JP5427703B2 - Aromatic polycarbonate resin composition and molded article - Google Patents

Description

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

  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 containing an aromatic sulfone sulfonate, an aromatic sulfonate, and, if necessary, a siloxane oligomer. The flame 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 that depending on the combination, the transparency of the polycarbonate resin is liable to be reduced, white turbidity occurs, haze decreases, and the transparency of the molded product. Had the problem of a decline.

  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 product 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, 30-100 mass% of branched aromatic polycarbonates (A1) manufactured by the transesterification method on the basis of a total of 100 mass% of (A1) and ( A2 ), 8 parts by mass of the phenoxyphosphazene flame retardant (B) with respect to a total of 100 parts by mass of the linear aromatic polycarbonate (A2) 70 to 0% by mass and (A1) and ( A2 ) produced by the interfacial polymerization method Is a polycarbonate resin composition comprising 18 parts by mass or less, and a fragrance comprising a powdery polycarbonate resin as at least a part of the linear aromatic polycarbonate (A2) A group polycarbonate resin composition is provided.

According to the second invention of the present invention, in the first invention, the branched aromatic polycarbonate (A1) is 50 to 95% by mass, and the linear aromatic polycarbonate (A2) is 50 to 5% by mass. % aromatic polycarbonate resin composition characterized in that in a proportion of is provided.

According to the third invention of the present invention, in the first invention, the perfluoroalkane metal salt (C) is further added in an amount of 0.01 to 100 parts by mass with respect to a total of 100 parts by mass of (A1) and ( A2 ). An aromatic polycarbonate resin composition characterized by containing 1 part by mass is provided.

According to the fourth 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). aromatic polycarbonate resin composition characterized by formulating 0.05 to 2 parts by weight is provided.

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

According to the sixth invention of the present invention, in any one of the first to fifth inventions, the aromatic polycarbonate resin composition is pre-blended with the phenoxyphosphazene flame retardant (B) in the powdery polycarbonate resin. An aromatic polycarbonate resin composition characterized by being obtained by mixing a masterbatch is provided.
Further, according to the seventh invention of the present invention, the branched aromatic polycarbonate (A1) produced by the transesterification method on the basis of a total of 100 mass% of (A1) and ( A2 ), 30 to 100 mass%, 8 parts by mass of the phenoxyphosphazene-based flame retardant (B) with respect to a total of 100 parts by mass of the linear aromatic polycarbonate (A2) 70 to 0% by mass and (A1) and ( A2 ) produced by the interfacial polymerization method. A method for producing a polycarbonate resin composition containing more than 18 parts by mass and comprising blending a powdery polycarbonate resin as at least part of the linear aromatic polycarbonate (A2) A method for producing a resin composition.

Furthermore, according to the eighth invention of the present invention, there is provided a molded product obtained from the aromatic polycarbonate resin composition of any one of the first to sixth inventions.

The aromatic polycarbonate resin composition of the present invention is excellent in mechanical strength, transparency and flame retardancy by combining a combination of a branched and linear polycarbonate resin, and further a phenoxyphosphazene flame retardant, and fluidity. Also excellent. 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 a branched aromatic polycarbonate (A1) 30 to 100% by mass produced by a transesterification method, and a linear aromatic polycarbonate (A2) 70 produced by an interfacial polymerization method. To 100 parts by mass of the aromatic polycarbonate resin (A) containing ˜0% by mass,
More than 8 parts by mass and 18 parts by mass or less of the phenoxyphosphazene flame retardant (B) is contained.

  Hereinafter, each component used for the aromatic polycarbonate resin composition of this invention is demonstrated in detail.

[2. Aromatic polycarbonate resin (A)]
[2.1 Branched polycarbonate by transesterification (A1)]
The branched polycarbonate (A1) produced by the transesterification method used in the present invention can be obtained by subjecting an aromatic dihydroxy compound and a carbonic acid diester as raw materials to melt polycondensation in the presence of a transesterification catalyst. .

-Aromatic dihydroxy compound As an aromatic dihydroxy compound which is one of the raw materials for producing an aromatic polycarbonate, 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- Hydroxyphenyl) 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.

  Moreover, the branched polycarbonate (A1) by the transesterification method is reacted with 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 preferred not to use these compounds.

