JP2014062203A - Aromatic polycarbonate resin composition and molded article using the resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate resin composition which suppresses oxidation during a molding process upon molding an aromatic polycarbonate resin, which has high transparency and little yellow discoloration and which can be suitably used for an optical molded article such as a light guide plate used in a liquid crystal display device or the like.SOLUTION: The aromatic polycarbonate resin composition is prepared by compounding, in (A) 100 parts by mass of an aromatic polycarbonate resin, (B) 0.001 to 0.05 parts by mass of a monovalent phenol (B-1) having a molecular weight of 200 or less per 1 gram equivalent and/or a divalent phenol (B-2) having a molecular weight of 200 or less per 1 gram equivalent, and (C) 0.005 to 0.5 parts by mass of a phosphite-based antioxidant.

Description

  The present invention relates to an aromatic polycarbonate resin composition and a molded article using the same. More specifically, the present invention relates to an aromatic polycarbonate resin composition useful as an optical molded product such as a light guide plate, a lens, and an optical fiber, and an optical molded product using the same.

  Aromatic polycarbonate resins are excellent in transparency, mechanical properties, thermal properties, electrical properties, weather resistance, and the like, and are used in optical molded products such as light guide plates, lenses, and optical fibers by taking advantage of the properties. In recent years, with an increase in demand for smartphones and the like, it has been required to increase screen brightness by increasing the transparency of light guide plates used in liquid crystal display devices.

In order to reduce the thickness of the light guide plate and increase the screen size, it is necessary to increase the fluidity of the resin. For this reason, it is necessary to increase the molding temperature. As a result, the aromatic polycarbonate resin is easily oxidized and discolored. In particular, an aromatic polycarbonate resin having a large amount of low molecular weight components is oxidized and colored during molding, and yellowing becomes strong.
In general, when an aromatic polycarbonate resin is molded, the resin melted by heating in the molding machine becomes free radicals of inorganic and organic free radicals, which attack the polycarbonate molecular chain to cleave the molecule, and alkyl Generate radicals (R.). This alkyl radical (R.) is oxidized to an alkoxy radical (RO.), And further attacks the polycarbonate molecule. Alkoxy radicals (RO •) become peroxy radicals (ROO •) and react with hydrogen to become hydroperoxides (ROOH; peroxides), which are temporarily stabilized. Since it is radicalized, the oxidation reaction proceeds. It is known that an antioxidant is generally added to block and stabilize this oxidation reaction.

  Phenolic antioxidants are generally used to stop the former radical reaction and stabilize it as hydroperoxide. The stabilized hydroperoxide is reduced to alcohol to stabilize it and re-radicalization is performed. Phosphite antioxidants are commonly used to prevent this.

Therefore, it is known that an aromatic polycarbonate resin efficiently suppresses oxidation by adding a combination of a phenolic antioxidant and a phosphite antioxidant as antioxidants (for example, patents). References 1 and 2).
However, in order to process into optical molded products such as light guide plates used in liquid crystal display devices etc., even if a small amount of phenolic antioxidant is added to the transparent polycarbonate resin, the color changes to yellow or brown and the transparency decreases. Since optical properties such as light guide performance deteriorate, it is generally known that when forming into an optical molded article such as a light guide plate, the phenolic antioxidant is not added to the transparent polycarbonate resin ( For example, see Patent Documents 3 and 4).
For this reason, when low-molecular-weight polycarbonates that tend to generate free radicals or polycarbonate resins that contain a large amount of oligomers are molded at high temperatures, phosphite antioxidants alone cannot suppress oxidation, resulting in strong yellowing and reduced transparency. However, there are cases where it cannot be used as an optical molded product.

JP 2003-206399 A JP 2011-174031 A Japanese Patent Laid-Open No. 2002-60609 JP 2009-40843 A

  The present invention has been made in view of the above circumstances, and suppresses oxidation during molding processing when molding an aromatic polycarbonate resin, in particular, a relatively low molecular weight polycarbonate or an aromatic polycarbonate resin having a large amount of oligomers. An aromatic polycarbonate resin composition that can be suitably used for an optical molded article such as a light guide plate used in a liquid crystal display device and the like having high transparency and little yellowing, and a molded article using the resin composition Is intended to provide.

  As a result of intensive research to achieve the above object, the present inventors have blended a specific amount of a monohydric phenol having a dihydric phenol and / or an alkyl group and a phosphite antioxidant into an aromatic polycarbonate resin. It has been found that the above problems can be solved by doing so. The present invention has been completed based on such findings.

〔Ｒ¹およびＲ²は、炭素数1〜６のアルキル基、Ｘは単結合、炭素数１〜８のアルキレン基、炭素数２〜８のアルキリデン基、炭素数５〜１５のシクロアルキレン基、炭素数５〜１５のシクロアルキリデン基、−Ｓ−、−ＳＯ−、−ＳＯ₂−、−Ｏ−、−ＣＯ−を示す。Ｒ³及びＲ⁴は炭素数１〜３のアルキル基、Ｙは炭素数２〜１５の直鎖又は分岐鎖のアルキレン基を示す。ａ〜ｄは、それぞれ独立に０〜４の整数、ｎは２〜２００の整数である。〕
３．前記１価フェノール（Ｂ−１）が、炭素数１〜７のアルキル基を有する１価フェノールである、上記1又は２に記載の芳香族ポリカーボネート樹脂組成物。
４．前記炭素数１〜７のアルキル基がｐ−ｔｅｒｔ−ブチル基である、上記３に記載の芳香族ポリカーボネート樹脂組成物。
５．前記（Ｂ）成分の２価フェノール（Ｂ−２）が、下記一般式（Ｉａ）で表される、
上記１〜４のいずれかに記載の芳香族ポリカーボネート樹脂組成物。

