JP2011178873A - Aromatic polycarbonate resin composition and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition and a molded article excellent in transparency and flame retardancy. <P>SOLUTION: The aromatic polycarbonate resin composition includes: 3 to 8 parts by mass of a phenoxy phosphazene flame retardant (B); and 0.05 to 0.3 parts by mass of an alkali or alkaline earth metal salt (C) of an aromatic sulfone sulfonic acid, based on 100 parts by mass of an aromatic polycarbonate resin (A) containing (i) a straight-chain aromatic polycarbonate produced by an interface polymerization method by 30 to 70 mass% and (ii) a branched aromatic polycarbonate produced by a transesterification method by 70 to 30 mass%. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an aromatic polycarbonate resin composition and a molded article, and more particularly to an aromatic polycarbonate resin composition and a molded article having excellent flame retardancy while maintaining the original transparency of the polycarbonate resin.

  Polycarbonate resins are resins having excellent heat resistance, mechanical properties, and electrical characteristics, and are widely used, for example, as automotive materials, electrical and electronic equipment materials, housing materials, and other parts manufacturing materials in industrial fields. In particular, the flame retardant polycarbonate resin composition is suitably used as a member for OA / information equipment such as a frame of a large flat display, a computer, a notebook computer, a mobile phone, a printer, and a copying machine. .

As means for imparting flame retardancy to a polycarbonate resin, conventionally, a halogen-based flame retardant or a phosphorus-based flame retardant has been added to the polycarbonate resin. However, a polycarbonate resin composition containing a halogen-based flame retardant containing chlorine or bromine may lead to a decrease in thermal stability or corrosion of a molding machine screw or molding die during molding processing. there were. In addition, the polycarbonate resin composition containing a phosphorus-based flame retardant inhibits the high transparency that is characteristic of the polycarbonate resin and causes a decrease in impact resistance and heat resistance, so that its use is limited. was there.
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.

On the other hand, metal salt compounds represented by organic alkali metal salt compounds and organic alkaline earth metal salt compounds such as alkali metal perfluoroalkanesulfonates and sodium aromatic sulfonates have been studied as useful flame retardants. .
For example, Patent Document 1 proposes a metal salt of a monomeric aromatic sulfonic acid represented by sodium sulfonate sodium salt, and Patent Document 2 discloses a metal salt of a monomeric aromatic sulfonic acid. Proposed.
However, the flame retardant effect obtained by such a metal salt compound is limited, and it has not yet been possible to obtain a satisfactory level of flame retardant. Moreover, even if the addition amount is increased so as to obtain a high flame retardant effect, the effect is not improved, but the flame retardant property is deteriorated.
Therefore, Patent Document 3 proposes a flame-retardant polycarbonate resin composition in which an aromatic sulfone sulfonate, an aromatic sulfonate, and optionally a siloxane oligomer are blended. The flame retardant effect was still limited.
(See Patent Documents 3 to 5).

Furthermore, a phosphazene compound has been proposed as a flame retardant and is also used in polycarbonate resins because of its high hydrolysis and heat resistance. However, the flame retardant effect alone is not sufficient. It is proposed that 0.1 to 40 parts by mass of a phenoxyphosphazene compound, 0.01 to 50 parts by mass of an organic alkali (earth) metal salt or organopolysiloxane is added to 100 parts by mass of a resin, and flame retardancy is thereby reduced. improves.
However, when these phosphazene-based flame retardants are used in combination with other flame retardants, there is a problem in that the transparency of the polycarbonate resin is likely to be lowered depending on the combination, especially during molding, the resin composition is long in the molding machine cylinder. In the case of stagnation or thick-wall molding, white turbidity occurs, haze decreases, and the transparency of the molded product decreases.

  Under such circumstances, there has been a strong demand for the development of a polycarbonate resin material having high flame retardancy while maintaining the excellent transparency of the polycarbonate resin itself.

Japanese Patent Publication No.57-43100 Japanese Examined Patent Publication No. 58-13589 Special table 2009-526899 JP 2001-200151 A

  An object of the present invention is to provide a polycarbonate resin composition capable of maintaining a high transparency inherent in a polycarbonate resin and obtaining a product having excellent flame retardancy, and a resin molded body formed by molding the polycarbonate resin composition.

  In order to solve the above-mentioned problems, the present inventors diligently studied the combination of an aromatic polycarbonate resin itself and a combination of a phosphazene compound and another flame retardant. And, by using an aromatic polycarbonate resin that combines a branched polycarbonate resin and a linear polycarbonate resin as a polycarbonate resin, by using a phenoxyphosphazene flame retardant and an aromatic sulfonesulfonate together, transparency and The inventors have found that a polycarbonate resin material having excellent flame retardancy can be obtained, and have completed the present invention.

  That is, according to 1st invention of this invention, (i) 30-70 mass% of linear aromatic polycarbonate (A1) manufactured by the interfacial polymerization method, and (ii) Branching manufactured by the transesterification method 3 to 8 parts by mass of the phenoxyphosphazene-based flame retardant (B) with respect to 100 parts by mass of the aromatic polycarbonate resin (A) containing 70 to 30% by mass of the aromatic aromatic polycarbonate (A2), An aromatic polycarbonate resin composition comprising 0.05 to 0.3 parts by mass of an alkaline earth metal salt (C) is provided.

  According to the second invention of the present invention, in the first invention, a full ester (D) of a polyhydric alcohol and an aliphatic carboxylic acid is further added to 100 parts by mass of the aromatic polycarbonate resin (A). 0.05 to 2 parts by mass of an aromatic polycarbonate resin composition is provided.

  According to the third invention of the present invention, in the first or second invention, the full ester (D) of a polyhydric alcohol and an aliphatic carboxylic acid is a full ester of pentaerythritol and an aliphatic carboxylic acid. An aromatic polycarbonate resin composition is provided.

  According to a fourth aspect of the present invention, in any one of the first to third aspects, the aromatic sulfonesulfonic acid metal salt (C) is diphenylsulfonesulfonic acid sodium or potassium salt. An aromatic polycarbonate resin composition is provided.

