JP2010209178A - Aromatic polycarbonate resin composition and molded article of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate resin composition having both flame retardancy and a transparency independent of the molding conditions. <P>SOLUTION: A resin composition includes a base resin comprising ≥20 mass% of an aromatic polycarbonate resin having a structural viscosity index N of ≥1.2 and a metal salt of fluoroalkylsulfonate containing a C-H bond, wherein the metal salt is contained in an amount of 0.1-1.25 ppm in terms of a metal concentration based on 100 pts.mass of the base resin. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an aromatic polycarbonate resin composition. More specifically, the present invention relates to an aromatic polycarbonate resin composition and an aromatic polycarbonate resin composition molded article having flame retardancy and high transparency that does not depend on molding conditions.

  Aromatic polycarbonate resin is a resin that excels in heat resistance, mechanical properties, and electrical properties, and is widely used in, for example, automotive materials, electrical / electronic equipment materials, housing materials, and other parts manufacturing materials in industrial fields. Yes. In particular, the flame-retardant aromatic polycarbonate resin composition is suitably used as a member of OA / information equipment such as a computer, a notebook computer, a mobile phone, a printer, and a copying machine.

  As a means for imparting flame retardancy to an aromatic polycarbonate resin, conventionally, a halogen-based flame retardant or a phosphorus-based flame retardant has been added to the aromatic polycarbonate resin. However, an aromatic polycarbonate resin composition containing a halogen-based flame retardant containing chlorine or bromine may cause a decrease in thermal stability or corrosion of a molding machine screw or a molding die during molding processing. There was a thing. In addition, aromatic polycarbonate resin compositions containing phosphorus-based flame retardants impair high transparency, which is a characteristic of aromatic polycarbonate resins, and cause a decrease in impact resistance and heat resistance. There was a limit. In addition, these halogen-based flame retardants and phosphorus-based flame retardants may cause environmental pollution at the time of product disposal and recovery, and in recent years, these flame retardants can be made flame retardant without using these flame retardants. It is desired.

  Under such circumstances, in recent years, organic alkali metal salt compounds and organic alkaline earth metal salt compounds (hereinafter, collectively referred to as “organic alkali (earth) metal salt compounds”) are useful as many flame retardants. It is being considered. When an organic alkali (earth) metal salt compound is used as a flame retardant, an effect can be obtained in a relatively small amount, and mechanical properties such as impact resistance inherent in an aromatic polycarbonate resin, heat resistance, electrical characteristics, etc. This is because flame retardancy can be imparted without impairing properties.

  Examples of the flame retardant technology for aromatic polycarbonate using an organic alkali (earth) metal salt compound include, for example, a method using a perfluoroalkylsulfonic acid alkali metal salt having 4 to 8 carbon atoms (see Patent Document 1), carbon number A flame retardant property is imparted to an aromatic polycarbonate resin using an alkali metal salt compound of perfluoroalkanesulfonic acid, such as a method of blending 1 to 3 alkali metal salts of perfluoroalkanesulfonic acid (see Patent Document 2). A method has been proposed.

  On the other hand, as a flame-retarding technique that does not use an alkali metal salt of perfluoroalkanesulfonic acid, for example, a method of adding a non-halogen aromatic sodium sulfonate (see Patent Document 3), a non-halogen aromatic sulfonic acid A method of imparting flame retardancy to an aromatic polycarbonate resin composition using an alkali metal salt compound of an aromatic sulfonic acid such as a method of adding a potassium salt (see Patent Document 4) has been proposed.

  In addition, aromatic polycarbonate resin compositions containing an organic alkali (earth) metal salt compound in an aromatic polycarbonate resin can prevent dripping during combustion and further improve flame retardancy. A method using a group polycarbonate resin (see Patent Document 5), a method using a silicone compound in combination (see Patent Documents 6 to 8), and the like have been proposed.

Japanese Patent Publication No. 47-40445 Japanese Patent Publication No.54-32456 JP 2000-169696 A JP 2001-181493 A JP 2000-336260 A JP-T-2004-524423 JP-A-8-208970 Special Table 2003-53940

  However, when the aromatic polycarbonate resin composition using the techniques described in Patent Documents 1 and 2 is molded under specific conditions, the excellent transparency of the aromatic polycarbonate resin may be inhibited. Specifically, although high transparency is likely to be obtained when the molding temperature is relatively high, for example, (i) lower from the viewpoint of preventing deterioration of mechanical properties due to decomposition of the aromatic polycarbonate resin at high temperature and from the viewpoint of energy saving. When molded at the molding temperature, (ii) when the product thickness is relatively large due to product design, (iii) when extrusion molding is performed to obtain a sheet-like molded product, the molded product becomes cloudy and transparent. May be significantly impaired.

  Further, as described in Patent Documents 3 and 4, an aromatic polycarbonate resin composition containing an aromatic (earth) metal salt compound of an aromatic sulfonic acid is a perfluoroalkane sulfone as described in Patent Documents 1 and 2. Compared to an aromatic polycarbonate resin composition containing an acid-alkali metal salt, flame retardancy tends to decrease, and transparency is lost even with a small amount.

  Furthermore, an aromatic polycarbonate resin composition obtained by simply blending an organic alkali (earth) metal salt compound as described above with an aromatic polycarbonate resin has an effect of reducing the burning time, but the aromatic polycarbonate resin composition during burning is recognized. There was a possibility that the dripping of objects occurred and the material just below was ignited.

  Further, in the techniques described in Patent Documents 5 to 8, there is no fundamental improvement effect with respect to the above-described transparency, and satisfactory transparency has not yet been obtained depending on molding conditions.

As described above, an aromatic polycarbonate resin composition having both flame retardancy and excellent transparency that does not depend on molding conditions has not yet been obtained, and an aromatic polycarbonate resin composition having such characteristics is strong. It was desired.
The present invention was devised in view of the above-mentioned problems, and has excellent mechanical, thermal, and electrical properties of the aromatic polycarbonate resin, and has both flame retardancy and transparency that does not depend on molding conditions. An object of the present invention is to provide an aromatic polycarbonate resin composition and a molded body comprising the same.

  In order to solve the above-mentioned problems, the present inventors diligently studied the relationship between the structure and amount of the organometallic salt compound to be blended, flame retardancy, and transparency in the aromatic polycarbonate resin and the organometallic salt compound. As a result, surprisingly, by adding a metal salt of a sulfonic acid having a specific organic skeleton to a specific aromatic polycarbonate resin so as to have a specific metal concentration, it has excellent flame retardancy, In addition, the present inventors have found that an aromatic polycarbonate resin composition having excellent transparency regardless of molding conditions (specifically, having high transparency even when molded at low temperature) can be obtained, and the present invention has been completed. It was.

  Here, “transparent” is defined as having a thickness of 3 mm and a haze (cloudiness value) measured according to JIS K-7105 of 10 or less. A more preferred transparent aromatic polycarbonate resin composition has a haze of 5 or less, and a particularly preferred aromatic polycarbonate resin composition has a haze of 2 or less.

  That is, the aromatic polycarbonate resin composition of the present invention comprises a base resin containing 20% by weight or more of an aromatic polycarbonate resin having a structural viscosity index N of 1.2 or more, and a metal of fluoroalkylsulfonic acid containing a C—H bond. And a metal concentration in the range of 0.1 ppm to 1.25 ppm in terms of metal concentration with respect to 100 parts by mass of the base resin.

At this time, it is preferable that this base resin contains a linear aromatic polycarbonate resin in the ratio of 80 mass% or less.
The metal salt preferably has a partial structure represented by the following formula (1).

［式（１）中、Ｍは金属元素を表す。］

[In formula (1), M represents a metal element. ]

  Further, the metal salt is preferably a metal salt of 1,1,2,2-tetrafluoroethanesulfonic acid, and is an alkali metal salt of 1,1,2,2, -tetrafluoroethanesulfonic acid. Is more preferable, and potassium 1,1,2,2-tetrafluoroethanesulfonate is particularly preferable.

The aromatic polycarbonate resin composition of the present invention preferably contains 0.01 to 3 parts by mass of the silicone compound with respect to 100 parts by mass of the base resin.
The silicone compound preferably has a phenyl group. Among these, the silicone compound is more preferably at least one selected from the group consisting of polymethylphenylsiloxane, phenyl group-containing cyclic siloxane, and a phenyl group-containing silane monomer represented by the following formula (2).

