JP4243512B2 - Polycarbonate resin composition, pellets thereof and molded article thereof - Google Patents

Description

【００９６】
（式中、Ａｒは炭素数６〜１２の芳香族炭化水素の芳香環上の水素基を２つ引き抜いた残基であり、ヘテロ原子を含有してもよい。ｎは０または１を示す。）
【００９７】
上記式（１）の化合物としては、例えば２，２’−ｐ−フェニレンビス（３，１−ベンゾオキサジン−４−オン）、２，２’−ｍ−フェニレンビス（３，１−ベンゾオキサジン−４−オン）、および２，２’−ｐ，ｐ’−ジフェニレンビス（３，１−ベンゾオキサジン−４−オン）などが例示される。
【００９８】
さらに上記紫外線吸収剤は、ラジカル重合が可能な単量体化合物の構造をとることにより、かかる紫外線吸収性単量体および／または光安定性単量体と、アルキル（メタ）アクリレートなどの単量体とを共重合したポリマー型の紫外線吸収剤であってもよい。前記紫外線吸収性単量体としては、（メタ）アクリル酸エステルのエステル置換基中にベンゾトリアゾール骨格、ベンゾフェノン骨格、トリアジン骨格、および環状イミノエステル骨格を含有する化合物が好適に例示される。
【００９９】
上記の中でもベンゾトリアゾール系およびヒドロキシフェニルトリアジン系が好ましく、特にヘッドランプレンズにおいてはベンゾトリアゾール系が好ましい。上記紫外線吸収剤は単独であるいは２種以上の混合物で用いてもよい。
【０１００】
紫外線吸収剤の配合量は、ポリカーボネート樹脂１００重量部に対して０．０００５〜３重量部が好ましく、０．０１〜２重量部がより好ましく、０．０２〜１重量部がさらに好ましく、０．０５〜０．５重量部が特に好ましい。
【０１０１】
（蛍光増白剤：Ｅ成分）
Ｅ成分の蛍光増白剤としてはクマリン系、ナフタルイミド系、ベンゾオキサゾリル系蛍光増白剤等があげられ、中でもクマリン系蛍光増白剤が好ましく、特に下記式（２）
【０１０２】
【化２】