  Moreover, according to 5th invention of this invention, the molded article obtained from the aromatic polycarbonate resin composition of the invention in any one of 1-4 is provided.

The aromatic polycarbonate resin composition of the present invention is a combination of a branched and linear polycarbonate resin, and further a combination of a phenoxyphosphazene flame retardant and an aromatic sulfone sulfonate, thereby providing mechanical strength, transparency and flame retardancy. Excellent fluidity. Regarding transparency, the haze change is small even in molding with a long cylinder residence time during molding, and it shows excellent transparency even in molded products with thick parts, so the color depth increases when colored, and the design Excellent in design and design. Moreover, the flame retardance has the outstanding flame retardance of achieving "V-0" in the vertical combustion test based on UL94.
Therefore, taking advantage of these features, it can be widely used as components of OA / information equipment such as a frame of a television and various large flat displays, a computer, a notebook computer, a mobile phone, a printer, and a copying machine.

Hereinafter, embodiments of the present invention will be described in detail.
[1. Overview]
The aromatic polycarbonate resin composition of the present invention comprises (i) 30 to 70% by mass of a linear aromatic polycarbonate (A1) produced by an interfacial polymerization method, and (ii) a branched fragrance produced by a transesterification method. 3 to 8 parts by mass of the phenoxyphosphazene flame retardant (B), 100 to 30 parts by mass of the aromatic polycarbonate resin (A) containing 70 to 30% by mass of the aromatic polycarbonate (A2), an aromatic sulfonesulfonic acid alkali or alkaline earth It contains 0.05 to 0.3 parts by mass of a metal salt (C).

Hereinafter, each component used for the aromatic polycarbonate resin composition of this invention is demonstrated in detail.
[2. Aromatic polycarbonate resin (A)]
(I) Linear polycarbonate (A1) by interfacial polymerization
The linear polycarbonate (A1) produced by the interfacial polymerization method used in the present invention is a known method from an aromatic dihydroxy compound and phosgene, for example, a method described in JP-A-2001-316467. Is an aromatic polycarbonate resin produced by

Aromatic dihydroxy compounds As aromatic dihydroxy compounds that are one of the raw materials for producing aromatic polycarbonates, for example, bis (4-hydroxydiphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2- Bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4 ′ -Dihydroxybiphenyl, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl, bis (4- Rokishifeniru) sulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone. These aromatic dihydroxy compounds can be used alone or in admixture of two or more. Among these aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (hereinafter also referred to as “bisphenol A” and sometimes abbreviated as “BPA”) is particularly preferable.

  The viscosity average molecular weight (Mv) of the aromatic linear polycarbonate (A1) by the interfacial polymerization method is preferably 12,000 to 50,000, more preferably 16,000 to 40,000, still more preferably 19 , 30,000 to 30,000. When the viscosity average molecular weight is less than 12,000, even when mixed with the branched polycarbonate (A2) produced by the transesterification method, the resulting resin composition has low impact strength or too low melt viscosity. Appearance and accuracy of the resulting molded product are likely to deteriorate. On the other hand, when the viscosity average molecular weight exceeds 50,000, it is difficult to mix with the branched polycarbonate (A2) produced by the transesterification method, and it is difficult to obtain a uniform composition. Further, the linear polycarbonate (A1) obtained by the interfacial polymerization method may contain a small amount of a branched polycarbonate obtained by the interfacial polymerization method. The content of the branched polycarbonate is 40% or less, preferably 30% or less in the interfacial polycarbonate.

(Ii) Branched polycarbonate by transesterification (A2)
The branched polycarbonate (A2) produced by the transesterification method (ii) used in the present invention is obtained by melt polycondensation using an aromatic dihydroxy compound and a carbonic acid diester as raw materials in the presence of a transesterification catalyst. be able to. Examples of the aromatic dihydroxy compound as the raw material include the same compounds as the aromatic dihydroxy compound exemplified as the raw material for producing the aromatic polycarbonate by the interface method, and bisphenol A is preferable.

  Moreover, (ii) Branched polycarbonate (A2) by the transesterification method is a carbonate precursor using a polyfunctional aromatic compound having 3 or more dihydroxy groups in one molecule as a part of the aromatic dihydroxy compound. However, it is preferable not to use these compounds.

Carbonic acid diesters Typical examples of carbonic acid diesters that are another raw material of the branched polycarbonate (A2) produced by the transesterification method include, for example, substituted diphenyl carbonates typified by diphenyl carbonate, ditolyl carbonate and the like. , Dialkyl carbonate represented by dimethyl carbonate, diethyl carbonate, di-t-butyl carbonate and the like. These carbonic acid diesters can be used alone or in admixture of two or more. Among these, diphenyl carbonate (hereinafter sometimes abbreviated as “DPC”) and substituted diphenyl carbonate are preferable.

  In addition, the carbonic acid diester may be substituted with dicarboxylic acid or dicarboxylic acid ester in an amount of preferably 50 mol% or less, more preferably 30 mol% or less. Representative dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate. When such a dicarboxylic acid or dicarboxylic acid ester is substituted, a polyester polycarbonate is obtained.

  These carbonic acid diesters (including the above-mentioned substituted dicarboxylic acids or esters of dicarboxylic acids; the same shall apply hereinafter) are usually used in excess with respect to the aromatic dihydroxy compounds. That is, it is used in a molar ratio within the range of 1.001 to 1.3, preferably 1.01 to 1.2 with respect to the aromatic dihydroxy compound. When the molar ratio is smaller than 1.001, the terminal OH group of the produced aromatic polycarbonate is increased, and the thermal stability and hydrolysis resistance are deteriorated. When the molar ratio is larger than 1.3, the aromatic Although the terminal OH group of the aromatic polycarbonate decreases, the rate of the transesterification reaction decreases under the same conditions, and it tends to be difficult to produce an aromatic polycarbonate having a desired molecular weight. In this invention, it is preferable to set it as the aromatic polycarbonate which adjusted terminal OH group content in the range of 50-2,000 ppm, Preferably it is 100-1,500 ppm, More preferably, it is 200-1,000 ppm.

