JPH04246460A - Flame-retarding polycarbonate resin composition - Google Patents
Flame-retarding polycarbonate resin compositionInfo
- Publication number
- JPH04246460A JPH04246460A JP2914791A JP2914791A JPH04246460A JP H04246460 A JPH04246460 A JP H04246460A JP 2914791 A JP2914791 A JP 2914791A JP 2914791 A JP2914791 A JP 2914791A JP H04246460 A JPH04246460 A JP H04246460A
- Authority
- JP
- Japan
- Prior art keywords
- polycarbonate resin
- flame
- resin composition
- metal salt
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 28
- 229920005668 polycarbonate resin Polymers 0.000 title claims abstract description 27
- 239000000203 mixture Substances 0.000 title claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 239000003063 flame retardant Substances 0.000 claims description 12
- -1 phosphate ester Chemical class 0.000 claims description 11
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 238000000465 moulding Methods 0.000 abstract description 7
- 239000007789 gas Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 229910001463 metal phosphate Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 10
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- YHZQOKUDQQISEW-UHFFFAOYSA-N 4-Cumylphenol Natural products C1=CC(C(C)C)=CC=C1C1=CC=C(O)C=C1 YHZQOKUDQQISEW-UHFFFAOYSA-N 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- CJWNFAKWHDOUKL-UHFFFAOYSA-N 2-(2-phenylpropan-2-yl)phenol Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1 CJWNFAKWHDOUKL-UHFFFAOYSA-N 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical group CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 150000002896 organic halogen compounds Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 1
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 101100288971 Mus musculus Lgals3bp gene Proteins 0.000 description 1
- 239000004419 Panlite Substances 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012255 powdered metal Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は難燃性ポリカーボネート
樹脂組成物に関するものである。更に詳しくは、ポリカ
ーボネート樹脂に特定の有機リン酸エステルの金属塩を
配合してなる難燃性ポリカーボネート樹脂組成物に関す
るものである。FIELD OF THE INVENTION This invention relates to flame-retardant polycarbonate resin compositions. More specifically, the present invention relates to a flame-retardant polycarbonate resin composition in which a metal salt of a specific organic phosphate ester is blended with a polycarbonate resin.
【０００２】0002
【従来の技術】従来より、ポリカーボネート樹脂を難燃
化する方法が数多く提案されている。その多くは、有機
ハロゲン化合物を添加するものである。例えば特公昭４
７−４４５３７号公報にはテトラブロモビスフェノール
Ａのオリゴマーを添加する方法が開示されている。しか
しながら、この方法では、かなりの量のハロゲン化合物
を添加する必要があるため、成形時の熱安定性が低下し
、更に成形時及び燃焼時に腐蝕性、有毒性のガスや煙を
発生する欠点がある。BACKGROUND OF THE INVENTION Many methods have been proposed to make polycarbonate resin flame retardant. Most of them add organic halogen compounds. For example, Tokuko Sho 4
No. 7-44537 discloses a method of adding an oligomer of tetrabromobisphenol A. However, this method requires the addition of a considerable amount of halogen compounds, which reduces thermal stability during molding and also produces corrosive and toxic gases and smoke during molding and combustion. be.
【０００３】この改良法の一つとして、特開昭５２−５
４７４１号〜特開昭５２−５４７４７号公報では芳香族
スルホン酸塩を添加する方法が提案されている。しかし
ながら、芳香族スルホン酸塩はポリカーボネート樹脂の
透明性を損なう欠点がある。[0003] As one of this improved method, Japanese Patent Application Laid-open No. 52-5
No. 4741 to JP-A-52-54747 propose a method of adding an aromatic sulfonate. However, aromatic sulfonates have the disadvantage of impairing the transparency of polycarbonate resins.
【０００４】また、特開昭５９−１４０２５５号公報、
特開昭６０−１４９６５８号公報にはビフェニル型芳香
族ホスホン酸の金属塩又はそのハロゲン化されたホスホ
ン酸の金属塩を添加する方法が提案されている。しかし
ながら、ビフェニル型芳香族ホスホン酸の金属塩又はハ
ロゲン化芳香族ホスホン酸の金属塩を添加するとポリカ
ーボネート樹脂が分解し、熱安定性が劣る欠点がある。[0004] Also, Japanese Patent Application Laid-Open No. 59-140255,
JP-A-60-149658 proposes a method of adding a metal salt of a biphenyl-type aromatic phosphonic acid or a metal salt of its halogenated phosphonic acid. However, when a metal salt of a biphenyl-type aromatic phosphonic acid or a metal salt of a halogenated aromatic phosphonic acid is added, the polycarbonate resin decomposes, resulting in poor thermal stability.
