an antistatic polycarbonate resin molded product according to any one of (a) to (e) above, and (g) the production method according to any one of (a) to (f) above It exists in an antistatic polycarbonate resin molded product.

The molded product injection-molded by the method of the present invention is suppressed in coloring to yellow and brown during melt kneading, molding, and in an environment where it is used at high temperature for a long time, and has poor appearance such as flow marks. It does not occur, and it has stable antistatic properties without significantly reducing mechanical strength, transparency, and heat resistance, so various molded products such as recording medium substrates and cartridges, various types of electrical / electronic / OA equipment, etc. Parts, building materials such as transparent sheets and films, miscellaneous parts, pachinko parts (circuit covers, chassis, pachinko ball guides, etc.), medical applications, window glass, meter covers, room lamps, tail lamp lenses, blinker lamps, headlamps This is useful in applications such as illumination for lenses or transparent members for vehicles, and further suitable for applications for transparent members for illumination.

The present invention will be described in detail.
Polycarbonate resin (A)
In the present invention, as the polycarbonate resin, aromatic polycarbonate, aliphatic polycarbonate, and aromatic-aliphatic polycarbonate can be used, and among them, aromatic polycarbonate is preferable. As the aromatic polycarbonate resin, a resin obtained by an interfacial polymerization method (phosgene method) in which an aromatic dihydroxy compound or a small amount of a polyhydroxy compound is reacted with phosgene, or a melting method (transesterification method) in which it is reacted with a carbonic acid diester. It is a linear or branched thermoplastic polymer or copolymer. Moreover, the resin by which the amount of OH group of the terminal group was adjusted by manufacturing by a melting method may be sufficient.

  As aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -P-diisopropylbenzene, hydroquinone, resorcinol, 4,4 -Dihydroxy diphenyl etc. are mentioned, Preferably bisphenol A is mentioned. In addition, for the purpose of further enhancing the flame retardancy, a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the aromatic dihydroxy compound and / or a polymer having a siloxane structure and containing phenolic hydroxyl groups at both ends. Or an oligomer can be used.

  In addition, in order to obtain a branched aromatic polycarbonate resin, a part of the above-mentioned aromatic dihydroxy compound is replaced with the following compound, that is, phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl). Heptene-2,4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenylheptene-3,1, Polyhydroxy compounds such as 3,5-tri (4-hydroxyphenyl) benzene and 1,1,1-tri (4-hydroxyphenyl) ethane, and 3,3-bis (4-hydroxyaryl) oxindole (= isa) Chin bisphenol), 5-chloruisatin bisphenol, 5,7-dichloroisatin bisphenol, 5-bromoisatin bisphenol, etc. May be substituted by thing. The amount of a compound of these substituted, the aromatic dihydroxy compound is 0.01 to 10 mol%, preferably 0.1 to 2 mol%.

Monovalent aromatic hydroxy compounds can be used to adjust the molecular weight of the polycarbonate resin, specifically m- and p-methylphenol, m- and p-propylphenol, p-tert-butylphenol and p. -Long chain alkyl substituted phenols and the like.
The polycarbonate resin (A) used in the present invention is preferably a polycarbonate resin derived from bisphenol A or an aromatic polycarbonate copolymer derived from bisphenol A and another aromatic dihydroxy compound. Furthermore, in the present invention, the polycarbonate resin may be used by mixing two or more kinds of resins.

  The viscosity average molecular weight of the polycarbonate resin (A) is a value converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent, preferably 13,000 to 40000, more preferably 14,000 to 30000, most preferably 15000. ~ 29000. When the viscosity average molecular weight is less than 13,000, mechanical strength such as impact strength is insufficient, and when it exceeds 40000, the fluidity tends to decrease.

Antistatic agent (B)
Antistatic agent (B) used in the present invention is a sulfonic acid phosphonium salt represented by the following general formula (1) (b).

（一般式（１）中、Ｒ^１は炭素数１〜４０のアルキル基又はアリール基であり、置換基を有していても良く、Ｒ^２〜Ｒ^５は、各々独立して水素原子、炭素数１〜１０のアルキル基又はアリール基であり、これらは同じでも異なっていてもよい。）
前記一般式（１）で示されるスルホン酸ホスホニウム塩（ｂ）は、ポリカーボネート樹脂（Ａ）１００重量部に対し、０．１〜５．０重量部配合されるが、好ましくは０．２〜３．０重量部、更に好ましくは０．３〜２．０重量部、特に好ましくは０．５〜１．８重量部である。０．１重量部未満では、帯電防止の効果は得られず、５．０重量部を超えると透明性や機械的強度が低下し、成形品表面にシルバーや剥離が生じて外観不良を引き起こし易い。

(In General Formula (1), R ¹ is an alkyl group having 1 to 40 carbon atoms or an aryl group, and may have a substituent, and R ^{2 to} R ⁵ are each independently a hydrogen atom or carbon. (It is an alkyl group or an aryl group of formulas 1 to 10, and these may be the same or different.)
The sulfonic acid phosphonium salt (b) represented by the general formula (1) is blended in an amount of 0.1 to 5.0 parts by weight, preferably 0.2 to 3 parts per 100 parts by weight of the polycarbonate resin (A). 0.0 part by weight, more preferably 0.3 to 2.0 parts by weight, particularly preferably 0.5 to 1.8 parts by weight. If the amount is less than 0.1 parts by weight, the antistatic effect cannot be obtained. If the amount exceeds 5.0 parts by weight, the transparency and mechanical strength are lowered, and silver or peeling occurs on the surface of the molded product, which easily causes poor appearance. .