Transesterification catalyst When the aromatic branched polycarbonate (A2) is produced by the transesterification method, a catalyst is used. In the aromatic polycarbonate production method of the present invention, the catalyst species is not limited, but generally an alkali metal compound, an alkaline earth metal compound, a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine system Basic compounds such as compounds are used, and among them, alkali metal compounds and / or alkaline earth metal compounds are particularly preferable. These may be used alone or in combination of two or more.

  Examples of the alkali metal compounds include inorganic alkali metal compounds such as lithium, sodium, potassium, rubidium, cesium hydroxide, carbonate, hydrogen carbonate compounds, and organic alkali metal compounds such as alcoholates, phenolates, and organic carboxylates. . Among these alkali metal compounds, cesium compounds are preferable, and specific examples of the most preferable cesium compounds are cesium carbonate, cesium hydrogen carbonate, and cesium hydroxide.

  In addition, as alkaline earth metal compounds, inorganic alkaline earth metal compounds such as beryllium, magnesium, calcium, strontium, barium hydroxide and carbonate, organic alkaline earth metals such as alcoholate, phenolate, and organic carboxylate There are compounds.

Among these catalysts, an alkali metal compound is desirable in order to obtain a branched polycarbonate (A2) having melting characteristics suitable for molding. The amount of the alkali metal ^{catalyst, 4 × 10 -7 ~1 × 10} -5 mol of alkali metal per mole of the aromatic dihydroxy compound, preferably 1 × ^{10 -6} ~6 × ¹⁰ -6 mol in the range Used in If the amount of the catalyst used is less than the above-mentioned amount, it becomes difficult to obtain a branched aromatic polycarbonate having a polymerization activity necessary for producing a branched polycarbonate (A2) having a desired molecular weight and melting characteristics suitable for molding.

In the present invention, the production method of the branched polycarbonate (A2) is not particularly limited as long as it can be polymerized with ordinary transesterification polycarbonate production equipment, but the catalyst type, the catalyst amount, the monomer charge ratio, the polymerization temperature, the residence time, These values vary depending on the polymerization conditions such as the degree of vacuum. For example, in the present invention, the polymerization reaction (transesterification reaction) of the branched polycarbonate (A2) is generally a reaction in two or more polymerization tanks, that is, two or more stages, usually in a multistage process of 3 to 7 stages. It is preferable to be implemented. Specific reaction conditions include temperature: 150 to 320 ° C., pressure: normal pressure to 2 Pa, average residence time: 5 to 150 minutes, and in each polymerization tank, discharge of by-product phenol as the reaction proceeds. In order to make it more effective, the temperature is set stepwise to higher temperature and higher vacuum within the above reaction conditions.
Note that the automatic control of the actual catalyst amount in the case of using a plurality of polymerization tanks in a multi-stage process is preferably continuous automatic control of the catalyst supply amount. In that case, 1 / of the residence time of the first polymerization tank Measurement and control must be completed within 3 minutes.

  In the branched polycarbonate (A2) produced by the above method, unlike the interface method, there is no chlorine element derived from phosgene or a reaction solvent, but the raw material monomer, catalyst, and aromatics by-produced by the transesterification reaction. Low molecular weight compounds such as monohydroxy compounds and polycarbonate oligomers remain. Among them, the raw material monomer and the aromatic monohydroxy compound are preferably removed because they have a large residual amount, heat aging resistance, hydrolysis resistance, and odor at the time of molding and use of the sheet. The residual amount of the aromatic monohydroxy compound is preferably 200 mass ppm or less, more preferably 100 mass ppm or less. The residual amount of the aromatic dihydroxy compound is preferably 200 ppm by mass or less, more preferably 150 ppm by mass or less. The residual amount of the carbonic acid diester compound is preferably 200 mass ppm or less. If the residual amount of the carbonic acid diester compound exceeds 200 mass ppm, an unpleasant odor is felt, which is not preferable as a sheet molding resin.

  There is no restriction | limiting in particular in the method of removing said various low molecular weight compounds, For example, you may devolatilize continuously with a vent type extruder. At that time, the basic transesterification catalyst remaining in the resin is preliminarily added with an acidic compound or a precursor thereof to deactivate, thereby suppressing side reactions during devolatilization, and efficiently starting monomer and Aromatic hydroxy compounds can be removed.

  There is no restriction | limiting in particular in the acidic compound to add, or its precursor, As long as it has an effect which neutralizes the basic transesterification catalyst used for a polycondensation reaction, all can be used. Specifically, hydrochloric acid, nitric acid, boric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, adipic acid, ascorbic acid, aspartic acid, azelaic acid, adenosine phosphoric acid, benzoic acid, Formic acid, valeric acid, citric acid, glycolic acid, glutamic acid, glutaric acid, cinnamic acid, succinic acid, acetic acid, tartaric acid, oxalic acid, p-toluenesulfinic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, nicotinic acid, picrine Examples thereof include Bronsted acids such as acid, picolinic acid, phthalic acid, terephthalic acid, propionic acid, benzenesulfinic acid, benzenesulfonic acid, malonic acid, maleic acid, and esters thereof. These may be used alone or in combination of two or more. Of these acidic compounds or precursors thereof, sulfonic acid compounds or ester compounds thereof, such as p-toluenesulfonic acid, methyl p-toluenesulfonate, butyl p-toluenesulfonate, and the like are particularly preferable.

  The addition amount of these acidic compounds or precursors thereof is 0.1 to 50 times mol, preferably 0.5 to 30 times mol, of the neutralization amount of the basic transesterification catalyst used in the polycondensation reaction. Selected from a range. The timing of adding the acidic compound or its precursor may be any time after the polycondensation reaction, and there is no particular limitation on the addition method, depending on the properties of the acidic compound or its precursor and the desired conditions, Any method such as a method of adding directly, a method of adding by dissolving in an appropriate solvent, a method of using a pellet or a flaky master batch may be used.

  The extruder used for devolatilization may be uniaxial or biaxial. The twin screw extruder is a meshing type twin screw extruder, and the rotation direction may be the same direction or different direction. For the purpose of devolatilization, those having a vent part after the acidic compound addition part are preferred. The number of vents is not limited, but usually a multistage vent of 2 to 10 stages is used. Moreover, in this extruder, additives, such as a stabilizer, a ultraviolet absorber, a mold release agent, and a coloring agent, can be added and knead | mixed with resin as needed.

