TW482808B - Flame retardant thermoplastic resin composition - Google Patents
Flame retardant thermoplastic resin composition Download PDFInfo
- Publication number
- TW482808B TW482808B TW88113751A TW88113751A TW482808B TW 482808 B TW482808 B TW 482808B TW 88113751 A TW88113751 A TW 88113751A TW 88113751 A TW88113751 A TW 88113751A TW 482808 B TW482808 B TW 482808B
- Authority
- TW
- Taiwan
- Prior art keywords
- weight
- mixture
- scope
- alkyl
- parts
- Prior art date
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
482808 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明( 發明背景 本發明是關於以聚碳酸醋為主的熱塑性模塑防火劑成 分,其獲改善之有助益於其在電器及電子產品框架上之應 用。耐燃性,熱安定性與抗應力碎裂性。此外,本發明之 樹脂成分在射出成型加工時不會有冒煙或滲透的現象。更 特定言之,本發明提供的以聚碳酸酯為主的熱塑性模塑成 分包括一聚碳酸酯,一橡膠重塑的接枝共聚物,一乙烯基 共聚物,一特定的聚磷化物及一單體磷化物之混合物;其 t聚磷化物之量少於5〇Wt%且等於或多於防火劑或如聚氯 化烯烴及對芳香族聚碳酸酯具防火性鹽類之丨〇 w t %。 ^石反酸酯模塑成分因具備極佳的透明度、高耐衝擊強 度及防火性而廣泛地運用在電子產品與汽車組件的零件上 。然因模塑過程中加工不易,聚碳酸酯樹脂通常與其他種 類樹脂摻合使用。例如包含了 一聚碳酸酯樹脂與一含苯乙 烯树月曰的模塑成分就同時具備易加工性與高缺口对衝擊強 度。 而且,用於家電用品及電腦的零件之聚破酸酯模塑成 分尤須具高抗燃性以防火。為達此目的,含函素並(或)含 銻的化合物已使用於熱塑性模塑成分中使具防火性。美國 專利第 4,983,658 號和 4,883,835 號(U.S· Pat. No· 4,983,658, No. 4,883,835)中’已採用含鹵素化合物為防火劑。然而,含鹵 素化合物在模塑過程中釋放函化氫氣體會導致模型本身腐 姓,同時也因燃燒時產生有毒氣體而具致命的危害性。 美國專利第 4,692,488 號(U.S· Pat· No· 4,692,488)記述熱 表紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐 — ί — — — — — — — - I I (請先閱讀背面之注意事項再填寫本頁) 訂---- 482808 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明(> 塑-性模塑成分使用不含_素的芳香族聚碳酸酯、不含鹵素 的本乙烯和丙烯月青共聚物、不含鹵素的填化物、四氟乙烯 I曰物及夕里的ABS接枝聚合物。在4,692,488號專利中使 用磷化物及全氟代烷類聚合物提高聚碳酸酯/ABS樹脂的 防火性’可防止燃燒過程中火焰粒子掉落的問題。雖然這 模塑成分的確有足夠的防火性與機械性質,但模塑過程中 防火移動,所明的”滲透現象(biee(jing 〇ut),,,有可能導 致表面龜裂的情形。 美國專利第 5,030,675 號(U.s. Pat· No· 5,030,675)中記述 抗燃性熱塑模塑成分由芳香族聚碳酸酯、ABS聚合物、聚 對苯一甲基烯烴及以磷酸酯類和聚氟化烯烴為防火劑組成 ’具有良好的抗應力碎裂性,但缺口耐衝擊強度不足,同 時在加工升溫過程中的熱安定性不佳。 聚磷酸酯是眾知的防火劑,日本專利第59_2〇2,24〇號 (JA 59-202,240)記述了***、聯苯二酚類(如對苯二酚 或雙酚A),與單酚類(如酚或甲酚)組成的產物。這些聚磷 酉义酉曰T以^作在聚胺或聚碳酸自旨内的防火劑。但是這份 專利中限制單體磷酸酯的用量在全部聚磷酸酯量之4 〇 w t % 以内。 美國專利第 5,204,394號(U.S. Pat. No· 5,204,394)記述一 高分子混合物,其中包含芳香族聚碳酸酯、一共聚物與( 或)含苯乙烯的接枝共聚物、以及作為防火劑的聚磷酸酯 。美國專利第 5,〇61,745 號(U.S· Pat. No· 5,〇61,745)記述的聚 石反酸s日模塑成分含芳香族聚碳酸酯、ABS接枝共聚物及以 Μ氏張尺度適財—雜準(CNS)A4規格(21〇T^i7 .r t. i 111 Aw ---— I i 11 訂·---------- (請先閱讀背面之注意事項再填寫本頁) A7 經濟部智慧財產局員工消費合作社印製 五、發明說明(乃) 磷酸酯單體為防火劑,並選擇性添加另一共聚物。在前述 的專利中,典型的磷化物是三芳基磷酸酯及聚磷酸酯。在 使用包含聚碳酸酯、含苯乙烯的接枝共聚物、乙烯基共聚 物為主的樹脂為防火劑模塑成分的例子中,抗應力碎裂性 主要取決於防火劑的揮發度(例如防火劑的分子量)以及聚 碳酸酯與防火劑的互適性。採用三芳基磷酸酯時,由於揮 發度,三芳基磷酸酯在表面形成薄層,會在模塑過程中出 現滲透現象。另一方面,當採用聚磷酸酯,防火劑蒸發造 成的渗透現象雖可減少,但當聚磷酸酯防火劑與聚碳酸酉旨 樹脂沒有良好的互適性時,防火劑移動到模塑零件的表面 仍會造成表面龜裂的情形。而且熱安定性因為聚磷酸酯熱 分解而降低,導致射出成形物表面有黑色斑。 美國專利第 5,672,645 號(U.S. Pat. No. 5,672,645)記述防 火性聚碳酸酯/ABS模塑成分包含一芳香族聚碳酸酯、一 乙烯基共聚物、一接枝共聚物、一單磷化物與一聚磷化物 組合的防火劑,以及一聚氣化烯烴。此專利中,間苯二紛 或對本二盼類的衍生物被用為一聚填化物防火劑,但已知 間苯二紛或對苯二酚類的低聚合體磷酸酯與聚碳酸酯樹脂 的互適性並不佳。所以這組成的耐衝擊強度會降低,且防 火劑移動到模塑零件表面造成的表面龜裂仍會發生。同時 這些間苯二酚或對苯二酚衍生的聚磷酸酯熱分解時也使得 模塑零件表面有色斑出現。 歐洲專利第0 767 204 A2陳述防火劑聚碳酸Sg/ABS 模塑成分,其中雙酚A類聚磷酸酯和單磷酸酯是與聚苯鱗 表紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) I ϋ ϋ I ϋ I H ϋ If ϋ ---?-------·裝 (請先閱讀背面之注意事項再填寫本頁) 訂---- ·· 經濟部智慧財產局員工消費合作社印製 482808 A7 五、發明說明(仑) 或聚碳酸酉旨混合。本專利中之模塑成分在射出成型加工時 沒有冒煙或渗透現象,且聚磷酸醋量超過防火劑量5〇 之磷酉旨混合物很容易處理。但本專利所述之樹脂成分在射 出成型加工時之防火性,耐衝擊強度及熱穩定性等性質上 相對較差。 ' 鑒於前述情況,本發明進行了更廣泛的研究,終於發 現一種結合良好的熱安定性、防火性、耐衝擊強度、易加 工性與外觀佳的新熱塑性模塑成分,其包含一聚碳酸酯、 一橡膠重塑接枝的共聚物,乙烯基共聚物,雙酚A衍生的 特定聚磷化物、聚氟化烯烴、及選擇性添加的單體磷化物 〇 本發明經由上述發現已經完成。 發明概述 本發明中的一物件是為提供一改良防火性、耐衝擊強 度、咼财熱性及加工時極佳之熱安定性的防火性熱塑性模 塑成分’其包含一聚碳酸酯、一橡膠重塑接枝共聚物、乙 烯基共聚物,雙酚A衍生的特定聚磷化物混合物、聚氟化 •烯烴、及聚磷酸酯量佔全部防火劑重量百分之10到5〇的單 體填化物。 本發明提供的熱塑性防火劑模塑成分包括: (A) 重量百分之40到95的不含鹵素之熱塑性聚碳酸酯; (B) 重量百分之1到50由接枝聚合法產生的接枝聚合物 (B-1)重量百分之5到95的混合物由 (B-1.1)重量百分之50到95的苯乙烯、α-甲基苯乙烯 ___8_ 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) L·J ^---------------^--------- (請先閱讀背面之注意事項再填寫本頁) 482808 A7 五、發明說明(4 ) 、函素或甲基取代環的苯乙稀、c「c8院基甲基丙稀 酸西旨、crc8烧基丙烯酸酷,或是它們的混合物,以 及 (B-1.2)重量百分之5到50的丙烯胯、甲基丙烯月青、 c8烷基曱基丙烯酸酯、Cl_C8烷基丙烯酸酯、順丁烯 二酐、CVC4烧基或苯基氮位取代的順丁烯二酿亞胺 ,或是它們的混合物,以及 (12)重量百分之5到95,玻璃轉化溫度低於_1〇它的聚 合物,選自下列組成中:丁二稀橡膠、丙稀酸橡膠、 乙烯/丙烯橡膠、苯乙烯/丁二烯橡膠、丙烯骑/丁 二烯橡膠、異戊二烯橡膠、EPDM橡膠、聚有基矽氧烷 衍生物,及它們的混合物, (C) 重量百分比〇到50的乙烯基共聚物或是由下列製備的 混合物 (C-1)重量百分之50到95的苯乙烯、α—甲基苯乙稀、 環取代的本乙歸r、CrC8烧基甲基丙烯酸|旨、CrC8烧基 丙浠酸S旨’或是它們的混合物,以及 (C-2)重量百分之50到5的丙烯胯、甲基丙烯腈、 烧基甲基丙烯酸酯、CrC8烷基丙烯酸酯、順丁烯二軒 、氮位取代的順丁烯二醯亞胺或是它們的混合物, (D) 重量百分之0.5到20 ((A)+(B)+(C)為百分基準)的混合 磷酸酯包含 (D-1)重量百分之10到50之具下列一般分子式(I)的聚 磷酸酯混合物 _ __9 ^紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公髮 (請先閱讀背面之注咅?事項再填寫本頁) 裝----- tlI_ 經濟部智慧財產局員工消費合作社印製 "tOZ.OUO五 、發明說明(V) A7 B7 其中482808 Printed A7 by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (BACKGROUND OF THE INVENTION The present invention relates to a thermoplastic moulding flame retardant component mainly composed of polycarbonate, which can be improved to benefit its use in electrical and electronics Application on the product frame. Flame resistance, thermal stability and stress chipping resistance. In addition, the resin component of the present invention will not emit smoke or penetrate during the injection molding process. More specifically, the present invention provides Polycarbonate-based thermoplastic molding ingredients include a polycarbonate, a rubber-reshaped graft copolymer, a vinyl copolymer, a specific polyphosphide and a monomer phosphide mixture; its t The amount of polyphosphide is less than 50 Wt% and is equal to or more than that of a fire retardant or a fire-resistant salt such as polychlorinated olefin and aromatic polycarbonate. Because of its excellent transparency, high impact strength and fire resistance, it is widely used in electronic products and automotive component parts. However, due to the difficulty of processing during the molding process, polycarbonate resins are often used with