【０１０３】
（但し、上記式中Ｒ₁はアミノ基、その誘導体またはヒドロキシル基を示し、Ｒ₂、Ｒ₃は水素原子、アルキル基またはフェニル基を示す。）で表される蛍光増白剤が好ましい。
【０１０４】
Ｅ成分の蛍光増白剤の配合量は、Ａ成分１００重量部に対して０．０００１〜３重量部が好ましく、０．０００５〜１重量部がより好ましく、０．０００５〜０．５重量部がさらに好ましく、０．００１〜０．５重量部が特に好ましく、０．００１〜０．１重量部が最も好ましい。
【０１０５】
（ヘーズ値）
該ポリカーボネート樹脂組成物は、その０．０３μｍの算術平均粗さ（Ｒａ）を有する厚み２ｍｍの平滑平板が０．１〜１％の範囲のヘーズ値を示し、実質的にフィラーを含まないことが好ましい。ヘーズ値はさらに好ましくは０．１〜０．５％の範囲である。
【０１０６】
ヘーズ値は、ヘーズメーターを用いて測定する。かかる平滑平板は、ペレットを所定の乾燥後、０．０３μｍの算術平均粗さ（Ｒａ）の金型表面から構成される金型キャビティ内に射出成形して得られる。金型表面の算術平均粗さ（Ｒａ）は、表面粗さ計を用いて測定する。
【０１０７】
（光安定剤）
また本発明のポリカーボネート樹脂組成物は、ビス（２，２，６，６−テトラメチル−４−ピペリジル）セバケート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）セバケート、テトラキス（２，２，６，６−テトラメチル−４−ピペリジル）−１，２，３，４−ブタンテトラカルボキシレート、テトラキス（１，２，２，６，６−ペンタメチル−４−ピペリジル）−１，２，３，４−ブタンテトラカルボキシレート、ポリ｛［６−（１，１，３，３−テトラメチルブチル）アミノ−１，３，５−トリアジン−２，４−ジイル］［（２，２，６，６−テトラメチルピペリジル）イミノ］ヘキサメチレン［（２，２，６，６−テトラメチルピペリジル）イミノ］｝、およびポリメチルプロピル３−オキシ−［４−（２，２，６，６−テトラメチル）ピペリジニル］シロキサンなどに代表されるヒンダードアミン系の光安定剤を使用することができる。また光安定剤は、ラジカル重合が可能な単量体化合物の構造をとることにより、光安定性単量体とアルキル（メタ）アクリレートなどの単量体とを共重合したポリマー型の紫外線吸収剤および／または光安定剤であってもよい。かかる光安定性単量体としては、（メタ）アクリル酸エステルのエステル置換基中にヒンダードアミン骨格を含有する化合物が好適に例示される。かかるポリマー型の光安定剤は、その共重合単量体中に前記の紫外線吸収性単量体を含むものであってもよい。
【０１０８】
ヒンダードアミン系光安定剤とベンゾトリアゾール系および／またはトリアジン系紫外線吸収剤との併用が耐候性を効果的に向上させる。かかる併用では両者の重量比（光安定剤／紫外線吸収剤）は９５／５〜５／９５の範囲が好ましく、８０／２０〜２０／８０の範囲がさらに好ましい（なお、ポリマー型の場合は単量体の重量比である）。
【０１０９】
上記光安定剤は単独であるいは２種以上の混合物で用いてもよい。光安定剤の使用量はポリカーボネート樹脂１００重量部に対して０．０００５〜３重量部が好ましく、０．０１〜２重量部がより好ましく、０．０２〜１重量部がさらに好ましく、０．０５〜０．５重量部が特に好ましい。
【０１１０】
（ブルーイング剤）
本発明のポリカーボネート樹脂組成物に、さらにブルーイング剤をポリカーボネート樹脂組成物中０．０５〜３ｐｐｍ（重量割合）使用することが好ましい。ポリカーボネート樹脂成形品の黄色味を消すために有効である。特に耐候性を付与した成形品の場合は、一定量の紫外線吸収剤が使用されているため「紫外線吸収剤の作用や色」によって樹脂製品が黄色味を帯びやすい現実があり、したがって成形品に自然な透明感を付与するためにはブルーイング剤の使用は非常に有効である。
【０１１１】
ここでブルーイング剤とは、橙色ないし黄色の光線を吸収することにより青色ないし紫色を呈する着色剤をいい、特に染料が好ましい。ブルーイング剤の配合により本発明のポリカーボネート樹脂組成物は、さらに良好な色相を達成する。好ましいブルーイング剤の配合量は樹脂組成物中０．５〜２．５ｐｐｍ、さらに好ましくは０．５〜２ｐｐｍの範囲である。
【０１１２】
ブルーイング剤としては代表例として、バイエル社のマクロレックスバイオレットＢおよびマクロレックスブルーＲＲや、サンド社のテラゾールブルーＲＬＳ、並びに有本化学工業社のプラストブルー８５８０などが挙げられる。
【０１１３】
（染顔料）
本発明のポリカーボネート樹脂組成物には、発明の目的を損なわない範囲で上記ブルーイング剤以外にも各種の染顔料を使用することができる。特に透明性を維持する点から、染料が好適である。好ましい染料としてはペリレン系染料、クマリン系染料、チオインジゴ系染料、アンスラキノン系染料、チオキサントン系染料、紺青等のフェロシアン化物、ペリノン系染料、キノリン系染料、キナクリドン系染料、ジオキサジン系染料、イソインドリノン系染料、およびフタロシアニン系染料などを挙げることができる。これら染料の使用量は、Ａ成分１００重量部あたり、０．０００１〜１重量部が好ましく、０．０００５〜０．５重量部がより好ましい。
【０１１４】
（帯電防止剤）
本発明のポリカーボネート樹脂組成物には、帯電防止性能が求められる場合があり、かかる場合、帯電防止剤を使用することが好ましい。かかる帯電防止剤としては、例えば（ｉ）ドデシルベンゼンスルホン酸ホスホニウム塩に代表されるアリールスルホン酸ホスホニウム塩、およびアルキルスルホン酸ホスホニウム塩などの有機スルホン酸ホスホニウム塩が挙げられる。該ホスホニウム塩は、Ａ成分１００重量部あたり５重量部以下の組成割合が適切であり、０．０５〜５重量部が好ましく、１〜３．５重量部がより好ましく、１．５〜３重量部の範囲がさらに好ましい。
【０１１５】
帯電防止剤としては例えば、（ｉｉ）有機スルホン酸リチウム、有機スルホン酸ナトリウム、有機スルホン酸カリウム、有機スルホン酸セシウム、有機スルホン酸ルビジウム、有機スルホン酸カルシウム、有機スルホン酸マグネシウム、有機スルホン酸バリウムなどの有機スルホン酸アルカリ（土類）金属塩が挙げられる。具体的には例えばドデシルベンゼンスルホン酸の金属塩やパーフルオロアルカンスルホン酸の金属塩などが例示される。有機スルホン酸アルカリ（土類）金属塩は、Ａ成分１００重量部あたり０．５重量部以下の組成割合が適切であり、０．００１〜０．３重量部が好ましく、０．００５〜０．２重量部がより好ましい。特にカリウム、セシウム、およびルビジウムなどのアルカリ金属塩が好適である。
【０１１６】
帯電防止剤としては、例えば（ｉｉｉ）アルキルスルホン酸アンモニウム塩、およびアリールスルホン酸アンモニウム塩などの有機スルホン酸アンモニウム塩が挙げられる。該アンモニウム塩は、Ａ成分１００重量部あたり０．０５重量部以下の組成割合が適切である。
【０１１７】
帯電防止剤としては、例えば（ｉｖ）ポリエーテルエステルアミドなどのポリ（オキシアルキレン）グリコール成分をその構成成分として含有するポリマーが挙げられる。該ポリマーはＡ成分１００重量部あたり５重量部以下が適切である。
【０１１８】
他の帯電防止剤としては、例えば、（ｖ）カーボンブラック、カーボンファイバー、カーボンナノチューブ、グラファイト、金属粉末、金属酸化物粉末などの非有機化合物が挙げられる。該非有機化合物は、Ａ成分１００重量部あたり０．０５重量部以下の組成割合が適切である。またこれらの（ｖ）に例示された非有機化合物は、帯電防止性能以外にも、熱線吸収剤として配合される場合がある。
【０１１９】
上記（ｉｖ）のポリマーにおいては、かかる単量体成分としてスルホン酸塩基で置換された成分を含有することができる。具体的には、芳香族ジカルボン酸およびポリ（オキシアルキレン）グリコール成分をその構成成分として含有するポリマーにおいて、４−ナトリウムスルホ−イソフタル酸ジメチル、５−ナトリウムスルホ−イソフタル酸ジメチル、４−カリウムスルホ−イソフタル酸ジメチル、５−カリウムスルホ−イソフタル酸ジメチル、２−ナトリウムスルホ−テレフタル酸ジメチル、および２−カリウムスルホ−テレフタル酸ジメチル等のスルホン酸塩基で置換された芳香族ジカルボン酸のエステルが共重合されてなるポリマーが例示される。かかるポリマーにおいてはスルホン酸塩基で置換されていない芳香族ジカルボン酸成分とスルホン酸塩基で置換されていない芳香族ジカルボン酸成分との割合は、両者の合計１００モル％中、後者の割合が好ましくは５〜５０モル％、より好ましくは８〜３５モル％、さらに好ましくは１０〜３０モル％である。
【０１２０】
（熱線吸収能を有する化合物）
本発明のポリカーボネート樹脂組成物には、本発明の目的が損なわれない量の熱線吸収能を有する化合物を使用することができる。該化合物としてはフタロシアニン系近赤外線吸収剤および炭素フィラーが好適に例示される。かかるフタロシアニン系近赤外線吸収剤としては例えば三井化学（株）製ＭＩＲ−３６２が市販され容易に入手可能である。炭素フィラーとしてはカーボンブラック、グラファイト（天然および人工のいずれも含み、さらにウイスカーを含む）、カーボンファイバー（気相成長法によるものを含む）、カーボンナノチューブ、およびフラーレンなどが例示され、好ましくはカーボンブラックおよびグラファイトである。これらは単独でまたは２種以上併用して使用することができる。フタロシアニン系近赤外線吸収剤は、ポリカーボネート樹脂（Ａ成分）１００重量部に対して０．００５〜０．２重量部が好ましく、０．００８〜０．１重量部がより好ましく、０．０１〜０．０７重量部がさらに好ましい。炭素フィラーは本発明の樹脂組成物中、０．１〜２００ｐｐｍ（重量割合）の範囲が好ましく、０．５〜１００ｐｐｍの範囲がより好ましく、１〜５０ｐｐｍの範囲がさらに好ましい。
【０１２１】
（難燃剤）
本発明のポリカーボネート樹脂組成物には、本発明の目的が損なわれない量の難燃剤を使用することができる。難燃剤としては、ハロゲン化ビスフェノールＡのポリカーボネート型難燃剤、有機塩系難燃剤、芳香族リン酸エステル系難燃剤、あるいは、ハロゲン化芳香族リン酸エステル型難燃剤等が挙げられ、それらを一種以上使用することができる。
【０１２２】
具体的にハロゲン化ビスフェノールＡのポリカーボネート型難燃剤は、テトラブロモビスフェノールＡのポリカーボネート型難燃剤、テトラブロモビスフェノールＡとビスフェノールＡとの共重合ポリカーボネート型難燃剤等である。
【０１２３】
具体的に有機塩系難燃剤は、ジフェニルスルホン−３，３’−ジスルホン酸ジカリウム、ジフェニルスルホン−３−スルホン酸カリウム、２，４，５−トリクロロベンゼンスルホン酸ナトリウム、２，４，５−トリクロロベンゼンスルホン酸カリウム、ビス（２，６−ジブロモ−４−クミルフェニル）リン酸カリウム、ビス（４−クミルフェニル）リン酸ナトリウム、ビス（ｐ−トルエンスルホン）イミドカリウム、ビス（ジフェニルリン酸）イミドカリウム、ビス（２，４，６−トリブロモフェニル）リン酸カリウム、ビス（２，４−ジブロモフェニル）リン酸カリウム、ビス（４−ブロモフェニル）リン酸カリウム、ジフェニルリン酸カリウム、ジフェニルリン酸ナトリウム、パーフルオロブタンスルホン酸カリウム、ラウリル硫酸ナトリウムあるいはカリウム、ヘキサデシル硫酸ナトリウムあるいはカリウム等である。有機塩系難燃剤は、Ａ成分１００重量部当たり、好ましくは０．０００１〜０．５重量部、より好ましくは０．００１〜０．２重量部、さらに好ましくは０．００３〜０．１５重量部で使用できる。
【０１２４】
具体的にハロゲン化芳香族リン酸エステル型難燃剤は、トリス（２，４，６−トリブロモフェニル）ホスフェート、トリス（２，４−ジブロモフェニル）ホスフェート、トリス（４−ブロモフェニル）ホスフェート等である。
【０１２５】
具体的に芳香族リン酸エステル系難燃剤は、トリフェニルホスフェート、トリス（２，６−キシリル）ホスフェート、テトラキス（２，６−キシリル）レゾルシンジホスフェート、テトラキス（２，６−キシリル）ヒドロキノンジホスフェート、テトラキス（２，６−キシリル）−４，４’−ビフェノールジホスフェート、テトラフェニルレゾルシンジホスフェート、テトラフェニルヒドロキノンジホスフェート、テトラフェニル−４，４’−ビフェノールジホスフェート、芳香環ソースがレゾルシンとフェノールでありフェノール性ＯＨ基を含まない芳香族ポリホスフェート、芳香環ソースがレゾルシンとフェノールでありフェノール性ＯＨ基を含む芳香族ポリホスフェート、芳香環ソースがヒドロキノンとフェノールでありフェノール性ＯＨ基を含まない芳香族ポリホスフェート、同様のフェノール性ＯＨ基を含む芳香族ポリホスフェート、（以下に示す「芳香族ポリホスフェート」は、フェノール性ＯＨ基を含む芳香族ポリホスフェートと含まない芳香族ポリホスフェートの両方を意味するものとする）芳香環ソースがビスフェノールＡとフェノールである芳香族ポリホスフェート、芳香環ソースがテトラブロモビスフェノールＡとフェノールである芳香族ポリホスフェート、芳香環ソースがレゾルシンと２，６−キシレノールである芳香族ポリホスフェート、芳香環ソースがヒドロキノンと２，６−キシレノールである芳香族ポリホスフェート、芳香環ソースがビスフェノールＡと２，６−キシレノールである芳香族ポリホスフェート、芳香環ソースがテトラブロモビスフェノールＡと２，６−キシレノールである芳香族ポリホスフェート等である。ハロゲン化芳香族リン酸エステル型難燃剤および芳香族リン酸エステル系難燃剤は、Ａ成分１００重量部当たり、好ましくは０．１〜２５重量部、より好ましくは１〜２０重量部、さらに好ましくは２〜１８重量部で使用できる。
【０１２６】
（他の樹脂やエラストマー）
本発明のポリカーボネート樹脂組成物は、品質要求の厳しい透明性の必要な用途に対しても、極めて良好な成形品を与えるものである。したがって、本発明のポリカーボネート樹脂組成物の最も好適な態様は、樹脂成分が実質的にポリカーボネート樹脂からなる組成物である。しかしながら本発明の樹脂組成物が有する良好な離型性能などは、他の樹脂やエラストマーを配合した場合にも発揮される。よって本発明のポリカーボネート樹脂組成物は、これらを適宜目的に応じて配合することもできる。
【０１２７】
かかる他の樹脂としては、例えばポリエチレンテレフタレート、ポリブチレンテレフタレート等のポリエステル樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリエーテルイミド樹脂、ポリウレタン樹脂、シリコーン樹脂、ポリフェニレンエーテル樹脂、ポリフェニレンスルフィド樹脂、ポリスルホン樹脂、ポリエチレン、ポリプロピレン等のポリオレフィン樹脂、ポリスチレン樹脂、アクリロニトリル／スチレン共重合体（ＡＳ樹脂）、アクリロニトリル／ブタジエン／スチレン共重合体（ＡＢＳ樹脂）、ポリメタクリレート樹脂、フェノール樹脂、エポキシ樹脂等の樹脂が挙げられる。
【０１２８】
また、エラストマーとしては、例えばイソブチレン／イソプレンゴム、スチレン／ブタジエンゴム、エチレン／プロピレンゴム、アクリル系エラストマー、ポリエステル系エラストマー、ポリアミド系エラストマー、コアシェル型のエラストマーであるＭＢＳ（メタクリル酸メチル／ステレン／ブタジエン）ゴム、ＭＡＳ（メタクリル酸メチル／アクリロニトリル／スチレン）ゴム等が挙げられる。
【０１２９】
他の樹脂やエラストマーは、ポリカーボネート樹脂（Ａ成分）１００重量部に対して、好ましくは５０重量部以下、より好ましくは４０重量部以下、さらに好ましくは３０重量部以下で使用される。一方、他の樹脂やエラストマーを配合する場合、その下限は１重量部以上が好ましい。
【０１３０】
（その他添加剤）
本発明のポリカーボネート樹脂組成物には、適宜目的に応じて各種無機充填材、流動改質剤、抗菌剤、光触媒系防汚剤、およびフォトクロミック剤などを配合することができる。
【０１３１】
（ポリカーボネート樹脂組成物の製造）
本発明のポリカーボネート樹脂組成物を製造するには、任意の方法が採用される。例えばＡ成分、Ｂ成分および任意の添加剤を、Ｖ型ブレンダー、ヘンシェルミキサー、メカノケミカル装置、押出混合機などの予備混合手段を用いて充分に混合する。場合により押出造粒器やブリケッティングマシーンなどによりかかる各成分の原料または予備混合物の造粒を行うことができる。その後かかる予備混合物は、ベント式二軸押出機に代表される溶融混練機で溶融混練され、その製造されるストランド等をペレタイザー等の機器によりペレット化する方法が挙げられる。
【０１３２】
他に、各成分をそれぞれ独立にベント式二軸押出機に代表される溶融混練機に供給する方法や、各成分の一部を予備混合した後、残りの成分と独立に溶融混練機に供給する方法なども挙げられる。各成分の一部を予備混合する方法としては例えば、本発明のＢ成分の脂肪酸フルエステルと他の成分とを予め予備混合した後、ポリカーボネート樹脂に混合または押出機に直接供給する方法が挙げられる。
【０１３３】
また予備混合する方法としては例えば、Ａ成分としてパウダーの形態を有するものを含む場合、かかるパウダーの一部と配合する添加剤とをブレンドして、パウダーで希釈した添加剤のマスターバッチとする方法が挙げられる。さらに一成分を独立に溶融押出機の途中から供給する方法なども挙げられる。なお、配合する成分に液状のものがある場合には、溶融押出機への供給にいわゆる液注装置、または液添装置を使用することができる。
【０１３４】
押出機としては、原料中の水分や、溶融混練樹脂から発生する揮発ガスを脱気できるベントを有するものが好ましく使用できる。ベントからは発生水分や揮発ガスを効率よく押出機外部へ排出するための真空ポンプが好ましく設置される。また押出原料中に混入した異物などを除去するためのスクリーンを押出機ダイス部前のゾーンに設置し、異物を樹脂組成物から取り除くことも可能である。かかるスクリーンとしては金網、スクリーンチェンジャー、焼結金属プレート（ディスクフィルターなど）などを挙げることができる。
【０１３５】
溶融混練機としては二軸押出機の他にバンバリーミキサー、混練ロール、単軸押出機、３軸以上の多軸押出機などを挙げることができる。
【０１３６】
上記の如く押出された樹脂は、直接切断してペレット化するか（いわゆるホットカット）、またはストランドを形成した後かかるストランドをペレタイザーで切断してペレット化される。ペレット化に際して外部の埃などの影響を低減する必要がある場合には、押出機周囲の雰囲気を清浄化することが好ましい。
【０１３７】
得られたペレットの形状は、円柱、角柱、および球状など一般的な形状を取り得るが、より好適には円柱である。かかる円柱の直径は好ましくは１〜５ｍｍ、より好ましくは１．５〜４ｍｍ、さらに好ましくは２〜３．３ｍｍである。一方、円柱の長さは好ましくは１〜３０ｍｍ、より好ましくは２〜５ｍｍ、さらに好ましくは２．５〜３．５ｍｍである。
【０１３８】
（第２の態様）
上記の如く本発明のＢ成分の脂肪酸フルエステルは、主成分たるエステル化合物と副成分たる遊離の脂肪族カルボン酸であることから、本発明のポリカーボネート樹脂組成物は、かかる２つの化合物を含有する樹脂組成物であるともいえる。したがってかかる点から本発明によれば、次の第２の態様の樹脂組成物が提供される。すなわち、本発明の第２の態様は、ポリカーボネート樹脂（Ａ成分）１００重量部、および４〜８価の炭素数５〜３０の脂肪族多価アルコールと炭素数１０〜２２の脂肪族カルボン酸とのフルエステル（Ｂ成分）０．００５〜２重量部からなる樹脂組成物であって、該組成物中の遊離脂肪族カルボン酸のカルボキシル基のモル数（Ｆｆ）とＢ成分のエステル結合のモル数（Ｆｅ）とのモル比（Ｆｆ：Ｆｅ）が８：９２〜３０：７０の範囲であるポリカーボネート樹脂組成物である。殊にかかる樹脂組成物は、目的とする成形品を製造するために使用されるペレットの形態であることが好ましい。
【０１３９】
（Ｆｆ：Ｆｅ）
樹脂組成物中の脂肪酸フルエステル化合物と脂肪族カルボン酸化合物との割合は、かかる樹脂組成物を¹Ｈ−ＮＭＲ測定することに算出される。なお、かかる測定は、ペレット中の脂肪族カルボン酸化合物の割合が極めて少量であることから、周波数６００ＭＨｚ以上のＮＭＲ測定装置を用いて測定することが必要である。かかる測定より算出される、遊離脂肪族カルボン酸のカルボキシル基のモル数（Ｆｆ）と脂肪族カルボン酸エステル化合物中のエステル結合のモル数（Ｆｅ）とのモル比（Ｆｆ：Ｆｅ）は、１０：９０〜２５：７５の範囲が好適であり、１２：８８〜２２：７８の範囲がより好適である。かかるＦｆ：Ｆｅは、例えばペンタエリスリトールエステルの場合には、次のように算出されることができる。すなわち、脂肪族カルボン酸成分（遊離酸化合物およびエステル化合物のいずれも含む）のカルボキシル基に結合したメチレン基の水素原子のシグナルは約２．３ｐｐｍに現れる。かかる領域のピーク面積をＳｃとする。一方、エステル結合と結合したペンタエリスリトール成分中のメチレン基の水素原子のシグナルは約４．１ｐｐｍに現れる。かかる領域のピーク面積をＳｅとする。これらより、
【０１４０】
Ｆｆ：Ｆｅ＝（Ｓｃ／２−Ｓｅ／２）：（Ｓｅ／２）
の関係からＦｆ：Ｆｅが算出されることができる（ＦｆとＦｅの合計が１００となるように換算する）。
【０１４１】
なお、かかるモル比は、ペレット製造時に配合される脂肪酸エステル中のその割合と必ずしも同一にはならない。これはペレット製造時の加熱等により脂肪酸エステル化合物のエステル結合が分解する場合があるためと考えられる。
【０１４２】
本発明の第２の態様において、Ａ成分のポリカーボネート樹脂は、第１の態様と同じである。Ｂ成分を構成する４〜８価の炭素数５〜３０の脂肪族多価アルコールおよび炭素数１０〜２２の脂肪族カルボン酸も、第１の態様と同じである。Ｂ成分の脂肪族カルボン酸は、パルミチン酸成分とステアリン酸成分とを含み、そのガスクロマトグラフ−質量分析法（ＧＣ／ＭＳ法）におけるピーク面積において、パルミチン酸成分の面積（Ｓｐ）とステアリン酸成分の面積（Ｓｓ）との合計が全脂肪族カルボン酸成分中８０％以上であり、かつ両者の面積比（Ｓｓ／Ｓｐ）が１．３〜３０であることが好ましい。面積比（Ｓｓ／Ｓｐ）の測定法は前述の通りである。
【０１４３】
またＣ〜Ｅ成分などの任意成分も、第１の態様と同様に含有していてもよい。
【０１４４】
（第３の態様）
本発明のポリカーボネート樹脂組成物は、上記の態様から上述の本発明の課題を解決し、車両用透明部材を成形するのに好適なペレットを与える。したがってかかる点から本発明によれば、次の第２の態様の樹脂組成物が提供される。すなわち、本発明の第３の態様は、ポリカーボネート樹脂（Ａ成分）１００重量部、および４〜８価の炭素数５〜３０の脂肪族多価アルコールと炭素数１０〜２２の脂肪族カルボン酸とのフルエステル（Ｂ成分）０．００５〜２重量部からなる樹脂組成物から形成されたペレットであって、
該ペレットの離型荷重測定法における離型荷重は、該Ａ成分に対し酸価０．８かつＴＧＡ（熱重量解析）における５％重量減少温度が３９６℃であるペンタエリスリトールテトラステアレートを該Ｂ成分と同量配合してなる樹脂組成物から形成されたペレットの同測定法における離型荷重に対して、８５％以下であることを満足するポリカーボネート樹脂組成物から形成されたペレットである。
【０１４５】
（離型荷重測定法）
離型荷重は、ペレットから図1に示すコップ状成形品を成形し、金型から突き出し離型させる際の荷重を測定する。離型荷重の測定は、突き出し用プレートにロードセルを設置し、突き出し時のロードセルにかかる力を測定し、その最大値を離型荷重とする。コップ状成形品を連続した４０ショット成形し、離型荷重を安定化させた後に連続３０ショットの成形を行い平均値を離型荷重（Ｎ）とする。コップ状成形品の内面側に相当する金型キャビティ（可動側金型キャビティ）の算術平均粗さ（Ｒａ）は、０．０３μｍとした。