-Carbonic acid diester As a typical example of the carbonic acid diester that is another raw material of the branched polycarbonate (A1) produced by the transesterification method, for example, substituted diphenyl typified by diphenyl carbonate, ditolyl carbonate, etc. Examples thereof include dialkyl carbonates typified by carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate. 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 A catalyst is used when manufacturing a branched aromatic polycarbonate (A1) by the transesterification method. In the present invention, the catalyst species is not limited, but generally a basic compound such as an alkali metal compound, an alkaline earth metal compound, a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound. 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 (A1) 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 amount, it becomes difficult to obtain a branched aromatic polycarbonate having a polymerization activity necessary for producing a branched polycarbonate (A1) having a desired molecular weight and a melting property suitable for molding.

In the present invention, the production method of the branched polycarbonate (A1) 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 (A1) 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.
In the case of using a plurality of polymerization tanks in a multistage process, the actual catalyst amount is preferably controlled automatically and continuously, and in that case, 1/3 of the residence time of the first polymerization tank is used. Measurement and control must be completed within.

  In the branched polycarbonate (A1) produced by the above method, unlike the interface method, there is no elemental chlorine derived from phosgene or reaction solvent, but the raw material monomer, catalyst, and aromatics by-produced by 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 (A1) obtained by the transesterification method used in the present invention usually has a viscosity average molecular weight selected from 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 (A2) having a high molecular weight produced by an interfacial polymerization method. Such a composition has 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, it is preferable that the branched polycarbonate (A1) obtained by the transesterification method contains a polycarbonate resin having a structural viscosity index N in a predetermined range in the whole amount or at a certain ratio. That is, in the polycarbonate resin (A1), 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 polycarbonate resin (A1), 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 · 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 exhibited, 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 (A1) obtained by the transesterification method preferably has a structural viscosity index N of 1.2 or more, more preferably 1.25 or more, and further preferably 1.28 or more. Moreover, it is 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 Logη _a = [(1−N) / N] × Logγ + C derived from the above formula, as described in, for example, Japanese Patent Application Laid-Open No. 2005-232442. It is also possible. In the formula, N: structural viscosity index, γ: shear rate, C: constant, η _a : 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 where 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.

[2.2 Linear polycarbonate by interfacial polymerization (A2)]
The linear polycarbonate (A2) produced by the interfacial polymerization method used in the present invention is produced from an aromatic dihydroxy compound and phosgene by a known method, for example, a method described in JP-A-2001-316467. It is a linear aromatic polycarbonate resin.

  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 above-described transesterification method, and bisphenol A is preferable.

  The viscosity average molecular weight (Mv) of the linear aromatic polycarbonate (A2) 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 (A1) 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 (A1) produced by the transesterification method, and it is difficult to obtain a uniform composition. The linear polycarbonate (A2) obtained by the interfacial polymerization method can also 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.

[2.3 Ratio of branched polycarbonate (A1) and linear polycarbonate (A2)]
The aromatic polycarbonate resin (A) according to the present invention includes a branched aromatic polycarbonate (A1) 30 to 100% by mass produced by a transesterification method, and a linear aromatic polycarbonate (A2) produced by an interfacial polymerization method. ) 70 to 0% by mass. Dispersibility becomes favorable by mix | blending a linear polycarbonate (A2). A preferred blending ratio is that containing 50 to 95% by mass of (A1) and 50 to 5% by mass of (A2). When the content of the branched polycarbonate (A1) is less than 30% by mass in the resin composition, the melting characteristics are lowered, and the accuracy and appearance of the molded product are inferior. If the content of the linear polycarbonate (A2) is low, the resin composition is easily hydrolyzed in the presence of an alkali sulfonesulfonic acid alkali or alkaline earth metal salt, such being undesirable. Particularly preferred content ratios are (A1) 70 to 95% by mass and (A2) 30 to 5% by mass.

  In the transesterified branched polycarbonate (A1) and the interfacial polymerization linear polycarbonate (A2) constituting the resin composition according to the present invention, a recycled material may be used for a part or all of those polycarbonates. 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、ｌは０又は１である。）

(In the formula (3), A is _{-C (CH 3) 2 -,} - SO 2 -, - S-, or a -O-, l 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 chain tolyloxy) Phosphazene Cyclic and / or linear phenoxy tolyl phenoxyphosphazene etc.).

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-described method to reverse polymerization at a temperature of 220 to 250 ° C., and the obtained linear dichloromethane having a polymerization degree of 3 to 10,000. Examples thereof include compounds obtained by substituting phosphazene with a phenoxy group. N of general formula (2) of this linear phenoxyphosphazene compound becomes like this. Preferably it is 3-1,000, 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 more than 8 parts by weight and 18 parts by weight, and more preferably 9 to 15 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin (A). By setting the amount to more than 8 parts by mass, the flame retardancy can be sufficiently improved, and by setting the amount to 18 parts by mass or less, the mechanical strength can be kept good.