other types of resins. Blended use. For example, it contains a polycarbonate resin and a styrene-containing molding component that has both easy processability and high notch impact strength. In addition, it is used for household appliances and computer parts. Ester molding components must especially have high flame resistance to prevent fire. To this end, compounds containing selenium and / or antimony have been used in thermoplastic molding components to make them fire resistant. US Patent Nos. 4,983,658 and No. 4,883,835 (US Pat. No. 4,983,658, No. 4,883,835) has used halogen-containing compounds as fire retardants. However, the release of hydrogen-containing hydrogen gas during the molding process by halogen-containing compounds will cause the model itself to rot, but also because of the Toxic gases are generated during combustion and are fatally hazardous. US Patent No. 4,692,488 (US Pat. No. 4,692,488) states that the paper size of the heat meter applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm — ί — — — — — — — —-II (Please read the notes on the back before filling out this page) Order ---- 482808 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Invention Description > Plastic-mold components use aromatic polycarbonates free of halogen, halogen-free ethylene and propylene moon copolymers, halogen-free fillers, tetrafluoroethylene compounds and ABS in the evening Graft polymers. The use of phosphides and perfluoroalkane polymers in Patent No. 4,692,488 to improve the fire resistance of polycarbonate / ABS resins' can prevent the problem of flame particles falling during combustion. Although this molding component does It has sufficient fire resistance and mechanical properties, but the fire resistance movement during the molding process, the "penetration phenomenon" (biee (jing ut)), may cause surface cracking. U.S. Patent No. 5,030,675 (Us Pat. No. 5,030,675) describes a flame-resistant thermoplastic molding composition consisting of aromatic polycarbonate, ABS polymer, polyparaphenylene olefin, and phosphate esters and polyfluorinated The olefin is a fire retardant composition, and has good resistance to stress cracking, but notched impact strength is insufficient, and the thermal stability during processing temperature rise is not good. Polyphosphate is a well-known fire retardant. Japanese Patent No. 59_2202, 240 (JA 59-202,240) describes phosphorus oxychloride and biphenyls (such as hydroquinone or bisphenol A). A product composed of monophenols (such as phenol or cresol). These polyphosphoric acids are used as flame retardants in the purpose of polyamines or polycarbonates. However, the amount of monomeric phosphate esters in this patent is limited to 40 wt% of the total amount of polyphosphates. US Pat. No. 5,204,394 (US Pat. No. 5,204,394) describes a polymer mixture containing an aromatic polycarbonate, a copolymer and / or a styrene-containing graft copolymer, and polyphosphoric acid as a flame retardant ester. The poly-acid inverse acid molding composition described in US Pat. No. 5,061,745 (US Pat. No. 5,061,745) contains an aromatic polycarbonate, an ABS graft copolymer, and M Zhang's scale suitable for wealth-miscellaneous standard (CNS) A4 specification (21〇T ^ i7 .r t. I 111 Aw ----- I i 11 order · ---------- (Please read the back first Please note this page, please fill in this page) A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (Yes) Phosphate ester monomer is a fire retardant, and another copolymer is optionally added. Phosphides are triaryl phosphates and polyphosphates. In the case of using polycarbonate, styrene-containing graft copolymers, and vinyl copolymer-based resins as the flame retardant molding component, stress crack resistance The crackability is mainly determined by the volatility of the fire retardant (such as the molecular weight of the fire retardant) and the compatibility of the polycarbonate and the fire retardant. When using triaryl phosphate, due to the volatility, the triaryl phosphate will form a thin layer on the surface, which will Penetration occurs during molding. On the other hand, when polyphosphate is used, Although the penetration phenomenon can be reduced, when the polyphosphate flame retardant does not have good compatibility with the polycarbonate resin, the fire retardant will still cause surface cracking when it moves to the surface of the molded part. Moreover, the thermal stability Polyphosphates are thermally decomposed and reduced, resulting in black spots on the surface of the injection molded article. US Pat. No. 5,672,645 (US Pat. No. 5,672,645) states that the flame-resistant polycarbonate / ABS molding composition contains an aromatic polycarbonate, A vinyl copolymer, a graft copolymer, a monophosphide and a polyphosphide fire retardant, and a polygasified olefin. In this patent, m-xylylene or derivatives of this diphenanthrene are It is used as a polyfill fire retardant, but it is known that the resorcinol or hydroquinone oligomer phosphate esters have poor compatibility with polycarbonate resins. Therefore, the impact resistance of this composition will decrease, In addition, surface cracks caused by the movement of the fire retardant to the surface of the molded part will still occur. At the same time, the resorcinol or hydroquinone-derived polyphosphate ester also causes colored spots on the surface of the molded part during thermal decomposition. Chau Patent No. 0 767 204 A2 states that the flame retardant polycarbonate Sg / ABS molding composition, in