【０１４６】
離型荷重の測定においては、比較用の標準樹脂組成物からなるペレットからの成形品の離型荷重を測定し、各サンプルの離型荷重の相対割合を算出する。基準値はポリカーボネート樹脂１００重量部に、酸価０．８かつＴＧＡ（熱重量解析）における５％重量減少温度が３９６℃であるペンタエリスリトールテトラステアレート０．２重量部を配合してなる樹脂組成物（ＳＲＣ−Ｉ）、並びに同ペンタエリスリトールテトラステアレート０．５重量部を配合してなる樹脂組成物（ＳＲＣ−ＩＩ）の離型荷重とする。
【０１４７】
離型荷重は、基準値に対して、８５％以下、好ましくは８０％以下である。
【０１４８】
該ペレット中の遊離脂肪族カルボン酸のカルボキシル基のモル数（Ｆｆ）とＢ成分のエステル結合のモル数（Ｆｅ）とのモル比（Ｆｆ：Ｆｅ）は、第１または第２の態様と同様、１０：９０〜３０：７０の範囲であることが好ましい。ＦｆとＦｅの測定方法は前述の通りである。
【０１４９】
脂肪族多価アルコールは、ペンタエリスリトールであることが好ましい。Ｂ成分の脂肪族カルボン酸はパルミチン酸成分とステアリン酸成分とを含み、そのガスクロマトグラフ−質量分析法（ＧＣ／ＭＳ法）におけるピーク面積において、パルミチン酸成分の面積（Ｓｐ）とステアリン酸成分（Ｓｓ）との合計が全脂肪族カルボン酸成分中８０％以上であり、かつ両者の面積比（Ｓｓ／Ｓｐ）が１．３〜３０であることが好ましい。面積比（Ｓｓ／Ｓｐ）の測定法は前述の通りである。
【０１５０】
該ペレットは、それから形成された０．０３μｍの算術平均粗さ（Ｒａ）を有する厚み２ｍｍの平滑平板が０．１〜１％の範囲のヘーズ値を示すものである、実質的にフィラーを含まないものが好ましい。ヘーズ値の測定法は前述の通りである。
【０１５１】
ペレットの形状は、最も好適には直径２〜３．３ｍｍ、長さ２．５〜３．５ｍｍの円柱状である。
【０１５２】
本発明の第３の態様においても、Ａ成分のポリカーボネート樹脂は、第１の態様と同じである。Ｂ成分を構成する４〜８価の炭素数５〜３０の脂肪族多価アルコールおよび炭素数１０〜２２の脂肪族カルボン酸は、第１の態様と同じである。またＣ〜Ｅ成分などの任意成分も、第１の態様と同様に含有していてもよい。
【０１５３】
（第４の態様）
本発明の第４の態様は、第１または第２の態様のポリカーボネート樹脂組成物からなる成形品である。かかる態様は、第３の態様のペレットから成形された成形品を包含する。
【０１５４】
成形品は、通常、ペレットを射出成形して得ることができる。かかる射出成形においては、通常の成形方法だけでなく、射出圧縮成形、射出プレス成形、ガスアシスト射出成形、インサート成形、インモールドコーティング成形、断熱金型成形、急速加熱冷却金型成形、二色成形、サンドイッチ成形、および超高速射出成形などを挙げることができる。また成形はコールドランナー方式およびホットランナー方式のいずれも選択することができる。
【０１５５】
また本発明によれば、ポリカーボネート樹脂組成物を押出成形し、各種異形押出成形品、シート、フィルムなどの形とすることもできる。またシート、フィルムの成形にはインフレーション法や、カレンダー法、キャスティング法なども使用可能である。さらに特定の延伸操作をかけることにより熱収縮チューブとして成形することも可能である。また本発明のポリカーボネート樹脂組成物を回転成形やブロー成形などにより中空成形品とすることも可能である。
【０１５６】
（表面処理）
さらに本発明の成形品には、各種の表面処理を行うことが可能である。表面処理としては、ハードコート、撥水・撥油コート、親水性コート、帯電防止コート、紫外線吸収コート、赤外線吸収コート、並びにメタライジング（蒸着など）などの各種の表面処理を行うことができる。表面処理方法としては、液剤のコーティングの他、蒸着法、溶射法、およびメッキ法が挙げられる。蒸着法としては物理蒸着法および化学蒸着法のいずれも使用できる。物理蒸着法としては真空蒸着法、スパッタリング、およびイオンプレーティングが例示される。化学蒸着（ＣＶＤ）法としては、熱ＣＶＤ法、プラズマＣＶＤ法、および光ＣＶＤ法などが例示される。
【０１５７】
本発明の成形品はその割れ耐性が改善されていることから、かかる表面処理を行うのに極めて適している。殊に溶剤などポリカーボネート樹脂に悪影響を与える因子を含む表面処理に本発明のポリカーボネート樹脂組成物は適し、特にハードコートに適している。
【０１５８】
本発明で使用するハードコート剤としては、シリコーン樹脂系ハードコート剤や有機樹脂系ハードコート剤などが例示される。シリコーン樹脂系ハードコート剤は、シロキサン結合をもった硬化樹脂層を形成するものであり、例えば、３官能シロキサン単位に相当する化合物（トリアルコキシシラン化合物など）を主成分とする化合物の部分加水分解縮合物、好ましくはさらに４官能シロキサン単位に相当する化合物（テトラアルコキシシラン化合物など）を含む部分加水分解縮合物、並びにさらにこれらにコロイダルシリカなどの金属酸化物微粒子を充填した部分加水分解縮合物などが挙げられる。シリコーン樹脂系ハードコート剤はさらに２官能性のシロキサン単位および１官能性のシロキサン単位を含んでよい。これらには縮合反応時に発生するアルコール（アルコキシシランの部分加水分解縮合物の場合）などが含まれるが、さらに必要に応じて任意の有機溶剤、水、あるいはこれらの混合物に溶解ないしは分散させてもよい。そのための有機溶剤としては、低級脂肪酸アルコール類、多価アルコールとそのエーテル、エステル類などが挙げられる。なお、ハードコート層には平滑な表面状態を得るため各種界面活性剤、例えば、シロキサン系、フッ化アルキル系界面活性剤などを添加してもよい。
【０１５９】
有機樹脂系ハードコート剤としては、例えば、メラミン樹脂、ウレタン樹脂、アルキド樹脂、アクリル樹脂、多官能アクリル樹脂などが挙げられる。ここで多官能アクリル樹脂としてはポリオールアクリレート、ポリエステルアクリレート、ウレタンアクリレート、エポキシアクリレート、ホスファゼンアクリレートなどの樹脂が挙げられる。
【０１６０】
これらハードコート剤のうち長期間の耐久性に優れ、かつ表面硬度が比較的高いシリコーン樹脂系ハードコート剤、または処理が比較的簡便でかつ良好なハードコート層が形成される紫外線硬化型のアクリル樹脂または多官能アクリル樹脂が好ましい。シリコーン樹脂系ハードコート剤はプライマー層とトップ層から構成されるいわゆる２コートタイプ、並びに１層のみから形成されるいわゆる１コートタイプのいずれも選択できる。
【０１６１】
かかるプライマー層（第１層）を形成する樹脂としては、各種ブロックイソシアネート成分およびポリオール成分からなるウレタン樹脂、アクリル樹脂、ポリエステル樹脂、エポキシ樹脂、メラミン樹脂、アミノ樹脂、およびポリエステルアクリレート、ウレタンアクリレート、エポキシアクリレート、ホスファゼンアクリレート、メラミンアクリレート、アミノアクリレートなどの各種多官能アクリル樹脂を挙げることができ、これらは単独でも２種以上を併用して使用することもできる。これらの中でも好ましくはアクリル樹脂、多官能アクリル樹脂が５０重量％、より好ましくは６０重量％以上含有するものを挙げることができ、特にアクリル樹脂およびウレタンアクリレートからなるものが好ましい。これらは未反応状態のものを塗布後所定の反応をさせて硬化樹脂とすること、並びに反応後の樹脂を直接塗布し硬化樹脂層を形成することのいずれも適用可能である。後者は通常樹脂を溶媒に溶解し溶液とした後、塗布されその後溶媒が除去される。また前者の場合も溶媒を使用することが一般的である。
【０１６２】
さらに、ハードコート層を形成する樹脂には、上述した光安定剤や紫外線吸収剤、並びに触媒、熱・光重合開始剤、重合禁止剤、シリコーン消泡剤、レベリング剤、増粘剤、沈殿防止剤、垂れ防止剤、難燃剤、有機・無機顔料・染料の各種添加剤および添加助剤を含むことができる。
【０１６３】
コート方法としては、バーコート法、ディップコート法、フローコート法、スプレーコート法、スピンコート法、ローラーコート法等の方法を、塗装される基材となる成形品の形状に応じて適宜選択することができる。中でも複雑な成形品形状に対応しやすいディップコート法、フローコート法、およびスプレーコート法が好ましい。
【０１６４】
【実施例】
以下に実施例を挙げて本発明をさらに説明する。なお、評価は下記の方法によって実施した。
【０１６５】
（Ｉ）脂肪酸フルエステルの評価方法
組成物の原材料として使用した脂肪酸エステル（Ｂ−１〜Ｂ−８）に関して、下記（１）〜（３）の評価を行った。評価結果を表１に示した。
【０１６６】
（１）脂肪酸フルエステルの酸価
ＪＩＳ Ｋ ００７０に準拠して中和滴定法により酸価（ＫＯＨｍｇ／ｇ）を求めた。
【０１６７】
（２）脂肪酸フルエステルの熱重量測定による５％重量減少温度
ＴＡ−ｉｎｓｔｒｕｍｅｎｔｓ社製のＨｉ−Ｒｅｓ ＴＧＡ２９５０ Ｔｈｅｒｍｏｇｒａｖｉｍｅｔｒｉｃ Ａｎａｌｙｚｅｒを使用し、Ｎ₂雰囲気下において２０℃／ｍｉｎで昇温させ、試料の減量が仕込み重量の５重量％となった時の温度をＴＧＡ５％重量減少温度として測定した。
【０１６８】
（３）脂肪族カルボン酸成分のＧＣ／ＭＳ測定面積比（Ｓｓ／Ｓｐ）
脂肪酸エステルの脂肪族カルボン酸成分の熱分解メチル化ＧＣ／ＭＳ法による測定は、以下の手順で実施した。
【０１６９】
ＧＣ／ＭＳ装置はＧＣ：ＨＰ６８９０型およびＭＳ：ＨＰ５９７３型（共にヒューレット・パッカード社製）を接続したものを使用し、熱分解装置はＪＨＰ−３（日本分析工業製）を使用した。
【０１７０】
試料をクロロホルムに溶解した溶液をはかり取り、その後クロロホルムを除去する方法により、約２０μｇの試料を熱分解装置用パイロホイル（日本分析工業製「Ｆ３５８」（３５８℃用））にはかり取った。さらにかかる試料に対し反応試剤として水酸化テトラメチルアンモニウム（ＴＭＡＨ）の２．５重量％メタノール溶液１０μｌを添加して、６０℃程度に加熱して溶媒を除去した後、上記熱分解装置により３５８℃で１０秒の条件で反応熱分解を実施した。
【０１７１】
ＧＣ／ＭＳ測定の条件は次のとおりであった。カラムはキャピラリー型カラムのＤＢ−５ＭＳ（３０ｍ×０．２５ｍｍ×０．２５μｍ、Ｊ＆Ｗ社製）を使用し、キャリアガスにはヘリウムガスを用いた。またキャリアガスは定圧モードを使用して７２．４ＫＰａ（１０．５ｐｓｉ）の一定値とし、４０℃での（初期の）ガス流量を１．３ｍｌ／ｍｉｎとした。さらにスプリット比は５０／１、注入口温度は３００℃、およびＧＣ／ＭＳの接続部の温度は２８０℃とした。カラム槽温度の条件は４０℃で５分間保持した後、２０℃／ｍｉｎの昇温速度で３２０℃まで昇温し、さらに３２０℃で５分間保持して測定を行った。またＭＳ装置はイオン化のモードとして電子衝撃イオン化（ＥＩ）モードを使用し、質量／電荷数（ｍ／ｚ）：２０〜５００の範囲で測定を行った。また１秒あたりのスキャン回数は約３とした。さらにイオン加速電圧などの設定はＰＦＴＢＡの標準サンプルを用いたオートチューニングにより設定した。上記の測定から、全脂肪族カルボン酸成分中におけるＳｓとＳｐとの合計の割合、およびそれらの面積比（Ｓｓ／Ｓｐ）を算出した。
【０１７２】
（ＩＩ）樹脂組成物の評価方法
後述する方法により製造された樹脂組成物に関して、下記（４）〜（１２）の評価を実施した。
【０１７３】
（４）¹Ｈ−ＮＭＲ測定（Ｆｆ：Ｆｅ）
後述する方法により各例において作成されたペレットから、３５ｍｇの試料を秤量し、かかる試料を０．５ｍｌの重クロロホルムに溶解して、得られた溶液を¹Ｈ−ＮＭＲ測定用のアンプル管に入れて、¹Ｈ−ＮＭＲ測定用試料を作成した。かかる測定用試料を周波数６００ＭＨｚのＮＭＲ測定装置（日本電子（株）製、ＪＮＭ−ａｌｐｈａ６００）により、¹Ｈ−ＮＭＲ測定した。測定条件は1サンプルにつき、積算回数２０４８回および測定時間約４時間とした。
【０１７４】
かかる測定よりＦｆ：Ｆｅを次のように算出した。すなわち、脂肪族カルボン酸成分（酸およびエステルのいずれも含む）のカルボキシル基に結合したメチレン基の水素原子のシグナルは約２．３ｐｐｍに現れる。かかる領域のピーク面積をＳｃとした。一方、エステル結合と結合したペンタエリスリトール成分中のメチレン基の水素原子のシグナルは約４．１ｐｐｍに現れる。かかる領域のピーク面積をＳｅとした。これらより、
【０１７５】
Ｆｆ：Ｆｅ＝（Ｓｃ／２−Ｓｅ／２）：（Ｓｅ／２）
の関係からＦｆ：Ｆｅを算出した（ＦｆとＦｅの合計が１００となるように換算した）。
【０１７６】
（５）成形品の透明性
日本電色（株）製ヘーズメーターＮＤＨ−３００Ａを用いて、厚さ２．０ｍｍの成形板（５０ｍｍ角板）の全光線透過率とＨａｚｅを測定した。かかる成形板は、後述する方法により作成されたペレットを所定の乾燥後、０．０３μｍの算術平均粗さ（Ｒａ）の金型表面から構成される金型キャビティ内に射出成形して製造し、得られた成形品のＲａが０．０３μｍであることを表面粗さ計を用いて確認した。全光線透過率は数値が高いほど透明性が高いことを示す。また、Ｈａｚｅは成形品の濁り度で、数値が低いほど濁りが少ないことを示す。
【０１７７】
（６）成形耐熱性の測定
最大型締め力が１４７０ｋＮの射出成形機（ファナック（株）製：Ｔ−１５０Ｄ）にて、シリンダー温度３４０℃、金型温度８０℃の条件で、上記（５）の場合と同じ金型を用いて成形サイクル６０秒にて成形した厚さ２ｍｍの５０ｍｍ角板を成形し、その角板の色相と、シリンダー温度３４０℃でシリンダー内に１０分間滞留させた後に成形した成形品の色相との差を次式の求めΔＥとして示した。
【０１７８】
ΔＥ＝（（Ｌ−Ｌ’）²＋（ａ−ａ’）²＋（ｂ−ｂ’）²）^1/2
（上記において（Ｌ、ａ、ｂ）値は滞留前の色相を表し、（Ｌ’、ａ’、ｂ’）値は滞留後の色相を表す）
【０１７９】
（７）離型性の測定
図１に示すコップ状成形品を金型から突き出し離型させる際の離型荷重を測定した。かかる離型荷重の測定は、突き出し用プレートにロードセル（ミネベア（株）製：ＣＭＭ１−５００Ｋ）を設置し、ロードセルの先端部が突き出しピンを突き出す構成を有する金型を用いて行った。かかる構成により突き出し時のロードセルにかかる力が測定され、その力の最大値を離型荷重とした。かかるコップ状成形品を連続した４０ショット成形し、離型荷重を安定化させた後に連続３０ショットの成形を行った平均値を離型荷重（Ｎ）とした。コップ状成形品の内面側に相当する金型キャビティ（可動側金型キャビティ）の算術平均粗さ（Ｒａ）は、０．０３μｍであった。コップ状成形品の成形条件は次の通りである。すなわち、成形機：住友重機械工業（株）製：ＳＳ７５ｔ、シリンダー温度３００℃、金型温度８０℃、充填時間１０秒、保圧１１８ＭＰａ、保圧時間１５秒、冷却時間２０秒であった。かかる条件により良好な成形品が得られた。
【０１８０】
かかる離型荷重の測定においては、比較用の標準樹脂組成物の離型荷重を測定し、各例のサンプルの離型荷重の相対割合を算出し、表に示した。かかる比較用の標準樹脂組成物は後述するＰＣ１００重量部にＢ−８のペンタエリスリトールテトラステアレート０．２重量部を配合してなる樹脂組成物（ＳＲＣ−Ｉ）、並びに同ペンタエリスリトールテトラステアレート０．５重量部を配合してなる樹脂組成物（ＳＲＣ−ＩＩ）とした。かかるＳＲＣ−ＩおよびＳＲＣ−ＩＩは実施例１の樹脂組成物と同様の条件で製造した。ＳＲＣ−Ｉの離型荷重は２３２０Ｎであり、ＳＲＣ−ＩＩの離型荷重は１６００Ｎであった。
（８）成形品のシルバーストリーク
前記（７）の離型荷重測定時に３０ショット連続成形されたコップ状成形品において、シルバーストリークの有無を観察した。３０個の成形品中のシルバーストリークを有する成形品の個数を表に示した。
（９）成形品の歪み（歪み−１）の観察
前記成形耐熱性の試験で作成した角板を使用し、偏光板によって成形品の歪み状態を目視で観察した。かかる観察においては、偏光板観察により生ずる縞模様の色変化および疎密の不均一さにより歪みの程度を評価した。
【０１８１】
×：流動方向に対する縞の数が多く、縞模様が密であり、各色間の境界が明確である
△：上記×に比較して縞の数は全体として少なめで、各色間の境界は不明確である。但し縁部には縞模様の密な部分が残る
○：上記△に比較してさらに縞の数は少なめであり、縞模様は疎であり、各色間の境界は不明確である
【０１８２】
（１０）成形品の歪み（歪み−２）の観察
図２に示す素通し型のヘッドランプレンズをシリンダー温度３２０℃および金型温度８０℃の条件で、射出成形機（住友重機械工業（株）製ＳＧ２６０Ｍ−ＨＰ）を用いて３０ショット分成形し、１２０℃で２時間アニール処理した。その後かかる成形品を偏光面が直行する２枚の偏光板の間に置き、その陰影（歪み−２）の有無を観察した。３０個の成形品を観察し、その陰影の程度を下記の基準に基づき評価した。
【０１８３】
○：陰影は、そのコントラストが比較的薄く、わずかに観察される
△：陰影は、そのコントラストがある程度強く、明確に観察される
×：陰影は、そのコントラストが強く、極めて明確かつ大面積にわたって観察される
【０１８４】
（１１）応力割れ試験
（１１−１）成形時の割れ
離型性の測定と同条件でコップ型成形品を１０００ショット連続成形し、成形直後に割れが発生したものを×、全く発生がしなかったものを○とした。
（１１−２）ハードコート処理後の割れ
上記（７−１）の成形で割れが発生しなかったコップ型成形品を１００個使用し、実施例に示すコーティング剤でハードコート処理を行い成形品にクラックが発生したものを×、全く発生がしなかったものを○とした。
【０１８５】
（１２）耐候性試験
最大型締め力が１４７０ｋＮの射出成形機にて、シリンダー温度３４０℃、金型温度８０℃の条件で、成形サイクル６０秒にて成形した厚さ２ｍｍの５０ｍｍ角板用いて、サンシャイン・ウェザーメーター（スガ試験機（株）製：ＷＥＬ−ＳＵＮ：ＨＣ−Ｂ）を使用し、ブラックパネル温度６３℃、湿度５０％、１８分間水噴霧と１０２分間噴霧無しの計１２０分サイクルで１０００時間処理した際の色相変化ΔＹＩ値を次式により算出した。
【０１８６】
ΔＹＩ ＝ 試験後の角板ＹＩ値 − 試験前の角板ＹＩ値
【０１８７】
（実施例１〜１１、比較例１〜９）
ビスフェノールＡとホスゲンから界面縮重合法により製造されたポリカーボネート樹脂（ＰＣ）１００重量部に、表２〜５記載の多価アルコールと脂肪族カルボン酸との各種エステル化合物（Ｂ成分）および他の添加剤（Ｃ〜Ｅ成分）を表２〜５記載の配合量で、さらにブルーイング剤（バイエル社製：マクロレックスバイオレットＢ）を０．０００２重量部配合し、ブレンダーにて混合した後、ベント式二軸押出機を用いて溶融混練しペレットを得た。ポリカーボネート樹脂に添加する添加剤はそれぞれ配合量の１０〜１００倍の濃度を目安に予めポリカーボネート樹脂との予備混合物を作成した後、ブレンダーによる全体の混合を行った。ベント式二軸押出機は（株）日本製鋼所製：ＴＥＸ３０α（完全かみ合い、同方向回転、２条ネジスクリュー）を使用した。混練ゾーンはベント口手前に１箇所のタイプとした。押出条件は吐出量２０ｋｇ／ｈ、スクリュー回転数１５０ｒｐｍ、ベントの真空度３ｋＰａであり、また押出温度は第１供給口からダイス部分まで２８０℃とし、ペレットを得た。
【０１８８】
得られたペレットを１２０℃で５時間、熱風循環式乾燥機にて乾燥した後、射出成形機を用いて、シリンダー温度３４０℃および金型温度８０℃の条件で、厚さ２ｍｍの５０ｍｍ角の角板を成形した。射出成形機はファナック（株）製：Ｔ−１５０Ｄを使用した。
【０１８９】
また、各例で得られたペレットを同様の方法で乾燥した後、シリンダー温度３２０℃および金型温度８０℃の条件で、図２に示す素通し型のヘッドランプレンズを射出成形機（住友重機械工業（株）製ＳＧ２６０Ｍ−ＨＰ）を用いて作成した。実施例の樹脂組成物から得られたヘッドランプレンズは、色相、透明性など外観が良好であった。
【０１９０】
さらに前記で得られたペレットを用いて同様に乾燥処理し、離型荷重の測定を行った。
【０１９１】
上記で得られた実施例のヘッドランプレンズを１２０℃で２時間アニール処理した後（上記評価（１０）を終了した後）、下記に示すコーティング用組成物（ｉ−１）をディップコート法により塗布し、２５℃で２０分間静置後、１２０℃で３０分間熱硬化させた。次いで該レンズ成形品に下記に示すコーティング用組成物（ｉｉ−１）をさらにディップコート法により塗布し、２５℃で２０分間静置後、１２０℃で２時間熱硬化させ、ハードコート処理を行った。得られたヘッドランプレンズを観察したところ割れの発生はなかった。
【０１９２】
表１〜５における記号表記の各成分は下記の通りである。
【０１９３】
（Ａ成分）
ＰＣ：ビスフェノールＡとホスゲンから界面縮重合法により製造された粘度平均分子量２２，５００のポリカーボネート樹脂パウダー（帝人化成（株）製：パンライトＬ−１２２５ＷＰ）
【０１９４】
（Ｂ成分）
Ｂ−１：酸価：９、ＴＧＡ５％重量減少温度：３２２℃、並びにＧＣ／ＭＳ法におけるステアリン酸成分の面積（Ｓｓ）とパルミチン酸成分の面積（Ｓｐ）との合計が全脂肪族カルボン酸成分中９４％であり、それらの面積比（Ｓｓ／Ｓｐ）が１．４４である、ペンタエリスリトールと脂肪族カルボン酸（ステアリン酸およびパルミチン酸を主成分とする）とのフルエステル（理研ビタミン（株）製：リケスターＥＷ−４００、水酸基価：６、ヨウ素価：０．４、該脂肪族カルボン酸は動物性油脂を原料とする。）
【０１９５】
Ｂ−３（比較用）：酸価：１、ＴＧＡ５％重量減少温度：３９０℃、並びにＳｓとＳｐとの合計が全脂肪族カルボン酸成分中９１％であり、それらの面積比（Ｓｓ／Ｓｐ）が１．１１である、ペンタエリスリトールと脂肪族カルボン酸（ステアリン酸およびパルミチン酸を主成分とする）とのフルエステル（コグニスジャパン（株）製：ロキシオールＶＰＧ−８６１、水酸基価：７、ヨウ素価：０、該脂肪族カルボン酸は植物性油脂を原料とする。）
【０１９６】
Ｂ−６（比較用）：酸価：２、ＴＧＡ５％重量減少温度：３７８℃、並びにＳｓとＳｐとの合計が全脂肪族カルボン酸成分中９０％であり、それらの面積比（Ｓｓ／Ｓｐ）が１．０７である、ペンタエリスリトールと脂肪族カルボン酸（ステアリン酸およびパルミチン酸を主成分とする）とのフルエステル（理研ビタミン株製：リケスターＥＷ−４４０Ａ、水酸基価：１２、ヨウ素価：０．４、該脂肪族カルボン酸は植物性油脂を原料とする。）
【０１９７】
Ｂ−７（比較用）：グリセリンモノ脂肪酸エステル（理研ビタミン株製：リケマールＳ−１００Ａ、酸価：０．８、水酸基価：３２７、ヨウ素価：１．８、およびＴＧＡ５％重量減少温度：２０５℃）
【０１９８】
Ｂ−２、Ｂ−４、およびＢ−５（比較用）：表１に示す組成割合で市販の脂肪酸フルエステルと試薬の脂肪族カルボン酸とを混合し、酸価および重量減少温度を制御した脂肪酸エステルを調整した。該調整はビーカーに脂肪酸エステルを所定量とり、８０℃に加熱して溶解し、該溶解物に所定量のステアリン酸（和光純薬（株）製、特級試薬）およびパルミチン酸（和光純薬（株）製、特級試薬）を添加し、電動ブレンダー（ブラウン社製）により混合し均一化した。前記より調整された脂肪酸フルエステルの評価項目（１）〜（３）の結果を表１に示す。
【０１９９】
Ｂ−８（比較用）：ペンタエリスリトールと前記試薬のステアリン酸とを常法により反応させて得られたペンエリスリトールテトラステアレート。かかる脂肪酸フルエステルの評価項目（１）〜（３）の結果を表１に示す。
【０２００】
【表１】

