1299742 玖、發明說明： 【發明所屬之技術領域】 本發明係關於氯化乙烯系樹脂組成物；詳言之， 除無毒性且具優越電絕緣性、熱安定性等特性之外 具有可防止經時變色性之特點的氯化乙烯系樹脂組 【先前技術】 在氣化乙烯樹脂中，於提昇成形加工時的耐熱性 性，以及提昇產品的電絕緣性、機械物性之目的下 入各種添加劑。譬如當使用於電線、絕緣膠布等用 況時，電絕緣性、熱安定性為必要者，習知便有使 三鹼式硫酸鉛或硬脂酸鉛等鉛系安定劑。 但是，近年隨對人體的安全性等環保問題逐漸受 提案有取代鉛系安定劑而改採用屬於無毒性安定劑 石類化合物、脂肪酸鋅、/3 -二酮化合物或其金屬； 曰本專利特開平5 - 6 5 3 8 0號公報）。調配有此無毒性 的氯化乙烯系樹脂組成物，在電絕緣性、熱安定性 性方面具優越效果。但是，在另一方面，若該等無 定劑在對產品外觀（表面）賦予光澤之目的下而調配 碳酸鈣，則產生隨時間經過而變色的新問題。 再者，取代鉛系安定劑之含有無毒性安定劑的氣 系樹脂組成物，除日本專利特開平5 - 6 5 3 8 0號公報 載者之外，亦提案有含水滑石類化合物與受阻胺系 的氯化乙烯系樹脂組成物（參照日本專利特開平5 -號公報）。此氯化乙婦系樹脂組成物亦如同上述日本 312/發明說明書(補件)/92-08/92116354 係關於 ，特別 成物。 或力口工 ，調配 途之情 用如： 重視， 的水滑 藝（參照 安定劑 、著色 毒性安 入輕質 化乙烯 中所記 化合物 271506 專利特 5 1299742 開平5 - 6 5 3 8 0號公報中所記載般，就經時變色方面而言， 仍殘留著待改善的問題。 如上所述，截至目前為止，無毒性、電絕緣性、熱安定 性的氯化乙烯系樹脂組成物雖已被開發，但是卻殘留著經 時變色的問題點。 【發明内容】 本發明者有鑒於習知諸項狀況，經深入鑽研之結果，發 現在含有輕質碳酸鈣的氣化乙烯系樹脂中，藉由調配入水 滑石類化合物、有機酸鋅化合物及冷-二酮的金屬鹽，除上 述電源絕緣性、耐熱性之外，尚可達大幅提昇防止產品經 時變色性的效果。 換句話說，本發明乃如下所述： 1 ) 一種氯化乙烯系樹脂組成物，其特徵為，在氣化乙烯 樹脂中，調配入輕質碳酸鈣、水滑石類化合物、有機酸鋅 化合物及卢-二酮金屬鹽。 2 )如申請專利範圍第1項之氯化乙烯系樹脂組成物，其 中，調配著比表面積值為5 m2 / g以上的輕質碳酸鈣。 【實施方式】 本發明中，所謂「氯化乙烯系樹脂」係指以氯化乙烯單 獨聚合物或氯化乙烯為主體的樹脂，譬如氯化乙烯與乙酸 乙烯、偏氣乙烯、乙烯、丙烯、甲基丙烯酸酯、胺基甲酸 酯的共聚物，接枝共聚物、或該等樹脂的摻合物等。 本發明中所採用的輕質碳酸鈣係在鈣鹽水溶液中添加 碳酸鹼溶液之時獲得之白色沉澱，亦稱「沉澱碳酸鈣」。當 6 312/發明說明書(補件)/92-08/92116354 1299742 將水滑石類化合物與有機酸鋅化合物一齊添加於氯化乙烯 系樹脂中之時，輕質碳酸鈣比表面積值為5 m2 / g以上者特 別在經時變色性方面出現較大作用，但是，依照本發明的 話，即便使用比表面積值為5 m2 / g以上且1 0 0 m2 / g以下的 輕質碳酸鈣之情況時，仍可極有效的防止長期變色性。 輕質碳酸鈣之用量係相對於氯化乙烯系樹脂1 0 0重量 份，採用0 . 1〜2 0 0重量份，最好採用1〜1 0 0重量份。 在本發明中，在合併使用輕質碳酸鈣的條件下，亦可添 加重質碳酸鈣。重質碳酸鈣係源自天然的碳酸鈣，可以方 解石、霰石、石灰石、大理石、白堊石等形態而產出者。 重質碳酸鈣併用程度可與輕質碳酸鈣相同。 本發明中所採用的水滑石類化合物一般式為 其中，M2 +係指由：Mg2+、Zn2+、 Fe2+、Mn2+、Co2+、Ni2 +及Cu2 +所組成之群組中選出之至少 一種2價陽離子；M3 +係指由：Al3+、Fe3+、Cr3 +及Co3 +所組 成之群組中選出之至少一種3價陽離子；An_係指由：or、 C〇32_、S〇42_、n〇3-及Cl_所組成之群組中選出之至少一種陰 離子；X表示係0<xS0.33的數值）。 水滑石類化合物的具體例可舉例如：M g 6 A 12 ( 0 H h 6 C〇3.4H2〇、Mg4.5Al2(OH：h3C〇3.3.5H2〇、Mg4.5Al2(OH)13C〇3、 Mg3.5Zni.〇Al2(OH)i3C〇3*3.5H2〇 等。市售品則有如： STARBIACE HT- 1、STARBIACE HT-7 > S T A R B I A C E Η T - P (均為 堺化學工業公司製）、阿爾佳麥沙-1、阿爾佳麥沙-2、阿爾 佳麥沙-3、阿爾佳麥沙-4、阿爾佳麥沙-5、D Η T - 4 A (均為協 312/發明說明書(補件)/92-08/921163 54 1299742 和化學工業公司製）等。 該等水滑石類化合物係相對於氯化乙烯系樹脂10 0重量 份而使用0 . 1〜1 0重量份，最好使用0 . 5〜5 . 0重量份。 本發明中所使用的有機酸鋅化合物係包含由羧酸與鋅 所構成的鹽，該羧酸可為鏈式羧酸（脂肪酸）、脂環式羧酸、 芳香族羧酸中之任一者，而且一分子中的羧基數目亦可為 單羧酸、二羧酸、三羧酸等任一者。特別以脂肪酸鋅為佳， 此例子可舉例如：硬脂酸鋅或棕櫚酸鋅、肉豆蔻酸鋅、月桂 酸鋅、辛酸鋅、山俞酸鋅等。有機酸鋅係相對於氯化乙烯 系樹脂1 0 0重量份而使用0 . 0 5〜5重量份，最好使用 0 . 1〜2 . 0重量份。 本發明中所採用的泠-二酮金屬鹽（或1,3-二酮金屬鹽） 係指一般式：RCOCH2COR’（式中，R與R’係相同或不同的碳 數1〜2 2之烷基、芳基）所示二酮或脫氫醋酸與金屬（如： 鋅；或鈣、鎂等鹼土族金屬）的鹽類。具體例可舉例如：二 苯醯甲烷、硬脂醯基苯醯甲烷、棕櫊醯基苯醯甲烷、苯醯 丙酮、脫氫醋酸與金屬（如鋅；或鈣、鎂等鹼土族金屬）的 鹽類。/3 -二酮金屬鹽係相對於氯化乙烯系樹脂1 0 0重量份 而使用0 . 0 0 1〜1 . 0重量份，最好使用0 . (Π〜0 . 5重量份。 在本發明中，亦可合併使用習知氯化乙烯系樹脂中所使 用的可塑劑、填充劑、熱安定化助劑、抗氧化劑、紫外線 吸收劑、環氧化合物、潤滑劑、顏料等。 本發明的氯化乙烯系樹脂組成物係在氯化乙烯樹脂 中，調配入輕質碳酸鈣、水滑石類化合物、有機酸鋅化合 8 312/發明說明書(補件)/92-08/921163 54 1299742 物及冷-二酮金屬鹽，利用一般方法在1 Ο 0〜2 2 0 °C下進行混 練而獲得，並使用於所需的產品製造中。 (實施例） 以下列舉實施例與比較例更具體的說明本發明。 (實施例1〜5及比較例1〜2 ) 將聚氣化乙烯（聚合度1 3 0 0 ) 1 0 0重量份、DINP(鄰苯二 甲酸二異壬酯）5 0重量份、輕質碳酸鈣（調配量：表1 )、硬 脂酸鋅0. 5重量份、水滑石1 . 0重量份、及表1所示添加 劑的調配物，於1 6 0 °C利用輥進行5分鐘的混練後，再利 用1 7 0 °C之壓機製成厚度1 mm的薄片。將所獲得薄片在以 5 0 °C、9 0 %溼度之條件運轉的恆溫恆濕機中，經暴露4 8小 時後再確認經時變色性的有無。此外，耐熱性的評估係利 用1 8 0 °C壓機施行1 0分鐘的衝壓（p r e s s )，然後判斷所獲 得薄片所擁有的變色性。另外，電絕緣性的評估係依據 J I S K - 6 7 2 3所規範的方法而實施。 表中各添加劑係採用如下所示者。 ·/?-二酮：二苯醯曱烷 • /3 -二酮金屬鹽B :脫氫醋酸鋅 •石-二酮金屬鹽C:二苯醯甲烷鋅 •輕質碳酸鈣：曰石鈣產製「V i g 〇 t ο 1 0」（商品名），比表 面積：約1 2 m2 / g •重質碳酸鈣：備北粉化公司製「索福東1 5 Ο Ο」 (評估基準） ◎:無變色 〇：略變色 312/發明說明書(補件)/92-08/92116354 1299742 X :大幅變色 表1 比較例 實施例 1 2 1 2 3 4 5 聚氯化乙烯 100 100 100 100 100 100 100 DINP 50 50 50 50 50 50 50 輕質碳酸鈣 20 30 20 20 30 30 30 硬脂酸鋅 0. 5 0. 5 0.5 0. 5 0.5 0. 5 0. 5 水滑石類化合物 1 1 1 1 1 1 1 冷-二酮 0.1 0.1 冷-二酮金屬鹽B 0.1 0.1 0.05 /3 -二酮金屬鹽C 0. 1 0. 1 0.05 經時變色性 X X ◎ ◎ ◎ ◎ ◎ 電絕緣性（Ω c m ) 2x 1012 6x 1012 4x 1013 5x 10 丨1 9x 1012 9x 1012 9x 10 丨2 财熱性 ◎ 〇 〇 〇 ◎ ◎ ◎ 由上述表1結果得知，如實施例1〜5所示，在調配著輕 質碳酸鈣的氯化乙烯系樹脂中，藉由調配水滑石類化合 物、有機酸鋅化合物及/3 -二酮金屬鹽，便可在毫無損及習 知性能（電絕緣性、熱安定性等）之情況下，明顯的改善經 時變色性。相對於此，如比較例1與2所示，即便添加冷-二酮，仍無法顯現出經時變色性的改善效果。 (實施例6〜1 0及比較例3〜4 ) 將聚氣化乙烯（聚合度1300)100重量份、TOTM(偏苯三 曱酸三辛酯）5 0重量份、輕質碳酸鈣（調配量：表2 )、重質 碳酸鈣（調配量：表2 )、硬脂酸鋅1 · 0重量份、水滑石1 . 0 重量份及表2所示添加劑的調配物，於1 6 0 °C利用輥進行5 分鐘的混練後，再利用1 7 0 °C壓機製成厚度1 mm的薄片。 將所獲得薄片在5 0 °C、9 0 %溼度之條件運轉的恆溫恆濕機 中，經暴露48小時後再確認經時變色性的有無。耐熱性的 評估係利用1 8 0 °C壓機施行3 0分鐘的衝壓，然後判斷所獲 10 1 Π/發明說明書(補件)/92-08/92l 16354 1299742 得薄片所擁有的變色性。另外，電絕緣性的評估係依據 J I S K - 6 7 2 3所規範的方法而實施。 表中各添加劑係採用如下所示者。 •/3-二酮：二苯醯曱烷 • /3 -二酮金屬鹽B :脫氫醋酸鋅 •/3-二酮金屬鹽C:二苯醯甲烷鋅 (評估基準） ◎:無變色 〇：略變色 X :大幅變色 表2 比較例 實施例 3 4 6 7 8 9 10 聚氯化乙烯 100 100 100 100 100 100 100 Τ0ΤΜ 50 50 50 50 50 50 50 輕質碳酸鈣 20 30 20 20 30 30 30 重質碳酸鈣 20 20 20 20 20 20 20 硬脂酸鋅 1 1 1 1 1 1 1 水滑石類化合物 1 1 1 1 1 1 1 /3 - 二酮 0.1 0.1 /3 -二酮金屬鹽B 0. 1 0.1 0.05 /3 -二酮金屬鹽C 0.1 0. 1 0.05 經時變色性 X X ◎ ◎ ◎ ◎ 電絕緣性（Ω c m ) lx 1013 5x 10 丨2 2x 10 丨3 3x 1013 8x 10 丨2 9x 10 丨2 8x 10 丨2 财熱性 ◎ 〇 〇 〇 ◎ ◎ ◎ 由上述表2 結果得知， 如實施- 例6〜1 0 所示， 在調配 著 輕質碳酸鈣與重質碳酸鈣的氯化乙烯系樹脂中，藉由調配 水滑石類化合物、有機酸鋅化合物及/5 -二酮金屬鹽，便可 在毫無損及習知性能（電絕緣性、熱安定性等）之情況下， 明顯的改善經時變色性。換句話說，調配輕質碳酸鈣之時， 亦可使用重質碳酸鈣。相對於此，如比較例3與4所示， 11 312/發明說明書(補件)/92-08/921163 54 1299742 果。 未使 滑石 得可 具有 果， 金屬 係領 即便添加/3 -二酮，仍無法顯現出經時變色性的改善 (產業上可利用性） 如上所述，本發明的氣化乙烯系樹脂組成物乃因為 用鉛系安定劑而無毒性，且藉由調配輕質碳酸鈣、水 類化合物、有機酸鋅化合物及/3 -二酮金屬鹽，除可獲 匹敵於鉛系安定劑的電絕緣性與熱安定性之外，特別 可防止經時變色性的極大優點。此經時變色的防止效 主要乃因為本組成物中，共存著輕質碳酸鈣與/3 -二酮 鹽的緣故所致。所以，實際可有效廣泛使用於電氣關 域等範疇中。 12 312/發明說明書(補件)/92-08/921163541299742 玖Invention Description: [Technical Field] The present invention relates to a chlorinated vinyl resin composition; in particular, it has a property of preventing non-toxicity and having superior electrical insulation properties, thermal stability and the like. A chlorinated vinyl resin group characterized by discoloration [Prior Art] In the gasified vinyl resin, various additives are added for the purpose of improving heat resistance during molding processing and improving electrical insulation properties and mechanical