which bisphenol A polyphosphate and monophosphate are the same as the polystyrene scale sheet paper scale applicable Chinese National Standard (CNS) A4 specification (210 X 297 public love) I ϋ ϋ I ϋ IH ϋ If ϋ ---? ------- · install (Please read the precautions on the back before filling this page) Order ---- ·· Intellectual Property of the Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperative Cooperative 482808 A7 V. Description of Invention (lun) or Polycarbonate Mixture. The molding ingredients in this patent did not emit smoke or penetrate during the injection molding process, and the amount of polyphosphate vinegar exceeded the fireproofing amount 5 The mixture of phosphoric acid and phosphonium is easy to handle. However, the resin components described in this patent are relatively inferior in properties such as fire resistance, impact strength and thermal stability during injection molding. '' In view of the foregoing, the present invention has undergone more extensive research and has finally found a new thermoplastic molding composition that combines good thermal stability, fire resistance, impact strength, ease of processing, and appearance, comprising a polycarbonate 1. A rubber remodeling graft copolymer, vinyl copolymer, specific polyphosphide derived from bisphenol A, polyfluorinated olefin, and optionally added monomer phosphide. The present invention has been completed through the above findings. SUMMARY OF THE INVENTION An object in the present invention is to provide a fire-resistant thermoplastic molding composition that has improved fire resistance, impact resistance, thermal properties, and excellent thermal stability during processing. It includes a polycarbonate, a rubber weight Plastic graft copolymers, vinyl copolymers, bisphenol A-derived specific polyphosphide mixtures, polyfluorinated olefins, and monomer fillers that account for 10 to 50 percent by weight of the total flame retardant . The thermoplastic flame retardant molding composition provided by the present invention comprises: (A) a halogen-free thermoplastic polycarbonate having a weight of 40 to 95 percent; (B) a weight of 1 to 50 percent by weight of a graft produced by a graft polymerization method; The mixture of branched polymer (B-1) 5 to 95 percent by weight (B-1.1) 50 to 95 percent by weight of styrene, α-methylstyrene ___8_ This paper size applies to Chinese national standards ( CNS) A4 size (210 X 297 mm) L · J ^ --------------- ^ --------- (Please read the precautions on the back before filling (This page) 482808 A7 V. Description of the invention (4), stilbene with a functional element or a methyl-substituted ring, c "c8-Cyclomethylacrylic acid, crc8-acrylic acid, or a mixture thereof, And (B-1.2) 5 to 50 percent by weight of propylene fluorene, methacrylic moonlight, c8 alkylfluorenyl acrylate, Cl_C8 alkyl acrylate, maleic anhydride, CVC4 alkyl or phenyl nitrogen Substituted maleimide, or a mixture thereof, and (12) a polymer having a glass transition temperature of less than 10% by weight from 5 to 95 percent, selected from the group consisting of butadiene Thin rubber, acrylic acid Rubber, ethylene / propylene rubber, styrene / butadiene rubber, propylene / butadiene rubber, isoprene rubber, EPDM rubber, polysiloxane derivatives, and mixtures thereof, (C) Weight Percents 0 to 50 vinyl copolymers or mixtures (C-1) prepared from the following 50 to 95% by weight of styrene, α-methylstyrene, ring-substituted benzine r, CrC8 Methacrylic acid | Crystalline, CrC8 alkylaminopropionate, or mixtures thereof, and (C-2) 50 to 5 percent by weight of acrylic acid, methacrylonitrile, and ethyl methacrylate , CrC8 alkyl acrylate, maleic acid, nitrogen-substituted maleic acid, or mixtures thereof, (D) 0.5 to 20% by weight ((A) + (B) + ( C) is a percentage basis) mixed phosphate ester containing (D-1) 10 to 50% by weight of a polyphosphate ester mixture with the following general formula (I) _ __9 ^ Paper size applies Chinese National Standard (CNS) A4 Specifications (210 X 297 issued (please read the note on the back? Matters before filling out this page) Packing ----- tlI_ Intellectual Property Bureau, Ministry of Economic Affairs, Consumer Consumption Cooperative System " tOZ.OUO V. invention is described in (V) A7 B7 wherein
Rl-〇- Γ 9 π P—0~ D 1 R3~—〇—p——〇- 0 1 0 R2 ^ R4」 Rs (I) R] R2、心及1^表示相互獨立的C6-C2G芳香族羥基或烷 基取代的芳香族羥基,R3表示由雙酚A得出的殘 基,Μ表示等於或大於丨的整數,以及 (D-2)重量百分之5〇到9〇的具下列一般分子式的單 體磷化物或其混合物 0Rl-〇- Γ 9 π P—0 ~ D 1 R3 ~ —〇—p——〇- 0 1 0 R2 ^ R4 」Rs (I) R] R2, heart and 1 ^ represent independent C6-C2G aromatics Group hydroxy or alkyl-substituted aromatic hydroxy, R3 represents a residue derived from bisphenol A, M represents an integer equal to or greater than 丨, and (D-2) 50 to 90 percent by weight has the following Monophosphates of general formula or mixtures thereof 0
(Π) 3-Ν 其中 經濟部智慧財產局員工消費合作社印製 R表示一烷基如第三丁基、異丙基、異丁基、異戊基、 第三戊基,Ν是0或一個從(含)ι到3的整數,以及(Ε)防 火劑。 較佳實施例之詳細說明 (Α)不含鹵素之熱塑性聚碳酸酯 本發明中適當的成分(Α)熱塑性芳香族聚碳酸酯大抵 由具下列分子式(瓜)的聯苯二齡與光氣、甲酸_素或碳酸 二酯類反應而成。(Π) 3-N where printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy, R represents a monoalkyl group such as third butyl, isopropyl, isobutyl, isopentyl, third pentyl, and N is 0 or one Integer from (inclusive) to 3, and (Ε) fire retardant. Detailed description of the preferred embodiment (A) Halogen-free thermoplastic polycarbonate The appropriate component (A) of the thermoplastic aromatic polycarbonate in the present invention is probably biphenyl second-generation with phosgene, Formate or carbonic acid diester.