［式（２）中、Ｒ^ａは炭素数１〜１８のアルキル基、炭素数６〜１２のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基、炭素数６〜１２のアリール基、炭素数７〜９のフェニルアルキル基からなる群より選ばれる少なくとも１種を表し、Ｒ^ｂは水素原子、炭素数１〜４のアルキル基、炭素数７〜９のフェニルアルキル基からなる群より選ばれる少なくとも１種を表し、ｎは１〜３の整数を表す。なお、Ｒ^ａ及び／又はＲ^ｂが２以上存在する場合には、Ｒ^ａ及び／又はＲ^ｂはそれぞれ同一の基であってもよく、異なる基であってもよい。ただし、Ｒ^ａのうち、少なくとも１つはフェニル基である。］

[In the formula (2), R ^a is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, carbon It represents at least one selected from the group consisting of phenylalkyl groups having 7 to 9 and ^Rb is selected from the group consisting of hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, and phenylalkyl groups having 7 to 9 carbon atoms. At least 1 type is represented, n represents the integer of 1-3. In addition, when two or more of R ^a and / or R ^b are present, R ^a and / or R ^b may be the same group or different groups. However, at least one of R ^a is a phenyl group. ]

  Further, the aromatic polycarbonate resin having a structural viscosity index N of 1.2 or more is preferably an aromatic polycarbonate resin produced by a transesterification reaction between an aromatic dihydroxy compound and a carbonic acid diester.

  The molded article of the aromatic polycarbonate resin composition of the present invention is formed by molding the aromatic polycarbonate resin composition of the present invention.

  The aromatic polycarbonate resin composition and the aromatic polycarbonate resin composition molded article of the present invention have both flame retardancy and high transparency that does not depend on molding conditions.

Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the embodiments and examples described below, and may be arbitrarily selected without departing from the scope of the present invention. You can change it to
In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. Further, the “group” of various compounds in the present specification may have a substituent without departing from the gist of the present invention.

[1. Overview]
The aromatic polycarbonate resin composition of the present invention comprises a base resin composed of an aromatic polycarbonate resin and a fluoroalkyl sulfonic acid containing a C—H bond (hereinafter referred to as “C—H bond-containing fluoroalkyl sulfonic acid” as appropriate). And a metal salt at least. The aromatic polycarbonate resin composition of the present invention preferably contains a silicone compound. Furthermore, the aromatic polycarbonate resin composition of the present invention may contain other components in addition to these unless the effects of the present invention are significantly impaired.

[2. Base resin (aromatic polycarbonate resin)]
The aromatic polycarbonate resin composition of the present invention includes a base resin composed of an aromatic polycarbonate resin. However, in the aromatic polycarbonate resin constituting the base resin, a certain proportion or more of the aromatic polycarbonate resin is an aromatic polycarbonate resin having a structural viscosity index N in a predetermined range.

The structural viscosity index N is an index for evaluating the flow characteristics of the melt. Usually, the melting characteristics of an aromatic polycarbonate resin can be expressed by the formula: γ = a · σ ^N. In the above formula, γ: shear rate, a: constant, σ: stress, N: structural viscosity index.
In the above formula, when N = 1, Newtonian fluidity is shown, and the non-Newtonian fluidity increases as the value of N increases. That is, the flow characteristics of the melt are evaluated by the magnitude of the structural viscosity index N. In general, an aromatic polycarbonate resin having a large structural viscosity index N tends to have a high melt viscosity in a low shear region. For this reason, when an aromatic polycarbonate resin having a large structural viscosity index N is mixed with another aromatic polycarbonate resin, dripping at the time of combustion of the obtained aromatic polycarbonate resin composition can be suppressed and flame retardancy can be improved. it can.

  In the aromatic polycarbonate resin composition of the present invention, the structural resin has a structural viscosity index N of usually 1.2 or more, preferably 1.25 or more, more preferably 1.3 or more, and usually 1.8 or less. Preferably, an aromatic polycarbonate resin of 1.7 or less is contained in a certain proportion or more. By containing an aromatic polycarbonate resin having a high structural viscosity index N in this way, dripping at the time of combustion of the aromatic polycarbonate resin composition of the present invention can be suppressed and flame retardancy can be improved. Moreover, the moldability of the aromatic polycarbonate resin composition of this invention can be maintained in a favorable range by making structural viscosity index N below the upper limit of the said range.

The “structural viscosity index N” is expressed by Log η _a = [(1−N) / N] × Log γ + C, which is derived from the above formula, for example, as described in Japanese Patent Application Laid-Open No. 2005-232442. It is also possible. In the above formula, N: structural viscosity index, γ: shear rate, C: constant, η _a : apparent viscosity. As seen from this equation, it is also possible to evaluate the N value from γ and eta _a at very different low shear region viscosity behavior. For example, the N value can be determined from η _a at γ = 12.16 sec ⁻¹ and γ = 24.32 sec ⁻¹ .

  In the aromatic polycarbonate resin composition of the present invention, the base resin is usually 20% by mass or more, preferably 50% by mass or more, more preferably 60% by mass of the above-described aromatic polycarbonate resin having the structural viscosity index N in a predetermined range. Including at least%. This is because, by combining with an aromatic polycarbonate resin having a structural viscosity index N in a predetermined range, the metal salt according to the present invention can remarkably exhibit a specific effect. In addition, there is no restriction | limiting in an upper limit, Although it is 100 mass% or less normally, Preferably it is 90 mass% or less, More preferably, it is 85 mass% or less.

  In addition, 1 type may be used for the aromatic polycarbonate resin in which the structural viscosity index N exists in the predetermined range, and 2 or more types may be used together by arbitrary combinations and ratios.

  Further, the base resin may include an aromatic polycarbonate resin having a structural viscosity index N outside the predetermined range in addition to the above-described aromatic polycarbonate resin having a structural viscosity index N within a predetermined range. Although there is no restriction | limiting in the kind, A linear aromatic polycarbonate resin is preferable especially. By combining an aromatic polycarbonate resin having a structural viscosity index N within a predetermined range and a linear aromatic polycarbonate resin, flame retardancy (anti-dripping property) and moldability (flowability) of the obtained aromatic polycarbonate resin composition ) Is easier to balance. From this point of view, it is particularly preferable that the base resin is composed of an aromatic polycarbonate resin having a structural viscosity index N in a predetermined range and a linear aromatic polycarbonate resin.

  When the base resin contains a linear aromatic polycarbonate resin, the proportion of the linear aromatic polycarbonate resin in the base resin is usually 80% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less. In addition, it is usually larger than 0% by mass, preferably 10% by mass or more, more preferably 15% by mass or more. By setting the linear aromatic polycarbonate resin in the above range, an advantage can be obtained by combining the aromatic polycarbonate resin having the structural viscosity index N in the predetermined range and the linear aromatic polycarbonate resin as described above. Good dispersibility of the flame retardant and other additives can be easily obtained.

  The base resin may contain only one type of aromatic polycarbonate resin having a structural viscosity index N outside the above predetermined range, or may contain two or more types in any combination and ratio. Therefore, the base resin may contain only one type of linear aromatic polycarbonate resin, or may contain two or more types in any combination and ratio.

  The molecular weight of the base resin according to the present invention is arbitrary and may be appropriately selected and determined. The viscosity average molecular weight [Mv] converted from the solution viscosity is usually 10,000 or more, preferably 16000 or more, more preferably 18000 or more. Moreover, it is 40000 or less normally, Preferably it is 30000 or less. By making the viscosity average molecular weight more than the lower limit of the above range, the mechanical strength of the aromatic polycarbonate resin composition of the present invention can be further improved, and more preferable when used for applications requiring high mechanical strength. Become. On the other hand, by making the viscosity average molecular weight not more than the upper limit of the above range, it is possible to suppress and improve the fluidity reduction of the aromatic polycarbonate resin composition of the present invention, so that the molding processability can be improved and the molding process can be easily performed Become. In addition, two or more types of aromatic polycarbonate resins having different viscosity average molecular weights may be mixed and used as the base resin. In this case, an aromatic polycarbonate resin having a viscosity average molecular weight outside the above preferred range is mixed. May be.

The viscosity average molecular weight [Mv] is obtained by using methylene chloride as a solvent and obtaining an intrinsic viscosity [η] (unit: dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer. , Η = 1.23 × 10 ⁻⁴ Mv ^0.83 . The intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g / dl).

  Although there is no restriction | limiting in the specific kind of aromatic polycarbonate resin which can be used as base resin, For example, the aromatic polycarbonate polymer formed by making an aromatic dihydroxy compound and a carbonate precursor react is mentioned. At this time, in addition to the aromatic dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. The aromatic polycarbonate polymer may be linear or branched. Furthermore, the aromatic polycarbonate polymer may be a homopolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units. Usually, such an aromatic polycarbonate polymer becomes a thermoplastic resin.