【０２０１】
（Ｃ成分の添加剤）
Ｃ１−１：ホスホナイト系熱安定剤（Ｓａｎｄｏｚ社製：サンドスタブＰ−ＥＰＱ）
Ｃ１−２：ホスファイト系熱安定剤（チバ・スペシャリティ・ケミカルズ社製：Ｉｒｇａｆｏｓ１６８）
Ｃ２−１：ヒンダードフェノール系酸化防止剤（チバ・スペシャリティ・ケミカルズ製：Ｉｒｇａｎｏｘ１０７６）
【０２０２】
（Ｄ成分の添加剤）
Ｄ−１：ベンゾトリアゾール系紫外線吸収剤（ケミプロ化成（株）製：ケミソーブ７９）
Ｄ−２：ヒドロキシフェニルトリアジン系紫外線吸収剤（チバ・スペシャリティ・ケミカルズ製：Ｔｉｎｕｖｉｎ１５７７）
Ｄ−３：環状イミノエステル系紫外線吸収剤（２，２’−ｍ−フェニレンビス（３，１−ベンゾオキサジン−４−オン）、竹本油脂（株）製：ＣＥｉ−Ｐ）
（Ｅ成分の添加剤）
Ｅ−１：クマリン系蛍光増白剤（ハッコールケミカル（株）製：ハッコールＰＳＲ）
【０２０３】
（ハードコート用組成物）
（１）コーティング用組成物（ｉ−１）
還流冷却器および撹拌装置を備え、窒素置換したフラスコ中にメチルメタクリレート（以下ＭＭＡと略称する）７０部、２−ヒドロキシエチルメタクリレート（以下ＨＥＭＡと略称する）３９部、アゾビスイソブチロニトリル（以下ＡＩＢＮと略称する）０．１８部および１，２−ジメトキシエタン２００部を添加混合し、溶解させた。次いで、窒素気流中７０℃で６時間攪拌下に反応させた。得られた反応液をｎ−ヘキサンに添加して再沈精製し、ＭＭＡ／ＨＥＭＡの組成比７０／３０（モル比）のコポリマー（アクリル樹脂（Ｉ））９０部を得た。該コポリマーの重量平均分子量はＧＰＣの測定（カラム；Ｓｈｏｄｅｘ ＧＰＣＡ−８０４、溶離液；ＴＨＦ）からポリスチレン換算で８０，０００であった。
【０２０４】
次にハードコート第１層用組成物として、前記アクリル樹脂（Ｉ）８部をメチルエチルケトン４０部、メチルイソブチルケトン２０部、エタノール５．２部、イソプロパノール１４部および２−エトキシエタノール１０部からなる混合溶媒に溶解し、次いでこの溶液にメチルトリメトキシシラン加水分解縮合物溶液（Ｘ）１０部を添加して２５℃で５分間攪拌し、さらにかかる溶液にメラミン樹脂（三井サイテック（株）製サイメル３０３）１部を添加して２５℃で５分間攪拌し、コーティング用組成物（ｉ−１）を調製した。
【０２０５】
（２）コーティング用組成物（ｉｉ−１）
上記と同様の装置を用いて、メチルトリメトキシシラン１４２部、蒸留水７２部、酢酸２０部を氷水で冷却下混合し、この混合液を２５℃で１時間攪拌し、イソプロパノール１１６部で希釈してメチルトリメトキシシラン加水分解縮合物溶液（Ｘ）３５０部を得た。一方、テトラエトキシシラン２０８部、０．０１Ｎ塩酸８１部を氷水で冷却下混合し、この混合液を２５℃で３時間攪拌し、イソプロパノール１１部で希釈してテトラエトキシシラン加水分解縮合物溶液（Ｙ）３００部を得た。
【０２０６】
さらにハードコート第２層用組成物として、水分散型コロイダルシリカ分散液（日産化学工業（株）製 スノーテックス３０ 固形分濃度３０重量％）１００部に蒸留水１２部、酢酸２０部を加えて攪拌し、この分散液に氷水浴で冷却下メチルトリメトキシシラン１３４部を加えた。この混合液を２５℃で１時間攪拌して得られた反応液に、テトラエトキシシラン加水分解縮合物溶液（Ｙ）２０部および硬化触媒として酢酸ナトリウム１部を加えイソプロパノール２００部で希釈してコーティング用組成物（ｉｉ−１）を調製した。
【０２０７】
【表２】

