TWI225504B - Polyolefin resin composition - Google Patents
Polyolefin resin composition Download PDFInfo
- Publication number
- TWI225504B TWI225504B TW89123774A TW89123774A TWI225504B TW I225504 B TWI225504 B TW I225504B TW 89123774 A TW89123774 A TW 89123774A TW 89123774 A TW89123774 A TW 89123774A TW I225504 B TWI225504 B TW I225504B
- Authority
- TW
- Taiwan
- Prior art keywords
- polyolefin
- resin composition
- based resin
- layered silicate
- parts
- Prior art date
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
Description
1225504 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（/ ) [技術領域] 本發明係關於可獲得優異難燃性之聚烯烴系樹脂組成 物、使用該聚烯烴系樹脂組成物所得之電線被覆用或密封 用之熱可塑性樹脂、以及絕緣電線。 [背景技術] 近年來’在遭遇廢塑膠處理與環境激素的問題上，聚 烯烴系樹脂因屬於一種對於環境所造成之污染小的材料乃 受到矚目。具體而言，作爲聚氯乙嫌系樹脂的替代材料， 正檢討著聚乙烯系樹脂與聚丙烯系樹脂。 惟，由於聚烯烴系樹脂屬非極性之物，很難從中發現 其印刷性、接著性、難燃性等之機能。尤其，由於聚烯烴 系樹脂爲燃燒性最高的一種樹脂，尋求其難燃性也就成爲 最困難的課題，目前，有許多的例子是將含鹵素難燃劑混 入聚嫌烴系樹脂中來作爲解決之道。 含鹵素難燃劑雖具優異之難燃化效果，且在成型性之 降低或成型體之機械強度的降低上也較少，惟使用時，在 成型加工時或燃燒時有產生大量之鹵系氣體之虞，所產生 之氣體會腐蝕機器、或對人體造成影響，是以從安全性的 角度來看，不使用含鹵素化合物、也就是無歯素難燃化處 理方法乃爲殷求之物。 作爲聚烯烴系樹脂之無鹵素難燃化技術之一，將燃燒 時不會發生有毒氣體的氫氧化鋁、氫氧化鎂、鹼性碳酸鎂 等之金屬化合物添加到聚烯烴系樹脂中的方法係揭示於特 開昭57-165437號公報與特開昭61-36343號公報等。 3 (請先閱讀背面之注意事項^寫本頁) i 裝 訂： .線 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1225504 A7 _ B7__— 五、發明說明（、） 惟，爲對於易燃性之聚烯烴系樹脂賦予充分的難燃性 ，必須添加大量的上述金屬化合物，其結果，所得之成型 體的機械強度會顯著地下降，有難以供做實用的問題。 上述之金屬化合物當中，若將氫氧化鋁、氫氧化鎂等 之金屬化合物添加到聚烯烴系樹脂中，則在燃燒時無法形 成被膜層，而會露出質脆的灰分、殘渣脫落，於是在早期 即失去絕熱層的機能，並無法阻止因材料的變形所導致的 延燒，此爲問題所在。 又，將磷系難燃劑添加到聚烯烴系樹脂中，利用燃燒 時之表面被膜形成所提供之氧阻絕效果，來獲得難燃性的 方法也被提出。惟，爲對於易燃性之聚烯烴系樹脂賦予充 分的難燃性，必須添加大量的磷系難燃劑，其結果，所得 之成型體的機械強度會顯著地下降，有難以供做實用的問 題。 將磷系難燃劑添加到聚烯烴系樹脂中之時，雖可在局 部地方形成被膜’惟無法以連續層的方式形成強固的被膜 層。又’由於局部形成之被膜的機械強度非常弱，於燃燒 時’會露出質脆的灰分、殘渣脫落，於是在早期即失去絕 經濟部智慧財產局員工消費合作社印制衣 熱層的機能’並無法阻止因材料的變形所導致的延燒，此 爲問題所在。 又，在特開平6-2470號公報中，係揭示於聚烯烴系樹 脂中添加赤磷或磷化合物、以及膨脹性石墨的樹脂組成物 。雖從氧指數來看，此樹脂組成物具有充分的難燃性，但 僅於局部地方形成被膜，無法以連續層的方式形^強固的 4 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297¾^ 1225504 A7 B7 五、發明說明（3) 被膜層。又，由於局部形成之被膜的機械強度非常弱，於 燃燒時，會露出質脆的灰分、殘渣脫落，於是在早期即失 去絕熱層的機能，並無法阻止因材料的變形所導致的延燒 ，此爲問題所在。 是以，若將聚烯烴系樹脂使用於例如成型爲片狀之作 爲難燃材料的壁的內襯材時，將無法滿足耐火試驗或防火 試驗的基準(即將表面加熱到l〇〇(TC時，內面的溫度被抑制 到260°C以下），不僅在耐火性上不足，且於耐火試驗、防 火試驗中，由於殘留質脆之灰分、殘渣脫落，於是在早期 即失去絕熱層的機能，此爲問題所在。 [發明之簡單說明] 本發明係鑒於上述問題所得之物，其目的在於提供一 種聚烯烴系樹脂組成物、使用該聚烯烴系樹脂組成物所得 之電線被覆用或密封用之熱可塑性樹脂、以及絕緣電線， 其在難燃性上優異、尤其可藉由燃燒時之形狀保持效果獲 得優異之難燃性，且在機械強度以及熱特性上亦優。 本發明係一種聚烯烴系樹脂組成物，其由聚烯烴系樹 脂100重量份與層狀矽酸鹽0.1〜1〇〇重量份所構成，將在 50kW/m2的加熱條件下加熱燃燒30分鐘所得之燃燒殘渣以 0.1cm/s來壓縮時，降伏點應力爲至少4.9X 103Pa。 本發明之聚烯烴系樹脂組成物，在50kW/m2的加熱條 件下加熱燃燒30分鐘時之最大放熱速度以低於800 kW/m2 爲佳。 上述之聚烯烴系樹脂，以擇自由乙烯之單聚物、丙烯 5 -------------^裝--- (請先閱讀背面之注意事項寫本頁) 訂· 線： 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1225504 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（f ) 之單聚物、乙烯或丙烯以及可與兩者進行共聚之α—嫌徑 之共聚物、乙烯與（甲基)丙烯酸酯之共聚物、以及乙嫌與 乙酸乙酯之共聚物所構成群之中至少1種的樹脂爲佳。 上述層狀矽酸鹽以蒙脫石以及/或是膨脹性雲母爲佳。 就上述層狀矽酸鹽而言，作爲結晶構造中之交換性陽 離子，以含有金屬離子爲佳。 上述金屬離子之一部分或全部藉陽離子系界面活性劑 來交換爲佳。 上述陽離子系界面活性劑，以具有4級銨鹽構造之（甲 基)丙烯酸系單體之單聚物、具有4級銨鹽構造之（甲基)丙 烯酸系單體與其他之（甲基)丙烯酸系單體以及/或是苯乙烯 系單體所得之共聚物、或是具有碳數至少爲6之烷基的4 級烷基磺酸鹽爲佳。 上述層狀矽酸鹽，藉由廣角X射線繞射測定法所測定 之(001)面之平均層間距離爲至少3nm、含有在聚烯烴系樹 脂組成物中以至多5層的狀態分散之物乃爲所希望的。更 佳係平均層間距離爲至少6nm。 本發明之聚烯烴系樹脂組成物，進一步以含有擇自_ 系化合物、金屬氫氧化物、以及三聚氰胺衍生物所梅 之中至少1種之化合物0.5〜100重量份爲佳。 上述磷系化合物以擇自赤磷、多磷酸銨、以及以 --------------- (請先閱讀背面之注意事項寫本頁)1225504 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (/) [Technical Field] The present invention relates to a polyolefin resin composition that can obtain excellent flame retardancy, and uses the polyolefin resin composition The obtained thermoplastic resin for covering or sealing electric wires, and insulated electric wires. [Background Art] In recent years, polyolefin resin has attracted attention because it is a material that causes little pollution to the environment when it comes to the problems of waste plastic treatment and environmental hormones. Specifically, polyethylene-based resins and polypropylene-based resins are being reviewed as alternatives to polyvinyl chloride-based resins. However, since polyolefin-based resins are non-polar, it is difficult to find functions such as printability, adhesion, and flame retardancy. In particular, since polyolefin-based resins are one of the most flammable resins, finding their flame retardancy has become the most difficult issue. At present, many examples include mixing halogen-containing flame retardants into polyphosphine-based resins. The solution. Although halogen-containing flame retardants have excellent flame retardancy effects, and have less reduction in moldability or reduction of the mechanical strength of the molded body, when used, a large amount of halogen-based compounds are generated during molding processing or combustion. The risk of gas is that the generated gas will corrode the machine or affect the human body. From a safety point of view, the use of halogen-free compounds, which is a non-flammable non-flammable treatment method, is a desirable thing. As one of the halogen-free flame-retardant technologies for polyolefin resins, a method of adding metal compounds such as aluminum hydroxide, magnesium hydroxide, and basic magnesium carbonate, which do not generate toxic gases during combustion, to polyolefin resins. It is disclosed in JP 57-165437 and JP 61-36343. 3 (Please read the notes on the back ^ write this page first) i Binding:. The size of the thread paper is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1225504 A7 _ B7 __— V. Description of the invention (,) However, in order to impart sufficient flame retardancy to a flammable polyolefin-based resin, it is necessary to add a large amount of the above-mentioned metal compound. As a result, the mechanical strength of the obtained molded body is significantly reduced, and there is a problem that it is difficult to make it practical. Among the above-mentioned metal compounds, if metal compounds such as aluminum hydroxide and magnesium hydroxide are added to the polyolefin-based resin, a coating layer cannot be formed during combustion, and brittle ash and residues fall off, so in the early stage That is to say, the function of the thermal insulation layer is lost, and the delayed burning caused by the deformation of the material cannot be prevented, which is the problem. In addition, a method of adding a phosphorus-based flame retardant to a polyolefin-based resin to obtain flame resistance by utilizing an oxygen barrier effect provided by the formation of a surface film during combustion is also proposed. However, in order to impart sufficient flame retardancy to a flammable polyolefin-based resin, a large amount of a phosphorus-based flame retardant must be added. As a result, the mechanical strength of the obtained molded body is significantly reduced, and it is difficult to make it practical. problem. When a phosphorus-based flame retardant is added to a polyolefin-based resin, a coating film can be formed locally, but a strong coating layer cannot be formed as a continuous layer. Also, because the mechanical strength of the locally formed film is very weak, when it burns, brittle ash and residues will fall off, so in the early stage, it lost the function of printing the thermal layer of the clothing consumer clothing cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The problem is that the burn-in caused by the deformation of the material cannot be prevented. Further, Japanese Patent Application Laid-Open No. 6-2470 discloses a resin composition in which a red phosphorus or a phosphorus compound and an expanded graphite are added to a polyolefin resin. Although the resin composition has sufficient flame retardancy from the point of view of oxygen index, it forms a film only in a local place and cannot be formed in a continuous layer. ^ Strong 4 This paper size applies the Chinese National Standard (CNS) A4 specification ( 210 X 297¾ ^ 1225504 A7 B7 V. Description of the invention (3) Coating layer. Also, because the mechanical strength of the locally formed coating film is very weak, brittle ash and residues will fall off during combustion, so the insulation is lost in the early stage. The function of the layer cannot prevent the post-sintering caused by the deformation of the material, which is a problem. Therefore, if a polyolefin-based resin is used in, for example, a lining material that is formed into a sheet-like wall as a flame retardant material, Will not meet the fire test or fire test standards (that is, the surface is heated to 100 (the temperature of the inner surface is suppressed to 260 ° C or less at TC)), which is not only insufficient in fire resistance, but also in fire tests and fire tests Because the residual brittle ash and residue fall off, the function of the insulation layer is lost in the early stage, which is the problem. [Simplified description of the invention] The present invention is obtained in view of the above problems. The object is to provide a polyolefin-based resin composition, a thermoplastic resin for covering or sealing an electric wire obtained by using the polyolefin-based resin composition, and an insulated wire, which are excellent in flame retardancy and are particularly suitable for borrowing. Excellent flame retardancy is obtained from the shape-retaining effect during combustion, and it is also excellent in mechanical strength and thermal characteristics. The present invention is a polyolefin-based resin composition comprising 100 parts by weight of a polyolefin-based resin and layered silicic acid. It is composed of 0.1 to 100 parts by weight of salt, and when the combustion residue obtained by heating and burning under a heating condition of 50 kW / m2 for 30 minutes is compressed at 0.1 cm / s, the drop point stress is at least 4.9X 103Pa. The maximum exothermic rate of the olefin-based resin composition when heated and burned under a heating condition of 50 kW / m2 for 30 minutes is preferably less than 800 kW / m2. The above-mentioned polyolefin-based resins are selected from free ethylene monomers and propylene. 5 ------------- ^ Install --- (Please read the notes on the back to write this page) Order: Thread: Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Employees' Cooperatives, this paper is suitable for China National Standard (CNS) A4 Grid (210 X 297 mm) 1225504 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Monomers of invention description (f), ethylene or propylene, and α-distinct copolymers that can be copolymerized with both. It is preferred that at least one of the resins consisting of a copolymer of ethylene, a copolymer of (meth) acrylate, and a copolymer of ethyl acetate and ethyl acetate be a montmorillonite and / or a layered silicate. Expansive mica is preferred. As for the above-mentioned layered silicate, as the exchangeable cation in the crystal structure, it is preferable to contain metal ions. It is better to exchange a part or all of the metal ions by a cationic surfactant. . The cationic surfactant is a monopolymer of a (meth) acrylic monomer having a level 4 ammonium salt structure, a (meth) acrylic monomer having a level 4 ammonium salt structure, and other (meth) A copolymer of an acrylic monomer and / or a styrene monomer or a quaternary alkyl sulfonate having an alkyl group having at least 6 carbon atoms is preferred. The layered silicate has a mean interlayer distance of (001) plane measured by a wide-angle X-ray diffraction measurement method of at least 3 nm, and is contained in a polyolefin resin composition dispersed in a state of at most 5 layers. As expected. More preferably, the average interlayer distance is at least 6 nm. The polyolefin-based resin composition of the present invention is further preferably 0.5 to 100 parts by weight of a compound containing at least one selected from the group consisting of a compound, a metal hydroxide, and melamine derivatives. The above phosphorus compounds are selected from red phosphorus, ammonium polyphosphate, and --------------- (Please read the precautions on the back first to write this page)
ir^J -線」 通式（1)所表示之磷化合物所構成群之中至少1種之_ 合物爲佳。 R3 (R2) (OR1) P =0 (1) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 1225504 A7 B7 五、發明說明（f) 式中，R1與R3係表示氫原子、碳數1〜16之院基或芳 基，R2係表示氫原子、羥基、碳數1〜16之院基、醇氧基、 芳基或芳氧基，R1、R2與R3可彼此相同或不同。 本發明之聚烯烴系樹脂組成物’以進一步含有層狀矽 酸鹽以外的矽酸鹽化合物〇·5〜20重量份爲佳。 本發明之聚烯烴系樹脂組成物’以進一步含有金屬氧 化物0.1〜10重量份爲佳。 本發明之聚烯烴系樹脂組成物’以進一步含有由：具 有相對於聚烯烴系樹脂顯示反應性之官能基的段落(A)嵌段 、相對於聚烯烴系樹脂具有親和性的段落(B)嵌段；所構成 之AB型嵌段共聚物爲佳。 本發明之聚烯烴系樹脂組成物’以進一步含有一具有 芳香族系羥基的化合物〇.〇丨〜3〇重量份爲佳。 使用本發明之聚烯烴系樹脂組成物之作爲電線被覆用 或密封用的熱可塑性樹脂亦爲本發明之一。 使用上述熱可塑性樹脂所成之絕緣電線亦爲本發明之 _丨·，‘ 0 [發明之詳細說明] 以下詳述本發明。 本發明之聚嫌煙系樹脂組成物係由聚嫌煙系樹脂1 〇〇 重量份與層狀矽酸鹽0.1〜100重量份所得者。 本發明所使用之聚烯烴系樹脂係將具有聚合性雙鍵的 烯烴系單體聚合所得者。 作爲上述烯烴系單體並無特別的限定，可舉出例如乙 7 -------------..— (請先閱讀背面之注意事項本頁) . 線- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1225504 A7 __B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（ 烯、丙烯、1 一丁烯、1 一戊烯、1 一己烯、丨一庚烯、丨_辛 烯、4一甲基一 1 一戊烯等之α—烯烴，或是丁二烯、異丙 烯等之共軛二烯等。該等烯烴系單體可單獨使用或倂用至 少2種。 作爲上述聚烯烴系樹脂並無特別的限定，可舉出例如 乙烯之單聚物、乙烯與α—烯烴之共聚物、乙烯與（甲基)丙 烯酸之共聚物、乙烯與（甲基)丙烯酸酯之共聚物、乙烯與 乙酸乙酯之共聚物、丙烯之單聚物、丙烯與α—烯烴之共 聚物、丙烯與乙烯之無規共聚物或嵌段共聚物、丁烯之單 聚物、丁二烯或異丙烯等之共軛二烯之單聚物或共聚物等 。該等烯烴系樹脂可單獨使用或倂用至少2種。又，於本 說明書中’所謂的（甲基)丙烯酸，意指丙烯酸或甲基丙烯 酸。 上述聚烯烴系樹脂當中，又以乙烯之單聚物、丙烯之 單聚物、乙烯或丙烯以及可與兩者進行共聚之α—烯烴之 共聚物、乙烯與（甲基)丙烯酸酯之共聚物、或是乙烯與乙 酸乙酯之共聚物爲佳。該等烯烴系樹脂可單獨使用或倂用 至少2種。 上述聚烯烴系樹脂之分子量與分子量分布上並無特別 的限定，重量平均分子量以5000~500萬爲佳，以2萬〜30 萬爲更佳；分子量分布(重量平均分子量/數平均分子量)以 1.1~80爲佳，以1.5〜40爲更佳。 本發明所使用之層狀矽酸鹽係含有層間之結晶構造中 具有交換性的矽酸鹽礦物。 8 (請先閱讀背面之注意事項再_寫本頁) .¾ . -線 ·! 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1225504 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（7) 作爲上述層狀矽酸鹽並無特別的限定，可舉出例如蒙 脫石、皂石、鋰蒙脫石、貝得石、富鎂蒙脫石、囊脫石等 之蒙脫石系黏土礦物；蛭石、埃洛石、膨脹性雲母’其中 以使用蒙脫石與膨脹性雲母爲佳。該等之層狀矽酸鹽可單 獨使用或倂用至少2種。 上述層狀矽酸鹽可爲天然品亦可爲合成品。 作爲上述層狀矽酸鹽，藉由使用以下述通式（1)所定義 之在形狀各向異性效果大的蒙脫石系黏土礦物或膨脹性雲 母，則由聚烯烴系樹脂組成物以及成型體之機械強度或氣 體防護性之提昇的觀點來看尤佳。 形狀各向異性效果=結晶表面(a)之面積/結晶表面(b)之 面積…(1) 作爲上述層狀矽酸鹽之陽離子交換容量並無特別的限 定，以50〜200毫當量/l〇〇g爲佳。若未達50毫當量/l〇〇g， 由於藉離子交換在結晶層間插入(intercalate)之陽離子系界 面活性劑的量變少，有時層間無法充分地非極性化，另一 方面，若超過200毫當量/100g，由於層狀矽酸鹽的層間結 合力變得強固，有時結晶薄片會難以剝離。 作爲上述交換性陽離子並無特別的限定，可舉出例如 鈉或鉀等之一價的金屬離子。 以其他的金屬離子來將交換性陽離子交換之時，所交 換之金屬離子，以具有藉由離子交換讓層狀矽酸鹽之酸度 較離子交換前提昇的效果爲佳。一旦層狀矽酸鹽之酸度提 昇，則與聚烯烴系樹脂或添加於聚烯烴系樹脂的添加劑的 9 (請先閱讀背面之注意事項再d寫本頁) 裝 · |線· 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1225504 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明) 反應性易於提昇，層狀矽酸鹽之分散性得以提昇。 本發明所使用之層狀矽酸鹽，結晶構造中之交換性陽 離子以二價之金屬離子進行離子交換乃爲所希望的。若以 超過二價的金屬離子來進行離子交換，則層狀矽酸鹽的層 間結合力會變強，層間剝離(去積層)將不會發生。 作爲上述二價之金屬離子並無特別的限定，可舉出例 如鎳、鎂、鈣等。以這些金屬離子來進行離子交換所能提 昇層狀矽酸鹽之酸度的效果，係依鎳、鎂、鈣的順序變大 〇 藉鎳、鎂、耗等之二價之金屬離子來進行離子交換來 提昇層狀矽酸鹽之結晶薄片之羥基的酸度，係於例如 NISHIHAMA 等所得之「Clay materials」（1997,32，p645〜651) 等中提出。右從燒結時之結晶薄片彼此之結合力的提昇、 易於形成強固的燒結被膜的觀點來看，以鎳離子或鎂離子 爲佳。 本發明所使用之層狀矽酸鹽，其結晶構造中以含有陽 離子系界面活性劑爲佳。作爲於層狀矽酸鹽之結晶構造中 含有陽離子系界面活性劑的方法，可舉出例如將層狀矽酸 鹽之結晶構造中以交換性陽離子形態存在的金屬離子之一 部分或全部，藉由陽離子系界面活性劑加以交換的方法。 作爲上述陽離子系界面活性劑並無特別的限定，可舉 出例如銨鹽、4級鐵鹽等。 作爲上述4級銨鹽並無特別的限定，可舉出例如具有 月桂基三甲基銨鹽、硬脂基三甲基銨鹽、三辛基銨鹽、二 10 (請先閱讀背面之注意事項再«I寫本頁) 太 言· Γ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1225504 Α7 Β7 經濟部智慧財產局員工消費合作社印製 五、發明說明（y) 硬脂基二甲基銨鹽、二硬化牛脂二甲基銨鹽、二硬脂基二 苯基銨鹽等之四級銨鹽構造的(共）聚合物等。該等之4級 銨鹽可單獨使用或倂用至少2種。又，於本說明書中，所 謂的(共)聚合物’意指聚合物或共聚物。 作爲上述具有4級銨鹽構造的（共)聚合物並無特別的 限定，可舉出例如將具有胺基 '烷胺基、二烷胺基等之（甲 基)丙烯酸系單體之單聚物、該等之（甲基)丙烯酸系單體與 其他之（甲基)丙烯酸系單體以及/或是苯乙烯、α—甲基苯 乙烯、乙烯基甲苯等之苯乙烯系單體所得之共聚物，以鹽 酸等進行4級銨鹽化所得之(共)聚合物。具有這些4級銨 鹽構造的(共)聚合物可單獨使用亦可倂用至少2種。 作爲上述陽離子系界面活性劑，若使用氧含有比例高 的(共)聚合物或具有苯乙烯等之芳香族環的(共)聚合物，由 於可促進有機不燃膜的形成，難燃性乃提昇。又，若於上 述層狀矽酸鹽之層間作爲交換性陽離子所含之金屬離子以 長鏈(共）聚合物來交換，則由於層狀矽酸鹽變得易於分散 剝離，於燃燒時形成均一之無機燒結被膜，難燃性乃提昇 〇 作爲上述4級鐵鹽並無特別的限定，可舉出例如十二 烷基三苯基辚鹽(DTPB)、甲基三苯基鐵鹽、月桂基三甲基 鐵鹽、硬脂基三甲基鱗鹽、三辛基鱗鹽、二硬脂基二甲基 鱗鹽、二硬脂基苯基鱗鹽等。該等之4級鱗鹽可單獨使用 或併用至少2種。 藉由使用4級鳞鹽作爲上述陽離子系界面活性劑，於 11 (請先閱讀背面之注意事項再^寫本頁) ¾ . 丨線' 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1225504 A7 B7 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 五、發明說明（iD ) 燃燒時在層狀矽酸鹽之層間插入易於固定化，在難燃性提 昇效果上會變大。此乃由於，相較於4級銨鹽或其他之插 入，4級鱗鹽本身之難燃性高所致。 又，由於4級鱗鹽含磷，其與後述之磷系化合物所具 機能同樣，於燃燒時會形成表面被膜，發揮氧阻絕效果。 此時，相較於將磷系化合物單獨地添加至聚烯烴系樹脂中 作爲難燃劑的情形，由於在層狀矽酸鹽之結晶薄片附近存 在著磷成分，藉由結晶薄片與磷成分的相互作用，可進行 更具效果的被膜形成。 