R ¹ in the general formula (1) is an alkyl group having 1 to 40 carbon atoms or an aryl group, and an aryl group is preferable from the viewpoint of transparency, heat resistance, and compatibility with a polycarbonate resin. A group derived from an alkylbenzene or alkylnaphthalene ring substituted with an alkyl group of 1 to 34, preferably 5 to 20, particularly 10 to 15 is preferable. Further, ^R 2 to R ⁵ of the general formula (1), each independently represent a hydrogen atom or an alkyl group or aryl group having 1 to 10 carbon atoms, preferably alkyl of 2 to 8 carbon atoms, More preferably, it is a 3-6 alkyl group, and especially a butyl group is preferable.

  Specific examples of the sulfonic acid phosphonium salt (b) in the present invention include tetrabutylphosphonium dodecylsulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, tributyloctylphosphonium dodecylbenzenesulfonate, tetraoctylphosphonium dodecylbenzenesulfonate, octadecylbenzenesulfone. Examples include tetraethylphosphonium acid, tributylmethylphosphonium dibutylbenzenesulfonate, triphenylphosphonium dibutylnaphthylsulfonate, and trioctylmethylphosphonium diisopropylnaphthylsulfonate. Of these, tetrabutylphosphonium dodecylbenzenesulfonate is preferred because it is compatible with polycarbonate and easily available.

Aromatic polycarbonate oligomer (C)
In addition to the antistatic agent (B) such as the sulfonic acid phosphonium salt (b) described above, the antistatic polycarbonate resin composition used in the present invention preferably contains a specific amount of the aromatic polycarbonate oligomer (C). . By blending the aromatic polycarbonate oligomer (C), it has good performance with a comprehensive balance of transparency, coloring during melt kneading and molding, fluidity, heat resistance, mechanical strength, antistatic properties, etc. A molded product can be obtained.

  The aromatic polycarbonate oligomer (C) is an oligomer having a viscosity average molecular weight in the range of 1,000 to 10,000, in order to develop a fluidity improving effect while maintaining a balance of physical properties such as impact resistance and transparency. The viscosity average molecular weight is preferably 1,500 to 9,000, more preferably 2,000 to 8,000. If the viscosity average molecular weight of the oligomer is less than 1,000, bleeding out from the molded product tends to occur during molding, and if the viscosity average molecular weight exceeds 10,000, the fluidity tends to decrease.

  The number average degree of polymerization (average value of the number of repeating structural units) of the aromatic polycarbonate oligomer (C) is usually 2 to 15, preferably 3 to 14, and more preferably 4 to 13. The oligomer tends to bleed out from the molded product at the time of molding when the degree of polymerization is 1, and the fluidity tends to decrease when the degree of polymerization exceeds 15.

  The aromatic polycarbonate oligomer (C) can be produced by reacting an aromatic dihydroxy compound with phosgene or a carbonic acid diester in the presence of a molecular weight regulator. As an aromatic dihydroxy compound, the aromatic dihydroxy compound used as a raw material of the aromatic polycarbonate resin mentioned above is mentioned, Preferably bisphenol A is used. As a molecular weight regulator, the monovalent aromatic hydroxy compound used for molecular weight adjustment of the aromatic polycarbonate resin mentioned above can be used, m- and p-methylphenol, m- and p-propylphenol, p-tert- Examples include butylphenol and p-long chain alkyl-substituted phenol.

  The aromatic polycarbonate oligomer (C) may be an oligomer obtained by copolymerization using two or more aromatic hydroxy compounds. Examples of combinations of aromatic hydroxy compounds include bisphenol A (BPA) and tetra Bromobisphenol A (TBA) is mentioned.

In this invention, the aromatic polycarbonate oligomer (C) manufactured by the method mentioned above is mix | blended with a specific amount to a resin composition.
The compounding ratio of the aromatic polycarbonate oligomer (C) is 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight, more preferably 0.5 to 3 parts per 100 parts by weight of the polycarbonate resin (A). Parts by weight. When the blending ratio of the aromatic polycarbonate oligomer (C) is less than 0.1 parts by weight, the fluidity improving effect is insufficient, and when it exceeds 10 parts by weight, the hue after heat aging is deteriorated and the impact strength is lowered.

The blending ratio (C) / (b) (weight ratio) of the aromatic polycarbonate oligomer (C) to the sulfonic acid phosphonium salt (b) (general formula (1)) is usually 2/100 to 2000/100, preferably 5/100 to 500/100, and more preferably 10/100 to 200/100.

Caprolactone polymer (D)
In the antistatic resin composition used in the present invention, it is preferable to further blend a specific amount of the caprolactone polymer (D). The caprolactone polymer (D) in the present invention is a polymer containing at least 70% by weight, preferably 75% by weight or more, more preferably 80% by weight or more, of a structural unit derived from ε-caprolactone in the polymer or It is a copolymer. Monomers copolymerized with ε-caprolactone include lactone monomers such as β-propiolactone, pivalolactone, butyrolactone, alkylene oxides such as ethylene oxide, 1,2-propion oxide, 1,3-propylene oxide, and tetrahydrofuran, styrene, methyl Examples thereof include unsaturated monomers such as methacrylate and butadiene, and coupling agents such as dimethyl terephthalate and diphenyl carbonate.

  As the caprolactone polymer (D), a part of the hydrogen atoms of the methylene chain of the ε-caprolactone unit may be substituted with a halogen atom or a hydrocarbon group, and the terminal of the caprolactone polymer is esterified or etherified. It may be terminal-modified by, for example. The production method of the caprolactone-based polymer is not particularly limited, but a method of ring-opening polymerization of ε-caprolactone using an appropriate initiator such as alcohol, glycol or water and a catalyst such as titanium tetrabutoxide or tin chloride is used. It is done.