〔Ｒ¹およびＲ²は、炭素数1〜６のアルキル基、Ｘは単結合、炭素数１〜８のアルキレン基、炭素数２〜８のアルキリデン基、炭素数５〜１５のシクロアルキレン基、炭素数５〜１５のシクロアルキリデン基、−Ｓ−、−ＳＯ−、−ＳＯ₂−、−Ｏ−、−ＣＯ−を示す。ａ及びｂは、それぞれ独立に０〜４の整数である。〕
６．前記２価フェノール（Ｂ−２）が、２，２-ビス（４−ヒドロキシフェニル）プロパンである、上記５に記載の芳香族ポリカーボネート樹脂組成物。
７．前記（Ｂ）成分が、前記１価フェノール（Ｂ−１）と前記２価フェノール（Ｂ−２）との混合物である、上記1〜６のいずれかに記載の芳香族ポリカーボネート樹脂組成物。
８．前記１価フェノール（Ｂ−１）がｐ−ｔｅｒｔ−ブチルフェノールであり、前記２価フェノール（Ｂ−２）が２，２-ビス（４−ヒドロキシフェニル）プロパンである、上記７に記載の芳香族ポリカーボネート樹脂組成物。
９．前記（Ｂ）成分が、少なくとも、ｐ−ｔｅｒｔ−ブチルフェノール、２，２-ビス（４−ヒドロキシフェニル）プロパン、及びｐ−ｔｅｒｔ−ブチルフェノールと２，２-ビス（４−ヒドロキシフェニル）プロパンとの混合物から選ばれ、樹脂組成物中に残留する未反応のｐ−ｔｅｒｔ−ブチルフェノールと２，２-ビス（４−ヒドロキシフェニル)プロパンとの合計量が５００ｐｐｍ未満である、上記1〜８のいずれかに記載の芳香族ポリカーボネート樹脂組成物。
１０．前記（Ｃ）成分のホスファイト系酸化防止剤が、ビス（２，４−ジクミルフェニル）ペンタエリスリトールジホスファイトである、上記１〜９のいずれかに記載の芳香族ポリカーボネート樹脂組成物。
１１．さらに、前記（Ａ）成分１００質量部に対して、（Ｄ）脂肪族環状エポキシ化合物０．００１〜０．５質量部を配合してなる、上記1〜１０のいずれかに記載の芳香族ポリカーボネート樹脂組成物。
１２．（Ｄ）成分の脂肪族環状エポキシ化合物が、３，４−エポキシシクロヘキセニルメチル−３’、４’−エポキシシクロヘキセンカルボキシレート、２，２−ビス（ヒドロキシメチル）−１−ブタノールの１，２−エポキシ−４−（２−オキシラニル）シクロヘキサン付加物及び、これらの混合物である、上記１１に記載の芳香族ポリカーボネート樹脂組成物。
１３．上記１〜１２のいずれかに記載の芳香族ポリカーボネート樹脂組成物を成形してなる成形品。 That is, this invention provides the following 1-12.
1. (A) For 100 parts by mass of aromatic polycarbonate resin, (B) monovalent phenol (B-1) having an alkyl group with a molecular weight of 200 or less per gram equivalent and / or a molecular weight per gram equivalent An aromatic polycarbonate resin obtained by blending 0.001 to 0.05 parts by mass of dihydric phenol (B-2) that is 200 or less and (C) 0.005 to 0.5 parts by mass of a phosphite antioxidant. Composition.
2. Aromatic polycarbonate resin in which the aromatic polycarbonate resin (A) has an aromatic homopolycarbonate resin (A-1) 40 to 100% by mass and a repeating unit represented by the following general formulas (I) and (II) 2. The aromatic polycarbonate resin composition according to 1 above, comprising 0 to 60% by mass of combined (A-2 ′).

[R ¹ and R ² are alkyl groups having 1 to 6 carbon atoms, X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, A cycloalkylidene group having 5 to 15 carbon atoms, —S—, —SO—, —SO ₂ —, —O—, and —CO— are shown. R ³ and R ^{4 each} represent an alkyl group having 1 to 3 carbon atoms, and Y represents a linear or branched alkylene group having 2 to 15 carbon atoms. a to d are each independently an integer of 0 to 4, and n is an integer of 2 to 200. ]
3. 3. The aromatic polycarbonate resin composition according to 1 or 2 above, wherein the monohydric phenol (B-1) is a monohydric phenol having an alkyl group having 1 to 7 carbon atoms.
4). 4. The aromatic polycarbonate resin composition according to 3 above, wherein the alkyl group having 1 to 7 carbon atoms is a p-tert-butyl group.
5. The dihydric phenol (B-2) as the component (B) is represented by the following general formula (Ia).
The aromatic polycarbonate resin composition according to any one of 1 to 4 above.

[R ¹ and R ² are alkyl groups having 1 to 6 carbon atoms, X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, A cycloalkylidene group having 5 to 15 carbon atoms, —S—, —SO—, —SO ₂ —, —O—, and —CO— are shown. a and b are each independently an integer of 0 to 4; ]
6). 6. The aromatic polycarbonate resin composition according to 5 above, wherein the dihydric phenol (B-2) is 2,2-bis (4-hydroxyphenyl) propane.
7). The aromatic polycarbonate resin composition according to any one of 1 to 6 above, wherein the component (B) is a mixture of the monohydric phenol (B-1) and the dihydric phenol (B-2).
8). The aromatic according to 7 above, wherein the monohydric phenol (B-1) is p-tert-butylphenol and the dihydric phenol (B-2) is 2,2-bis (4-hydroxyphenyl) propane. Polycarbonate resin composition.
9. The component (B) is at least p-tert-butylphenol, 2,2-bis (4-hydroxyphenyl) propane, and a mixture of p-tert-butylphenol and 2,2-bis (4-hydroxyphenyl) propane Any one of 1 to 8 above, wherein the total amount of unreacted p-tert-butylphenol and 2,2-bis (4-hydroxyphenyl) propane remaining in the resin composition is less than 500 ppm The aromatic polycarbonate resin composition described.
10. The aromatic polycarbonate resin composition according to any one of 1 to 9 above, wherein the phosphite antioxidant of the component (C) is bis (2,4-dicumylphenyl) pentaerythritol diphosphite.
11. Furthermore, the aromatic polycarbonate in any one of said 1-10 formed by mix | blending 0.001-0.5 mass part of (D) aliphatic cyclic epoxy compounds with respect to 100 mass parts of said (A) component. Resin composition.
12 The aliphatic cyclic epoxy compound of component (D) is 1,2-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, 1,2-bis (hydroxymethyl) -1-butanol 12. The aromatic polycarbonate resin composition according to 11 above, which is an epoxy-4- (2-oxiranyl) cyclohexane adduct and a mixture thereof.
13. A molded product formed by molding the aromatic polycarbonate resin composition according to any one of 1 to 12 above.

  According to the present invention, the monovalent phenol (B-1) and / or divalent phenol (B-2) and (C) having a specific alkyl group as the component (B) in the aromatic polycarbonate resin of the component (A). ) By adding a specific amount of the component phosphite-based antioxidant, an aromatic polycarbonate resin composition in which yellowing that occurs during molding at high temperature is reduced is obtained, and a molded article using the resin composition In particular, a molded product suitable as an optical molded product such as a light guide plate used in a liquid crystal display device or the like can be obtained.

  The aromatic polycarbonate resin composition of the present invention has (B) a monohydric phenol (B-1) having an alkyl group with a molecular weight of 200 or less per gram equivalent based on 100 parts by mass of (A) aromatic polycarbonate resin. ) And / or 0.001 to 0.05 parts by weight of dihydric phenol (B-2) having a molecular weight per gram equivalent of 200 or less, and (C) 0.005 to 0.5 phosphite antioxidant. It is formed by blending parts by mass. Hereinafter, each component used in the aromatic polycarbonate resin composition of the present invention and other components will be described.

[(A) aromatic polycarbonate resin]
The (A) aromatic polycarbonate resin used in the aromatic polycarbonate resin composition of the present invention is produced by a reaction between a diol component containing at least a dihydric phenol and a carbonate precursor. Specifically, Aromatic homopolycarbonate resin (A-1) produced using one kind of dihydric phenol, two or more kinds of dihydric phenols, or one or two or more kinds of dihydric phenols and other diols And an aromatic polycarbonate copolymer (A-2) produced by a reaction with a carbonate precursor. Accordingly, the (A) aromatic polycarbonate resin in the present invention is not particularly limited and includes various polycarbonate resins. Here, the divalent phenol is a compound having two phenolic hydroxyl groups in one molecule.
As a manufacturing method of these (A) aromatic polycarbonate resins, for example,
A diol component containing at least a dihydric phenol and a carbonate precursor are subjected to a solution method or a melting method. Specifically, an alkaline aqueous solution of a diol component containing at least a dihydric phenol is reacted with phosgene in the presence of an organic solvent such as methylene chloride. It is possible to use those produced by an interfacial polymerization reaction or a transesterification reaction between a diol component containing at least a dihydric phenol and diphenyl carbonate.