在上述4級鱗鹽當中，以使用至少具有碳數6之烷基 的4級烷基鱗鹽爲佳。若烷基之碳數未滿6，則烷基辚離 子之親水性會變強，有時無法將層狀矽酸鹽之層間充分地 非極性化。 本發明所使用之層狀矽酸鹽，藉由廣角X射線繞射測 定法所測定之(001)面之平均層間距離爲至少3nm、含有在 聚烯烴系樹脂組成物中以至多5層的狀態分散之物乃爲所 希望的。 上述層狀矽酸鹽之層數與其比例可藉由透過型電子顯 微鏡攝影來計算出。 上述所謂的層狀矽酸鹽之平均層間距離，意指以微細 薄片狀結晶爲層的情況下之平均的層間距離，其可藉由X 射線繞射峰値以及透過型電子顯微鏡攝影來算出、也就是 可藉由廣角X射線繞射測定法來算出。 若上述平均層間距離在至少3nm，由於聚烯烴系樹脂 12 (請先閱讀背面之注意事項再¾寫本頁) % 訂· -丨線· 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1225504 A7 ^_B7 五、發明說明（// ) 變得容易進入層狀矽酸鹽之層間，層狀矽酸鹽之結晶薄片 層乃分離爲至多5層，增加界面面積。層間裂開爲至少 3nm，意味著層狀矽酸鹽在燃燒時會處於易於分散之狀態 ，進一步分散爲至多5層之狀態，意味著層間之相互作用 力的變弱會造成層狀矽酸鹽之積層體的一部分分散。從而 ，若上述層狀矽酸鹽含有平均層間距離爲至少3nm、在聚 烯烴系樹脂組成物中以至多5層的狀態分散之物，則本發 明之聚烯烴系樹脂組成物，將易於獲致難燃性、機械強度 、以及氣體防護性等之機能。 上述平均層間距離以至少6nm爲佳。若平均層間距離 達至少6nm，由於層狀矽酸鹽之結晶薄片層之每一層會分 離，層狀矽酸鹽之結晶薄片間之相互作用幾乎弱到可以忽 略，是以構成層狀砂酸鹽之結晶薄片在聚嫌烴系樹脂中之 分層狀態可朝離碎安定化的方向邁進。 一般認爲，藉由令在結晶狀態爲多數層的層狀矽酸鹽 產生層剝離，則由於結晶薄片的數目或層狀矽酸鹽的界面 面積增加，再者，結晶薄片間的距離也變小，故燃燒時之 層狀矽酸鹽的結晶薄片的移動可易於形成燒結體。 經濟部智慧財產局員工消費合作社印製 (請先閱讀背面之注意事項再邊寫本頁) -線- 於本發明所使用之層狀矽酸鹽，總層狀矽酸鹽之1〇重 量％分散爲至多5層是所希望的。更佳爲20重量％以上。 又，只要分層爲至多5層，將可得到上述所說之效果，而 分層爲至多3層會更具效果。作爲更具效果的分層狀態， 以成爲單離層狀薄片化爲佳。 亦即，若上述層狀矽酸鹽，其上述平均層間距離爲至 13 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公楚） 1225504 A7 B7 五、發明說明（1\) 少3nm、含有在聚烯烴系樹脂組成物中分散爲至多5層之 物，則本發明之聚烯烴系樹脂組成物易於形成燒結體，該 燒結體可成爲難燃被膜。由於此燒結體會隨著分散的進行 在燃燒的早期形成，其不僅可阻絕來自外界之氧的供給， 亦可阻絕因燃燒所產生之可燃氣體，乃可獲致優異之難燃 性。 本發明所使用之層狀矽酸鹽亦可藉由具有官能基(該官 能基能與端面之羥基產生化學鍵結或展現化學親和性)之化 合物來處理。 作爲上述能與羥基產生化學鍵結或是展現化學親和性 的官能基並無特別的限定，可舉出例如醇氧基、環氧基、 羧基、羥基、順丁烯二酸基、異氰酯基、醛基等之與羥基 的化學親和性高的官能基。 作爲上述具有官能基(該官能基能與上述羥基產生化學 鍵結或展現化學親和性)之化合物並無特別的限定，可舉出 例如含有上述各種官能基的矽烷化合物、鈦酸酯化合物、 環氧丙基化合物、羧酸類、醇類等，其中又以矽烷化合物 爲佳。該等之化合物可單獨使用亦可倂用至少2種類。 作爲上述矽烷化合物並無特別的限定，可舉出例如乙 烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三（/3 — 甲氧乙氧基)砂院、7—胺丙基三甲氧基砂院、^ 一胺基丙 基甲基一甲氧基砂院、7—胺丙基二甲基甲氧基砂垸、7 一胺丙基三乙氧基矽烷、r一胺丙基甲基二乙氧基矽烷、 r一胺丙基二甲基乙氧基矽烷、甲基三乙氧基矽烷、二甲 14 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項寫本頁) · ，-線- 經濟部智慧財產局員工消費合作社印製 1225504 A7 ___B7____ 五、發明說明（/ )) 基二甲氧基矽烷、三甲基甲氧基矽烷、己基三甲氧基矽烷 、己基三乙氧基矽烷、N—/3(胺乙基）r 一胺丙基三甲氧基 矽烷、N—/?(胺乙基）r 一胺丙基三乙氧基矽烷、N—万（胺 乙基）r 一胺丙基甲基二甲氧基矽烷、十八烷基三甲氧基矽 垸、十八院基三乙氧基砍院、甲基丙嫌氧基丙基甲基 二甲氧基矽烷、r一甲基丙烯氧基丙基三甲氧基矽烷、τ 一甲基丙烯氧基丙基甲基二乙氧基矽烷、r一甲基丙烯氧 基丙基三乙氧基矽烷等。該等之化合物可單獨使用亦可倂 用至少2種類。 上述層狀矽酸鹽的添加量相對於聚烯烴系樹脂100重 量份爲0.1〜100重量份。若未滿0.1重量份，在形成燒結體 上會變得困難，所得之聚烯烴系樹脂組成物以及成型體之 難燃性將不充分，另一方面，若超過100重量份，所得之 聚烯烴系樹脂組成物以及成型體的比重會變大，有損其實 用性。較佳爲5〜100重量份。 經濟部智慧財產局員工消費合作社印製 ------------- 裝--- (請先閱讀背面之注意事項寫本頁) --線- 作爲於上述聚烯烴系樹脂中分散層狀矽酸鹽的方法， 可舉出例如（1)使用施行過有機化處理之層狀矽酸鹽的方法 ;(2)在層狀矽酸鹽存在下發泡來分散的方法等。上述（1)法 與(2)法可個別單獨使用或將兩者倂用。藉由使用此種分散 方法，可於上述聚烯烴系樹脂中更均一、微細地分散層狀 矽酸鹽。 上述之（1)於層狀矽酸鹽施行有機化處理之方法，可舉 出例如（1-1)將層狀矽酸鹽之結晶構造中作爲交換性陽離子 所含之金屬離子以上述陽離子系界面活性劑來交換之方法 15 $紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱)--- 1225504 A7 _ B7 五、發明說明（/f) ;(卜2)對存在於層狀矽酸鹽之結晶表面的羥基，以可與羥 基形成化學鍵結或展現化學親和性的官能基以及/或是在分 子末端具有至少1個之反應性官能基的化合物來化學修飾 之方法；（1-3)對層狀砂酸鹽之結晶表面，以具有陰離子性 界面活性能之試劑以及/或是具有陰離子性界面活性能且分 子鏈中之陰離子部位以外具有至少1個反應性官能基之試 劑來化學修飾之方法等。該等之方法可單獨使用亦可倂用 至少2種。 作爲上述(2)在層狀矽酸鹽存在下發泡來分散的方法， 可舉出例如(2-1)相對於聚烯烴系樹脂100重量份與層狀矽 酸鹽0.1〜100重量份所構成之組成物，於高壓下含浸在常 溫常壓下爲氣體狀之化合物，接著，讓此氣體狀之化合物 在組成物內氣化形成發泡體來分散之方法，（2-2)事先於層 狀矽酸鹽之層間加入熱分解型發泡劑，然後加熱該熱分解 型發泡劑加以分解形成發泡構造來分散之方法等。該等之 方法可單獨使用亦可併用至少2種。 經濟部智慧財產局員工消費合作社印製 上述層狀矽酸鹽之層間的剝離，其結晶薄片在聚烯烴 系樹脂中愈爲分散，則結晶薄片間平均距離愈小，於燃燒 時上述層狀矽酸鹽的結晶薄片的移動愈易形成燒結體。又 ，上述層狀矽酸鹽之結晶薄片愈爲分散，則聚烯烴系樹脂 一層狀矽酸鹽複合材料的彈性率或氣體防護性愈顯著提昇 〇 上述的現象皆是由於層狀矽酸鹽與聚烯烴系樹脂的界 面面積隨著結晶薄片的分散度的提昇而增大之故。亦即， 16 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） 1225504 A7 __ B7 五、發明說明（ί &) 由於藉由限制在上述聚烯烴系樹脂與層狀矽酸鹽之接箸面 的聚烯烴系樹脂的分子運動，聚烯烴系樹脂之彈性率等之 機械強度增加，故結晶薄片的分散度愈爲提昇，將可寅有 效率地增加聚烯烴系樹脂的機械強度。 又’在聚合物中，由於氣體分子遠較無機物來得易於 擴散，在複合材料中擴散氣體分子之際，係一邊迂迴無機 物一邊進行擴散。從而，在本發明方面同樣地，層狀矽酸 鹽之結晶薄片的分散度愈爲提昇，愈可有效率地增加聚烯 烴系樹脂之氣體防護性。 本發明之聚烯烴系樹脂組成物，將在50kW/m2的加熱 條件下加熱燃燒30分鐘所得之燃燒殘渣以O.lcm/s來麽縮 時，降伏點應力爲至少4.9xi03Pa。 爲獲致聚烯烴系樹脂組成物之燒結體之作爲難燃被膜 的機能，有必要保持燒結體的形狀直到燃燒結束，若壓縮 聚烯烴系樹脂組成物的燃燒殘渣之際不存在降伏點，僅微 小的力量燃燒殘渣即會崩潰。又，即使存在降伏點，若降 伏點應力未達4.9X103Pa，同樣地微小的力量會造成燃燒殘 渣的崩潰。較佳爲至少4.9xi03Pa。 本發明之聚烯烴系樹脂組成物，在50kW/m2的加熱條 件下加熱燃燒30分鐘時之最大放熱速度以低於800 kW/m2 爲佳。若超過800 kW/m2，由於燃燒時之火勢過大，會難以 抑制聚烯烴系樹脂組成物的燃燒。較佳爲低於400 kW/m2。 本發明之聚烯烴系樹脂組成物，進一步以含有磷系化 合物、金屬氫氧化物、或是三聚氰胺衍生物爲佳。上述磷 17 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再d寫本頁) · -線- 經濟部智慧財產局員工消費合作社印製 1225504 Α7 Β7 五、發明說明（/厶） 系化合物、金屬氫氧化物、以及三聚氰胺衍生物，可壞竭 使用或倂用至少2種。 作爲上述隣系化合物並無特別的限定，可舉出例如$ 磷、多磷酸銨、以及以下述通式（1)所表示之磷化合物等。 其中又以下述通式⑴所表示之磷化合物爲適宜。該等;^_ 系化合物可單獨使用亦可倂用至少2種類。 R3 (R2) (OR1) P = 0 (1) 式中，R1與R3係表示氫原子、碳數1〜16之烷基或$ 基，R2係表示氫原子、羥基、碳數1〜16之烷基、醇氧基、 芳基或芳氧基，R1、R2與R3可彼此相同或不同。若上述碳 數超過16，由於磷之相對含有率會變低，有時在難燃性賦 予效果上將不充分。 作爲上述赤磷，基於耐濕性的提昇或防止添加於聚燦 烴系樹脂進行混練之際的自然起火，其表面以樹脂被覆之 物乃爲所希望的。 作爲上述多磷酸銨，可爲施行三聚氰胺改質等之表面 處理之物。 經濟部智慧財產局員工消費合作社印製 作爲上述以通式（1)所表示之磷化合物並無特別的限定 ’可舉出例如甲基燐酸、甲基燐酸二甲酯、甲基燐酸二乙 酯、乙基燐酸、丙基燐酸、丁基燐酸、2—甲基一丙基燐酸 、特丁基燐酸、2,3—二甲基一丁基燐酸、辛基燐酸、苯基 燐酸、二辛基苯基燐酸酯、二甲基次燐酸、甲基乙基次燐 酸、甲基丙基次燐酸、二乙基次燐酸、二辛基次燐酸、苯 基次燐酸、二乙基苯基次燐酸、二苯基次燐酸、雙(4一甲 18 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1225504 Α7 Β7 經濟部智慧財產局員工消費合作社印製 五、發明説明（ί)) 氧基苯基)次燐酸等。該等之磷化合物可單獨使用或倂用至 少2種類。 上述磷系化合物之添加量，相對於聚烯烴系樹脂100 重量份，以0·5〜100重量份爲佳。若未滿0.5重量份，有時 無法獲得充分之難燃性提昇效果，另一方面，若超過100 重量份，有時由聚烯烴系樹脂組成物所得之成型體的機械 強度會降低。更佳係2〜50重量份。 作爲上述金屬氫氧化物並無特別的限定，可舉出例如 氫氧化鎂、氫氧化鋁、氫氧化鈣、碳鈉鋁石、鋁酸鈣、二 水和石膏等，其中又以氫氧化鎂、氫氧化鋁爲佳。該等之 金屬氫氧化物可單獨使用或倂用至少2種類。若倂用至少 2種類之金屬氫氧化物，由於個別之金屬氫氧化物在不同 的溫度下開始分解脫水反應，可獲得更高的難燃性賦予效 又’上述金屬氫氧化物亦可爲藉表面處理劑施以表面 處理之物。作爲上述表面處理劑並無特別的限定，可舉出 例如矽烷系偶合劑、鈦酸酯系偶合劑、鋁系偶合劑、聚乙 烯基醇系表面處理劑、環氧系表面處理劑、高級脂肪酸系 表面處理劑等。該等之表面處理劑可單獨使用或倂用至少 2種類。 上述金屬氫氧化物的添加量，相對於聚烯烴系樹脂 100重量份，以0.5〜1〇〇重量份爲佳。若未滿0.5重量份， 有時無法獲得充分之難燃性提昇效果，另一方面，若超過 1〇〇重量份，雖難燃性可更爲提昇，惟有時會發生比重的 _ 19 本纸張尺度適用中國國家標準（CNS ) Α4規格（210 Χ297公釐） (請先閱讀背面之注意事項再 -裝_ 、1Τ 線 1225504 A7 B7 五、發明説明（（(f) 增大或柔軟性的欠缺等之不佳情形。更佳係20〜60重量份 〇 由於上述金屬氫氧化物在燃燒時的高溫下發生吸熱脫 水反應，在吸熱後會放出水分子使得燃燒處的溫度下降， 從而發揮滅火的效果。又，由於本發明之聚烯烴系樹脂組 成物含有層狀矽酸鹽，金屬氫氧化物所提供之難燃性提昇 效果可進一步增大。其理由在於，基於上述層狀矽酸鹽之 燃燒時之被膜形成所提供之難燃性提昇效果與基於金屬氫 氧化物之吸熱脫水反應所提供之難燃性提昇效果交互地出 現，從而助長了個別之效果。 作爲上述三聚氰胺衍生物並無特別的限定，可舉出例 如三聚氰胺、三聚氰胺氰酯、三聚氰胺異氰酯、磷酸三聚 氰胺、於前述之物施以表面處理所得者等。該等之三聚氰 胺衍生物可單獨使用或併用至少2種類。在上述表面處理 方面，可舉出與施於金屬氫氧化物上之處理爲同樣的處理 〇 經濟部智慧財產局員工消资合作社印製 上述三聚氰胺衍生物的添加量，相對於聚烯烴系樹脂 100重量份，以0.5〜100重量份爲佳。若未滿0.5重量份， 有時無法獲得充分之難燃性提昇效果，另一方面，若超過 100重量份，有時會造成本發明之聚烯烴系樹脂組成物的 物性降低、或是妨礙層狀矽酸鹽形成燒結被膜。更佳係 1〜30重量份。 本發明之聚烯烴系樹脂組成物，爲進一步提昇其難燃 性，以含有上述層狀矽酸鹽以外的矽酸鹽化合物爲佳。 ________20_ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1225504 A7 ___B7 五、發明説明(1) 作爲上述矽酸鹽化合物並無特別的限定，可舉出例如 矽灰石、硬矽鈣石等之矽酸鈣類；滑石、活性白土、高嶺 土、海泡石、依摩谷萊特（imogolite)等之黏土礦物類；二 氧化矽系輕型(balloon)類等，其中，基於對上述層狀矽酸 鹽之親和性或粒子徑之選擇性爲優異的考量，以使用滑石 爲佳。該等之矽酸鹽化合物可單獨使用或併用至少2種類 〇 又，作爲上述砂酸鹽化合物，以具有與層狀政酸鹽之 平均粒子徑相異之物爲佳。藉由將上述具有與層狀砍酸鹽 之平均粒子徑相異之矽酸鹽化合物添加至本發明之聚稀烴 系樹脂組成物中，於燃燒時層狀矽酸鹽或砂酸鹽化合物等 之無機成分可作爲燒結體輕易地被覆於燃燒表面，而可車垔 易地形成強固的難燃被膜。 上述矽酸鹽化合物之添加量，相對於聚烯烴系樹脂 100重量份，以0·5〜20重量份爲佳。若未滿0.5重量份，有 時無法獲得充分之難燃性提昇效果，另一方面，若超過20 重量份，有時由聚烯烴系樹脂組成物所得之成型體的機械 強度會降低、比重會變得過高。更佳係2〜10重量份。 經濟部智慧財產局員工消費合作社印製 爲進一步提昇本發明之聚烯烴系樹脂組成物之難燃性 ，以含有金屬氧化物爲佳。 作爲上述金屬氧化物並無特別的限定，可舉出例如氧 化銅（I )、氧化銅（Π)、氧化鎂（瓜）、氧化鈣、二氧化鈦、 二氧化鉻、氧化鉻（Π)、氧化鉻（瓜)、氧化鉻（IV)、氧化鋁 、氧化銻（π)、氧化銻（v)、氧化釔（m)、氧化銦（I)、氧化 21 ^^浪尺度適用中國國家標準（〇奶）八4規格（210乂297公釐） 1225504 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（W) 銦（Π)、氧化銦（瓜）、氧化鉀、氧化銀（I )、氧化銀（Π)、氧 化鍺（Π)、氧化鍺（IV)、氧化鈷（Π)、氧化鈷（瓜）、氧化錫( π)、氧化錫（iv)、氧化絶、氧化鉈（I)、氧化鉈（m)、氧化 鎢（IV)、氧化鎢（vi)、氧化鈦（π)、氧化鈦（瓜）、氧化鈦（IV) 、氧化鋅、氧化鐵（π)、氧化鐵（m)、氧化鋇、氧化錳(w) 、氧化鉬（iv)、氧化鉬（vi)、氧化鋰、氧化釕(谓)等。該等 之金屬氧化物可單獨使用或倂用至少2種。 上述金屬氧化物，其作爲本發明之聚烯烴系樹脂組成 物燃燒之際之促進有機不燃被膜之形成的觸媒來作用，其 具有藉由形成更強固之有機不燃被膜來獲致高難燃性之機 tb ° 上述金屬氧化物之添加量，相對於聚烯烴系樹脂100 重量份，以0.1〜10重量份爲佳。若未滿0.1重量份，有時 無法獲得充分之難燃性提昇效果，另一方面，若超過10重 量份，有時會造成本發明之聚烯烴系樹脂組成物的物性降 低。更佳係0.2〜5重量份。 爲進一步提昇本發明之聚烯烴系樹脂組成物之難燃性 ，以含有由：具有相對於聚烯烴系樹脂顯示反應性之官能 基的段落(A)嵌段、相對於聚烯烴系樹脂具有親和性的段落 (B)嵌段；所構成之AB型嵌段共聚物爲佳。 作爲上述段落(A)嵌段之官能基，只要爲可與層狀矽酸 鹽之結晶表面所存在的羥基行化學鍵結的官能基或具有化 學親和性之官能基則無特別之限定，可舉出例如羧基、環 氧基等。 _____22__ 本紙張尺度適用中國國家標隼（CNS ) A4規格（210X297公釐） 1225504 A7 B7 五、發明説明（v丨） 作爲上述段落(A)嵌段，以在分子中具有複數之上述官 能基爲佳。又，作爲上述段落(A)嵌段之分子量並無特別的 限定，以1 X 104〜5χ104爲佳。若超過5χ104，有時段落(A) 嵌段之自由度會降低，與層狀矽酸鹽之反應性會受到阻礙 〇 上述段落(B)嵌段，以與本發明之聚烯烴系樹脂組成物 中做爲主成分所使用之聚烯烴系樹脂爲相同種類之物爲佳 ’更佳爲完全相同之聚烯烴系樹脂。 又，就上述段落(B)嵌段之分子量而言並無特別的限定 ，以1X104〜5χ104爲佳。若超過5χ104，有時段落(B)嵌段之 自由度會降低，無法得到充分之分散性提昇效果。 由上述段落(A)嵌段與段落(B)嵌段所構成之AB型嵌段 共聚物，其與ΑΒΑ型嵌段共聚物相異，由於具有相對於聚 烯烴系樹脂顯示反應性之官能基的段落(A)嵌段、以及相對 於聚烯烴系樹脂具有親和性的段落(B)嵌段位於兩端，除了 可有效率地促進上述層狀矽酸鹽的層間剝離，亦可提升層 狀矽酸鹽之對於聚烯烴系樹脂中的分散性。 經濟部智慧財產局員工消費合作社印製 爲進一步提昇本發明之聚烯烴系樹脂組成物之難燃性 ，以含有具芳香族系羥基之化合物爲佳。 作爲上述具芳香族系羥基之化合物，只要爲可捕捉自 由基之物即可，並無特別的限定，可舉出例如2,6—二一特 丁基一對甲酚、2,6 —二一特丁基一4一乙基酚醛、2,2'—甲 撐雙(4一甲基一6—特丁基酚醛）、三乙二醇一雙[3 — (3—特 丁基一 5 —甲基一 4 一羥苯基)丙酸酯、1，6-己二醇一雙[3 — 23__ 本紙張尺度適用中國國家標準（CNS ) A4規格（210、乂297公釐1 1225504 A7 B7 五 (3,5一一一特丁基一4一羥苯基)丙酸酯]、2,4—雙一(正辛基 硫代）一6 — (4〜羥基—3,5 一二一特苯胺基）一 u，5_三嗪、 2,2一硫代一二乙撐雙[3 — (3,5 —二一特丁基一4一羥苯基)丙 酸酯]、十八烷基一3 — (3,5 —二一特丁基一4一羥苯基)丙酸 酯]、Ν，ΝΓ—六甲撐雙(3,5_二一特丁基一4一羥基一肉桂醯 胺）、3,5 —二〜特丁基一4一羥苯基膦酸酯—二乙酯、u，5 一三甲基一2,4,6—三(3,5 —二一特丁基一4一羥苯基）苯、雙 (3,5 —二一特丁基一4一羥苯基膦酸乙酯)鈣、三一(3,5一二一 特丁基一4-羥苯基)異氰酸酯、2,4一雙[(辛基硫代）甲基]一 〇一甲酚、異辛基一3 — (3,5 —二一特丁基一4一羥苯基)丙酸 酯、3,9 一雙{1，1一二甲基 2—特丁基一4 一羥基一5 一甲苯基)丙醯基氧基]乙基}2,4,8，1〇 —四氧代螺[5,5]十一烷 、對苯基苯酚、沒食子酸等。該等之具有芳香族系羥基之 化合物可單獨使用或併用至少2種類。 在燃燒時之高熱下聚烯烴系樹脂經熱分解成爲燃燒性 氣體的過程中，上述具有芳香族系經基之化合物會捕捉分 解生成物之自由基，發揮延遲燃燒反應的機能。 上述具有芳香族系羥基之化合物的添加量，相對於聚 烯烴系樹脂100重量份，以0.01〜30重量份爲佳。若未滿 〇·〇1重量份，有時無法獲得充分之難燃性提昇效果，另一 方面，若超過30重量份，有時會造成本發明之聚烯烴系樹 脂組成物的物性降低、或是妨礙層狀矽酸鹽形成燒結被膜 。更佳係0.05〜10重量份。 於本發明之聚烯烴系樹脂組成物中，在不致妨礙本發 24 ^^^適用中國國家標準（€阳）八4規格（21(^297公釐） --------堯-- (請先閲讀背面之注意事項再填 頁)"ir ^ J-line" is preferably a compound of at least one of the group consisting of phosphorus compounds represented by the general formula (1). R3 (R2) (OR1) P = 0 (1) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1225504 A7 B7 V. Description of the invention ( f) In the formula, R1 and R3 represent a hydrogen atom, a radical or an aryl group having 1 to 16 carbon atoms, and R2 represents a hydrogen atom, a hydroxyl group, a radical having a carbon number of 1 to 16 or an alcohol group, an aryl group, or an aromatic group. The oxy groups, R1, R2 and R3 may be the same as or different from each other. The polyolefin-based resin composition 'of the present invention preferably further contains 0.5 to 20 parts by weight of a silicate compound other than the layered silicate. The polyolefin-based resin composition of the present invention 'further contains a metal oxide 0. It is preferably 1 to 10 parts by weight. The polyolefin-based resin composition of the present invention may further include a paragraph (A) block having a functional group exhibiting reactivity with respect to the polyolefin-based resin, and a paragraph (B) having affinity with the polyolefin-based resin. Block; the AB-type block copolymer formed is preferred. The polyolefin-based resin composition of the present invention 'further contains a compound having an aromatic hydroxyl group. 〇 丨 ~ 30 weight parts are preferred. The thermoplastic resin using the polyolefin-based resin composition of the present invention for coating or sealing electric wires is also one aspect of the present invention. The insulated wire formed by using the above thermoplastic resin is also the present invention. ‘0 [Detailed description of the invention] The present invention is described in detail below. The polysmoke-based resin composition of the present invention is composed of 1,000 parts by weight of a polysmoke-based resin and a layered silicate of 0. 1 to 100 parts by weight. The polyolefin-based resin used in the present invention is obtained by polymerizing an olefin-based monomer having a polymerizable double bond. The olefin-based monomer is not particularly limited, and examples thereof include ethyl 7 -------------. . — (Please read the caution page on the back first). Line-This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 1225504 A7 __B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (ene, propylene, 1-butene, 1- 1 Α-olefins such as pentene, 1-hexene, 丨 heptene, 丨 octene, 4-methyl-1 1 pentene, etc., or conjugated dienes such as butadiene, isopropylene, etc. The olefin-based monomer may be used singly or in combination of at least two types. The polyolefin-based resin is not particularly limited, and examples thereof include a monopolymer of ethylene, a copolymer of ethylene and an α-olefin, and ethylene and (methyl ) Copolymer of acrylic acid, copolymer of ethylene and (meth) acrylate, copolymer of ethylene and ethyl acetate, monomer of propylene, copolymer of propylene and α-olefin, random copolymer of propylene and ethylene Or a block copolymer, a monopolymer of butene, a monopolymer or copolymer of conjugated diene such as butadiene or isopropylene, etc. These olefin resins can be used alone or in combination of at least two kinds. In this specification, 'the so-called (meth) acrylic acid means propylene Or methacrylic acid. Among the above-mentioned polyolefin resins, there are monopolymers of ethylene, monopolymers of propylene, ethylene or propylene, and copolymers of α-olefins copolymerizable with both, ethylene and (meth) Copolymers of acrylic esters or copolymers of ethylene and ethyl acetate are preferred. These olefin-based resins can be used alone or in combination of at least two types. The molecular weight and molecular weight distribution of the above-mentioned polyolefin-based resins are not particularly limited. The weight average molecular weight is preferably 5,000 to 5 million, and more preferably 20,000 to 300,000; the molecular weight distribution (weight average molecular weight / number average molecular weight) is 1. 1 ~ 80 is preferred, with 1. 5 ~ 40 is more preferable. The layered silicate used in the present invention contains a silicate mineral having exchangeability in the crystal structure between layers. 8 (Please read the notes on the back before writing this page). ¾. -Line ·! This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) 1225504 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (7) As the above-mentioned layered silicate It is not particularly limited, and examples thereof include montmorillonite-based clay minerals such as montmorillonite, saponite, hectorite, beidec, magnesia-rich montmorillonite, and cystite; vermiculite and halloysite "Expansive mica" Among them, montmorillonite and expansive mica are preferred. These layered silicates can be used alone or in combination of at least two kinds. The layered silicate may be a natural product or a synthetic product. As the layered silicate, a montmorillonite-based clay mineral or an expansive mica having a large shape anisotropy effect as defined by the following general formula (1) is used to form a polyolefin-based resin composition and molding From the standpoint of improving the mechanical strength of the body or the gas barrier property. Shape anisotropy effect = area of crystal surface (a) / area of crystal surface (b) ... (1) The cation exchange capacity of the layered silicate is not particularly limited, and it is 50 to 200 milliequivalents / l. 〇〇g is better. If it is less than 50 milliequivalents / 100g, the amount of cationic surfactants intercalated between the crystal layers by ion exchange will be reduced, and the interlayers may not be sufficiently non-polarized. On the other hand, if it exceeds 200 Milli-equivalent / 100g, because the interlayer bonding force of the layered silicate becomes strong, the crystalline flakes may be difficult to peel off. The exchangeable cation is not particularly limited, and examples thereof include monovalent metal ions such as sodium and potassium. When exchangeable cations are exchanged with other metal ions, the exchanged metal ions have the effect of increasing the acidity of the layered silicate by ion exchange compared to that before ion exchange. Once the acidity of the layered silicate is increased, it is compatible with polyolefin resins or additives added to polyolefin resins (please read the precautions on the back before writing this page). Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1225504 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention) The reactivity is easy to improve and the dispersibility of the layered silicate is improved. In the layered silicate used in the present invention, it is desirable that the exchangeable cations in the crystalline structure undergo ion exchange with divalent metal ions. When ion exchange is performed with metal ions exceeding two valence, the interlayer bonding force of the layered silicate will be strong, and interlayer peeling (delamination) will not occur. The divalent metal ion is not particularly limited, and examples thereof include nickel, magnesium, and calcium. The effect of increasing the acidity of the layered silicate by ion exchange with these metal ions is that the order of nickel, magnesium, and calcium becomes larger. Ion exchange is performed by using bivalent metal ions such as nickel, magnesium, and consumption. To increase the acidity of the hydroxyl group of the crystalline flakes of the layered silicate, it is proposed in, for example, "Clay materials" (1997, 32, p645 ~ 651) obtained by NISHIHAMA and the like. Right from the viewpoint of improving the bonding force between the crystalline flakes during sintering and easy formation of a strong sintered film, nickel ions or magnesium ions are preferred. The layered silicate used in the present invention preferably contains a cationic surfactant in its crystal structure. As a method of including a cationic surfactant in the crystal structure of the layered silicate, for example, a part or all of the metal ions existing in the form of exchangeable cations in the crystal structure of the layered silicate can be exemplified by Method for exchanging cationic surfactants. The cationic surfactant is not particularly limited, and examples thereof include an ammonium salt and a fourth-order iron salt. The fourth-order ammonium salt is not particularly limited, and examples thereof include lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl ammonium salt, and di 10 (please read the precautions on the back first) «I write this page again] Taiyan · Γ This paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 1225504 Α7 Β7 Printed by the Consumers’ Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of invention (y) (Co) polymers made of quaternary ammonium salts such as stearyl dimethyl ammonium salt, di-hardened tallow dimethyl ammonium salt, and distearyl diphenyl ammonium salt. These grade 4 ammonium salts can be used alone or in combination of at least two kinds. In the present specification, the (co) polymer 'means a polymer or a copolymer. The (co) polymer having a quaternary ammonium salt structure is not particularly limited, and examples thereof include monopolymerization of a (meth) acrylic monomer having an amine 'alkylamino group, a dialkylamino group, or the like. (Meth) acrylic monomers and other (meth) acrylic monomers, and / or styrene monomers such as styrene, α-methylstyrene, and vinyl toluene. The copolymer is a (co) polymer obtained by subjecting it to a fourth-order ammonium salt with hydrochloric acid or the like. The (co) polymers having these quaternary ammonium salt structures may be used alone or in combination of at least two kinds. As the above-mentioned cationic surfactant, if a (co) polymer having a high oxygen content ratio or a (co) polymer having an aromatic ring such as styrene is used, the formation of an organic noncombustible film is promoted, and the flame retardancy is improved. . In addition, if the metal ions contained as exchangeable cations between the layers of the layered silicate are exchanged with a long-chain (co) polymer, the layered silicate becomes easily dispersed and peeled, and becomes uniform during combustion. The inorganic sintered coating is improved in flame resistance. The fourth-order iron salt is not particularly limited, and examples thereof include dodecyl triphenylphosphonium salt (DTPB), methyl triphenyl iron salt, and lauryl. Trimethyl iron salt, stearyl trimethyl scale salt, trioctyl scale salt, distearyl dimethyl scale salt, distearyl phenyl scale salt, and the like. These grade 4 scale salts can be used alone or in combination of at least two kinds. By using grade 4 scale salt as the above-mentioned cationic surfactant, in 11 (Please read the precautions on the back before writing this page) ¾. 丨 Line 'This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 1225504 A7 B7 Printed by the Consumer Cooperatives of the Ministry of Economic Affairs and Intellectual Property of the Ministry of Education 5. Description of Invention (iD) Layered silicate during combustion The interlayer insertion is easy to fix, and the flame retardant improvement effect will increase. This is due to the higher flame retardancy of the scale 4 salt itself compared to the level 4 ammonium salt or other insertions. In addition, since the 4th-grade scaly salt contains phosphorus, it has the same function as a phosphorus-based compound described later, and forms a surface film during combustion to exert an oxygen barrier effect. At this time, compared to the case where a phosphorus-based compound is separately added to a polyolefin-based resin as a flame retardant, the phosphorus component exists near the crystalline flakes of the layered silicate. Interaction enables more effective film formation. Among the above-mentioned fourth-order scale salts, a fourth-order alkyl scale salt having an alkyl group having at least 6 carbon atoms is preferably used. If the carbon number of the alkyl group is less than 6, the hydrophilicity of the alkyl sulfonium ion becomes strong, and the layer of the layered silicate cannot be sufficiently depolarized in some cases. The layered silicate used in the present invention has a state in which the average interlayer distance of the (001) plane is at least 3 nm, as measured by a wide-angle X-ray diffraction measurement method, and is contained in a polyolefin resin composition in a state of at most 5 layers. The scattered things are desired. The number of layers of the layered silicate and the ratio thereof can be calculated by transmission electron microscope photography. The so-called average interlayer distance of the layered silicate refers to the average interlayer distance in the case of using fine flake crystals as a layer, which can be calculated by X-ray diffraction peak chirping and transmission electron microscope photography. That is, it can be calculated by a wide-angle X-ray diffraction measurement method. If the above average interlayer distance is at least 3nm, due to polyolefin resin 12 (Please read the precautions on the back before writing this page)% Order ·-丨 Line · This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1225504 A7 ^ _B7 V. Description of the invention (//) It becomes easy to enter the layers of the layered silicate, and the crystalline thin layer of the layered silicate is separated into up to 5 layers to increase the interface area. Interlayer cracking is at least 3nm, which means that the layered silicate will be in a state of being easily dispersed during combustion, and further dispersed into a state of up to 5 layers, meaning that the weakening of the interaction force between the layers will cause the layered silicate Part of the laminated body is dispersed. Therefore, if the above-mentioned layered silicate contains an average interlayer distance of at least 3 nm and is dispersed in a polyolefin-based resin composition in a state of at most 5 layers, the polyolefin-based resin composition of the present invention will easily be difficult to obtain. Flammability, mechanical strength, and gas barrier properties. The average interlayer distance is preferably at least 6 nm. If the average interlayer distance is at least 6 nm, since each layer of the crystalline flake layer of the layered silicate will be separated, the interaction between the crystalline flakes of the layered silicate is almost weak enough to be ignored, so that the layered silicate is formed. The layered state of the crystalline flakes in the polyhydrocarbon-based resin can be moved toward stability. It is generally considered that by exfoliating the layered silicate that has a large number of layers in the crystalline state, the number of crystal flakes or the interface area of the layered silicate increases, and the distance between the crystal flakes also changes. It is small, so the movement of the crystalline flakes of the layered silicate during combustion can easily form a sintered body. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the precautions on the back before writing this page)-line-the layered silicate used in the present invention, 10% by weight of the total layered silicate Dispersion of up to 5 layers is desirable. It is more preferably 20% by weight or more. In addition, as long as it is layered into at most 5 layers, the above-mentioned effects can be obtained, and layering into at most 3 layers is more effective. As a more effective layered state, it is preferable to be a single-layered thin sheet. That is, if the above layered silicate has an average interlayer distance of 13 to the paper size, the Chinese National Standard (CNS) A4 specification (210 X 297 cm) is applicable. 1225504 A7 B7 V. Description of the invention (1 \) Less If the polyolefin resin composition at 3 nm is dispersed in up to five layers, the polyolefin resin composition of the present invention can easily form a sintered body, and the sintered body can be a flame-resistant coating. Since this sintered body is formed in the early stage of combustion as the dispersion progresses, it can not only block the supply of oxygen from the outside, but also block the combustible gas produced by combustion, and can obtain excellent flame resistance. The layered silicate used in the present invention can also be treated by a compound having a functional group capable of forming a chemical bond with a hydroxyl group on the end face or exhibiting chemical affinity. The functional group capable of forming a chemical bond with a hydroxyl group or exhibiting chemical affinity is not particularly limited, and examples thereof include an alcohol group, an epoxy group, a carboxyl group, a hydroxyl group, a maleic acid group, and an isocyanate group. A functional group having a high chemical affinity with a hydroxyl group such as an aldehyde group and an aldehyde group. The compound having a functional group (the functional group can be chemically bonded to the hydroxyl group or exhibit chemical affinity) is not particularly limited, and examples thereof include silane compounds, titanate compounds, and epoxy resins containing the various functional groups Propyl compounds, carboxylic acids, alcohols, etc., of which silane compounds are preferred. These compounds can be used alone or in combination of at least two types. The silane compound is not particularly limited, and examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (/ 3-methoxyethoxy) sand, and 7-aminopropyl Trimethoxy sand ash, ^ aminoaminopropyl methyl methoxy sand ash, 7-aminopropyl dimethyl methoxy sand ash, 7 amine propyl triethoxy silane, r amine propyl Methylmethyldiethoxysilane, r-aminopropyldimethylethoxysilane, methyltriethoxysilane, dimethyl 14 This paper size applies to China National Standard (CNS) A4 (210 X 297) (%) (Please read the notes on the back to write this page first) · ·--Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1225504 A7 ___B7____ 5. Description of the invention (/) Dimethoxysilane, trimethyl Methoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, N- / 3 (aminoethyl) r monoaminopropyltrimethoxysilane, N-/? (Aminoethyl) r monoaminepropyl Triethoxysilane, N-methylene (aminoethyl) r monoaminopropylmethyldimethoxysilane, octadecyltrimethoxysilane, octadecyl Triethoxy radical, methacryloxypropylmethyldimethoxysilane, r-methacryloxypropyltrimethoxysilane, τ-methacryloxypropylmethyldi Ethoxysilane, r-methacryloxypropyltriethoxysilane, etc. These compounds can be used alone or in combination of at least two types. The addition amount of the layered silicate is 0 to 100 parts by weight of the polyolefin resin. 1 to 100 parts by weight. If less than 0. 1 part by weight makes it difficult to form a sintered body, and the obtained polyolefin-based resin composition and molded article have insufficient flame retardancy. On the other hand, if it exceeds 100 parts by weight, the obtained polyolefin-based resin composition The specific gravity of the object and the molded body becomes large, which impairs its practicality. It is preferably 5 to 100 parts by weight. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -------------- Packing --- (Please read the notes on the back first to write this page) --- Line-as the above polyolefin resin Examples of the method for intermediately dispersing the layered silicate include (1) a method using an organically treated layered silicate; (2) a method for dispersing by foaming in the presence of the layered silicate, and the like . The above methods (1) and (2) can be used individually or in combination. By using this dispersion method, the layered silicate can be more uniformly and finely dispersed in the polyolefin resin. The method of (1) organically treating the layered silicate includes, for example, (1-1) metal ions contained in the crystalline structure of the layered silicate as exchangeable cations. Method for exchanging surfactant 15 $ Paper size is applicable to Chinese National Standard (CNS) A4 specification (210 X 297 public love) --- 1225504 A7 _ B7 V. Description of the invention (/ f); (b) A method for chemically modifying the hydroxyl group on the crystalline surface of the layered silicate with a functional group capable of forming a chemical bond with the hydroxyl group or exhibiting chemical affinity and / or a compound having at least one reactive functional group at the molecular end; (1-3) For the crystal surface of layered oxalate, use an agent having anionic interfacial activity and / or have anionic interfacial activity and have at least one reactive functional group other than the anion site in the molecular chain Reagents to chemical modification methods. These methods can be used alone or in combination of at least two. As the method of (2) foaming and dispersing in the presence of a layered silicate, for example, (2-1) with respect to 100 parts by weight of a polyolefin-based resin and a layered silicate 0. A method of impregnating a composition composed of 1 to 100 parts by weight under a high pressure at a normal temperature and normal pressure into a gaseous compound, and then gasifying the gaseous compound in the composition to form a foam to disperse, ( 2-2) A method of adding a thermally decomposable foaming agent between the layers of the layered silicate in advance, and then heating and decomposing the thermally decomposable foaming agent to form a foaming structure and dispersing. These methods can be used alone or in combination of at least two. The delamination of the layered silicate printed by the employee cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the more the crystalline flakes are dispersed in the polyolefin resin, the smaller the average distance between the crystalline flakes. The movement of the crystal flakes of the acid salt is more likely to form a sintered body. In addition, the more the crystalline flakes of the layered silicate are dispersed, the more the elasticity or gas barrier property of the layered silicate composite material of the polyolefin resin is improved. The above phenomena are due to the layered silicate The interface area with the polyolefin-based resin increases as the degree of dispersion of the crystal flakes increases. That is, 16 paper sizes are applicable to Chinese National Standard (CNS) A4 specifications (210 X 297 public love) 1225504 A7 __ B7 V. Description of the invention (ί &) Due to the limitation on the above-mentioned polyolefin resin and layered silicon The molecular motion of the polyolefin-based resin on the interface of the acid salt and the mechanical strength of the polyolefin-based resin's elasticity increase, so the dispersion of the crystalline flakes is more improved, which will increase the efficiency of the polyolefin-based resin. Mechanical strength. Also, in the polymer, since the gas molecules are far easier to diffuse than the inorganic substances, when the gas molecules are diffused in the composite material, the diffusion is performed while bypassing the inorganic substances. Therefore, similarly in the aspect of the present invention, the more the degree of dispersion of the crystalline flakes of the layered silicate is improved, the more effectively the gas barrier property of the polyolefin resin can be increased. The polyolefin-based resin composition of the present invention, the combustion residue obtained by heating and burning under a heating condition of 50kW / m2 for 30 minutes to O. When lcm / s shrinks, the drop point stress is at least 4. 