  The compounding quantity of a caprolactone type polymer (D) is 0.01-8 weight part with respect to 100 weight part of polycarbonate resin (A). If it is less than 0.01 part by weight, the effect of preventing coloring is insufficient, and if it exceeds 5 parts by weight, the heat resistance, antistatic property and transparency are likely to deteriorate. The amount of caprolactone-based polymer is preferably 0.05 to 5 parts by weight, more preferably 0.08 to 4 parts by weight, and particularly preferably 0.1 to 3 parts by weight.

In the present invention, the blending ratio (weight ratio) of the caprolactone-based polymer (D) to the sulfonic acid phosphonium salt (b) (general formula (1)) is (D) / (b) for preventing coloring during molding. In general, it is 1/20 to 20/1, preferably 1/10 to 10/1, more preferably 1/8 to 5/1, and particularly preferably 1/5 to 1/1.
In the present invention, the blending ratio (weight ratio) of the aromatic polycarbonate oligomer (C) and the caprolactone polymer (D) is (C) / (D) for maintaining a balance between impact resistance and heat resistance. In general, it is 1/20 to 10/1, preferably 1/10 to 8/1, more preferably 1/5 to 5/1, and particularly preferably 1/3 to 4/1.

  Further, in the present invention, the total blending amount [(C + D)] of the aromatic polycarbonate oligomer (C) and the caprolactone polymer (D) with respect to 100 parts by weight of the polycarbonate resin (A) is the impact resistance and heat resistance. In order to maintain the balance, it is usually 0.11 to 20 parts by weight, preferably 0.15 to 10 parts by weight, more preferably 0.5 to 7 parts by weight, particularly preferably 1.0 to 3.0 parts by weight. is there.

  The number average molecular weight (GPC measurement) of the caprolactone-based polymer (D) is preferably 1,000 to 100,000. If the number average molecular weight is less than 1,000, the heat resistance tends to be insufficient, and if it exceeds 100,000, the processability and transparency tend to decrease. The number average molecular weight of the caprolactone-based polymer is more preferably 5,000 to 50,000, and further preferably 10,000 to 30,000 from the viewpoint of transparency. When a caprolactone polymer having a high molecular weight is used, whitening may occur. This is because the caprolactone polymer forms a domain and is dispersed in the matrix, forming a sea-island structure. This is probably because there is a difference. In order to prevent the whitening phenomenon and promote transparency, it is preferable to cause a transesterification reaction between the polycarbonate resin (A) and the (D) caprolactone-based polymer. It is preferable to mix and knead the transesterification catalyst.

  Specific examples of the transesterification reaction catalyst include p-toluenesulfonic acid, trifluoroacetic acid, acidic substances such as inorganic acids or Lewis acids such as boron trifluoride, basic substances such as sodium hydroxide and various amines, alkali metals Or a metal salt such as an alkaline earth metal acetate, and a compound of zinc, manganese, cobalt, antimony, germanium, titanium, tin, etc., preferably a compound of zinc, antimony, titanium, tin, Tetraalkyl titanates, zinc acetate, stannous acetate, and antimony trioxide are preferred. Although transesterification may proceed without using a catalyst, in order to cause the transesterification reaction more reliably, the amount of the transesterification reaction catalyst is preferably 0. 001 to 0.2 parts by weight. When the blending amount is less than 0.001 part by weight, the effect of promoting the transesterification reaction is insufficient, and when it exceeds 0.2 part by weight, coloring or the like tends to occur. The blending amount of the transesterification reaction catalyst is more preferably 0.005 to 0.1 parts by weight, still more preferably 0.004 to 0.08 parts by weight.

Phosphorus stabilizer (E)
In the antistatic resin composition used in the present invention, it is preferable that a specific amount of a phosphorus-based stabilizer (E) is further added from the viewpoint that the thermal stability can be improved. Examples of the phosphorous stabilizer (E) include phosphorous acid, phosphoric acid, phosphorous acid ester, phosphoric acid ester, etc. Among them, phosphite, which contains trivalent phosphorus and easily exhibits a discoloration suppressing effect. Phosphites such as phosphonite are preferred.

  Examples of the phosphite include triphenyl phosphite, tris (nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tris (tridecyl) phosphite. Phyto, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, water Bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butyl) Ruphenyldi (tridecyl) phosphite), tetra (tridecyl) 4,4'-isopropylidene diphenyldiphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, dilaurylpentaerythritol diphosphite Phosphite, distearyl pentaerythritol diphosphite, tris (4-tert-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite 2,2'-methylenebis (4,6-di -tert- butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite and the like.

Moreover, as phosphonite, tetrakis (2,4-di-iso-propylphenyl)
-4,4'-biphenylenediphosphonite, tetrakis (2,4-di-n-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4 , 4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3 '-Biphenylenediphosphonite, tetrakis (2,6-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-n-butylphenyl) -4,4'- Biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylene diphosphonite, tetrakis (2,6 Di -tert- butylphenyl) 4,3'-biphenylene diphosphonite, and tetrakis (2,6-di -tert- butylphenyl) -3,3'-biphenylene diphosphonite, and the like.

  Examples of the acid phosphate include methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, and lauryl phosphate. Phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonyl phenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid Sulfate, dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, di-2-ethylhexyl acid phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distearyl acid phenyl Acid phosphate, bisnonylphenyl acid phosphate, etc. are mentioned.