【０２０８】
【表３】

【０２０９】
【表４】

【０２１０】
【表５】

【０２１１】
上記表から本発明のポリカーボネート樹脂組成物は、良好な透明性、成形耐熱性、離型性、および割れ耐性、並びに低減された成形品歪みを有し、さらに好適な樹脂組成物は耐候性にも優れることが分かる。本発明のポリカーボネート樹脂組成物を用いて成形した場合、離型性が良好であることは、離型荷重および離型荷重の割合が小さいことだけでなく、成形品が型離れする際に生ずる音が小さいことからもわかる。さらに良好な離型性にも関わらず、ハードコートの密着性においても良好である。
【０２１２】
さらに実施例のペレットから成形された前記のヘッドランプレンズ成形品をＨＩＤランプ（松下電工（株）製：ＨＩＤハンディライト・プロ、白色メタルハライドランプ）を用いて照射したところ、実施例５および６からの成形品は、レンズの外周部のみが蛍光による青みの発色が観察された。すなわち、かかる成形品は特異な意匠性を有するヘッドランプレンズであった。なお、かかる照射は、レンズの凹面側から３０ｃｍ離れた距離で行い、観察はレンズの凸側の中心法線から４５°（斜め４５°）から行った。
【０２１３】
【発明の効果】
本発明によれば、良好な透明性、成形耐熱性を有し、成形品に良好な離型性、割れ耐性、低減された歪み、耐候性を付与するポリカーボネート樹脂組成物が提供される。
【０２１４】
また、本発明によれば、かかるポリカーボネート樹脂組成物から形成された、透明性、耐熱性、離型性、割れ耐性、耐候性に優れ、歪みの少ないペレットが提供される。
【０２１５】
さらに、本発明によれば、かかるポリカーボネート樹脂組成物からなる、透明性、耐熱性、離型性、割れ耐性、耐候性に優れ、歪みの少ない成形品が提供される。
【０２１６】
本発明の成形品は、透明性、耐熱性、および離型性に優れ、成形品内部の歪みが低減され、さらに割れ耐性が改善されていることから、高い品質が要求される各種の透明部材において好適である。
【０２１７】
かかる透明部材としては例えば、車両用透明部材、建設機械の窓ガラス、ビル、家屋、および温室などの窓ガラス、ガレージおよびアーケードなどの屋根、照灯用レンズ、信号機レンズ、光学機器のレンズ、ミラー、眼鏡、ゴーグル、消音壁、バイクの風防、銘板、太陽電池カバーまたは太陽電池基材、ディスプレー装置用カバー、タッチパネル、並びに遊技機（パチンコ機など）用部品（回路カバー、シャーシ、パチンコ玉搬送ガイドなど）などがある。
【０２１８】
特に本発明の成形品は、品質要求が高く大型の成形品である車両用透明部材に好適に用いられ、車両用灯具レンズ、特にヘッドランプレンズ、さらに詳しくは素通し型のヘッドランプレンズが好適に用いられる。ここで素通し型のヘッドランプレンズは、集光作用をリフレクターで行うランプのカバー、ランプユニットを一体として有するランプユニットのカバーおよびこれらに類するものを含む。
【０２１９】
したがって本発明のポリカーボネート樹脂組成物、そのペレットおよび、その成形品は、各種電子・電気機器、ＯＡ機器、車両部品、機械部品、その他農業資材、漁業資材、搬送容器、包装容器、遊戯具および雑貨などの各種分野に有用であり、その奏する産業上の利用性は格別である。
【図面の簡単な説明】
【図１】図１は、実施例において離型荷重の測定に用いられたコップ状成形品の概略図である。［１−Ａ］は、その正面図である。［１−Ｂ］は、その側面図である。成形品突き出し部とＺピン部の両方が同時に突き出されることにより、成形品が金型キャビティから離型される。成形品突き出しピンとＺピンは同一のプレートに固定され、かかるプレートをロードセル先端部が押し出すことにより、成形品の突き出しが行われる。
【図２】図２は、実施例において成形した自動車の素通し型ヘッドランプレンズの概略図である。［２−Ａ］は、その正面図（成形時のプラテン面に投影した図である。したがってかかる面積が最大投影面積となる）である。［２−Ｂ］は、そのＡ−Ａ線断面図である（該レンズはドーム状の形状である）。
【符号の説明】
図中の符号は以下の通りである。
１ コップ状成形品本体（肉厚はいずれの部分も４ｍｍ）
２ コップ状成形品内側底面部
３ コップ状成形品内周部
４ コップ状成形品上面周縁部
５ コップ状成形品突き出し部（成形品中心、直径１５ｍｍの円形）
６ ゲート（幅３ｍｍ、厚み１．５ｍｍ）
７ ランナー（径８ｍｍ、上下部は半球形、中央部は円柱形）
８ スプルー（長さ６０ｍｍ）
９ Ｚピン部（径８ｍｍ、長さ８ｍｍ）
１０ コップ状成形品高さ（２０ｍｍ）
１１ コップ状成形品底面側の直径（６３ｍｍ）
１２ コップ状成形品底面肉厚（４ｍｍ）
１３ コップ状成形品の直径（７０ｍｍ）
２１ ヘッドランプレンズ本体
２２ レンズのドーム状部分
２３ レンズの外周部分
２４ 成形品のゲート（幅３０ｍｍ、ゲート部の厚み４ｍｍ）
２５ スプルー（ゲート部の直径７ｍｍφ）
２６ レンズの外周部分の直径（２２０ｍｍ）
２７ レンズのドーム部分の直径（２００ｍｍ）
２８ レンズのドーム部分の高さ（２０ｍｍ）
２９ レンズ成形品の厚み（４ｍｍ）[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polycarbonate resin composition, pellets thereof and molded articles thereof. More specifically, it has good transparency and molding heat resistance, and gives the molded article good mold release, reduced internal strain and improved cracking resistance, preferably further weather resistance, especially for vehicle transparency The present invention relates to a polycarbonate resin composition suitable for members, pellets thereof and molded articles thereof.
[0002]
[Prior art]
Polycarbonate resins have excellent transparency, heat resistance, mechanical strength, etc., and are therefore widely used in electrical, mechanical, automotive, medical applications and the like. Polycarbonate resins are widely used in various transparent members due to the various excellent features described above. In particular, application to a transparent member for vehicles for the purpose of weight reduction has been widely attempted. Examples of such a transparent member for a vehicle include a headlamp lens, a resin window glass, a rear lamp lens, and a meter cover. These members are characterized by their complicated and large shapes and extremely high demands on the quality of the molded product.
[0003]
When these members are formed by injection molding using a polycarbonate resin composition, the following points may be problematic.
[0004]
That is, there is a problem that it is difficult to obtain a molded product having good releasability, less internal distortion, and less cracking. More specifically, when a large amount of release agent is added to give good release properties, either internal distortion or cracking of the molded product is likely to occur. On the other hand, when the release agent is reduced, the occurrence of cracks due to an increase in the release resistance increases. Such a transparent member is required to have transparency, molding heat resistance, and weather resistance.
[0005]
Here, the internal distortion of the molded article is a distortion observed as a non-uniform shadow portion in the polarizing plate observation, and is not reduced by a normal annealing process, but may be conspicuous in some cases. (For convenience, this distortion may be referred to as “distortion-2”). Strain-2 is likely to occur when the molding temperature during molding is high, the molding machine is large, and there are many staying parts.
[0006]
On the other hand, the distortion observed due to the color change of the striped pattern of the polarizing plate or the uneven density of the polarizing plate, which is well known, is a distortion that is reduced to some extent by the annealing treatment (when this distortion is referred to as “distortion-1” for convenience). There is). The main component of the strain-1 is strain of individual polymer molecular chains caused by thermal stress or the like.
[0007]
Since the strain-1 is a cause of cracks during the hard coat treatment and in the long-term characteristics, reduction thereof is required. Although distortion-2 does not cause problems such as visibility when used under natural light such as a window glass, reduction thereof may be required. The reason for this will be described later.
[0008]
Further, in many cases, the vehicle transparent member is subjected to a surface treatment such as a hard coat treatment. However, cracks may occur in the molded product in the hard coat treatment. Such cracking of the molded product occurs even if annealing is performed before the hard coat treatment. Therefore, it is considered that some factor of the polycarbonate resin composition promotes the occurrence of cracking of the molded product at the time of molding and annealing, but this factor is reduced to reduce the resistance to cracking of the molded product (hereinafter simply referred to as “crack resistance”). Need to be improved).
[0009]
As described above, the transparent member for vehicles has good transparency and molding heat resistance, and the molded article has good release properties, reduced internal strain and improved crack resistance, preferably further weather resistance. There is a need for a polycarbonate resin composition to be imparted.
[0010]
As described above, the manufacture of a transparent member for a vehicle, particularly a large member, has characteristics different from the manufacture of an optical disk substrate which is a typical optical molded product of polycarbonate resin. The production of an optical disk substrate is a molding that requires a very high processing temperature, but on the other hand, it is a molding with a very short molding cycle and a simple shape (a constant thickness and a resin flow is not complicated). From this point, the resin composition is required to have different characteristics from those of the optical disk substrate.
[0011]
Conventionally, a method of blending a fatty acid ester is widely known as a method for improving the mold releasability of a polycarbonate resin, and among them, glycerin monostearate is often used. However, in the polycarbonate resin composition to which glycerin monostearate was added, the strain-2 was clearly observed, and it could not be said that the crack resistance was sufficient.
[0012]
As release agents used for polycarbonate resins, full esters of aliphatic polyhydric alcohols and aliphatic carboxylic acids such as pentaerythritol tetrastearate are also widely known. Various proposals have been made for the purpose of further improving the quality of the polycarbonate resin composition to which the full ester is added. Hereinafter, a full ester of an aliphatic polyhydric alcohol and an aliphatic carboxylic acid may be simply referred to as “fatty acid full ester”.
[0013]
A polycarbonate resin composition containing an ester of pentaerythritol in which an OH group content and an acid value of an ester compound are extremely reduced is disclosed as a release agent (Patent Document 1).
[0014]
Further, a polycarbonate resin comprising a polycarbonate resin and an internal mold release agent having an acid value of 0.6 to 1.6 of 90% or more of full ester, an iodine value of 0.1 to 1.3, and a metal element Sn content of 5 to 300 ppm. A composition is disclosed (Patent Document 2).
[0015]
[Patent Document 1]
JP-A-2-69556
[Patent Document 2]
JP 2001-192543 A
[0016]
[Problems to be solved by the invention]
The present invention has good transparency and molding heat resistance, and gives the molded article good mold release, reduced internal strain, and improved crack resistance, preferably further weather resistance, especially for vehicles. Another object of the present invention is to provide a polycarbonate resin composition suitable for a transparent member, a pellet thereof and a molded product thereof.
[0017]
The present inventors diligently studied to solve the above problems.
[0018]
1stly, since the said subject exists in the point which the mold release property provided with a mold release agent and another characteristic are incompatible, the present inventors examined the kind of mold release agent as one of the solution factors. .
[0019]
Second, the cause of cracking was examined. As a result, it was speculated that cracks during molding may cause solvent cracks due to the additive components such as the release agent partially remaining on the mold surface coming into contact with the high-temperature molded product during molding. . In particular, it was found that cracks are likely to occur on the edge side of the molded product because the distortion tends to increase and the release agent and the like are easily deposited. In addition, it is considered that the main cause of cracking in the hard coat treatment after annealing is that the residual stress is not completely removed by the annealing treatment. The possibility of deterioration was also considered. Therefore, the conclusion that the kind of release agent is important also in this point was obtained.
[0020]
Thirdly, the cause of distortion-2 was examined. As a result, the following conclusions were reached. In injection molding, the resin flows into the mold by fountain flow, and the resin that flows in later is filled in such a manner as to push the already-flowed resin. For example, when observed from the cross section, a state in which the fluidized layers of the resin are overlapped is observed. In an injection molded product having such properties, if uneven frictional force is generated between the fluidized layers, the flow of the resin is disturbed, resulting in a large difference in the density between the fluidized layers, or vortices that cause the upper and lower layers to rise and fall. A case of reverse rotation occurs. It has been found that such a state is observed as a non-uniform shadow portion in the above polarizing plate observation. That is, it can be said that the uneven shadow is distortion of the fluidized bed of the resin. It has also been found that such strain-2 is likely to occur when the thermal load of the resin is excessive. Therefore, it was speculated that the decomposition product was gasified as a cause of uneven frictional force between the fluidized layers. Furthermore, as the strain-2 is observed more severely, a slight increase in residence time may cause defects such as silver generation, discoloration, and internal clouding (white haze) in the molded product. found. That is, it can be said that the resin composition with less strain-2 hardly causes molding defects and can be widely applied to various molded products. Moreover, when long-term characteristics are taken into consideration, those with less distortion than those with much distortion are preferably obtained. In particular, distortion-2 is often regarded as a drawback when replacing glass products, when applied to optical products, and when applied to automotive parts. For the above reasons, there is a case where reduction of distortion-2 is required.
[0021]
Therefore, it has been concluded that in order to improve the strain-2, it is necessary to add an additive that smoothes the flow of the resin and hardly generates gas or decomposition products. The release agent is considered to have an effect of smoothing the flow of the resin, and therefore, it was considered important to contain a release agent that hardly generates gas and decomposition products.
[0022]
As a result of further intensive studies under the above-described studies, the present inventors have found that a resin composition containing a specific amount of a specific fatty acid full ester in a polycarbonate resin can solve the above-mentioned problems, and completes the present invention. It came to.
[0023]
[Means for Solving the Problems]
  The present invention relates to a full ester (component B) of 4 to 8 valent aliphatic polyhydric alcohol having 5 to 30 carbon atoms and aliphatic carboxylic acid having 10 to 22 carbon atoms with respect to 100 parts by weight of the polycarbonate resin (component A). ) 0.005 to 2 parts by weightand
0.0005 to 1 part by weight of at least one stabilizer (C component) selected from the group consisting of a phosphorus stabilizer (C1 component) and a hindered phenol antioxidant (C2 component)A resin composition comprising:
  The aliphatic carboxylic acid of component B contains a palmitic acid component and a stearic acid component, and the peak area in the gas chromatograph-mass spectrometry (GC / MS method) shows the area (Sp) of the palmitic acid component and stearic acid. The total of the component area (Ss) is 80% or more of the total aliphatic carboxylic acid component, and the area ratio (Ss / Sp) of both is 1.3 to 30,
  The component B is a polycarbonate resin composition having a 5% weight loss temperature in TGA (thermogravimetric analysis) of 250 to 360 ° C. and an acid value of 4 to 20.
[0025]
The component B preferably has a 5% weight loss temperature of 280 to 360 ° C. in TGA (thermogravimetric analysis). The component B preferably has an acid value of 4-18. The area ratio (Ss / Sp) is preferably 1.3 to 10. The aliphatic polyhydric alcohol preferably has 5 to 10 carbon atoms. The aliphatic polyhydric alcohol is preferably pentaerythritol and / or dipentaerythritol. The component B preferably has a hydroxyl value in the range of 0.1-30. The component B preferably has an iodine value of 10 or less. 0.0005 to 1 weight of at least one stabilizer (C component) selected from the group consisting of a phosphorus stabilizer (C1 component) and a hindered phenol antioxidant (C2 component) with respect to 100 parts by weight of component A It is preferable to blend parts. It is preferable to blend 0.0005 to 3 parts by weight of an ultraviolet absorber (component D) with respect to 100 parts by weight of the component A. It is preferable to blend 0.0001-3 parts by weight of a brightening agent (E component) with respect to 100 parts by weight of the component A. The polycarbonate resin composition is a composition having a smooth plate having a thickness of 2 mm having an arithmetic average roughness (Ra) of 0.03 μm and a haze value in the range of 0.1 to 1%, and substantially free of filler. It is preferable that
[0026]
The present invention relates to 100 parts by weight of a polycarbonate resin (component A) and a full ester (component B) of a 4 to 8 valent aliphatic polyhydric alcohol having 5 to 30 carbon atoms and an aliphatic carboxylic acid having 10 to 22 carbon atoms. A resin composition comprising 0.005 to 2 parts by weight of the number of moles of carboxyl groups (Ff) of the free aliphatic carboxylic acid in the composition and the number of moles of ester bonds (Fe) of the B component A polycarbonate resin composition having a ratio (Ff: Fe) in the range of 8:92 to 30:70 is included.
[0027]
The aliphatic carboxylic acid constituting the B component includes a palmitic acid component and a stearic acid component, and the peak area in the gas chromatograph-mass spectrometry (GC / MS method) of the palmitic acid component area (Sp) The total with the stearic acid component (Ss) is preferably 80% or more of the total aliphatic carboxylic acid component, and the area ratio (Ss / Sp) of both is preferably 1.3-30. 0.0005 to 1 weight of at least one stabilizer (C component) selected from the group consisting of a phosphorus stabilizer (C1 component) and a hindered phenol antioxidant (C2 component) with respect to 100 parts by weight of component A It is preferable to contain a part. It is preferable to contain 0.0005-3 weight part of ultraviolet absorbers (D component) with respect to 100 weight part of this A component. It is preferable to contain 0.0001-3 weight part of fluorescent whitening agents (E component) with respect to 100 weight part of this A component.
[0028]
The present invention also relates to 100 parts by weight of a polycarbonate resin (component A) and a full ester (component B) of a 4 to 8 valent aliphatic polyhydric alcohol having 5 to 30 carbon atoms and an aliphatic carboxylic acid having 10 to 22 carbon atoms. ) Pellets formed from a resin composition comprising 0.005 to 2 parts by weight,
The release load in the method for measuring the release load of the pellet is obtained by changing pentaerythritol tetrastearate having an acid value of 0.8 and a 5% weight loss temperature of 396 ° C. in TGA (thermogravimetric analysis) to the component A. The pellet formed from the polycarbonate resin composition which satisfies that it is 85% or less with respect to the mold release load in the same measuring method of the pellet formed from the resin composition formed by mix | blending the same quantity as a component is included.
[0029]
The molar ratio (Ff: Fe) of the number of moles of carboxyl groups (Ff) of the free aliphatic carboxylic acid in the pellets to the number of moles of ester bonds (Fe) of the B component is in the range of 10:90 to 30:70. Preferably there is. The aliphatic polyhydric alcohol is preferably pentaerythritol. The aliphatic carboxylic acid constituting the B component includes a palmitic acid component and a stearic acid component, and the peak area in the gas chromatograph-mass spectrometry (GC / MS method) of the palmitic acid component area (Sp) The total with the stearic acid component (Ss) is preferably 80% or more of the total aliphatic carboxylic acid component, and the area ratio (Ss / Sp) of both is preferably 1.3-30. In the pellet, a smooth flat plate having a thickness of 2 mm having an arithmetic average roughness (Ra) of 0.03 μm formed therefrom exhibits a haze value in the range of 0.1 to 1%, and is substantially free of filler. preferable.
[0030]
The present invention includes a molded article comprising the polycarbonate resin composition. Moreover, this invention includes the molded article shape | molded from the said pellet. The molded article is preferably subjected to a hard coat treatment on the surface thereof. The molded article is preferably a transparent member for vehicles. The vehicle transparent member is preferably a vehicle lamp lens.
[0031]
DETAILED DESCRIPTION OF THE INVENTION
The details of the present invention will be further described below.
[0032]
(First aspect)
In the first aspect of the present invention, a 4- to 8-valent aliphatic polyhydric alcohol and an aliphatic carboxylic acid having 10 to 22 carbon atoms are added to 100 parts by weight of the polycarbonate resin (component A). A resin composition comprising 0.005 to 2 parts by weight of a full ester (B component), wherein the B component has a 5% weight loss temperature of 250 to 360 ° C. in TGA (thermogravimetric analysis), And it is a polycarbonate resin composition characterized by the acid value being 4-20.
[0033]
(Polycarbonate resin: Component A)
The polycarbonate resin used as the component A in the present invention is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the reaction method include an interfacial polymerization method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.
[0034]
Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl). ) Propane (commonly called bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl)- 1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) Pentane, 4,4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′-(m-phenylenediisopropyl Pyridene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (3,5 -Dibromo-4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) ) Fluorene and the like. The polycarbonate resin of the present invention can be selected from either a homopolymer of the above dihydric phenol and a copolymer composed of two or more dihydric phenols.
[0035]
Among them, bis (4-hydroxyphenyl) alkane homopolymers such as bisphenol A, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, bis (4-hydroxyphenyl) alkane (bisphenol) A), 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, and α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene, 9,9-bis (4- A copolymer composed of two or more dihydric phenols selected from hydroxy-3-methylphenyl) fluorene is preferably used, and a bisphenol A homopolymer is particularly preferable.
[0036]
As the carbonate precursor, carbonyl halide, carbonic acid diester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.
[0037]
In producing polycarbonate resin from the above dihydric phenol and carbonate precursor by various polymerization methods, a catalyst, a terminal terminator, an antioxidant for preventing the dihydric phenol from being oxidized, etc., as necessary. May be used. The polycarbonate resin of the present invention is a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. A copolymer polycarbonate resin copolymerized with a bifunctional alcohol (including an alicyclic group), and a polyester carbonate resin copolymerized with the bifunctional carboxylic acid and the bifunctional alcohol together. Moreover, the mixture which mixed 2 or more types of the obtained polycarbonate resin may be sufficient.
[0038]
Examples of trifunctional or higher polyfunctional aromatic compounds include 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane. Can be used.
[0039]
When a polyfunctional compound that produces a branched polycarbonate is included, the ratio is 0.001-1 mol%, preferably 0.005-0.9 mol%, particularly preferably 0.01-0, based on the total amount of the aromatic polycarbonate. 0.8 mol%. In particular, in the case of the melt transesterification method, a branched structure may occur as a side reaction. The amount of the branched structure is also 0.001 to 1 mol%, preferably 0.005 to 0.005% in the total amount of the aromatic polycarbonate. Those having 9 mol%, particularly preferably 0.01 to 0.8 mol% are preferred. In addition, about this ratio¹It is possible to calculate by H-NMR measurement.
[0040]
The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of the aliphatic difunctional carboxylic acid include sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid and other straight-chain saturated aliphatic dicarboxylic acids, and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.
[0041]
Further, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can also be used.
[0042]
The reaction by the interfacial polymerization method is usually a reaction between a dihydric phenol and phosgene, and is reacted in the presence of an acid binder and an organic solvent. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and pyridine.
[0043]
As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used.
[0044]
In addition, catalysts such as tertiary amines and quaternary ammonium salts can be used for promoting the reaction, and monofunctional phenols such as phenol, p-tert-butylphenol, p-cumylphenol, etc. as molecular weight regulators. Are preferably used. Furthermore, examples of monofunctional phenols include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, and triacontylphenol. These monofunctional phenols having a relatively long chain alkyl group are effective when improvement in fluidity and hydrolysis resistance is required.
[0045]
The reaction temperature is usually 0 to 40 ° C., the reaction time is several minutes to 5 hours, and the pH during the reaction is preferably kept at 10 or higher.
[0046]
The reaction by the melting method is usually a transesterification reaction between a dihydric phenol and a carbonic acid diester, and the dihydric phenol and the carbonic acid diester are mixed in the presence of an inert gas and reacted at 120 to 350 ° C. under reduced pressure. The degree of vacuum is changed stepwise, and finally the phenols produced at 133 Pa or less are removed from the system. The reaction time is usually about 1 to 4 hours.
[0047]
Examples of the carbonic acid diester include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Among them, diphenyl carbonate is preferable.
[0048]
A polymerization catalyst can be used to accelerate the polymerization rate. Examples of the polymerization catalyst include alkali metal and alkaline earth metal hydroxides such as sodium hydroxide and potassium hydroxide, boron and aluminum hydroxides, Alkali metal salt, alkaline earth metal salt, quaternary ammonium salt, alkoxide of alkali metal or alkaline earth metal, organic acid salt of alkali metal or alkaline earth metal, zinc compound, boron compound, silicon compound, germanium compound, Examples thereof include catalysts usually used for esterification and transesterification of organic tin compounds, lead compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds and the like. A catalyst may be used independently and may be used in combination of 2 or more types. The amount of these polymerization catalysts used is preferably 1 × 10 with respect to 1 mol of dihydric phenol as a raw material.^-8~ 1x10^-3Equivalent weight, more preferably 1 × 10^-7~ 5x10^-FourIt is selected in the range of equivalents.
[0049]
In the polymerization reaction, in order to reduce phenolic end groups, for example, 2-chlorophenyl phenyl carbonate, 2-methoxycarbonylphenyl phenyl carbonate, 2-ethoxycarbonylphenyl phenyl carbonate, etc. Compounds can be added.
[0050]
Further, in the melt transesterification method, it is preferable to use a deactivator that neutralizes the activity of the catalyst. The amount of the deactivator is preferably 0.5 to 50 mol with respect to 1 mol of the remaining catalyst. Further, it is used in a proportion of 0.01 to 500 ppm, more preferably 0.01 to 300 ppm, and particularly preferably 0.01 to 100 ppm with respect to the aromatic polycarbonate after polymerization. Preferred examples of the deactivator include phosphonium salts such as tetrabutylphosphonium dodecylbenzenesulfonate and ammonium salts such as tetraethylammonium dodecylbenzyl sulfate.
[0051]
The details of reaction formats other than those described above are also well known in books and patent publications.
[0052]
The molecular weight of the polycarbonate resin is preferably 10,000 to 100,000, more preferably 15,000 to 30,000, still more preferably 17,000 to 27,000, and particularly preferably 18,000 to 25,000. When a polycarbonate resin having such a viscosity average molecular weight is used, the resin composition of the present invention has sufficient strength and good melt fluidity during molding. Such good melt fluidity is preferable because it enables further reduction of molding strain. Moreover, when it is in the above range, resistance to secondary processing such as hard coat treatment is sufficient. The polycarbonate resin may be obtained by mixing those having a viscosity average molecular weight outside the above range.
[0053]
The viscosity average molecular weight (M) of the polycarbonate resin was a specific viscosity (η determined at 20 ° C. from a solution of 0.7 g of the polycarbonate resin in 100 ml of methylene chloride._sp) Is inserted into the following equation.
[0054]
η_sp/C=[η]+0.45×[η]²c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10^-FourM^0.83
c = 0.7
[0055]
Examples of the polycarbonate resin according to the present invention include the following. That is, it consists of an aromatic polycarbonate (PC1) having a viscosity average molecular weight of 70,000 to 300,000 and an aromatic polycarbonate (PC2) having a viscosity average molecular weight of 10,000 to 30,000, and the viscosity average molecular weight is 15,000 to An aromatic polycarbonate having a viscosity of 40,000, preferably 20,000 to 30,000 (hereinafter sometimes referred to as “high molecular weight component-containing aromatic polycarbonate”) can also be used.
[0056]
Such a high molecular weight component-containing aromatic polycarbonate increases the entropy elasticity of the polymer due to the presence of PC1, and is more advantageous at the time of injection press molding suitably used in the case of a large-sized molded product. For example, appearance defects such as hesitation marks can be further reduced, and the condition range of injection press molding can be expanded accordingly. On the other hand, the low molecular weight component of the PC2 component lowers the overall melt viscosity, promotes relaxation of the resin, and enables molding with lower strain. A similar effect is also observed in a polycarbonate resin containing a branched component.
[0057]
(Fatty acid full ester: B component)
The B component used in the present invention is a full ester of a 4 to 8 valent aliphatic polyhydric alcohol having 5 to 30 carbon atoms and an aliphatic carboxylic acid having 10 to 22 carbon atoms, and the B component is TGA ( The 5% weight loss temperature in thermogravimetric analysis) is 250 to 360 ° C., and the acid value thereof is 4 to 20. In the present invention, the full ester does not necessarily have an esterification rate of 100%, but may be 80% or more, and preferably 85% or more.
[0058]
(TGA)
In the present invention, the 5% weight loss temperature (hereinafter sometimes simply referred to as “weight reduction temperature”) in TGA (thermogravimetric analysis) measurement of B component satisfies 250 to 360 ° C. It has been found that it is possible to reduce the mold release force (improving mold release properties). Moreover, a full ester satisfying such conditions is excellent in crack resistance. When the weight reduction temperature exceeds 360 ° C., it is difficult to reduce the release force. Further, if the weight reduction temperature is too low, the heat resistance is insufficient, which may cause discoloration or a decrease in cracking resistance, and therefore it is preferably 250 ° C. or higher. The range of the weight reduction temperature is more preferably 280 to 360 ° C, further preferably 300 to 350 ° C, particularly preferably 310 to 340 ° C.
[0059]
The weight reduction temperature is determined as a temperature at which a 5% weight reduction is observed in a measurement condition in which the temperature is increased from 23 ° C. in a nitrogen gas atmosphere to 600 ° C. at a temperature increase rate of 20 ° C./min.
[0060]
(Acid value)
Furthermore, the present invention satisfies the range where the acid value of the component B is in the range of 4 to 20, thereby reducing the release force (improving the release property) more than that of the conventional full ester, and the distortion (particularly strain − in the molded product). It has been found that the reduction in 2) and the improvement of crack resistance can be achieved. If the acid value is less than 4, it is difficult to reduce the releasing force, and those having an acid value exceeding 20 are not preferable in terms of thermal stability. The acid value is more preferably in the range of 4 to 18, and further preferably in the range of 5 to 15. In the fatty acid full ester which is the B component used in the present invention, an acid component such as a free fatty acid is present in an amount corresponding to the acid value. Here, the acid value is the number of mg of potassium hydroxide required to neutralize free fatty acids contained in 1 g of the sample, and can be determined by the method defined in JIS K 0070.
[0061]
The reason why the fatty acid full ester satisfying the above conditions can reduce the releasing force (improving the releasing property), reduce the distortion inside the molded product and improve the cracking resistance is not clear, but it is considered as follows. It is done. When the weight reduction temperature is in the range corresponding to the melt processing temperature of the polycarbonate resin of 360 ° C. or less, the aliphatic full ester has good heat resistance but produces a certain amount of volatile matter. It is considered that the volatile matter is gasified at the time of the molding process, so that it tends to be biased toward the tip of the fountain flow generated when the resin mold is filled, and as a result, it is biased at a high concentration on the molded product surface. Thereby, the further improvement of mold release property is achieved. The object to be measured by the acid value is mainly unreacted free carboxylic acid, which is easily gasified at the time of molding processing due to its relatively low molecular weight. It is thought that it contributes to improvement of moldability. Therefore, there is a certain degree of correlation between the acid value and the weight loss temperature. (If the fatty acid full esters of the same species are compared, the weight reduction temperature decreases as the acid value increases).
[0062]
On the other hand, the gasification component can cause non-uniform frictional forces between the resin flow layers, thus increasing the strain-2. However, since the present invention is a full ester, the slipperiness between polycarbonate molecules is improved as compared with half esters and the like. Accordingly, even when the resin flow inside the mold becomes complicated, the resin flow becomes smooth, and it is considered that the distortion (strain-2) inside the molded product is reduced due to the superior effect. That is, when the intermolecular frictional force is high, locally generated nonuniform frictional force disturbs the flow of the resin, but when the overall frictional force is low, it is expected that the influence is difficult to occur. Furthermore, it is presumed that the reason why the distortion due to the disturbance of the resin flow does not increase is that the ratio of the volatile matter is moderate and the component does not increase in a chain like the cracked gas.
[0063]
In addition, the component B is a full ester, which has a good chemical resistance itself, and is weak in attacking the polycarbonate resin. This is considered to improve the cracking resistance of the molded product. In addition, the above-mentioned effects, particularly the effect of reducing the aggressiveness to the polycarbonate resin and suppressing the deterioration of the polycarbonate resin, are considered to be more effective when used in combination with a phosphorus stabilizer and a hindered phenol antioxidant described later. It is done.
[0064]
As described above, it is possible to improve the release force by allowing a certain amount of gasification component to move to the surface, and the preferred embodiment of the present invention is a mixture of various components in a complicated manner. Therefore, it is extremely reasonable to specify the constitution of the present invention by the weight reduction temperature and acid value of the fatty acid full ester (component B).
[0065]
As mentioned above, the fatty acid full ester of component B referred to in the present invention is a generic term for not only the ester compound itself but also a mixture of the compound and a free aliphatic carboxylic acid compound. Further, by utilizing the fact that the value of the acid value and the weight reduction temperature varies depending on the ratio of the free aliphatic carboxylic acid as described above, an aliphatic carboxylic acid is separately added to the fatty acid full ester having a low acid value or a high weight reduction temperature. It is also possible to adjust the fatty acid ester having the target acid value and weight reduction temperature by adding. Similarly, it is possible to prepare a fatty acid full ester satisfying the conditions of the present invention by mixing two or more fatty acid esters having different acid values and weight reduction temperatures.
[0066]
(Method for producing fatty acid full ester)
The manufacturing method of said specific fatty acid full ester is not specifically limited, Conventionally well-known various methods can be utilized for aliphatic polyhydric alcohol and aliphatic carboxylic acid. In addition, in order to satisfy the specific conditions of the present invention, a slight excess of aliphatic carboxylic acid is required rather than a theoretical equivalent of aliphatic polyhydric alcohol and aliphatic carboxylic acid to complete the reaction over a sufficient period of time. It is preferable to react with an acid and complete the reaction at a relatively early stage.
[0067]
Examples of the reaction catalyst include organic tin compounds such as sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, calcium oxide, barium oxide, magnesium oxide, zinc oxide, sodium carbonate, potassium carbonate, and 2-ethylhexyltin. Is mentioned.
[0068]
(Aliphatic polyhydric alcohol)
The polyhydric alcohol used for the B component is an aliphatic polyhydric alcohol having 4 to 8 valences and 5 to 30 carbon atoms. The valence of the aliphatic polyvalent alcohol is preferably 4-6, and the number of carbon atoms is preferably 5-12, more preferably 5-10. The aliphatic polyvalent alcohol may contain an ether bond in the carbon chain. Specific examples of the aliphatic polyhydric alcohol include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. And dipentaerythritol are preferable, and pentaerythritol is particularly preferable.
[0069]
(Aliphatic carboxylic acid)
Examples of the aliphatic carboxylic acid having 10 to 22 carbon atoms used for the component B include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, and octadecane. Saturated aliphatic carboxylic acids such as acids (stearic acid), nonadecanoic acid, icosanoic acid, and docosanoic acid, and unsaturateds such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetoleic acid Mention may be made of aliphatic carboxylic acids.
[0070]
Among the above, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferable. Of these, saturated aliphatic carboxylic acids are preferred. In particular, stearic acid and palmitic acid are preferred.
[0071]
Aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from natural fats and oils such as animal fats (such as beef tallow and pork fat) and vegetable fats (such as palm oil). Accordingly, an aliphatic carboxylic acid such as stearic acid is usually a mixture containing other carboxylic acid components having different numbers of carbon atoms. In the production of the component B of the present invention, stearic acid and palmitic acid which are produced from such natural oils and fats and are in the form of a mixture containing other carboxylic acid components are preferably used. The preferable aspect of the composition ratio of each component in this mixture is as follows.
[0072]
(Ss / Sp)
That is, the aliphatic carboxylic acid constituting the B component contains a palmitic acid component and a stearic acid component, and the peak area in the pyrolysis methylated GC / MS (gas chromatography-mass spectrometry) method is the area of the palmitic acid component ( The total of Sp) and the area (Ss) of the stearic acid component is preferably 80% or more of the total aliphatic carboxylic acid, and the area ratio (Ss / Sp) of both is 1.3 to 30.
[0073]
Here, pyrolysis methylation GC / MS method means that a fatty acid full ester as a sample and a reaction reagent methyl ammonium hydroxide are reacted on a pyrofil to decompose the fatty acid full ester and produce a methyl ester derivative of the fatty acid. This is a method of performing GC / MS measurement on such a derivative.
[0074]
The total of Sp and Ss is preferably 85% or more, more preferably 90% or more, and still more preferably 91% or more in the total aliphatic carboxylic acid component. On the other hand, the total of Sp and Ss can be set to 100%, but is preferably 98% or less and more preferably 96% or less from the viewpoint of manufacturing cost. Moreover, said area ratio (Ss / Sp) has the preferable range of 1.3-30. The range of 1.3-10 is more preferable, the range of 1.3-4 is further more preferable, and the range of 1.3-3 is particularly preferable. These mixing ratios need not be satisfied with a single aliphatic carboxylic acid, but may be satisfied by mixing two or more aliphatic carboxylic acids.
[0075]
Examples of the fats and oils that can be used as the raw material for the aliphatic carboxylic acid satisfying the above mixing ratio include animal fats and oils such as beef tallow and lard, and linseed oil, safflower oil, sunflower oil, soybean oil, corn oil, and peanut oil. And vegetable oils such as cottonseed oil, sesame oil, and olive oil. Among these, animal fats and oils are preferable in view of containing more stearic acid, and beef tallow is more preferable. Furthermore, among the beef tallow, oleostearin containing a lot of saturated components such as stearic acid and palmitic acid is preferable.
[0076]
(Hydroxyl value)
The hydroxyl value of the component B is preferably low from the viewpoints of thermal stability, mold release force reduction and crack resistance, while too low is not preferable because the cost increases due to an increase in production time. The range of 0.1-30 is suitable for the hydroxyl value of B component, the range of 1-30 is preferable, and the range of 2-20 is more preferable. Here, the hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated, and can be determined by the method defined in JIS K 0070. .
[0077]
(Iodine number)
In the B component of the present invention, the iodine value is preferably low from the viewpoint of thermal stability. The iodine value of the component B is preferably 10 or less, and more preferably 1 or less. The iodine value is an amount obtained by converting the amount of halogen to be bonded to the number of g of iodine when halogen is reacted with 100 g of a sample, and can be obtained by a method defined in JIS K0070.
[0078]
Furthermore, the polycarbonate resin composition of the present invention has an effect of reducing a small amount of carbide generated in the molded product. Since such carbides scatter light depending on the intensity of the light source and the angle of light, they may be observed as white bands (white haze) in the molded product. Also in this respect, the polycarbonate resin composition of the present invention has suitable characteristics.
[0079]
The compounding quantity of the fatty acid full ester of B component is 0.005-2 weight part with respect to 100 weight part of polycarbonate resin (A component), 0.01-1 weight part is preferable, 0.05-0.5 Part by weight is more preferred. When the fatty acid full ester of component B exceeds the above range and is too small, the releasability is not sufficiently improved and the cracking resistance is also lowered. On the other hand, when the amount of the fatty acid full ester of component B exceeds the above range, the transparency of the molded product is impaired, and the cracking resistance may also be decreased due to a decrease in molding heat resistance.
[0080]
(Phosphorus stabilizer: C1 component)
Examples of phosphorus stabilizers (C1 component) that are one of the C components include those already known as heat stabilizers for polycarbonate resins, such as phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Is done.
[0081]
Examples of the phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl Monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris (diethylphenyl) phos Phyto, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite Ite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6 -Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, Examples thereof include bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, and the like.
[0082]
Still other phosphite compounds that react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite 2,2′-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite.
[0083]
Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.
[0084]
Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)- More preferred is phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.
[0085]
Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.
[0086]
The phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, phosphite compounds or phosphonite compounds are preferable. In particular, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite and bis (2,4-di-) tert-Butylphenyl) -phenyl-phenylphosphonite is preferred. A combination of these and a phosphate compound is also a preferred embodiment.
[0087]
(Hindered phenolic antioxidant: C2 component)
As a hindered phenolic antioxidant (C2 component) which is one of the C components used in the present invention, an antioxidant applicable to various resins and the like can be used. Examples of the hindered phenol antioxidant include α-tocopherol, butylhydroxytoluene, sinapy alcohol, vitamin E, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel). ) Propionate, 2-tert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- ( N, N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2 ′ -Methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-methyle Bis (2,6-di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol) ) 2,2′-ethylidene-bis (4,6-di-tert-butylphenol), 2,2′-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3- Methyl-6-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6 (3-tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4′-thiobis (6-tert-butyl-m-cresol), 4,4 ′ -Thiobis (3-methyl-6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide 4,4′-di-thiobis (2,6-di-tert-butylphenol), 4,4′-tri-thiobis (2,6-di-tert-butylphenol) Nol), 2,2-thiodiethylenebis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy -3 ′, 5′-di-tert-butylanilino) -1,3,5-triazine, N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butyl Phenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl) 4-hydroxyphenyl) isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, and tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl) propionate] methane and the like. All of these are readily available. The said hindered phenolic antioxidant can be used individually or in combination of 2 or more types.
[0088]
The stabilizer for component C is preferably added in an amount of 0.0005 to 1 part by weight per 100 parts by weight of component A. More preferably, the C component is 0.001 to 0.5 parts by weight, even more preferably 0.005 to 0.3 parts by weight, and particularly preferably 0.01 to 0 parts by weight per 100 parts by weight of the A component. .2 parts by weight.
[0089]
More preferably, the C component contains both the C1 component phosphorus stabilizer and the C2 component hindered phenol antioxidant. Therefore, the C1 component is 0.0002 to 0.4 parts by weight and the C2 component is 0.0002 to 0.8 parts by weight with respect to 100 parts by weight of the A component, and the total of the C1 component and the C2 component is 0.0005 to 1 part by weight is preferable, the C1 component is 0.0005 to 0.3 part by weight and the C2 component is 0.0005 to 0.6 part by weight, and the total is 0.001 to 0.5 part by weight. More preferably, the C1 component is 0.002 to 0.2 parts by weight, the C2 component is 0.002 to 0.4 parts by weight, and the total is 0.005 to 0.3 parts by weight. More preferably, the C1 component is 0.005 to 0.1 parts by weight, the C2 component is 0.005 to 0.15 parts by weight, and the total is particularly preferably 0.01 to 0.2 parts by weight.
[0090]
(Ultraviolet absorber: D component)
The polycarbonate resin composition of the present invention is suitable for a transparent member for vehicles such as a headlamp lens, a resin window glass, a rear lamp lens, and a meter cover. Since such a member is required to have weather resistance, the polycarbonate resin of the present invention is preferably formed by further blending an ultraviolet absorber (component D).
[0091]
Specific examples of the ultraviolet absorber for component D of the present invention include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-benzophenone, Hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxy Benzophenone, bis (5-benzoyl-4 Hydroxy-2-methoxyphenyl) methane, 2-hydroxy -4-n-dodecyloxy benzoin phenone, and 2-hydroxy-4-methoxy-2'-carboxy benzophenone may be exemplified.
[0092]
Specific examples of the ultraviolet absorber include, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole in the benzotriazole series. 2- (2-hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′- Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) ) Benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazol 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5- tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p -Phenylenebis (1,3-benzoxazin-4-one), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2'-Hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and co-polymerized with the monomer 2 such as a copolymer with a possible vinyl monomer and a copolymer of 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole with a vinyl monomer copolymerizable with the monomer Examples include polymers having a -hydroxyphenyl-2H-benzotriazole skeleton.
[0093]
Specifically, the ultraviolet absorber is, for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4, 4-hydroxyphenyltriazine). 6-diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxyphenol 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) ) -5-butyloxyphenol and the like. Furthermore, the phenyl group of the above exemplary compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. Examples of the compound are phenyl groups.
[0094]
Furthermore, as an ultraviolet absorber, the cyclic imino ester type compound shown by following formula (1) can be mentioned.
[0095]
[Chemical 1]