9xi03Pa. In order to obtain the function of the sintered body of the polyolefin-based resin composition as a flame-resistant coating, it is necessary to maintain the shape of the sintered body until the end of combustion. If the combustion residue of the polyolefin-based resin composition is compressed, there is no drop point, which is only small Burning residue of power will collapse. Also, even if there is a drop point, if the drop point does not reach 4. 9X103Pa, the same small force will cause the combustion residue to collapse. Preferably it is at least 4. 9xi03Pa. The polyolefin resin composition of the present invention preferably has a maximum heat release rate of less than 800 kW / m2 when heated and burned for 30 minutes under a heating condition of 50 kW / m2. If it exceeds 800 kW / m2, it is difficult to suppress the combustion of the polyolefin-based resin composition due to excessive fire during combustion. It is preferably less than 400 kW / m2. The polyolefin-based resin composition of the present invention preferably further contains a phosphorus-based compound, a metal hydroxide, or a melamine derivative. The above phosphorus 17 paper size is applicable to Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before writing this page) · -line-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1225504 Α7 Β7 5. Description of the invention (/ 厶) Series compounds, metal hydroxides, and melamine derivatives, which can be used in depletion or at least two kinds. The adjacent compound is not particularly limited, and examples thereof include phosphorus, ammonium polyphosphate, and a phosphorus compound represented by the following general formula (1). Among them, a phosphorus compound represented by the following general formula ⑴ is suitable. These ^ _ series compounds can be used alone or in combination of at least 2 types. R3 (R2) (OR1) P = 0 (1) In the formula, R1 and R3 represent a hydrogen atom, an alkyl group of 1 to 16 carbons or a radical, and R2 represents a hydrogen atom, a hydroxyl group, or a carbon number of 1 to 16 Alkyl, alcoholoxy, aryl or aryloxy, R1, R2 and R3 may be the same or different from each other. When the carbon number is more than 16, the relative content of phosphorus may be lowered, and the flame retardance imparting effect may be insufficient. As the above-mentioned red phosphorus, it is desirable to improve the moisture resistance or prevent natural fire when added to a polybranched resin for kneading, and a resin-coated surface is desirable. The ammonium polyphosphate may be a surface treated with melamine modification or the like. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs as the phosphorus compound represented by the general formula (1) is not particularly limited. Examples include methyl acetic acid, dimethyl methyl acetate, and diethyl methacetate. , Ethyl acetic acid, propyl acetic acid, butyl acetic acid, 2-methyl monopropyl acetic acid, tert-butyl acetic acid, 2,3-dimethyl monobutyl acetic acid, octyl acetic acid, phenyl acetic acid, dioctyl Phenylphosphonic acid, dimethylhyperacid, methylethylhyperacid, methylpropylhyperacid, diethylhyperacid, dioctylhyperacid, phenylhyperacid, diethylphenylhyperacid , Diphenyl hypoarsinic acid, bis (4,1,18,18) This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 1225504 Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ί)) oxyphenyl) hypophosphonic acid and the like. These phosphorus compounds can be used alone or in combination of at least two types. The amount of the phosphorus compound to be added is preferably 0.5 to 100 parts by weight based on 100 parts by weight of the polyolefin resin. If less than 0. 5 parts by weight may not provide a sufficient flame retardancy improving effect. On the other hand, if it exceeds 100 parts by weight, the mechanical strength of a molded article obtained from a polyolefin-based resin composition may decrease. More preferably, it is 2 to 50 parts by weight. The metal hydroxide is not particularly limited, and examples thereof include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, sootite, calcium aluminate, dihydrate, and gypsum. Among them, magnesium hydroxide, Aluminum hydroxide is preferred. These metal hydroxides can be used alone or in combination of at least two kinds. If at least two kinds of metal hydroxides are used, since individual metal hydroxides begin to decompose and dehydrate at different temperatures, a higher flame retardance imparting effect can be obtained. The surface treatment agent is a surface-treated substance. The surface treatment agent is not particularly limited, and examples thereof include a silane-based coupling agent, a titanate-based coupling agent, an aluminum-based coupling agent, a polyvinyl alcohol-based surface treatment agent, an epoxy-based surface treatment agent, and a higher fatty acid. Department of surface treatment agents. These surface treatment agents can be used alone or in combination of at least two types. The addition amount of the above metal hydroxide is 0. 0 with respect to 100 parts by weight of the polyolefin resin. 5 to 100 parts by weight is preferred. If less than 0. 5 parts by weight, sometimes it is not possible to obtain a sufficient flame retardancy improvement effect. On the other hand, if it exceeds 100 parts by weight, the flame retardancy may be improved, but the specific gravity may sometimes occur. China National Standard (CNS) A4 specification (210 x 297 mm) (Please read the precautions on the back before installing-1_ line 1225504 A7 B7 V. Description of the invention (((f) increase or lack of flexibility, etc. Poor condition. More preferably, it is 20 to 60 parts by weight. As the above metal hydroxide undergoes an endothermic dehydration reaction at a high temperature during combustion, water molecules are released after the endothermic heat to reduce the temperature at the combustion site, thereby exerting the effect of extinguishing fire. In addition, since the polyolefin-based resin composition of the present invention contains a layered silicate, the flame retardancy-improving effect provided by the metal hydroxide can be further increased. The reason for this is that when the layered silicate is burned, The flame retardant improvement effect provided by the film formation and the flame retardant improvement effect provided by the endothermic dehydration reaction based on the metal hydroxide appear alternately, thereby promoting individual effects. The melamine derivative is not particularly limited, and examples thereof include melamine, melamine cyanate, melamine isocyanate, melamine phosphate, and those obtained by subjecting the aforementioned materials to surface treatment. These melamine derivatives can be used alone or Use at least two types. For the above surface treatment, the same treatment as that applied to the metal hydroxide can be cited. The addition amount of the melamine derivative printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is relative to that of the surface treatment. Polyolefin resin 100 parts by weight, with 0. 5 to 100 parts by weight is preferred. If less than 0. 5 parts by weight may not obtain a sufficient flame retardancy improving effect. On the other hand, if it exceeds 100 parts by weight, the physical properties of the polyolefin-based resin composition of the present invention may be lowered or the layered silicic acid may be hindered. The salt forms a sintered film. More preferably, it is 1 to 30 parts by weight. In order to further improve the flame retardancy of the polyolefin-based resin composition of the present invention, it is preferable to contain a silicate compound other than the layered silicate. ________20_ This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 1225504 A7 ___B7 V. Description of the invention (1) The silicate compound is not particularly limited, and examples include wollastonite and hard silicon. Calcium silicates such as calcium stone; clay minerals such as talc, activated white clay, kaolin, sepiolite, imogolite; etc .; silicon dioxide-based light (balloon), etc., based on the above layer The affinity of the silicate or the selectivity of the particle diameter is an excellent consideration, and the use of talc is preferred. These silicate compounds can be used singly or in combination of at least two kinds. It is preferable that the silicate compound has a substance different from the average particle diameter of the layered salt. By adding the above-mentioned silicate compound having an average particle diameter different from that of the layered cholate salt to the polyolefin resin composition of the present invention, the layered silicate or oxalate compound and the like are formed during combustion. The inorganic component can be easily coated on the combustion surface as a sintered body, and it can easily form a strong flame-resistant film. The amount of the silicate compound to be added is preferably 0.5 to 20 parts by weight based on 100 parts by weight of the polyolefin resin. If less than 0. 5 parts by weight may not obtain a sufficient flame retardancy improving effect. On the other hand, if it exceeds 20 parts by weight, the mechanical strength of a molded article obtained from a polyolefin resin composition may decrease and the specific gravity may become excessive. high. More preferably, it is 2 to 10 parts by weight. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs To further improve the flame retardancy of the polyolefin-based resin composition of the present invention, it is preferable to contain metal oxides. The metal oxide is not particularly limited, and examples thereof include copper oxide (I), copper oxide (Π), magnesium oxide (melon), calcium oxide, titanium dioxide, chromium dioxide, chromium oxide (Π), and chromium oxide. (Melon), chromium (IV) oxide, alumina, antimony oxide (π), antimony oxide (v), yttrium oxide (m), indium oxide (I), and oxidation 21 ^^ Wave standards are applicable to Chinese national standards (〇 奶) 8 4 specifications (210 乂 297 mm) 1225504 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (W) Indium (Π), indium oxide (melon), potassium oxide, silver oxide (I) , Silver oxide (Π), germanium oxide (Π), germanium (IV) oxide, cobalt oxide (Π), cobalt oxide (melon), tin oxide (π), tin oxide (iv), oxide oxide, hafnium oxide (I ), Hafnium oxide (m), tungsten oxide (IV), tungsten oxide (vi), titanium oxide (π), titanium oxide (melon), titanium oxide (IV), zinc oxide, iron oxide (π), iron oxide ( m), barium oxide, manganese oxide (w), molybdenum oxide (iv), molybdenum oxide (vi), lithium oxide, ruthenium oxide, etc. These metal oxides can be used alone or in combination of at least two kinds. The above metal oxide functions as a catalyst for promoting the formation of an organic non-combustible film when the polyolefin-based resin composition of the present invention is burned. It has a high flame-retardant property by forming a stronger organic non-combustible film. Machine tb ° The amount of the above-mentioned metal oxide added, relative to 100 parts by weight of the polyolefin resin, is 0. It is preferably 1 to 10 parts by weight. If less than 0. If it is 1 part by weight, a sufficient flame retardancy improving effect may not be obtained. On the other hand, if it exceeds 10 parts by weight, the physical properties of the polyolefin-based resin composition of the present invention may be lowered. Better Department 0. 2 to 5 parts by weight. In order to further improve the flame retardancy of the polyolefin-based resin composition of the present invention, a paragraph (A) block having a functional group exhibiting a reactivity with respect to the polyolefin-based resin is included, and has affinity with the polyolefin-based resin. The paragraph (B) of the block; the AB-type block copolymer constituted is preferred. The functional group of the block of the above paragraph (A) is not particularly limited as long as it is a functional group capable of chemically bonding to a hydroxyl group existing on the crystal surface of the layered silicate or a functional group having chemical affinity. Examples are carboxyl, epoxy, and the like. _____22__ This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 1225504 A7 B7 V. Description of the invention (v 丨) As the block of paragraph (A) above, the above functional group with plural in the molecule is good. The molecular weight of the block in the above paragraph (A) is not particularly limited, but it is preferably 1 × 104 to 5 × 104. If it exceeds 5x104, the degree of freedom of the block of the paragraph (A) may be reduced, and the reactivity with the layered silicate may be hindered. The block of the paragraph (B) described above may interact with the polyolefin resin composition of the present invention. The polyolefin-based resin used as the main component is preferably the same kind of thing, and more preferably, it is the same polyolefin-based resin. The molecular weight of the block in the above paragraph (B) is not particularly limited, but is preferably 1 × 104 to 5 × 104. If it exceeds 5x104, the degree of freedom of the block of paragraph (B) may be reduced, and a sufficient dispersibility improvement effect may not be obtained. The AB-type block copolymer composed of the above paragraph (A) block and paragraph (B) block is different from the ABBA block copolymer, and has a functional group that exhibits reactivity with polyolefin resins. The paragraph (A) block and the paragraph (B) block having an affinity for polyolefin resins are located at both ends, which can effectively promote the interlayer peeling of the layered silicate and improve the layer shape. Dispersibility of silicate in polyolefin resin. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs To further improve the flame retardancy of the polyolefin-based resin composition of the present invention, it is preferable to contain a compound having an aromatic hydroxyl group. The compound having an aromatic hydroxyl group is not particularly limited as long as it can capture radicals, and examples thereof include 2,6-di-tert-butyl-p-cresol, and 2,6-di 1 t-butyl 4-ethyl phenol, 2,2'-methylene bis (4-methyl-6-t-butyl phenol), triethylene glycol, bis [3 — (3-t-butyl-5 —Methyl-1, 4-hydroxyphenyl) propionate, 1,6-hexanediol, bis [3 — 23__ This paper size applies to China National Standard (CNS) A4 specifications (210, 乂 297 mm 1 1225504 A7 B7 Penta (3,5 one-one t-butyl-4 hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4 ~ hydroxy-3,5 one two one Tertanilide) mono-u, 5-triazine, 2,2-monothio-diethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 18 Alkyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Ν, ΝΓ-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-cinnamon Hydrazine), 3,5-di-tert-butyl-4-hydroxyphenylphosphonate-diethyl ester, u, 5-trimethyl-2,4,6-tri (3,5-dione Butyl- 4-hydroxyphenyl) benzene, bis (3,5-di-tert-butyl-4-hydroxyphenylphosphonate ethyl) calcium, tris (3,5-di-tert-butyl-4-hydroxyphenyl) ) Isocyanate, 2,4-bis [(octylthio) methyl] -10-cresol, isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate 3,9 bis {1,1-dimethyl2-tert-butyl-4, hydroxy-5 5-tolyl) propanyloxy] ethyl} 2,4,8,10-tetraoxo Spiro [5,5] undecane, p-phenylphenol, gallic acid, etc. These compounds having an aromatic hydroxyl group can be used alone or in combination of at least two kinds. When the polyolefin-based resin is thermally decomposed into a flammable gas under the high heat during combustion, the compound having an aromatic radical will capture the free radicals of the decomposition products and exert the function of retarding the combustion reaction. The addition amount of the compound having an aromatic hydroxyl group is 0. 0 with respect to 100 parts by weight of the polyolefin resin. It is preferably from 01 to 30 parts by weight. If it is less than 0.001 parts by weight, a sufficient flame retardancy-improving effect may not be obtained. On the other hand, if it exceeds 30 parts by weight, the physical properties of the polyolefin-based resin composition of the present invention may be reduced, or It prevents the layered silicate from forming a sintered film. Better Department 0. 05 ~ 10 parts by weight. In the polyolefin-based resin composition of the present invention, the Chinese National Standard (€ yang) 8 4 specifications (21 (^ 297 mm)) are applied so as not to hinder the hair. ^ ---- Yao- -(Please read the notes on the back before filling in the page)