  Examples of aromatic dihydroxy compounds among monomers used as raw materials for aromatic polycarbonate resins include 2,2-bis (4-hydroxyphenyl) propane (ie, bisphenol A), bis (4-hydroxyphenyl). Methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxy) -3-methylphenyl) propane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2- Bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane Bis (hydroxyaryl) alkanes such as bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane;

Bis such as 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (Hydroxyaryl) cycloalkanes;

Cardostructure-containing bisphenols such as 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene;

Dihydroxy diaryl ethers such as 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether;

Dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide;

Dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide;

Dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone;

Examples include hydroquinone, resorcin, and 4,4'-dihydroxydiphenyl.

Among these, bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane is particularly preferable from the viewpoint of impact resistance.
In addition, 1 type may be used for an aromatic dihydroxy compound and it may use 2 or more types together by arbitrary combinations and a ratio.

Among the monomers used as the raw material for the aromatic polycarbonate resin, examples of the carbonate precursor include carbonyl halide, carbonate ester, haloformate and the like. Specific examples include phosgene; diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; and dihaloformates of dihydric phenols.
In addition, 1 type may be used for a carbonate precursor and it may use 2 or more types together by arbitrary combinations and a ratio.

-Manufacturing method of aromatic polycarbonate resin The manufacturing method of aromatic polycarbonate resin is not specifically limited, Arbitrary methods are employable. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. Hereinafter, a particularly preferable one of these methods will be specifically described.

.. Interfacial polymerization method The case where an aromatic polycarbonate resin is produced by the interfacial polymerization method will be described. In the interfacial polymerization method, in the presence of an organic solvent inert to the reaction and an aqueous alkali solution, the pH is usually kept at 9 or higher, and an aromatic dihydroxy compound and a carbonate precursor (preferably phosgene) are reacted and then polymerized. An aromatic polycarbonate resin is obtained by interfacial polymerization in the presence of a catalyst. In the reaction system, a molecular weight adjusting agent (terminal terminator) may be present if necessary, and an antioxidant may be present for preventing the oxidation of the aromatic dihydroxy compound.

  The aromatic dihydroxy compound and the carbonate precursor are as described above. Of the carbonate precursors, phosgene is preferably used, and the method using phosgene is particularly called a phosgene method.

  Examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene. It is done. In addition, 1 type may be used for an organic solvent and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the alkali compound contained in the alkaline aqueous solution include alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogen carbonate, among which sodium hydroxide and water Potassium oxide is preferred. In addition, an alkali compound may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  Although there is no restriction | limiting in the density | concentration of the alkali compound in alkaline aqueous solution, Usually, in order to control pH in the alkaline aqueous solution of reaction to 10-12, it is used at 5-10 mass%. For example, when phosgene is blown, the molar ratio of the bisphenol compound and the alkali compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. Among these, it is preferable that the ratio is 1: 2.0 or more, usually 1: 3.2 or less, and more preferably 1: 2.5 or less.

  Examples of the polymerization catalyst include tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine and pyridine; quaternary such as trimethylbenzylammonium chloride, tetramethylammonium chloride and triethylbenzylammonium chloride. An ammonium salt etc. are mentioned. In addition, 1 type may be used for a polymerization catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the molecular weight regulator include compounds having a monovalent phenolic hydroxyl group. Specific examples include m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. In addition, a molecular weight regulator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The usage-amount of a molecular weight regulator is 0.5 mol or more normally with respect to 100 mol of aromatic dihydroxy compounds, Preferably it is 1 mol or more, and is 50 mol or less normally, Preferably it is 30 mol or less. By making the usage-amount of a molecular weight modifier into this range, the thermal stability and hydrolysis resistance of an aromatic polycarbonate resin composition can be improved.

In the reaction, the order of mixing the reaction substrate, reaction medium, catalyst, additive and the like is arbitrary as long as the desired aromatic polycarbonate resin is obtained, and an appropriate order may be set arbitrarily. For example, when phosgene is used as the carbonate precursor, the molecular weight regulator can be mixed at any time as long as it is from the reaction (phosgenation) of the aromatic dihydroxy compound and phosgene to the start of the polymerization reaction. .
In addition, reaction temperature is 0-40 degreeC normally, and reaction time is normally several minutes (for example, 10 minutes)-several hours (for example, 6 hours).

-Melt transesterification method Next, the case where an aromatic polycarbonate resin is manufactured by the melt transesterification method is demonstrated. In the melt transesterification method, for example, a transesterification reaction between a carbonic acid diester and an aromatic dihydroxy compound is performed.

The aromatic dihydroxy compound is as described above.
On the other hand, examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate; diphenyl carbonate; substituted diphenyl carbonate such as ditolyl carbonate, and the like. Among these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is more preferable. In addition, 1 type may be used for carbonic acid diester, and it may use 2 or more types together by arbitrary combinations and a ratio.

  The ratio of the aromatic dihydroxy compound and the carbonic acid diester is arbitrary as long as the desired aromatic polycarbonate resin can be obtained, but it is preferable to use equimolar amounts or more of the carbonic acid diester with respect to 1 mol of the aromatic dihydroxy compound. It is more preferable to use 01 mol or more. The upper limit is usually 1.30 mol or less. By setting it as such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.

  In an aromatic polycarbonate resin, the amount of terminal hydroxyl groups tends to have a great influence on thermal stability, hydrolysis stability, color tone, and the like. For this reason, you may adjust the amount of terminal hydroxyl groups as needed by a well-known arbitrary method. In the melt transesterification method, an aromatic polycarbonate resin in which the amount of terminal hydroxyl groups is adjusted can be usually obtained by adjusting the mixing ratio of the carbonic diester and the aromatic dihydroxy compound; the degree of vacuum during the transesterification reaction, and the like. . In addition, the molecular weight of the aromatic polycarbonate resin obtained can also be adjusted by this operation.

When adjusting the amount of terminal hydroxyl groups by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound, the mixing ratio is as described above.
Further, as a more aggressive adjustment method, there may be mentioned a method in which a terminal terminator is mixed separately during the reaction. Examples of the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, carbonic acid diesters, and the like. In addition, 1 type may be used for a terminal terminator and it may use 2 or more types together by arbitrary combinations and a ratio.

  When producing an aromatic polycarbonate resin by the melt transesterification method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among these, for example, it is preferable to use an alkali metal compound and / or an alkaline earth metal compound. In addition, auxiliary compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. In addition, 1 type may be used for a transesterification catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

In the melt transesterification method, the reaction temperature is usually 100 to 320 ° C. The pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, a melt polycondensation reaction may be performed under the above-mentioned conditions while removing a by-product such as an aromatic hydroxy compound.
The melt polycondensation reaction can be performed by either a batch method or a continuous method. When performing by a batch type, the order which mixes a reaction substrate, a reaction medium, a catalyst, an additive, etc. is arbitrary as long as a desired aromatic polycarbonate resin is obtained, What is necessary is just to set an appropriate order arbitrarily. However, among them, the melt polycondensation reaction is preferably carried out in a continuous manner in consideration of the stability of the aromatic polycarbonate resin and the aromatic polycarbonate resin composition.

  In the melt transesterification method, a catalyst deactivator may be used as necessary. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. In addition, a catalyst deactivator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. Preferably it is 5 equivalents or less. Furthermore, it is 1 ppm or more normally with respect to aromatic polycarbonate resin, and is 100 ppm or less normally, Preferably it is 20 ppm or less.

.. Method for producing aromatic polycarbonate resin having structural viscosity index N in a predetermined range Especially when producing an aromatic polycarbonate resin having a structural viscosity index N in a predetermined range among aromatic polycarbonate resins, the above-mentioned aromatic polycarbonate is used. What is necessary is just to manufacture according to the manufacturing method of resin. At this time, it is preferable to produce a branched aromatic polycarbonate resin because an aromatic polycarbonate resin having a structural viscosity index N in a predetermined range is easily obtained. This is because the aromatic polycarbonate resin having a branched structure tends to have a high structural viscosity index N.

  Examples of the method for producing the branched aromatic polycarbonate resin include the methods described in JP-A-8-259687, JP-A-8-245782, and the like. In the methods described in these documents, when the aromatic dihydroxy compound and the carbonic acid diester are reacted by the melt transesterification method, the structural viscosity is selected without using a branching agent by selecting the catalyst conditions or production conditions. An aromatic polycarbonate resin having a high index and excellent hydrolytic stability can be obtained.

  Further, as another method for producing an aromatic polycarbonate resin having a branched structure, in addition to the aromatic dihydroxy compound and the carbonate precursor, which are the raw materials of the above-mentioned aromatic polycarbonate resin, a trifunctional or higher polyfunctional aromatic A method of copolymerizing these compounds by interfacial polymerization or melt transesterification is used.

  Examples of the trifunctional or higher polyfunctional aromatic compound include 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-hydroxyphenyl) heptene-3, 1,3,5-tri (4-hydroxyphenyl) benzene, Polyhydroxy compounds such as 1,1,1-tri (4-hydroxyphenyl) ethane;

3,3-bis (4-hydroxyaryl) oxindole (that is, isatin bisphenol), 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like. Of these, 1,1,1-tri (4-hydroxyphenyl) ethane is preferred.

