JP2008031397A

JP2008031397A - Chlorine-containing resin composition

Info

Publication number: JP2008031397A
Application number: JP2006227138A
Authority: JP
Inventors: Shigehiro Koga; 重宏古賀
Original assignee: DAIDO KASEI KK
Current assignee: DAIDO KASEI KK
Priority date: 2006-07-28
Filing date: 2006-07-28
Publication date: 2008-02-14

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which can be subjected to processing with long-term stability in a usual processing temperature range by any processing method, by adding a chlorinated polyethylene and a relatively inexpensive heat stabilizer to a vinylidene chloride resin and a vinyl chloride resin and without impairing the characteristics of the both resins. <P>SOLUTION: The resin composition is formed by adding, to 100 parts by weight of a vinylidene chloride resin and a vinyl chloride resin in total, one or more part by weight of a chlorinated polyethylene and 0.5-10.0 parts by weight of hydrotalcite expressed by chemical formula [Mg<SB>2</SB>Al(OH)<SB>16</SB>CO<SB>3</SB>4H<SB>2</SB>O]. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は塩化ビニリデン樹脂と塩化ビニル樹脂の混合物の熱安定性、加工性に関するもので、いかなる加工法においても、両樹脂の特徴を生かしつつ、通常の加工温度で長時間安定して加工できる樹脂組成物に関する。 The present invention relates to the thermal stability and processability of a mixture of a vinylidene chloride resin and a vinyl chloride resin, and in any processing method, a resin that can be processed stably for a long time at a normal processing temperature while taking advantage of the characteristics of both resins. Relates to the composition.

塩化ビニリデン樹脂は塩化ビニル樹脂と違って結晶性樹脂であり単純に混合混練しても均一に分散せずその物理的性質は非常に弱く脆い。且つ、塩化ビニリデン樹脂は塩化ビニル樹脂に比べて非常に熱安定性が悪く、且つ汎用加工法における加工温度範囲が狭い。即ち塩化ビニル樹脂用の汎用的な熱安定剤を用いた場合、押出加工温度範囲である１５０〜１８０℃では１０分前後で急速に脱塩酸反応を起こし劣化、黒化してしまう。又、両樹脂の改質剤、相溶化剤として塩素化ポリエチレンを用いることは公知の事実であるが、上述の現象により実用化には至っていない。 Unlike vinyl chloride resin, vinylidene chloride resin is a crystalline resin, and even if it is simply mixed and kneaded, it does not disperse uniformly and its physical properties are very weak and brittle. In addition, vinylidene chloride resin has very poor thermal stability as compared with vinyl chloride resin, and the processing temperature range in a general-purpose processing method is narrow. That is, when a general-purpose heat stabilizer for vinyl chloride resin is used, the dehydrochlorination reaction is rapidly caused in about 10 minutes at the extrusion temperature range of 150 to 180 ° C., resulting in deterioration and blackening. Although it is a known fact that chlorinated polyethylene is used as a modifier and compatibilizer for both resins, it has not been put into practical use due to the phenomenon described above.

本発明は塩化ビニリデン樹脂と塩化ビニル樹脂の混合物に塩素化ポリエチレン及び比較的安価な熱安定剤を添加することにより両樹脂の特徴を損なうことなく、いかなる加工法においても、通常の加工温度範囲で長時間、安定して加工生産できる樹脂組成物を提供することを課題とする。 The present invention adds a chlorinated polyethylene and a relatively inexpensive heat stabilizer to a mixture of a vinylidene chloride resin and a vinyl chloride resin, and does not impair the characteristics of both resins. It is an object to provide a resin composition that can be processed and produced stably for a long time.