、τ 經濟部智慧財產局員工消費合作社印製 1225504 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（V1)) 明所欲達成之課題的範圍內，可依必要性添加例如用以將 聚烯烴系樹脂之結晶細微化讓其物性均一化之結晶核劑、 防氧化劑、熱安定劑、光安定劑、紫外線吸收劑、潤滑劑 、加工助劑、難燃劑、防帶電劑等之各種添加劑。 本發明之聚烯烴系樹脂組成物，可藉由各種方法來製 作。作爲本發明之聚烯烴系樹脂組成物之製造方法並無特 別的限定，可舉出例如（1)將必要成分之聚烯烴系樹脂以及 層狀矽酸鹽、希望含有之上述各種難燃性提昇劑或依必要 性添加之各種添加劑，藉擠壓機、二輥子、班伯里 (Bumbary)混練機等進行熔融混練之方法；（2)在溶解上述聚 烯烴系樹脂與層狀矽酸鹽兩者之有機溶劑中進行複合(混合 )之方法；（3)使用含有遷移金屬錯合物之層狀矽酸鹽來聚合 烯烴系單體複合之方法等。 作爲於上述之方法(3)所使用之遷移金屬錯合物，只要 可聚合烯烴系單體之物即可，並無特別的限定’可舉出例 如4、5、10、11族之金靥錯合物。 本發明之聚烯烴系樹脂組成物的用途並無特別的限定 ，可廣泛地使用於需要難燃性之用途上’例如可適切地使 用於電線被覆、密封、表面層等，其中又以適用於電線被 覆用以及密封用之樹脂爲佳。於電線被覆用以及密封用之 樹脂中，爲防止火災時經由電線延燒，必須具備難燃性 (JIS C 3005)。 使用本發明之聚嫌烴系樹脂組成物所得之作爲電線被 覆用以及密封用之熱可塑性樹脂亦爲本發明之一。又’使 25 (請先閱讀背面之注意事項再填一 Γ 、τ Γ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) 1225504 A7 B7 五、發明説明（4) 用上述熱可塑性樹脂所得之絕緣電線亦爲本發明之一 ° [用以實施發明之最佳形態] 以下揭示實施例更詳細地說明本發明’爲本發明並不 侷限於這些實施例中。又，實施例中所說之「份」係「重 量份」的意思。 (實施例1) 1.遷移金屬錯合物所造就之層狀矽酸鹽中之金屬離子 的交換, Τ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1225504 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (V1)) Within the scope of the subject to be achieved, you can add, for example, Crystal nucleating agents, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, lubricants, processing aids, flame retardants, antistatic agents, etc., which are used to refine the crystals of polyolefin-based resins to make their properties uniform. Of various additives. The polyolefin-based resin composition of the present invention can be produced by various methods. The method for producing the polyolefin-based resin composition of the present invention is not particularly limited, and examples thereof include (1) improvement of the above-mentioned various flame retardances by including polyolefin resins and layered silicates as essential components, and the above-mentioned desirable flame retardants. Additives or various additives added as necessary, melt-kneading by extruder, two rollers, bulk kneading machine, etc .; (2) dissolve both the polyolefin resin and the layered silicate (3) a method of polymerizing an olefin-based monomer by using a layered silicate containing a migration metal complex, and the like. The migration metal complex used in the above method (3) is not particularly limited as long as it is a polymerizable olefin-based monomer. For example, a gold tincture of Groups 4, 5, 10, and 11 may be mentioned. Complex. The use of the polyolefin-based resin composition of the present invention is not particularly limited, and it can be widely used for applications requiring flame resistance. For example, it can be suitably used for wire coating, sealing, surface layer, etc. Resin for wire covering and sealing is preferred. Resin for wire coating and sealing must have flame resistance (JIS C 3005) in order to prevent fire from spreading through the wire during fire. The thermoplastic resin used for covering and sealing electric wires obtained by using the poly (hydrocarbon) resin composition of the present invention is also one of the present invention. Also 'make 25 (please read the notes on the back before filling in Γ, τ Γ) This paper size applies Chinese National Standard (CNS) A4 specifications (210X297 mm) 1225504 A7 B7 V. Description of the invention (4) Use the above thermoplasticity The insulated wire obtained from the resin is also one of the inventions [the best form for implementing the invention] The following disclosed examples explain the present invention in more detail. The present invention is not limited to these examples. Also, in the examples, "Part" means "parts by weight." (Example 1) 1. Exchange of metal ions in a layered silicate formed by migration of a metal complex
將蒙脫石（商品名「班克魯A」，豐順礦業公司製造 )5g與蒸館水495g裝入燒瓶中，進一步，爲擴張層間距離 ，乃添加二甲苯（試藥，和光純藥工業公司製造），使用馬 達攪拌機於常溫下攪拌約2小時，調製出蒙脫石之膨脹漿 料。接著，將二環戊二烯基鈦二氯化物•二硬脂基二甲銨 0.27g添加至上述膨脹漿料中，使用馬達攪拌機，於常溫下 進行24小時攪拌之後，以離心分離裝置分離固形分。爲去 除附著於上述固形分之多餘量，乃於蒸餾水中將上述固形 分再度分散後，進一步重複2次之以離心分離裝置分離固 形分的操作。使用真空乾燥機將所得之固形分在50°C下真 空乾燥48小時後，將獲得之組成物當作含有遷移金屬錯合 物之有機層狀矽酸鹽來使用。產量係5.10g。以此爲MMT 一A。 2.乙烯之聚合 對300mL之耐壓玻璃容器內進行氬氣置換後，添加先 前所調製出之含有遷移金屬錯合物之有機層狀矽酸鹽(即添 一 26 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填· 裝丨 頁 線 經濟部智慧財產局員工消費合作社印製 1225504 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（·<) 加有二環二戊烯基鈦二氯化物•二硬脂基二甲銨的蒙脫石) 之MMT—A 5.00g，溶解於甲苯l5〇mL中。進一步藉注射 器以10分鐘的時間將甲基阿爾摩吉三（1〇重量％甲苯溶液 ，阿魯得力吉公司製造)30mL滴入。接著，將乙烯氣體導 入容器內，將系統內保持在l.lkg/cm2之壓力下，於〇°C進 行4小時聚合。反應後，於系統內加入甲醇300mL停止反 應，將沉澱之聚合物回收，得到層狀矽酸鹽/聚合物複合體 組成物（I)13.5g。 針對所得之層狀矽酸鹽/聚合物複合體組成物（I )，使 用傅里葉變換型紅外分光計(FT — IR)進行解析，觀測來自 聚乙烯之721CHT1之峰値。再者，以熱重量測定裝置(TGA) 解析之結果，於所得之層狀矽酸鹽/聚合物複合體組成物（I )中之無機成分量爲46重量％。 3.聚乙烯樹脂與層狀矽酸鹽之複合 對小型擠壓機(商品名「TEX30」，日本製鋼所公司製 造）中，讓聚乙烯樹脂(商品名「HB530」，日本波力康姆公 司製造)與層狀矽酸鹽/聚合物複合體組成物（I )以重量比爲 92.3/7.7的方式進料，以設定溫度200°C熔融混練，然後將 擠出之單股(strand)以造粒機顆粒化。將所得之顆粒以調溫 成200°C之熱壓機成型爲厚度3mm或厚度l〇〇#m之板狀物 ，製作出評價用樣品。 (實施例2) 1·遷移金屬錯合物•含有烷基銨鹽之有機層狀矽酸鹽 的合成 _______27__ 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐）5 g of montmorillonite (trade name "Banker A", manufactured by Fengshun Mining Co., Ltd.) and 495 g of steamed hall water were put into a flask, and further, xylene (reagent, Wako Pure Chemical Industries, Ltd.) was added to expand the distance between layers. (Manufactured by the company), using a motor mixer to stir at room temperature for about 2 hours to prepare an expanded slurry of montmorillonite. Next, 0.27 g of dicyclopentadienyl titanium dichloride and distearyldimethylammonium was added to the above-mentioned expanded slurry, and after stirring at room temperature for 24 hours using a motor stirrer, the solid was separated by a centrifugal separation device. Minute. In order to remove the excess amount attached to the solid content, the solid content was dispersed again in distilled water, and then the operation of separating the solid content by a centrifugal separation device was repeated twice more. The obtained solid content was vacuum-dried at 50 ° C for 48 hours using a vacuum dryer, and the obtained composition was used as an organic layered silicate containing a migrating metal complex. The yield is 5.10g. This is MMT-A. 2. Polymerization of ethylene After replacing the argon gas in a 300 mL pressure-resistant glass container, add the organic layered silicate containing the migration metal complex previously prepared (that is, add a 26 paper size to the Chinese national standard) (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling and loading. Page line Printed by the Consumer Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1225504 A7 B7 Printed by the Employee Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Description of the invention (<) 5.00 g of MMT-A with dicyclodipentenyl titanium dichloride, distearyl dimethyl ammonium), dissolved in 150 mL of toluene. Further borrow a syringe 30 mL of methyl almogitri (10% by weight toluene solution, manufactured by Aludeliki) was added dropwise over a period of 10 minutes. Next, ethylene gas was introduced into the container, and the inside of the system was maintained at 1.1 kg / cm2. Polymerization was performed at 0 ° C for 4 hours under pressure. After the reaction, 300 mL of methanol was added to the system to stop the reaction, and the precipitated polymer was recovered to obtain 13.5 g of a layered silicate / polymer composite composition (I). For the obtained The silicate / polymer composite composition (I) was analyzed using a Fourier transform infrared spectrometer (FT-IR), and the peak 値 of 721CHT1 from polyethylene was observed. Furthermore, a thermogravimetric measuring device was used. As a result of (TGA) analysis, the amount of inorganic components in the obtained layered silicate / polymer composite composition (I) was 46% by weight. 3. The composite pair of polyethylene resin and layered silicate was small In an extruder (trade name "TEX30", manufactured by Japan Steel Works), a polyethylene resin (trade name "HB530", manufactured by Polycom Japan) and a layered silicate / polymer composite composition (I) Feed in a weight ratio of 92.3 / 7.7, melt-knead at a set temperature of 200 ° C, and pelletize the extruded strand with a pelletizer. The resulting pellets are tempered to 200 A hot press at ° C was formed into a plate having a thickness of 3 mm or a thickness of 100 # m to produce a sample for evaluation. (Example 2) 1. · Migration metal complex · Organic layered layer containing an alkylammonium salt Synthesis of silicate _______27__ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)
1225504 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（yL) 將蒙脫石（商品名「班克魯A」，豐順礦業公司製造 )5g與蒸餾水495g裝入1L之燒瓶中，進一步，爲擴張層間 距離’乃添加二甲苯（試藥，和光純藥工業公司製造），使 用馬達攪拌機於常溫下攪拌約2小時，調製出蒙脫石之膨 脹漿料。接著，將二環戊//鈦二氯化物〇.27g添加至上述膨 脹漿料中，使用馬達攪拌機，於常溫下進行24小時攪拌。 進一步將作爲陽離子系界面活性劑之二硬脂基二甲銨氯化 物(和光純藥工業公司製造)2.88g以及濃鹽酸O.OOlg添加至 上述膨脹漿料中，使用馬達攪拌機，於常溫下進行8小時 攪拌之後，以離心分離裝置分離固形分。爲去除附著於上 述固形分之多餘量，乃於蒸餾水中將上述固形分再度分散 後’進一步重複2次之以離心分離裝置分離固形分的操作 。使用真空乾燥機將所得之固形分在50°C下真空乾燥48小 後’將獲得之組成物當作含有遷移金屬錯合物•烷基銨鹽 之有機層狀矽酸鹽來使用。產量係8.01g。以此爲MMT—B 〇 2.乙烯之聚合 對300mL之耐壓玻璃容器內進行氬氣置換後，添加先 前所調製出之含有遷移金屬錯合物•烷基銨鹽之有機層狀 矽酸鹽(即添加有二環//鈦二氯化物·二硬脂基二甲銨氯化 物的蒙脫石)之MMT—B 7.〇〇g，溶解於甲苯150mL中。進 一步藉注射器以10分鐘的時間將甲基阿爾摩吉三（10重量 %甲苯溶液，阿魯得力吉公司製造)3〇mL滴入。接著，將乙 烯氣體導入容器內，將系統內保持在l.lkg/cm2之壓力下， 28 本紙張尺度適用中國國家標準（CNS ) A4規格（2i〇X 297公釐） 請 先 閲 讀 背 意 事 項 再 頁 装 訂 線 1225504 A7 B7 五、發明説明 於0°C進行4小時聚合。反應後，於系統內加入甲醇3〇〇mL 停止反應，將沉澱之聚合物回收，得到層狀砂酸鹽/聚合物 複合體組成物（n)17.5g。 針對所得之層狀矽酸鹽/聚合物複合體組成物（n),使 用傅里葉變換型紅外分光計(FT —IR)進行解析，觀測來自 聚乙烯之721cm·1之峰値。再者，以熱重量測定裝置(TGA) 解析之結果，於所得之層狀矽酸鹽/聚合物複合體組成物（Π )中之無機成分量爲43重量％。 3.聚乙烯樹脂與層狀矽酸鹽之複合 對小型擠壓機(商品名「TEX30」，日本製鋼所公司製 造）中，讓聚乙烯樹脂(商品名「HB530」，日本波力康姆公 司製造)與層狀矽酸鹽/聚合物複合體組成物（Π)以重量比爲 92.3/7.7的方式進料，以設定溫度200°C熔融混練，然後將 擠出之單股以造粒機顆粒化。將所得之顆粒以調溫成200 °C之熱壓機成型爲厚度3mm或厚度100#m之板狀物，製 作出評價用樣品。 (實施例3) 讓二硬脂基二甲基4級銨鹽處理蒙脫石(商品名「鈕艾 斯本D」，豐順礦業公司製造)500g於亨謝爾混合機中一邊 攪拌、一邊以3分鐘的時間滴入乙烯基三甲氧基矽烷(試藥 ，信越化學工業公司製造)之2重量％水溶液100g。於滴入 結束後，進一步進行10分鐘的攪拌。將所得之處理粉末保 持在調溫成70°C之減壓乾燥機中，進行8小時乾燥。以此 爲 MMT—C。 29 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填頁) •裝· 訂 經濟部智慧財產局員工消費合作社印製 1225504 A7 B7 五、發明説明（Wf") 於小型擠壓機(商品名「TEX30」，日本製鋼所公司製 造）中，將聚乙烯樹脂(商品名「EA9」，日本波力康姆公司 製造)與MMT—C以重量比爲92.3/7.7的方式進料，進一步 ，爲達成讓乙烯基三甲氧基矽烷所含之不飽和鍵相對於聚 丙烯樹脂進行接枝反應之目的，乃使用2,5—二甲基一2,5 — 雙(特丁基過氧）己烷(商品名「帕亥吉三25B」，半衰期1 分中之溫度：180°C，日本油脂公司製造）。上述過氧化物 係以柱塞栗(plunger pump)對於聚丙嫌樹脂添加達0.1重量％ 。以設定溫度200°C熔融混練，然後將擠出之單股以造粒 機顆粒化。將所得之顆粒以調溫成20(TC之熱壓機成型爲 厚度3mm或厚度100μm之板狀物，製作出評價用樣品。 (實施例4) 作爲層狀矽酸鹽，係使用將蒙脫石(商品名「班克魯A 」，豐順礦業公司製造)5g以二硬脂基二甲基4級銨鹽預先 進行離子交換所得之物。以此爲MMT-D。作爲聚丙烯樹 脂，爲提昇聚丙烯樹脂與層狀矽酸鹽的親和性，乃使用相 對於聚丙烯樹脂（商品名「EA9」，日本波力康姆公司製造 )100份添加了 15份之無水順丁烯二酸改質丙烯低聚物(商 品名「優美克斯1001」’官能基含有量：〇.23mmol/g，三 洋化成工業公司製造）。 於拉伯埔拉斯特密爾(labplastmili)(東洋精機公司製造) 中讓上述聚丙烯樹脂與層狀矽酸鹽進料，以設定溫度2〇〇 °(：熔融混練。組成係聚丙烯樹脂/無水順丁烯二酸改質丙烯 低聚物/MMT-D=82.3/10/7.7(重量比）。 —____ 30 本紙張尺度適用中國國家標隼（CNS ) A4規格（210X297公釐） " I--------批衣—— (請先閲讀背面之注意事項再填頁) -5-¾ 線 經濟部智慧財產局員工消費合作社印製 1225504 A7 _ B7 五、發明説明（y/ ) 將所得之複合組成物以熔融壓機在2Q(^C預熱5分鐘 之後，以壓力9.8MPa擠壓工分鐘，成型爲lmm厚度的片 狀物。將1mm厚度的片狀物切出3Cm四方，放入高壓蒸鍋 中，接著密封高壓蒸鍋，將內部溫度設定成較聚丙烯樹脂 的熔點高10°C。其次’以高壓將碳酸氣體注入高壓蒸鍋中 ，讓高壓蒸鍋內之內壓保持在16.7MPa的狀態下30分鐘。 再者，將內部溫度設定成較聚丙烯樹脂的熔點低1(TC，在 此狀態下快速地抽除高壓蒸鍋內的氣體，讓內壓回到常壓 。以調溫成200°C之熱壓機將所得之發泡體成型爲厚度 3mm或厚度100/zm之板狀物，製作出評價用樣品。 (實施例5) 經濟部智慧財產局員工消費合作社印製 對小型擠壓機(商品名「TEX30」，日本製鋼所公司製 造）中，讓聚丙烯樹脂(商品名「EA9」，日本波力康姆公司 製造)82.3份、無水順丁烯二酸改質丙烯低聚物（商品名^ 優美克斯1001」，官能基含有量：0.23mmol/g，三洋化成 工業製造)5份、以及MMT—D7.7份進料，以設定溫度200 °C熔融混練，然後將擠出之單股以造粒機顆粒化。將所得 之顆粒以調溫成200°C之熱壓機成型爲厚度3mm或厚度 100#m之板狀物，製作出評價用樣品。 (實施例6) 除了對小型擠壓機(商品名「TEX30」，日本製鋼所公 司製造）中添加多磷酸銨(商品名「AP422」，日本聚烯烴公 司製造)5份以外，其餘與實施例5同樣’製作出評價用樣 品。 _31 ____ 尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1225504 A7 B7 五、發明説明（)ΰ) (實施例7) 除了取代多磷酸銨5份，改添加苯膦酸(大八化學公司 製造)5份以外，其餘與實施例6同樣，製作出評價用樣品 〇 (實施例8) 除了取代多磷酸銨5份，改添加高級脂肪酸處理氫氧 化鎂(商品名「集思瑪5〗」，協和化學工業公司製造)25份 以外’其餘與實施例6同樣，製作出評價用樣品。 (實施例9) 除了取代多磷酸銨5份，改添加三聚氰胺氰酸酯(商品 名「Ρ—6」，平均粒徑·· 3.7/zm，日產化學公司製造)20份 以外’其餘與實施例6同樣，製作出評價用樣品。 (實施例10) 除了取代多磷酸銨5份，改添加滑石(商品名「P—6」 ，平均粒徑：3.7//m，日本滑石公司製造)5份以外，其餘 與實施例6同樣，製作出評價用樣品。 (實施例11) 除了取代多磷酸銨5份，改添加由聚丙烯嵌段與羧酸 改質聚丙烯嵌段所構成之嵌段共聚物(商品名「CB — OM12 」，段落(A)嵌段與段落(B)嵌段的分子量皆爲1.5X104,克 拉雷公司製造)5份、並未添加無水順丁烯二酸改質丙烯低 聚物以外，其餘與實施例6同樣，製作出評價用樣品。 (實施例12) .除了取代聚丙烯樹脂以及無水順丁烯二酸改質丙烯低 32 ------- (請先閱讀背面之注意事項再填1¾頁) 、? Γ 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1225504 Α7 Β7 五、發明説明) 聚物，分別改採乙烯一丙烯酸乙酯共聚物（商品名「A4250 」，日本聚烯烴公司製造）、無水順丁烯二酸改質乙烯低聚 物（商品名「ER403A」，日本聚烯烴公司製造）以外’其餘 與實施例5同樣，製作出評價用樣品。 (實施例13) 除了不使用無水順丁烯二酸改質乙烯低聚物(商品名「 ER403A」，日本聚烯烴公司製造)以外，其餘與實施例12 同樣，製作出評價用樣品。 (實施例14) 除了取代聚丙烯樹脂以及無水順丁烯二酸改質丙嫌低 聚物，分別改採乙烯一丙烯酸乙酯共聚物（商品名「A4250 」，日本聚烯烴公司製造）、無水順丁烯二酸改質乙烯低聚 物（商品名「ER403A」，日本聚烯烴公司製造)以外，其餘 與實施例8同樣，製作出評價用樣品。 (實施例15) 除了進〜步添加氧化銅（Π)(日進開姆克公司製造）1·5 份以外，其餘與實施例14同樣，製作出評價用樣品。 (實施例16) 除了取代氧化銅（Π)1.5份，改添加氧化錫（Π)(昭和化 工公司製造)1.5份以外，其餘與實施例14同樣，製作出評 價用樣品。 (實施例17) 除了取代氧化銅（Π)1.5份，改添加氧化鋅(界化學工業 公司製造）1·〇份以外，其餘與實施例15同樣，製作出評價 ---------裝-- (請先閱讀背面之注意事項再填|^頁) 、1Τ 線 經濟部智慧財產局員工消費合作社印製 ^度適用CNS ) Α4規格(210 Χ 297公釐 1 0^ 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（jl) 用樣品。 (實施例18) 除了進一步添加對苯砸2.0份以外，其餘與實施例14 同樣，製作出評價用樣品。 (實施例19) 對小型擠壓機(商品名「TEX30」，日本製鋼所公司製 造）中，讓聚乙烯樹脂(商品名「HB530」，日本波力康姆公 司製造)82.3份以及MMT—D 7.7份進料，以設定溫度200 °0熔融混練，然後將擠出之單股以造粒機顆粒化。將所得 之顆粒以調溫成200°C之熱壓機成型爲厚度3mm或厚度 100//m之板狀物，製作出評價用樣品。 (實施例20) 除了進一步添加多磷酸銨(商品名「AP422」，日本聚 烯烴公司製造)5份以外，其餘與實施例19同樣，製作出評 價用樣品。 (實施例21) 除了將聚乙烯樹脂（商品名「HB530」，日本波力康姆 公司製造)之量設定爲85.3份、且進一步添加羥基乙基異氰 酸酯(THEIC)2份以外，其餘與實施例20同樣，製作出評 價用樣品。 (實施例22) 將蒙脫石（商品名「班克魯A」，豐順礦業公司製造 )5g與蒸餾水495g裝入燒瓶中，使用馬達攪拌機於常溫下 攪拌約2小時，調製出蒙脫石之膨脹漿料。