  Although various things are mentioned as a bivalent phenol, Preferably, the compound represented by the following general formula (Ia) is mentioned.

R ¹ and R ² in formula (Ia) are alkyl groups having 1 to 6 carbon atoms, X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, and 5 to 15 carbon atoms. cycloalkylene group, a cycloalkylidene group having 5 to 15 carbon atoms, -S -, - SO -, - SO 2 -, - O -, - shows a CO-. a and b are each independently an integer of 0 to 4; X is preferably a branched alkylene group having 2 to 8 carbon atoms, more preferably a branched alkylene group having 2 to 6 carbon atoms, and a and b are each independently preferably an integer of 0 to 2, More preferably 0. Specific examples of the compound represented by the general formula (Ia) include 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, 1,1- Bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) cycloalkane, bis (4- Hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone and the like.
Moreover, hydroquinone, resorcin, catechol, etc. are mentioned as dihydric phenols other than the compound represented by the said general formula (Ia).
Furthermore, as a dihydric phenol that can be used in the present invention, a phenol-modified diol derived from hydroxybenzoic acid or an alkyl ester thereof, an acid chloride and a polyether diol disclosed in JP-A-2009-40843, Polyorganosiloxanes having phenolic hydroxyl groups at both ends can also be preferably used. When the above-mentioned phenol-modified diol or polyorganosiloxane having a phenolic hydroxyl group is used as a divalent phenol, the above-mentioned (A-2) obtained by using in combination with the divalent phenol represented by the general formula (Ia) Or an aromatic homopolycarbonate resin (A-1) obtained by using the aromatic polycarbonate copolymer and a dihydric phenol represented by the general formula (Ia) It is preferable to mix and use.

  (A) Aliphatic diol and alicyclic diol can be mentioned as diol components other than dihydric phenol used when manufacturing aromatic polycarbonate resin. Aliphatic diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-decanediol 1,10-decanediol, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polyalkylene glycol such as polytetramethylene glycol, and the like. Examples of the alicyclic diol include 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol and the like. When the diol component other than the dihydric phenol is included, it is desirable to improve the mechanical properties such as impact resistance so that the dihydric phenol is 50 mol% or more, preferably 60 mol% or more. .

The (A) aromatic polycarbonate resin in the present invention is particularly preferably a bis (hydroxyphenyl) alkane-based, particularly bisphenol A as a main raw material, as a divalent phenol.
A suitable branching agent may be used together with the dihydric phenol. As this branching agent, a trihydric or higher polyhydric phenol, specifically 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′ , Α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene, phloroglucin, isatin bis (o-cresol) and the like.
Examples of the carbonate precursor include carbonyl halide, carbonyl ester, and haloformate. Specific examples include phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, and diethyl carbonate.

(A) As a molecular weight regulator used as a molecular terminal group of aromatic polycarbonate resin, what is necessary is just what is normally used for superposition | polymerization of a polycarbonate, and various monohydric phenols can be used.
Specific examples include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, bromophenol, tribromophenol, and nonylphenol.

  (A) As an aromatic polycarbonate resin particularly preferable in the present invention, (A) an aromatic homopolycarbonate resin (A-1) using a divalent phenol, particularly preferably bisphenol A is used as the aromatic polycarbonate resin in the present invention. The resulting bisphenol A aromatic homopolycarbonate resin (A-1 ′), or (ii) derived from the aromatic homopolycarbonate resin (A-1) and the hydroxybenzoic acid or its alkyl ester, acid chloride and polyether diol A mixed resin of the aromatic polycarbonate copolymer (A-2 ′) contained in the above (A-2) obtained by using the phenol-modified diol and the dihydric phenol of the general formula (Ia) Particularly preferred.

Next, an aromatic polycarbonate copolymer (A) obtained by using the above-mentioned hydroxybenzoic acid or an alkyl ester thereof, an acid chloride and a phenol-modified diol derived from a polyether diol and a dihydric phenol of the general formula (Ia) -2 ') will be described.
The aromatic polycarbonate copolymer (A-2 ′) obtained by using the phenol-modified diol and the divalent phenol of the general formula (Ia) is a repeating unit represented by the following general formulas (I) and (II). Have The aromatic polycarbonate copolymer (A-2 ′) is an aromatic polycarbonate copolymer obtained by copolymerizing a phenol-modified diol, and can be produced by a conventional production method called an interfacial polymerization method. . That is, it can be produced by a method in which a carbonate precursor such as a dihydric phenol of the general formula (Ia), a phenol-modified diol and phosgene is reacted.
Specifically, for example, in an inert solvent such as methylene chloride, in the presence of a known acid acceptor or molecular weight regulator, a catalyst or a branching agent is added as necessary, and dihydric phenol, phenol-modified diol. And a carbonate precursor such as phosgene.

[R ¹ and R ² are alkyl groups having 1 to 6 carbon atoms, X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, A cycloalkylidene group having 5 to 15 carbon atoms, —S—, —SO—, —SO ₂ —, —O—, and —CO— are shown. R ³ and R ^{4 each} represent an alkyl group having 1 to 3 carbon atoms, and Y represents a linear or branched alkylene group having 2 to 15 carbon atoms. a to d are each independently an integer of 0 to 4, and n is an integer of 2 to 200. ]

The alkyl group of R ^{1 to} R ⁴ may be linear or branched. Specific examples of the alkyl group for R ¹ and R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, n -A hexyl group, an isohexyl group, etc. can be mentioned.
Specific examples of the alkyl group for R ³ and R ⁴ include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
Further, R ¹ and R ² may each independently be a cyclic hydrocarbon group such as a cyclopentyl group or a cyclohexyl group.
Examples of the alkylene group having 1 to 8 carbon atoms of X include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylylene group, and a hexylene group.
Examples of the alkylidene group having 2 to 8 carbon atoms of X include an ethylidene group and an isopropylidene group.
Examples of the cycloalkylene group having 5 to 15 carbon atoms of X include a cyclopentylene group and a cyclohexylene group. Examples of the cycloalkylidene group having 5 to 15 carbon atoms of X include a cyclopentylidene group and a cyclohexylidene group.

  Examples of the dihydric phenol include compounds represented by the following general formula (Ia).

R ¹ and R ² , a and b, and X in the general formula (Ia) are as described above.
There are various dihydric phenols represented by the general formula (Ia), and 2,2-bis (4-hydroxyphenyl) propane [common name: bisphenol A] is particularly preferable. Examples of bisphenols other than bisphenol A include bis (hydroxyaryl) alkanes, bis (hydroxyaryl) cycloalkanes, dihydroxyaryl ethers, dihydroxydiaryl sulfides, dihydroxydiaryl sulfoxides, dihydroxydiaryl sulfones, and dihydroxydiphenyls. , Dihydroxydiarylfluorenes, dihydroxydiaryladamantanes, and others, bis (4-hydroxyphenyl) diphenylmethane, 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisphenol, 10,10-bis (4 -Hydroxyphenyl) -9-anthrone, 1,5-bis (4-hydroxyphenylthio) -2,3-dioxapentaene and α, ω-bishydroxyphene Such as Le polydimethylsiloxane compounds. These dihydric phenols may be used alone or in combination of two or more.