[4. Perfluoroalkane metal salt (C)]
In the present invention, it is preferable to further blend a perfluoroalkane metal salt (C).
The perfluoroalkanesulfonic acid metal salt is preferably an alkali metal salt of perfluoroalkanesulfonic acid, an alkaline earth metal salt of perfluoroalkanesulfonic acid, or the like, and more preferably a perfluoroalkanesulfonic acid metal salt. Examples include sulfonic acid alkali metal salts having a fluoroalkane group and sulfonic acid alkaline earth metal salts having a C 4-8 perfluoroalkane group.
Specific examples of the perfluoroalkanesulfonic acid metal salt include sodium perfluorobutanesulfonate, potassium perfluorobutanesulfonate, sodium perfluoromethylbutanesulfonate, potassium perfluoromethylbutanesulfonate, sodium perfluorooctanesulfonate, Examples include potassium perfluorooctane sulfonate and tetraethylammonium salt of perfluorobutane sulfonic acid.
Among these, potassium perfluorobutanesulfonate is particularly preferable.

  The preferable content of the organic sulfonic acid metal salt is 0.01 to 1 part by weight, more preferably 0.02 to 0.5 part by weight, and particularly 0.03 to 0.00 part, with respect to 100 parts by weight of the polycarbonate resin composition. 3% by mass. When the content is less than 0.01% by mass, it is difficult to obtain sufficient flame retardancy, and when it exceeds 1% by mass, the thermal stability and hydrolysis resistance tend to be lowered.

[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 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 (A2) and (A2), (B) to (D), and other components added as necessary or desired, can be 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.

[7.1 Masterbatch]
The polycarbonate resin composition of the present invention is produced by blending together polycarbonate resins (A1) and (A2), a phenoxyphosphazene flame retardant (B), an aromatic sulfonesulfonic acid metal salt (C), and other necessary components. Although a method may be used, the manufacturing method of melt-kneading this masterbatch with a polycarbonate resin composition after obtaining the masterbatch compound described below may be used.

Specifically, the polycarbonate resin composition of the present invention is preliminarily mixed with a powdery polycarbonate resin in order to improve the dispersibility of the phenoxy phosphazene flame retardant (B) in the resin composition and in the molded product. Thus, it is preferable to obtain a masterbatch containing a high concentration flame retardant (B) and melt knead it with other components to obtain a polycarbonate resin composition having a predetermined composition. More preferably, by blending into the powdered linear polycarbonate resin (A2) having a specific surface area of 0.01 to ⁵ mm ² / g and a particle size of 60 to 95% by mass of 180 to 1,700 μm, After obtaining a polycarbonate-phenoxyphosozenene-based flame retardant (B) containing a larger amount of phenoxyphosofacene-based flame retardant (B) than the final blending amount, the master batch needs to be in the form of pellets or granules A production method of obtaining a polycarbonate resin composition by melt-kneading with an amount of the polycarbonate resins (A1) and (A2) and other components is preferred.

  Examples of the method for producing the master batch include a method of mixing using a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, and the like, and the use of a drum tumbler is preferred. It is preferable that the compounding quantity of the flame retardant (B) in a polycarbonate phenoxy phosphazene series flame retardant (B) masterbatch is 20-120 mass parts with respect to 100 mass parts of polycarbonate resin, More preferably, it is 25- 100 parts by mass. By melting and kneading such a polycarbonate-phenoxyphosozen flame retardant (B) masterbatch at the time of production, the dispersibility of the flame retardant (B) is improved and the appearance of the molded product is improved.

Similarly to the above, in order to improve the dispersibility of the perfluoroalkane metal salt (C) and obtain stable combustibility, the perfluoroalkane metal salt (C) is subjected to the same master batch method as described above. It is also preferable to apply.
By melt-kneading with the master batch at the time of manufacture, the molded product obtained from the polycarbonate resin composition not only has a better appearance, but also can suppress variations in combustibility.