properties of the product. For example, when it is used in electric wires, insulating tapes, etc., electrical insulation and thermal stability are necessary. Conventionally, lead-based stabilizers such as tribasic lead sulfate or lead stearate are available. However, in recent years, with the environmental protection issues such as the safety of the human body, it has been gradually proposed to replace the lead-based stabilizer and to use non-toxic stabilizers, fatty acid zinc, /3-dione compounds or their metals; Kaiping 5 - 6 5 3 8 0). The non-toxic chlorinated vinyl resin composition is excellent in electrical insulation and thermal stability. On the other hand, however, if the above-mentioned refrigerant is formulated with calcium carbonate for the purpose of imparting gloss to the appearance (surface) of the product, a new problem of discoloration over time is generated. Further, in place of the lead-based stabilizer, a gas-based resin composition containing a non-toxic stabilizer is also proposed to contain a hydrotalcite-like compound and a hindered amine in addition to those disclosed in Japanese Patent Laid-Open Publication No. Hei-5-6 358. A chlorinated vinyl resin composition (refer to Japanese Patent Laid-Open No. Hei-5-). This chlorinated ethylenic resin composition is also a special product as described in the above Japanese 312/Invention Manual (Supplement)/92-08/92116354. Or the power of the mouth, the use of the way of the transfer such as: the importance of, the water slide art (refer to the stabilizer, coloring toxicity into the lightened ethylene in the compound 271506 patent special 5 1299742 Kaiping 5 - 6 5 3 8 0 bulletin As described in the above, there is still a problem to be improved in terms of discoloration over time. As described above, the chlorinated vinyl resin composition having no toxicity, electrical insulating properties, and thermal stability has been However, the inventors have found that in the case of the conventional conditions, it has been found that in the gasified vinyl resin containing light calcium carbonate, In addition to the above-mentioned power source insulation and heat resistance, the metal salt of the hydrotalcite compound, the organic acid zinc compound and the cold-diketone can be greatly improved to prevent the discoloration of the product over time. The invention is as follows: 1) A chlorinated vinyl resin composition characterized in that, in a vaporized ethylene resin, a light calcium carbonate, a hydrotalcite compound, and an organic acid zincation are formulated. And bis-ketone metal salts. 