  As the molecular weight regulator, various types can be used as long as they are usually used for polymerization of polycarbonate resin. Specifically, as monohydric phenol, for example, phenol, on-butylphenol, mn-butylphenol, pn-butylphenol, o-isobutylphenol, m-isobutylphenol, p-isobutylphenol, ot -Butylphenol, mt-butylphenol, pt-butylphenol, on-pentylphenol, mn-pentylphenol, pn-pentylphenol, on-hexylphenol, mn-hexylphenol, pn-hexylphenol, pt-octylphenol, o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, on-nonylphenol M-nonylphenol, pn-nonylphenol, o-cumylphenol, m-cumylphenol, p-cumylphenol, o-naphthylphenol, m-naphthylphenol, p-naphthylphenol; 2,5-di 2,4-di-t-butylphenol; 3,5-di-t-butylphenol; 2,5-dicumylphenol; 3,5-dicumylphenol; p-cresol, bromophenol, tribromo Phenol, monoalkylphenol having a linear or branched alkyl group having an average carbon number of 12 to 35 in the ortho position, meta position or para position; 9- (4-hydroxyphenyl) -9- (4-methoxyphenyl) fluorene 9- (4-hydroxy-3-methylphenyl) -9- (4-methoxy-3-methylphenyl); Le) fluorene; 4- (1-adamantyl) phenol and the like. Among these monohydric phenols, pt-butylphenol, p-cumylphenol, p-phenylphenol and the like are preferably used.

  As the catalyst in the interfacial polymerization method, a phase transfer catalyst such as a tertiary amine or a salt thereof, a quaternary ammonium salt, a quaternary phosphonium salt, or the like can be preferably used. Examples of the tertiary amine include triethylamine, tributylamine, N, N-dimethylcyclohexylamine, pyridine, dimethylaniline and the like, and examples of the tertiary amine salt include hydrochlorides and bromates of these tertiary amines. Etc. Examples of the quaternary ammonium salt include trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributylbenzylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium chloride, and tetrabutylammonium bromide. Examples thereof include butylphosphonium chloride and tetrabutylphosphonium bromide. These catalysts may be used alone or in combination of two or more. Among the above catalysts, tertiary amines are preferable, and triethylamine is particularly preferable.

  There are various kinds of inert organic solvents. For example, dichloromethane (methylene chloride); trichloromethane; carbon tetrachloride; 1,1-dichloroethane; 1,2-dichloroethane; 1,1,1-trichloroethane; 1,1,2-trichloroethane; -Tetrachloroethane; 1,1,2,2-tetrachloroethane; pentachloroethane; chlorinated hydrocarbons such as chlorobenzene, toluene, acetophenone, and the like. These organic solvents may be used alone or in combination of two or more. Of these, methylene chloride is particularly preferred.

Further, as a branching agent in the polymerization reaction, for example, 1,1,1-tris (4-hydroxyphenyl) ethane; 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methyl Ethyl] phenyl] ethylidene] bisphenol; α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene; 1- [α-methyl-α- (4′-hydroxyphenyl) Ethyl] -4- [α ', α'-bis (4 "-hydroxyphenyl) ethyl] benzene; a compound having three or more functional groups such as phloroglysin, trimellitic acid, and isatin bis (o-cresol) may be used. it can.
The phenol-modified diol used in the present invention is represented by the following general formula (IIa).

In general formula (IIa), in the formula, R ³ and R ⁴ each independently represent an alkyl group having 1 to 3 carbon atoms, and Y represents a linear or branched alkylene group having 2 to 15 carbon atoms. c and d are each independently an integer of 0 to 4, and n is an integer of 2 to 200.
Examples of the alkyl group represented by R ³ and R ⁴ include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. If there are a plurality of R ^3, a plurality of R ³ may be the same or different from each other, if R ⁴ is plural, R ⁴ may be the same or different from each other. Examples of the linear or branched alkylene group having 2 to 15 carbon atoms represented by Y include alkylene groups such as ethylene group, propylene group, butylene group, isobutylene group, pentylene group and isopentylene group, ethylidene group, propylidene group, isopropylene group. Examples include alkylidene residues such as a lidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group. n is preferably 2 to 200, more preferably 6 to 70.
The phenol-modified diol represented by the general formula (IIa) is represented by the following general formula (IV) or general formula (V):

The compound derived | led-out by the esterification reaction or transesterification from the hydroxy benzoic acid represented by these, or its alkylester, and the polyether diol mentioned later.
In the general formula (V) and the general formula (IV), R ³ represents an alkyl group having 1 to ³ carbon atoms. c is an integer of 0-4. The alkyl group having 1 to 3 carbon atoms is as described above.
In general formula (V), R ⁴ represents an alkyl group having 1 to 3 carbon atoms, and R ⁵ represents an alkyl group having 1 to 10 carbon atoms. d is an integer of 0-4. Examples of the alkyl group having 1 to 10 carbon atoms include n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group and octyl in addition to the above-described alkyl group having 1 to 3 carbon atoms. Group, 2-ethylhexyl group, decyl group and the like.
Examples of the hydroxybenzoic acid represented by the general formula (IV) include p-hydroxybenzoic acid, m-hydroxybenzoic acid, o-hydroxybenzoic acid (salicylic acid), and alkyl having 1 to 3 carbon atoms on the benzene ring. Examples thereof include those substituted with a group.
Typical examples of the alkyl ester of hydroxybenzoic acid represented by the general formula (V) include p-hydroxybenzoic acid methyl ester, p-hydroxybenzoic acid ethyl ester, and p-hydroxybenzoic acid n-propyl ester. .

The polyether diol is represented by HO— (Y—O) _n —H [Y is the same as described in the general formula (II)], and is a linear or branched alkyl having 2 to 15 carbon atoms. It consists of repeating ethers. Specific examples include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Polytetramethylene glycol is particularly preferable from the viewpoint of availability and hydrophobicity.
The repeating number n of the ether part of the polyether diol is 2 to 200, preferably 6 to 70. When n is 2 or more, the efficiency at the time of copolymerizing the phenol-modified diol is good, and when n is 70 or less, there is an advantage that the decrease in heat resistance of the PC copolymer is small.

The esterification reaction or transesterification reaction of hydroxybenzoic acid or its alkyl ester and polyether diol is carried out in the presence of a tin-based catalyst.
The amount of the tin-based catalyst used is usually about 0.01 to 10% by mass, preferably about 0.05 to 5% by mass, and more preferably 0, based on hydroxybenzoic acid or hydroxybenzoic acid alkyl ester. About 1 to 3% by mass. Sufficient reaction activity is obtained when the content is 0.01% by mass or more, and side reactions are suppressed by being 10% by mass or less, and the amount of phosphoric acid aqueous solution or solid adsorbent described later is reduced. Using the aromatic polycarbonate copolymer (A-2 ′) obtained by copolymerizing the phenol-modified diol, the tin content in the resulting phenol-modified diol can be reduced. This is preferable because yellowing of the molded product during molding can be further prevented.
Therefore, it is desirable to purify the phenol-modified diol obtained by these methods to reduce the tin content to 0.5 ppm or less. Specifically, the reaction crude liquid containing the phenol-modified diol is dissolved in a phosphoric acid aqueous solution or solid adsorption. The tin content in the phenol-modified diol can be reduced by the purification method of washing with an agent. An aromatic polycarbonate copolymer (A-2 ′) having repeating units represented by the general formulas (I) and (II) can be obtained by interfacial polymerization using this phenol-modified diol.