本発明者は本課題を解決するために様々な工夫を試みたが、その中で化学式（Ｍｇ_２ＡＬ（ＯＨ）_１６ＣＯ_３・４Ｈ_２Ｏ）で表されるハイドロタルサイトのみが両樹脂及び塩素化ポリエチレンの混合物に対して特異な熱安定性を示すことを見出し本発明を完成させた。即ち、塩化ビニリデン樹脂１０〜９０重量部、塩化ビニル樹脂９０〜１０重量部、あわせて１００重量部に対して塩素化ポリエチレン１、０重量部以上、化学式（Ｍｇ_２ＡＬ（ＯＨ）_１６ＣＯ_３・４Ｈ_２Ｏ）で表されるハイドロタルサイト０．５〜１０重量部よりなる熱安定性、加工性、物理的性質の改良された樹脂組成物である。The present inventor has tried various devices to solve the problem, and only hydrotalcite represented by the chemical formula (Mg ₂ AL (OH) ₁₆ CO ₃ .4H ₂ O) is included in both resins and The present invention has been completed by finding that it exhibits a specific thermal stability with respect to a mixture of chlorinated polyethylene. That is, 10 to 90 parts by weight of vinylidene chloride resin, 90 to 10 parts by weight of vinyl chloride resin, and 100 parts by weight of chlorinated polyethylene, 0 parts by weight or more, chemical formula (Mg ₂ AL (OH) ₁₆ CO _3. It is a resin composition with improved thermal stability, workability, and physical properties comprising 0.5 to 10 parts by weight of hydrotalcite represented by 4H ₂ O).

本発明の樹脂組成物を用いることにより、塩化ビニリデン樹脂のもつ機能的特性である耐熱性、ガスバリヤー性、難燃性、耐薬品性を損なうことなく、塩化ビニル樹脂の持つ特性、例えば耐候性、加工性、物理的性質を生かした製品を作ることが出来る。且つ本樹脂組成物には特別高価な化合物を含んでいないので比較的安価であり、経済性、実用性に優れている。 By using the resin composition of the present invention, the characteristics of vinyl chloride resin, such as weather resistance, without impairing the functional properties of vinylidene chloride resin, such as heat resistance, gas barrier properties, flame retardancy, and chemical resistance. , Making use of processability and physical properties. In addition, since the resin composition does not contain a particularly expensive compound, it is relatively inexpensive and excellent in economic efficiency and practicality.

ここで云う塩化ビニリデン樹脂とは通常塩化ビニリデンと他の単量体例えば塩化ビニル、アクリル酸エステル、酢酸ビニル等との共重合体であるが、塩化ビニリデン成分が５０重量％以上のものを云う。 The vinylidene chloride resin referred to here is usually a copolymer of vinylidene chloride and other monomers such as vinyl chloride, acrylate ester, vinyl acetate, etc., and means a vinylidene chloride component of 50% by weight or more.

ここで云う塩化ビニル樹脂とは塩化ビニル単独重合体の他に例えばアクリル酸エステル、酢酸ビニル、エチレン、プロピレン等のオレフィン等の共重合体も含み、塩化ビニル成分が６０重量％以上のものを云う。 The vinyl chloride resin referred to here includes, in addition to a vinyl chloride homopolymer, for example, a copolymer of an olefin such as an acrylate ester, vinyl acetate, ethylene, propylene, etc., and a vinyl chloride component of 60% by weight or more. .

本発明に用いられる塩素化ポリエチレンとは溶融指数（メルトインデックス）が０．１〜１０で塩素含有量が２０〜４５重量％のものが好ましい。形状は粒状よりも均一に分散しやすい粉末状が望ましい。添加量は１．０重量部以上であり１．０重量部以下では効果が充分でない。 The chlorinated polyethylene used in the present invention preferably has a melt index (melt index) of 0.1 to 10 and a chlorine content of 20 to 45% by weight. The shape is preferably a powder form that is more easily dispersed uniformly than a granular form. The addition amount is 1.0 part by weight or more, and if it is 1.0 part by weight or less, the effect is not sufficient.