A polyfunctional aromatic compound can be used by substituting a part of the aromatic dihydroxy compound. The amount of the polyfunctional aromatic compound used is usually 0.01 mol% or more, preferably 0.1 mol% or more, and usually 10 mol% or less, preferably 3 mol, based on the aromatic dihydroxy compound. % Or less.
In addition, a polyfunctional aromatic compound may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

Examples of the branched structure contained in the aromatic polycarbonate resin obtained by the melt transesterification method include structures of the following formulas (i) to (iv). In the following formulas (i) to (iv), X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, or 5 carbon atoms. 15 cycloalkylidene group or,, -O -, - S - , - CO -, - SO -, - SO 2 - a divalent group selected from the group consisting of groups represented by.

  As a method for producing an aromatic polycarbonate resin having a structural viscosity index N in a predetermined range, among the methods described above, a production method for producing an aromatic polycarbonate resin having a branched structure by the above-described melt transesterification method is particularly preferable. This is because it can be manufactured from a relatively inexpensive and easily available industrial material. For this reason, the base resin is also preferably produced by a melt transesterification method.

  The terminal hydroxyl group concentration of the aromatic polycarbonate resin used as the base resin is arbitrary and may be appropriately selected and determined, but is usually 1000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less. Thereby, the residence heat stability and color tone of the aromatic polycarbonate resin composition of the present invention can be further improved. The lower limit is usually 10 ppm or more, preferably 30 ppm or more, and more preferably 40 ppm or more, particularly in the case of an aromatic polycarbonate resin produced by the melt transesterification method. Thereby, the fall of molecular weight can be suppressed and the mechanical characteristic of the aromatic polycarbonate resin composition of this invention can be improved more.

  The unit of the terminal hydroxyl group concentration is the weight of the terminal hydroxyl group expressed in ppm relative to the weight of the aromatic polycarbonate resin. The measurement method is colorimetric determination (method described in Macromol. Chem. 88 215 (1965)) by the titanium tetrachloride / acetic acid method.

-Other matters regarding aromatic polycarbonate resin By the way, the above-mentioned aromatic polycarbonate resin is not limited to an aromatic polycarbonate resin alone (the aromatic polycarbonate resin alone is not limited to an embodiment containing only one kind of aromatic polycarbonate resin, for example, Used in the meaning including an embodiment including a plurality of types of aromatic polycarbonate resins having different monomer compositions and molecular weights), or a combination of an alloy (mixture) of an aromatic polycarbonate resin and another thermoplastic resin. May be used. Furthermore, for example, for the purpose of further increasing the flame retardancy, the aromatic polycarbonate resin may be configured as a copolymer mainly composed of an aromatic polycarbonate resin, such as a copolymer with an oligomer or polymer having a siloxane structure. Good.
However, even when the aromatic polycarbonate resin is used in combination with other thermoplastic resins, the content of the metal salt according to the present invention (described later) is the same as that of the aromatic polycarbonate resin excluding the other thermoplastic resins. The mass is defined as 100 parts by mass.

In addition, the aromatic polycarbonate resin may contain an aromatic polycarbonate ligomer in order to improve the appearance and fluidity of the molded product. The viscosity average molecular weight [Mv] of this aromatic polycarbonate ligomer is usually 1500 or more, preferably 2000 or more, and usually 9500 or less, preferably 9000 or less. Furthermore, the aromatic polycarbonate ligomer contained is preferably 30% by mass or less of the aromatic polycarbonate resin (including the aromatic polycarbonate oligomer).
In addition, when the aromatic polycarbonate resin contains an aromatic polycarbonate oligomer, the content of the metal salt according to the present invention (described later) is 100 parts by mass based on the total mass of the aromatic polycarbonate resin including the aromatic polycarbonate oligomer. Shall be determined.

Furthermore, the aromatic polycarbonate resin used in the present invention may be not only a virgin raw material but also an aromatic polycarbonate resin regenerated from a used product (a so-called material recycled aromatic polycarbonate resin). Examples of the used products include: optical recording media such as optical disks; light guide plates; vehicle window glass, vehicle headlamp lenses, windshields and other vehicle transparent members; water bottles and other containers; eyeglass lenses; Examples include architectural members such as glass windows and corrugated sheets. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.
However, the regenerated aromatic polycarbonate resin is preferably 80% by mass or less, more preferably 50% by mass or less, among the aromatic polycarbonate resins contained in the aromatic polycarbonate resin composition of the present invention. preferable. The regenerated aromatic polycarbonate resin is likely to have been subjected to deterioration such as heat deterioration and aging deterioration, so when such an aromatic polycarbonate resin is used more than the above range, the hue and mechanical properties are lowered. It is because there is a possibility of making it.

[3. Metal salt]
The aromatic polycarbonate resin composition of the present invention includes a metal salt of a fluoroalkylsulfonic acid containing a C—H bond (ie, a C—H bond-containing fluoroalkylsulfonic acid). By containing the metal salt according to the present invention, an aromatic polycarbonate resin composition having flame retardancy and high transparency not only when molded at high temperature but also when molded at low temperature can be realized. . The reason why such an excellent effect is obtained is not clear, but according to the study of the present inventors, the conventionally used metal salt of perfluoroalkylsulfonic acid has a blending amount that provides desired flame retardancy. When blended into an aromatic polycarbonate resin within the range of (flame retardant effective blending amount), it tends to aggregate and cloud easily at a specific temperature, whereas C—H bond-containing fluoroalkylsulfonic acid metal salts have C When a part of —F bond is replaced by C—H, the aggregated state in the aromatic polycarbonate resin changes, so that the compounding amount range in which aggregation is difficult to occur, and the flame retardant effective compounding amount that provides desired flame retardancy This is presumed to be balanced with the range.

  The metal salt according to the present invention is a metal salt of fluoroalkylsulfonic acid containing a C—H bond. Here, the C—H bond-containing fluoroalkylsulfonic acid that is an organic group of the metal salt according to the present invention is not particularly limited as long as a part of the fluorine atom of the perfluoroalkylsulfonic acid is replaced with a hydrogen atom. However, what has the following structures is preferable.

  In the C—H bond-containing fluoroalkylsulfonic acid that is an organic group of the metal salt according to the present invention, the alkyl group may be a chain or a ring. Further, when the alkyl group is a chain, it may be a straight chain or a branched chain. Furthermore, carbon number of the said alkyl group is 1 or more normally, Preferably it is 2 or more, and is 8 or less normally, Preferably it is 4 or less, More preferably, it is 3 or less. When the carbon number of the alkyl group of the C—H bond-containing fluoroalkylsulfonic acid is within this range, the transparency of the aromatic polycarbonate resin composition is more easily expressed.

  The number of hydrogen atoms contained in the C—H bond-containing fluoroalkylsulfonic acid is not limited as long as it is 1 or more, but is usually 3 or less, preferably 2 or less, and more preferably 1. By keeping the number of hydrogen atoms within this range, the heat resistance of the metal salt itself can be improved.

  Further, the number of fluorine atoms contained in the C—H bond-containing fluoroalkylsulfonic acid is not limited as long as it is 1 or more, but is preferably 2 or more, more preferably 3 or more, and usually 20 or less, preferably 16 Below, more preferably 8 or less, particularly preferably 4 or less. By keeping the number of fluorine atoms within this range, the heat resistance of the metal salt itself is improved, and as a result, the deterioration of the mechanical properties of the aromatic polycarbonate resin is suppressed, effective flame retardancy and transparency, and good It becomes easier to obtain a hue.

  Further, the ratio (H / F) of the number of hydrogen atoms and the number of fluorine atoms contained in the C—H bond-containing fluoroalkylsulfonic acid is usually 0.05 or more, preferably 0.1 or more, more preferably 0.8. It is 2 or more, and is usually 2 or less, preferably 1.5 or less, more preferably 0.5 or less. If the ratio (H / F) is too small, the cohesiveness of the metal salt is increased and the dispersibility in the aromatic polycarbonate resin is remarkably lowered, so that it may be difficult to obtain transparency. Moreover, since heat resistance of metal salt itself will fall when ratio (H / F) is too large, there exists a possibility of the fall of the physical property of an aromatic polycarbonate resin composition, and a hue deterioration.

  In the C—H bond-containing fluoroalkylsulfonic acid, the position of the hydrogen atom is arbitrary as long as the effects of the present invention are not significantly impaired, but the carbon atom to which the sulfonic acid group is bonded is bonded to the carbon atom to which the hydrogen atom is bonded. It is preferable. Among these, the metal salt according to the present invention preferably has a partial structure represented by the following formula (1). In the following formula (1), M represents a metal element.

