TW200413462A - Vinyl chloride resin composition - Google Patents

Vinyl chloride resin composition Download PDF

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Publication number
TW200413462A
TW200413462A TW092116354A TW92116354A TW200413462A TW 200413462 A TW200413462 A TW 200413462A TW 092116354 A TW092116354 A TW 092116354A TW 92116354 A TW92116354 A TW 92116354A TW 200413462 A TW200413462 A TW 200413462A
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TW
Taiwan
Prior art keywords
calcium carbonate
vinyl chloride
resin composition
zinc
light calcium
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TW092116354A
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Chinese (zh)
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TWI299742B (en
Inventor
Koichi Tsuda
Takanobu Osima
Toshihiro Nishii
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Sakai Chemical Industry Co
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Publication of TW200413462A publication Critical patent/TW200413462A/en
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Publication of TWI299742B publication Critical patent/TWI299742B/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

This invention relates to a kind of vinyl chloride resin composition, which is formed by adding light calcium carbonate, hydrotalcite compound, zinc organic acid compound and β -dione metal salt in a vinyl chloride resin, in which the light calcium carbonate preferably has a specific surface area value greater than 5 m2/g. The invented vinyl chloride resin composition is not toxic, has excellent electrical insulation and thermal stability and can prevent coloration over time.

Description

200413462 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 具有可防止經時變色性之特點的氯化乙烯系樹脂 【先前技術】 在氯化乙稀樹脂中，於提昇成形加工時的耐熱 性，以及提昇產品的電絕緣性、機械物性之目的 入各種添加劑。譬如當使用於電線、絕緣膠布等 況時，電絕緣性、熱安定性為必要者，習知便有 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 提案有取代鉛系安定劑而改採用屬於無毒性安定 石類化合物、脂肪酸鋅、/3 -二酮化合物或其金；! 曰本專利特開平5 - 6 5 3 8 0號公報）。調配有此無毒 的氣化乙稀糸樹脂組成物’在電絕緣性、熱安定 性方面具優越效果。但是，在另一方面，若該等 定劑在對產品外觀（表面）賦予光澤之目的下而調 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 系樹脂組成物，除日本專利特開平5 - 6 5 3 8 0號公 載者之外，亦提案有含水滑石類化合物與受阻胺 的氯化乙烯系樹脂組成物（參照曰本專利特開平 號公報）。此氯化乙烯系樹脂組成物亦如同上述曰 312/發明說明書(補件)/92-08/92116354 ，係關於 外，特別 組成物。 性或加工 下，調配 用途之情 使用如： 受重視， 劑的水滑 8鹽（參照 性安定劑 性、著色 無毒性安 配入輕質 氣化乙烯 報中所記 系化合物 5-271506 本專利特 5 200413462 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 現在含有輕質碳酸妈的氯化乙稀系樹脂中，藉由調配入水 滑石類化合物、有機酸鋅化合物及/3 -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-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以上的輕質碳酸妈。 【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、曱基丙烯酸酯、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|弓係在_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 200413462 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 皿2 + 1-^3 + “01〇2八11-"，111112〇(其中，^12 + 係指由：河22+、2112+、200413462 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a vinyl chloride resin composition; in particular, it is non-toxic and has excellent electrical insulation and thermal stability properties, which can prevent discoloration over time. Chlorinated vinyl based resins [Prior technology] Various additives are added to chlorinated vinyl resins for the purpose of improving the heat resistance during molding and improving the electrical insulation and mechanical properties of products. For example, when it is used in electric wires and insulating tapes, electrical insulation and thermal stability are necessary. Lead-based stabilizers such as tribasic lead sulfate and lead stearate are conventionally known. However, in recent years, with environmental protection issues such as human safety, it has been proposed to replace lead-based stabilizers with non-toxic stabilizers, zinc fatty acids, / 3-diketone compounds, or gold; 5-6 5 3 8 0). Blending this non-toxic, gasified ethylene resin composition ′ has excellent effects in terms of electrical insulation and thermal stability. However, on the other hand, if the calcium carbonate is adjusted for the purpose of imparting gloss to the appearance (surface) of the product, a new problem arises in that the color changes with time. In addition, instead of lead-based stabilizers, non-toxic stabilizer-based resin compositions have been proposed, in addition to those disclosed in Japanese Patent Laid-Open No. 5-6 5 3 8 0, and hydrotalcite compounds and hindered amines have also been proposed. Chlorinated vinyl resin composition (refer to Japanese Patent Application Laid-open No. Hei. This chlorinated vinyl-based resin composition is similar to the above-mentioned 312 / Invention Specification (Supplement) / 92-08 / 92116354, which is a special composition other than the above. In the case of sex or processing, the use of the formulation is as follows: Attach great importance to the water-sliding 8 salt of the agent (refer to stabilizers, coloring non-toxic, and compound into the compound described in the lightweight gasification ethylene newspaper 5-271506. This patent As described in Japanese Patent Publication No. 5 200413462, Kaiping No. 5-6 5 3 8 0, in terms of changing color over time, # remains to be improved. As mentioned above, so far, it has no toxicity, electrical insulation, Although thermally stable vinyl chloride resin composition has been developed, the problem of discoloration with time remains. [Summary of the Invention] The present inventors have found out in In the light-weight carbonic acid-containing chlorinated vinyl resin, by mixing hydrotalcite-based compounds, organic acid zinc compounds, and / 3-dione metal salts, in addition to the above-mentioned power supply insulation properties and heat resistance, The effect of preventing the product from changing color over time is greatly improved. In other words, the present invention is as follows: 1) A chlorinated vinyl resin composition, characterized in that light carbonic acid is blended into a gasified vinyl resin. , Hydrotalcite compound, an organic zinc compound and - dione metal. 2) The vinyl chloride-based resin composition according to item 1 of the scope of the patent application, wherein a light carbonated carbon dioxide having a specific surface area value of 5 m2 / g or more is blended. [Embodiment] In the present invention, the "chlorinated vinyl resin" refers to a resin mainly composed of a vinyl chloride polymer alone or vinyl chloride, such as vinyl chloride and vinyl acetate, vinylidene chloride, ethylene, propylene, Copolymers of fluorenyl acrylates and urethanes, graft copolymers, or blends of these resins. The light carbonic acid used in the present invention is a white precipitate obtained when an alkali carbonate solution is added to a saline solution, which is also called "precipitated calcium carbonate". When 6 312 / Invention Note (Supplement) / 92-08 / 92116354 200413462 added hydrotalcite compounds and organic acid zinc compounds to vinyl chloride resins, the specific surface area of light calcium carbonate was 5 m2 Those above / g have a greater effect on discoloration over time, but according to the present invention, even when light calcium carbonate having a specific surface area value of 5 m2 / g or more and 100 m2 / g or less is used, , Can still be extremely effective in preventing long-term discoloration. The amount of the light calcium carbonate is 0.1 to 200 parts by weight, and preferably 1 to 100 parts by weight relative to 100 parts by weight of the vinyl chloride-based 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, chalk, etc. The combined use of heavy calcium carbonate can be the same as that of light calcium carbonate. The general formula of the hydrotalcite compounds used in the present invention is D 2 + 1- ^ 3 + "01〇2 八 11- ", 111112〇 (where, ^ 12 + means: 22+, 211-2,