本発明に用いられるハイドロタルサイトとは化学式（Ｍｇ_２ＡＬ（ＯＨ）_１６ＣＯ_３・４Ｈ_２Ｏ）で表され別名ハイドロタルク石、或いはマナセアイトとも呼ばれ、天然に産する。塩化ビニリデン樹脂１００重量部に対して０．５〜１０．０重量部好ましくは１．０〜５．０重量部添加される。０．５重量部以下では効果が充分ではなく、１０重量部以上添加しても効果は変わらない。The hydrotalcite used in the present invention is represented by a chemical formula (Mg ₂ AL (OH) ₁₆ CO ₃ .4H ₂ O), and is also called hydrotalcite or manaceite, and is naturally produced. 0.5 to 10.0 parts by weight, preferably 1.0 to 5.0 parts by weight, are added to 100 parts by weight of vinylidene chloride resin. If the amount is 0.5 parts by weight or less, the effect is not sufficient, and the effect is not changed even if 10 parts by weight or more is added.

この他に添加剤として必要に応じて、酸化防止剤、滑剤、強化剤、スリップ剤、帯電防止剤、顔料、無機及び有機の充填剤等を添加することは一向に差し支えない。更に他樹脂と混合・混練してブレンド物を作る場合も本組成物は有効である。 In addition to this, it is possible to add an antioxidant, a lubricant, a reinforcing agent, a slip agent, an antistatic agent, a pigment, an inorganic or organic filler, and the like as necessary. Furthermore, the composition is also effective when a blend is made by mixing and kneading with another resin.

本発明の樹脂組成物は通常の混合装置例えばヘンシェルミキサー（商品名）、スーパーミキサー（商品名）、リボンブレンダー等を用いて混合し、直接又は押出機等で造粒後、射出成形法、押出し成形法、ブロー成形法、プレス成形法、カレンダー成形法等により目的とする成形品の製造に供される。 The resin composition of the present invention is mixed using an ordinary mixing apparatus such as a Henschel mixer (trade name), a super mixer (trade name), a ribbon blender, etc., and granulated directly or by an extruder, followed by an injection molding method or extrusion. It is used for production of a desired molded product by a molding method, a blow molding method, a press molding method, a calendar molding method, or the like.

比較例１Comparative Example 1

塩化ビニリデン樹脂（塩化ビニル２０重量％を含む共重合体）１００重量部に対して塩素化ポリエチレン（ダイソー社製ダイソラックＧ２４５）５重量部及びハイドロタルサイト２．０重量部を添加し、ロール温度１６０℃にセットした８インチロールに投入した。そしてこの組成物が熱分解寸前迄の時間即ちロールに粘着するまでの時間を測定した。又上記と同一配合、同一条件で５分間混練し約１．２ミリメートル厚のシートを作成した。このシートを２枚重ねて１６０℃にセントしたプレス機で２ミリメートル厚のシートを作成し、ＪＩＳＡ６００８に準じてショパー式引張り試験機で引張強度及び伸びを測定した。更にＪＩＳＫ７２０６に準ずる軟化温度試験法により耐熱性の評価を行った。（結果を［表１］に記す）5 parts by weight of chlorinated polyethylene (Daisolac G245 manufactured by Daiso Corporation) and 2.0 parts by weight of hydrotalcite are added to 100 parts by weight of vinylidene chloride resin (a copolymer containing 20% by weight of vinyl chloride), and the roll temperature is 160. It put into an 8-inch roll set at ° C. The time until the composition was just before thermal decomposition, that is, the time until the composition adhered to the roll was measured. A sheet having a thickness of about 1.2 millimeters was prepared by kneading for 5 minutes under the same composition and conditions as above. Two sheets of this sheet were stacked to produce a 2 mm thick sheet with a press machine that was centric at 160 ° C., and the tensile strength and elongation were measured with a shopper type tensile tester according to JIS A6008. Furthermore, heat resistance was evaluated by a softening temperature test method according to JISK7206. (The results are shown in [Table 1])