2) A vinyl chloride resin composition according to the first aspect of the patent application, wherein a light calcium carbonate having a specific surface area value of 5 m 2 /g or more is formulated. [Embodiment] In the present invention, the term "chlorinated vinyl resin" means a resin mainly composed of a vinyl chloride monomer or a vinyl chloride, such as ethylene chloride and vinyl acetate, ethylene oxide, ethylene, and propylene. a copolymer of methacrylate, urethane, a graft copolymer, or a blend of such resins, and the like. The light calcium carbonate used in the present invention is a white precipitate obtained by adding an alkali carbonate solution to an aqueous calcium salt solution, also referred to as "precipitated calcium carbonate". When 6 312 / invention specification (supplement) / 92-08/92116354 1299742 when the hydrotalcite compound is added together with the organic acid zinc compound in the vinyl chloride resin, the light calcium carbonate specific surface area value is 5 m2 / The above g has a large effect especially in terms of discoloration over time, but according to the present invention, even when a light calcium carbonate having a specific surface area value of 5 m 2 /g or more and 1 0 0 m 2 /g or less is used, It is still extremely effective in preventing long-term discoloration. The amount of the light calcium carbonate is from 0.1 to 200 parts by weight, preferably from 1 to 100 parts by weight, based on 100 parts by weight of the chlorinated ethylene resin. In the present invention, heavy calcium carbonate may be added under the condition that light calcium carbonate is used in combination. Heavy calcium carbonate is derived from natural calcium carbonate and can be produced in the form of calcite, vermiculite, limestone, marble, and chalk. The combination of heavy calcium carbonate is the same as that of light calcium carbonate. The hydrotalcite compound used in the present invention is generally wherein M2 + means at least one divalent cation selected from the group consisting of: Mg2+, Zn2+, Fe2+, Mn2+, Co2+, Ni2+, and Cu2+; M3 + means at least one trivalent cation selected from the group consisting of: Al3+, Fe3+, Cr3+, and Co3+; An_ refers to: or, C〇32_, S〇42_, n〇3- and At least one anion selected from the group consisting of Cl_; X represents the value of the line 0 < xS 0.33). Specific examples of the hydrotalcite-based compound include, for example, M g 6 A 12 ( 0 H h 6 C〇3.4H2〇, Mg4.5Al2 (OH: h3C〇3.3.5H2〇, Mg4.5Al2(OH)13C〇3, Mg3.5Zni.〇Al2(OH)i3C〇3*3.5H2〇, etc. Commercially available products are: STARBIACE HT-1, STARBIACE HT-7 > STARBIACE Η T - P (all manufactured by 堺Chemical Industries) Alga Mesha-1, Alga Mesa-2, Alga Mesha-3, Alga Mesa-4, Alga Mesha-5, D Η T - 4 A (all are 312/inventive manuals ( (1) The parts of the hydrotalcite-based compound are used in an amount of 0.1 to 10 parts by weight, preferably 10 parts by weight, based on 100 parts by weight of the chlorinated vinyl resin. 0. 