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：ΑΓ+、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：0ΙΓ、 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 1 2 ( 0 Η )! 6 CO”4H2〇、Mg4.5Al2(OH)13C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、ST ARB I ACE HT-7、STARBI ACE HT-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 7 312/發明說明書(補件)/92-08/92116354 200413462 和化學工業公司製）等。 ’ 該等水滑石類化合物係相對於氣化乙烯系樹脂1 〇 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：硬脂酸鋅或棕橺酸鋅、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/3 -二酮金屬鹽（或1，3 -二酮金屬鹽） 係指一般式：R C 0 C Η 2 C 0 R ’（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 苯醯曱烷、硬脂醯基苯醯甲烷、棕櫚醯基苯醯曱烷、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氣化乙烯系樹脂1 〇 〇重量份 而使用0 . 0 0 1〜1 . 0重量份，最好使用0 . 0 1〜0 · 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。 本發明的氯化乙稀系樹脂組成物係在氯化乙稀樹脂 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 200413462 物及/3 -二酮金屬鹽，利用一般方法在1 0 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 ) 將聚氯化乙烯（聚合度1300)100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，财熱性的評估係利 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 • /3 -二酮金屬鹽C :二苯醯甲烷鋅 •輕質碳酸鈣：日石鈣產製「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 9 312/發明說明書(補件)/92-08/921163 54 200413462 X :大幅變色 表1 比較例 實施例 1 2 1 2 3 4 5 聚氯化乙稀 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 /3 -二酮金屬鹽B 0.1 0.1 0.05 冷-二S同金屬鹽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 10丨3 5x 1013 9x 1012 9x 1012 9x 10】2 对熱性 ◎ 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/3 -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、Τ0ΤΜ(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4 8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 10 312/發明說明書(補件)/92-08/92116354 200413462 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。 •石-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 :二苯醯曱烷鋅 (評估基準） ◎:無變色 〇：略變色 X :大幅變色 表 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 yS -二酮 0. 1 0.1 泠-二酮金屬鹽B 0.1 0. 1 0. 05 yS -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 10丨3 8x 10 丨2 9x 10丨2 8x 10】2 耐熱性 ◎ 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/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。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 200413462 即便添加/3 -二酮，仍無法顯現出經時變色性的改善效果。 (產業上可利用性） 如上所述，本發明的氯化乙烯系樹脂組成物乃因為未使 用鉛系安定劑而無毒性，且藉由調配輕質碳酸鈣、水滑石 類化合物、有機酸鋅化合物及/3 -二酮金屬鹽，除可獲得可 匹敵於鉛系安定劑的電絕緣性與熱安定性之外，特別具有 可防止經時變色性的極大優點。此經時變色的防止效果， 主要乃因為本組成物中，共存著輕質碳酸鈣與/3 -二酮金屬 鹽的緣故所致。所以，實際可有效廣泛使用於電氣關係領 域等範疇中。 12 312/發明說明書(補件)/92-08/92116354At least one divalent cation selected from the group consisting of Fe2 +, Mn2 +, Co2 +, Ni2 +, and Cu2 +; M3 + means at least one selected from the group consisting of: AΓ +, Fe3 +, Cr3 +, and Co3 + A trivalent cation; An_ refers to at least one anion selected from the group consisting of: 0Γ, co32-, so42-, no03- and Cl_; X represents an 0 < xS0.33 Value). Specific examples of the hydrotalcite-based compound include, for example: M g 6 A 1 2 (0 Η)! 6 CO ”4H2〇, Mg4.5Al2 (OH) 13C〇3.3.5H2〇, Mg4.5Al2 (OH) 13C〇3 , Mg3.5Zni.〇Al2 (OH) i3C〇3 * 3.5H2〇, etc. Commercial products are: STARBIACE HT-1, ST ARB I ACE HT-7, STARBI ACE HT-P System), Alga Matsa-1, Alga Matsa-2, Alga Matsa-3, Alga Matsa-4, Alga Matsa-5, D Η T-4 A (all 7 312 / Invention specification (Supplement) / 92-08 / 92116354 200413462 and Chemical Industry Co., Ltd.) etc. 