  Among the metal salts according to the present invention having a partial structure represented by the formula (1), those represented by the following formula (3) are particularly preferable.

In Formula (3), R ¹ and R ² each independently represent at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group, a fluoroalkyl group, and an oxyfluoroalkyl group. .

Here, as the monovalent hydrocarbon group, any monovalent hydrocarbon group can be used. However, the carbon number is usually 1 or more, preferably 2 or more, and is usually 14 or less, preferably 6 or less, more preferably 3 or less. When the carbon number of the monovalent hydrocarbon group falls within this range, dispersibility in the aromatic polycarbonate resin is improved, and transparency of the aromatic polycarbonate resin composition is easily obtained.
The monovalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Further, it may be a chain or a ring, and may be a straight chain or a branched chain. For example, a chain alkyl group such as a methyl group or an ethyl group, an alkyl group such as a cycloalkyl group such as a cyclohexyl group; an alkenyl group such as a vinyl group or an allyl group; an alkynyl group such as an ethynyl group or a propargyl group; Aryl groups such as a phenyl group and a naphthyl group;

In the above fluoroalkyl group and oxyfluoroalkyl group, the alkyl group may be a chain or a ring. Further, when the alkyl group is a chain, it may be a straight chain or a branched chain. Furthermore, carbon number of the said alkyl group is 1 or more normally, Preferably it is 2 or more, and is 14 or less normally, Preferably it is 6 or less, More preferably, it is 3 or less. When the carbon number of the alkyl group is within this range, the dispersibility in the aromatic polycarbonate resin is excellent, and the transparency of the aromatic polycarbonate resin composition is easily obtained.
The fluoroalkyl group and the oxyfluoroalkyl group are preferably a perfluoroalkyl group and a peroxyfluoroalkyl group, respectively.

Examples of the fluoroalkyl group include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and the like. Of these, a trifluoromethyl group is preferable.
Examples of the oxyfluoroalkyl group include an oxytrifluoromethyl group, an oxypentafluoroethyl group, and an oxyheptafluoropropyl group. Of these, an oxytrifluoromethyl group is preferable.

Among those described above, R ¹ and R ² are preferably each independently a fluorine atom, a fluoroalkyl group, or an oxyfluoroalkyl group, more preferably a fluorine atom or a fluoroalkyl group, and a fluorine atom. It is particularly preferred. It is because it is easy to obtain industrially.

In the formula (3), M represents a metal element.
When the example of the metal salt represented by said Formula (3) is given, what is shown by following formula (4)-(8) will be mentioned. In the following formulas (4) to (8), M represents a metal element.

  Among them, 1,1,2,2-tetrafluoroethanesulfonic acid metal salt represented by the formula (4) and 1,1,2,3,3,3-hexafluoro represented by the formula (5) Propanesulfonic acid metal salts are preferred, and 1,1,2,2-tetrafluoroethanesulfonic acid metal salts are particularly preferred.

  The metal (corresponding to M in the above formulas (1) and (3) to (8)) included in the metal salt according to the present invention is preferably an alkali metal or an alkaline earth metal. In addition to suppressing dripping at the time of combustion of the aromatic polycarbonate resin composition of the present invention, flame retardancy can be further increased, and mechanical properties such as impact resistance, heat resistance, electrical characteristics, etc. possessed by the aromatic polycarbonate resin This is because the properties of can be maintained well.

  Among these, examples of the alkali metal include lithium, sodium, potassium, rubidium, cesium and the like. Examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium, barium and the like. Of these, lithium, potassium, sodium, cesium, magnesium, and calcium are preferable. Further, an alkali metal is preferable to an alkaline earth metal, and therefore lithium, sodium, potassium, and cesium are more preferable, sodium and potassium are further preferable, and potassium is particularly preferable.

Specific examples of preferred metal salts according to the present invention include sodium 1,1,2,2-tetrafluoroethanesulfonate, potassium 1,1,2,2-tetrafluoroethanesulfonate, 1,1, Cesium 2,2-tetrafluoroethanesulfonate, sodium 1,1,2,3,3,3-hexafluoropropanesulfonate, potassium 1,1,2,3,3,3-hexafluoropropanesulfonate, , 1,2,3,3,3-hexafluoropropanesulfonic acid cesium and the like. Among these, potassium 1,1,2,2-tetrafluoroethanesulfonate is particularly preferable.
In addition, the metal salt which concerns on this invention may use 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

The amount of the metal salt according to the present invention contained in the aromatic polycarbonate resin composition of the present invention is 0.1 ppm or more, preferably 0.12 ppm or more, more preferably, in terms of metal concentration with respect to 100 parts by mass of the base resin. It is 0.15 ppm or more, more preferably 0.2 ppm or more, particularly preferably 0.5 ppm or more, and 1.25 ppm or less, preferably 1.2 ppm or less, more preferably 1.15 ppm or less, still more preferably 1. 1 ppm or less, particularly preferably 1 ppm or less. When the metal concentration is below the lower limit of the above range, the flame retardancy of the aromatic polycarbonate resin composition of the present invention may be insufficient. Moreover, when it exceeds the upper limit of the said range, it exists in the tendency which inhibits the transparency of the aromatic polycarbonate resin composition of this invention.
In addition, the said metal concentration is content of the metal which the metal salt based on this invention has with respect to 100 mass parts of total amounts of base resin.

[4. Silicone compound]
The aromatic polycarbonate resin composition of the present invention may contain a silicone compound for the purpose of further stabilizing or improving the flame retardancy. This silicone compound usually acts as a so-called flame retardant aid.

The silicone compound usually has the following four units (that is, M unit represented by formula (9), D unit represented by formula (10), T unit represented by formula (11), and It is comprised from at least 1 sort (s) of Q unit represented by Formula (12). In the following formulas (9) to (12), R each independently represents an organic group, and among them, preferably represents the same group as R ^{3 to} R ⁸ described later.

  Examples of such silicone compounds include M / D, M / D / T, M / D / T / Q, M / D / Q, M / T, M / T / Q, Combinations of M / Q system, M system, D system, D / T system, D / T / Q system, D / Q system, T system, T / Q system and the like can be mentioned.

  The D-only silicone compound also includes cyclic siloxanes such as D3 (trimer), D4 (tetramer), D5 (pentamer), and D6 (hexamer).

In the silicone compound, the monofunctional M unit is represented by R ³ R ⁴ R ⁵ SiO _0.5 . The two functional groups of the D ^units, represented by R ⁶ R _{7 SiO 1.0.} The trifunctional D unit is represented by R ⁸ SiO _1.5 . Furthermore, the tetrafunctional Q unit is represented by SiO _2.0 .
Here, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents an organic group, and among them, preferably represents a monovalent hydrocarbon group having 1 to 30 carbon atoms. Examples of this hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl and cyclohexyl groups; alkenyl groups such as vinyl and allyl groups; aryl groups such as phenyl and the like. It is done. Of these, a methyl group and a phenyl group are preferable. Examples of organic groups other than hydrocarbon groups include epoxy groups and methacryloxy groups.

  Especially, as a silicone compound concerning this invention, what has a phenyl group in a molecule | numerator is preferable. When the silicone compound contains a phenyl group, the dispersibility of the silicone compound in the aromatic polycarbonate resin composition of the present invention is improved, and the flame retardancy and transparency of the aromatic polycarbonate resin composition of the present invention are improved. Tend to.

  Examples of such a silicone compound include polydiphenylsiloxane, polymethylphenylsiloxane, phenyl group-containing cyclic siloxane, and phenyl group-containing silane monomer.

  Polydiphenylsiloxane is a silicone compound having one or more repeating units represented by the following formula (13).

  Polymethylphenylsiloxane is a silicone compound having one or more repeating units represented by any of the following formulas (14) to (17).

  The properties of the polydiphenylsiloxane and the polymethylphenylsiloxane are not particularly limited and may be appropriately selected and used, such as solid and liquid. However, when it is liquid, the preferred viscosity is 25 ℃, usually 1 centistokes (cSt) or more, preferably 4 centistokes or more, and usually 300 centistokes or less, preferably 20 centistokes or less. is there.

  Examples of the phenyl group-containing cyclic shiroquinsan include a silicone compound represented by the following formula (18).

In formula (18), each R ^x independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, or an arylalkoxy group having 7 to 36 carbon atoms. Represents a group selected from the group consisting of a group, an aryl group having 6 to 14 carbon atoms, and an alkyl substituted aryl group having 6 to 14 carbon atoms and an aryl substituent having 1 to 30 carbon atoms. However, each R ^x may be the same or different. However, at least one of R ^x represents a phenyl group. M represents an integer of 0 or more and 7 or less.

  Examples of such a phenyl group-containing cyclic siloxane include octaphenylcyclotetrasiloxane, hexaphenylcyclotrisiloxane, octaphenoxycyclotetrasiloxane, and alkoxycyclosiloxane.