  The above aromatic polycarbonate copolymer (A-2 ′) has better molding fluidity than ordinary aromatic homopolycarbonate resins, and has a small thickness and is especially used for optical molded products such as liquid crystal display devices. When molding an optical molded product such as an optical plate, it is possible to prevent the occurrence of defective filling of the molding resin into the injection mold and molding distortion of the molded product after molding. Therefore, the aromatic polycarbonate of the present invention It is preferable to use it as the component (A) of the resin composition. When the aromatic polycarbonate copolymer (A-2 ′) is used as the component (A) of the aromatic polycarbonate resin composition of the present invention, it is used by mixing with the aromatic homopolycarbonate resin (A-1) described above. The blending ratio of the aromatic homopolycarbonate resin (A-1) 40 to 100% by mass and the aromatic polycarbonate copolymer (A-2 ′) 0 to 60% by mass, preferably (A-1) 60 It is preferable to maintain a blending ratio of ˜95 mass% and (A-2 ′) 5 to 40 mass% in order to maintain a balance between mechanical properties such as impact resistance and molding fluidity.

  As described above, when the aromatic homopolycarbonate resin (A-1) is used alone as the aromatic polycarbonate resin of the component (A) used in the present invention, different types of aromatic homopolycarbonate resins (A-1) are used. When the aromatic polycarbonate copolymer (A-2) is used alone, when different types of aromatic polycarbonate copolymers (A-2) are used in combination, The homopolycarbonate resin (A-1) and the aromatic polycarbonate copolymer (A-2) may be used in combination, but the molecular weight is 10000-25000, preferably 11000-20000, in terms of viscosity average molecular weight. It is preferable to adjust and use. For example, when a high molecular weight aromatic homopolycarbonate resin is used, the viscosity average molecular weight can be adjusted within the above range by mixing with a low molecular weight aromatic homopolycarbonate resin.

[(B) monohydric phenol having an alkyl group, dihydric phenol]
In the aromatic polycarbonate resin composition of the present invention, as the component (B), a monovalent phenol (B-1) having an alkyl group having a molecular weight per gram equivalent of 200 or less and / or a molecular weight per gram equivalent Is a dihydric phenol (B-2) having a molecular weight of 200 or less. Here, “monohydric phenol (B-1) having an alkyl group having a molecular weight of 200 or less per gram equivalent” is a monohydric phenol having a molecular weight of 200 or less per gram equivalent, Has a group. “Divalent phenol (B-2) having a molecular weight per gram equivalent of 200 or less” is a dihydric phenol, has a molecular weight of 200 or less per gram equivalent, and has an alkyl group.
Here, in the case of monohydric phenol, the molecular weight per gram equivalent indicates the molecular weight of itself and indicates that the molecular weight is 200 or less. In the case of a dihydric phenol, the molecular weight per gram equivalent indicates a value obtained by dividing the molecular weight of the dihydric phenol by 2 and indicates that the value is 200 or less.

  The component (B) used in the present invention is added for the purpose of capturing radicals generated when the (A) aromatic polycarbonate resin is heated and melted in a molding machine and stabilizing it as hydroperoxide. Component (B) requires a molecular weight per gram equivalent of 200 or less. When the molecular weight per gram equivalent is higher than 200, the radical scavenging function is lowered, and the component (B) itself causes coloring such as yellowing due to thermal deterioration or the like, which is not preferable.

<Monohydric phenol (B-1) having an alkyl group with a molecular weight per gram equivalent of 200 or less>
Among the components (B), examples of the monovalent phenol (B-1) having an alkyl group having a molecular weight per gram equivalent of 200 or less include compounds represented by the following general formula (VI).

In the general formula (VI), R ⁵ represents an alkyl group, and d represents an integer of 1 to 5. d is preferably an integer of 1 to 3, more preferably d is 1 or 2, and most preferably d is 1. The alkyl group R ^5, preferably an alkyl group having a carbon number of 1-7. The alkyl group is preferably branched, and particularly preferably a tetrabutyl group. Specific examples of the compound represented by (VI) include 2-methylphenol, 3-methylphenol, 4-methylphenol, 2-4-dimethylphenol, 3-4-dimethylphenol, 2-ethylphenol, 3- Ethylphenol, 4-ethylphenol, 2-4-diethylphenol, 3-4-diethylphenol, 2-n-butylphenol, 3-n-butylphenol, 4-n-butylphenol, 2-tert-butylphenol, 3-tert- Butylphenol, 4-tert-butylphenol (p-tert-butylphenol), 2-n-pentylphenol, 3-n-pentylphenol, 4-n-pentylphenol, 2-n-hexylphenol, 3-n-hexylphenol, 4-n-hexylphenol, etc. Things and may be the molecular weight per gram equivalent is exemplified as the monovalent phenol component (B-1) having a 200 or less is an alkyl group. These monohydric phenol (B-1) components having an alkyl group may be used alone or in combination of two or more. These monovalent phenol (B-1) components having an alkyl group are included in a compound used as a terminal terminator when producing an aromatic polycarbonate resin. The monohydric phenol having an alkyl group preferably has a molecular weight per gram equivalent of 109 to 180, and the monohydric phenol (B-1) component having an alkyl group described above is preferably used. Among these, 4-tert-butylphenol (p-tert-butylphenol) is particularly preferably used.

<Dihydric phenol (B-2) having a molecular weight per gram equivalent of 200 or less>
Among the components (B), examples of the divalent phenol (B-2) having a molecular weight per gram equivalent of 200 or less include the compounds represented by the following general formula (Ia).

R ¹ and R ² , a and b, and X in the general formula (Ia) are as described above. As the dihydric phenol (B-2) component having a molecular weight per gram equivalent of 200 or less, various compounds can be used as described above, and examples of preferred compounds include 2,2-bis. (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) ) Propane, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis ( 4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone, etc. Is mentioned. The divalent phenol (B-2) component preferably has a molecular weight per gram equivalent of 74 to 160, and among these compounds, it is used as a main raw material for aromatic polycarbonate resin. It is preferable to use 2,2-bis (4-hydroxyphenyl) propane [bisphenol A].

  The monovalent phenol (B-1) component having an alkyl group with a molecular weight of 200 or less per gram equivalent as the component (B) in the present invention and a divalent phenol with a molecular weight of 200 or less per gram equivalent ( In (B-2), the component (B-1) or the component (B-2) may be used alone, or the component (B-1) and the component (B-2) are used in combination. You can also.