  The branched polycarbonate (A2) obtained by the transesterification method used in the present invention usually has a viscosity average molecular weight in the range of 12,000 to 40,000. Preferably it is 16,000-35,000, More preferably, it is 19,000-30,000, Most preferably, it is 20,000-28,000. Those having a viscosity average molecular weight of less than 12,000 are difficult to obtain a resin composition having a desired viscosity average molecular weight even when mixed with a linear polycarbonate (A1) having a high molecular weight produced by an interfacial polymerization method. Such compositions have problems such as low impact strength and reduced sheet formability. On the other hand, at 50,000 or more, the miscibility with interfacial linear polycarbonate tends to be inferior, causing fish eyes and the like. This is not preferable.

  Furthermore, the branched polycarbonate (A2) obtained by the transesterification method preferably contains the total amount of polycarbonate resin having a structural viscosity index N in a predetermined range or a certain ratio or more. That is, in the polycarbonate resin (A2), it is usually 20% by mass or more, preferably 50% by mass or more, and more preferably 60% by mass or more. There is no restriction | limiting in the upper limit of content of predetermined N polycarbonate resin in a polycarbonate resin (A2), Usually, it is 100 mass% or less, Preferably it is 90 mass% or less, More preferably, it is 85 mass% or less.

  The structural viscosity index N is an index for evaluating the flow characteristics of a melt as described in detail in the document “Rheology for chemists” (Chemical Doujin, 1982, pp. 15-16). . Usually, the melting characteristics of polycarbonate resin can be expressed by the formula: γ = a · σN. 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, a 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 a polycarbonate resin having a large structural viscosity index N is mixed with another polycarbonate resin, dripping at the time of combustion of the obtained polycarbonate resin composition can be suppressed, and flame retardancy can be improved. However, in order to maintain the moldability of the obtained polycarbonate resin composition in a favorable range, the structural viscosity index N of the polycarbonate resin is preferably not excessively large.

Therefore, the branched polycarbonate (A2) obtained by the transesterification method preferably has a structural viscosity index N of usually 1.2 or more, more preferably 1.25 or more, and further preferably 1.28 or more. In addition, it is usually preferably 1.8 or less, more preferably 1.7 or less.
A high structural viscosity index N means that the polycarbonate resin has a branched chain. By containing a polycarbonate resin having a high structural viscosity index N in this way, dripping of the polycarbonate resin composition during combustion is suppressed. , Flame retardancy can be improved.

The “structural viscosity index N” is expressed by Logηa = [(1−N) / N] × Logγ + C, which is derived from the above formula, as described in, for example, JP-A-2005-232442. Is also possible. In the above formula, N: structural viscosity index, γ: shear rate, C: constant, ηa: apparent viscosity.
As can be seen from this equation, the N value can also be evaluated from γ and ηa in a low shear region in which the viscosity behavior is greatly different. For example, the N value can be determined from ηa at γ = 12.16 sec−1 and γ = 24.32 sec−1.

  An aromatic polycarbonate resin having a structural viscosity index N of 1.2 or more is obtained by a melting method (transesterification method) as described in JP-A-8-259687 and JP-A-8-245782, for example. When reacting an aromatic dihydroxy compound and a carbonic acid diester, an aromatic polycarbonate resin having a high structural viscosity index and excellent hydrolytic stability can be obtained without adding a branching agent by selecting catalyst conditions or production conditions. be able to.

  The aromatic polycarbonate resin (A) according to the present invention comprises (i) 30 to 70% by mass of a linear polycarbonate (A1) produced by an interfacial polymerization method, and (ii) a branched polycarbonate produced by a transesterification method. (A2) 70 to 30% by mass, preferably (i) (A1) 40 to 60% by mass and (ii) 60 to 40% by mass. When the content of the linear polycarbonate (i) is lower than 30% by mass in the resin composition, the resin composition is subject to hydrolysis in the presence of an alkali sulfonesulfonic acid alkali or alkaline earth metal salt. Since it becomes easy, it is not preferable. On the other hand, if the content of the branched polycarbonate (A2) in (ii) is lower than 30% by mass in the resin composition, the melting characteristics are lowered, and the accuracy and appearance of the molded product are inferior.

  The (i) interfacial polymerization linear polycarbonate (A1) and (ii) transesterification branched polycarbonate (A2) constituting the resin composition according to the present invention have a recycled material in part or all of the polycarbonate. May be used. The blending ratio of the recycled polycarbonate in 100% by mass of the polycarbonate resin composition can be appropriately selected according to the required performance of the molded product, but is usually 50% by mass or less, preferably 30% by mass or less.

[3. Phenoxyphosphazene flame retardant (B)]
The phenoxyphosphazene flame retardant (B) used in the present invention is an organic compound having —P═N— bond in the molecule, preferably a cyclic phosphazene compound represented by the following general formula (1), the following general formula ( 2) and a crosslinked phosphazene compound in which at least one phosphazene compound selected from the group consisting of the following general formula (1) and the following general formula (2) is crosslinked by a crosslinking group. At least one compound selected from the group consisting of: As the crosslinked phosphazene compound, those crosslinked by a crosslinking group represented by the following general formula (3) are preferable from the viewpoint of flame retardancy.
The phenoxyphosphazene flame retardant (B) has a high flame retardant effect, and can exhibit excellent flame retardancy even with a small content, particularly when used in combination with the aromatic sulfonesulfonic acid metal salt (C) described later. Therefore, it is possible to suppress the decrease in mechanical strength and the generation of gas that may occur due to the blending of the flame retardant.

（式（１）中、ｍは３〜２５の整数であり、Ｒ^１は、同一又は異なっていてもよく、アリール基又はアルキルアリール基を示す。）

(In formula (1), m is an integer of 3 to 25, and R ¹ may be the same or different and represents an aryl group or an alkylaryl group.)