[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 1-4 and Comparative Examples 1-6)
The raw materials used are as follows.
[raw materials]
(A) Aromatic polycarbonate resin (poly-4,4-isopropylidene diphenyl carbonate)
(A-1) Branched aromatic polycarbonate resin obtained by transesterification “Novarex (registered trademark) M7027BF” manufactured by Mitsubishi Engineering Plastics Co., Ltd. Viscosity average molecular weight 27,000, structural viscosity index N value 1.4
(A-2) Linear aromatic polycarbonate resin obtained by an interfacial polymerization method “Iupilon (registered trademark) E-2000FN” manufactured by Mitsubishi Engineering Plastics Co., Ltd. Viscosity average molecular weight 26,000
(Powder, specific surface area: 1.2 mm ² / g, particle diameter of 180 to 1,700 μm: 90% by mass)

(B) Phenoxyphosphazene flame retardant (B-1) Trade name “SPB-100” manufactured by Otsuka Chemical Co., Ltd. (Phenoxyphosphazene flame retardant mainly composed of cyclic phenoxyphosphazene)

(C-1) Perfluorobutanesulfonic acid potassium salt Product name “Bayowet C4” manufactured by LANXESS
(C-2) As the other flame retardant, the following phosphoric ester-based flame retardant (C-2) was used.
1,3-phenylenebis (dixylenyl) phosphate, trade name “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd.

(D) Release agent (D-1) Pentaerythritol tetrastearate (PETS)
Product name "Roxyol VPG861" manufactured by Cognis Japan
(D-2) Stearyl stearate Product name “Unistar M9676” manufactured by NOF Corporation

[1. Production of composition pellets]
Each component shown in the following Table 1 was blended so as to have the ratio (mass ratio) shown in the table, mixed with a tumbler, and then a twin screw extruder (TEX30XCT) manufactured by Nippon Steel Works, equipped with 1 vent. The molten resin composition kneaded under vent suction under the conditions of a screw speed of 200 rpm, a discharge rate of 20 kg / hour, and a barrel temperature of 270 ° C., rapidly cooled in a water tank in a water tank, and pelletized using a pelletizer To obtain pellets of the polycarbonate resin composition.
In Examples 2 to 4, the total amount of the powdery polycarbonate resin E-2000FN (A-2) and the total amount of the phenoxyphosphazene flame retardant (B-1) were used as a master blend. Was blended with other components so as to have a predetermined composition.
The obtained resin composition was subjected to various evaluations by the following methods.

(Method for evaluating physical properties of molded products)
[2. Formation of ISO physical property evaluation dumbbell]
The pellet obtained in 1 above was dried at 120 ° C. for 5 hours, and then injection molded under the conditions of a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. using a J55AD type injection molding machine manufactured by Nippon Steel. A test dumbbell (4 mm) was molded.

[3. Molding of color plate for hue evaluation]
The pellet obtained in 1 above was dried at 120 ° C. for 5 hours, and then injection molded under the conditions of a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. using a J55AD type injection molding machine manufactured by Nippon Steel, An evaluation color plate (3 mm) was molded.

[4. Molding of thick color plate]
After the pellets obtained in 1 above were dried at 120 ° C. for 5 hours, using a NEX80-9E molding machine manufactured by Nissei Plastic Industry Co., Ltd., under conditions of a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. A thick color plate having a thickness of 5 mm, a length of 65 mm, and a width of 45 mm was formed.

[5. Molding of combustion test piece]
The pellet obtained in 1 above was dried at 120 ° C. for 5 hours, and then injection molded under the conditions of a cylinder temperature of 270 ° C. and a mold temperature of 80 ° C. using a J55AD type injection molding machine manufactured by Nippon Steel. Test pieces for a UL test having a thickness of 125 mm, a width of 13 mm, a thickness of 1.5 mm, and a thickness of 2.5 mm were formed.

[6. Combustibility evaluation (UL94)]
Flame retardant evaluation is performed by the UL Underwriters Laboratories (UL) in the United States underwriters laboratories (UL) after conditioning UL test specimens obtained by the above method for 48 hours in a temperature-controlled room at 23 ° C and 50% humidity. The UL94 test (combustion test of plastic materials for equipment parts) was conducted. UL94V is a method for evaluating the flame retardance from the afterflame time and drip properties after indirect flame of a burner for 10 seconds on a test piece of a predetermined size held vertically. , V-1 and V-2, and those outside the standard were NG.

[7. Fluidity evaluation (melt volume rate, MVR)]
The pellet obtained in 1 above was dried at 120 ° C. for 5 hours, and then measured under the conditions of a temperature of 300 ° C. and a load of 1.2 kgf in accordance with JIS K7210. The unit is ^cm 3 / 10min. MVR is an indicator of fluidity, and the higher the value, the better the fluidity.