[(C) Phosphite antioxidant]
In the aromatic polycarbonate resin composition of the present invention, a phosphite antioxidant is used as the component (C). The phosphite antioxidant used as the component (C) captures radicals generated when the (A) aromatic polycarbonate resin is heated and melted in the molding machine with the component (B), and as a result Used to reduce peroxides to more stable alcohols. Alcohol generated by modifying hydroperoxide generated when the aromatic polycarbonate resin is heated and melted in a molding machine is stable without causing a coloring such as yellowing. Therefore, by using the component (B) and the component (C) in combination with the aromatic polycarbonate resin (A), an aromatic polycarbonate resin composition with reduced coloring such as yellowing can be obtained.

  (C) The phosphite antioxidant is not particularly limited, and those conventionally used for aromatic polycarbonate resins can be used. Specifically, triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, trinonyl phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite Phyto, distearyl pentaerythritol diphosphite, tricyclohexyl phosphite, monobutyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis ( 2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol Such as diphosphite and dicyclohexyl pentaerythritol diphosphite, and the like. Among these, it is preferable to use a pentaerythritol diphosphite-based compound, and bis (2,4-dicumylphenyl) pentaerythritol diphosphite represented by the following formula is a trade name: Doverphos S-9229PC (manufactured by Dober Chemical) ) And is particularly preferable because it is particularly excellent in hydrolysis resistance.

[Blend ratio of component (B) and component (C) to component (A)]
The aromatic polycarbonate resin composition of the present invention is a monohydric phenol having an alkyl group having a molecular weight of 200 or less per gram equivalent as the component (B) with respect to 100 parts by mass of the (A) aromatic polycarbonate resin. B-1) and / or divalent phenol (B-2) having a molecular weight per gram equivalent of 200 or less is required to be blended in an amount of 0.001 to 0.05 parts by mass. When the blending amount of the component (B) is less than 0.001 part by mass, the effect of preventing coloring such as yellowing is lowered, which is not preferable. Moreover, when the compounding quantity of (B) component exceeds 0.05 mass part, (B) component will remain unreacted and may cause mold contamination, or the obtained aromatic polycarbonate resin composition In the case of a molded product, the transparency may decrease or the cloudiness may occur. (B) The preferable compounding quantity of a component is 0.003-0.02 mass part, More preferably, it is 0.005-0.01 mass part.
Moreover, the aromatic polycarbonate resin composition of this invention mix | blends 0.005-0.5 mass part of (C) phosphite type antioxidant with respect to 100 mass parts of (A) aromatic polycarbonate resin. I need it. When the amount of component (C) is less than 0.005 parts by mass, the effect of preventing coloration such as yellowing is lowered, which is not preferable. Moreover, when the compounding quantity of (C) component exceeds 0.5 mass part, since heat-and-moisture resistance falls, it is unpreferable. (C) The preferable compounding quantity of a component is 0.01-0.2 mass part, More preferably, it is 0.02-0.1 mass part.

[(D) Aliphatic cyclic epoxy compound]
The aromatic polycarbonate resin composition of the present invention preferably contains an aliphatic cyclic epoxy compound as the component (D) in order to further improve the hydrolysis resistance. The (D) component alicyclic epoxy compound refers to an alicyclic epoxy group, that is, a cycloaliphatic compound having an epoxy group in which one oxygen atom is added to an ethylene bond in the aliphatic ring. What is represented by the following formulas (1) to (10) shown in Kaihei 11-158364 is suitably used.

（Ｒ：Ｈ又はＣＨ₃）

(R: H or CH ₃ )

（Ｒ：Ｈ又はＣＨ₃）

(R: H or CH ₃ )

（ａ＋ｂ＝１又は２）

(A + b = 1 or 2)

（ａ＋ｂ＋ｃ＋ｄ＝１〜３）

(A + b + c + d = 1-3)

（ａ＋ｂ＋ｃ＝ｎ（整数），Ｒ：炭化水素基）

(A + b + c = n (integer), R: hydrocarbon group)

（ｎ：整数）

(N: integer)

（Ｒ：炭化水素基）

(R: hydrocarbon group)

（ｎ：整数，Ｒ：炭化水素基）

(N: integer, R: hydrocarbon group)

  Among the alicyclic epoxy compounds, the compound represented by the formula (1), the formula (7) or the formula (10) is excellent in compatibility with the aromatic polycarbonate resin and does not impair the transparency. More preferably used. For example, the compound represented by the formula (1) is obtained as 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (registered trademark: Celoxide 2021P, manufactured by Daicel Chemical Industries, Ltd.). be able to. In addition, as a compound represented by the formula (10), 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (registered trademark: EHPE3150, Daicel) Available from Chemical Industry Co., Ltd. Further, as a mixture of Celoxide 2021P and EHPE3150, EHPE3150CE (registered trademark) commercially available from Daicel Chemical Industries, Ltd. can also be preferably used.

  By blending the alicyclic epoxy compound of component (D) with the aromatic polycarbonate resin composition of the present invention, the hydrolysis resistance is further improved and the transparency can be further improved. (D) The compounding quantity of an alicyclic epoxy compound is about 0.001-0.5 mass part normally with respect to 100 mass parts of (A) aromatic polycarbonate resin, Preferably it is 0.005-0.1 mass. Parts, more preferably 0.01 to 0.05 parts by weight.

  When the aromatic polycarbonate resin composition of the present invention is obtained by melting using an extruder or the like to obtain a composition such as pellets, the amount of the component (B) remaining in the aromatic polycarbonate resin composition is less than 500 ppm. It is preferable that By setting the amount of the remaining component (B) to be less than 500 ppm, the optical characteristics can be improved. The amount of the remaining component (B) is preferably less than 200 ppm.

In the aromatic polycarbonate resin composition of the present invention, various additives may be blended as necessary in addition to the above-described components as long as the effects of the present invention are not impaired. Various additives include, for example, UV absorbers such as benzotriazole and benzophenone, light stabilizers such as hindered amines, aliphatic carboxylic acid ester compounds, paraffinic compounds, silicone oil, polyethylene wax, and other internal lubricants. And conventional flame retardants, flame retardant aids, mold release agents, antistatic agents, colorants and the like.
The present invention also provides a molded article comprising the above aromatic polycarbonate resin composition. There are no particular limitations on the method for producing the molded article of the present invention, and various conventionally known molding methods such as injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, and foam molding. Etc. can be used. The molded product can be suitably used as an optical molded product such as a light guide plate for LCD, a lens, and a light guide ring of an automobile headlamp.

  Examples The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

[Production Example of Aromatic Polycarbonate Copolymer (A-2 ′)]
(Production Example 1 of a phenol-modified diol copolymerization comonomer)
[Synthesis of polytetramethylene glycol-bis (4-hydroxybenzoate): average molecular weight of PTMG chain = 2000]
Under nitrogen, 100% by mass of polytetramethylene glycol (PTMG, Mn = 2000) and 16.7% by mass of methyl p-hydroxybenzoate were heated at 210 ° C. in the presence of 0.05% by mass of dibutyltin oxide, and methanol was added. Distilled off.
The reaction system was depressurized, and excess methyl p-hydroxybenzoate was distilled off.
After the reaction product was dissolved in methylene chloride, 8% by mass aqueous sodium hydrogen carbonate solution was added to the methylene chloride solution, vigorously mixed for 20 minutes, and the methylene chloride phase was collected by centrifugation.
The methylene chloride phase was concentrated under reduced pressure to obtain polytetramethylene glycol-bis (4-hydroxybenzoate) as a copolymerized comonomer of phenol-modified diol.
As a result of quantifying p-hydroxybenzoic acid and methyl p-hydroxybenzoate by high performance liquid chromatography (HPLC), p-hydroxybenzoic acid was less than 10 ppm by mass, and methyl p-hydroxybenzoate was 0.2% by mass. there were.
The HPLC measurement method uses an ODS-3 column manufactured by GL Sciences Inc., a column temperature of 40 ° C., a 1: 2 mixed solvent of 0.5 mass% phosphoric acid aqueous solution and acetonitrile, and a flow rate of 1.0 mL / min. Measured with
The quantification was calculated based on a calibration curve with a standard.