（式（２）中、ｎは３〜１０，０００の整数であり、Ｘは、−Ｎ＝Ｐ（ＯＲ^１）_３基又は−Ｎ＝Ｐ（Ｏ）ＯＲ^１基を示し、Ｙは、−Ｐ（ＯＲ^１）_４基又は−Ｐ（Ｏ）（ＯＲ^１）_２基を示す。Ｒ^１は同一又は異なっていてもよく、アリール基又はアルキルアリール基を示す。）

(In Formula (2), n is an integer of 3 to 10,000, X represents —N═P (OR ¹ ) ₃ group or —N═P (O) OR ¹ group, Y represents — P (OR ¹ ) ₄ group or -P (O) (OR ¹ ) ₂ group is shown, R ¹ may be the same or different and represents an aryl group or an alkylaryl group.

（式（３）中、Ａは−Ｃ（ＣＨ_３）_２−、−ＳＯ_２−、−Ｓ−、又は−Ｏ−であり、ｑは０又は１である。）

(In the formula (3), A is _{-C (CH 3) 2 -,} - SO 2 -, - S-, or a -O-, q is 0 or 1.)

Examples of the cyclic and / or chain phenoxyphosphazene compounds represented by the general formulas (1) and (2) include, for example, phenoxyphosphazene, (poly) tolyloxyphosphazene (for example, o-tolyloxyphosphazene, m-tolyloxyphosphazene). P-tolyloxyphosphazene, o, m-tolyloxyphosphazene, o, p-tolyloxyphosphazene, m, p-tolyloxyphosphazene, o, m, p-tolyloxyphosphazene, etc.), (poly) xylyloxyphosphazene and cyclic and / or linear C _1-6 alkyl C _6-20 aryloxy phosphazene etc., (poly) phenoxy tolyloxy phosphazene (e.g., phenoxy o- tolyloxy phosphazene, a phenoxy m- tolyloxyethyl phosphazene, a phenoxy p- Toriruoki Phosphazenes, phenoxy o, m-tolyloxyphosphazenes, phenoxy o, p-tolyloxyphosphazenes, phenoxy m, p-tolyloxyphosphazenes, phenoxy o, m, p-tolyloxyphosphazenes), (poly) phenoxyxyloxyphosphazenes And cyclic and / or chain C _6-20 aryl C _1-10 alkyl C _6-20 aryloxy phosphazene such as (poly) phenoxytolyloxyxyloxyphosphazene, preferably cyclic and / or chain phenoxy Phosphazene, cyclic and / or chain C _1-3 alkyl C _6-20 aryloxyphosphazene, C _6-20 aryloxy C _1-3 alkyl C _6-20 aryloxyphosphazene (eg, cyclic and / or tolyloxyphosphazene, ring And / or a chain phenoxy tolyl phenoxyphosphazene like.

As the cyclic phosphazene compound represented by the general formula (1), cyclic phenoxyphosphazene in which R ¹ is a phenyl group is particularly preferable. Examples of such a cyclic phenoxyphosphazene compound include hexachlorocyclotriphosphazene, octachlorocyclohexane, and a mixture of cyclic and linear chlorophosphazene obtained by reacting ammonium chloride and phosphorus pentachloride at a temperature of 120 to 130 ° C. Examples include compounds such as phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decaffenoxycyclopentaphosphazene obtained by removing a cyclic chlorophosphazene such as cyclotetraphosphazene and decachlorocyclopentaphosphazene and then substituting with a phenoxy group. . The cyclic phenoxyphosphazene compound is preferably a compound in which m in the general formula (1) is an integer of 3 to 8, and may be a mixture of compounds having different m. Among them, a mixture of compounds in which m = 3 is 50% by mass or more, m = 4 is 10 to 40% by mass, and m = 5 or more is 30% by mass or less is preferable.

As the chain phosphazene compound represented by the general formula (2), chain phenoxyphosphazene in which R ¹ is a phenyl group is particularly preferable. Such a chain phenoxyphosphazene compound is obtained by, for example, subjecting hexachlorocyclotriphosphazene obtained by the above-mentioned method to reverse polymerization at a temperature of 220 to 250 ° C. Examples include compounds obtained by substitution with a phenoxy group. N of general formula (2) of this linear phenoxyphosphazene compound becomes like this. Preferably it is 3-1000, More preferably, it is 3-100, More preferably, it is 3-25.

Examples of the crosslinked phenoxyphosphazene compound include a compound having a crosslinked structure of 4,4′-sulfonyldiphenylene (bisphenol S residue) and a crosslinked structure of 2,2- (4,4′-diphenylene) isopropylidene group. Compounds having a crosslinked structure of 4,4′-diphenylene groups, such as compounds, compounds having a crosslinked structure of 4,4′-oxydiphenylene groups, compounds having a crosslinked structure of 4,4′-thiodiphenylene groups, etc. Is mentioned.
Moreover, as the crosslinked phosphazene compound, a crosslinked phenoxyphosphazene compound obtained by crosslinking a cyclic phenoxyphosphazene compound in which R ¹ is a phenyl group in the general formula (1) with a crosslinking group represented by the general formula (3), or the above A crosslinked phenoxyphosphazene compound obtained by crosslinking a chain phenoxyphosphazene compound in which R ¹ is a phenyl group in the general formula (2) with a crosslinking group represented by the general formula (3) is preferable from the viewpoint of flame retardancy, and cyclic A crosslinked phenoxyphosphazene compound obtained by crosslinking a phenoxyphosphazene compound with a crosslinking group represented by the general formula (3) is more preferable.
The content of the phenylene group in the crosslinked phenoxyphosphazene compound is such that the cyclic phosphazene compound represented by the general formula (1) and / or the all phenyl groups in the chain phenoxyphosphazene compound represented by the general formula (2) and Based on the number of phenylene groups, it is usually 50 to 99.9%, preferably 70 to 90%. The crosslinked phenoxyphosphazene compound is particularly preferably a compound having no free hydroxyl group in the molecule.