  Among the phosphites used as the phosphorus stabilizer (E) in the present invention, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) ) Pentaerythritol diphosphite is preferred, and tris (2,4-di-tert-butylphenyl) phosphite is particularly preferred in terms of good heat resistance and resistance to hydrolysis.

  The phosphorus stabilizer (E) used in the present invention can be blended by mixing two or more kinds, but the total blending ratio of the phosphorus stabilizer (E) is usually 100 parts by weight of the polycarbonate resin. 0.01 to 1.0 part by weight, preferably 0.03 to 0.5 part by weight, more preferably 0.05 to 0.2 part by weight. If the amount is less than 0.01 part by weight, the effect as a stabilizer is insufficient, and the molecular weight and the hue are deteriorated easily during molding. Deterioration tends to occur more easily.

  Moreover, the total compounding ratio (E) / (b) (weight ratio) with respect to the sulfonic acid phosphonium salt (b) (general formula (1)) of the phosphorus stabilizer (E) is 0.5 / 100 to 50/100. Preferably, it is 1/100 to 20/100, more preferably 2/100 to 15/100, and the blending ratio of the phosphorus stabilizer (E) to the aromatic polycarbonate oligomer (C) (E) / (C) (weight ratio) is usually 0.1 / 100 to 1000/100, preferably 1/100 to 200/100, more preferably 2/100 for the purpose of preventing thermal deterioration during molding. ~ 40/100.

  Furthermore, the blending ratio (E) / (D) (weight ratio) of the phosphorus stabilizer (E) to the caprolactone polymer (D) is usually 1/500 to 3/1 in order to prevent thermal deterioration during molding. Preferably, it is 1/100 to 1/1, and more preferably 1/15 to 1/3.

Phenolic antioxidant (F)
In the antistatic resin composition used in the present invention, a specific amount of a phenolic antioxidant (F) is further added to improve the mechanical strength, transparency and hue of the polycarbonate resin composition. It is preferable in that it has. Among the phenolic antioxidants (F) that can be used in the present invention, the use of a phenolic antioxidant having a specific structure represented by the following general formula (2) in the molecule is fluidity, transparency, While maintaining antistatic properties, it is preferable in terms of preventing deterioration of hue and improving mechanical strength.

（一般式（２）中、Ｒ^６〜Ｒ^８は、各々独立して水素原子、又は炭素数１〜３のアルキル
基を示し、ｔ−Ｂｕは、ｔｅｒｔ−ブチル基を示す。）

(In General Formula (2), R ^{6 to} R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and t-Bu represents a tert-butyl group.)

R ^{6 to} R ⁸ in the general formula (2) are substituents that are not bulky than the tert-butyl group,
Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In the present invention, it is important that the steric environment around the hydroxyl group is not bulky. As R ^{6 to} R ⁸ , a linear alkyl group is preferable, and a group having 2 or less carbon atoms is preferable. Furthermore, a methyl group or a hydrogen atom is preferable.
In the present invention, it is preferred from the viewpoint of enhancing the antioxidant effect substituents R ⁶ and / or R ⁷ is an alkyl group having 1 to 3 carbon hydrogen atom or a carbon.

  Specific examples of the phenolic antioxidant having a specific structure represented by the general formula (2) in the molecule include 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4 ′. -Butylidenebis (6-tert-butyl-3-methylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 3,9-bis [2- {3 -(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol Bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 1,6-hexanediol bis [β- (3-tert -Butyl-4-hydroxy-5-methylphenyl) propionate], pentaerythritol-tetrakis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], octadecyl [β- (3-tert- Butyl-4-hydroxy-5-methylphenyl) propionate] and the like.

  Among these, 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 1,1,3-tris (2-methyl-) is required in that heat resistance is required when kneaded with a polycarbonate resin. 4-hydroxy-5-tert-butylphenyl) butane, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl ] -2,4,8,10-tetraoxaspiro [5.5] undecane is preferred, especially 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 3 , 9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10 Tetraoxaspiro [5.5] undecane is preferred.

  In the present invention, the phenolic antioxidant (F) can be blended in a combination of two or more, and the blending ratio of the phenolic antioxidant (F) is usually 0 with respect to 100 parts by weight of the polycarbonate resin. 0.01 to 1.0 part by weight, preferably 0.03 to 0.5 part by weight, more preferably 0.05 to 0.2 part by weight. If the amount is less than 0.01 part by weight, the effect as an antioxidant tends to be insufficient. If the amount exceeds 1.0 part by weight, the amount tends to be excessive, and conversely, the occurrence of silver or the deterioration of hue tends to occur. is there.

  The blending ratio (F) / (b) (weight ratio) of the phenolic antioxidant (F) to the sulfonic acid phosphonium salt (b) of the general formula (1) is 0.5 / 100 to 50/100. Yes, preferably 1/100 to 20/100, more preferably 2/100 to 15/100, and the blending ratio of the phenolic antioxidant (F) to the aromatic polycarbonate oligomer (C) (F) / (C) (weight ratio) is usually 0.1 / 100 to 1000/100, preferably 1/100 to 200/100, more preferably 2/100 to prevent deterioration of hue during molding. 40/100. Further, the blending ratio (F) / (D) (weight ratio) of the phenolic antioxidant (F) to the caprolactone polymer (D) is usually 1/100 to 3 / in order to prevent thermal deterioration during molding. 1, preferably 1/40 to 1/1, and more preferably 1/15 to 1/2.