  Examples of the phenyl group-containing silane monomer include a silicone compound represented by the following formula (2).

In the formula (2), R ^a is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a carbon number. It represents at least one selected from the group consisting of 7 to 9 phenylalkyl groups.
R ^b represents at least one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenylalkyl group having 7 to 9 carbon atoms.
n represents an integer of 1 to 3.
In addition, when two or more of R ^a and / or R ^b are present, R ^a and / or R ^b may be the same group or different groups.
However, among the R ^a, at least one is a phenyl group.

  Examples of such a phenyl group-containing silane monomer include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrisilanol, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldisilanol, triphenylmethoxysilane, triphenylethoxysilane, And triphenylsilanol. Of these, phenyltrimethoxysilane, diphenyldimethoxysilane, and triphenylsilanol are preferable.

  Among the exemplified silicone compounds, it is preferable to use at least one selected from the group consisting of polymethylphenylsiloxane, phenyl group-containing cyclic siloxane, and a phenyl group-containing silane monomer represented by the formula (2). This is because these tend to have an excellent balance between flame retardancy and transparency.

Furthermore, the silicone compound may contain functional groups such as a silanol group, an epoxy group, an alkoxy group, a hydrosilyl (SiH) group, and a vinyl group in addition to the organic group described above in the molecule. By containing these special functional groups, the compatibility between the silicone compound and the aromatic polycarbonate resin may be improved, or the reactivity during combustion may be improved, thereby increasing the flame retardancy.
In addition, 1 type may be used for a silicone compound and it may use 2 or more types together by arbitrary combinations and a ratio.

  The content of the silicone compound in the aromatic polycarbonate resin composition of the present invention is usually 0.01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass with respect to 100 parts by mass of the base resin. Or more, more preferably 0.2 parts by mass or more, particularly preferably 0.25 parts by mass or more, and usually 3 parts by mass or less, preferably 2.5 parts by mass or less, more preferably 2 parts by mass or less, Preferably it is 1.5 mass parts or less, Most preferably, it is 1 mass part or less. If the content of the silicone compound is too small, there is a possibility that a sufficient flame retardant effect cannot be obtained. If the content is too large, gas is likely to be generated, or the appearance of the aromatic polycarbonate resin composition is poor. there is a possibility.

[5. Other ingredients]
If necessary, the aromatic polycarbonate resin composition of the present invention may contain other components in addition to those described above as long as the effects of the present invention are not significantly impaired. Examples of other components include other resins of various aromatic polycarbonate resins and various resin additives. In addition, 1 type may contain other components and 2 or more types may contain them by arbitrary combinations and ratios.

Other resins Examples of other resins include thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, and polybutylene terephthalate resin; polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer ( AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES resin) Resins; Polyolefin resins such as polyethylene resins and polypropylene resins; Polyamide resins; Polyimide resins; Polyetherimide resins; Polyurethane resins; Polyphenylene ether resins; Fido resin; polysulfone resin; polymethacrylate resin and the like. In addition, 1 type may contain other resin and 2 or more types may contain it by arbitrary combinations and ratios.

-Resin additives Examples of resin additives include heat stabilizers, antioxidants, mold release agents, UV absorbers, dyes and pigments, flame retardants, anti-dripping agents, antistatic agents, antifogging agents, lubricants, and anti-blocking agents. Agents, fluidity improvers, plasticizers, dispersants, antibacterial agents and the like. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.
Hereinafter, the example of an additive suitable for the aromatic polycarbonate resin composition of this invention is demonstrated concretely.

.. Heat stabilizer Examples of the heat stabilizer include phosphorus compounds. Any known phosphorous compound can be used. Specific examples include phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphoric acid Group 1 or Group 2B metal phosphates such as potassium, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, and the like. Among these, an organic phosphate compound represented by the following formula (19) and an organic phosphate compound represented by the following formula (20) are preferable.

O = P (OH) _s (OR ⁹ ) _3-s (19)
In the above formula (19), R ⁹ represents an alkyl group or an aryl group. Among them, R ⁹ is an alkyl group having usually 1 or more, preferably 2 or more, and usually 30 or less, preferably 25 or less, or an aryl group having usually 6 or more and usually 30 or less carbon atoms. It is more preferable. Furthermore, R ⁹ is an alkyl group than an aryl group. In the case where R ⁹ is present 2 or more, may be different even among R ⁹ are each identical.
In formula (19), s is usually 0 or more, preferably 1 or more, and usually represents an integer of 2 or less.

(In the formula ^{(20), R 10} represents an alkyl group or an aryl group. Among these ^{R 10,} the number 1 to 30 alkyl group carbon or, is preferably an aryl group having 6 to 30 carbon atoms. R ¹⁰ may be the same or different from each other.

Preferable specific examples of the phosphite represented by the above formula (19) include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.
In addition, 1 type may contain the heat stabilizer and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the heat stabilizer is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more with respect to 100 parts by mass of the base resin. It is not more than part by mass, preferably not more than 0.7 part by mass, more preferably not more than 0.5 part by mass. If the amount of the heat stabilizer is too small, the heat stabilization effect may be insufficient. If the amount of the heat stabilizer is too large, the effect may reach a peak and may not be economical.

.. Antioxidants Examples of antioxidants include hindered phenol antioxidants. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] Methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesi Tylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4- Hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis ( Octylthio) -1,3,5-triazin-2-ylamino) phenol and the like.

Of these, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate are preferable. . These two phenolic antioxidants are commercially available from Ciba Specialty Chemicals under the names “Irganox 1010” and “Irganox 1076”.
In addition, 1 type may contain antioxidant and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the antioxidant is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 1 part by mass or less, preferably 0.5 part by mass with respect to 100 parts by mass of the base resin. Or less. If there are too few antioxidants, the effect as an antioxidant may become inadequate, and when there are too many antioxidants, an effect may reach | attain and it may become economical.

.. Release agent Examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000, polysiloxane silicone oil, and the like. .

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

  As aliphatic carboxylic acid in ester of aliphatic carboxylic acid and alcohol, the same thing as the said aliphatic carboxylic acid can be used, for example. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable. In addition, an aliphatic includes an alicyclic compound here.

  Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. Is mentioned.

  In addition, said ester may contain aliphatic carboxylic acid and / or alcohol as an impurity. Moreover, although said ester may be a pure substance, it may be a mixture of a plurality of compounds. Furthermore, the aliphatic carboxylic acid and alcohol which combine to form one ester may be used alone or in combination of two or more in any combination and ratio.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons. Further, these hydrocarbons may be partially oxidized.

Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
The number average molecular weight of the aliphatic hydrocarbon is preferably 5000 or less.
The aliphatic hydrocarbon may be a single substance, but even a mixture of various constituent components and molecular weights can be used as long as the main component is within the above range.

  Examples of the polysiloxane silicone oil include dimethyl silicone oil, methylphenyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone.

  In addition, 1 type may contain the mold release agent mentioned above, and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the release agent is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 2 parts by mass or less, preferably 1 part by mass or less, relative to 100 parts by mass of the base resin. It is. If the content of the release agent is too small, the effect of releasability may not be sufficient. If the content is too high, degradation of hydrolysis resistance, mold contamination during injection molding, and the like may occur.

..Ultraviolet absorbers Examples of ultraviolet absorbers include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic acid ester compounds, Examples include organic ultraviolet absorbers such as hindered amine compounds. Of these, organic ultraviolet absorbers are preferred. A benzotriazole compound is particularly preferable.

  Specific examples of the benzotriazole compound include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl. ] -Benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methyl) Phenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2′-hydroxy-3 ′, 5'-di-tert-amyl) -benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2 ' -Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] and the like. Among them, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazole) 2-yl) phenol] is preferred, and 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole is particularly preferred. Specific examples of such benzotriazole compounds include “Seasorb 701”, “Seesorb 705”, “Seesorb 703”, “Seesorb 702”, “Seesorb 704” and “Seesorb 704” manufactured by Sipro Kasei Co., Ltd. Seasorb 709, “Biosorb 520”, “Biosorb 582”, “Biosorb 580”, “Biosorb 583” manufactured by Kyodo Yakuhin Co., Ltd. “Chemisorb 71”, “Chemisorb 72” manufactured by Chemipro Kasei Co., Ltd. "LA-32", "LA-38", "LA-36", "LA-34", "LA-31" manufactured by Adeka Company, "Chinubin P", "Tinubin 234" manufactured by Ciba Specialty Chemicals, "Tinubin 326", "Tinubin 327", "Tinubin 328" And the like.