[Production of aromatic polycarbonate oligomer solution]
Add 2,000 ppm sodium dithionite to 5.6 mass% sodium hydroxide aqueous solution to bisphenol A (BPA) that is dissolved later, and dissolve BPA to a BPA concentration of 13.5 mass%. Then, an aqueous sodium hydroxide solution of BPA was prepared.
Phosgene was continuously passed through a tubular reactor having an inner diameter of 6 mm and a tube length of 30 m at a flow rate of 4.0 kg / hr at a flow rate of 40 L / hr of sodium hydroxide aqueous solution of BPA and 15 L / hr of methylene chloride.
The tubular reactor had a jacket percentage, and the temperature of the reaction solution was kept at 40 ° C. or less by passing cooling water through the jacket.
The reaction solution exiting the tubular reactor was continuously introduced into a 40-liter baffled tank reactor equipped with a receding blade, and further BPA aqueous sodium hydroxide solution 2.8 L / hr, 25 mass%. Sodium hydroxide aqueous solution 0.07L / hr, water 17L / hr, 1 mass% triethylamine aqueous solution was added at 0.64L / hr, and reaction was performed.
The reaction liquid overflowing from the tank reactor was continuously extracted and allowed to stand to separate and remove the aqueous phase, and the methylene chloride phase was collected.
The aromatic polycarbonate oligomer thus obtained had a concentration of 329 g / L and a chloroformate group concentration of 0.74 mol / L.

[Production of Aromatic Polycarbonate Copolymer (A-2 ′)]
In a 50 L tank reactor equipped with a baffle plate, a paddle type stirring blade and a cooling jacket, 15 L of the aromatic polycarbonate oligomer solution prepared above, 8.9 L of methylene chloride, polytetramethylene glycol-bis (4- Hydroxybenzoate) 325 g (average molecular weight of PTMG chain = 2000) and 8.7 mL of triethylamine were added, and 1710 g of a 6.4 mass% aqueous sodium hydroxide solution was added thereto with stirring, and aromatic polycarbonate oligomer and polytetramethylene glycol were added for 10 minutes. Reaction of -bis (4-hydroxybenzoate) was performed.
In this polymerization solution, methylene chloride solution of pt-butylphenol (PTBP) (225 g of PTBP dissolved in 2.0 L of methylene chloride), sodium hydroxide aqueous solution of BPA (617 g of NaOH and 1.9 g of sodium dithionite in water) (A solution obtained by dissolving 930 g of BPA in an aqueous solution dissolved in 9.0 L) was added, and the polymerization reaction was carried out for 50 minutes.
After adding 15 L of methylene chloride for dilution and stirring for 10 minutes, the organic phase was separated into an organic phase containing an aromatic polycarbonate copolymer (A-2 ′) and an aqueous phase containing excess BPA and NaOH, and the organic phase was isolated. .

The methylene chloride solution of the aromatic polycarbonate copolymer (A-2 ′) thus obtained was washed successively with 15% by volume of 0.03 mol / L NaOH aqueous solution and 0.2 mol / L hydrochloric acid. Then, washing with pure water was repeated until the electric conductivity in the aqueous phase after washing became 0.01 μS / m or less.
The methylene chloride solution of the aromatic polycarbonate copolymer (A-2 ′) obtained by washing was concentrated and ground, and the obtained flakes were dried at 100 ° C. under reduced pressure.
The amount of polytetramethylene glycol-bis (4-hydroxybenzoate) residue determined by NMR was 4.0% by mass.
The viscosity number was 38.1 (Mv = 13500) measured in accordance with ISO 1628-4 (1999) (hereinafter, the viscosity number was measured in the same manner).

The performance test of the resin composition obtained in each example was performed as follows.
(1) Viscosity number (VN)
The viscosity number (VN) of the pellets obtained according to ISO 1628 was measured.
(2) Viscosity average molecular weight (Mw)
The viscosity average molecular weight (Mw) was determined by measuring the viscosity of a methylene chloride solution at 20 ° C. using an Ubbelohde viscometer, and determining the intrinsic viscosity [η] from this, [η] = 1.23 × 10 ⁻⁵ Mv It is a value calculated by the equation of ^0.83 .
(3) Residual phenol content The contents of bisphenol A (BPA) and p-tert-butylphenol (PTBP) in the obtained pellets were measured by gas chromatography.
(4) YI value (yellow index)
The obtained pellet was injection-molded, and a flat plate (test piece) having a size of 50 mm × 100 mm × 5 mm obtained after being held in a mold at 280 ° C. for 50 seconds was “SZ” manufactured by Nippon Denshoku Industries Co., Ltd. The YI value (yellow index) was measured according to JIS K7105 using “−90”. The higher this value, the higher the yellowness and the more colored.
(5) Optical characteristics About the injection molded product obtained by injection-molding the obtained pellet, total light transmittance, straight light transmittance, and haze were measured by the following methods, respectively.
(I) Total light transmittance In accordance with JIS K7105, a flat plate of 50 mm × 100 mm × 5 mm is prepared as a test piece from the obtained pellet, and an SZ Sigma 90 tester manufactured by Nippon Denshoku Industries Co., Ltd. is used. And measured. It shows that it is excellent in transparency, so that this figure is high.
(Ii) Straight light transmittance The above-mentioned 50 mm × 100 mm × 5 mm flat plate is used as a test piece, and a straight ray from a light source of an automatic variable angle photometer (Goniophotometer GP-1R manufactured by Murakami Color Research Laboratory) is tested. The intensity of transmitted light was measured with a movable light receiver from the normal direction of the piece, and the straight light transmittance was determined. It shows that it is excellent in transparency, so that this figure is high.
(Iii) Haze value Based on the measurement method described in JIS K7105, the haze value was measured at a temperature of 23 ° C. using the flat plate of 50 mm × 100 mm × 5 mm. The lower this value, the lower the whiteness and the better the transparency.
(6) Moisture resistance test The obtained pellet was injection molded to obtain a flat plate (test piece) having a size of 50 mm x 100 mm x 5 mm, and this plate was used using a constant temperature and humidity tester LH33 manufactured by Nagano Science Co., Ltd. Then, the YI value of the plate after being kept for a predetermined time under the humidity condition of 65 ° C. × 95% was measured. The smaller the difference in YI value at each predetermined time, the smaller the color change, which is preferable.