'These hydrotalcite-based compounds are used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the gasified vinyl resin. Part by weight, preferably from 0.5 to 5.0 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). , Alicyclic carboxylic acid, aromatic carboxylic acid, and the number of carboxyl groups in one molecule may be any of monocarboxylic acid, dicarboxylic acid, tricarboxylic acid, etc. Especially preferred is zinc fatty acid, This example could be: stearic acid Or zinc palmitate, zinc myristate, zinc laurate, zinc octoate, zinc behenate, etc. Zinc organic acid is used in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the vinyl chloride resin. Preferably, 0.1 to 2.0 parts by weight are used. The / 3-diketone metal salt (or 1,3-diketone metal salt) used in the present invention refers to the general formula: RC 0 C Η 2 C 0 A diketone or dehydroacetic acid represented by R '(where R and R' are the same or different alkyl groups and aryl groups having 1 to 2 carbon atoms) and metals (such as: zinc; or alkaline earth such as calcium and magnesium) Metal) salts. Specific examples may include: diphenylmethane, stearylmethane, methane, palmityl, phenylmethane, phenylmethane, acetone, dehydroacetic acid and metals such as zinc; or calcium, Alkaline earth metals such as magnesium) salts. / 3-diketone metal salts are used in an amount of 0.000 1 to 1.0 parts by weight based on 1,000 parts by weight of the gasified ethylene-based resin, and preferably 0.0. 1 to 0. 5 parts by weight. In the present invention, plasticizers, fillers, heat stabilizers, antioxidants, and ultraviolet absorbers used in conventional vinyl chloride resins may be used in combination. Agents, epoxy compounds, lubricants, pigments, etc. The chlorinated ethylene resin composition of the present invention is based on chlorinated ethylene resin, and is blended with light calcium carbonate, hydrotalcite compounds, and zinc organic acid compound 8 312 / Invention specification (Supplement) / 92-08 / 921163 54 200413462 and / 3-dione metal salt, obtained by mixing and training at 100 ~ 2 2 0 ° C by a general method, and used in all The required products are being manufactured. (Examples) Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. (Examples 1 to 5 and Comparative Examples 1 to 2) 100 parts by weight of polyvinyl chloride (polymerization degree 1300), 50 parts by weight of DINP (diisononyl phthalate), light calcium carbonate (mixed Amount: Table 1), 0.5 parts by weight of zinc stearate, 1.0 part by weight of hydrotalcite, and the additives shown in Table 1, knead with a roller for 5 minutes at 160 ° C, and then Sheets with a thickness of 1 mm were made using a press at 170 ° C. The obtained sheet was exposed to a constant temperature and humidity machine operating at 50 ° C and 90% humidity for 48 hours, and then the presence or absence of discoloration was confirmed. In addition, the evaluation of financial and thermal properties was performed by pressing at 180 ° C for 10 minutes (pres s), and then the discoloration property of the obtained sheet was judged. In addition, the evaluation of electrical insulation is performed in accordance with the method specified by J I S K-6 7 2 3. Each additive in the table is as shown below. · /?-Diketone: Dibenzoxane • / 3 -dione metal salt B: Dehydro zinc acetate • / 3 -dione metal salt C: Zinc diphenylmethane • Light calcium carbonate: Nissan calcium Produced "V ig 〇 1 0" (trade name), specific surface area: about 12 m 2 / g • Heavy calcium carbonate: "Suofudong 1 5 Ο Ο" manufactured by Beibei Powder Co., Ltd. (evaluation standard) ◎ : No discoloration 0: Slight discoloration 9 312 / Invention specification (Supplement) / 92-08 / 921163 54 200413462 X: Large discoloration Table 1 Comparative Example Example 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 0.5 0.5 Hydrotalcite 1 1 1 1 1 1 1 Cold-diketone 0.1 1 0. 1 / 3-diketone metal salt B 0.1 0.1 0.05 Cold-diketone with metal salt C 0. 1 0. 