l· ----^-------裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 482808 A7l · ---- ^ ------- Install -------- Order --------- (Please read the precautions on the back before filling this page) 482808 A7
(Η) 五、發明說明( Η 其中 Α表一單鍵的Cl_Cs的烯烴,I到q的二烯烴,到匕的環 二烯烴,硫或二氧化硫。 具分子式(瓜)聯苯二酚的特定例子有對苯二酚、間笨 二酚、4,4-二羥基聯苯、2,2-雙-(4-羥苯基)丙烷、2,‘雙_(4_ 羥苯基)-2-甲基丁烷、ι,ΐ-雙_(4_羥苯基)_環己烷、2,孓雙气弘 氯-4-羥苯基)丙烷、2,2-雙-(3,5-二溴-4-羥苯基)丙烷。在 這些中較好的是2,2-雙-(4-經苯基)丙烧、2,2-雙-(3,5-二 氯-4-羥苯基)丙烷及込丨-雙气仁羥苯基)_環己烷。最廣泛受 歡迎使用的芳香族聚碳酸酯是由雙酚A,2,2_雙_(4_羥苯基 )丙烷所製備的。 至於本發明適合的(A)聚碳酸酯的平均分子量介於 10,0 0 0到20 0,0 0 0之間(Mw平均重量,例如以超離心法或 光散射法測量),較好的是15,000到80,000之間。 併入此發明成分中的適當(A)聚碳酸酯可以用已知的 方法來分支化,特別是混合0.05到2mol·%的三個或更多官 •能基的化合物(以使用的聯苯二酚總量為基準),例如有三 個或更多個紛團。 本發明適合的聚碳酸酯包含了單質聚碳酸g旨與共聚合 的聚碳酸酯類。(A)化合物也可以是上述指定的熱塑性聚 碳酸酯的摻合物。 (A)聚碳酸酯可被經由以酯類先質(例如雙官能基的魏 π 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) Γ J---r-------裝--------訂--------- (請先閲讀背面之江意事頊存填寫本買) 經濟部智慧財產局員工消費合作社印製 A7 ______ B7 五、發明說明(g ) ^代進仃聚合反應後得到的芳香族聚碳酸S旨部分或全部 (B)接枝共聚物 本發明使用的接枝共聚物是由下列單體製備的 丨)重1百分之5到95(以(B)為基準)的混合物由 (B-U)重量百分之5〇到95的苯乙烯、以一甲基苯乙烯 白素或甲基取代環的苯乙烯、烷基甲基丙烯酸酯 、Ci-q烷基丙烯酸酯,或是它們的混合物,以及 (B-1.2)重量百分之5到5〇的丙烯腈、甲基丙烯腈、Cr 8燒基甲基丙細酸醋、CrCs烧基丙烯酸酯、順丁烯二酐 、CrC4烷基或苯基氮位取代的順丁烯二醯亞胺或是它們 的混合物,以及 % (B-2)重量百分之5到95,玻璃轉化溫度低於_1〇它的聚 合物,選擇自下列組成中:丁二烯橡膠、丙烯酸橡膠、乙 烯/丙烯橡膠、苯乙烯/丁二烯橡膠、丙烯骑/丁二烯橡 膠、異戊二烯橡膠、EPDM橡膠、聚有基矽氧烷衍生物, 及它們的混合物。 經濟部智慧財產局員工消費合作社印製(Η) 5. Description of the invention (Η where A represents a single-bonded Cl_Cs olefin, I to q dienes, to cyclic dienes, sulfur or sulfur dioxide. Specific examples of molecular formula (melon) biphenyl Hydroquinone, resorcinol, 4,4-dihydroxybiphenyl, 2,2-bis- (4-hydroxyphenyl) propane, 2, 'bis_ (4_hydroxyphenyl) -2-methyl Butane, ι, fluorene-bis- (4-hydroxyphenyl) _cyclohexane, 2, fluorene-bis-chloro-4-hydroxyphenyl) propane, 2,2-bis- (3,5-di Bromo-4-hydroxyphenyl) propane. Of these, 2,2-bis- (4-transphenyl) propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) propane, and 込 丨 -digas are preferred. Enhydroxyphenyl) _cyclohexane. The most widely used aromatic polycarbonates are made from bisphenol A, 2,2-bis- (4-hydroxyphenyl) propane. As for the (A) polycarbonate suitable for the present invention, the average molecular weight is between 10,000 and 20,000 (Mw average weight, for example, measured by ultracentrifugation or light scattering method). It is between 15,000 and 80,000. Suitable (A) polycarbonates incorporated in the ingredients of this invention can be branched by known methods, especially by mixing 0.05 to 2 mol ·% of three or more functional compounds (with biphenyls used) Total diphenols as a benchmark), for example, three or more clumps. Suitable polycarbonates for the present invention include elementary polycarbonates and copolymerized polycarbonates. The compound (A) may be a blend of the thermoplastic polycarbonates specified above. (A) Polycarbonate can be prepared with an ester precursor (such as bi-functional Wei π). The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm). Γ J --- r --- ---- Equipment -------- Order --------- (Please read Jiang Yishi on the back and fill in this purchase) Printed by A7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs ______ B7 V. Description of the invention (g) ^ Partially or wholly (B) graft copolymer of aromatic polycarbonate S obtained after substituting 仃 polymerization reaction The graft copolymer used in the present invention is prepared from the following monomers 丨) 1 to 5 to 95 percent (based on (B)) mixture consisting of (BU) 50 to 95 percent styrene, monomethylstyrene or methyl substituted ring styrene , Alkyl methacrylates, Ci-q alkyl acrylates, or mixtures thereof, and (B-1.2) acrylonitrile, methacrylonitrile, Cr 8 methyl based on 5 to 50 percent by weight Acrylic acid, CrCs alkyl acrylate, maleic anhydride, CrC4 alkyl or phenyl nitrogen-substituted maleimide, or mixtures thereof, and% (B-2) by weight 5 to 95, glass Polymers with a conversion temperature below -10, selected from the following compositions: butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, propylene / butadiene rubber, isoprene Ethylene rubber, EPDM rubber, polysiloxane derivatives, and mixtures thereof. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs
CrCs烷基丙烯酸酯或crC8烷基甲基丙烯酸酯各是丙 稀酸或曱基丙烯酸與帶有一個到八個碳原子一元醇的酯類 ’特定例子包括曱基丙烯酸曱酯、曱基丙烯酸乙酯及曱基 丙烯酸丙酯,對曱基丙烯酸曱酯而言,曱基丙烯酸酯尤佳 較適當的(B)接枝共聚物包括聚丁二烯、丁二烯/苯 乙烯共聚物與和苯乙烯及(或)丙烯贿或是烷基甲基丙烯酸 12_ 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 808 A7 B7CrCs alkyl acrylate or crC8 alkyl methacrylate each is an ester of acrylic acid or fluorenyl acrylic acid and a monohydric alcohol having one to eight carbon atoms. Specific examples include fluorenyl acrylate, ethyl methacrylate Esters and propyl methacrylate. For fluorenyl acrylate, methacrylate is particularly suitable. (B) Graft copolymers include polybutadiene, butadiene / styrene copolymer, and benzene. Ethylene and / or propylene bribe or alkyl methacrylic acid 12_ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 808 A7 B7
五、發明說明(q ) 經濟部智慧財產局員工消費合作社印製 酉曰接枝的丙烯酸橡膠,這些當中,AB S聚合物特別適於(B) 接枝共聚物。 為增進耐衝擊強度和模製表面,(B-2)橡膠較好的粒 子大小是0 · 0 5到4 //m。 (B)成分接枝共聚物可用傳統製備接枝共聚物的方法 製備,特別是乳化聚合、懸浮聚合、溶液或本體聚合法。 準備(B)共聚物較好的方法是採用乳化聚合或本體聚合。 (c)乙烯基共聚物 本發明使用的(C )成分乙烯基共聚物之製備由 (C-1)重量百分之50到95的苯乙烯、α-甲基苯乙烯、 %取代的苯乙烯、crcs烷基甲基丙烯酸酯、Ci_C8烷基丙 稀酸酯,或是它們的混合物,以及 (C-2)重量百分之50到5的丙烯月青、甲基丙烯胯、c i 8 烧基曱基丙烯酸酯、CrC8烷基丙烯酸酯、順丁烯二酐、 氮位取代的順丁烯二醯亞胺,或是它們的混合物。V. Description of the invention (q) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, grafted acrylic rubber. Among these, ABS polymer is particularly suitable for (B) graft copolymer. To improve the impact strength and molding surface, the preferred particle size of (B-2) rubber is 0 · 0 5 to 4 // m. The component (B) graft copolymer can be prepared by a conventional method for preparing a graft copolymer, and particularly, an emulsion polymerization, suspension polymerization, solution or bulk polymerization method. A better method for preparing (B) copolymer is to use emulsion polymerization or bulk polymerization. (c) Vinyl copolymer The (C) component vinyl copolymer used in the present invention is prepared from (C-1) 50 to 95 percent by weight of styrene, α-methylstyrene, and% substituted styrene. , Crcs alkyl methacrylate, Ci_C8 alkyl acrylate, or mixtures thereof, and (C-2) 50 to 5 percent by weight of propylene moongreen, methacrylium, ci 8 alkyl Fluorenyl acrylate, CrC8 alkyl acrylate, maleic anhydride, nitrogen-substituted maleimide, or a mixture thereof.