比較例２Comparative Example 2

塩化ビニル樹脂（カネカ社製Ｓ１００１）１００重量部に対し比較例１で用いた塩素化ポリエチレン５重量部、ハイドロタルサイト２重量部を添加し比較例１と同様の条件及び方法で熱分解時間を測定した。更に比較例１と同様の条件及び方法でサンプルを作成し引張強度、伸びを測定、耐熱性の評価を行った。（結果を［表１］に記す） 5 parts by weight of chlorinated polyethylene and 2 parts by weight of hydrotalcite used in Comparative Example 1 were added to 100 parts by weight of a vinyl chloride resin (S1001 manufactured by Kaneka Corporation), and the thermal decomposition time was adjusted under the same conditions and method as in Comparative Example 1. It was measured. Further, a sample was prepared under the same conditions and method as in Comparative Example 1, the tensile strength and elongation were measured, and the heat resistance was evaluated. (The results are shown in [Table 1])

比較例３Comparative Example 3

比較例１で用いた塩化ビニリデン樹脂５０重量部、比較例２で用いた塩化ビニル樹脂５０重量部合わせて１００重量部に対してハイドロタルサイト２．０を添加し比較例１と同様の条件及び方法で熱分解時間を測定した。更に比較例１と同様の条件及び方法でサンプルを作成し引張強度、伸びを測定、耐熱性の評価を行った。（結果を［表１］に記す）Hydrotalcite 2.0 was added to 100 parts by weight of 50 parts by weight of the vinylidene chloride resin used in Comparative Example 1 and 50 parts by weight of the vinyl chloride resin used in Comparative Example 2, and the same conditions as in Comparative Example 1 and The pyrolysis time was measured by the method. Further, a sample was prepared under the same conditions and method as in Comparative Example 1, the tensile strength and elongation were measured, and the heat resistance was evaluated. (The results are shown in [Table 1])

比較例４、実施例１，２Comparative Example 4, Examples 1 and 2

比較例１、２で用いた塩化ビニリデン樹脂５０重量部、塩化ビニル樹脂５０重量部、塩素化ポリエチレン５重量部に対し、ハイドロタルサイト０，３、１．０、２．０重量部を夫々添加し、比較例１と同様の条件及び方法で熱分解時間を測定した。更に比較例１と同様の条件及び方法でサンプルを作成し引張強度、伸びを測定、耐熱性の評価を行った。（結果を［表１］に記す） Hydrotalcite 0, 3, 1.0, and 2.0 parts by weight were added to 50 parts by weight of vinylidene chloride resin, 50 parts by weight of vinyl chloride resin, and 5 parts by weight of chlorinated polyethylene used in Comparative Examples 1 and 2, respectively. The pyrolysis time was measured under the same conditions and method as in Comparative Example 1. Further, a sample was prepared under the same conditions and method as in Comparative Example 1, the tensile strength and elongation were measured, and the heat resistance was evaluated. (The results are shown in [Table 1])

比較例５，６Comparative Examples 5 and 6

比較例１，２で用いた塩化ビニリデン樹脂５０重量部、塩化ビニル樹脂５０重量部、塩素化ポリエチレン５重量部に対して、錫系安定剤（アデカ社製アデカスタブ４６５Ｅ）２重量部又はバリウムー亜鉛系複合安定剤（アデカ社製アデカスタブＡＣ２９０）２重量部を夫々添加し、比較例１と同様の条件及び方法で熱分解時間を測定した。更に比較例１と同様の条件及び方法でサンプルを作成し引張強度、伸びを測定、耐熱性の評価を行った。（結果を［表２］に記す） 2 parts by weight of a tin-based stabilizer (Adeka Stab 465E manufactured by Adeka) or barium-zinc system with respect to 50 parts by weight of vinylidene chloride resin, 50 parts by weight of vinyl chloride resin and 5 parts by weight of chlorinated polyethylene used in Comparative Examples 1 and 2 Two parts by weight of a composite stabilizer (Adeka Stub AC290 manufactured by Adeka) were added, and the thermal decomposition time was measured under the same conditions and method as in Comparative Example 1. Further, a sample was prepared under the same conditions and method as in Comparative Example 1, the tensile strength and elongation were measured, and the heat resistance was evaluated. (The results are shown in [Table 2])