  Specific examples of the benzophenone compound include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-n-dodecyloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4 Examples include '-dimethoxybenzophenone. Specific examples of such benzophenone compounds include “Seesorb 100”, “Seesorb 101”, “Seesorb 101S”, “Seesorb 102” and “Seesorb 103” manufactured by Sipro Kasei Co., Ltd. “Biosorb 100”, “Biosorb 110”, “Biosorb 130”, manufactured by Kemipro Kasei Co., Ltd. “Chemisorb 10”, “Chemisorb 11”, “Chemisorb 11S”, “Chemisorb 12”, “Chemsorb 13”, “Chemisorb 111” BASF “Ubinur 400”, BASF “Ubinur M-40”, BASF “Ubinur MS-40”, Cytec Industries “Thiasorb UV9”, “Thiasorb UV284”, “Thiasorb UV531”, “Thiasorb” UV24 ", Ade Company Ltd. "ADK STAB 1413", and "ADEKA STAB LA-51" and the like.

  Specific examples of the salicylate compound include phenyl salicylate and 4-tert-butylphenyl salicylate. Specific examples of such salicylate compounds include “Seasorb 201” and “Seasorb 202” manufactured by Sipro Kasei Co., Ltd., “Chemisorb 21” and “Chemisorb 22” manufactured by Chempro Corporation. .

  Specific examples of the cyanoacrylate compound include ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and the like. Examples of such cyanoacrylate compounds include, for example, “Seasorb 501” manufactured by Sipro Kasei Co., Ltd., “Biosorb 910” manufactured by Kyodo Pharmaceutical Co., Ltd., “Ubisolator 300” manufactured by Daiichi Kasei Co., Ltd., BASF Corporation. “Ubinurur N-35”, “Ubinurur N-539” and the like can be mentioned.

  Specific examples of the oxanilide compound include 2-ethoxy-2'-ethyloxalinic acid bis-arinide and the like. Specific examples of such oxalinide compounds include “Sanduboa VSU” manufactured by Clariant.

  Specific examples of the malonic acid ester compound include 2- (alkylidene) malonic acid esters and 2- (1-arylalkylidene) malonic acid esters. Especially, what is shown by following formula (21) is preferable.

（式（２１）において、Ｘは、水素原子、置換基を有していてもよい、炭素数１〜８のアルキル基若しくはアルコキシ基、または、炭素数２〜１０のアルケニル基を示し、Ｒ^１１およびＲ^１２はそれぞれ独立に炭素数１〜６のアルキル基を表わす。）

(In Formula (21), X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group, or an alkenyl group having 2 to 10 carbon atoms, which may have a substituent, and R ¹¹ And R ¹² each independently represents an alkyl group having 1 to 6 carbon atoms.)

In Formula (21), X represents a hydrogen atom, an optionally substituted alkyl group or alkoxy group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms.
The carbon number of the alkyl group and the alkoxy group in X is usually 1 or more, usually 8 or less, preferably 6 or less, more preferably 4 or less. Moreover, the alkyl group in an alkyl group or an alkoxy group may be linear or branched. Examples of this alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group and the like.
Of X, the alkenyl group preferably has an ester group as a substituent. The carbon number of the alkenyl group including the carbon number of the substituent is usually 2 or more, preferably 3 or more, more preferably 4 or more, and usually 10 or less, preferably 8 or less. Among these, X itself is preferably a 2- (alkylidene) malonic acid ester which is a malonic acid ester moiety of the above formula (21), and among them, the same malonic acid with the benzene ring of the formula (21) as the center. Those having an ester residue are more preferred, and those having a para-position are particularly preferred.

In the formula (21), R ¹¹ and R ¹² represent an alkyl group having 1 to 6 carbon atoms. Of ^these, the carbon number of ^{R 11} and ^{R 12} 1-4 preferred. The alkyl group represented by R ¹¹ and R ¹² each may be linear, it may be branched. Specific examples of R ¹¹ and R ¹² include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group and the like. Of these, a methyl group is more preferred. R ¹¹ and R ¹² may be the same or different.

  Examples of such a malonic ester UV absorber include “PR-25” manufactured by Clariant Japan, “B-CAP” manufactured by Ciba Specialty Chemicals, and the like.

  The content of the ultraviolet absorber is usually 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and usually 3 parts by mass or less, preferably 1 part by mass or less with respect to 100 parts by mass of the base resin. It is. If the content of the ultraviolet absorber is too small, the effect of improving the weather resistance may be insufficient, and if it is too large, mold deposits and the like may occur. In addition, 1 type may contain the ultraviolet absorber and 2 or more types may contain it by arbitrary combinations and a ratio.

-Dye / pigment Examples of the dye / pigment include inorganic pigments, organic pigments, and organic dyes.
Examples of inorganic pigments include sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine blue; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, zinc- Oxide pigments such as iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black and copper-iron black; chromic pigments such as chrome lead and molybdate orange; Examples include Russian pigments.

  Examples of organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine, iso Examples thereof include condensed polycyclic dyes such as indolinone and quinophthalone; anthraquinone, heterocyclic and methyl dyes.

Of these, titanium oxide, carbon black, cyanine-based, quinoline-based, anthraquinone-based, and phthalocyanine-based compounds are preferable from the viewpoint of thermal stability.
In addition, 1 type may contain the dye / pigment, and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the dye / pigment is usually 5 parts by mass or less, preferably 3 parts by mass or less, more preferably 2 parts by mass or less with respect to 100 parts by mass of the base resin. If the content of the dye / pigment is too large, the impact resistance may not be sufficient.

-Anti-dripping agent Examples of the anti-dripping agent include fluoroolefin resins. The fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure. Specific examples include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, and the like. Of these, tetrafluoroethylene resin and the like are preferable. Examples of the fluoroethylene resin include a fluoroethylene resin having a fibril forming ability.

Examples of the fluoroethylene resin having a fibril forming ability include Teflon (registered trademark) 6J manufactured by Mitsui / Dupont Fluorochemical Co., Polyflon F201L, Polyflon F103 manufactured by Daikin Chemical Industries, and the like. Furthermore, as a commercial item of the aqueous dispersion liquid of fluoroethylene resin, Teflon (trademark) 30J by Mitsui DuPont Fluorochemical Co., Ltd., Fullon D-1 by Daikin Chemical Industries, etc. are mentioned, for example. Furthermore, a fluoroethylene polymer having a multilayer structure obtained by polymerizing vinyl monomers can also be used, and specific examples thereof include METABRENE A-3800 manufactured by Mitsubishi Rayon Co., Ltd.
In addition, 1 type may contain the dripping inhibitor and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the anti-dripping agent is usually 0.001 parts by mass or more, preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, particularly preferably 0.02 parts per 100 parts by mass of the base resin. It is usually not less than 1 part by mass, preferably not less than 0.5 part by mass, more preferably not less than 0.3 part by mass, particularly preferably not less than 0.1 part by mass. If the amount of the anti-dripping agent is too small, the flame retardancy effect of the anti-dripping agent may be insufficient. If the amount is too large, the appearance of the molded product molded from the aromatic polycarbonate resin composition and the mechanical strength may be reduced. May occur or the transparency may be significantly reduced.

[6. Method for producing aromatic polycarbonate resin composition]
There is no restriction | limiting in the manufacturing method of the aromatic polycarbonate resin composition of this invention, For example, the manufacturing method of a well-known thermoplastic resin composition is employable widely.
To give specific examples, the base resin and metal salt according to the present invention, and the silicone compound and other components to be blended as necessary are mixed in advance using various mixers such as a tumbler and a Henschel mixer. For example, it can be produced by melt-kneading with a mixer such as a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader.

Also, for example, without mixing each component in advance, or only a part of the components is mixed in advance, and then fed to an extruder using a feeder and melt kneaded to produce the aromatic polycarbonate resin composition of the present invention. You can also
Also, for example, by mixing a part of the components in advance and supplying the resulting mixture to an extruder and melt-kneading it as a master batch, the master batch is again mixed with other components and melt-kneaded. The aromatic polycarbonate resin composition of the present invention can also be produced. In this case, it is preferable to mix a metal salt with a base resin in advance to prepare a masterbatch, and then mix and melt knead with other components, since dispersibility may be excellent and extrusion workability is excellent. In addition, for the purpose of improving the dispersibility of the metal salt, the metal salt can be previously dissolved in a solvent such as water or an organic solvent and then kneaded.

[7. advantage]
The aromatic polycarbonate resin composition of the present invention has high flame retardancy and further has high transparency that does not depend on molding conditions. Here, not depending on molding conditions means that not only when molding at high temperature (typically a temperature exceeding 300 ° C.) but also when molding at low temperature (typically a temperature of 250 ° C. or less) compared with before molding. Therefore, the decrease in transparency is small.
Moreover, the aromatic polycarbonate resin composition of the present invention usually has the advantages of high impact resistance, high heat resistance, good hue, and excellent hydrolysis resistance.