CrC8烷基丙烯酸酯或Crc:8烷基曱基丙烯酸酯各是丙 烯酸或甲基丙烯酸與帶有一個到八個碳原子一元醇的酯類 • 特疋例子包括甲基丙稀酸甲S旨、2-甲基丙烯酸乙醋及甲 基丙烯酸丙酯,對甲基丙烯酸酯類而言,甲基丙烯酸甲酉旨 尤佳。 (C )成分的共聚物常是(b)成分在接枝聚合反應中的二 級產物’特別是當大量的單體接枝到少量的橡膠時產生。 依照本發明的(C)共聚物使用量並不包含這些二級接枝聚 合反應的產物。 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) -—I ^--------^---------AWI (請先閱讀背面之注意事項再填寫本頁) 482808 丙 可 A7 B7 五、發明說明(Θ ) (c)成分共聚物為不含橡膠的樹脂 不包含橡膠。 1王物貝匕們 2好的(C)共聚物為從甲基丙烯旨與甲 甲㈣備的,可採用游離基聚合法,特別是藉由乳化聚合 、懸浮聚合、溶液或本體聚合法的。 Λ 較好的(C)共聚物亦可由苯乙稀與丙稀騰選擇性加甲 基丙燁酉夂甲酉曰)、α_甲基苯乙稀和丙婦腺選擇性加甲基丙 烯酸甲醋)、或由苯乙烯與α—甲基苯乙烯(選擇性加甲基 烯酸甲酯)所製備。 (C)成分苯乙烯/丙烯月青共聚物本身為已知物質,其1 由如為離積聚合法,特別是乳化聚合、懸浮聚合、溶液或 本體聚合來製備。較佳的(C)成分共聚物的分子量Mw(平 均重量,由光散射或沉澱法決定)是在15,000到200,00()。 混合在本發明成分中的(C)共聚物亦可以是苯乙烯與 順丁烯二酐經由相同的單體在連續本體或溶液聚合中轉換 不完全時的任意共聚物。 適當的苯乙稀-順丁烯二酐任意共聚物之兩成分比例 •變化範圍很廣,較好的順丁烯二酐是介於重量百分5到25% ’適當的(C)成分苯乙烯_順丁烯二酐共聚物的分子量(平 均分子數’ Μη)可變範圍很廣,由6〇,〇〇〇到2〇〇,〇〇〇最佳。 本身的特性黏度(Intrinsic viscosity)最好在0.3到0·9間。 除了苯乙烯,(C)乙烯基共聚物亦可含環取代苯乙烯 ’例如對苯乙烯、乙烯基甲苯、2,‘對甲基苯乙烯和其他 取代基的苯乙婦(例如0C-甲基苯乙婦)。 X 297公釐) I,-------·裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 482808 A7 經濟部智慧財產局員工消費合作社印製 五、發明說明(〗\ ) 上述的乙烯基共聚物可單獨使用或是與其他兩種以上 的乙烯基共聚物混合使用。 (D)磷脂混合物 本專利發明之熱塑性模塑防火劑成分包含(D-1)和 (D-2)之混合物。根據所需要的性質目的,(d-Ι)和(D-2)之 重量比可變動的範圍很大。此混合物包含1〇〜5〇wt%之(ο- ΐ)和 50 〜 90wt% 之 (D-2) 。 較佳之 比例為 10〜47wt% 之 (D-1) 和90〜53wt%之(D-2)。最佳的比例為15〜45wt%之(D-1), 85 〜55wt% 之(D_2) 〇 如這領域中所習知的,雙酚A衍生之聚磷酸酯是藉由反應 氧氯化構及雙酚A和如酚或曱酚之單酚所合成出來的。由 於聚磷酸酯生產程序的本質,單體磷酸酯(D-2)總被含於 反應混合物中。為了要得到有特定成分之磷酯(D)混合物 ,可添加入磷酸三苯酯之商業用單體磷酸酯。 (D)之較佳成分為每個磷酯分子含有1〇3〜2.0個磷原子之 平均數,更佳者為1.03〜1·6個磷原子平均數。 (D-1)聚填自旨化物 本發明的熱塑性模塑成分包含(D-1)聚磷酯化物和(D-2 )早體鱗化物之混合物作為防火劑。 (D-1)成分是一具下列分子式(I )的磷酸S旨混合物。CrC8 alkyl acrylate or Crc: 8 alkyl fluorenyl acrylates are each an ester of acrylic acid or methacrylic acid and a monohydric alcohol with one to eight carbon atoms. Specific examples include methyl methacrylate, 2-Ethyl methacrylate and propyl methacrylate. For methacrylates, formamidine methacrylate is particularly preferred. The copolymer of component (C) is often a secondary product of component (b) in the graft polymerization reaction, especially when a large amount of monomers are grafted to a small amount of rubber. The amount of the (C) copolymer used according to the present invention does not include the products of these secondary graft polymerization reactions. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)--I ^ -------- ^ --------- AWI (Please read the precautions on the back first Fill out this page again) 482808 Bing A7 B7 V. Description of the invention (Θ) (c) The component copolymer is a rubber-free resin and does not include rubber. 1 King Wu Bei Deng 2 Good (C) copolymers are prepared from methacrylic acid and methyl formaldehyde, and can be used in free radical polymerization, especially by emulsion polymerization, suspension polymerization, solution or bulk polymerization. . Λ The better (C) copolymer can also be selected from styrene and propylene to add methylpropionamidine (a), α-methylstyrene, and propyl methacrylate to selectively add methyl methacrylate Vinegar), or from styrene and α-methylstyrene (optionally with methyl methacrylate). (C) The component styrene / propylene moongreen copolymer itself is a known substance, and 1 is prepared by, for example, an ionization polymerization method, in particular, emulsion polymerization, suspension polymerization, solution or bulk polymerization. The molecular weight Mw (average weight, determined by light scattering or precipitation method) of the preferred (C) component copolymer is 15,000 to 200,00 (). The (C) copolymer mixed in the ingredients of the present invention may be any copolymer in which the conversion of styrene and maleic anhydride through the same monomer is incomplete in continuous bulk or solution polymerization. Appropriate two component ratio of any copolymer of styrene-maleic anhydride • Wide range of variation, better maleic anhydride is 5 to 25% by weight 'Appropriate (C) component benzene The molecular weight (average number of molecules' Mη) of the ethylene-maleic anhydride copolymer varies widely, and is optimal from 60,000 to 20,000. The intrinsic viscosity (Intrinsic viscosity) is preferably between 0.3 and 0.9. In addition to styrene, (C) vinyl copolymers can also contain ring-substituted styrenes such as p-styrene, vinyltoluene, 2, 'p-methylstyrene, and other substituted styrenes (such as 0C-methyl Acetophenone). X 297 mm) I, ------- · install -------- order --------- (Please read the precautions on the back before filling out this page) Ministry of Economy Wisdom Printed by the Consumer Cooperative of the Property Bureau 482808 A7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention () \ The above vinyl copolymers can be used alone or in combination with two or more other vinyl copolymers . (D) Phospholipid mixture The thermoplastic molding flame retardant component of the present invention contains a mixture of (D-1) and (D-2). The weight ratio of (d-1) and (D-2) can vary widely depending on the required properties. This mixture contains 10 to 50 wt% (ο--) and 50 to 90 wt% (D-2). The preferred ratio is 10 to 47 wt% (D-1) and 90 to 53 wt% (D-2). The best ratio is (D-1) of 15 ~ 45wt%, (D_2) of 85 ~ 55wt%. As is well known in the art, bisphenol A-derived polyphosphates are formed by reactive oxychlorination. And bisphenol A and monophenols such as phenol or acetol. Due to the nature of the polyphosphate production process, the monomeric phosphate (D-2) is always contained in the reaction mixture. In order to obtain a phosphorus ester (D) mixture with a specific composition, a commercial monomeric phosphate ester of triphenyl phosphate can be added. The preferred component of (D) is an average number of 103 to 2.0 phosphorus atoms per phosphoester molecule, and more preferably an average number of 1.03 to 1.6 phosphorus atoms. (D-1) Polyfill compound The thermoplastic molding composition of the present invention contains a mixture of (D-1) a polyphosphonate and (D-2) a precursor scaly compound as a fire retardant. The component (D-1) is a mixture of phosphoric acid S having the following formula (I).