[0096]
(In the formula, Ar is a residue obtained by extracting two hydrogen groups on the aromatic ring of an aromatic hydrocarbon having 6 to 12 carbon atoms, and may contain a hetero atom. N represents 0 or 1. )
[0097]
Examples of the compound of the above formula (1) include 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2′-m-phenylenebis (3,1-benzoxazine- 4-one), and 2,2′-p, p′-diphenylenebis (3,1-benzoxazin-4-one).
[0098]
Furthermore, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that the ultraviolet absorbent monomer and / or the light stable monomer and a single amount of alkyl (meth) acrylate or the like can be obtained. It may be a polymer type ultraviolet absorber copolymerized with a body. Preferred examples of the ultraviolet absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, and a cyclic imino ester skeleton in the ester substituent of (meth) acrylic acid ester.
[0099]
Among these, benzotriazole and hydroxyphenyltriazine are preferable, and benzotriazole is particularly preferable for a headlamp lens. You may use the said ultraviolet absorber individually or in mixture of 2 or more types.
[0100]
The blending amount of the ultraviolet absorber is preferably 0.0005 to 3 parts by weight, more preferably 0.01 to 2 parts by weight, still more preferably 0.02 to 1 part by weight with respect to 100 parts by weight of the polycarbonate resin. 05 to 0.5 parts by weight are particularly preferred.
[0101]
(Fluorescent brightener: E component)
Examples of the fluorescent brightening agent for component E include coumarin-based, naphthalimide-based, and benzoxazolyl-based fluorescent brighteners. Among them, coumarin-based fluorescent brighteners are preferred, and in particular, the following formula (2)
[0102]
[Chemical formula 2]