【０００５】本願発明者等は、有機リン酸エステルの金
属塩を添加したポリカーボネート樹脂が難燃性及び耐熱
性に優れていることを見出し、特願昭６３−１２２０７
０号として提案した。しかしながら、この方法で添加量
を多くした場合には透明性がやや阻害されるという問題
か生じた。この問題を解決するために、ポリカーボネー
ト樹脂に特定のハロゲン化有機リン酸エステルの金属塩
を配合することを特願昭６３−１９７０９３号として提
案した。しかしながら、この方法で添加量を多くした場
合には透明性は維持できるが成形品がやや黄変するとい
う問題が見出された。The inventors of the present invention discovered that polycarbonate resin to which a metal salt of an organic phosphate ester was added has excellent flame retardancy and heat resistance, and filed Japanese Patent Application No. 12207-1983.
I proposed it as No. 0. However, when using this method to increase the amount added, a problem arose in that transparency was somewhat impaired. In order to solve this problem, it was proposed in Japanese Patent Application No. 197093/1983 to incorporate a metal salt of a specific halogenated organic phosphate ester into polycarbonate resin. However, it has been found that when the amount added is increased using this method, although transparency can be maintained, the molded product becomes slightly yellowed.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、ポリカーボ
ネート樹脂の透明性を損なうことなく、成形時及び燃焼
時に腐蝕性ガスを発生しない、成形時の熱安定性に優れ
た難燃性ポリカーボネート樹脂組成物を提供することを
目的とする。[Problems to be Solved by the Invention] The present invention provides a flame-retardant polycarbonate resin composition that does not impair the transparency of the polycarbonate resin, does not generate corrosive gas during molding or combustion, and has excellent thermal stability during molding. The purpose is to provide something.
【０００７】本発明者は、この問題を解決するために更
に鋭意検討した結果、ポリカーボネート樹脂にクミルフ
ェニルエステル化された特定のリン酸の金属塩を配合す
ることで透明性に優れ、成形時の熱安定性が良好で且つ
充分な難燃性を呈する実用的な材料が得られることを見
出し、本発明に到達した。[0007] As a result of further intensive studies to solve this problem, the inventor of the present invention found that by blending a specific metal salt of phosphoric acid esterified with cumyl phenyl into a polycarbonate resin, it has excellent transparency and can be easily formed during molding. The inventors have discovered that it is possible to obtain a practical material that has good thermal stability and sufficient flame retardancy, and has arrived at the present invention.
【０００８】[0008]
【課題を解決するための手段】本発明は、ポリカーボネ
ート樹脂１００重量部に、下記一般式［１］[Means for Solving the Problems] The present invention provides 100 parts by weight of polycarbonate resin with the following general formula [1]
【０００９
】0009
]
【化２】
［但し、式中Ｘは水素又はハロゲン原子、Ｍはアルカリ
金属］で示される有機リン酸エステルの金属塩の少なく
ともー種を０．００１〜５重量部配合してなる難燃性ポ
リカーボネート樹脂組成物に係るものである。[Formula 2] [However, in the formula, X is a hydrogen or halogen atom, and M is an alkali metal] Flame retardant compound containing at least 0.001 to 5 parts by weight of a metal salt of an organic phosphate ester This relates to a polycarbonate resin composition.
【００１０】本発明で使用するポリカーボネート樹脂は
、二価フェノールとカーボネート前駆体とを溶液法又は
溶融法で反応させて製造されるものである。二価フェノ
ールとしては２，２−ビス（４−ヒドロキシフェニル）
プロパン（通称ビスフェノールＡ）を主たる対象とする
が、その一部又は全部を他の二価フェノールで置換えて
もよい。他の二価フェノールとしては、例えばビス（４
−ヒドロキシフェニル）メタン、２，２−ビス（４−ヒ
ドロキシ−３，５−ジメチルフェニル）プロパン、２，
２−ビス（４−ヒドロキシ−３，５−ジブロモフェニル
）プロパン、２，２−ビス（４−ヒドロキシ−３−メチ
ルフェニル）プロパン、ビス（４−ヒドロキシフェニル
）サルファイド、ビス（４−ヒドロキシフェニル）スル
ホン等があげられる。また、カーボネート前駆体として
はカルボニルハライド、ハロホルメート等かあげられ、
具体的にはホスゲン、ジフェニルカーボネート、二価フ
ェノールのジハロホルメート及びそれらの混合物である
。The polycarbonate resin used in the present invention is produced by reacting a dihydric phenol with a carbonate precursor by a solution method or a melt method. As a dihydric phenol, 2,2-bis(4-hydroxyphenyl)
The main target is propane (commonly known as bisphenol A), but part or all of it may be replaced with other dihydric phenols. Other dihydric phenols include, for example, bis(4
-hydroxyphenyl)methane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,
2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl) Examples include sulfone. In addition, carbonate precursors include carbonyl halide, haloformate, etc.