Ri —Ο—P〇 R2 (請先閱讀背面之注意事項再填寫本頁) · n mmtmm I —mm n I ϋ 0r n I ϋ I ϋ in I - 一 R3· R4 本紙張尺度適用中國國家標準格⑽x -Rs (I) A7 B7 五、發明說明(/ 其中 R1、R2、R4 及 r5 表示 相互獨立的C^C2。芳香族經基或 烧基取代的C6、芳香族經基,R3表示由雙❹得出的殘 基,Μ表不大於或等於丨的整數。 較佳的(D-1)成分是分子式⑴所表示之聚鱗酸醋混 合物,其中Μ等於1,2,3,4,或5。 (D-2)單體磷化物 (D_2)成分是具下列分子式(Π)的單體磷化物或其混合 物 0Ri —〇—P〇R2 (Please read the notes on the back before filling in this page) · n mmtmm I —mm n I ϋ 0r n I ϋ I ϋ in I-one R3 · R4 ⑽x -Rs (I) A7 B7 V. Description of the invention (/ where R1, R2, R4 and r5 represent independent C ^ C2. Aromatic or C6 substituted aromatic groups, R3 means double Residues obtained by ❹, M is not greater than or equal to the integer 丨. The preferred component (D-1) is a polyphosphoric acid ester mixture represented by the formula ⑴, where M is equal to 1, 2, 3, 4, or 5. (D-2) The monomer phosphide (D_2) component is a monomer phosphide having the following formula (Π) or a mixture thereof 0
R 其中R where
NN
J3-N (Π) 經濟部智慧財產局員工消費合作社印製 R表示一烷基例如第三丁基、異丙基、異丁基、異戊 基、第三戊基,N是〇或一個從(含)ι到3的整數。 較好的(D-2)成分是烷基取代的磷酸酯衍生物,包含 重量百分0到20%的三烷基苯磷酸酯(N=3)、〇到50%的二 烷基苯磷酸單苯酯(N=2)、0到60%的單烷基苯磷酸二苯酯 (N=l)與10到100%的磷酸三苯酯(N=0)。較好的取代基r是 第三丁基及異丙基,以第三丁基為最佳。混合的第三丁苯 磷酸酯和混合的異丙苯磷酸酯的混合物亦佳。 (E)防火劑 本發明的熱塑性模塑成分中含防火劑以改進其防火性 。特別是一聚氟化婦烴和(或)一對芳香族聚碳酸酯有防火 —_ 1^ k紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) hill·— I I I I Aw ---I--I I ^ ---— — — — — — (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 482808 A7J3-N (Π) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, R represents a monoalkyl group such as third butyl, isopropyl, isobutyl, isopentyl, third pentyl, N is 0 or one from (Inclusive) ι to 3 integers. The preferred (D-2) component is an alkyl-substituted phosphate derivative, containing 0 to 20% by weight of trialkylbenzene phosphate (N = 3) and 0 to 50% of dialkylbenzene phosphate Monophenyl ester (N = 2), 0 to 60% monoalkylphenyl diphenyl phosphate (N = 1), and 10 to 100% triphenyl phosphate (N = 0). The preferred substituents r are tert-butyl and isopropyl, and tert-butyl is most preferred. Mixtures of mixed tertiary styrene phosphate and mixed cumene phosphate are also preferred. (E) Fire retardant The thermoplastic molding composition of the present invention contains a fire retardant to improve its fire resistance. In particular, a polyfluorinated women's hydrocarbon and / or a pair of aromatic polycarbonates are fire-resistant — _ 1 ^ k paper size is applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) hill · — IIII Aw- --I--II ^ ----- — — — — — (Please read the notes on the back before filling out this page) Printed by the Intellectual Property Bureau Staff Consumer Cooperatives, Ministry of Economic Affairs 482808 A7
聚氟化烯烴藉由在樹脂中形成微纖維網降低防火熱塑 性樹脂在燃燒時的熔流,並增加樹脂的收縮,從而減少燃 燒時溶融樹脂的滴落。 运些聚亂化物可用已知過程生產,例如由四氟乙婦在 水’1貝中藉著游離基形成的催化劑,如納、卸、按的過氧 二硫酸鹽類在壓力7到71 kg/cm2及0°C到200°C (20°c到100°c 較佳)溫度下,進行聚合反應。 這些聚氟化烯烴可以粉末狀或乳狀使用,乳狀的氟化 烯烴顯現良好的分配性,但卻使準備過程變複雜。因此, 使用粉狀聚氟化烯烴時即希望能使其均勻地散佈在所有的 樹脂中形成微纖維網狀結構。 本發明適用的聚氟化烯烴平均粒徑介於到〇 〇5到 1000//m,密度為2.0g/cm3到2.3g/cm3。 有防火性之鹽類在商業上一般被用為聚碳酸酯為主的 樹脂。所有適於聚碳酸酯為主樹脂之鹽類均可被用於本發 明之成分。特別的例子為salts of sulf〇nates,s〇dium trichlorobenzene sulfonate, salts of sulfone sulfonates, potassium salt of diphenylsulfone sulfonate, salts of alkane sulfonic acid 及 s〇dium aluminum hexafluoride. 摻合在組成中的聚氟化烯烴使用量為重量百分〇〇5到 本紙張尺度刺悄目家規格(210 x “ ) r f IK Aw ^--------t---------— (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 482808 A7 ---------_—一 五、發明說明(A) 5·0 ’以基本樹脂(A)+(B)+(C)為重量百分基準,且摻掉鹽 類量為基本樹脂量(A)+(B)+(C)之百分之0.014。 除了上述提到的成分外,本發明的熱塑性模塑組成尚 可包含傳統的添加劑如潤滑劑、脫模劑、成核劑、去靜電 劑、安定劑、填充料、加強物,·加上染料和色素。混合的 模塑填充或加強化合物最多可佔到百分之六十,較佳為重 里百分之10到40(以基本樹脂(a)+(B)+(C)為重量百分基準) 〇 此熱塑性模塑成分可根據傳統製備樹脂成分的技術來 製備,例如將組成(包括不同的添加劑)混合在一起,在擠 出機中以融態擠壓成粒狀。 本發明的模塑組成可使用在任何種類的模塑生產上, 特別適用於需要展現高缺口耐衝擊強度和抗應力碎裂性的 電器及電子產品框架上(如電腦外殼零件)。 复Jfe例之#細說明 (A) 聚碳酸酉旨 平均分子量(Mw)20,000的以雙酚a為主的聚碳酸酯。 (B) 橡膠重塑接枝共聚物 重里百为之45的聚二丁烯乳膠、36的苯乙烯、14的丙 細月青、15 0的去離子水混合,並加入1 · 〇的油酸钟、〇 · 4的氳 過氧異丙苯,加入〇·3的硫醇為主的鏈移轉劑到混合溶液 中,所得溶液置放在75°C下5小時以製備ABS接枝共聚乳 膠,加1%的硫酸溶液到所得的粉末狀接枝共聚物中。 n -- ......- _ 18 本紙張尺度適用中國國豕標準(CNS)A4規格(210 X 297公愛)----- ,h --------訂----- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 482808 Α7 Β7 五、發明說明(6 ) (C) 乙稀基共聚物 混合重量百分70的苯乙烯、30的丙稀骑、i2〇的去離 子水、0.2的偶氮雙異丁月青及加入〇·5的磷酸鈣。苯乙烯一 丙烯腺SAN)樹脂共聚物由懸浮聚合法製備’所得產物隨 後沖洗、脫水及乾燥。得到粉末狀的SAN共聚物。 (D-1)低聚合體磷化物 (D) -磷酯混合物 (Da)雙酚A式聚磷酸酯 採用之雙紛A式聚填酸S旨是一鱗酸S旨混合物其成分可 以通用分子式(I)表示,其中RdUoRs為苯環,Μ為 〇,1,2,3,4,磷酸三苯酯之量為磷酸酯混合物之3wt%,而每 一磷酸酯分子之磷原子平均值為2.1。 (Db)磷酸三苯酯(TPP)。 (Dc)—第三丁基取代的單體磷酸酯之混合物。 (Dc)採用第三丁基取代的單體磷酸酯之混合物,包含 重量百分0.5%的磷酸三苯酯、33 ·2°/〇的第三丁苯基磷酸二 苯酯、49.5%的雙(第三丁苯基)磷酸單苯酯(N=l)、12.5% .的磷酸三(第三丁苯基)酯。 (Ε)聚氟化烯烴 採用美國杜邦公司的Teflon(商標)7AJ。 範例一和二與比較範例一和二 所有的成分均與一抗氧化劑和熱安定劑混合,擠入一 雙螺旋桿的壓出機(L/D=35,φ==45)。擠出物壓成粒狀, --19 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公髮) ▼ 丨 j----------^------—丨訂---------^w. (請先閱讀背面之注意事項再填寫本頁) 482808 A7 --------B7______ 五、發明說明(夂) 測试機械性質的試粒用1G。2射出成型機在2坑溫度下製 成。 滲透現象的測量是藉觀察一射出成型之容器,其為用 40 OZ射出成形機在250。〇溫度下製成,大小長、寬、高、 厚度為200mmx 200mmx 3mm。 熱安定性為測量射出成形後大小為200mmx 50mmx 的模塑零件表面黑斑紋的出現。射出成形溫度從280 C艾化到320 C,同時射出壓力和速度亦改變。為考慮到 實際射出成型加工程序中使用各式之射出成型加工條件, 包括高溫或高射出速度等相對嚴苛的不同條件均被測試。 表中可看出雙紛A衍生之聚填酸酯和單體磷酸酯之混 合物(其中雙酚A衍生之聚磷酸酯量為防火劑之丨〇〜5〇wt%) 較之比較實例1和2(防火劑中超過50%為雙酚A衍生之聚磷 H曰)有較高之耐衝擊強度,較佳耐火性及特別好之熱安 定性。 … 甚者’所有之實例及比較實施例在射出成型時均未見 滲透現象。 