  In the present invention, the phenoxyphosphazene flame retardant (B) includes a cyclic phenoxyphosphazene compound represented by the above general formula (1) and a cyclic phenoxyphosphazene compound represented by the above general formula (1) by a crosslinking group. From the viewpoint of flame retardancy and mechanical properties, at least one selected from the group consisting of crosslinked phenoxyphosphazene compounds formed by crosslinking is preferable.

  The content of the phenoxyphosphazene flame retardant (B) is 3 to 8 parts by mass, and more preferably 4 to 7 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A). By setting it as 3 mass parts or more, a flame retardance can fully be improved, and mechanical strength can be kept favorable by setting it as 8 mass parts or less.

[4. Aromatic sulfonesulfonic acid alkali or alkaline earth metal salt (C)]
In the present invention, an aromatic sulfonic acid alkali metal salt or alkaline earth metal salt (C) of aromatic sulfone is used as the aromatic sulfonic acid metal salt. It functions as a flame retardant for further improving the flame retardancy of the phenoxyphosphazene (B), and is excellent in terms of thermal stability when mixed with a polycarbonate resin.
In addition, the aromatic sulfonesulfonic acid metal salt (C) is obtained by bonding two aromatic rings by a sulfone group, and one or both aromatic rings may be condensed aromatic rings. The aromatic ring preferably has no substituent or only has an alkyl group having 1 to 4 carbon atoms as a substituent.

  The metal of the aromatic sulfonesulfonic acid metal salt (C) is an alkali metal or alkaline earth metal, and includes sodium, lithium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium and the like. Among them, as alkali metals, sodium and potassium are preferable, and as alkaline earth metals, magnesium, calcium and cesium are preferable from the viewpoint of compatibility with polycarbonate resin and imparting flame retardancy, and aromatic sulfonesulfonic acid metal salts are It may be a mixture of two or more.

  Examples of the aromatic sulfonesulfonic acid metal salt (C) include sodium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-sulfonate, disodium diphenylsulfone-3 · 3′-disulfonate, diphenylsulfone-3 · Preferable examples include dipotassium 3′-disulfonate.

  The content of the aromatic sulfonesulfonic acid alkali or alkaline earth metal salt (C) is 0.05 to 0.3 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate (A). If the amount is less than 0.05 parts by mass, the effect of improving the flame retardancy of the obtained polycarbonate resin composition is insufficient, and if it exceeds 0.3 parts by mass, the thermal stability during molding of the polycarbonate resin composition and the physical properties in the wet heat test A decrease occurs. The content is preferably 0.07 to 0.2 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A).

[5. Full ester of polyhydric alcohol and aliphatic carboxylic acid (D)]
The aromatic polycarbonate resin composition of the present invention preferably contains a full ester (D) of a polyhydric alcohol and an aliphatic carboxylic acid as a release agent.
The full ester (D) of a polyhydric alcohol and an aliphatic carboxylic acid is preferably a full ester of an aliphatic polyhydric alcohol having 3 to 10 carbon atoms and 3 to 6 carbon atoms and an aliphatic carboxylic acid having 10 to 19 carbon atoms. Esters are preferred.
Examples of the preferable polyhydric aliphatic alcohol for forming the ester of component (D) include glycerin, trimethylolpropane, pentaerythritol, mesoerythritol, pentitol, hexitol, sorbitol, and preferably glycerin, penta Erythritol, especially pentaerythritol.
As the ester, glycerin tristearate and pentaerythritol tetrastearate are preferably used, and pentaerythritol tetrastearate is particularly preferred.

The esterified product of the polyhydric aliphatic alcohol and the aliphatic carboxylic acid is preferably a full esterified product. In the present invention, the “full esterified product” needs to have an esterification rate of 100%. 80% or more, more preferably 85% or more, and particularly preferably 90% or more.
In addition, (D) component may use together 2 or more types of esterified products from which aliphatic carboxylic acid and polyhydric aliphatic alcohol which comprise it differ, and esterified products from which esterification rate differs.

  Content of the full ester (D) of a polyhydric alcohol and aliphatic carboxylic acid is 0.05-2 mass parts with respect to 100 mass parts of aromatic polycarbonate resin (A). If the content is less than 0.05 parts by mass, no improvement effect is seen in the mold release properties and the appearance of the molded product. Conversely, if the content exceeds 2 parts by mass, the transparency of the molded product is impaired. In addition, there are problems such as degradation of hydrolysis resistance and mold contamination during injection molding. Particularly preferred is 0.05 to 0.5 parts by weight. By combining with such a specific fatty acid ester, the aromatic polycarbonate resin composition of the present invention can have good transparency and releasability.

[6. Other ingredients]
In the aromatic polycarbonate resin composition of the present invention, other resins, various resin additives, and the like may be used as necessary in addition to the above-described components as long as the effects of the present invention are not impaired. .
Specific examples of the other resins include polyolefin resins such as polyethylene resins and polypropylene resins, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, and polymethacrylates. Examples thereof include resins, polyester resins, acrylonitrile-styrene-butadiene copolymer resins (ABS), and the like.

  Resin additives include impact modifiers, dyes and pigments, antistatic agents, antifogging agents, lubricants and antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, fluorescent whitening agents, Examples of inorganic resin additives include glass fibers, glass milled fibers, glass flakes, glass beads, carbon fibers, silica, alumina, calcium sulfate powder, gypsum, gypsum whiskers, barium sulfate, talc, Examples include inorganic fillers such as mica, calcium silicate, carbon black, and graphite. These may be used alone or in combination of two or more in any ratio.

[6.1 Heat stabilizer and antioxidant]
The aromatic polycarbonate resin composition of the present invention further includes a heat stabilizer and an antioxidant for the purpose of suppressing yellowing that occurs during melt processing and when used for a long time at high temperatures, and further suppressing mechanical strength reduction. It is preferable to contain an agent.
As the heat stabilizer and the antioxidant, any conventionally known one can be used. Among them, a phosphorus compound is preferable as the heat stabilizer, and a phenol compound is preferable as the antioxidant, and these may be used in combination. Phosphorus compounds are generally effective in improving the residence stability at high temperatures and heat stability when using resin moldings when melt-kneading polycarbonate resins, and phenol compounds are generally effective in heat aging resistance, etc. The heat resistance stability when using the polycarbonate resin molded body is high. Further, by using a phosphorus compound and a phenol compound in combination, the effect of improving the colorability is further improved.