5 parts by weight. The organic acid zinc compound used in the present invention contains a salt composed of a carboxylic acid and zinc, and the carboxylic acid may be a chain carboxylic acid (fatty acid) or an alicyclic carboxylic acid. Any one of an acid and an aromatic carboxylic acid, and the number of carboxyl groups in one molecule may be any of a monocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid, etc. Particularly, a fatty acid zinc is preferable, and for example, for example, :Steak Zinc or zinc palmitate, zinc myristate, zinc laurate, zinc octoate, zinc behenate, etc. The organic acid zinc is used in an amount of 0.05 parts by weight relative to 100 parts by weight of the chlorinated vinyl resin. Preferably, 0. 1 to 2. 0 parts by weight. The ruthenium-dione metal salt (or 1,3-diketone metal salt) used in the present invention means a general formula: RCOCH2COR' (wherein R and R' is a salt of a diketone or a dehydroacetic acid represented by the same or different carbon number 1 to 2 2 alkyl group or aryl group, and a metal (for example, zinc; or an alkaline earth metal such as calcium or magnesium). For example, salts of diphenylmethane methane, stearyl benzoquinone methane, palm phenyl hydrazine methane, phenyl hydrazine acetone, dehydroacetic acid and metals such as zinc; or alkaline earth metals such as calcium and magnesium may be mentioned. The /3 -dione metal salt is used in an amount of from 0.01 to 1 part by weight based on 100 parts by weight of the chlorinated vinyl resin. Preferably, 0 parts by weight is used. (Π~0. 5 parts by weight. In the present invention, a plasticizer, a filler, a thermal stabilizer, an antioxidant, an ultraviolet absorber, and an epoxidation used in a conventional chlorinated vinyl resin may be used in combination. a compound, a lubricant, a pigment, etc. The chlorinated vinyl resin composition of the present invention is blended into a light calcium carbonate, a hydrotalcite compound, and an organic acid zinc compound in a vinyl chloride resin. Pieces) /92-08/921163 54 1299742 The product and the cold-dione metal salt are obtained by kneading at a temperature of 1 Ο 0 to 2 2 ° ° C by a general method, and are used in the manufacture of a desired product. (Examples) Hereinafter, the present invention will be more specifically described by way of examples and comparative examples. (Examples 1 to 5 and Comparative Examples 1 to 2) Polyethylene oxide (degree of polymerization: 1 300) 100 parts by weight, DINP (diisononyl phthalate) 50 parts by weight, light weight Calcium carbonate (mixing amount: Table 1), zinc stearate 0.5 parts by weight, hydrotalcite 1.0 parts by weight, and the formulation of the additives shown in Table 1, at a temperature of 160 ° C for 5 minutes using a roller After the mixing, a sheet having a thickness of 1 mm was formed by using a press of 170 ° C. The obtained sheet was subjected to a constant