比較例１，２で用いた塩化ビニリデン樹脂２０重量部、塩化ビニル樹脂８０重量部、塩素化ポリエチレン５重量部に対してハイドロタルサイト２重量部を添加し、比較例１と同様の条件及び方法で熱分解時間を測定した。更に比較例１と同様の条件及び方法でサンプルを作成し引張強度、伸びを測定、耐熱性の評価を行った。（結果を［表２］に記す） The same conditions and method as in Comparative Example 1 except that 2 parts by weight of hydrotalcite is added to 20 parts by weight of vinylidene chloride resin, 80 parts by weight of vinyl chloride resin and 5 parts by weight of chlorinated polyethylene used in Comparative Examples 1 and 2. The pyrolysis time was measured at Further, a sample was prepared under the same conditions and method as in Comparative Example 1, the tensile strength and elongation were measured, and the heat resistance was evaluated. (The results are shown in [Table 2])

比較例１，２で用いた塩化ビニリデン樹脂８０重量部、塩化ビニル樹脂２０重量部、塩素化ポリエチレン５重量部に対してハイドロタルサイト２重量部を添加し、比較例１と同様の条件及び方法で熱分解時間を測定した。更に比較例１と同様の条件及び方法でサンプルを作成し引張強度、伸びを測定、耐熱性の評価を行った。（結果を［表２］に記す） The same conditions and method as in Comparative Example 1 except that 2 parts by weight of hydrotalcite is added to 80 parts by weight of vinylidene chloride resin, 20 parts by weight of vinyl chloride resin and 5 parts by weight of chlorinated polyethylene used in Comparative Examples 1 and 2. The pyrolysis time was measured at Further, a sample was prepared under the same conditions and method as in Comparative Example 1, the tensile strength and elongation were measured, and the heat resistance was evaluated. (The results are shown in [Table 2])

比較例７、実施例５Comparative Example 7 and Example 5

比較例１，２で用いた塩化ビニリデン樹脂５０重量部、塩化ビニル樹脂５０重量部、ハイドロタルサイト２重量部に対して塩素化ポリエチレンを夫々０．５，２，０重量部添加し、比較例１と同様の条件及び方法で熱分解時間を測定した。更に比較例１と同様の条件及び方法でサンプルを作成し引張強度、伸びを測定、耐熱性の評価を行った。（結果を［表２］に記す）

Comparative Examples 1 and 2 were added 0.5, 20, and 0 parts by weight of chlorinated polyethylene to 50 parts by weight of vinylidene chloride resin, 50 parts by weight of vinyl chloride resin, and 2 parts by weight of hydrotalcite, respectively. The pyrolysis time was measured under the same conditions and method as in 1. Further, a sample was prepared under the same conditions and method as in Comparative Example 1, the tensile strength and elongation were measured, and the heat resistance was evaluated. (The results are shown in [Table 2])

Claims

塩化ビニリデン樹脂１０〜９０重量部、塩化ビニル樹脂９０〜１０重量部、合わせて１００重量部に対して塩素化ポリエチレン１．０重量部以上、化学式（Ｍｇ_２ＡＬ（ＯＨ）_１６ＣＯ_３・４Ｈ_２Ｏ）で表されるハイドロタルサイト０．５〜１０重量部よりなる熱安定性、加工性、物理的物性の改良された樹脂組成物。10 to 90 parts by weight of vinylidene chloride resin, 90 to 10 parts by weight of vinyl chloride resin, 1.0 part by weight or more of chlorinated polyethylene with respect to 100 parts by weight in total, chemical formula (Mg ₂ AL (OH) ₁₆ CO ₃ .4H ₂ A resin composition having improved thermal stability, workability, and physical properties, comprising 0.5 to 10 parts by weight of hydrotalcite represented by O).