Specifically, they are phosgene, diphenyl carbonate, dihaloformates of dihydric phenols, and mixtures thereof.
【００１１】ポリカーボネート樹脂の重合度は特に制限
されないが、通常粘度平均分子量で表して１０，０００
〜５０，０００、好ましくは１３，０００〜４０，００
０である。かかるポリカーボネート樹脂を製造するに際
し、必要に応じて適当な分子量調節剤、加工性改善のた
めの分岐剤、反応を促進するための触媒等を使用するこ
とができる。また、かくて得られたポリカーボネート樹
脂の二種以上を混合して使用してもよい。The degree of polymerization of the polycarbonate resin is not particularly limited, but is usually 10,000 expressed in viscosity average molecular weight.
~50,000, preferably 13,000-40,00
It is 0. When producing such a polycarbonate resin, a suitable molecular weight regulator, a branching agent for improving processability, a catalyst for promoting reaction, etc. can be used as necessary. Furthermore, two or more of the polycarbonate resins thus obtained may be used in combination.
【００１２】本発明で難燃剤として使用する有機リン酸
エステルの金属塩は前記一般式［１］で示されるもので
あり、式中Ｘは水素又はハロゲン原子であり、ハロゲン
原子としては臭素又は塩素が好ましい。また、Ｍで表さ
れるアルカリ金属としては特にＫ又はＮａが好ましい。
かかる有機リン酸エステルの金属塩は、例えばクミルフ
ェノール又はハロゲン化クミルフェノールとオキシ塩化
リンとを反応させることによって容易に製造することが
できる。The metal salt of an organic phosphate ester used as a flame retardant in the present invention is represented by the above general formula [1], where X is hydrogen or a halogen atom, and the halogen atom is bromine or chlorine. is preferred. Further, as the alkali metal represented by M, K or Na is particularly preferable. Such metal salts of organic phosphate esters can be easily produced, for example, by reacting cumylphenol or halogenated cumylphenol with phosphorus oxychloride.
【００１３】一般式［１］の有機リン酸エステルの金属
塩の配合割合は、ポリカーボネート樹脂１００重量部に
対して０．００１〜５重量部であり、好ましくは０．０
０５〜２重量部である。０．００１重量部未満では難燃
効果が不充分であり、５重量部を超えると熱安定性が低
下するばかりか、かえって燃焼性が上昇するようになる
。また、従来の有機ハロゲン系難燃剤と併用することに
よってその難燃効果を大幅に向上することができ、両者
の使用量を著しく減少させることもできる。The blending ratio of the metal salt of the organic phosphate ester of general formula [1] is 0.001 to 5 parts by weight, preferably 0.0 parts by weight, based on 100 parts by weight of the polycarbonate resin.
05 to 2 parts by weight. If it is less than 0.001 parts by weight, the flame retardant effect will be insufficient, and if it exceeds 5 parts by weight, not only will the thermal stability decrease, but the flammability will even increase. Further, by using it in combination with conventional organic halogen flame retardants, the flame retardant effect can be greatly improved, and the amounts of both can be significantly reduced.
【００１４】本発明の樹脂組成物を製造するには、任意
の方法が採用される。例えば粉末状のポリカーボネート
樹脂と粉末状の一般式［１］の有機リン酸エステルの金
属塩をスーパーミキサー、タンブラー等を用いてドライ
ブレンドしてもよく、また一般式［１］の有機リン酸エ
ステルの金属塩をポリカーボネート樹脂の粉末に添加し
てから乾燥混合する方法でもよい。Any method can be used to produce the resin composition of the present invention. For example, a powdered polycarbonate resin and a powdered metal salt of an organic phosphate ester of the general formula [1] may be dry blended using a super mixer, a tumbler, etc. Alternatively, the metal salt may be added to the polycarbonate resin powder and then dry mixed.