[8. Transparency evaluation (haze)]
Using a color plate test piece having a thickness of 3 mm obtained by the above method and a thick color plate having a thickness of 5 mm, it was measured with an NDH-2000 type haze meter manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K-7136. The haze (%) is an index used as a measure of the white turbidity of the resin, and the smaller the numerical value, the higher the transparency.
Moreover, the 5 mm test piece was observed with the naked eye from the thickness direction, and the presence or absence of white haze was observed.

[9. Color tone evaluation (YI)]
Using a color plate test piece having a thickness of 3 mm obtained by the above method, it was measured by a transmission method using a SE2000 type spectrocolorimeter manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K7105. A smaller YI value is preferable because the degree of yellowing of the resin is lower.

[10. Heat resistance (deflection temperature under load, HDT)]
Both ends of the 4 mm ISO dumbbell test piece obtained by the above method were cut to a length of 80 mm, and the deflection temperature under load was measured according to ISO 75-1. Higher HDT is preferred because of better heat resistance.
The above evaluation results are shown in Table 1.

From the results in Table 1, the following can be understood.
The resin compositions of Examples 1 to 4 have excellent flame retardancy (V-0) and high transparency (haze, 3 mm), which is good even in a thick portion of 5 mm.
On the other hand, Comparative Example 1 is inferior in flame retardancy to V-2 because the amount of branched polycarbonate resin is less than 30% by mass, and Comparative Example 2 has no flame retardancy because it does not use a branched polycarbonate resin. Unfortunately, since Comparative Example 3 has a large amount of phenoxyphosphazene, the fluidity (MVR), color tone (YI), and heat resistance (HDT) are poor. In Comparative Example 4, only a sulfonic acid metal salt was blended in place of phenoxyphosphazene, but the flame retardancy at 1.5 mm was poor (V-2), and the transparency was insufficient and 5 mm. The haze at the thickness is particularly bad.
In Comparative Example 5, since the amount of phenoxyphosphazene is small, even if a sulfonic acid metal salt is used in combination, the combustibility is insufficient (V-2). Comparative Example 6 uses a phosphate ester flame retardant, but has poor flame retardancy and poor heat resistance.

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. Since the molded product having a thick part also exhibits excellent transparency, when it is colored, the depth of the color tone increases, and the design and design are 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 (8)

30 to 100% by mass of a branched aromatic polycarbonate (A1) produced by a transesterification method and a linear aromatic polycarbonate produced by an interfacial polymerization method based on a total of 100% by mass of (A1) and ( A2 ) (A2) A polycarbonate resin obtained by blending more than 8 parts by mass and 18 parts by mass or less of the phenoxyphosphazene flame retardant (B) with respect to a total of 100 parts by mass of 70 to 0% by mass and (A1) and ( A2 ). An aromatic polycarbonate resin composition comprising a powdery polycarbonate resin as at least part of the linear aromatic polycarbonate (A2).   2. The aromatic according to claim 1, wherein the branched aromatic polycarbonate (A1) is blended in a proportion of 50 to 95% by mass and the linear aromatic polycarbonate (A2) is blended in a proportion of 50 to 5% by mass. Polycarbonate resin composition. Furthermore, 0.01-1 mass part of perfluoroalkane metal salt (C) is mix | blended with respect to a total of 100 mass parts of (A1) and ( A2 ), The aromatic polycarbonate of Claim 1 characterized by the above-mentioned. Resin composition.   Further, 0.05 to 2 parts by mass of a full ester (D) of a polyhydric alcohol and an aliphatic carboxylic acid is blended with respect to 100 parts by mass of the aromatic polycarbonate resin (A). The aromatic polycarbonate resin composition described.   The aromatic polycarbonate resin composition according to claim 4, 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 is obtained by mixing a master batch in which the phenoxyphosphazene flame retardant (B) is blended in advance with the powdery polycarbonate resin. The aromatic polycarbonate resin composition according to claim 1. 30 to 100% by mass of a branched aromatic polycarbonate (A1) produced by a transesterification method and a linear aromatic polycarbonate produced by an interfacial polymerization method based on a total of 100% by mass of (A1) and ( A2 ) (A2) The polycarbonate resin composition which mix | blends more than 8 mass parts and 18 mass parts or less of a phenoxyphosphazene flame retardant (B) with respect to a total of 100 mass parts of 70-0 mass% and (A1) and ( A2 ). A method for producing an aromatic polycarbonate resin composition comprising blending a powdery polycarbonate resin as at least a part of the linear aromatic polycarbonate (A2).   The molded article obtained from the aromatic polycarbonate resin composition of any one of Claims 1-6.