temperature and humidity machine operated at 50 ° C and 90% humidity, and the presence or absence of discoloration over time was confirmed after exposure for 48 hours. Further, the heat resistance was evaluated by applying a press for 10 minutes (p r e s s ) using a press at 180 ° C, and then judging the discoloration possessed by the obtained sheet. In addition, the evaluation of electrical insulation is carried out in accordance with the method specified in J I S K - 6 7 2 3 . Each of the additives in the table is as follows. ·/?-dione: diphenyl decane • /3 -dione metal salt B: zinc dehydroacetate • stone-diketone metal salt C: diphenyl hydrazine methane zinc • light calcium carbonate: calcium strontium "V ig 〇t ο 1 0" (trade name), specific surface area: approx. 1 2 m2 / g • Heavy calcium carbonate: "Suofudong 1 5 Ο Ο" prepared by Kitami Powder Co., Ltd. (evaluation basis) ◎: No discoloration 〇: slight discoloration 312 / invention specification (supplement) / 92-08/92116354 1299742 X : large discoloration table 1 comparative example embodiment 1 2 1 2 3 4 5 polyvinyl chloride 100 100 100 100 100 100 100 DINP 50 50 50 50 50 50 50 Light calcium carbonate 20 30 20 20 30 30 30 Zinc stearate 0. 5 0. 5 0.5 0. 5 0.5 0. 5 0. 5 Hydrotalcite compound 1 1 1 1 1 1 1 Cold-diketone 0.1 0.1 cold-diketone metal salt B 0.1 0.1 0.05 /3 -dione metal salt C 0. 1 0. 1 0.05 Temporary discoloration XX ◎ ◎ ◎ ◎ ◎ Electrical insulation (Ω cm ) 2x 1012 6x 1012 4x 1013 5x 10 丨1 9x 1012 9x 1012 9x 10 丨2 财 ◎ ◎ ◎ From the results of Table 1 above, as shown in Examples 1 to 5, the light calcium carbonate is formulated. chlorine In the vinyl resin, by blending the hydrotalcite compound, the organic acid zinc compound, and the /3 -dione metal salt, it is possible to significantly improve the conventional properties (electrical insulation, thermal stability, etc.) without any loss of conventional properties (electrical insulation, thermal stability, etc.). Improves discoloration over time. On the other hand, as shown in Comparative Examples 1 and 2, even if cold-diketone was added, the effect of improving discoloration over time could not be exhibited. (Examples 6 to 10 and Comparative Examples 3 to 4) 100 parts by weight of polycondensed ethylene (degree of polymerization: 1300), 50 parts by weight of TOTM (trioctyl trimellitate), and light calcium carbonate (mixing Amount: Table 2), heavy calcium carbonate (formulation amount: Table 2), zinc stearate 1 · 0 parts by weight, hydrotalcite 1.0 parts by weight and the formulation of the additives shown in Table 2, at 1 60 ° C After 5 minutes of kneading with a roller, a sheet having a thickness of 1 mm was formed by using a press at 170 °C. The presence or absence of discoloration over time was confirmed after exposure to the constant temperature and humidity machine