Γ I I ^ --------訂·-------- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 x 297公釐) 482808 五、發明說明(、Λ)Polyfluorinated olefins reduce the melt flow of the fire-resistant thermoplastic resin during combustion by forming a microfiber web in the resin, and increase the shrinkage of the resin, thereby reducing dripping of the molten resin during combustion. These chaotic compounds can be produced by known processes, such as catalysts formed by tetrafluoroethane in water '1 by free radicals, such as sodium, unloaded, and pressed peroxodisulfates at a pressure of 7 to 71 kg / cm2 and a temperature of 0 ° C to 200 ° C (preferably 20 ° c to 100 ° c), the polymerization reaction is performed. These polyfluorinated olefins can be used in the form of powder or milk. The milky fluorinated olefin shows good distribution, but complicates the preparation process. Therefore, when using a powdery polyfluorinated olefin, it is desirable to make it uniformly dispersed in all resins to form a microfiber network structure. The average particle diameter of the polyfluorinated olefin suitable for the present invention is between 0.05 and 1000 // m, and the density is between 2.0 g / cm3 and 2.3 g / cm3. Fire-resistant salts are commonly used commercially as polycarbonate-based resins. All salts suitable for polycarbonate-based resins can be used as ingredients in the present invention. Specific examples are salts of sulfonates, sodium trichlorobenzene sulfonate, salts of sulfone sulfonates, potassium salt of diphenylsulfone sulfonate, salts of alkane sulfonic acid and sodium aluminum hexafluoride. Polyfluorinated olefins incorporated in the composition are used The amount is weight percent 0.05 to this paper size. (210 x ") rf IK Aw ^ -------- t ----------- (Please read the back first Please pay attention to this page, please fill in this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 482808 A7 ---------_— V. Description of the invention (A) 5.0 · 'Base resin (A) + (B) + (C) is the basis of weight percentage, and the amount of salt to be added is 0.014% of the basic resin amount (A) + (B) + (C). In addition to the ingredients mentioned above, the present invention The thermoplastic molding composition can still contain traditional additives such as lubricants, release agents, nucleating agents, destaticizers, stabilizers, fillers, reinforcements, plus dyes and pigments. Mixed molding fillers or reinforcements The compound may account for up to 60%, preferably 10 to 40% by weight (based on the basic resin (a) + (B) + ( C) is the weight percentage basis) 〇 This thermoplastic molding composition can be prepared according to the traditional technique of preparing resin composition, for example, the composition (including different additives) is mixed together and extruded into pellets in an extruder in a molten state. The molding composition of the present invention can be used in any kind of molding production, and is particularly suitable for electrical and electronic product frames (such as computer housing parts) that need to exhibit high notch impact strength and stress crack resistance. Jfe 例 之 #Detailed description (A) Polycarbonate based on bisphenol a with an average molecular weight (Mw) of 20,000. (B) Polydibutyl with 45 weight percent of rubber remodeling graft copolymer Ethylene latex, 36 styrene, 14 acrylic cranthine, 150 deionized water were mixed, and 1.0 oleic acid bell, 0.4 cumene peroxycumene, and 0.3 sulfur were added. An alcohol-based chain transfer agent was mixed into the mixed solution, and the resulting solution was placed at 75 ° C for 5 hours to prepare an ABS graft copolymer latex. A 1% sulfuric acid solution was added to the obtained powdered graft copolymer. N -......- _ 18 This paper size applies to China National Standard (CNS) A4 Grid (210 X 297 public love) -----, h -------- Order ----- (Please read the precautions on the back before filling out this page) Intellectual Property Bureau Staff Consumer Cooperatives Printed 482808 Α7 Β7 V. Description of the invention (6) (C) Ethylene copolymer mixed with 70% by weight of styrene, 30% by weight, i2O deionized water, 0.2 azobisisobutyrene and 0.5 mg of calcium phosphate was added. The styrene-acrylic gland SAN) resin copolymer is prepared by suspension polymerization 'and the product is then washed, dehydrated and dried. A powdery SAN copolymer was obtained. (D-1) Oligomeric phosphide (D)-Phosphate ester mixture (Da) Bisphenol A polyphosphoric acid used for bisphenol A polyphosphoric acid S is a monophosphonic acid S purpose mixture whose components can have a general molecular formula (I) indicates that RdUoRs is a benzene ring, M is 0,1,2,3,4, the amount of triphenyl phosphate is 3% by weight of the phosphate ester mixture, and the average phosphorus atom of each phosphate molecule is 2.1 . (Db) Triphenyl phosphate (TPP). (Dc)-a mixture of third butyl-substituted monomeric phosphates. (Dc) a mixture of monomeric phosphate esters substituted with a third butyl group, containing 0.5% by weight of triphenyl phosphate, 33.2 ° / ° tert-butylphenyl diphenyl phosphate, and 49.5% bis (Third-butylphenyl) phosphate monophenyl ester (N = 1), 12.5% Tris (third-butylphenyl) phosphate. (E) Polyfluorinated olefin Teflon (trademark) 7AJ from DuPont, USA was used. Examples 1 and 2 and Comparative Examples 1 and 2 All ingredients were mixed with an antioxidant and a heat stabilizer and extruded into a twin screw extruder (L / D = 35, φ == 45). The extrudate is pressed into granules, --19 This paper size is applicable to China National Standard (CNS) A4 specifications (210 X 297 public hair) ▼ 丨 j ---------- ^ ------ — 丨 Order --------- ^ w. (Please read the notes on the back before filling out this page) 482808 A7 -------- B7______ V. Description of the invention (夂) Testing mechanical properties The test granules use 1G. The 2-injection molding machine is made at a 2-pit temperature. The permeation phenomenon was measured by observing an injection-molded container, which was made with a 40 OZ injection molding machine at 250. 