接著，將十二 34 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） ^ —---------裝-- (請先閱讀背面之注意事項再填頁) 訂 線1225504 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (yL) 5g of montmorillonite (trade name "Banker A", manufactured by Fengshun Mining Company) and 495g of distilled water were placed in a 1L flask Furthermore, in order to expand the distance between layers, xylene (test reagent, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and a motor mixer was used to stir at room temperature for about 2 hours to prepare an expanded slurry of montmorillonite. Next, 0.27 g of dicyclopentane // titanium dichloride was added to the above-mentioned expansion slurry, and the mixture was stirred at room temperature for 24 hours using a motor stirrer. Further, 2.88 g of distearyldimethylammonium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and OOlg of concentrated hydrochloric acid as cationic surfactants were added to the above-mentioned expanded slurry, and the mixture was carried out at room temperature using a motor stirrer. After stirring for 8 hours, the solid content was separated by a centrifugal separator. In order to remove the excess amount attached to the solid content, the solid content was re-dispersed in distilled water, and the operation of separating the solid content by a centrifugal separation device was repeated twice more. The solid content obtained was vacuum-dried at 50 ° C for 48 hours using a vacuum dryer. The obtained composition was used as an organic layered silicate containing a migration metal complex and an alkylammonium salt. The yield is 8.01g. This was MMT-B 〇2. Polymerization of ethylene was replaced with argon gas in a 300 mL pressure-resistant glass container, and an organic layered silicate containing a migration metal complex and an alkyl ammonium salt prepared previously was added. (Ie, montmorillonite to which bicyclo // titanium dichloride / distearyldimethylammonium chloride) was added was dissolved in 150 mL of toluene. Further, 30 mL of methyl almogitri (10% by weight toluene solution, manufactured by Aludeljic) was added dropwise by a syringe for 10 minutes. Next, introduce ethylene gas into the container, and keep the system under a pressure of 1.1 kg / cm2. 28 paper sizes are applicable to the Chinese National Standard (CNS) A4 specification (2iOX 297 mm) Please read the precautions first Binding line 1225504 A7 B7 5. Description of the invention Polymerization was carried out at 0 ° C for 4 hours. After the reaction, 300 mL of methanol was added to the system to stop the reaction, and the precipitated polymer was recovered to obtain 17.5 g of a layered oxalate / polymer composite composition (n). The obtained layered silicate / polymer composite composition (n) was analyzed using a Fourier transform infrared spectrometer (FT-IR), and a peak 721 cm · 1 of polyethylene was observed. In addition, as a result of analysis by a thermogravimetric measurement device (TGA), the amount of inorganic components in the obtained layered silicate / polymer composite composition (Π) was 43% by weight. 3. In a compound extruder of polyethylene resin and layered silicate (trade name "TEX30", manufactured by Japan Steel Works), polyethylene resin (trade name "HB530", Polycom Japan) (Manufacturing) and layered silicate / polymer composite composition (Π) were fed in a weight ratio of 92.3 / 7.7, melt-kneaded at a set temperature of 200 ° C, and then extruded the single strand into a pelletizer. Granulated. The obtained pellets were formed into a plate having a thickness of 3 mm or a thickness of 100 # m by a hot press adjusted to 200 ° C to prepare a sample for evaluation. (Example 3) 500 g of distearyl dimethyl quaternary ammonium salt was used to treat montmorillonite (trade name "Neo Aspen D", manufactured by Fengshun Mining Company) while stirring in a Henschel mixer. 100 g of a 2% by weight aqueous solution of vinyltrimethoxysilane (Reagent, manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise over 3 minutes. After completion of the dropping, stirring was further performed for 10 minutes. The obtained treated powder was kept in a reduced-pressure dryer adjusted to 70 ° C and dried for 8 hours. Take this as MMT-C. 29 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the precautions on the back before filling in the pages) • Binding and ordering printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 1225504 A7 B7 V. Invention Description (Wf ") In a small extruder (trade name "TEX30", manufactured by Japan Steel Works), a polyethylene resin (trade name "EA9", manufactured by Polycom Corporation) and MMT-C are used to weigh The ratio is 92.3 / 7.7, and further, in order to achieve the graft reaction of the unsaturated bond contained in vinyltrimethoxysilane with respect to the polypropylene resin, 2,5-dimethyl-2 is used. , 5 — Bis (tert-butylperoxy) hexane (trade name "Pahegi III 25B", temperature within 1 minute of half-life: 180 ° C, manufactured by Japan Oil Corporation). The above-mentioned peroxide is added to the polypropylene resin by a plunger pump up to 0.1% by weight. Melt and knead at a set temperature of 200 ° C, and then extrude the single strand into pellets using a pelletizer. The obtained granules were formed into a plate having a thickness of 3 mm or a thickness of 100 μm by a thermostatic press at a temperature of 20 ° C. to produce a sample for evaluation. (Example 4) As a layered silicate, montmorillonite was used. 5g of stone (trade name "Banker A", manufactured by Fengshun Mining Co., Ltd.) is obtained by pre-exchanging distearyldimethyl quaternary ammonium salt. This is MMT-D. As a polypropylene resin, In order to improve the affinity between the polypropylene resin and the layered silicate, 15 parts of anhydrous maleic acid is added to 100 parts of polypropylene resin (trade name "EA9", manufactured by Polycom Corporation). Modified propylene oligomer (brand name "Umilux 1001" functional group content: 0.23 mmol / g, manufactured by Sanyo Chemical Industries, Ltd.). Labplastmili (Toyo Seiki Co., Ltd.) The above-mentioned polypropylene resin and layered silicate were fed during the production) at a set temperature of 200 ° (: melt-kneading. Composition polypropylene resin / anhydrous maleic acid modified propylene oligomer / MMT- D = 82.3 / 10 / 7.7 (weight ratio). —____ 30 This paper size applies to Chinese national standard ( CNS) A4 size (210X297mm) " I -------- Approve clothes—— (Please read the precautions on the back before filling in the page) -5-¾ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Preparation 1225504 A7 _ B7 V. Description of the invention (y /) The obtained composite composition was preheated by a melt press at 2Q (^ C for 5 minutes, and then extruded at a pressure of 9.8 MPa for 1 minute to form a sheet with a thickness of 1 mm. Cut a 1mm-thick sheet into a 3Cm square and place it in a high-pressure steamer, then seal the high-pressure steamer, and set the internal temperature to 10 ° C higher than the melting point of the polypropylene resin. Next, 'carbonate gas at high pressure Fill the autoclave, and keep the internal pressure in the autoclave at 16.7 MPa for 30 minutes. Furthermore, set the internal temperature to 1 ° C lower than the melting point of the polypropylene resin. Remove the gas in the high-pressure steamer and return the internal pressure to normal pressure. The obtained foam was formed into a plate with a thickness of 3 mm or a thickness of 100 / zm by a hot press adjusted to 200 ° C, and an evaluation was made. (Example 5) Printed on a small extruder (Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs) In the product name "TEX30", manufactured by the Japan Steel Corporation, 82.3 parts of polypropylene resin (trade name "EA9", manufactured by Polycom Japan), anhydrous maleic acid modified propylene oligomer (trade name) ^ Umilux 1001 ", functional group content: 0.23mmol / g, manufactured by Sanyo Chemical Industry Co., Ltd.) 5 parts, and MMT-D7.7 parts were fed, melt-kneaded at a set temperature of 200 ° C, and then extruded the single The strands were granulated with a granulator. The obtained granules were formed into a plate having a thickness of 3 mm or a thickness of 100 # m by a hot press adjusted to 200 ° C to prepare a sample for evaluation. (Example 6) Except adding 5 parts of ammonium polyphosphate (trade name "AP422", manufactured by Japan Polyolefin Corporation) to a small extruder (trade name "TEX30", manufactured by Japan Steel Works Co., Ltd.), the rest were the same as in the example. 5 Similarly, a sample for evaluation was prepared. _31 ____ Applicable to China National Standard (CNS) A4 specifications (210X297 mm) 1225504 A7 B7 V. Description of the invention () ΰ) (Example 7) In addition to replacing 5 parts of ammonium polyphosphate, add phenylphosphonic acid (Da Ya Chemical Except for 5 parts, other parts were prepared in the same manner as in Example 6 (Example 8) except that 5 parts of ammonium polyphosphate was replaced, and higher fatty acid-treated magnesium hydroxide was added (trade name "Setima 5" ", Manufactured by Kyowa Chemical Industry Co., Ltd.) Except for 25 parts, the rest were the same as in Example 6, and samples for evaluation were prepared. (Example 9) Except replacing 5 parts of ammonium polyphosphate, and adding 20 parts of melamine cyanate (trade name "P-6", average particle size · 3.7 / zm, manufactured by Nissan Chemical Co., Ltd.), the rest are examples 6 Similarly, an evaluation sample was prepared. (Example 10) Except replacing 5 parts of ammonium polyphosphate and adding 5 parts of talc (trade name "P-6", average particle size: 3.7 // m, manufactured by Japan Talc Corporation), the rest were the same as in Example 6, An evaluation sample was prepared. (Example 11) In addition to replacing 5 parts of ammonium polyphosphate, a block copolymer (trade name "CB — OM12") composed of a polypropylene block and a carboxylic acid modified polypropylene block was added instead, and the paragraph (A) was embedded. The molecular weight of the segment and the segment (B) are both 1.5X104, manufactured by Claret.) Except that anhydrous maleic acid modified propylene oligomer was not added, the rest were the same as in Example 6, and evaluation was made. With samples. (Example 12) In addition to replacing polypropylene resin and anhydrous maleic acid modified propylene lower 32 ------- (Please read the precautions on the back before filling in page 1¾),? Γ Intellectual Property of the Ministry of Economic Affairs The paper size printed by the Bureau ’s Consumer Cooperatives applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 1225504 A7 B7 V. Description of the invention) Polymers, respectively, ethylene-ethyl acrylate copolymer (trade name "A4250") Except for "Nippon Polyolefins Co., Ltd." and anhydrous maleic acid modified ethylene oligomer (trade name "ER403A", manufactured by Japan Polyolefin Co., Ltd.), the rest were the same as in Example 5, and samples for evaluation were produced. (Example 13) A sample for evaluation was produced in the same manner as in Example 12, except that the anhydrous maleic acid modified ethylene oligomer (trade name "ER403A", manufactured by Japan Polyolefin Corporation) was not used. (Example 14) Except for the replacement of polypropylene resin and anhydrous maleic acid modified propylene oligomer, ethylene-ethyl acrylate copolymer (trade name "A4250", manufactured by Japan Polyolefin Corporation), and anhydrous A sample for evaluation was produced in the same manner as in Example 8 except that the maleic acid modified ethylene oligomer (trade name "ER403A", manufactured by Japan Polyolefin Corporation) was used. (Example 15) A sample for evaluation was prepared in the same manner as in Example 14 except that 1.5 parts of copper oxide (Π) (manufactured by Nissin Kemco) was added. (Example 16) A sample for evaluation was prepared in the same manner as in Example 14 except that 1.5 parts of copper oxide (Π) was replaced by 1.5 parts of tin oxide (Π) (manufactured by Showa Chemical Co., Ltd.). (Example 17) Evaluation was made in the same manner as in Example 15 except that 1.5 parts of copper oxide (Π) was replaced, and 1.0 parts of zinc oxide (manufactured by Jie Chemical Industry Co., Ltd.) was added. -Installation-(Please read the notes on the back before filling in the ^ page), 1T printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the consumer consumer cooperatives of ^ Applicable CNS) Α4 specifications (210 x 297 mm 1 0 ^ Ministry of Economics Wisdom A7 B7 printed by the Consumer Cooperatives of the Property Bureau V. Samples of invention description (jl) (Example 18) Except the addition of 2.0 parts of p-phenylene, the same as in Example 14, a sample for evaluation was produced. (Example 19) For small extruder (trade name "TEX30", manufactured by Japan Steel Works), 82.3 parts of polyethylene resin (trade name "HB530", manufactured by Polycom Japan) and 7.7 parts of MMT-D The material is melt-kneaded at a set temperature of 200 ° 0, and then the extruded single strand is granulated by a granulator. The obtained granules are formed into a thickness of 3mm or a thickness of 100 // m by a hot press adjusted to 200 ° C. The plate-like material was used to prepare a sample for evaluation. (Example 20) Except for 5 parts of ammonium phosphate (trade name "AP422", manufactured by Japan Polyolefin Corporation), the same samples as in Example 19 were used to make evaluation samples. (Example 21) A polyethylene resin (trade name "HB530", Japan (Except for Polycomm) was set to 85.3 parts, and 2 parts of hydroxyethyl isocyanate (THEIC) was further added. The rest was the same as in Example 20, and a sample for evaluation was prepared. (Example 22) Montmorillonite (Brand name "Banklu A", manufactured by Fengshun Mining Co.) 5g and 495g of distilled water were put into a flask, and stirred at room temperature for about 2 hours using a motor stirrer to prepare an expanded slurry of montmorillonite. II 34 This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm) ^ —--------- install-(please read the precautions on the back before filling in the page)
0^ 5 5 2 2 I 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（W 烷基三苯基辚溴化物0.27g添加至上述膨脹漿料中，使用 馬達攪拌機，於常溫下進行24小時攪拌後’以離心分離裝 置分離固形分。爲去除附著於上述固形分之多餘量，乃於 蒸餾水中將上述固形分再度分散後，進一步重複2次之以 離心分離裝置分離固形分的操作。使用真空乾燥機將所得 之固形分在50°C下真空乾燥48小後’將獲得之組成物當作 含有鱗鹽之層狀矽酸鹽來使用。產量係5.10g。以此爲 MMT—E。以熱重量測定裝置(TGA)解析上述MMT—E之結 果，於MMT—E中之無機成分量爲46重量％。 對小型擠壓機(商品名「TEX30」，日本製鋼所公司製 造沖，讓聚丙烯樹脂(商品名「EA9」，日本波力康姆公司 製造）82.3份、無水順丁烯二酸改質丙烯低聚物（商品名「 優美克斯1001」，官能基含有量：〇.23mmol/g，三洋化成 工業製造)7.7份、以及MMT—E 7.7份進料，以設定溫度 200°C熔融混練，然後將擠出之單股以造粒機顆粒化。將所 得之顆粒以調溫成200°C之熱壓機成型爲厚度3mm或厚度 ΙΟΟμπι之板狀物，製作出評價用樣品。 (實施例23) 除了進一步添加多磷酸銨(商品名「AP422」，日本聚 烯烴公司製造)5份以外，其餘與實施例22同樣，製作出評 價用樣品。 (實施例24) 除了進一步添加高級脂肪酸處理氫氧化鎂(商品名「集 思瑪51」，協和化學工業公司製造)20份以外，其餘與實 __ 35_ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填頁) -裝·0 ^ 5 5 2 2 I Printed by A7 B7, Consumer Cooperatives, Bureau of Intellectual Property, Ministry of Economic Affairs. 5. Description of the invention (0.27g of alkyltriphenylphosphonium bromide is added to the above expansion slurry. Use a motor stirrer at room temperature. After stirring for 24 hours, the solid content was separated by a centrifugal separation device. In order to remove the excess amount attached to the solid content, the solid content was dispersed again in distilled water, and then the solid content was separated by the centrifugal separation device twice more. Operation. Use a vacuum dryer to dry the obtained solid content under vacuum at 50 ° C for 48 hours. 'Use the obtained composition as a layered silicate containing scale salt. The yield is 5.10 g. This is MMT. —E. As a result of analyzing the above-mentioned MMT-E by a thermogravimetric measuring device (TGA), the amount of inorganic components in the MMT-E was 46% by weight. For a small extruder (trade name "TEX30", manufactured by the Japan Steel Corporation) And make 82.3 parts of polypropylene resin (trade name "EA9", manufactured by Polycom Japan), anhydrous maleic acid modified propylene oligomer (trade name "Youmeix 1001", functional group content) : 〇.23mmo l / g, manufactured by Sanyo Chemical Industry Co., Ltd.) and 7.7 parts of MMT-E and 7.7 parts of MMT-E were melt-kneaded at a set temperature of 200 ° C, and then the extruded single strand was pelletized by a pelletizer. The obtained pellets were adjusted by A hot press at a temperature of 200 ° C was formed into a plate having a thickness of 3 mm or 100 μm to produce a sample for evaluation. (Example 23) In addition to the addition of ammonium polyphosphate (trade name "AP422", manufactured by Japan Polyolefin Corporation) ) Except for 5 parts, the same samples as in Example 22 were used to prepare samples for evaluation. (Example 24) 20 parts were prepared by further adding higher fatty acid-treated magnesium hydroxide (trade name "Setima 51", manufactured by Kyowa Chemical Industry Co., Ltd.) Except the rest and the actual __ 35_ This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling in the page)-Loading ·