  Examples of the phosphorus compound used in the present invention include phosphorous acid, phosphoric acid, phosphite ester, phosphate ester, etc. Among them, phosphite contains trivalent phosphorus and easily exhibits a discoloration suppressing effect. Phosphites such as phosphonite are preferred.

  Specific examples of the phosphite include triphenyl phosphite, tris (nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, and tris. (Tridecyl) phosphite, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyl dipropylene glycol diphosphite, tetraphenyl tetra (tridecyl) pentaerythritol tetra Phosphite, hydrogenated bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4′-butylidene-bis (3-methyl-6-t rt-butylphenyldi (tridecyl) phosphite) tetra (tridecyl) 4,4'-isopropylidenediphenyldiphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, dilauryl Pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris (4-tert-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, hydrogenated bisphenol A pentaerythritol phosphite Polymer, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphos Aito, 2,2'-methylenebis (4,6-di -tert- butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite and the like.

  Examples of phosphonites include tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-n-butylphenyl) -4,4′-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylene diphospho Knight, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, Tetrakis (2,6-di-n-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6- -Tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, and tetrakis (2,6-di-) tert-butylphenyl) -3,3′-biphenylenediphosphonite.

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

  Among the phosphites, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) penta Erythritol diphosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite are preferable, and heat resistance is good. Tris (2,4-di-tert-butylphenyl) phosphite is particularly preferred in that it is difficult to hydrolyze.

  As the antioxidant, a phenol compound having a specific structure in the molecule is preferable. Specifically, for example, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (6-tert -Butyl-3-methylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 3,9-bis [2- {3- (3-tert- Butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [β- (3 -Tert-butyl-4-hydroxy-5-methylphenyl) propionate], 1,6-hexanediol bis [β- (3-tert-butyl) Ru-4-hydroxy-5-methylphenyl) propionate], pentaerythritol-tetrakis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], octadecyl [β- (3-tert-butyl) -4-hydroxy-5-methylphenyl) propionate] and the like.

  Among these, 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 1,1,3-tris (2-methyl-) is necessary because it is necessary to suppress yellowing when kneaded with a polycarbonate resin. 4-hydroxy-5-tert-butylphenyl) butane, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl ] -2,4,8,10-tetraoxaspiro [5.5] undecane is preferred, especially 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 3 , 9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,1 - tetraoxaspiro [5.5] undecane is preferred.

  The content of the heat stabilizer and the antioxidant used in the present invention may be appropriately selected and determined, but is usually 0.0001 to 0.5 mass with respect to 100 mass parts of the aromatic polycarbonate resin (A). Part, preferably 0.0003 to 0.3 part by weight, particularly preferably 0.001 to 0.1 part by weight. If the content of the heat stabilizer or the antioxidant is too small, the effect is insufficient. On the other hand, if the content is too large, the molecular weight of the polycarbonate resin may be lowered or the hue may be lowered.

[7. Production method of polycarbonate resin composition]
In order to produce the polycarbonate resin composition of the present invention, the above-described components (A1) and (A2), (B) to (D), and other components added as necessary or desired, are directly or sequentially added to the polycarbonate. May be mixed or kneaded.
Specific examples include each of the above components, and other components blended as necessary, for example, using a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single or twin screw extruder, a kneader, etc. And a melt kneading method. The temperature for melt kneading is not particularly limited, but is usually in the range of 240 to 320 ° C.

[8. Molded body]
The polycarbonate resin composition of the present invention can be produced by molding pelletized pellets by various molding methods. Further, the resin melt-kneaded by an extruder can be directly made into a sheet, a film, a profile extrusion-molded product, a blow-molded product, an injection-molded product or the like without going through pellets.
The polycarbonate resin composition according to the present invention can be used as a molding material for various molded products. There is no limitation on the shape, pattern, color, size, etc. of the molded product, and it may be set arbitrarily according to the application. As the applicable molding method, a method applicable to the molding of a thermoplastic resin can be applied as it is, an injection molding method, an extrusion molding method, a hollow molding method, a rotational molding method, a compression molding method, a differential pressure molding method, a transfer molding. Law.

  Since the molded product according to the present invention is excellent in transparency and flame retardancy, it can be used for various large flat display frames such as televisions, OA / information devices such as computers, notebook computers, mobile phones, printers, and copiers. Useful for parts.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not construed as being limited to the following examples.
In the following Examples and Comparative Examples, “part” and “%” mean “part by mass” and “% by mass” unless otherwise specified.

(Examples 1-6 and Comparative Examples 1-9)
The raw materials used are as follows.
[raw materials]
(A) Aromatic polycarbonate resin (poly-4,4-isopropylidene diphenyl carbonate)
(A1) Linear aromatic polycarbonate resin (A1-1) obtained by the interfacial polymerization method:
"Iupilon (registered trademark) H-4000N" manufactured by Mitsubishi Engineering Plastics
Viscosity average molecular weight 16,000
(A1-2):
"Iupilon (registered trademark) E-2000N" manufactured by Mitsubishi Engineering Plastics
Viscosity average molecular weight 26,000
(A2) Branched aromatic polycarbonate resin obtained by transesterification “NOVAREX (registered trademark) M7027BF” manufactured by Mitsubishi Engineering Plastics
Viscosity average molecular weight 27,000, structural viscosity index N value 1.4

(B) Phenoxyphosphazene flame retardant Cyclic phenoxyphosphazene manufactured by Fushimi Pharmaceutical Co., Ltd., trade name “FP-110”

(C) Organometallic salt (C-1) Potassium diphenylsulfone sulfonate Product name “KSS” manufactured by Vertellus
(C-2) Perfluorobutanesulfonic acid potassium salt Product name “Bayowet C4” manufactured by LANXESS
(C-3) Perfluorobutanesulfonic acid potassium salt Product name “F114P” manufactured by DIC Corporation
(C-4) Sodium paratoluenesulfonic acid salt “Chemguard (trade name) NATS” manufactured by Chemebridge International

(D-1) Pentaerythritol tetrastearate (PETS)
Product name "Roxyol VPG861" manufactured by Cognis Japan
(D-2) Pentaerythritol distearate (PTDS)
“UNISTAR (trade name) H476D” manufactured by NOF Corporation

(Examples 1-6 and Comparative Examples 1-9)
Each component shown in Table 1 and Table 2 was blended so as to have the ratio (mass ratio) shown in each table, mixed with a tumbler, and then charged into the hopper of a twin screw extruder (12 blocks, TEX30XCT) did. Each resin component was melt-kneaded under conditions of a cylinder temperature of 270 ° C., 200 rpm, and an extrusion rate of 25 kg / hour to obtain pellets. The obtained resin composition was subjected to various evaluations by the following methods.