in which the obtained sheet was operated under the conditions of 50 °C and 90% humidity. The evaluation of the heat resistance was carried out by using a 180 °C press for 30 minutes of stamping, and then judging the discoloration possessed by the obtained sheet of 10 1 Π / invention specification (supplement) / 92-08/92l 16354 1299742. In addition, the evaluation of electrical insulation is carried out in accordance with the method specified in J I S K - 6 7 2 3 . Each of the additives in the table is as follows. •/3-dione: diphenyl decane • /3 -dione metal salt B: zinc dehydroacetate •/3-dione metal salt C: diphenyl hydrazine methane zinc (assessment basis) ◎: no discoloration 〇 : Slightly discolored X: Large discoloration Table 2 Comparative Example Example 3 4 6 7 8 9 10 Polyvinyl chloride 100 100 100 100 100 100 100 Τ0ΤΜ 50 50 50 50 50 50 50 Light calcium carbonate 20 30 20 20 30 30 30 Heavy calcium carbonate 20 20 20 20 20 20 20 Zinc stearate 1 1 1 1 1 1 1 Hydrotalcite compound 1 1 1 1 1 1 1 /3 - Dione 0.1 0.1 /3 -dione metal salt B 0. 1 0.1 0.05 /3 -dione metal salt C 0.1 0. 1 0.05 Temporary discoloration XX ◎ ◎ ◎ ◎ Electrical insulation (Ω cm ) lx 1013 5x 10 丨2 2x 10 丨3 3x 1013 8x 10 丨2 9x 10丨2 8x 10 丨2 Finance ◎ 〇〇〇 ◎ ◎ ◎ From the results of Table 2 above, as shown in Example - Example 6~10, chlorinated ethylene blended with light calcium carbonate and heavy calcium carbonate In the resin, by blending a hydrotalcite compound, an organic acid zinc compound and a/5-diketone metal salt, the conventional properties (electrical insulation, heat stability) can be obtained without any loss. Case, etc.), when the discoloration was significantly improved. In other words, heavy calcium carbonate can also be used when blending light calcium carbonate. On the other hand, as shown in Comparative Examples 3 and 4, 11 312 / invention specification (supplement) / 92-08/921163 54 1299742. The talc is not provided with a fruit, and the metal collar does not exhibit an improvement in discoloration over time even if a /3 -dione is added (industrial availability). As described above, the vaporized ethylene-based resin composition of the present invention Because it is non-toxic with lead-based stabilizers, and it can be used to match the electrical insulation of lead-based stabilizers by blending light calcium carbonate, water compounds, zinc compounds of organic acids and /3 -dione metal salts. In addition to thermal stability, it is particularly advantageous to prevent discoloration over time. The preventive effect of this discoloration over time is mainly due to the coexistence of light calcium carbonate and /3 -dione salt in the present composition. Therefore, it can be effectively used in a wide range of areas such as electrical relations. 12 312/Invention Manual (supplement)/92-08/92116354