  In the present invention, by blending the phenolic antioxidant (F) in combination with the phosphorus stabilizer (E) described above, the mechanical strength and transparency of the polycarbonate resin composition having antistatic properties, This produces a remarkable effect on the improvement of hue and the like. The blending ratio (F) / (E) (weight ratio) of the phenolic antioxidant (F) of the present invention to the phosphorus stabilizer (E) is 25/100 to 250/100, preferably 50/100 to 200 /. 100, more preferably 75/100 to 125/100.

Weather resistance improver (G)
The antistatic resin composition used in the present invention preferably further contains a specific amount of a weather resistance improver (G) for the purpose of improving the weather resistance. As the weather resistance improver (G), generally known compounds can be used as ultraviolet absorbers and light stabilizers, and their functions are to absorb visible light and ultraviolet light energy and convert them into thermal energy. A mechanism for detoxification by this, a mechanism for detoxifying precursors generated by photochemical action, and the like have been proposed.

  Examples of the weather resistance improver (G) include various types of compounds such as benzophenone series, benzotriazole series, salicylic acid ester series, benzoate series, triazine series, hindered amine series, cinnamyl series, and the like. These may be used alone or in admixture of two or more.

  Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4. -Octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy Examples include -4-methoxybenzophenone-5-sulfonic acid trihydrate, bis (2-hydroxy-3-benzoyl-6-methoxyphenyl) methane, and the like.

  Examples of the benzotriazole compounds include 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) -2H-benzotriazole. 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole, 2- (3 5-di-t-octyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3-lauryl- 5-methyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5 Chloro-2H-benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-bis (1-methyl-1-) Phenylethyl) -2-hydroxyphenyl) -2H-benzotriazole, bis (3- (2H-benzotriazol-2-yl) -2-hydroxy-5-methylphenyl) methane, bis (3- (2H-benzotriazole) -2-yl) -2-hydroxy-5- (1,1,3,3-tetramethylbutyl) phenyl) methane, bis (3- (2H-benzotriazol-2-yl) -2-hydroxy-5 Cumylphenyl) methane, bis (3- (2H-benzotriazol-2-yl) -2-hydroxy-5-octylphenyl) methane, 1,1-bis (3 (2H-benzotriazol-2-yl) -2-hydroxy-5-methylphenyl) octane, 1,1-bis (3- (2H-5-chlorobenzotriazol-2-yl) -2-hydroxy-5 Methylphenyl) octane, 1,2-ethanediylbis (3- (2H-benzotriazol-2-yl) -2-hydroxybenzoate), 1,12-dodecandiylbis (3- (2H-benzotriazol-2-yl) -4-hydroxybenzoate), 1,3-cyclohexanediylbis (3- (5-chloro-2H-benzotriazol-2-yl) -2-hydroxybenzoate), 1,4-butanediylbis (3- (2H-benzo) Triazol-2-yl) -4-hydroxy-5-methylphenylethanoate), 3,6-dioxa-1, 8-octanediylbis (3- (5-methoxy-2H-benzotriazol-2-yl) -4-hydroxyphenylethanoate), 1,6-hexanediylbis (3- (3- (2H-benzotriazole- 2-yl) -4-hydroxy-5-t-butylphenyl) propionate), p-xylenediylbis (3- (3- (2H-benzotriazol-2-yl) -4-hydroxyphenyl) propionate), bis (3- (2H-benzotriazol-2-yl) -4-hydroxytoluyl) malonate, bis (2- (3- (2H-benzotriazol-2-yl) -4-hydroxy-5-octylphenyl) ethyl) Terephthalate, bis (3- (2H-benzotriazol-2-yl) -4-hydroxy-5-propyltoluyl) o Tagioate, 2- (2H-benzotriazol-2-yl) -6-phthalimidomethyl-4-methylphenol, 2- (2H-benzotriazol-2-yl) -6-phthalimidoethyl-4-methylphenol, 2- (2H-benzotriazol-2-yl) -6-phthalimidooctyl-4-methylphenol, 2- (2H-benzotriazol-2-yl) -6-phthalimidomethyl-4-tert-butylphenol, 2- (2H- And benzotriazol-2-yl) -6-phthalimidomethyl-4-cumylphenol, 2- (2H-benzotriazol-2-yl) -4,6-bis (phthalimidomethyl) phenol, and the like.

Examples of the salicylic acid ester compounds include phenyl salicylate, 2,4-ditertiary butylphenyl 3,5-ditertiary butyl 4-hydroxybenzoate, and the like.
Examples of the benzoate compound include 2,4-di-t-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate.
Examples of the triazine compound include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol.

  Examples of hindered amine compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and bis (1 Octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6, -pentamethyl-4-piperidyl) -2- (3,5-di-t -Butyl-4-hydroxybenzyl) -2-n-butylmalonate, dimethyl succinate 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly ((6- (1,1,3,3-Tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl) ((2,2,6,6-tetramethyl-4-piperidyl ) Imino Hexamethylene ((2,2,6,6, -tetramethyl-4-piperidyl) imino)), N, N′-bis (3-aminopropyl) ethylenediamine · 2,4-bis (N-butyl-N—) (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -6-chloro-1,3,5-triazine condensate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) ) 1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate and the like.

  Examples of other weather resistance improvers include 2-ethoxy-2′-ethyl-oxalic acid bisanilide, ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3- Examples include diphenyl acrylate.