【００１５】得られた組成物は、そのまま又は押出機で
ペレット状にして通常の射出成形、押出成形、圧縮成形
等の方法で成形品にすることができる。かくして得られ
る成形品は優れた透明性を保持している。The obtained composition can be made into a molded product as it is or by making it into pellets using an extruder and using conventional methods such as injection molding, extrusion molding, and compression molding. The molded article thus obtained retains excellent transparency.
【００１６】本発明の組成物には、必要に応じて任意の
添加剤、例えば安定剤、離型剤、滑剤、帯電防止剤、紫
外線吸収剤、有機ハロゲン化合物系難燃剤等を添加する
ことができる。また、透明性を犠牲にするならばフッ素
系ポリマー、シリコン系ポリマー、無機充填剤、ガラス
繊維、カーボン繊維等を添加することができる。[0016] If necessary, arbitrary additives such as stabilizers, mold release agents, lubricants, antistatic agents, ultraviolet absorbers, organic halogen compound flame retardants, etc. may be added to the composition of the present invention. can. Further, if transparency is sacrificed, fluorine-based polymers, silicon-based polymers, inorganic fillers, glass fibers, carbon fibers, etc. can be added.
【００１７】[0017]
【実施例】以下に実施例をあげて本発明を具体的に説明
する。[Examples] The present invention will be explained in detail with reference to Examples below.
【００１８】[0018]
【実施例１〜３及び比較例１〜３】予め乾燥した粘度平
均分子量が約２３，０００のビスフェノールＡポリカー
ボネート樹脂［帝人化成（株）製パンライトＬ−１２５
０］１００重量部に、表１記載の添加剤を表記載の量添
加し、Ｖ型ブレンダ−により予備混合した後、直ちにシ
リンダ−温度２８０℃に設定した単軸ベント式押出機［
ナタカタニ（株）製ＶＳＫ−３０］により押出してペレ
ット化した。得られたペレットを１２０℃で６時間乾燥
した後、射出成形機［住友重機工業（株）製サイキャッ
プＳ４８０／１５０］によりシリンダー温度２９０℃、
金型温度９０℃で５インチ×１／２インチ×１／１６イ
ンチの試験片を成形し、この試験片を用いてＵＬ−９４
の燃焼試験及び目視による外観評価を行い、結果を表１
に示した。なお、表中の添加剤の種類における記号は下
記の通りである。[Examples 1 to 3 and Comparative Examples 1 to 3] Pre-dried bisphenol A polycarbonate resin having a viscosity average molecular weight of about 23,000 [Panlite L-125 manufactured by Teijin Kasei Ltd.]
0] Add the additives listed in Table 1 in the amounts listed in the table to 100 parts by weight, premix in a V-type blender, and then immediately set the cylinder temperature to 280°C in a single-screw vent type extruder [
VSK-30 (manufactured by Natakatani Co., Ltd.) was extruded into pellets. After drying the obtained pellets at 120°C for 6 hours, the cylinder temperature was set at 290°C using an injection molding machine [Cycap S480/150 manufactured by Sumitomo Heavy Industries, Ltd.].
A 5 inch x 1/2 inch x 1/16 inch test piece was molded at a mold temperature of 90°C, and this test piece was used to meet the UL-94 standard.
A combustion test and visual appearance evaluation were conducted, and the results are shown in Table 1.
It was shown to. The symbols for the types of additives in the table are as follows.
【００１９】Ａ：４−クミルフェノールとオキシ塩化リ
ンとを脱塩化水素剤存在下に反応させてジアリールリン
酸クロリドとし、これを加水分解することにより合成し
た下記構造のものである。A: The following structure was synthesized by reacting 4-cumylphenol and phosphorus oxychloride in the presence of a dehydrochlorinating agent to obtain diarylphosphoric acid chloride, which was then hydrolyzed.
【００２０】[0020]
【化３】
Ｂ：４−クミルフェノールを常法でブロム化し、これと
オキシ塩化リンとを脱塩化水素剤存在下に反応させてジ
アリールリン酸クロリドとし、これを加水分解すること
により合成した下記構造のものである。[Chemical formula 3] B: Synthesized by brominating 4-cumylphenol in a conventional manner, reacting this with phosphorus oxychloride in the presence of a dehydrochlorinating agent to obtain diarylphosphoric acid chloride, and hydrolyzing this. It has the following structure.