1 0.05 Color change over time XX ◎ ◎ ◎ ◎ ◎ Electrical insulation (Ω cm) 2x 1012 6x 1012 4x 10 丨 3 5x 1013 9x 1012 9x 1012 9x 10】 2 Thermal resistance ◎ 〇〇〇 ◎ ◎ ◎ From the results in Table 1 above, as shown in Examples 1 to 5 With light calcium carbonate By blending a hydrotalcite compound, a zinc organic acid compound, and a / 3-diketone metal salt in a vinyl chloride-based resin, the conventional properties (electrical insulation, thermal stability, etc.) can be maintained without impairing the conventional properties. , Obviously improve the discoloration with time. In contrast, as shown in Comparative Examples 1 and 2, even when / 3-dione was added, the effect of improving the discoloration with time could not be exhibited. (Examples 6 to 10 and Comparative Examples 3 to 4) 100 parts by weight of polygasified ethylene (polymerization degree 1300), 50 parts by weight of TOTM (trioctyl trimellitate), light calcium carbonate (mixed Amount: Table 2), heavy calcium carbonate (Mixed amount: Table 2), 1.0 parts by weight of zinc stearate, 1.0 part by weight of hydrotalcite and the additives shown in Table 2, at 160 ° C After kneading with a roller for 5 minutes, a sheet with a thickness of 1 mm was made using a press at 170 ° C. The obtained sheet was subjected to a constant temperature and humidity machine operated at 50 ° C and a humidity of 90%, and the presence or absence of discoloration with time was confirmed after 48 hours of exposure. The heat resistance was evaluated by using a press at 180 ° C for 30 minutes, and then judging the obtained 10 312 / Invention Specification (Supplement) / 92-08 / 92116354 200413462 for the discoloration of the sheet. In addition, the evaluation of electrical insulation is performed in accordance with the method specified by J I S K-6 7 2 3. Each additive in the table is as shown below. • Lithium-dione: dibenzoxane • / 3-dione metal salt B: zinc dehydroacetate • / 3-dione metal salt C: zinc diphenylfluorene (evaluation standard) ◎: No discoloration. : Slight discoloration X: Large discoloration table Comparative Example Example 3 4 6 7 8 9 10 Polyvinyl chloride 100 100 100 100 100 100 100 100 T0 50 50 50 50 50 50 50 Light calcium carbonate 20 30 20 20 30 30 30 Heavy Quality calcium carbonate 20 20 20 20 20 20 20 zinc stearate 1 1 1 1 1 1 1 hydrotalcite compounds 1 1 1 1 1 1 1 yS-dione 0.1 1 0.1 ling-dione metal salt B 0.1 0. 1 0. 05 yS -Diketone metal salt C 0.1 0. 1 0.05 Color change over time XX ◎ ◎ ◎ ◎ ◎ Electrical insulation (Ω cm) lx 1013 5x 10 丨 2 2x 10 丨 3 3x 10 丨 3 8x 10 丨2 9x 10 丨 2 8x 10】 2 Heat resistance ◎ 〇〇〇 ◎ ◎ ◎ From the results in Table 2 above, as shown in Examples 6 to 10, light calcium carbonate and heavy calcium carbonate were blended with chlorine. By blending a hydrotalcite compound, an organic zinc compound, and a / 3-diketone metal salt in a vinyl resin, the conventional properties (electrical insulation and thermal stability) can be maintained without loss. Under), where, when significant discoloration was improved. In other words, when formulating light calcium carbonate, heavy calcium carbonate can also be used. In contrast, as shown in Comparative Examples 3 and 4, 11 312 / Invention Specification (Supplement) / 92-08 / 921163 54 200413462 Even if / 3-dione was added, the effect of improving the discoloration with time could not be exhibited. (Industrial Applicability) As described above, the vinyl chloride-based resin composition of the present invention is non-toxic because it does not use a lead-based stabilizer, and is blended with light calcium carbonate, a hydrotalcite-based compound, and zinc organic acid. The compound and the / 3-diketone metal salt have the great advantage of being able to rival the lead-based stabilizers in terms of electrical insulation and thermal stability, as well as preventing discoloration over time. This effect of preventing discoloration with time is mainly due to the coexistence of light calcium carbonate and a metal salt of / 3-dione in the composition. Therefore, it can be effectively and widely used in the fields of electrical relations. 12 312 / Invention Specification (Supplement) / 92-08 / 92116354