[Method for evaluating physical properties of molded products]
(1) Combustibility The obtained resin composition was injection-molded under the conditions of a set temperature of 280 ° C. and a mold temperature of 80 ° C. using an injection molding machine J50 manufactured by Nippon Steel Works, and had a length of 127 mm and a width of 12. A molded product having a thickness of 7 mm and a thickness of 2.5 mm was obtained as a test piece. About the obtained test piece, the vertical combustion test based on UL94 was done, the flammability result was set to V-0, V-1, V-2 from the favorable order, and the thing outside a specification was classified into NG.

(2) Haze (2mm, 5mm)
In accordance with JIS K-7136, a plate-like molded product (thickness of 2 mm and 5 mm) manufactured by the same method as above was used as a test piece, and NDH-2000 type haze meter manufactured by Nippon Denshoku Industries Co., Ltd. The haze at 5 mm thickness was measured. The haze (%) is a value used as a measure of the turbidity of the resin, and the smaller the value, the better the transparency.

(3) Change in haze When molding a plate-shaped product by the above method, a test piece was prepared in the same manner except that the cylinder was kept at a setting temperature of 320 ° C. for 20 minutes. Then, the haze was measured and the change in haze (%) was observed.

(4) MVR (melt volume rate)]
The pellets of the obtained composition were measured under the conditions of a temperature of 300 ° C. and a load of 1.2 kgf according to JIS K7210.
MVR is an index of fluidity, and in the present invention, it is a measure indicating whether or not the molecular weight of the polycarbonate resin has been reduced.
The above evaluation results are shown in Tables 1 and 2.

From the results in Table 1, the following can be understood.
The resin compositions of Examples 1 to 6 have excellent flame retardancy (V-0) and exhibit high transparency (haze, 2 mm), which is good even in a thick portion of 5 mm. Further, it can be seen that even when the retention molding is performed for 20 minutes, the change in haze is very small at 3%. Example 3 uses pentaerythritol full ester as a release agent, but shows an excellent haze value, but Example 6 using a diester has a poor change in haze when subjected to retention molding. It is confirmed that it is preferable to use an ester.

On the other hand, from Table 2, Comparative Example 1 is inferior in flame retardancy to V-2 because the amount of the branched polycarbonate resin is less than 30% by mass, and Comparative Example 2 does not use the branched polycarbonate resin. The flame retardancy is poor, and Comparative Example 3 has a flame retardance of V-2 because the amount of phenoxyphosphazene is insufficient. Although the comparative example 4 mix | blends phosphoric acid ester instead of phenoxyphosphazene, a flame retardance will deteriorate.
In Comparative Example 5, since potassium perfluorobutanesulfonate was used alone, the combustibility was insufficient (V-1), and the haze was very poor. In Comparative Example 6, since potassium perfluorotan sulfonate was used instead of potassium diphenyl sulfone sulfonate, the flame retardancy was further deteriorated to V-2, and the 5 mm thick haze was worse than that of the Example.
In Comparative Example 7, potassium perfluorobutanesulfonate was changed to a powder form, and the flame retardancy was V-2 as in Comparative Example 6, but the haze value was a good value compared with Comparative Example 6. showed that. Comparative Example 8 is inferior in flame retardancy because the amount of potassium diphenyl sulfone sulfonate is not appropriate, and Comparative Example 9 uses a commonly used paratoluenesulfonic acid sodium salt as an aromatic sulfonic acid metal salt. However, it turns out that both flame retardancy and haze are bad.

As described above, the aromatic polycarbonate resin composition of the present invention is excellent in flame retardancy and transparency and fluidity as compared with conventional flame retardant polycarbonate compositions. The haze change is small even in molding with a long cylinder residence time during molding, and excellent transparency is exhibited even in molded products with thick parts, so the color depth increases when colored, improving design and design Excellent.
Therefore, taking advantage of these features, as parts of various large flat display frames such as televisions (for example, 40 inches or more), OA / information equipment such as computers, notebook computers, mobile phones, printers, copiers, etc. Can be used widely.

Claims (5)

(I) 30 to 70% by mass of a linear aromatic polycarbonate (A1) produced by an interfacial polymerization method, and (ii) 70 to 30% by mass of a branched aromatic polycarbonate (A2) produced by a transesterification method. 3 to 8 parts by mass of the phenoxyphosphazene flame retardant (B), 0.05 to 0.5% of the aromatic sulfonesulfonic acid alkali or alkaline earth metal salt (C) with respect to 100 parts by mass of the aromatic polycarbonate resin (A) to be contained. An aromatic polycarbonate resin composition comprising 0.3 part by mass.   Furthermore, 0.05-2 mass parts of full ester (D) of a polyhydric alcohol and aliphatic carboxylic acid is contained with respect to 100 mass parts of aromatic polycarbonate resin (A). The aromatic polycarbonate resin composition described.   The aromatic polycarbonate resin composition according to claim 1 or 2, wherein the full ester (D) of a polyhydric alcohol and an aliphatic carboxylic acid is a full ester of pentaerythritol and an aliphatic carboxylic acid.   The aromatic polycarbonate resin composition according to any one of claims 1 to 3, wherein the aromatic sulfonesulfonic acid metal salt (C) is sodium or potassium diphenylsulfonesulfonate.   The molded article obtained from the aromatic polycarbonate resin composition of any one of Claims 1-4.