  Among the weather resistance improvers described above, benzotriazole compounds are preferred from the viewpoint of compatibility with polycarbonate and little influence on physical properties. Among them, 2- (2-hydroxy-5-t-octylphenyl) -2H-benzoate is preferred. Triazole, bis (3- (2H-benzotriazol-2-yl) -2-hydroxy-5- (1,1,3,3-tetramethylbutyl) phenyl) methane, bis (3- (2H-benzotriazole- 2-yl) -2-hydroxy-5-cumylphenyl) methane, 2- (3,5-bis (1-methyl-1-phenylethyl) -2-hydroxyphenyl) -2H-benzotriazole are preferred, in particular 2- (2-Hydroxy-5-t-octylphenyl) -2H-benzotriazole is preferred.

  The compounding ratio of the weather resistance improver (G) used in the present invention is 0.01 to 3.0 parts by weight, preferably 0.03 to 1.0 parts per 100 parts by weight of the aromatic polycarbonate (A). Part by weight, more preferably 0.1 to 0.8 part by weight. If the amount is less than 0.01 parts by weight, the effect tends to be insufficient. If the amount exceeds 3.0 parts by weight, mold contamination during injection molding tends to occur. The weather resistance improver can be used alone or in combination.

  In the present invention described above, the blending ratio (G) / (C) (weight ratio) of the weather resistance improver (G) to the aromatic polycarbonate oligomer (C) is usually 0.1 / 100 to 3000/100, preferably 1. / 100 to 300/100, more preferably 3/100 to 160/100, and the blending ratio (G) / (D) (weight ratio of the weather resistance improver (G) to the caprolactone polymer (D) ) Is usually 1/50 to 5/1, preferably 1/20 to 2/1, more preferably 1/10 to 1/1. The weather resistance improver (G) is preferably used in combination with the phenolic antioxidant (F), and the blending ratio (G) of the weather resistance improver (G) to the phenolic antioxidant (F). / (F) (weight ratio) is usually 0.1 to 20, preferably 0.5 to 10, and more preferably 1.0 to 5.0.

Antistatic polycarbonate resin composition (J)
The antistatic polycarbonate resin composition (J) used in the present invention has other polymers, flame retardants, impact resistance improvers, plasticizers, mold release agents, and the like that provide desired characteristics without departing from the spirit of the present invention. Agents, lubricants, compatibilizers, colorants (pigments such as carbon black and titanium oxide, dyes such as bluing agents), glass fibers, glass beads, glass flakes, carbon fibers, fibrous magnesium, potassium titanate whiskers, ceramics You may contain 1 type, or 2 or more types, such as reinforcing agents, such as a whisker, mica, talc, clay, and a calcium silicate, a filler.

Among the various additives described above, in the present invention, in order to suppress coloration more effectively, a bluing agent ( H ), for example, DAIRESIN BLUE G manufactured by Mitsubishi Chemical Corporation, preferably MACROLEX BLUE manufactured by LANXESS Corporation. It is preferable to mix an anthraquinone-based bluing agent such as RR, MACROLEX BLUE 3R manufactured by LANXESS Corporation, or MACROLEX VIOLET 3R manufactured by LANXESS Corporation.

As the method for preparing the antistatic polycarbonate resin composition (J) used in the present invention, the polycarbonate resin (A) can be prepared by various methods well known to those skilled in the art at any stage up to immediately before the final molded product is melt-molded. ), The antistatic agent (B) mentioned above, and if necessary, an aromatic polycarbonate oligomer (C), a caprolactone polymer (D), a phosphorus stabilizer (E), a phenolic antioxidant (F), weather resistance The method of mix | blending and knead | mixing a property improving agent (G) is mentioned.
Examples of the blending method include a method using a tumbler, a Henschel mixer, a super mixer, etc., and a method of quantitatively feeding to an extruder hopper with a feeder and mixing. Examples of the kneading method include a method using a single screw extruder, a twin screw extruder, and the like. In order to improve the dispersibility of the antistatic agent, it is more preferable to use a twin screw extruder.

Furthermore, since the sulfonic acid phosphonium salt (b) preferably used as the antistatic agent (B) used in the present invention may be a viscous liquid at room temperature, it is specifically supplied to the extruder by the following method. Can do.
(1) The phosphonium salt of sulfonic acid (b) is heated and the viscosity is lowered, and then blended with a polycarbonate resin, an aromatic polycarbonate oligomer, a caprolactone polymer and other stabilizers using a super mixer or the like. After that, the method of supplying to an extruder.
(2) A method in which the phosphonium salt of sulfonic acid (b) is heated and directly supplied to the extruder using a liquid supply apparatus in a state where the viscosity is lowered. Necessary components other than (b) are blended in advance and kneaded with an antistatic agent in an extruder.
(3) The phosphonium salt of sulfonic acid (b) is heated to lower the viscosity, and then a master agent of high concentration (b) and polycarbonate resin is prepared. Thereafter, the remaining polycarbonate resin, aromatic polycarbonate oligomer, caprolactone polymer, and other necessary additives are added to the master agent, and the mixture is mixed using a tumbler, Henschel mixer, etc., and an extruder. How to supply to.

Manufacturing method of antistatic polycarbonate resin molded product The molding method of the molded product of the present invention is preferably an injection molding method in that the shear rate during molding can be controlled relatively easily. The injection molding method is not only a normal injection molding method but also injection compression molding, injection press molding, gas assist injection molding, insert molding, in-mold coating molding, heat insulation mold molding, rapid heating / cooling mold molding, two-color molding. , Sandwich molding, ultra-high speed injection molding, and the like. In addition, either a cold runner method or a hot runner method can be selected for molding.