【００２１】[0021]
【化４】
Ｃ：４−クミルフェノールを常法でクロル化し、これと
オキシ塩化リンとを脱塩化水素剤存在下に反応させてジ
アリールリン酸クロリドとし、これを加水分解すること
により合成した下記構造のものである。[Chemical formula 4] C: Synthesized by chlorinating 4-cumylphenol in a conventional manner, reacting this with phosphorus oxychloride in the presence of a dehydrochlorinating agent to obtain diarylphosphoric acid chloride, and hydrolyzing this. It has the following structure.
【００２２】[0022]
【化５】
Ｄ：下記構造のものである［アデカ・アーガス（株）製
ＮＡ−１０］。embedded image D: It has the following structure [NA-10 manufactured by Adeka Argus Co., Ltd.].
【００２３】[0023]
【化６】
Ｅ：４−ブロモフェノールとオキシ塩化リンとを脱塩化
水素剤存在下に反応させてジアリールリン酸クロリドと
し、これを加水分解することにより合成した下記構造の
ものである。embedded image E: This compound has the following structure and was synthesized by reacting 4-bromophenol and phosphorus oxychloride in the presence of a dehydrochlorinating agent to obtain diarylphosphoric acid chloride, which was then hydrolyzed.
【００２４】[0024]
【化７】[C7]
【００２５】[0025]
【表１】[Table 1]
【００２６】[0026]
【発明の効果】本発明の組成物はＵＬ−９４の燃焼性試
験において優れた難燃性を示し、且つフッ素系ポリマー
やガラス繊維を添加しないときは透明であり、成形及び
燃焼時の腐蝕性ガスの発生が少ない。このように本発明
の組成物は、従来の難燃性ポリカーボネート組成物に比
して優れた性能を有するので、広範囲の用途に使用する
ことができる。Effects of the Invention The composition of the present invention exhibits excellent flame retardancy in the UL-94 flammability test, is transparent when no fluoropolymer or glass fiber is added, and has low corrosion resistance during molding and combustion. Less gas is generated. As described above, the composition of the present invention has superior performance compared to conventional flame-retardant polycarbonate compositions, and therefore can be used in a wide range of applications.
Claims (1)
、下記一般式［１］ 【化１】 ［但し、式中Ｘは水素又はハロゲン原子、Ｍはアルカリ
金属］で示される有機リン酸エステルの金属塩の少なく
ともー種を０．００１〜５重量部配合してなる難燃性ポ
リカーボネート樹脂組成物。Claim 1: To 100 parts by weight of polycarbonate resin, a metal salt of an organic phosphate ester represented by the following general formula [1] [wherein X is a hydrogen or halogen atom, and M is an alkali metal] is added. A flame-retardant polycarbonate resin composition containing 0.001 to 5 parts by weight of at least one species.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2914791A JP2591538B2 (en) | 1991-01-31 | 1991-01-31 | Flame retardant polycarbonate resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2914791A JP2591538B2 (en) | 1991-01-31 | 1991-01-31 | Flame retardant polycarbonate resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04246460A true JPH04246460A (en) | 1992-09-02 |
| JP2591538B2 JP2591538B2 (en) | 1997-03-19 |
Family
ID=12268151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2914791A Expired - Fee Related JP2591538B2 (en) | 1991-01-31 | 1991-01-31 | Flame retardant polycarbonate resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2591538B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06184419A (en) * | 1992-12-21 | 1994-07-05 | Teijin Chem Ltd | Flame-retardant aromatic polycarbonate resin composition |
| JPH06184422A (en) * | 1992-12-21 | 1994-07-05 | Teijin Chem Ltd | Flame-retardant polycarbonate resin composition |
| JPH06184421A (en) * | 1992-12-21 | 1994-07-05 | Teijin Chem Ltd | Flame-retardant aromatic polycarbonate resin composition |
-
1991
- 1991-01-31 JP JP2914791A patent/JP2591538B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06184419A (en) * | 1992-12-21 | 1994-07-05 | Teijin Chem Ltd | Flame-retardant aromatic polycarbonate resin composition |
| JPH06184422A (en) * | 1992-12-21 | 1994-07-05 | Teijin Chem Ltd | Flame-retardant polycarbonate resin composition |
| JPH06184421A (en) * | 1992-12-21 | 1994-07-05 | Teijin Chem Ltd | Flame-retardant aromatic polycarbonate resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2591538B2 (en) | 1997-03-19 |
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