[0103]
(In the above formula, R₁Represents an amino group, a derivative thereof or a hydroxyl group, and R₂, R_ThreeRepresents a hydrogen atom, an alkyl group or a phenyl group. ) Is preferred.
[0104]
The compounding amount of the fluorescent brightener of component E is preferably 0.0001 to 3 parts by weight, more preferably 0.0005 to 1 part by weight, and more preferably 0.0005 to 0.5 parts by weight with respect to 100 parts by weight of component A. Is more preferable, 0.001 to 0.5 part by weight is particularly preferable, and 0.001 to 0.1 part by weight is most preferable.
[0105]
(Haze value)
In the polycarbonate resin composition, a smooth flat plate having a thickness of 2 mm having an arithmetic average roughness (Ra) of 0.03 μm exhibits a haze value in the range of 0.1 to 1%, and is substantially free of filler. preferable. The haze value is more preferably in the range of 0.1 to 0.5%.
[0106]
The haze value is measured using a haze meter. Such a smooth flat plate is obtained by subjecting the pellets to predetermined drying and then injection molding into a mold cavity constituted by a mold surface having an arithmetic average roughness (Ra) of 0.03 μm. The arithmetic average roughness (Ra) of the mold surface is measured using a surface roughness meter.
[0107]
(Light stabilizer)
The polycarbonate resin composition of the present invention includes bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis. (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1 , 2,3,4-butanetetracarboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2, 2,6,6-tetramethylpiperidyl) imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, and polymethylpropyl 3-oxy- [4- (2,2,6, - can be used tetramethyl) piperidinyl] hindered amine light stabilizer represented by a siloxane. The light stabilizer is a polymer-type ultraviolet absorber obtained by copolymerizing a light-stable monomer and a monomer such as alkyl (meth) acrylate by taking the structure of a monomer compound capable of radical polymerization. And / or a light stabilizer. As such a photostable monomer, a compound containing a hindered amine skeleton in the ester substituent of (meth) acrylic acid ester is preferably exemplified. Such a polymer-type light stabilizer may contain the ultraviolet absorbing monomer in the copolymerization monomer.
[0108]
The combined use of a hindered amine light stabilizer and a benzotriazole-based and / or triazine-based UV absorber effectively improves the weather resistance. In such a combination, the weight ratio of the two (light stabilizer / ultraviolet absorber) is preferably in the range of 95/5 to 5/95, and more preferably in the range of 80/20 to 20/80 (in the case of a polymer type, it is Is the weight ratio of the mer).
[0109]
You may use the said light stabilizer individually or in mixture of 2 or more types. The amount of the light stabilizer used is preferably 0.0005 to 3 parts by weight, more preferably 0.01 to 2 parts by weight, still more preferably 0.02 to 1 part by weight, based on 100 parts by weight of the polycarbonate resin. -0.5 part by weight is particularly preferred.
[0110]
(Bluing agent)
In the polycarbonate resin composition of the present invention, it is preferable to use 0.05 to 3 ppm (weight ratio) of a bluing agent in the polycarbonate resin composition. This is effective for eliminating the yellow color of the polycarbonate resin molded product. In particular, in the case of molded products with weather resistance, since a certain amount of UV absorber is used, there is a reality that resin products tend to be yellowish due to the `` action and color of the UV absorber ''. The use of a bluing agent is very effective for imparting natural transparency.
[0111]
Here, the bluing agent refers to a colorant that exhibits a blue or purple color by absorbing light of orange or yellow color, and a dye is particularly preferable. By blending the bluing agent, the polycarbonate resin composition of the present invention achieves an even better hue. A preferable blending amount of the bluing agent is in the range of 0.5 to 2.5 ppm, more preferably 0.5 to 2 ppm in the resin composition.
[0112]
Representative examples of the bluing agent include Macrolex Violet B and Macrolex Blue RR from Bayer, Terrasol Blue RLS from Sand, and Plast Blue 8580 from Arimoto Chemical Industry.
[0113]
(Dye and pigment)
In the polycarbonate resin composition of the present invention, various dyes and pigments can be used in addition to the bluing agent as long as the object of the invention is not impaired. In particular, a dye is preferable from the viewpoint of maintaining transparency. Preferred dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, isoindo Examples thereof include linone dyes and phthalocyanine dyes. The amount of these dyes used is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight per 100 parts by weight of component A.
[0114]
(Antistatic agent)
The polycarbonate resin composition of the present invention may require antistatic performance, and in such a case, it is preferable to use an antistatic agent. Examples of the antistatic agent include (i) an organic sulfonic acid phosphonium salt such as an aryl sulfonic acid phosphonium salt typified by dodecylbenzenesulfonic acid phosphonium salt and an alkyl sulfonic acid phosphonium salt. The phosphonium salt has an appropriate composition ratio of 5 parts by weight or less per 100 parts by weight of component A, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, and 1.5 to 3 parts by weight. A range of parts is more preferred.
[0115]
Examples of the antistatic agent include (ii) lithium organic sulfonate, organic sodium sulfonate, organic potassium sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. Organic sulfonate alkali (earth) metal salts of Specifically, for example, metal salts of dodecylbenzenesulfonic acid, metal salts of perfluoroalkanesulfonic acid, and the like are exemplified. The organic sulfonate alkali (earth) metal salt has a composition ratio of 0.5 parts by weight or less per 100 parts by weight of component A, preferably 0.001 to 0.3 parts by weight, and 0.005 to 0.005. 2 parts by weight is more preferred. In particular, alkali metal salts such as potassium, cesium, and rubidium are preferable.
[0116]
Examples of the antistatic agent include (iii) organic sulfonic acid ammonium salts such as alkyl sulfonic acid ammonium salt and aryl sulfonic acid ammonium salt. The composition ratio of the ammonium salt is 0.05 parts by weight or less per 100 parts by weight of the component A.
[0117]
Examples of the antistatic agent include (iv) a polymer containing a poly (oxyalkylene) glycol component such as polyether ester amide as a constituent component. The polymer is suitably 5 parts by weight or less per 100 parts by weight of component A.
[0118]
Examples of other antistatic agents include (v) non-organic compounds such as carbon black, carbon fiber, carbon nanotube, graphite, metal powder, and metal oxide powder. The composition ratio of the non-organic compound is 0.05 parts by weight or less per 100 parts by weight of the component A. In addition to the antistatic performance, the non-organic compounds exemplified in (v) may be blended as a heat ray absorbent.
[0119]
The polymer (iv) can contain a component substituted with a sulfonate group as the monomer component. Specifically, in a polymer containing an aromatic dicarboxylic acid and a poly (oxyalkylene) glycol component as its constituent components, 4-sodium sulfo-dimethyl isophthalate, 5-sodium sulfo-dimethyl isophthalate, 4-potassium sulfo- Esters of aromatic dicarboxylic acids substituted with sulfonate groups such as dimethyl isophthalate, 5-potassium sulfo-dimethyl isophthalate, 2-sodium sulfo-dimethyl terephthalate, and 2-potassium sulfo-dimethyl terephthalate are copolymerized. The following polymer is exemplified. In such a polymer, the ratio of the aromatic dicarboxylic acid component not substituted with the sulfonate group and the aromatic dicarboxylic acid component not substituted with the sulfonate group is preferably the latter ratio in the total of 100 mol% of both. It is 5-50 mol%, More preferably, it is 8-35 mol%, More preferably, it is 10-30 mol%.
[0120]
(Compound with heat-absorbing ability)
In the polycarbonate resin composition of the present invention, a compound having a heat-absorbing ability in an amount that does not impair the object of the present invention can be used. Preferred examples of the compound include phthalocyanine-based near infrared absorbers and carbon fillers. As such a phthalocyanine-based near infrared absorber, for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available. Examples of the carbon filler include carbon black, graphite (including both natural and artificial, and whisker), carbon fiber (including those produced by vapor phase growth), carbon nanotubes, and fullerenes, preferably carbon black And graphite. These can be used alone or in combination of two or more. The phthalocyanine-based near infrared absorber is preferably 0.005 to 0.2 parts by weight, more preferably 0.008 to 0.1 parts by weight, and 0.01 to 0 parts per 100 parts by weight of the polycarbonate resin (component A). 0.07 part by weight is more preferable. In the resin composition of the present invention, the carbon filler is preferably in the range of 0.1 to 200 ppm (weight ratio), more preferably in the range of 0.5 to 100 ppm, and still more preferably in the range of 1 to 50 ppm.
[0121]
(Flame retardants)
In the polycarbonate resin composition of the present invention, an amount of flame retardant that does not impair the object of the present invention can be used. Examples of flame retardants include halogenated bisphenol A polycarbonate flame retardants, organic salt flame retardants, aromatic phosphate ester flame retardants, and halogenated aromatic phosphate ester flame retardants. It can be used above.
[0122]
Specifically, the polycarbonate type flame retardant of halogenated bisphenol A is a polycarbonate type flame retardant of tetrabromobisphenol A, a copolymer polycarbonate type flame retardant of tetrabromobisphenol A and bisphenol A, or the like.
[0123]
Specifically, the organic salt flame retardants are diphenyl sulfone-3,3′-disulfonate dipotassium, potassium diphenylsulfone-3-sulfonate, sodium 2,4,5-trichlorobenzenesulfonate, 2,4,5-trisulfonate. Potassium chlorobenzenesulfonate, potassium bis (2,6-dibromo-4-cumylphenyl) phosphate, sodium bis (4-cumylphenyl) phosphate, potassium bis (p-toluenesulfone) imide, potassium bis (diphenylphosphate) imide, Potassium bis (2,4,6-tribromophenyl) phosphate, potassium bis (2,4-dibromophenyl) phosphate, potassium bis (4-bromophenyl) phosphate, potassium diphenylphosphate, sodium diphenylphosphate, Potassium perfluorobutane sulfonate, sodium lauryl sulfate Um or potassium hexadecyl sulfate, sodium or potassium. The organic salt flame retardant is preferably 0.0001 to 0.5 parts by weight, more preferably 0.001 to 0.2 parts by weight, and further preferably 0.003 to 0.15 parts by weight per 100 parts by weight of the component A. Can be used in departments.
[0124]
Specifically, the halogenated aromatic phosphate ester type flame retardant is tris (2,4,6-tribromophenyl) phosphate, tris (2,4-dibromophenyl) phosphate, tris (4-bromophenyl) phosphate, etc. is there.
[0125]
Specifically, the aromatic phosphate ester flame retardant is triphenyl phosphate, tris (2,6-xylyl) phosphate, tetrakis (2,6-xylyl) resorcin diphosphate, tetrakis (2,6-xylyl) hydroquinone diphosphate. , Tetrakis (2,6-xylyl) -4,4′-biphenol diphosphate, tetraphenylresorcin diphosphate, tetraphenylhydroquinone diphosphate, tetraphenyl-4,4′-biphenol diphosphate, aromatic ring source is resorcin and phenol Aromatic polyphosphates that do not contain phenolic OH groups, aromatic ring sources are resorcin and phenol, aromatic polyphosphates that contain phenolic OH groups, aromatic ring sources are hydroquinone and phenol, and are phenolic Aromatic polyphosphates not containing H groups, similar aromatic polyphosphates containing phenolic OH groups, ("Aromatic polyphosphates" shown below are aromatic polyphosphates containing phenolic OH groups and aromatic polyphosphates not containing Aromatic polyphosphates whose aromatic ring sources are bisphenol A and phenol, aromatic polyphosphates whose aromatic ring source is tetrabromobisphenol A and phenol, aromatic ring sources are resorcin and 2 , 6-xylenol aromatic polyphosphate, aromatic polyphosphates whose aromatic ring sources are hydroquinone and 2,6-xylenol, aromatic polyphosphates whose aromatic ring sources are bisphenol A and 2,6-xylenol, aromatic rings The source is tetrabromobisph Aromatic polyphosphates such a Nord A and 2,6-xylenol. The halogenated aromatic phosphate ester type flame retardant and the aromatic phosphate ester type flame retardant are preferably 0.1 to 25 parts by weight, more preferably 1 to 20 parts by weight, still more preferably, per 100 parts by weight of the component A. 2 to 18 parts by weight can be used.
[0126]
(Other resins and elastomers)
The polycarbonate resin composition of the present invention provides a very good molded article even for applications requiring transparency with severe quality requirements. Therefore, the most preferred embodiment of the polycarbonate resin composition of the present invention is a composition in which the resin component is substantially composed of a polycarbonate resin. However, the good release performance of the resin composition of the present invention is also exhibited when other resins and elastomers are blended. Therefore, the polycarbonate resin composition of the present invention can be appropriately blended according to the purpose.
[0127]
Examples of such other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyethylene, and polypropylene. And other resins such as polyolefin resin, polystyrene resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), polymethacrylate resin, phenol resin, and epoxy resin.
[0128]
As the elastomer, for example, isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, MBS (methyl methacrylate / sterene / butadiene) which is a core-shell type elastomer. Examples thereof include rubber and MAS (methyl methacrylate / acrylonitrile / styrene) rubber.
[0129]
The other resin or elastomer is preferably used in an amount of 50 parts by weight or less, more preferably 40 parts by weight or less, and still more preferably 30 parts by weight or less with respect to 100 parts by weight of the polycarbonate resin (component A). On the other hand, when other resins and elastomers are blended, the lower limit is preferably 1 part by weight or more.
[0130]
(Other additives)
In the polycarbonate resin composition of the present invention, various inorganic fillers, flow modifiers, antibacterial agents, photocatalytic antifouling agents, photochromic agents, and the like can be blended as appropriate according to the purpose.
[0131]
(Manufacture of polycarbonate resin composition)
Arbitrary methods are employ | adopted in order to manufacture the polycarbonate resin composition of this invention. For example, the A component, the B component, and optional additives are sufficiently mixed using a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer. In some cases, the raw materials or premixtures of these components can be granulated by an extrusion granulator or a briquetting machine. Thereafter, such a premix is melt-kneaded by a melt-kneader represented by a vent type twin-screw extruder, and the produced strand or the like is pelletized by a device such as a pelletizer.
[0132]
In addition, a method of supplying each component independently to a melt kneader represented by a vent type twin screw extruder, or a part of each component is premixed and then supplied to the melt kneader independently of the remaining components. The method of doing is also mentioned. Examples of the method of premixing a part of each component include a method in which the fatty acid full ester of component B of the present invention and other components are premixed in advance, and then mixed with a polycarbonate resin or directly supplied to an extruder. .
[0133]
In addition, as a premixing method, for example, when a component having a powder form is included as the component A, a part of the powder and an additive to be blended are blended to form a master batch of the additive diluted with powder. Is mentioned. Furthermore, the method etc. which supply one component independently from the middle of a melt extruder are mentioned. In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt extruder.
[0134]
As the extruder, one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing the foreign substance mixed in the extrusion raw material in the zone in front of the extruder die. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (such as a disk filter), and the like.
[0135]
Examples of the melt kneader include a banbury mixer, a kneading roll, a single screw extruder, a multi-screw extruder having three or more axes, in addition to a twin screw extruder.
[0136]
The resin extruded as described above is directly cut into pellets (so-called hot cut), or after forming strands, the strands are cut with a pelletizer to be pelletized. When it is necessary to reduce the influence of external dust during pelletization, it is preferable to clean the atmosphere around the extruder.
[0137]
Although the shape of the obtained pellet can take general shapes, such as a cylinder, a prism, and a spherical shape, it is more preferably a cylinder. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.
[0138]
(Second aspect)
As described above, since the fatty acid full ester of component B of the present invention is an ester compound as a main component and a free aliphatic carboxylic acid as a subcomponent, the polycarbonate resin composition of the present invention contains these two compounds. It can be said that it is a resin composition. Therefore, according to this invention, the resin composition of the following 2nd aspect is provided from this point. That is, the second aspect of the present invention is a polycarbonate resin (component A) 100 parts by weight, a 4- to 8-valent aliphatic polyhydric alcohol having 5 to 30 carbon atoms and an aliphatic carboxylic acid having 10 to 22 carbon atoms. A resin composition comprising 0.005 to 2 parts by weight of a full ester (B component) of the above, wherein the number of moles (Ff) of the carboxyl group of the free aliphatic carboxylic acid in the composition and the mole of the ester bond of the B component It is a polycarbonate resin composition whose molar ratio (Ff: Fe) to the number (Fe) is in the range of 8:92 to 30:70. In particular, the resin composition is preferably in the form of pellets used to produce the desired molded article.
[0139]
(Ff: Fe)
The ratio of the fatty acid full ester compound and the aliphatic carboxylic acid compound in the resin composition is the same as that of the resin composition.¹Calculated by measuring H-NMR. In addition, since the ratio of the aliphatic carboxylic acid compound in a pellet is very small, this measurement needs to be measured using an NMR measuring apparatus having a frequency of 600 MHz or more. The molar ratio (Ff: Fe) between the number of moles of carboxyl groups of free aliphatic carboxylic acid (Ff) and the number of moles of ester bonds (Fe) in the aliphatic carboxylic acid ester compound calculated from such measurement is 10 : The range of 90-25: 75 is suitable, and the range of 12: 88-22: 78 is more suitable. For example, in the case of pentaerythritol ester, Ff: Fe can be calculated as follows. That is, the signal of the hydrogen atom of the methylene group bonded to the carboxyl group of the aliphatic carboxylic acid component (including both free acid compounds and ester compounds) appears at about 2.3 ppm. The peak area of this region is Sc. On the other hand, the hydrogen atom signal of the methylene group in the pentaerythritol component bonded to the ester bond appears at about 4.1 ppm. Let the peak area of such a region be Se. From these,
[0140]
Ff: Fe = (Sc / 2-Se / 2) :( Se / 2)
From the relationship, Ff: Fe can be calculated (converted so that the sum of Ff and Fe is 100).
[0141]
In addition, this molar ratio is not necessarily the same as that ratio in the fatty acid ester blended at the time of pellet production. This is presumably because the ester bond of the fatty acid ester compound may be decomposed by heating or the like during pellet production.
[0142]
In the second aspect of the present invention, the polycarbonate resin of component A is the same as in the first aspect. The 4- to 8-valent aliphatic polyhydric alcohol having 5 to 30 carbon atoms and the aliphatic carboxylic acid having 10 to 22 carbon atoms constituting the B component are the same as in the first embodiment. The aliphatic carboxylic acid of component B contains a palmitic acid component and a stearic acid component, and the peak area in the gas chromatograph-mass spectrometry method (GC / MS method), the area (Sp) of the palmitic acid component and the stearic acid component The total area (Ss) is 80% or more of the total aliphatic carboxylic acid component, and the area ratio (Ss / Sp) of both is preferably 1.3 to 30. The method for measuring the area ratio (Ss / Sp) is as described above.
[0143]
Moreover, arbitrary components, such as a C-E component, may be contained similarly to the 1st aspect.
[0144]
(Third aspect)
The polycarbonate resin composition of this invention solves the subject of the above-mentioned this invention from said aspect, and provides the pellet suitable for shape | molding the transparent member for vehicles. Therefore, according to this invention, the resin composition of the following 2nd aspect is provided from this point. That is, the third aspect of the present invention includes 100 parts by weight of a polycarbonate resin (component A), a 4- to 8-valent aliphatic polyhydric alcohol having 5 to 30 carbon atoms and an aliphatic carboxylic acid having 10 to 22 carbon atoms. Pellets formed from a resin composition comprising 0.005 to 2 parts by weight of full ester (component B) of
The release load in the method for measuring the release load of the pellet is obtained by changing pentaerythritol tetrastearate having an acid value of 0.8 and a 5% weight loss temperature of 396 ° C. in TGA (thermogravimetric analysis) to the component A. It is a pellet formed from a polycarbonate resin composition satisfying that it is 85% or less with respect to the mold release load in the same measurement method of a pellet formed from a resin composition blended in the same amount as the component.
[0145]
(Release load measurement method)
For the release load, the cup-shaped molded product shown in FIG. 1 is formed from the pellets, and the load at the time of releasing from the mold is measured. The release load is measured by installing a load cell on the ejection plate, measuring the force applied to the load cell during ejection, and taking the maximum value as the release load. The cup-shaped molded product is continuously formed into 40 shots, and after the release load is stabilized, the continuous 30 shots are formed, and the average value is defined as the release load (N). The arithmetic average roughness (Ra) of the mold cavity (movable mold cavity) corresponding to the inner surface side of the cup-shaped molded product was 0.03 μm.
[0146]
In the measurement of the mold release load, the mold release load of the molded product from the pellet made of the standard resin composition for comparison is measured, and the relative proportion of the mold release load of each sample is calculated. The standard value is a resin composition comprising 100 parts by weight of a polycarbonate resin and 0.2 parts by weight of pentaerythritol tetrastearate having an acid value of 0.8 and a 5% weight reduction temperature of 396 ° C. in TGA (thermogravimetric analysis). The release load of the resin composition (SRC-II) formed by blending 0.5 part by weight of the product (SRC-I) and the same pentaerythritol tetrastearate.
[0147]
The mold release load is 85% or less, preferably 80% or less with respect to the reference value.
[0148]
The molar ratio (Ff: Fe) of the number of moles of the carboxyl group of the free aliphatic carboxylic acid (Ff) and the number of moles of the ester bond of the B component (Fe) in the pellet is the same as in the first or second embodiment. It is preferably in the range of 10:90 to 30:70. The measuring method of Ff and Fe is as above-mentioned.
[0149]
The aliphatic polyhydric alcohol is preferably pentaerythritol. The aliphatic carboxylic acid of component B contains a palmitic acid component and a stearic acid component, and in the peak area of the gas chromatograph-mass spectrometry (GC / MS method), the area (Sp) of the palmitic acid component and the stearic acid component ( Ss) is preferably 80% or more of the total aliphatic carboxylic acid component, and the area ratio (Ss / Sp) of both is preferably 1.3 to 30. The method for measuring the area ratio (Ss / Sp) is as described above.
[0150]
The pellet substantially comprises a filler, wherein a 2 mm thick flat plate formed from 0.03 μm arithmetic mean roughness (Ra) exhibits a haze value in the range of 0.1 to 1%. None is preferred. The method for measuring the haze value is as described above.
[0151]
The shape of the pellet is most preferably a cylindrical shape having a diameter of 2 to 3.3 mm and a length of 2.5 to 3.5 mm.
[0152]
Also in the third aspect of the present invention, the component A polycarbonate resin is the same as in the first aspect. The 4- to 8-valent aliphatic polyhydric alcohol having 5 to 30 carbon atoms and the aliphatic carboxylic acid having 10 to 22 carbon atoms constituting the B component are the same as in the first embodiment. Moreover, arbitrary components, such as a C-E component, may be contained similarly to the 1st aspect.
[0153]
(Fourth aspect)
A fourth aspect of the present invention is a molded article made of the polycarbonate resin composition of the first or second aspect. Such an embodiment includes a molded article formed from the pellet of the third embodiment.
[0154]
The molded product can be usually obtained by injection molding pellets. In such injection molding, not only ordinary molding methods, but also injection compression molding, injection press molding, gas assist injection molding, insert molding, in-mold coating molding, heat insulation mold molding, rapid heating / cooling mold molding, two-color molding. , Sandwich molding, and ultra-high speed injection molding. In addition, either a cold runner method or a hot runner method can be selected for molding.
[0155]
Moreover, according to this invention, a polycarbonate resin composition can be extrusion-molded and it can also be made into shapes, such as various profile extrusion molded articles, a sheet | seat, a film. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. The polycarbonate resin composition of the present invention can be made into a hollow molded product by rotational molding, blow molding or the like.
[0156]
(surface treatment)
Further, the molded article of the present invention can be subjected to various surface treatments. As the surface treatment, various surface treatments such as a hard coat, a water / oil repellent coat, a hydrophilic coat, an antistatic coat, an ultraviolet absorption coat, an infrared absorption coat, and metalizing (evaporation) can be performed. Examples of the surface treatment method include liquid deposition, vapor deposition, thermal spraying, and plating. As the vapor deposition method, either a physical vapor deposition method or a chemical vapor deposition method can be used. Examples of physical vapor deposition include vacuum vapor deposition, sputtering, and ion plating. Examples of the chemical vapor deposition (CVD) method include a thermal CVD method, a plasma CVD method, and a photo CVD method.
[0157]
The molded article of the present invention is very suitable for performing such surface treatment because its crack resistance is improved. In particular, the polycarbonate resin composition of the present invention is suitable for surface treatment including a factor that adversely affects the polycarbonate resin such as a solvent, and particularly suitable for a hard coat.
[0158]
Examples of the hard coat agent used in the present invention include a silicone resin hard coat agent and an organic resin hard coat agent. The silicone resin hard coat agent forms a cured resin layer having a siloxane bond. For example, partial hydrolysis of a compound mainly composed of a compound corresponding to a trifunctional siloxane unit (trialkoxysilane compound, etc.). Condensates, preferably partially hydrolyzed condensates containing compounds corresponding to tetrafunctional siloxane units (tetraalkoxysilane compounds, etc.), and partially hydrolyzed condensates further filled with metal oxide fine particles such as colloidal silica Is mentioned. The silicone resin hard coat agent may further contain a bifunctional siloxane unit and a monofunctional siloxane unit. These include alcohols generated during the condensation reaction (in the case of a partially hydrolyzed condensate of alkoxysilane), etc., but if necessary, may be dissolved or dispersed in any organic solvent, water, or a mixture thereof. Good. Examples of the organic solvent for this purpose include lower fatty acid alcohols, polyhydric alcohols and ethers thereof, and esters. In addition, in order to obtain a smooth surface state, various surfactants such as siloxane-based and alkyl fluoride-based surfactants may be added to the hard coat layer.
[0159]
Examples of the organic resin hard coat agent include melamine resin, urethane resin, alkyd resin, acrylic resin, and polyfunctional acrylic resin. Here, examples of the polyfunctional acrylic resin include resins such as polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate, and phosphazene acrylate.
[0160]
Among these hard coat agents, silicone resin hard coat agents with excellent long-term durability and relatively high surface hardness, or UV curable acrylics that can be processed with a relatively simple and good hard coat layer. A resin or a polyfunctional acrylic resin is preferred. The silicone resin hard coat agent can be selected from a so-called two-coat type composed of a primer layer and a top layer and a so-called one-coat type formed from only one layer.
[0161]
Examples of the resin that forms such a primer layer (first layer) include urethane resins, acrylic resins, polyester resins, epoxy resins, melamine resins, amino resins, and polyester acrylates, urethane acrylates, and epoxy resins, which are composed of various blocked isocyanate components and polyol components. Various polyfunctional acrylic resins such as acrylate, phosphazene acrylate, melamine acrylate, amino acrylate and the like can be mentioned, and these can be used alone or in combination of two or more. Among these, an acrylic resin and a polyfunctional acrylic resin preferably include 50% by weight, more preferably 60% by weight or more, and those composed of an acrylic resin and a urethane acrylate are particularly preferable. These can be applied either by applying a predetermined reaction after application of an unreacted material to obtain a cured resin, or by directly applying the reacted resin to form a cured resin layer. In the latter case, the resin is usually dissolved in a solvent to form a solution, which is then applied and then the solvent is removed. In the former case, a solvent is generally used.
[0162]
Furthermore, the resin that forms the hard coat layer includes the above-mentioned light stabilizer and ultraviolet absorber, catalyst, thermal / photopolymerization initiator, polymerization inhibitor, silicone antifoaming agent, leveling agent, thickener, precipitation prevention. Agents, sag-preventing agents, flame retardants, various additives of organic / inorganic pigments / dyes, and auxiliary additives can be included.
[0163]
As a coating method, a method such as a bar coating method, a dip coating method, a flow coating method, a spray coating method, a spin coating method, or a roller coating method is appropriately selected depending on the shape of a molded product to be coated. be able to. Of these, the dip coating method, the flow coating method, and the spray coating method, which can easily cope with complicated molded product shapes, are preferable.
[0164]
【Example】
The following examples further illustrate the present invention. Evaluation was carried out by the following method.
[0165]
(I) Evaluation method of fatty acid full ester
The following (1) to (3) were evaluated for the fatty acid esters (B-1 to B-8) used as raw materials of the composition. The evaluation results are shown in Table 1.
[0166]
(1) Acid value of fatty acid full ester
The acid value (KOHmg / g) was determined by neutralization titration in accordance with JIS K 0070.
[0167]
(2) 5% weight loss temperature by thermogravimetry of fatty acid full ester
Using Hi-Res TGA2950 Thermographic Analyzer manufactured by TA-instruments, N₂The temperature was raised at 20 ° C./min in an atmosphere, and the temperature when the weight loss of the sample reached 5% by weight of the charged weight was measured as the TGA 5% weight reduction temperature.
[0168]
(3) GC / MS measurement area ratio of aliphatic carboxylic acid component (Ss / Sp)
The measurement by the pyrolysis methylation GC / MS method of the aliphatic carboxylic acid component of the fatty acid ester was carried out by the following procedure.
[0169]
The GC / MS apparatus used was a GC: HP6890 type and MS: HP5973 type (both manufactured by Hewlett-Packard), and the thermal decomposition apparatus used was JHP-3 (manufactured by Nippon Analytical Industries).
[0170]
A solution in which the sample was dissolved in chloroform was weighed, and then about 20 μg of the sample was weighed on a pyrofoil for thermal decomposition equipment (“F358” (for 358 ° C.) manufactured by Nihon Analytical Industries). Furthermore, after adding 10 μl of a 2.5 wt% methanol solution of tetramethylammonium hydroxide (TMAH) as a reaction reagent to such a sample, the solvent was removed by heating to about 60 ° C., and then 358 ° C. using the above thermal decomposition apparatus. The reaction pyrolysis was carried out under the conditions of 10 seconds.
[0171]
The conditions for the GC / MS measurement were as follows. The column was a capillary type DB-5MS (30 m × 0.25 mm × 0.25 μm, manufactured by J & W), and helium gas was used as the carrier gas. The carrier gas was set to a constant value of 72.4 KPa (10.5 psi) using the constant pressure mode, and the (initial) gas flow rate at 40 ° C. was set to 1.3 ml / min. Further, the split ratio was 50/1, the inlet temperature was 300 ° C., and the GC / MS connection temperature was 280 ° C. The column bath temperature was maintained at 40 ° C. for 5 minutes, then heated to 320 ° C. at a temperature increase rate of 20 ° C./min, and further held at 320 ° C. for 5 minutes for measurement. Moreover, the MS apparatus used the electron impact ionization (EI) mode as an ionization mode, and measured in mass / charge number (m / z): 20-500. The number of scans per second was about 3. Further, the ion acceleration voltage and the like were set by auto-tuning using a standard sample of PFTBA. From the above measurement, the total ratio of Ss and Sp in the total aliphatic carboxylic acid component and the area ratio (Ss / Sp) were calculated.
[0172]
(II) Evaluation method of resin composition
The following evaluations (4) to (12) were performed on the resin composition produced by the method described later.
[0173]
(4)¹H-NMR measurement (Ff: Fe)
From the pellets prepared in each case by the method described later, a 35 mg sample is weighed, and the sample is dissolved in 0.5 ml of deuterated chloroform.¹Put in an ampoule tube for H-NMR measurement,¹A sample for H-NMR measurement was prepared. Such a measurement sample was measured with an NMR measuring apparatus having a frequency of 600 MHz (manufactured by JEOL Ltd., JNM-alpha600).¹1 H-NMR measurement was performed. Measurement conditions were set to 2048 times of integration and about 4 hours of measurement time per sample.
[0174]
From this measurement, Ff: Fe was calculated as follows. That is, the signal of the hydrogen atom of the methylene group bonded to the carboxyl group of the aliphatic carboxylic acid component (including both acid and ester) appears at about 2.3 ppm. The peak area of this region was Sc. On the other hand, the hydrogen atom signal of the methylene group in the pentaerythritol component bonded to the ester bond appears at about 4.1 ppm. The peak area of this region was Se. From these,
[0175]
Ff: Fe = (Sc / 2-Se / 2) :( Se / 2)
From the relationship, Ff: Fe was calculated (converted so that the sum of Ff and Fe was 100).
[0176]
(5) Transparency of molded products
Using Nippon Denshoku Co., Ltd. haze meter NDH-300A, the total light transmittance and Haze of a 2.0 mm thick molded plate (50 mm square plate) were measured. Such a molded plate is manufactured by injection molding into a mold cavity composed of a mold surface having an arithmetic average roughness (Ra) of 0.03 μm after predetermined drying of the pellets produced by the method described later, It was confirmed by using a surface roughness meter that Ra of the obtained molded product was 0.03 μm. The higher the numerical value of the total light transmittance, the higher the transparency. Haze is the turbidity of the molded product. The lower the value, the less turbidity.
[0177]
(6) Measurement of molding heat resistance
Using the same mold as in the case of (5) above, using an injection molding machine with a maximum mold clamping force of 1470 kN (manufactured by FANUC Corporation: T-150D) under conditions of a cylinder temperature of 340 ° C. and a mold temperature of 80 ° C. The difference between the hue of the 2 mm-thick 50 mm square plate molded in a molding cycle of 60 seconds, and the hue of the molded product molded after being retained in the cylinder for 10 minutes at a cylinder temperature of 340 ° C. Is expressed as ΔE in the following equation.
[0178]
ΔE = ((L−L ′)²+ (A-a ')²+ (B−b ′)²)^1/2
(In the above, the (L, a, b) value represents the hue before residence, and the (L ′, a ′, b ′) value represents the hue after residence)
[0179]
(7) Measurement of releasability
The mold release load when the cup-shaped molded article shown in FIG. 1 was protruded from the mold and released was measured. The release load was measured using a mold having a structure in which a load cell (manufactured by Minebea Co., Ltd .: CMM1-500K) was installed on a protruding plate, and the tip of the load cell protruded a protruding pin. With this configuration, the force applied to the load cell at the time of ejection was measured, and the maximum value of the force was taken as the release load. The cup-shaped molded product was continuously formed into 40 shots, and the average value obtained by forming 30 continuous shots after stabilizing the release load was defined as the release load (N). The arithmetic average roughness (Ra) of the mold cavity (movable mold cavity) corresponding to the inner surface side of the cup-shaped molded product was 0.03 μm. The molding conditions for the cup-shaped molded product are as follows. That is, molding machine: manufactured by Sumitomo Heavy Industries, Ltd .: SS75t, cylinder temperature 300 ° C., mold temperature 80 ° C., filling time 10 seconds, holding pressure 118 MPa, holding pressure 15 seconds, cooling time 20 seconds. Under such conditions, a good molded product was obtained.
[0180]
In the measurement of the mold release load, the mold release load of the comparative standard resin composition was measured, and the relative ratio of the mold release load of each sample was calculated and shown in the table. Such a standard resin composition for comparison includes a resin composition (SRC-I) obtained by blending 0.2 parts by weight of B-8 pentaerythritol tetrastearate with 100 parts by weight of PC described later, and the same pentaerythritol tetrastearate. A resin composition (SRC-II) containing 0.5 part by weight was prepared. Such SRC-I and SRC-II were produced under the same conditions as in the resin composition of Example 1. The release load of SRC-I was 2320N, and the release load of SRC-II was 1600N.
(8) Silver streak of molded product
The presence or absence of silver streaks was observed in the cup-shaped molded product continuously molded for 30 shots at the time of measuring the release load of (7). The number of molded products having silver streaks among the 30 molded products is shown in the table.
(9) Observation of distortion (strain-1) of the molded product
The square plate created by the said molding heat resistance test was used, and the distortion state of the molded product was visually observed with the polarizing plate. In this observation, the degree of distortion was evaluated based on the color change of striped pattern caused by polarizing plate observation and uneven density.
[0181]
X: The number of stripes in the flow direction is large, the stripe pattern is dense, and the boundary between each color is clear
(Triangle | delta): Compared with said x, there are few stripes on the whole, and the boundary between each color is unclear. However, the striped pattern remains on the edge.
○: Compared with the above Δ, the number of stripes is smaller, the stripe pattern is sparse, and the boundary between each color is unclear.
[0182]
(10) Observation of distortion (strain-2) of the molded product
The through-type headlamp lens shown in FIG. 2 is molded for 30 shots using an injection molding machine (SG260M-HP manufactured by Sumitomo Heavy Industries, Ltd.) under conditions of a cylinder temperature of 320 ° C. and a mold temperature of 80 ° C. Annealing was performed at 120 ° C. for 2 hours. Thereafter, the molded product was placed between two polarizing plates whose polarization planes were orthogonal, and the presence or absence of the shadow (distortion-2) was observed. Thirty molded articles were observed, and the degree of shading was evaluated based on the following criteria.
[0183]
○: The shadow has a relatively thin contrast and is slightly observed
Δ: The shadow is clearly observed with a certain degree of contrast.
X: The shadow has a strong contrast, is very clear and is observed over a large area
[0184]
(11) Stress crack test
(11-1) Cracking during molding
A cup-shaped molded product was continuously molded for 1000 shots under the same conditions as the measurement of releasability. The case where cracks occurred immediately after the molding was indicated as x, and the case where no cracks occurred was indicated as ◯.
(11-2) Crack after hard coat treatment
100 cup-shaped molded products that did not generate cracks in the molding of (7-1) above were used. Hard coating was performed with the coating agent shown in the examples, and no cracks were generated in the molded products. The ones that did not do were marked with ○.
[0185]
(12) Weather resistance test
Using an injection molding machine with a maximum mold clamping force of 1470 kN, a sunshine weather meter (50 mm square plate with a thickness of 2 mm molded in a molding cycle of 60 seconds under conditions of a cylinder temperature of 340 ° C. and a mold temperature of 80 ° C. When Suga Test Instruments Co., Ltd. product: WEL-SUN: HC-B) was used, and the black panel temperature was 63 ° C., the humidity was 50%, the water spraying for 18 minutes and the water spraying for 102 minutes for a total of 120 minutes for 1000 hours. The hue change ΔYI value was calculated by the following equation.
[0186]
ΔYI = Square plate YI value after test-Square plate YI value before test
[0187]
(Examples 1-11, Comparative Examples 1-9)
Various ester compounds (component B) of polyhydric alcohols and aliphatic carboxylic acids listed in Tables 2 to 5 and other additions to 100 parts by weight of a polycarbonate resin (PC) produced from bisphenol A and phosgene by an interfacial condensation polymerization method The blending agent (C to E component) is blended in the amounts shown in Tables 2 to 5, and 0.0002 parts by weight of a bluing agent (manufactured by Bayer: Macrolex Violet B) is blended and mixed in a blender, and then vented. Pellets were obtained by melt-kneading using a twin screw extruder. The additives to be added to the polycarbonate resin were preliminarily prepared with a polycarbonate resin in advance with a concentration of 10 to 100 times the blending amount as a guide, and then the whole was mixed by a blender. The vent type twin screw extruder used was TEX30α (completely meshing, rotating in the same direction, two-thread screw) manufactured by Nippon Steel Works. The kneading zone was of one type before the vent opening. Extrusion conditions were a discharge rate of 20 kg / h, a screw rotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusion temperature of 280 ° C. from the first supply port to the die part to obtain pellets.
[0188]
The obtained pellets were dried in a hot air circulation dryer at 120 ° C. for 5 hours, and then, using an injection molding machine, the cylinder temperature was 340 ° C. and the mold temperature was 80 ° C. A square plate was formed. As the injection molding machine, T-150D manufactured by FANUC CORPORATION was used.
[0189]
Further, after drying the pellets obtained in each example by the same method, the through-type headlamp lens shown in FIG. 2 was injected into an injection molding machine (Sumitomo Heavy Industries) under the conditions of a cylinder temperature of 320 ° C. and a mold temperature of 80 ° C. It was created using SG260M-HP manufactured by Kogyo Co., Ltd. The headlamp lenses obtained from the resin compositions of the examples had good appearance such as hue and transparency.
[0190]
Further, the pellets obtained above were similarly dried and the release load was measured.
[0191]
After annealing the headlamp lens of the Example obtained above at 120 ° C. for 2 hours (after completing the evaluation (10)), the coating composition (i-1) shown below was subjected to dip coating. It was applied, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 30 minutes. Next, the coating composition (ii-1) shown below was further applied to the lens molded article by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 2 hours to perform a hard coat treatment. It was. Observation of the obtained headlamp lens revealed no cracking.
[0192]
Each component of the symbol notation in Tables 1-5 is as follows.
[0193]
(A component)
PC: Polycarbonate resin powder having a viscosity average molecular weight of 22,500 produced from bisphenol A and phosgene by an interfacial condensation polymerization method (manufactured by Teijin Chemicals Ltd .: Panlite L-1225WP)
[0194]
(B component)
B-1: Acid value: 9, TGA 5% weight loss temperature: 322 ° C., and the total of the area of stearic acid component (Ss) and the area of palmitic acid component (Sp) in the GC / MS method is total aliphatic carboxylic acid Full ester of pentaerythritol and aliphatic carboxylic acid (mainly stearic acid and palmitic acid), which is 94% of the components and the area ratio (Ss / Sp) is 1.44 (RIKEN vitamin ( Co., Ltd .: Riquester EW-400, hydroxyl value: 6, iodine value: 0.4, and the aliphatic carboxylic acid is derived from animal fats and oils.)
[0195]
B-3 (for comparison): acid value: 1, TGA 5% weight loss temperature: 390 ° C., and the total of Ss and Sp is 91% in the total aliphatic carboxylic acid component, and the area ratio (Ss / Sp ) Is a full ester of pentaerythritol and an aliphatic carboxylic acid (mainly stearic acid and palmitic acid) (cognis Japan KK: Roxyol VPG-861, hydroxyl value: 7, iodine Value: 0, the aliphatic carboxylic acid is derived from vegetable oil.
[0196]
B-6 (for comparison): acid value: 2, TGA 5% weight loss temperature: 378 ° C., and the total of Ss and Sp is 90% in the total aliphatic carboxylic acid component, and the area ratio (Ss / Sp ) Is a full ester of pentaerythritol and an aliphatic carboxylic acid (mainly stearic acid and palmitic acid) (Riken Vitamin Co., Ltd .: Riquester EW-440A, hydroxyl value: 12, iodine value: 1.07) 0.4. The aliphatic carboxylic acid is derived from vegetable oil.)
[0197]
B-7 (for comparison): Glycerin mono fatty acid ester (manufactured by Riken Vitamin Co., Ltd .: Riquemar S-100A, acid value: 0.8, hydroxyl value: 327, iodine value: 1.8, and TGA 5% weight loss temperature: 205 ℃)
[0198]
B-2, B-4, and B-5 (for comparison): Commercial fatty acid full ester and reagent aliphatic carboxylic acid were mixed at the composition ratio shown in Table 1, and the acid value and the weight reduction temperature were controlled. Fatty acid esters were prepared. This adjustment takes a predetermined amount of fatty acid ester in a beaker and dissolves by heating to 80 ° C., and a predetermined amount of stearic acid (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) and palmitic acid (Wako Pure Chemical ( Co., Ltd., special grade reagent) was added and mixed with an electric blender (Brown) to make it uniform. Table 1 shows the results of the evaluation items (1) to (3) of the fatty acid full ester prepared as described above.
[0199]
B-8 (for comparison): Penerythritol tetrastearate obtained by reacting pentaerythritol with stearic acid as a reagent by a conventional method. Table 1 shows the results of the evaluation items (1) to (3) of the fatty acid full ester.
[0200]
[Table 1]