[8. Molded body]
The above-described aromatic polycarbonate resin composition of the present invention is usually molded into some shape and used as a molded body (aromatic polycarbonate resin composition molded body of the present invention). There is no restriction | limiting in the shape, pattern, color, dimension, etc. of this molded object, What is necessary is just to set arbitrarily according to the use of the molded object.

  Examples of molded articles include electric / electronic devices and parts thereof, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building members, various containers, leisure goods / miscellaneous goods, lighting equipment, and the like. . Among these, it is particularly suitable for use in electrical / electronic devices, OA devices, information terminal devices, housings for home appliances, cover members, vehicle exterior / skin components, and interior components.

  Examples of the electrical / electronic devices, OA devices, information terminal devices, housings for home appliances, and cover members include display devices such as personal computers, game machines, and televisions, printers, copiers, scanners, fax machines, electronic notebooks, and PDAs. , Electronic desk calculators, electronic dictionaries, cameras, video cameras, mobile phones, recording media drives and readers, housings for mice, numeric keys, CD players, MD players, portable radios, portable audio players, covers, keyboards, buttons And a switch member.

  In addition, examples of the vehicle exterior / skin parts and interior parts include head lamps, helmet shields, inner door handles, center panels, instrument panels, console boxes, luggage floor boards, car navigation display housings, and interiors. Illuminating equipment members and the like can be mentioned. Vehicles are not limited to automobiles, but include two-wheeled automobiles, agricultural vehicles, special vehicles for civil engineering, and railroad vehicles.

  The manufacturing method of a molded object is not specifically limited, The molding method generally employ | adopted about the thermoplastic resin can be employ | adopted arbitrarily. For example, injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, rapid heating mold were used. Molding method, foam molding (including supercritical fluid), insert molding method, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press Examples include molding methods. Moreover, the shaping | molding method using a hot runner system can also be employ | adopted.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented without departing from the gist of the present invention. In the following description, “parts” means “parts by mass” based on mass standards unless otherwise specified.

[Manufacture of resin pellets]
Each component described in Table 2 to be described later was blended in the proportions (mass ratio) described in Tables 3 to 5, and mixed for 20 minutes with a tumbler, and then manufactured by Nippon Steel Works (TEX30HSST) equipped with 1 vent. Supplied, kneaded under the conditions of screw rotation speed 200rpm, discharge rate 15kg / hour, barrel temperature 280 ° C, the molten resin extruded in a strand form is quenched in a water tank, pelletized using a pelletizer, aromatic polycarbonate resin A composition was obtained.

[Preparation of UL test specimen]
After the pellets of the aromatic polycarbonate resin composition obtained by the above-described production method were dried at 120 ° C. for 5 hours, using a J50-EP type injection molding machine manufactured by Nippon Steel, the cylinder temperature was 270 ° C., the mold A test piece having a length of 125 mm, a width of 13 mm, and a thickness of 3 mm was molded by injection molding under the conditions of a temperature of 80 ° C. and a molding cycle of 30 seconds. The obtained molded body was used as a UL test sample, and flame retardancy was evaluated in the following manner.

  The flame retardant evaluation of each aromatic polycarbonate resin composition was determined by the United States Underwriters Laboratories (UL) after conditioning UL test samples in a temperature-controlled room at 23 ° C and 50% humidity for 48 hours. The UL94 test (combustion test of plastic materials for equipment parts) was conducted. UL94V is a method for evaluating flame retardancy from the after-flame time and drip properties after indirect flame of a burner for 10 seconds on a test piece of a predetermined size held vertically, V-0, V- In order to have flame retardancy of 1 and V-2, it is necessary to satisfy the criteria shown in Table 1 below.

  Here, the after-flame time is the length of time for which the flammable combustion of the test piece is continued after the ignition source is moved away. The cotton ignition by the drip is determined by whether or not the labeling cotton, which is about 300 mm below the lower end of the test piece, is ignited by a drip from the test piece. Further, when any one of the five samples did not satisfy the above criteria, it was evaluated as NR (not rated) because V-2 was not satisfied. The results are shown in Tables 3-5.

[Preparation of plate-shaped molded body (test piece for transparency evaluation)]
After the pellets of the aromatic polycarbonate resin composition obtained by the above-described production method were dried at 120 ° C. for 5 hours, the cylinder temperature was 300 ° C. and 250 ° C. using a J50-EP type injection molding machine manufactured by Nippon Steel. Each was molded by injection molding under conditions of a mold temperature of 80 ° C. and a molding cycle of 30 seconds to form a plate-shaped molded body having a length of 90 mm, a width of 50 mm, and a thickness of 3 mm. The obtained molded body was used as a test piece for transparency evaluation, and transparency was evaluated in the following manner. The results are shown in Tables 3-5.

[Transparency evaluation]
Based on JIS K-7105, the plate-shaped molded article described above was used as a test piece, and the haze value measured with an NDH-2000 type haze meter manufactured by Nippon Denshoku Industries Co., Ltd. was used. The results are shown in Tables 3-5. Haze is used as a measure of the turbidity of the resin. Haze means that the smaller the value, the higher the transparency.

From Table 3, an aromatic polycarbonate resin (base resin) containing an aromatic polycarbonate resin A-3 having a structural viscosity index N within a predetermined range and a metal salt B of fluoroalkylsulfonic acid containing a C—H bond. -1 and the metal concentration of the metal salt B-1 within a predetermined range (each example) is excellent in flame retardancy, and at high temperature (300 ° C.) and low temperature (250 ° C.) It turns out that it is excellent in transparency both at the time of molding.
On the other hand, from Tables 4 and 5, in each comparative example not satisfying the above requirements, Comparative Examples 1, 2, 4, 6, 7 to 9 have insufficient flame retardancy, and Comparative Examples 3, 5, 8, 10 and 11 show that the transparency during low temperature molding is insufficient.
From the above, it has been confirmed that the unique configuration of the aromatic polycarbonate resin composition of the present invention can provide a unique effect of having both flame retardancy and high transparency independent of molding conditions.

  The present invention can be used in a wide range of industrial fields. For example, electric / electronic devices and parts thereof, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building members, various containers, leisure It is suitable for use in the fields of goods, miscellaneous goods, lighting equipment and the like.

Claims (11)

Containing a base resin containing 20% by mass or more of an aromatic polycarbonate resin having a structural viscosity index N of 1.2 or more, and a metal salt of a fluoroalkylsulfonic acid containing a C—H bond,
An aromatic polycarbonate resin composition comprising the metal salt in a range of 0.1 ppm to 1.25 ppm in terms of metal concentration with respect to 100 parts by mass of the base resin. The aromatic polycarbonate resin composition according to claim 1, wherein the base resin contains a linear aromatic polycarbonate resin in a proportion of 80% by mass or less. The aromatic polycarbonate resin composition according to claim 1 or 2, wherein the metal salt has a partial structure represented by the following formula (1).

[In formula (1), M represents a metal element. ] The aromatic polycarbonate resin composition according to any one of claims 1 to 3, wherein the metal salt is a metal salt of 1,1,2,2-tetrafluoroethanesulfonic acid. The aromatic polycarbonate resin composition according to any one of claims 1 to 4, wherein the metal salt is an alkali metal salt of 1,1,2,2-tetrafluoroethanesulfonic acid. The aromatic polycarbonate resin composition according to any one of claims 1 to 5, wherein the metal salt is potassium 1,1,2,2-tetrafluoroethanesulfonate. The aromatic polycarbonate resin composition according to claim 1, wherein the silicone compound is contained in an amount of 0.01 to 3 parts by mass with respect to 100 parts by mass of the base resin. The aromatic polycarbonate resin composition according to claim 7, wherein the silicone compound has a phenyl group. The silicone compound is at least one selected from the group consisting of polymethylphenylsiloxane, phenyl group-containing cyclic siloxane, and a phenyl group-containing silane monomer represented by the following formula (2). The aromatic polycarbonate resin composition according to 8.

[In Formula (2),
R ^a is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a phenylalkyl having 7 to 9 carbon atoms. Represents at least one selected from the group consisting of groups,
R ^b represents at least one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenylalkyl group having 7 to 9 carbon atoms,
n represents an integer of 1 to 3.
In addition, when two or more of R ^a and / or R ^b are present, R ^a and / or R ^b may be the same group or different groups.
However, at least one of R ^a is a phenyl group. ] The aromatic polycarbonate resin having a structural viscosity index N of 1.2 or more is an aromatic polycarbonate resin produced by a transesterification reaction between an aromatic dihydroxy compound and a carbonic acid diester. The aromatic polycarbonate resin composition according to any one of the above. An aromatic polycarbonate resin composition molded article obtained by molding the aromatic polycarbonate resin composition according to any one of claims 1 to 10.