In the present invention, an injection molding of an antistatic polycarbonate resin composition (J) is performed in order to stably mold a molded article having a high level of antistatic properties from a resin composition containing a relatively small amount of an antistatic agent. For the conditions, it is particularly important to select the maximum shear rate of the antistatic resin composition (J) when passing through the gate. Here, the maximum shear rate is calculated by the following formula.
γ ₀ = 6Q / wh ²
γ ₀ : Maximum shear rate (1 / sec)
Q: Injection flow rate (mm ³ / sec)
w: Gate width (mm)
h: Gate thickness (mm)
That is, in order to obtain a stable molded article such as antistatic property, in the molding method of the present invention, the maximum shear rate of the resin composition (J) when passing through the gate is 1500 to 10,000 / sec, preferably 2000. -9500 / sec, more preferably 2500-9000 / sec, particularly preferably 3000-8500 / sec. When the maximum shear rate exceeds 10,000 / sec, the surface specific resistance value increases, and sufficient antistatic properties cannot be exhibited. Furthermore, inconveniences such as difficulty in injecting the resin into the mold or filling the mold details become difficult, and appearance defects such as flow marks are likely to occur. In addition, when the maximum shear rate is less than 1500 / sec, the resin melt-injected into the mold flows in a slight wave and solidifies before adhering to the mirror-finished mold surface. It becomes skin-like and the appearance deteriorates.
The “gate” is the narrowest part of the resin flow path immediately before the molded product cavity, and is usually the part that separates the molded product from the runner. The vertical cross section of the flow path is usually rectangular. None, the long side corresponds to the width (w) of the gate and the short side corresponds to the thickness (h) of the gate. As a gate system, a direct gate, a side gate, a pinpoint gate, a fan gate, a submarine gate, etc. can be applied. Side gates and pinpoint gates are often used as the gate method for polycarbonate molded products. In the side gate method, the gate thickness is desired to be designed as thin as possible from the viewpoint of finishing, but if it is too thin, filling failure may occur, so the gate thickness is 40 to 90 of the molded product thickness. %, Preferably 50 to 80%.

In the injection molding method of the present invention, the resin temperature of the molding machine is two hundred and seventy to three hundred twenty ° C., good preferable is 280 ° C. to 310 ° C.. When the resin temperature is less than 270 ° C., the viscosity of the molten resin is high, and appearance defects and filling defects are likely to occur. If it exceeds 320 ° C., the molded product will be discolored or burnt.
The mold temperature is 40 to 120 ° C., good preferable is 60 to 90 ° C.. When the mold temperature is less than 40 ° C, the appearance of the molded product is deteriorated. When the mold temperature is higher than 120 ° C, the solidification time of the molten resin filled in the mold becomes longer, and the molding cycle becomes longer. This is not preferable.
The molding cycle in the injection molding method of the present invention is 10 to 120 sec, preferably 20 to 80 sec, particularly preferably 30 to 70 sec. If the molding cycle is less than 10 seconds, mold release defects are likely to occur, and if it exceeds 120 seconds, the resin is discolored in the molding machine or the production efficiency is lowered.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. In the following examples, “parts” represents “parts by weight”, and the raw materials to be used, the polycarbonate resin composition production method and the molding method, and the physical property evaluation methods are shown below.

〔raw materials〕
(1) Aromatic polycarbonate resin: manufactured by Mitsubishi Engineering Plastics / trade name Iupilon S-2000 (registered trademark) / viscosity average molecular weight: 23,000 (abbreviated as “polycarbonate resin A-1” in Tables 1 to 3) To do).
(2) Phosphonic acid phosphonium salt: Takemoto Yushi Co., Ltd./trade name MEC-100 / dodecylbenzenesulfonic acid tetrabutylphosphonium salt (abbreviated as “antistatic agent B-1” in Tables 1 to 3) .
(3) Aromatic polycarbonate oligomer: Mitsubishi Engineering Plastics Co., Ltd./trade name PC oligomer AL071 / viscosity average molecular weight: 5,000 / number average degree of polymerization: 8 (in Tables 1 to 3, "Oligomer C-1" Abbreviated).
(4) Caprolactone-based polymer: Daicel Chemical Industries, Ltd./trade name Plaxel H1P / number average molecular weight 10,000 (abbreviated as “caprolactone polymer D-1” in Tables 1 to 3)

(5) Phosphorus stabilizer: Asahi Denka Kogyo Co., Ltd./trade name ADK STAB 2112 / Tris (2,4-di-tert-butylphenyl) phosphite (in Tables 1 to 3, "Phosphorus stabilizer E-1 For short).
(6) Phenol antioxidant: Asahi Denka Kogyo Co., Ltd./Brand name ADK STAB AO-80 / 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyl Oxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (abbreviated as “antioxidant F-1” in Tables 1 to 3).

(7) Weather resistance improver: manufactured by Sipro Kasei Co., Ltd./trade name SEESORB 709 / benzotriazole ultraviolet absorber 2- (2-hydroxy-5-t-octylphenyl) -2H-benzotriazole (Table-1) 3 is abbreviated as “weather resistance improver G-1”).
(8) Blueing agent In the resin compositions of all examples and comparative examples, (H-1) LANXESS Co., Ltd./trade name macro as a blueing agent (H) with respect to 100 parts of the polycarbonate resin. Rex Blue RR was mixed with 0.00048 part, and (H-2) LANXESS Co., Ltd./trade name Macrolex Violet 3R was mixed with 0.00048 part.