、1T 線 ΠΖ】 5 5 2 2 A7 B7 五、發明説明（ 施例22同樣，製作出評價用樣品。 (實施例25) 除了進一步添加矽烷偶合劑處理氫氧化鎂(商品名「集 思瑪5PH」，協和化學工業公司製造)20份以外，其餘與實 施例22同樣，製作出評價用樣品。 (實施例26) 除了進一步添加三聚氰胺氰酸酯（日產化學公司製造 )20份以外，其餘與實施例22同樣，製作出評價用樣品。 (實施例27) 除了取代無水順丁烯二酸改質丙烯低聚物，改使用由 聚丙烯嵌段與羧酸改質聚丙烯嵌段所構成之嵌段共聚物(商 品名「CB — 0M12」，段落(A)嵌段與段落(B)嵌段的分子量 皆爲1.5X104，克拉雷公司製造)以外，其餘與實施例22同 樣，製作出評價用樣品。 (實施例28) 除了取代聚丙烯樹脂以及無水順丁烯二酸改質丙烯低 聚物，分別改採聚乙烯樹脂（商品名「HB530」，日本波力 康姆公司製造）、無水順丁烯二酸改質乙烯低聚物（商品名 「ER403A」，日本聚烯烴公司製造）以外，其餘與實施例 22同樣，製作出評價用樣品。 (實施例29) 除了進一步添加多磷酸銨(商品名「AP422」，日本聚 烯烴公司製造)5份以外，其餘與實施例28同樣，製作出評 價用樣品。 ____36 _ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） " 裝-- (請先閱讀背面之注意事項再填買) 訂 線 經濟部智慧財產局員工消费合作社印製 12 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（7^9 (實施例30) 除了進一步添加高級脂肪酸處理氫氧化鎂(商品名「集 思瑪5〗」，協和化學工業公司製造)20份以外，其餘與實 施例28同樣，製作出評價用樣品。 (實施例31) 除了進一步添加矽烷偶合劑處理氫氧化鎂(商品名「集 思瑪5PH」，協和化學工業公司製造)20份以外，其餘與實 施例28同樣，製作出評價用樣品。 (實施例32) 除了進一步添加三聚氰胺氰酸酯（日產化學公司製造 )20份以外，其餘與實施例28同樣，製作出評價用樣品。 (實施例33) 除了進一步添加氫氧化鎂(商品名「集思瑪5〗」，協和 化學工業公司製造)20份以及氧化銅（Π)(日進開姆克公司製 造）1.5份以外，其餘與實施例28同樣，製作出評價用樣品 〇 (實施例34) 除了取代無水順丁烯二酸改質乙烯低聚物，改添加由 聚乙烯嵌段與羧酸改質聚乙烯嵌段所構成之嵌段共聚物(商 品名「CB — OM22」，克拉雷公司製造)以外，其餘與實施 例28同樣，製作出評價用樣品。 (實施例35) 將蒙脫石（商品名「班克魯A」，豐順礦業公司製造 )5g與蒸餾水495g裝入燒瓶中，使用馬達攪拌機於常溫下 ____ 37 _ _ 本紙張又度適用中國國家標準（ CNS ) A4規格（210X 297公釐） ' (請先閱讀背面之注意事項再填1T line ΠZ] 5 5 2 2 A7 B7 V. Description of the invention (Similar to Example 22, a sample for evaluation was prepared. (Example 25) In addition to further adding a silane coupling agent to process magnesium hydroxide (trade name "Jisma 5PH" ", Manufactured by Kyowa Chemical Industry Co., Ltd.) Except for 20 parts, the rest were prepared in the same manner as in Example 22. (Example 26) Except for adding 20 parts of melamine cyanate (manufactured by Nissan Chemical Co., Ltd.), the rest were implemented. A sample for evaluation was prepared in the same manner as in Example 22. (Example 27) Instead of the anhydrous maleic acid modified propylene oligomer, an insert composed of a polypropylene block and a carboxylic acid modified polypropylene block was used instead. Except for the segment copolymer (brand name “CB — 0M12”, the molecular weight of the paragraph (A) block and the paragraph (B) block are both 1.5 × 104, manufactured by Claret)), the rest are the same as in Example 22, and were prepared for evaluation. (Example 28) Except for the replacement of polypropylene resin and anhydrous maleic acid modified propylene oligomer, polyethylene resin (trade name "HB530", manufactured by Polycom Co., Ltd.) and anhydrous sodium were used. Butenoic acid Except for the modified ethylene oligomer (trade name "ER403A", manufactured by Nippon Polyolefins Co., Ltd.), a sample for evaluation was prepared in the same manner as in Example 22. (Example 29) An ammonium polyphosphate (trade name "AP422") was further added ”, Manufactured by Japan Polyolefins Co., Ltd.), except for 5 parts, the remaining samples were prepared in the same manner as in Example 28. ____36 _ This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) " Packing-( Please read the precautions on the back before filling in) Order line Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy 12 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy A7 B7 V. Description of the invention (7 ^ 9 (Example 30) Except A sample for evaluation was prepared in the same manner as in Example 28 except that 20 parts of further higher fatty acid-treated magnesium hydroxide (trade name "Jisma 5", manufactured by Kyowa Chemical Industry Co., Ltd.) were added. (Example 31) Except for 20 parts of silane coupling agent-treated magnesium hydroxide (trade name "Setima 5PH", manufactured by Kyowa Chemical Industry Co., Ltd.), the remainder was evaluated in the same manner as in Example 28. (Example 32) A sample for evaluation was prepared in the same manner as in Example 28 except that 20 parts of melamine cyanate (manufactured by Nissan Chemical Co., Ltd.) was further added. (Example 33) A magnesium hydroxide was further added ( The product name is "Setima 5", except for 20 parts of Kyowa Chemical Industry Co., Ltd. and 1.5 parts of copper oxide (Π) (manufactured by Nikken Kemko Co., Ltd.). The rest were the same as in Example 28, and evaluation samples were prepared. Example 34) In addition to the anhydrous maleic acid modified ethylene oligomer, a block copolymer (trade name "CB — OM22") composed of a polyethylene block and a carboxylic acid modified polyethylene block was added instead. Except for Claret Inc.), the same procedure as in Example 28 was carried out to prepare a sample for evaluation. (Example 35) 5 g of montmorillonite (trade name "Banker A", manufactured by Fengshun Mining Co., Ltd.) and 495 g of distilled water were put into a flask, and a paper mixer was used at room temperature to ____ 37 _ _ This paper is applicable again China National Standard (CNS) A4 specification (210X 297 mm) '' (Please read the precautions on the back before filling
•裝I 訂 線 1225504 A7 B7 五、發明説明（ 攪拌約2小時，調製出蒙脫石之膨脹漿料。接著，將氯化 鎳(和光純藥工業公司製造)〇.7g添加至上述膨脹漿料中， 使用馬達攪拌機，於常溫下進行4小時攪拌後，添加二硬 脂基二甲基4級銨鹽0.7g，進行24小時攪拌後，以離心分 離裝置分離固形分。爲去除附著於上述固形分之多餘量， 乃於蒸餾水中將上述固形分再度分散後，進一步重複2次 之以離心分離裝置分離固形分的操作。使用真空乾燥機將 所得之固形分在50°C下真空乾燥48小後，將獲得之組成物 當作鎳離子交換層狀矽酸鹽來使用。產量係5.10g。以此爲 MMT—F。以熱重量測定裝置(TGA)解析上述MMT—F之結 果，於MMT—F中之無機成分量爲80重量％。 對小型擠壓機(商品名「TEX30」，日本製鋼所公司製 造）中，讓聚丙烯樹脂(商品名「EA9」，日本波力康姆公司 製造)82.3份、無水順丁烯二酸改質丙烯低聚物（商品名「 優美克斯1001」，官能基含有量：〇.23mmol/g，三洋化成 工業製造)7.7份、多磷酸銨(商品名「AP422」，日本聚烯 烴公司製造)5份以及MMT—F 7.7份進料，以設定溫度200 °(：熔融混練，然後將擠出之單股以造粒機顆粒化。將所得 之顆粒以調溫成200°C之熱壓機成型爲厚度3mm或厚度 100/zm之板狀物，製作出評價用樣品。 (實施例36) 除了取代聚丙烯樹脂以及無水順丁烯二酸改質丙烯低 聚物’分別改採聚乙烯樹脂(商品名「HB530」，日本波力 康姆公司製造）、無水順丁烯二酸改質乙烯低聚物（商品名 ____ — 38 _ ^紙張尺度適用中國國家標準（CNS ) A4規格（210 X297公釐） (請先閲讀背面之注意事項再填一• I line 1225504 A7 B7 V. Description of the invention (Stir for about 2 hours to prepare the swelling slurry of montmorillonite. Next, add 0.7 g of nickel chloride (manufactured by Wako Pure Chemical Industries, Ltd.) to the above-mentioned expansion slurry. In the material, after stirring at room temperature for 4 hours using a motor stirrer, 0.7 g of distearyldimethyl quaternary ammonium salt was added, and after stirring for 24 hours, the solid content was separated by a centrifugal separation device. The excess solid content is obtained by redispersing the solid content in distilled water, and then repeating the operation of separating the solid content by a centrifugal separation device twice. The obtained solid content is vacuum-dried at 50 ° C for 48 hours using a vacuum dryer. After being small, the obtained composition was used as a nickel ion-exchange layered silicate. The yield was 5.10 g. This was MMT-F. The results of the above MMT-F were analyzed by a thermogravimetric device (TGA). The amount of inorganic components in MMT-F is 80% by weight. In a small extruder (trade name "TEX30", manufactured by Japan Steel Works), polypropylene resin (trade name "EA9", Polycom Corporation, Japan) (Manufactured) 82.3 Anhydrous maleic acid modified propylene oligomer (brand name "Umilux 1001", functional group content: 0.23 mmol / g, manufactured by Sanyo Chemical Industries) 7.7 parts, ammonium polyphosphate (brand name "AP422" , Japan Polyolefin Corporation) 5 parts and MMT-F 7.7 parts were fed at a set temperature of 200 ° (: melt kneading, and then the extruded single strand was pelletized by a pelletizer. The resulting pellets were tempered into A hot press at 200 ° C was formed into a plate with a thickness of 3 mm or a thickness of 100 / zm to produce samples for evaluation. (Example 36) Except for the substitution of polypropylene resin and anhydrous maleic acid modified propylene oligomer 'Reverted to polyethylene resin (trade name "HB530", manufactured by Polycom Japan) and anhydrous maleic acid modified ethylene oligomer (trade name ____ — 38 _ ^ Paper size applies Chinese national standards (CNS) A4 size (210 X297 mm) (Please read the notes on the back before filling in one
裝IInstall I
、1T 經濟部智慧財產局員工消費合作社印製 1225504 A7 B7 經濟部智慧財產局員工消f合作社印製 五、發明説明) 「ER403A」，日本聚烯烴公司製造）以外，其餘與實施例 35同樣，製作出評價用樣品。 (比較例1) 除了不添加層狀矽酸鹽，改單獨使用聚丙烯樹脂(商品 名「EA9」，日本波力康姆公司製造)以外，其餘與實施例 1同樣，製作出評價用樣品。 (比較例2) 除了不添加層狀矽酸鹽，改於聚丙烯樹脂（商品名「 EA9」，日本波力康姆公司製造）10〇份中添加多磷酸銨(商 品名「AP422」，日本聚烯烴公司製造）100份以外，其餘 與實施例1同樣，製作出評價用樣品。 (比較例3) 除了不添加層狀矽酸鹽，改於聚丙烯樹脂（商品名「 EA9」，日本波力康姆公司製造）丨〇〇份中添加氫氧化鋁(金 屬氫氧化物）100份以外，其餘與實施例1同樣，製作出評 價用樣品。 (比較例4) 除了於聚丙烯樹脂（商品名「EA9」，日本波力康姆公 司製造)92.3份中添加未進行離子交換之精製蒙脫石（商品 名「克尼皮亞F」，克尼米尼工業公司製造)7·7份以外， 其餘與實施例1同樣，製作出評價用樣品。 (比較例5) 除了於聚丙烯樹脂(商品名「ΕΑ9」，日本波力康姆公 司製造)92.3份中添加二硬脂基二甲基4級銨鹽處理蒙脫石 39 — (請先閲讀背面之注意事項再填頁) 、τ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 1225504 A7 ------ B7 五、發明説明 (商品名「紐艾斯本D」，豐順礦業公司製造)7.7份以外， 其餘與實_ 1同樣，製作出評價用樣品。 (比較例6) 除了取代聚丙烯樹脂，改採聚乙烯樹脂（商品名「 HB530」’日本波力康姆公司製造)以外，其餘與比較例3 同樣，製作出評價用樣品。 (比較例7) 一 除了取代聚丙烯樹脂，改採乙烯一丙烯酸乙酯共聚物（ 商品名「A4250」，日本聚烯烴公司製造)以外，其餘與比 較例3贿，製作出隨用樣品。 對實施例1〜實施例36以及比較例1~比較例7所得之 評價用樣品的性能((1)平均層間距離、⑵延伸度、（3)燃燒 殘渣之狀態及降伏點應力 、（4)最大放熱速度、（5)自我滅火 性)藉以下的方法來評價。結果係示於表1及表2。 (1) 平均層間距離：使用χ射線繞射測定裝置(商品名 「RINT11QQ」’力格庫公司製造），測定由評價用樣品之層 狀砂酸鹽之積層面的繞射所得之繞射峰値之2|9，藉下式 之「布拉克之繞射式」來算出層狀矽酸鹽之(001)面間隔。 A=2dsin0(A=1.54d :層狀矽酸鹽之面間隔，0 :繞射 角） 將上述式所求得之d當作平均層間距離。 (2) 延伸度：於溫度20°C、濕度50%RH的環境氣氛下 ，依據〗IS K 6251「加硫橡膠之拉伸試驗方法」，測定評 價用樣品之啞鈴狀3號形試驗片之斷裂時延伸度直到750% 本紙張尺度適用中國國家標準（CNS ) Α4規格（210x297公董） I 装-- (請先閱讀背面之注意事項再填ml:育)1T printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1225504 A7 B7 printed by the Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the cooperative V. Invention Description) "ER403A", manufactured by Japan Polyolefin Corporation). An evaluation sample was prepared. (Comparative Example 1) A sample for evaluation was produced in the same manner as in Example 1 except that a layered silicate was not added and a polypropylene resin (trade name "EA9", manufactured by Polycom Corporation) was used alone. (Comparative Example 2) Except that layered silicate was not added, ammonium polyphosphate (trade name "AP422") was added to 100 parts of a polypropylene resin (trade name "EA9", manufactured by Polycom Corporation) in Japan. Except for 100 parts of Polyolefin Co., the rest were the same as in Example 1, and samples for evaluation were produced. (Comparative Example 3) Instead of adding a layered silicate, a polypropylene resin (trade name "EA9", manufactured by Polycom Corporation) was added to aluminum hydroxide (metal hydroxide) 100 parts. Except for the remaining parts, the same procedures as in Example 1 were performed to prepare samples for evaluation. (Comparative Example 4) In addition to 92.3 parts of a polypropylene resin (trade name "EA9", manufactured by Polycom Corporation), refined montmorillonite (trade name "Knipia F", g Except for 7.7 parts (manufactured by Nimini Industry Co., Ltd.), the same procedures as in Example 1 were used to prepare samples for evaluation. (Comparative Example 5) Except adding 92.3 parts of polypropylene resin (trade name "ΕΑ9", manufactured by Polycom Corporation) to distearyldimethyl-4 ammonium salt to treat montmorillonite 39-(Please read first Note on the back page), τ This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 1225504 A7 ------ B7 V. Description of the invention (brand name "New Eisben D ”, Manufactured by Fengshun Mining Co., Ltd.) Except for 7.7 parts, the rest were the same as the actual sample, and evaluation samples were produced. (Comparative Example 6) A sample for evaluation was produced in the same manner as in Comparative Example 3, except that instead of polypropylene resin, polyethylene resin (trade name "HB530" 'manufactured by Polycom Corporation) was used. (Comparative Example 7) 1. Except for replacing the polypropylene resin with an ethylene-ethyl acrylate copolymer (trade name "A4250", manufactured by Japan Polyolefin Corporation), the rest was compared with Comparative Example 3 to produce a sample for use. Performance of the evaluation samples obtained in Examples 1 to 36 and Comparative Examples 1 to 7 ((1) average interlayer distance, elongation, (3) state of combustion residues and stresses at yield points, (4) The maximum heat release rate and (5) self-extinguishing property) were evaluated by the following methods. The results are shown in Tables 1 and 2. (1) Average interlayer distance: Using a X-ray diffraction measurement device (trade name "RINT11QQ" manufactured by Rigaku Corporation), the diffraction peaks obtained by measuring the diffraction of the layered layer of oxalate on the evaluation sample were measured.値 之 2 | 9, the (001) plane interval of layered silicate is calculated by the following formula "Blaque's diffraction formula". A = 2dsin0 (A = 1.54d: interplanar interval of layered silicate, 0: diffraction angle) Let d obtained by the above formula be regarded as the average interlayer distance. (2) Elongation: Under the ambient atmosphere of temperature 20 ° C and humidity 50% RH, according to [IS K 6251 "Tensile Test Method for Vulcanized Rubber", determine the dumbbell-shaped No. 3 test piece of the evaluation sample. Elongation at break up to 750% This paper size applies to Chinese National Standard (CNS) Α4 size (210x297 male director) I Pack-(Please read the precautions on the back before filling in ml: Yu)