Claims (1)

200413462 拾、申請專利範圍： 1. 一種氯化乙烯系樹脂組成物，其特徵為，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 化合物及/3 -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，調配著比表面積為5 m2 / g以上的輕質碳酸鈣。 13 312/發明說明書(補件)/92-08/921163 54 200413462 柒、指定代表圖： (一） 本案指定代表圖為：第（ ）圖。 (二) 本代表圖之元件代表符號簡單說明： 無 捌、本案若有化學式時，請揭示最能顯示發明特徵的化學式： 無 4 312/發明說明書(補件)/92-08/92116354200413462 Scope of patent application: 1. A chlorinated vinyl resin composition, characterized in that light calcium carbonate, hydrotalcite compounds, zinc organic acid compounds and / 3-2 are blended into the chlorinated vinyl resin. Ketone metal salt. 2. The vinyl chloride-based resin composition according to item 1 of the patent application range, wherein a light calcium carbonate having a specific surface area of 5 m2 / g or more is blended. 13 312 / Invention Specification (Supplement) / 92-08 / 921163 54 200413462 柒. Designated Representative Map: (1) The designated representative map in this case is: (). (II) Brief description of the representative symbols of the components in this representative diagram: None 捌 If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None 4 312 / Invention Specification (Supplement) / 92-08 / 92116354
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CN104194188A (en) * 2014-07-28 2014-12-10 安徽威萨重工机械有限公司 Polyvinyl chloride cable material
CN109593291A (en) * 2018-10-29 2019-04-09 赵顺全 A kind of preparation method of the medicinal stiff sheet of thermostabilization PVC

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CN1260289C (en) 2006-06-21
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TWI299742B (en) 2008-08-11
CN1517399A (en) 2004-08-04

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