Examples 1-8 and Comparative Examples 1-5
Melting at a cylinder temperature of 260 ° C. using a single screw extruder with a screw diameter of 40 mm (“VS-40” manufactured by Tanabe Plastics Machinery Co., Ltd.) at a blending ratio consisting of the resin composition of the type shown in Table 1. The pellets made of the aromatic polycarbonate composition were obtained by kneading and strand cutting. About the obtained pellet, the viscosity number, the viscosity average molecular weight, and the amount of residual phenols were measured. Moreover, the obtained pellet was molded using a Nissei Resin Co., Ltd. injection molding machine (model: ES1000), and a flat plate having a size of 50 mm × 100 mm × 5 mm molded at a temperature of 280 ° C. was used. Then, optical characteristics and moisture resistance tests were conducted. The results are shown in Table 1.

[Note] In Table 1,
* 1: Idemitsu Kosan Co., Ltd., bisphenol A aromatic homopolycarbonate [FN 1500, viscosity average molecular weight is 14500]
* 2: Idemitsu Kosan Co., Ltd., bisphenol A aromatic homopolycarbonate [FN1300, viscosity average molecular weight is 11500]
* 3: Aromatic polycarbonate copolymer (A-2 ′) produced in the above production example [viscosity average molecular weight is 13500]
* 4: p-tert-butylphenol (PTBP)
* 5: Bisphenol A (BPA)
* 6: Bis (2,4-dicumylphenyl) pentaerythritol diphosphite [trade name: Doverphos S-9229PC (manufactured by Dover Chemical)]
* 7: Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol di-phosphite [PEP36, manufactured by ADEKA Corporation]
* 8: 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate (registered trademark: Celoxide 2021P, manufactured by Daicel Chemical Industries, Ltd.)
* 9: Silicone oil [KR-511 (organopolysiloxane having phenyl group, methoxy group and vinyl group), manufactured by Shin-Etsu Chemical Co., Ltd.]
* 10: Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate [phenolic antioxidant irganox 1076, manufactured by BASF Corp.]

[Evaluation results]
Examples 1 to 8 shown in Table 1 show aromatic polycarbonate resin compositions. The composition has a low YI value, reduced yellowing during molding, total light transmittance, straight light beam It is shown that the optical characteristics such as transmittance and haze are excellent. Also, in the moisture resistance test, it is shown that the decrease in YI is low and yellowing is prevented for a long time. On the other hand, the compositions of Comparative Examples 1 and 5 are aromatic polycarbonate resin compositions obtained without blending the component (B) of the present invention. Examples 1 to 6 and Example 8 It can be seen that the YI value is high and the optical properties and moisture resistance are inferior to those of the aromatic polycarbonate resin composition. The composition of Comparative Example 2 shows an aromatic polycarbonate resin composition containing 0.075 part of the component (B). The YI value increases, the haze increases, and the light transmittance also decreases. It turns out that adding (B) component excessively is not preferable. Comparative Example 3 shows an aromatic polycarbonate resin composition using a phenolic antioxidant in place of the component (C) of the present invention, but the YI value is high, which is not preferable. . In Comparative Example 4, an aromatic homopolycarbonate resin and an aromatic polycarbonate copolymer are used in combination as an aromatic polycarbonate resin as the component (A), and the components (B) and (D) of the present invention are not blended. The obtained aromatic polycarbonate resin composition is shown. It can be seen that the composition of this comparative example has a higher YI value in the moisture resistance test than that of Example 7, and is inferior in moisture resistance.

  The aromatic polycarbonate resin composition of the present invention is useful for applications of optical molded products such as light guide plates, lenses, optical fibers, and the like because it has little yellowing due to discoloration or deterioration during molding and is excellent in transparency.

Claims (13)

  (A) For 100 parts by mass of aromatic polycarbonate resin, (B) monovalent phenol (B-1) having an alkyl group with a molecular weight of 200 or less per gram equivalent and / or a molecular weight per gram equivalent An aromatic polycarbonate resin obtained by blending 0.001 to 0.05 parts by mass of dihydric phenol (B-2) that is 200 or less and (C) 0.005 to 0.5 parts by mass of a phosphite antioxidant. Composition. Aromatic polycarbonate resin in which the aromatic polycarbonate resin (A) has an aromatic homopolycarbonate resin (A-1) 40 to 100% by mass and a repeating unit represented by the following general formulas (I) and (II) The aromatic polycarbonate resin composition of Claim 1 which consists of 0-60 mass% of union (A-2 ').

[R ¹ and R ² are alkyl groups having 1 to 6 carbon atoms, X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, A cycloalkylidene group having 5 to 15 carbon atoms, —S—, —SO—, —SO ₂ —, —O—, and —CO— are shown. R ³ and R ^{4 each} represent an alkyl group having 1 to 3 carbon atoms, and Y represents a linear or branched alkylene group having 2 to 15 carbon atoms. a to d are each independently an integer of 0 to 4, and n is an integer of 2 to 200. ]   The aromatic polycarbonate resin composition according to claim 1 or 2, wherein the monohydric phenol (B-1) is a monohydric phenol having an alkyl group having 1 to 7 carbon atoms.   The aromatic polycarbonate resin composition according to claim 3, wherein the alkyl group having 1 to 7 carbon atoms is a p-tert-butyl group. The aromatic polycarbonate resin composition according to any one of claims 1 to 4, wherein the divalent phenol (B-2) as the component (B) is represented by the following general formula (Ia).

[R ¹ and R ² are alkyl groups having 1 to 6 carbon atoms, X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, A cycloalkylidene group having 5 to 15 carbon atoms, —S—, —SO—, —SO ₂ —, —O—, and —CO— are shown. a and b are each independently an integer of 0 to 4; ]   The aromatic polycarbonate resin composition according to claim 5, wherein the dihydric phenol (B-2) is 2,2-bis (4-hydroxyphenyl) propane.   The aromatic polycarbonate resin composition according to any one of claims 1 to 6, wherein the component (B) is a mixture of the monohydric phenol (B-1) and the dihydric phenol (B-2).   The fragrance according to claim 7, wherein the monohydric phenol (B-1) is p-tert-butylphenol and the dihydric phenol (B-2) is 2,2-bis (4-hydroxyphenyl) propane. Group polycarbonate resin composition.   The component (B) includes p-tert-butylphenol, 2,2-bis (4-hydroxyphenyl) propane, or a mixture of p-tert-butylphenol and 2,2-bis (4-hydroxyphenyl) propane. The total amount of unreacted p-tert-butylphenol and 2,2-bis (4-hydroxyphenyl) propane remaining in the resin composition is less than 500 ppm, according to any one of claims 1 to 8. Aromatic polycarbonate resin composition.   The aromatic polycarbonate resin composition according to any one of claims 1 to 9, wherein the phosphite antioxidant of the component (C) is bis (2,4-dicumylphenyl) pentaerythritol diphosphite.   Furthermore, the aromatic in any one of Claims 1-10 formed by mix | blending 0.001-0.5 mass part of (D) aliphatic cyclic epoxy compounds with respect to 100 mass parts of said (A) component. Polycarbonate resin composition.   The aliphatic cyclic epoxy compound of component (D) is 1,2-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, 1,2-bis (hydroxymethyl) -1-butanol The aromatic polycarbonate resin composition according to claim 11, which is an epoxy-4- (2-oxiranyl) cyclohexane adduct and a mixture thereof.   A molded article formed by molding the aromatic polycarbonate resin composition according to any one of claims 1 to 12.