〇Made at temperature, length, width, height, thickness 200mmx 200mmx 3mm. Thermal stability is a measure of the appearance of black streaks on the surface of a molded part having a size of 200mmx 50mmx after injection molding. The injection molding temperature changed from 280 C to 320 C, and the injection pressure and speed also changed. In order to take into account the various injection molding processing conditions used in the actual injection molding process, different severe conditions including high temperature or high injection speed are tested. In the table, it can be seen that the mixture of Bisphenol A-derived polyfiller and monomeric phosphate esters (where the amount of bisphenol A-derived polyphosphates is 0-50% by weight of the fire retardant) is compared with Comparative Examples 1 and 2 (more than 50% of the fire retardant is bisphenol A-derived polyphosphorus H). It has higher impact strength, better fire resistance and particularly good thermal stability. … Even in all the examples and comparative examples, no penetration was observed during injection molding. Γ II ^ -------- Order · -------- (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs x 297 mm) 482808 V. Description of the invention (, Λ)
Α7 Β7 序號 實例1-2 比較實例卜2 1 2 1 2 (Α)聚碳酸g旨 80 67 67 50 (B)接枝共聚物 10 13 13 20 (C)SAN 10 20 20 30 (Da)低聚合體磷酸酯 5.8 4 11 6.2 (Db)磷酸三苯酯(TPP) 3.1 10 3 5.8 (Dc)第三丁基取代單磷 酸酯的混合物 3.1 - - - (D-1)和(D-2)佔全 部 磷酸酯之重量百 分比 D-1 47 28 76 50 D-2 53 72 24 50 (E)聚氟化烯烴 0.4 0.2 0.2 0 UL 94(1/16,’)(1) V-0 V-0 V-1 V-2 Izod财衝擊強度 (l/8n,kgcm/cm)(2) 42 39 35 31 抗熱性(VST,°C)(3) 94 84 85 74 滲透現象 0 0 0 0 熱安定性(黑斑紋)(6) 〇 〇 X 菩王) (1) UL94(l/16n)根據UL94VB 測試。 (2) Izod耐衝擊強度根據ASTMD256测試 (3) 抗熱性根據ASTM D1525測試。 口 (4) 滲透現象 〇:沒有觀察到滲透現象。 X :觀察到滲透現象。 經濟部智慧財產局員工消費合作社印製 (5)熱安定性Α7 Β7 No. Example 1-2 Comparative Example Bu 2 1 2 1 2 (A) Polycarbonate g 80 67 67 50 (B) Graft copolymer 10 13 13 20 (C) SAN 10 20 20 30 (Da) Oligomerization Phosphate 5.8 4 11 6.2 (Db) Triphenyl phosphate (TPP) 3.1 10 3 5.8 (Dc) Mixture of third butyl substituted monophosphate 3.1---(D-1) and (D-2) account for Weight percentage of total phosphate esters D-1 47 28 76 50 D-2 53 72 24 50 (E) Polyfluorinated olefin 0.4 0.2 0.2 0 UL 94 (1/16, ') (1) V-0 V-0 V -1 V-2 Izod impact strength (l / 8n, kgcm / cm) (2) 42 39 35 31 Thermal resistance (VST, ° C) (3) 94 84 85 74 Penetration phenomenon 0 0 0 0 Thermal stability ( (Dark streaks) (6) 〇〇X 王) (1) UL94 (l / 16n) tested according to UL94VB. (2) Izod impact resistance tested according to ASTMD256 (3) Heat resistance tested according to ASTM D1525. Mouth (4) Penetration phenomenon 〇: No penetration phenomenon was observed. X: Penetration was observed. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (5) Thermal stability
〇 Δ X 沒有觀測到黑斑紋。 視射出成形狀況有時可觀測 時常觀測到黑斑紋。 〗黑斑、、文〇 ΔX No dark spots were observed. The appearance of the injection molding is sometimes observed, and black streaks are often observed. 〖Black spots, and text
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW88113751A TW482808B (en) | 1999-08-11 | 1999-08-11 | Flame retardant thermoplastic resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW88113751A TW482808B (en) | 1999-08-11 | 1999-08-11 | Flame retardant thermoplastic resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
TW482808B true TW482808B (en) | 2002-04-11 |
Family
ID=21641878
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW88113751A TW482808B (en) | 1999-08-11 | 1999-08-11 | Flame retardant thermoplastic resin composition |
Country Status (1)
Country | Link |
---|---|
TW (1) | TW482808B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI480327B (en) * | 2007-12-05 | 2015-04-11 | Lg Chemical Ltd | Flame retardant polycarbonate resin composition having high infrared transmission |
-
1999
- 1999-08-11 TW TW88113751A patent/TW482808B/en not_active IP Right Cessation
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI480327B (en) * | 2007-12-05 | 2015-04-11 | Lg Chemical Ltd | Flame retardant polycarbonate resin composition having high infrared transmission |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0970997B1 (en) | Flame retardant polycarbonate/abs composition | |
CA2300219C (en) | Abs mouldable materials containing polycarbonate, non-flammable and resistant to stress crack | |
JP3991032B2 (en) | Flame retardant thermoplastic resin composition | |
JP4264413B2 (en) | Flame retardant thermoplastic resin composition | |
TWI251607B (en) | Flame-retardant polycarbonate-ABS moulding compositions | |
TW473507B (en) | Flame-proof, reinforced polycarbonate ABS moulding compositions | |
TW589346B (en) | Flame retardant thermoplastic resin composition | |
JP4046371B2 (en) | Flame retardant thermoplastic resin composition | |
JPH0619003B2 (en) | Thermoplastic molding composition having flame resistance | |
JPS624747A (en) | Thermoplastic polycarbonate molding composition | |
TW455612B (en) | Polycarbonate-ABS moulding compositions | |
JPH0219148B2 (en) | ||
JP4585659B2 (en) | Flame retardant resin composition and molded product therefrom | |
TWI248458B (en) | Flame-resistant and heat-resistant polycarbonate compositions | |
JPH064758B2 (en) | Flame-retardant thermoplastic molding composition | |
TW482808B (en) | Flame retardant thermoplastic resin composition | |
JPS6368661A (en) | High impact resistant-flame resistant molding composition | |
JP2002003727A (en) | Flame-retardant resin composition | |
JPS6357667A (en) | Thermoplastic forming composition | |
KR101411825B1 (en) | Char generating agent, and abs resin composition using thereof | |
KR101378865B1 (en) | Polycarbonate resin composition having both good uninflammability and good impact resistance and molded article thereof | |
KR20110071746A (en) | Non-halogen flameproof polycarbonate resin composition | |
US20080275161A1 (en) | Flameproof Thermoplastic Resin Composition | |
JP2002155179A (en) | Flame-retardant resin composition | |
US20070244229A1 (en) | Flameproof Thermoplastic Resin Composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
GD4A | Issue of patent certificate for granted invention patent | ||
MM4A | Annulment or lapse of patent due to non-payment of fees |