[Preparation of polycarbonate resin composition]
For 100 parts of polycarbonate resin (A-1) produced from bisphenol A and phosgene by the interfacial condensation polymerization method, sulfonic acid phosphonium salt (antistatic agent B-1), aromatic polycarbonate oligomer (C-1), caprolactone A polymer (D-1), a phosphorus stabilizer (E-1), an antioxidant (F-1) and a weather resistance improver (G-1) are blended in the amounts shown in Tables 1 to 3 above. After blending with a predetermined blending agent (H) and mixing with a blender, the mixture was melt-kneaded using a vent type twin screw extruder and pelletized to obtain a polycarbonate resin composition (J). Since the sulfonic acid phosphonium salt (antistatic agent B-1) is a viscous liquid at room temperature, the blending method is such that (B-1) is heated in advance to lower the viscosity, and the ratio of (B-1) is A preliminary mixture with the polycarbonate resin (A-1) so as to be 10% by weight was prepared with a super mixer, and then all raw materials were mixed using a tumbler blender so as to obtain a predetermined component composition. The vent type twin-screw extruder used was TEX30XCT (completely meshed, rotating in the same direction, two-thread screw) manufactured by Nippon Steel Works. The extrusion conditions were a cylinder temperature of 280 ° C., a discharge rate of 25 kg / h, and a screw rotation speed of 200 rpm.

[Molding of resin composition]
Prepared resin composition pellets of (J), 5 hours at 120 ° C., dried in a hot air circulation type dryer, Meiki Co., Ltd., using a M150AII-SJ injection molding machine, formed shape Resin temperature, mold temperature, and resin at the time of passing through the gate shown in Tables 1 to 3 under conditions of a cycle of 60 sec and using a side gate (gate width: 6.9 mm, gate thickness: 2.4 mm, gate land: 2.5 mm) The disk (1) (diameter 100 mm, wall thickness 3.2 mm) was injection molded under the conditions of the maximum shear rate of the composition (J).

[Method of evaluating physical properties of molded products]
(1) Surface resistance value: About the disc (1) with a thickness of 3.2 mm, the surface resistance value was measured according to ASTM-D257.
(2) Appearance of molded product: The surface state of the molded product (skin skin, flow mark, transparency, silver, wrinkles, etc.) was visually observed.

表−１及び表−２から明らかなように、本発明の成形法で成形した実施例１〜９の成形品は、帯電防止性と外観に優れていた。樹脂の流動性、耐熱性に起因する外観不良も認められなかった。しかし、表−３から明らかなように、最大せん断速度の高い条件で成形した比較例１〜４の成形品は、表面固有抵抗値が大きく、充分な帯電防止特性ではなかった。さらに成形品の表面にフローマークによる外観不良や透明性の低下が発生していた。また、最大せん断速度の低い条件で成形した比較例５の成形品は、充填不良により成形品の表面にユズ肌状態の外観不良や透明性の低下が発生していた。

As is clear from Table-1 and Table-2, the molded articles of Examples 1 to 9 molded by the molding method of the present invention were excellent in antistatic properties and appearance. There was no appearance defect due to the fluidity and heat resistance of the resin. However, as is apparent from Table 3, the molded products of Comparative Examples 1 to 4 molded under conditions with a high maximum shear rate had large surface specific resistance values and did not have sufficient antistatic properties. In addition, the appearance of the flow mark and a decrease in transparency occurred on the surface of the molded product. Further, in the molded product of Comparative Example 5 molded under the condition of a low maximum shear rate, the appearance of a crushed skin state or a decrease in transparency occurred on the surface of the molded product due to poor filling.

Claims (6)

0.1 to 5.0 parts by weight of the sulfonic acid phosphonium salt (b) represented by the following general formula (1) as the antistatic agent (B ) with respect to 100 parts by weight of the polycarbonate resin (A)

(In General Formula (1), R ¹ is an alkyl group having 1 to 40 carbon atoms or an aryl group, and may have a substituent, and R ^{2 to} R ⁵ are each independently a hydrogen atom or carbon. (It is an alkyl group or an aryl group of formulas 1 to 10, and these may be the same or different.)
When a molded product is injection-molded from a polycarbonate resin composition (J) blended with resin at a molding machine resin temperature of 270 to 320 ° C. and a mold temperature of 40 to 120 ° C., the maximum shear of the resin composition (J) when passing through the gate A method for producing an antistatic polycarbonate resin molded product, wherein the speed is set to 1500 to 10,000 / sec. The polycarbonate resin composition (J) is, with respect to the polycarbonate resin (A) 100 parts by weight of 0.1 to 10 parts by weight of Kaoru aromatic polycarbonate oligomer (C), and, caprolactone-based polymer (D) 0. The method for producing an antistatic polycarbonate resin molded article according to claim 1, wherein 01 to 8 parts by weight are blended.   The said polycarbonate resin composition (J) mix | blends 0.01-1.0 weight part of phosphorus stabilizers (E) with respect to 100 weight part of polycarbonate resin (A), It is characterized by the above-mentioned. 3. A method for producing an antistatic polycarbonate resin molded article according to 1 or 2. The polycarbonate resin composition (J) contains 0.01 to 1 phenolic antioxidant (F) having a structure represented by the following general formula (2) in the molecule with respect to 100 parts by weight of the polycarbonate resin (A). The method for producing an antistatic polycarbonate resin molded article according to any one of claims 1 to 3, wherein 0.0 part by weight is blended.

(In General Formula (2), R ^{6 to} R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and t-Bu represents a tert-butyl group.)   The polycarbonate resin composition (J) comprises 0.01 to 3.0 parts by weight of a weather resistance improver (G) with respect to 100 parts by weight of the polycarbonate resin (A). Item 5. A method for producing an antistatic polycarbonate resin molded article according to any one of Items 1 to 4.   The antistatic polycarbonate resin molded product obtained by the manufacturing method in any one of Claims 1-5.