[0201]
(C component additive)
C1-1: Phosphonite heat stabilizer (manufactured by Sandoz: Sandstub P-EPQ)
C1-2: Phosphite heat stabilizer (Ciba Specialty Chemicals, Inc .: Irgafos 168)
C2-1: Hindered phenol antioxidant (Ciba Specialty Chemicals: Irganox 1076)
[0202]
(D component additive)
D-1: Benzotriazole-based ultraviolet absorber (Kemipro Kasei Co., Ltd .: Chemisorb 79)
D-2: Hydroxyphenyltriazine UV absorber (Ciba Specialty Chemicals: Tinuvin 1577)
D-3: Cyclic imino ester ultraviolet absorber (2,2'-m-phenylenebis (3,1-benzoxazin-4-one), manufactured by Takemoto Yushi Co., Ltd .: CEi-P)
(E component additive)
E-1: Coumarin-based fluorescent whitening agent (manufactured by Hakkol Chemical Co., Ltd .: Hakkol PSR)
[0203]
(Composition for hard coat)
(1) Coating composition (i-1)
In a flask equipped with a reflux condenser and a stirrer and purged with nitrogen, 70 parts of methyl methacrylate (hereinafter abbreviated as MMA), 39 parts of 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA), azobisisobutyronitrile (hereinafter referred to as “MAB”) 0.18 parts (abbreviated as AIBN) and 200 parts of 1,2-dimethoxyethane were added, mixed and dissolved. Subsequently, it was made to react under stirring at 70 degreeC in nitrogen stream for 6 hours. The obtained reaction solution was added to n-hexane and purified by reprecipitation to obtain 90 parts of a copolymer (acrylic resin (I)) having a composition ratio of MMA / HEMA of 70/30 (molar ratio). The weight average molecular weight of the copolymer was 80,000 in terms of polystyrene from the measurement of GPC (column; Shodex GPCA-804, eluent: THF).
[0204]
Next, as the composition for the hard coat first layer, 8 parts of the acrylic resin (I) is mixed with 40 parts of methyl ethyl ketone, 20 parts of methyl isobutyl ketone, 5.2 parts of ethanol, 14 parts of isopropanol and 10 parts of 2-ethoxyethanol. Then, 10 parts of methyltrimethoxysilane hydrolysis condensate solution (X) was added to this solution and stirred at 25 ° C. for 5 minutes. To this solution was added melamine resin (Cymel 303, Mitsui Cytec Co., Ltd.). ) 1 part was added and stirred at 25 ° C. for 5 minutes to prepare a coating composition (i-1).
[0205]
(2) Coating composition (ii-1)
Using the same apparatus as above, 142 parts of methyltrimethoxysilane, 72 parts of distilled water and 20 parts of acetic acid were mixed with cooling with ice water, and the mixture was stirred at 25 ° C. for 1 hour and diluted with 116 parts of isopropanol. Thus, 350 parts of methyltrimethoxysilane hydrolysis condensate solution (X) was obtained. On the other hand, 208 parts of tetraethoxysilane and 81 parts of 0.01N hydrochloric acid were mixed with cooling with ice water, the mixture was stirred at 25 ° C. for 3 hours, diluted with 11 parts of isopropanol, and the tetraethoxysilane hydrolyzed condensate solution ( Y) 300 parts were obtained.
[0206]
Furthermore, as a composition for the hard coat second layer, 12 parts of distilled water and 20 parts of acetic acid are added to 100 parts of a water-dispersed colloidal silica dispersion (Snowtex 30 solid content concentration: 30% by weight, manufactured by Nissan Chemical Industries, Ltd.). The mixture was stirred, and 134 parts of methyltrimethoxysilane was added to the dispersion while cooling in an ice water bath. To this reaction liquid obtained by stirring this mixed liquid at 25 ° C. for 1 hour, 20 parts of tetraethoxysilane hydrolysis condensate solution (Y) and 1 part of sodium acetate as a curing catalyst were added and diluted with 200 parts of isopropanol to coat. A composition for use (ii-1) was prepared.
[0207]
[Table 2]

[0208]
[Table 3]

[0209]
[Table 4]

[0210]
[Table 5]

[0211]
From the above table, the polycarbonate resin composition of the present invention has good transparency, molding heat resistance, releasability, and cracking resistance, and reduced distortion of the molded product, and more suitable resin composition is weather resistant. Can also be seen as excellent. When molded using the polycarbonate resin composition of the present invention, good mold release is not only due to the small mold release load and the ratio of mold release load, but also the sound produced when the molded product is released from the mold. It can be seen from the fact that is small. Despite the good releasability, the hard coat adhesion is also good.
[0212]
Further, when the above-mentioned headlamp lens molded product molded from the pellets of the example was irradiated using an HID lamp (manufactured by Matsushita Electric Works Co., Ltd .: HID Handy Light Pro, white metal halide lamp), from Examples 5 and 6 In this molded product, only the outer peripheral portion of the lens was observed to develop blue color due to fluorescence. That is, such a molded product is a headlamp lens having a unique design. Such irradiation was performed at a distance of 30 cm from the concave surface side of the lens, and observation was performed from 45 ° (diagonal 45 °) from the center normal line on the convex side of the lens.
[0213]
【The invention's effect】
According to the present invention, there is provided a polycarbonate resin composition having good transparency and molding heat resistance and imparting good release properties, crack resistance, reduced strain and weather resistance to a molded product.
[0214]
Moreover, according to this invention, the pellet formed from this polycarbonate resin composition which is excellent in transparency, heat resistance, mold release property, crack resistance, and weather resistance, and has few distortions is provided.
[0215]
Furthermore, according to the present invention, a molded article comprising such a polycarbonate resin composition, which is excellent in transparency, heat resistance, releasability, crack resistance and weather resistance and has little distortion is provided.
[0216]
The molded article of the present invention is excellent in transparency, heat resistance and releasability, reduced distortion inside the molded article, and further improved crack resistance, so various transparent members that require high quality Is preferable.
[0217]
Examples of such transparent members include vehicle transparent members, window glass for construction machinery, window glass for buildings, houses, and greenhouses, roofs such as garages and arcades, lighting lenses, traffic light lenses, lenses for optical devices, and mirrors. , Glasses, goggles, noise barrier, motorcycle windshield, nameplate, solar cell cover or solar cell substrate, display device cover, touch panel, and parts for game machines (pachinko machines, etc.) (circuit covers, chassis, pachinko ball transport guides) Etc.).
[0218]
In particular, the molded product of the present invention is preferably used for a transparent member for a vehicle which is a large molded product with high quality requirements, and a vehicle lamp lens, particularly a headlamp lens, more specifically, a through-type headlamp lens is preferably used. Used. Here, the through-type headlamp lens includes a lamp cover that performs a condensing function with a reflector, a lamp unit cover that has the lamp unit as an integral unit, and the like.
[0219]
Therefore, the polycarbonate resin composition of the present invention, its pellets and its molded products are various electronic / electrical equipment, OA equipment, vehicle parts, machine parts, other agricultural materials, fishery materials, transport containers, packaging containers, playground equipment and miscellaneous goods. It is useful in various fields such as, and its industrial utility is exceptional.
[Brief description of the drawings]
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a schematic view of a cup-shaped molded product used for measuring a release load in Examples. [1-A] is a front view thereof. [1-B] is a side view thereof. The molded product is released from the mold cavity by projecting both the molded product projecting portion and the Z pin portion at the same time. The molded product ejecting pin and the Z pin are fixed to the same plate, and the molded product is ejected by pushing out the plate from the tip of the load cell.
FIG. 2 is a schematic view of a through-type headlamp lens of an automobile molded in the example. [2-A] is a front view (projected on the platen surface during molding. Therefore, such an area is the maximum projected area). [2-B] is a cross-sectional view taken along the line AA (the lens has a dome shape).
[Explanation of symbols]
The symbols in the figure are as follows.
1 Cup-shaped molded product (wall thickness is 4 mm for all parts)
2 Inside bottom of cup-shaped molded product
3 Inner periphery of cup-shaped molded product
4 Upper edge of cup-shaped molded product
5 Cup-shaped molded product protrusion (center of molded product, circular shape with a diameter of 15 mm)
6 Gate (width 3mm, thickness 1.5mm)
7 Runner (diameter 8mm, upper and lower parts are hemispherical, center is cylindrical)
8 Sprue (length 60mm)
9 Z pin part (diameter 8mm, length 8mm)
10 Cup shaped product height (20mm)
11 Diameter on the bottom side of cup-shaped molded product (63mm)
12 Thickness of bottom surface of cup-shaped molded product (4mm)
13 Diameter of cup-shaped molded product (70mm)
21 Headlamp lens body
22 Dome of lens
23 Lens outer periphery
24 Gate of molded product (width 30mm, gate thickness 4mm)
25 sprue (gate diameter 7mmφ)
26 Lens outer diameter (220mm)
27 Diameter of lens dome (200mm)
28 Lens dome height (20mm)
29 Thickness of lens molding (4mm)

Claims (15)

For 100 parts by weight of polycarbonate resin (component A),
4-8 divalent full ester of an aliphatic polyhydric alcohol and aliphatic carboxylic acids having a carbon number of 10 to 22 5 to 30 carbon atoms (B component) 0.005 parts by weight and
A resin composition comprising 0.0005 to 1 part by weight of at least one stabilizer (C component) selected from the group consisting of a phosphorus stabilizer (C1 component) and a hindered phenol antioxidant (C2 component) . Because
The B component aliphatic carboxylic acid includes a palmitic acid component and a stearic acid component, and the peak area in the gas chromatograph-mass spectrometry (GC / MS method) of the palmitic acid component area (Sp) and stearic acid The total of the component area (Ss) is 80% or more of the total aliphatic carboxylic acid component, and the area ratio (Ss / Sp) of both is 1.3 to 30,
The B component has a 5% weight loss temperature in TGA (thermogravimetric analysis) of 250 to 360 ° C. and an acid value of 4 to 20, and is a polycarbonate resin composition. The polycarbonate resin composition according to claim 1, wherein the component B has a 5% weight reduction temperature of 280 to 360 ° C. in TGA (thermogravimetric analysis). The polycarbonate resin composition according to claim 1, wherein the component B has an acid value of 4 to 18. Area ratio (Ss / Sp) is a polycarbonate resin composition according to claim 1 is 1.3 to 10. The polycarbonate resin composition according to claim 1, wherein the aliphatic polyhydric alcohol has 5 to 10 carbon atoms. The polycarbonate resin composition according to claim 5 , wherein the aliphatic polyhydric alcohol is pentaerythritol and / or dipentaerythritol. The polycarbonate resin composition according to claim 1, wherein the component B has a hydroxyl value in the range of 0.1 to 30. The polycarbonate resin composition according to claim 1, wherein the component B has an iodine value of 10 or less. The polycarbonate resin composition of Claim 1 formed by mix | blending 0.0005-3 weight part of ultraviolet absorbers (D component) with respect to 100 weight part of A component. The polycarbonate resin composition of Claim 1 formed by mix | blending 0.0001-3 weight part of fluorescent whitening agents (E component) with respect to 100 weight part of A components. The polycarbonate resin composition contains substantially a filler, in which a smooth flat plate having a thickness of 2 mm having an arithmetic average roughness (Ra) of 0.03 μm exhibits a haze value in a range of 0.1 to 1%. The composition according to claim 1, which is not present. A molded article comprising the polycarbonate resin composition according to claim 1. The molded article according to claim 12 , wherein the molded article has a hard coat treatment on the surface thereof. The molded article according to claim 13 , wherein the molded article is a transparent member for a vehicle. The molded article according to claim 14 , wherein the vehicle transparent member is a vehicle lamp lens.

Images