、1T 線 經濟部智慧財產局員工消費合作社印製 1225504 A7 B7 五、發明説明（4 ) / 。若直到750%仍未斷裂則記載爲750%以上、若未滿750% 即斷裂則記載其斷裂時延伸度。 (3) 燃燒殘渣之狀態及降伏點應力：依據ASTM E 1354 「建築材料之燃燒性試驗方法」，對評價用樣品之試驗片 (100mmXl00mmX3mm厚度)以圓錐形熱量計照射50kW/m2 之熱束使其燃燒。接著，以目視的方式觀察燃燒殘渣的狀 態，同時使用強度測定裝置，測定燃燒殘渣以〇.lcm/s來壓 縮時之降伏點應力。 [判定基準] 〇· · ·降伏點應力在4.9xi03Pa以上 (◎· ••降伏點應力在1.5xi〇4Pa以上） (4) 最大放熱速度：與(3)同樣地對評價用樣品之試驗片 ,(100mmXl00mmX3mm厚度)以圓錐形熱量計照射50kW/m2 之熱線使其燃燒，測定最大放熱速度(kW/m2)。 〇· · ·最大放熱速度在800 kW/m2以下 (◎· · ·最大放熱速度超過800 kW/m2) (5) 自我滅火性：依據ASTM D 2863「以氧指數爲基準 之塑膠之燃燒性標準試驗方法」，任由評價用樣品試驗片 (70mmX6mmX3mm厚度)進行燃燒試驗，以下述之判定基 準評價自我滅火性。又，於本試驗中，在維持試驗片之燃 燒上所需之氧與氮之混合氣體中之最低氧濃度(容量％)的數 値係稱爲氧指數，當以既定之氧濃度進行燃燒時，將可持 續燃燒至少3分鐘或是在3分鐘以內燃燒掉至少50mm的 情形定爲可維持燃燒，此時之氧濃度稱爲試驗片之氧指數 41 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填、 11¾頁 經濟部智慧財產局員工消費合作社印製 1225504 A7 B7 五、發明説明（l[b) 。亦即，在氧指數以下的氧濃度會自我滅火。 表1 經濟部智慧財產局員工消費合作社印製 聚烯烴 層狀矽酸鹽 難燃劑 其他添加劑 1 聚乙烯 MMT—A — 一 2 聚乙烯 MMT—B —— 一 3 聚丙烯 MMT—C — 一 4 聚丙烯 MMT—D 一 無水順丁烯二酸改質丙嫌低聚物 5 聚丙烯 MMT—D 一 無水順丁烯二酸改質丙嫌低聚物 6 聚丙烯 MMT—D 多磷酸銨 無水順丁烯二酸改質丙烯低聚物 7 聚丙烯 MMT—D 苯膦酸 無水順丁烯二酸改質丙烯低聚物 8 聚丙烯 MMT—D 氫氧化錶(KISUMA5J) 無水順丁烯二酸改質丙烯低聚物 9 聚丙烯 MMT—D 三聚氰胺氰酸酯 無水順丁烯二酸改質丙烯低聚物 10 聚丙烯 MMT—D 滑石 無水順丁烯二酸改質丙烯低聚物 實 11 聚丙烯 MMT—D — PP—竣酸改質PP 施 12 EEA MMT—D 一 無水順丁烯二酸改質乙烯低聚物 例 13 EEA MMT—D 一 一. 14 EEA MMT—D 氫氧化鎂(KISUMA5J) 無水順丁烯二酸改質乙嫌低聚物 15 EEA MMT—D 氫氧化鎂(KISUMA5J)氧化銅 無水順丁烯二酸改質乙烯低聚物 16 EEA MMT—D 氫氧化鎂(KISUMA5J)氧化錫 無水順丁烯二酸改質乙烯低聚物 Π EEA MMT—D 氫氧化鎂(KISUMA5J)氧化鋅 無水順丁烯二酸改質乙烯低聚物 18 EEA MMT—D 氫氧化鎂(KISUMA5J) PPP 無水順丁烯二酸改質乙烯低聚物 19 聚乙烯 MMT—D — 無水順丁烯二酸改質乙烯低聚物 20 聚乙烯 MMT—D 多磷酸銨 — 21 聚乙烯 MMT—D 多磷酸銨 _ 22 聚丙烯 MMT—E 一 無水順丁烯二酸改質丙烯低聚物 23 聚丙烯 MMT—E 多磷酸銨 無水順丁烯二酸改質丙烯低聚物 24 聚丙烯 MMT—E 氫氧化鎂(KISUMA5J) 無水順丁烯二酸改質丙烯低聚物 25 聚丙烯 MMT—E 氫氧化鎂(KISUMA5PH) 無水順丁烯二酸改質丙烯低聚物 26 聚丙烯 MMT—E 三聚氰胺氰酸酯 無水順丁烯二酸改質丙烯低聚物 27 聚丙烯 MMT—E — PP—羧酸改質PP 28 聚乙烯 MMT—E 一 無水順丁烯二酸改質乙烯低聚物 42 I--------装-- (請先閲讀背面之注意事項再填|^;百0 訂 線 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1225504Line 1T Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1225504 A7 B7 V. Description of Invention (4) /. If it is not broken up to 750%, it will be described as 750% or more, and if it is broken below 750%, it will be described as the elongation at break. (3) State of combustion residue and stress at falling point: According to ASTM E 1354 "Test method for flammability of building materials", a test piece (100mmX100mmX3mm thickness) of an evaluation sample is irradiated with a heat beam of 50 kW / m2 using a conical calorimeter. Its burning. Next, the state of the combustion residue was observed visually, and at the same time, the stress at the drop point when the combustion residue was compressed at 0.1 cm / s was measured using a strength measuring device. [Judgment Criteria] 〇 ··· The stress at the falling point is 4.9xi03Pa or more (◎ · •• The stress at the falling point is 1.5xi04Pa or more) (4) The maximum heat release rate: The test piece for the evaluation sample is the same as (3) ((100mmXl00mmX3mm thickness) irradiate a 50 kW / m2 hot wire with a conical calorimeter to burn it, and measure the maximum heat release rate (kW / m2). 〇 ··· Maximum heat release rate is below 800 kW / m2 (◎ ··· Maximum heat release rate is above 800 kW / m2) (5) Self-extinguishing property: According to ASTM D 2863 "Flammability Standard for Plastics Based on Oxygen Index "Test method", the sample test piece for evaluation (70 mm X 6 mm X 3 mm thickness) was subjected to a combustion test, and the self-extinguishing property was evaluated based on the following criteria. In addition, in this test, the number of minimum oxygen concentration (volume%) in the mixed gas of oxygen and nitrogen required to maintain the combustion of the test piece is called the oxygen index, and when combustion is performed at a predetermined oxygen concentration The continuous burning for at least 3 minutes or the burning of at least 50mm within 3 minutes is considered to maintain the burning. The oxygen concentration at this time is called the oxygen index of the test piece. 41 This paper applies the Chinese National Standard (CNS) A4. Specifications (210 X 297 mm) (Please read the notes on the back before filling in, 11¾ pages printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economy 1225504 A7 B7 V. Description of the invention (l [b). That is, the oxygen index The following oxygen concentrations will self-extinguish. Table 1 Polyolefin layered silicate flame retardant printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and other additives 1 Polyethylene MMT—A — One 2 Polyethylene MMT — B — One 3 Polypropylene MMT—C — 4 Polypropylene MMT—D Anhydrous maleic acid modified propylene oligomer 5 Polypropylene MMT—D Anhydrous maleic acid modified propylene oligomer 6 Polypropylene MMT—D polyphosphorus Ammonium acid anhydrous maleic acid modified propylene oligomer 7 polypropylene MMT-D benzenephosphonic acid anhydrous maleic acid modified propylene oligomer 8 polypropylene MMT-D hydroxide table (KISUMA5J) anhydrous maleic acid Maleic acid modified propylene oligomer 9 Polypropylene MMT-D Melamine cyanate anhydrous maleic acid modified propylene oligomer 10 Polypropylene MMT-D Talc anhydrous maleic acid modified propylene oligomer Example 11 Polypropylene MMT—D — PP — Complete acid modification PP Application 12 EEA MMT—D Anhydrous maleic acid modified ethylene oligomer Example 13 EEA MMT—D One by one. 14 EEA MMT—D Hydroxide Magnesium (KISUMA5J) anhydrous maleic acid modified ethylene oligomer 15 EEA MMT-D magnesium hydroxide (KISUMA5J) copper oxide anhydrous maleic acid modified ethylene oligomer 16 EEA MMT-D magnesium hydroxide (KISUMA5J) tin oxide anhydrous maleic acid modified ethylene oligomer Π EEA MMT-D magnesium hydroxide (KISUMA5J) zinc oxide anhydrous maleic acid modified ethylene oligomer 18 EEA MMT-D magnesium hydroxide (KISUMA5J) PPP anhydrous maleic acid modified ethylene oligomer 19 polyethylene MMT-D — anhydrous Butenedioic acid modified ethylene oligomer 20 Polyethylene MMT—D ammonium polyphosphate — 21 Polyethylene MMT—D ammonium polyphosphate _ 22 Polypropylene MMT—E Anhydrous maleic acid modified propylene oligomer 23 Polypropylene MMT—E Ammonium polyphosphate anhydrous maleic acid modified propylene oligomer 24 Polypropylene MMT—E Magnesium hydroxide (KISUMA5J) Anhydrous maleic acid modified propylene oligomer 25 Polypropylene MMT-E Magnesium hydroxide (KISUMA5PH) anhydrous maleic acid modified propylene oligomer 26 polypropylene MMT-E melamine cyanate anhydrous maleic acid modified propylene oligomer 27 polypropylene MMT-E — PP-carboxyl Acid-modified PP 28 Polyethylene MMT-E Anhydrous maleic acid modified ethylene oligomer 42 I -------- pack-(Please read the precautions on the back before filling | ^; 百0 Alignment This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 1225504
A B7 五、發明説明（ψΙ) 經濟部智慧財產局員工消費合作社印製 29 聚乙烯 MMT—E 多磷酸銨 無水順丁烯二酸改質乙嫌低聚物 30 聚乙烯 MMT—E 氫氧化鎂(KISUMA5J) 無水順丁烯二酸改質乙烯低聚物 31 聚乙烯 MMT-E 氫氧化鎂(KISUMA5PH) 無水順丁烯二酸改質乙烯低聚物 32 聚乙烯 MMT—E 三聚氰胺氰酸醋 無水順丁烯二酸改質乙烯低聚物 33 聚乙烯 MMT—E 氫氧化鎂(KISUMA5J)氧化銅 無水順丁烯二酸改質乙烯低聚物 34 聚乙烯 MMT—E — PE—羧酸改質PE 35 聚丙烯 MMT—F 多磷酸銨 無水順丁烯二酸改質丙烯低聚物 36 聚乙烯 MMT-F 多磷酸銨 無水順丁烯二酸改質乙烯低聚物 1 聚丙烯 — 一 — 2 聚丙烯 一 多磷酸銨 一 比 3 聚丙烯 一 氫氧化鋁 一 較 4 聚丙烯 精製MMT 一 一 例 5 聚丙烯 新 S-BEN_D 一 一 6 聚乙烯 一 氫氧化鋁 一 7 EEA — 氫氧化鋁 — 表2 平均層間距離 延伸度(％) 難燃殘渣 降伏點應力(kPa) 1 至少6nm 至少750 ◎ 15 2 至少6nm 至少750 ◎ 16 3 至少6nm 至少750 ◎ 19 4 至少6nm 至少750 ◎ 22 5 3nm 至少750 〇 10 6 至少6nm 至少750 〇 23 7 至少6nm 至少750 〇 21 8 至少6nm 至少750 ◎ 30 9 至少6nm 至少750 ◎ 25 10 至少6nm 至少750 ◎ 23 11 至少6nm 至少750 ◎ 23 實 12 4nm 至少750 〇 12 施 13 4nm 至少750 0 11 例 14 至少6nm 至少750 〇 31 43 l·---------^! (請先閱讀背面之注意事項再填頁)A B7 V. Description of Invention (ψΙ) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 29 Polyethylene MMT-E Ammonium polyphosphate anhydrous maleic acid modified ethylene oligomer 30 Polyethylene MMT-E magnesium hydroxide (KISUMA5J) anhydrous maleic acid modified ethylene oligomer 31 polyethylene MMT-E magnesium hydroxide (KISUMA5PH) anhydrous maleic acid modified ethylene oligomer 32 polyethylene MMT-E melamine cyanate anhydrous Maleic acid modified ethylene oligomer 33 polyethylene MMT-E magnesium hydroxide (KISUMA5J) copper oxide anhydrous maleic acid modified ethylene oligomer 34 polyethylene MMT-E — PE-carboxylic acid modified PE 35 polypropylene MMT-F ammonium polyphosphate anhydrous maleic acid modified propylene oligomer 36 polyethylene MMT-F ammonium polyphosphate anhydrous maleic acid modified ethylene oligomer 1 polypropylene — one — 2 Polypropylene-ammonium polyphosphate-ratio 3 Polypropylene-aluminum hydroxide-ratio 4 Polypropylene-refined MMT 1-case 5 New polypropylene S-BEN_D 1- 6 Polyethylene-aluminum hydroxide 7 EEA — Aluminum hydroxide — Table 2 Average inter-layer distance elongation (%) Flammable residue drop point stress (kPa) 1 at least 6nm at least 750 ◎ 15 2 at least 6nm at least 750 ◎ 16 3 at least 6nm at least 750 ◎ 19 4 at least 6nm at least 750 ◎ 22 5 3nm at least 750 〇10 6 at least 6nm at least 750 〇23 7 at least 6nm at least 750 〇21 8 at least 6nm at least 750 ◎ 30 9 at least 6nm at least 750 ◎ 25 10 at least 6nm at least 750 ◎ 23 11 at least 6nm at least 750 ◎ 23 real 12 4nm at least 750 〇12 application 13 4nm at least 750 0 11 cases 14 At least 6nm At least 750 〇31 43 l · --------- ^! (Please read the precautions on the back before filling in the page)
、1T 線 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨〇><297公釐） 1225504 A7 B7 五、發明説明（h) 15 至少6nm 至少750 〇 30 16 至少6nm 至少750 〇 30 17 至少6nm 至少750 〇 30 18 至少6nm 至少750 〇 30 19 4nm 至少750 〇 14 20 至少6nm 至少750 〇 27 21 至少6nm 至少750 〇 35 22 至少6nm 至少750 ◎ 25 23 至少6nm 至少750 ◎ 27 24 至少6nm 至少750 ◎ 26 25 至少6nm 至少750 ◎ 26 26 至少6nm 至少750 ◎ 30 27 至少6nm 至少750 ◎ 25 28 至少6nm 至少750 ◎ 26 29 至少6nm 至少750 ◎ 30 30 至少6nm 至少750 ◎ 20 31 至少6nm 至少750 ◎ 20 32 至少6nm 至少750 ◎ 20 33 至少6nm 至少750 ◎ 30 34 至少6nm 至少750 ◎ 25 35 至少6nm 至少750 ◎ 35 36 至少6nm 至少750 ◎ 35 1 一 至少750 未生成殘渣 一 2 — 350 局部地被膜形成 3.0 比 3 —· 450 燃燒殘渣膨脹 4.0 較 4 1.4nm 250 局部地被膜形成 1.0 例 5 3.5nm 至少750 局部地被膜形成 3.0 6 — 275 燃燒殘渣膨脹 4.0 7 — 310 燃燒殘渣膨脹 4.0 ------澤-- (請先閱讀背面之注意事項再填ml·頁) 經濟部智慧財產局員工消費合作社印製 *關於實施例 5、8、9、12、14〜19、24、25、30、3卜 33可確認自我滅火性。 44 1225504 A7 B7 五、發明説明) 由表1與表2可明顯看出，由實施例卜實施例36之 本發明之聚烯烴系樹脂組成物所構成之評價用樣品，皆在 燃燒時藉層狀矽酸鹽形成燒結體，而保持燃燒殘渣的形狀 ，且該燃燒殘渣以O.lcm/s壓縮時具有降伏點’又降伏點應 力爲至少4.9 X103Pa。藉此，即使於燃燒後亦不會發生形狀 崩潰，在自我滅火性上優異，而具有不會發生延燒之優異 的難燃性。又，於斷裂時之延伸度也全部高於750%，且柔 軟性方面亦優。 相對於此，由表2可明顯看出，由不含層狀矽酸鹽之 比較例1〜比較例3、以及比較例6與比較例7的聚烯烴系 樹脂組成物所構成之評價用樣品，不含層狀矽酸鹽之比較 例1〜比較例3、以及比較例6與比較例7之聚烯烴系樹脂 組成物所得之評價用樣品，由於不會生成燃燒殘渣或是燃 燒殘渣的形狀無法保持，故自我滅火性差，難燃性不佳。 又，由層狀矽酸鹽之平均層間距離未滿3nm之比較例4之 聚烯烴系樹脂組成物所得之評價用樣品，其自我滅火性差 ，難燃性不佳。 經濟部智慧財產局員工消費合作社印製 又，在比較例5方面，其層間距離雖爲3.5nm，惟認 定其不存在著分散爲5層以下之層狀矽酸鹽，並未對難燃 性造成很大的影響。在燃燒被膜形成上亦僅侷限於部分地 方，未能保持強度。 [產業上之可利用性] 由於本發明具有上述之構成，於燃燒時藉層狀矽酸鹽 形成燒結體，燃燒殘渣之形狀乃得以保持。藉此，所提供 45 1225504 A7 B71. The paper size of the 1T line is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 〇 < 297 mm) 1225504 A7 B7 5. Description of the invention (h) 15 at least 6nm at least 750 〇30 16 at least 6nm at least 750 〇 30 17 at least 6nm at least 750 〇30 18 at least 6nm at least 750 〇30 19 4nm at least 750 〇14 20 at least 6nm at least 750 〇27 21 at least 6nm at least 750 〇35 22 at least 6nm at least 750 ◎ 25 23 at least 6nm at least 750 ◎ 27 24 At least 6nm at least 750 ◎ 26 25 at least 6nm at least 750 ◎ 26 26 at least 6nm at least 750 ◎ 30 27 at least 6nm at least 750 ◎ 25 28 at least 6nm at least 750 ◎ 26 29 at least 6nm at least 750 ◎ 30 30 at least 6nm at least 750 ◎ 20 31 at least 6nm at least 750 ◎ 20 32 at least 6nm at least 750 ◎ 20 33 at least 6nm at least 750 ◎ 30 34 at least 6nm at least 750 ◎ 25 35 at least 6nm at least 750 ◎ 35 36 at least 6nm at least 750 ◎ 35 1-at least 750 residues not generated 2- 350 Local coating formation 3.0 to 3 — · 450 Combustion residue expansion 4.0 to 4 1.4nm 250 Local coating formation 1.0 Example 5 3.5 nm at least 750 Locally formed a film 3.0 6 — 275 Combustion residue expansion 4.0 7 — 310 Combustion residue expansion 4.0 ------ Ze-(Please read the precautions on the back before filling ml · page) Ministry of Economic Affairs Intellectual Property Bureau Printed by the employee's consumer cooperative. * With respect to Examples 5, 8, 9, 12, 14 to 19, 24, 25, 30, 3, and 33, self-extinguishing properties can be confirmed. 44 1225504 A7 B7 V. Description of the invention It is obvious from Tables 1 and 2 that the evaluation samples made of the polyolefin-based resin composition of the present invention in Example 36 and Example 36 were borrowed during combustion. The shaped silicate forms a sintered body while maintaining the shape of the combustion residue, and the combustion residue has a drop point when compressed at 0.1 cm / s, and the drop point stress is at least 4.9 × 103 Pa. Thereby, shape collapse does not occur even after burning, and it is excellent in self-extinguishing property, and it has excellent flame retardancy without burning. In addition, the elongation at break is all higher than 750%, and the flexibility is also excellent. In contrast, as apparent from Table 2, an evaluation sample composed of the polyolefin-based resin composition of Comparative Examples 1 to 3, and Comparative Examples 6 and 7 containing no layered silicate. Since the evaluation samples obtained from the polyolefin resin compositions of Comparative Examples 1 to 3 and Comparative Examples 6 and 7 that do not contain layered silicate, combustion residues or shapes of combustion residues are not generated. Unable to maintain, so poor self-extinguishing, poor flame retardancy. In addition, the evaluation sample obtained from the polyolefin-based resin composition of Comparative Example 4 having an average interlayer distance of layered silicates of less than 3 nm had poor self-extinguishing properties and poor flame retardancy. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In Comparative Example 5, although the interlayer distance is 3.5nm, it is determined that there is no layered silicate dispersed into 5 or less layers. Make a big impact. The formation of the combustion film was also limited to some areas, and the strength could not be maintained. [Industrial Applicability] Since the present invention has the above-mentioned structure, a sintered body is formed by layered silicate during combustion, and the shape of the combustion residue is maintained. With this, provided 45 1225504 A7 B7
五、發明説明V. Description of the invention
之聚烯烴系樹脂組成物，即使於燃燒後亦不會發生形狀崩 潰，在形狀保持性、自我滅火性上優異，不會發生延燒’ 具有優異之難燃性，再者，機械強度亦優，並可保持透明 性。又，依據本發明，除了可顯著地改善聚烯烴系樹脂之 彈性率與氣體防護性這些物性，在基於分子鏈之束縛造成 熱變形溫度上升所得之耐熱性、基於無機結晶造成核劑效 果所得之尺寸安定性等各物性方面亦能大幅地提昇。 (請先閲讀背面之注意事項再填Hi頁) 、1· 經濟部智慧財產局員工消費合作社印製 46 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）The polyolefin-based resin composition does not collapse in shape even after burning, and is excellent in shape retention and self-extinguishing properties, and does not cause post-burning. It has excellent flame resistance, and also has excellent mechanical strength. And maintain transparency. In addition, according to the present invention, in addition to remarkably improving the physical properties of the polyolefin resin such as the elastic modulus and gas barrier properties, the heat resistance obtained by increasing the thermal deformation temperature caused by the bondage of the molecular chain and the effect obtained by the nucleating agent caused by the inorganic crystal Various physical properties such as dimensional stability can also be greatly improved. (Please read the notes on the back before filling in the Hi page) 1. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 46 This paper size applies to China National Standard (CNS) A4 (210X 297 mm)
Claims (1)
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32279899 | 1999-11-12 | ||
| JP34216899 | 1999-12-01 | ||
| JP37122699 | 1999-12-27 | ||
| JP2000014747 | 2000-01-24 | ||
| JP2000029112 | 2000-02-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TWI225504B true TWI225504B (en) | 2004-12-21 |
Family
ID=34596156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW89123774A TWI225504B (en) | 1999-11-12 | 2000-11-10 | Polyolefin resin composition |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI225504B (en) |
-
2000
- 2000-11-10 TW TW89123774A patent/TWI225504B/en not_active IP Right Cessation
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100698890B1 (en) | Polyolefin resin composition | |
| Laoutid et al. | New prospects in flame retardant polymer materials: From fundamentals to nanocomposites | |
| Hamdani et al. | Flame retardancy of silicone-based materials | |
| CA2402880C (en) | Flameproof polymer composition | |
| TWI462971B (en) | Flame retardant polymer compositions | |
| US20150004343A1 (en) | Polyolefin flame retardant composition and synergists thereof | |
| WO2017070893A1 (en) | Ceramic silicone rubber, preparation method and use thereof | |
| CA2622680C (en) | Flame-retardant composition | |
| Chang et al. | Flame retardancy and thermal stability of ethylene-vinyl acetate copolymer nanocomposites with alumina trihydrate and montmorillonite | |
| TW419500B (en) | Process for producing flame-retardant, silane-crosslinked polyolefin | |
| JP2006321934A (en) | Fire retardant thermoplastic resin composition and its molded article and electric wire | |
| JP2002356574A (en) | Foamable thermoplastic resin composition, thermoplastic resin foamed material and laminated composite | |
| CN114341245A (en) | Flame retardant polymer compositions and methods of use | |
| US20050260404A1 (en) | Sheet-form molding | |
| JP3635567B2 (en) | Polyolefin resin composition | |
| JP2000226585A (en) | Flame retardant | |
| Hassan et al. | Enhanced thermal, mechanical and fire-retarding properties of polystyrene sulphonate-grafted-nanosilica/polypropylene composites | |
| TWI225504B (en) | Polyolefin resin composition | |
| JP3574426B2 (en) | Sheet-like molded body | |
| JP2006145910A (en) | Noninflammable sheet for internal illumination signboard | |
| JP4088080B2 (en) | Flame retardant resin composition | |
| JP2003007155A (en) | Manufacturing method of coated electric wire | |
| JP2004160818A (en) | Decorative sheet | |
| JP3784260B2 (en) | Polyolefin resin composition | |
| JP4189202B2 (en) | Sheet-like molded body and decorative sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |