JP2001200122A - Chlorinated vinyl chloride-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a chlorinated vinyl chloride-based resin composition having high tensile strength at high temperature and high heat resistance without impairing impact resistance at low temperature. SOLUTION: This composition is obtained by using a chlorinated vinyl chloride-based resin composition comprising 100 pts.wt. (I) chlorinated vinyl chloride-based resin having 62-70 wt.% degree of chlorination, 5-12 pts.wt. (II) ABS particles having >60 wt.% butadiene content in the particles and 0.5-4 pts.wt. (III) chlorinated vinyl chloride-based resin having 600-1,500 degree of polymerization before chlorination and 58-62 wt.% degree of chlorination.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、塩素化塩化ビニル
系樹脂組成物、特に低温での耐衝撃強度を犠牲にせずに
耐熱性が高く、しかも高温での引張強度が強い成形用塩
素化塩化ビニル系樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chlorinated vinyl chloride resin composition, and more particularly to a chlorinated vinyl chloride resin composition having high heat resistance without sacrificing impact strength at low temperatures and having high tensile strength at high temperatures. The present invention relates to a vinyl resin composition.

【０００２】[0002]

【従来の技術】塩素化塩化ビニル系樹脂の成形物は、耐
熱性が高いという特徴を有し、従来の塩化ビニル系樹脂
の成形物では加熱変形するために使用できないような比
較的高温での用途に用いられている。例えば、塩化ビニ
ル系樹脂成形物よりも熱変形温度が２０〜４０℃も高い
ことを利用して、熱水用パイプとして塩素化塩化ビニル
系樹脂成形物が用いられる。あるいは、塩化ビニル系樹
脂成形物よりも熱変形温度が高いことを利用して、熱の
かかる家電用のシートとして塩素化塩化ビニル系樹脂成
形物が用いられる。2. Description of the Related Art A molded article of a chlorinated vinyl chloride resin has a feature of high heat resistance, and is used at a relatively high temperature at which a conventional molded article of a vinyl chloride resin cannot be used due to heat deformation. Used for applications. For example, a chlorinated vinyl chloride resin molded article is used as a pipe for hot water, utilizing the fact that the heat distortion temperature is higher by 20 to 40 ° C. than that of a vinyl chloride resin molded article. Alternatively, a chlorinated vinyl chloride-based resin molded product is used as a sheet for household appliances to which heat is applied, utilizing the fact that the heat deformation temperature is higher than that of the vinyl chloride-based resin molded product.

【０００３】一方、塩素化塩化ビニル系樹脂の成形物
は、高温での引張強度が強い反面で、低温での耐衝撃性
が弱いことが知られている。この低温での耐衝撃性が弱
いことを克服するために、塩素化塩化ビニル系樹脂組成
物においてＡＢＳ，ＭＢＳ等の耐衝撃改良剤を配合する
ことが知られている。これらの耐衝撃吸収剤は低温での
耐衝撃性を向上するものの十分ではなかった。この問題
を解決するために、特公昭４９−１８１０２では、塩素
化塩化ビニル系樹脂組成物において、ＡＢＳ及び／又は
ＭＢＳと塩素化ポリエチレンを配合することを提案して
いる。しかし、塩素化塩化ビニル系樹脂組成物に塩素化
ポリエチレンを配合することで耐衝撃性は優れて改善さ
れるものの、塩素化塩化ビニル系樹脂成形物の軟化温度
が下がり、高温での引張強度が低下するため、塩素化塩
化ビニル系樹脂組成物としては不十分なものであった。On the other hand, it is known that a molded article of a chlorinated vinyl chloride resin has a high tensile strength at a high temperature, but has a low impact resistance at a low temperature. In order to overcome the low impact resistance at low temperatures, it is known to incorporate an impact modifier such as ABS or MBS into a chlorinated vinyl chloride resin composition. These shock absorbers improve the impact resistance at low temperatures but are not satisfactory. In order to solve this problem, Japanese Patent Publication No. 18182/1972 proposes blending ABS and / or MBS with chlorinated polyethylene in a chlorinated vinyl chloride resin composition. However, although the impact resistance is improved and improved by blending chlorinated polyethylene with the chlorinated vinyl chloride resin composition, the softening temperature of the chlorinated vinyl chloride resin molded product decreases, and the tensile strength at high temperatures decreases. Therefore, the chlorinated vinyl chloride resin composition was insufficient.

【０００４】[0004]

【発明が解決しようとする課題】本発明の目的は、低温
での耐衝撃性を犠牲にせずに、耐熱性が高く、しかも高
温での引張強度も高い、好ましい塩素化塩化ビニル系樹
脂組成物を提供することにある。An object of the present invention is to provide a preferred chlorinated vinyl chloride resin composition having high heat resistance and high tensile strength at high temperatures without sacrificing impact resistance at low temperatures. Is to provide.

【０００５】[0005]

【課題を解決するための手段】すなわち、本発明は、塩
素化度が６２〜７０重量％である塩素化塩化ビニル系樹
脂(I)１００重量部、粒子中のブタジエン含有量が６０
重量％より大きいＡＢＳ粒子(II)５〜１２重量部、およ
び塩素化度が５８〜６２重量％である塩素化塩化ビニル
系樹脂(III)０．５〜４重量部からなる塩素化塩化ビニ
ル系樹脂組成物、に関する。That is, according to the present invention, 100 parts by weight of a chlorinated vinyl chloride resin (I) having a chlorination degree of 62 to 70% by weight and a butadiene content in particles of 60% are used.
5 to 12 parts by weight of ABS particles (II) having a chlorination degree of 58 to 62% by weight, and 0.5 to 4 parts by weight of a chlorinated vinyl chloride resin (III) having a chlorination degree of 58 to 62% by weight. A resin composition.

【０００６】[0006]

【発明の実施の形態】本発明で用いられる塩素化塩化ビ
ニル系樹脂は、通常、原料として塩化ビニル系樹脂を用
い、同塩化ビニル系樹脂を水性媒体中に分散した状態で
塩素を供給し、それに水銀灯を照射するか、加熱塩素化
するか、触媒の存在下で塩素化するなど水性媒体中で塩
素化する方法、塩化ビニル系樹脂を気層中、水銀灯の照
射下で塩素化を行うなど気層中で塩素化する方法などに
より製造される。原料である塩素化前の塩化ビニル系樹
脂の平均重合度は、通常６００から１５００，好ましく
は６００〜１３００、より好ましくは６００〜１２００
であり、塩素化塩化ビニル系樹脂の塩素化度は６２〜７
０重量％、好ましくは６３〜７０重量％、より好ましく
は６４〜７０重量％である。塩素化塩化ビニル系樹脂の
塩素化度が６２重量％未満であれば、十分な耐熱性を有
する組成物が得られず、一方、塩素化度が７０重量％を
越えると、溶融粘度が高くなり、樹脂組成物の加工に技
術的な困難を伴うので、好ましくない。原料の塩化ビニ
ル系樹脂(I)としては、塩化ビニルの単独重合体、およ
び塩化ビニルと他の共重合可能な単量体、例えば、エチ
レン、プロピレン、酢酸ビニル、塩化アリル、アリルグ
リシジルエーテル、アクリル酸エステル、ビニルエーテ
ル等との共重合体を包含する。BEST MODE FOR CARRYING OUT THE INVENTION The chlorinated vinyl chloride resin used in the present invention usually uses a vinyl chloride resin as a raw material, and supplies chlorine in a state where the vinyl chloride resin is dispersed in an aqueous medium. Chlorination in an aqueous medium such as irradiation with a mercury lamp, chlorination with heating, or chlorination in the presence of a catalyst, chlorination in a gas phase of a vinyl chloride resin, irradiation with a mercury lamp, etc. It is produced by a method of chlorination in a gas phase. The average degree of polymerization of the vinyl chloride resin before chlorination as a raw material is generally 600 to 1500, preferably 600 to 1300, and more preferably 600 to 1200.
The chlorination degree of the chlorinated vinyl chloride resin is 62 to 7
0% by weight, preferably 63 to 70% by weight, more preferably 64 to 70% by weight. When the chlorination degree of the chlorinated vinyl chloride resin is less than 62% by weight, a composition having sufficient heat resistance cannot be obtained. On the other hand, when the chlorination degree exceeds 70% by weight, the melt viscosity increases. However, it is not preferable because processing of the resin composition involves technical difficulties. As the raw material vinyl chloride resin (I), homopolymers of vinyl chloride, and other copolymerizable monomers with vinyl chloride, for example, ethylene, propylene, vinyl acetate, allyl chloride, allyl glycidyl ether, acrylic Includes copolymers with acid esters, vinyl ethers and the like.

【０００７】本発明では、粒子中のブタジエン含有量が
６０重量％より大きいＡＢＳ粒子(II)５〜１２重量部を
用いる。ここでＡＢＳとは、アクリロニトリルとブタジ
エンとスチレンの共重合体であり、ブタジエン含有量が
６０重量％より大きいＡＢＳとしてＧＥ Ｓｐｅｃｉａ
ｌｔｙ Ｃｈｅｍｉｃａｌｓ社製のＢｌｅｎｄｅｘ３３
８あるいはＢｌｅｎｄｅｘ３３６等が知られている。In the present invention, 5 to 12 parts by weight of ABS particles (II) having a butadiene content in the particles of more than 60% by weight are used. Here, ABS is a copolymer of acrylonitrile, butadiene and styrene, and GE Specia is an ABS having a butadiene content of more than 60% by weight.
Blendex33 manufactured by lty Chemicals
8 or Blendex 336 are known.

【０００８】ここで、ブタジエン含有量が６０重量％よ
り小さいと、低温での耐衝撃強度が低下する。また、Ａ
ＢＳの配合量が２重量部未満だと成形品の耐衝撃物性が
低下し、８重量部を越えると塩素化塩化ビニル系樹脂が
持つ特性である耐熱性が低下する。Here, if the butadiene content is less than 60% by weight, the impact strength at low temperatures decreases. Also, A
If the blending amount of BS is less than 2 parts by weight, the impact resistance of the molded article is reduced, and if it exceeds 8 parts by weight, the heat resistance, which is a characteristic of the chlorinated vinyl chloride resin, is reduced.

【０００９】本発明では、更に、塩素化度が５８〜６２
重量％の塩素化塩化ビニル系樹脂(III)を０．５〜４重
量部配合する。この塩素化塩化ビニル系樹脂(III)は、
前記、塩素化塩化ビニル系樹脂(I)と同様に、原料とし
て平均重合度が、６００〜１５００，好ましくは６００
〜１３００、より好ましくは６００〜１２００の塩化ビ
ニル系樹脂を用い、塩素化塩化ビニル系樹脂(I)と同様
の方法で塩素化して製造される。ただし、このとき塩素
化塩化ビニル系樹脂(III)の塩素化度が５８〜６２重量
％になるように調整する必要がある。これにより、加工
性が向上し、物性的にも、高温引っ張り強度、軟化点が
向上の効果が得られる。塩素化塩化ビニル系樹脂(III)
の塩素化度が５８重量％より小さい場合には所望の効果
を得るために、原料の塩化ビニル樹脂の重合度を上げる
必要があり加工が容易でなくなる。６２重量％より大き
い場合は、所望の低温での耐衝撃強度が得られない等の
問題がある。また、この塩素化塩化ビニル系樹脂の配合
量が０．５重量部未満であると所望の低温での耐衝撃強
度が得られず、４重量部を越えると所望の高温での引張
強度が得られない。[0009] In the present invention, the chlorination degree may be 58 to 62.
0.5 to 4 parts by weight of chlorinated vinyl chloride resin (III) is blended. This chlorinated vinyl chloride resin (III)
As in the case of the chlorinated vinyl chloride resin (I), the average degree of polymerization is 600 to 1500, preferably 600
To 1,300, more preferably 600 to 1200, chlorinated in the same manner as the chlorinated vinyl chloride resin (I). However, at this time, it is necessary to adjust the chlorination degree of the chlorinated vinyl chloride resin (III) to be 58 to 62% by weight. Thereby, the workability is improved, and the effect of improving the high-temperature tensile strength and the softening point is obtained. Chlorinated vinyl chloride resin (III)
If the degree of chlorination is less than 58% by weight, it is necessary to increase the degree of polymerization of the raw material vinyl chloride resin in order to obtain the desired effect, which makes processing difficult. If it is more than 62% by weight, there is a problem that a desired low-temperature impact strength cannot be obtained. If the amount of the chlorinated vinyl chloride resin is less than 0.5 part by weight, the desired low-temperature impact strength cannot be obtained, and if it exceeds 4 parts by weight, the desired high-temperature tensile strength can be obtained. I can't.

【００１０】[0010]

【実施例】以下に実施例および比較例を挙げて本発明を
具体的に説明する。しかし、本発明は以下の実施例のみ
に限定されるわけではない。尚、実施例および比較例
中、「部」または「％」は、特に記載のない限り「重量
部」または「重量％」である。The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited only to the following examples. In Examples and Comparative Examples, “parts” or “%” is “parts by weight” or “% by weight” unless otherwise specified.

【００１１】（実施例１）重合度１０００の塩化ビニル
樹脂を後塩素化して塩素化度が６７％の塩素化塩化ビニ
ル樹脂(I)を得た。この塩素化塩化ビニル樹脂(I)１００
部に、Ｂｌｅｎｄｅｘ３３８（ブタジエンを７０％含有
するＡＢＳ粒子、ＧＥ ＳｐｅｃｉａｌｔｙＣｈｅｍｉ
ｃａｌｓ社製）(II)８部、重合度１０００の塩化ビニル
系樹脂を後塩素化して得た塩素化度５９％の塩素化塩化
ビニル系樹脂(III)１部、安定剤としてブチル錫系安定
剤２部、安定化助剤として合成ゼオライトを１部、滑剤
を２部、充填剤として二酸化チタン４部を加えた。この
配合物のハンドブレンドをおこない均一な配合物を得
た。(Example 1) A vinyl chloride resin having a polymerization degree of 1000 was post-chlorinated to obtain a chlorinated vinyl chloride resin (I) having a chlorination degree of 67%. This chlorinated vinyl chloride resin (I) 100
In the part, Blendex 338 (ABS particles containing 70% butadiene, GE Specialty Chemi
(II), 8 parts, 1 part of chlorinated vinyl chloride resin (III) having a degree of chlorination of 59% obtained by post-chlorination of a vinyl chloride resin having a polymerization degree of 1000, butyltin-based stabilizer as a stabilizer 2 parts of an agent, 1 part of a synthetic zeolite as a stabilizing aid, 2 parts of a lubricant, and 4 parts of titanium dioxide as a filler were added. The blend was hand blended to obtain a uniform blend.

【００１２】このブレンド配合物を、２００℃の８イン
チのロールにて３分間混練し、２０５℃のプレス機にて
１０分間プレス後に切削して試験片を得た。ＪＩＳ Ｋ
７１１０に準じて−７℃でのアイゾット衝撃試験をお
こなったところアイゾット衝撃試験値は７．４ｋｇ・ｃ
ｍ／ｃｍ²であった。また、ＪＩＳ Ｋ ７１１３に準
じて８２℃での引張試験をおこなったところ、引張強度
は２６９ｋｇ／ｃｍ²であった。また、ＪＩＳ Ｋ ７
２０６に準じた５ｋｇ荷重でのＶｉｃａｔ軟化点は１１
７．７℃だった。This blend was kneaded with an 8-inch roll at 200 ° C. for 3 minutes, pressed with a press machine at 205 ° C. for 10 minutes, and then cut to obtain a test piece. JIS K
When an Izod impact test at -7 ° C was performed according to 7110, the Izod impact test value was 7.4 kg · c.
m / cm ² . Further, when a tensile test was conducted at 82 ° C. according to JIS K 7113, the tensile strength was 269 kg / cm ² . In addition, JIS K7
The Vicat softening point at 5 kg load according to 206 is 11
7.7 ° C.

【００１３】（実施例２）重合度１０００の塩化ビニル
樹脂を後塩素化して塩素化度が６７％の塩素化塩化ビニ
ル樹脂(I)を得た。この塩素化塩化ビニル樹脂(I)１００
部に、Ｂｌｅｎｄｅｘ３３８（ブタジエンを７０％含有
するＡＢＳ粒子、ＧＥ ＳｐｅｃｉａｌｔｙＣｈｅｍｉ
ｃａｌｓ社製）(II)９部、重合度１０００の塩化ビニル
系樹脂を後塩素化して得た塩素化度５９％の塩素化塩化
ビニル系樹脂(III)２部、安定剤としてブチル錫系安定
剤２部、安定化助剤として合成ゼオライトを１部、滑剤
を２部、充填剤として二酸化チタン４部を加えた。この
配合物のハンドブレンドをおこない均一な配合物を得
た。Example 2 A vinyl chloride resin having a polymerization degree of 1000 was post-chlorinated to obtain a chlorinated vinyl chloride resin (I) having a chlorination degree of 67%. This chlorinated vinyl chloride resin (I) 100
In the part, Blendex 338 (ABS particles containing 70% butadiene, GE Specialty Chemi
9%, 2 parts of chlorinated vinyl chloride resin (III) having a degree of chlorination of 59% obtained by post-chlorination of a vinyl chloride resin having a polymerization degree of 1000, and butyltin-based stabilizer as a stabilizer. 2 parts of an agent, 1 part of a synthetic zeolite as a stabilizing aid, 2 parts of a lubricant, and 4 parts of titanium dioxide as a filler were added. The blend was hand blended to obtain a uniform blend.

【００１４】このブレンド配合物を、２００℃の８イン
チのロールにて３分間混練し、２０５℃のプレス機にて
１０分間プレス後に切削して試験片を得た。ＪＩＳ Ｋ
７１１０に準じて−７℃でのアイゾット衝撃試験をお
こなったところアイゾット衝撃試験値は７．１ｋｇ・ｃ
ｍ／ｃｍ²であった。また、ＪＩＳ Ｋ ７１１３に準
じて８２℃での引張試験をおこなったところ、引張強度
は２６５ｋｇ／ｃｍ²であった。また、ＪＩＳ Ｋ ７
２０６に準じた５ｋｇ荷重でのＶｉｃａｔ軟化点は１１
７．２℃だった。The blend was kneaded with an 8-inch roll at 200 ° C. for 3 minutes, pressed with a press machine at 205 ° C. for 10 minutes, and then cut to obtain a test piece. JIS K
When an Izod impact test at -7 ° C. was performed according to 7110, the Izod impact test value was 7.1 kg · c.
m / cm ² . When a tensile test was conducted at 82 ° C. in accordance with JIS K 7113, the tensile strength was 265 kg / cm ² . In addition, JIS K7
The Vicat softening point at 5 kg load according to 206 is 11
7.2 ° C.

【００１５】（比較例１）重合度１０００の塩化ビニル
樹脂を後塩素化して塩素化度が６７％の塩素化塩化ビニ
ル樹脂(I)を得た。この塩素化塩化ビニル樹脂１００部
に、Ｂｌｅｎｄｅｘ３３８（ブタジエンを７０％含有す
るＡＢＳ粒子、ＧＥ ＳｐｅｃｉａｌｔｙＣｈｅｍｉｃ
ａｌｓ社製）(II)７部、Ｔｙｒｉｎ ３６１５Ｐ（塩素
含有量３６％の塩素化ポリエチレン、ダウ・スペシャリ
ティー・ケミカルズ社製）２部、安定剤としてブチル錫
系安定剤２部、安定化助剤として合成ゼオライトを１
部、滑剤を２部、充填剤として二酸化チタン４部を加え
た。この配合物のハンドブレンドをおこない均一な配合
物を得た。Comparative Example 1 A vinyl chloride resin having a degree of polymerization of 1000 was post-chlorinated to obtain a chlorinated vinyl chloride resin (I) having a degree of chlorination of 67%. Blendex 338 (ABS particles containing 70% butadiene, GE Specialty Chemical) was added to 100 parts of the chlorinated vinyl chloride resin.
als) (7 parts), 2 parts of Tyrin 3615P (chlorinated polyethylene having a chlorine content of 36%, manufactured by Dow Specialty Chemicals), 2 parts of a butyltin-based stabilizer as a stabilizer, and a stabilizing assistant As synthetic zeolite
Parts, 2 parts of a lubricant and 4 parts of titanium dioxide as a filler were added. The blend was hand blended to obtain a uniform blend.

【００１６】このブレンド配合物を、２００℃の８イン
チのロールにて３分間混練し、２０５℃のプレス機にて
１０分間プレス後に切削して試験片を得た。ＪＩＳ Ｋ
７１１０に準じて−７℃でのアイゾット衝撃試験をお
こなったところアイゾット衝撃試験値は７．１ｋｇ・ｃ
ｍ／ｃｍ²であった。また、ＪＩＳ Ｋ ７１１３に準
じて８２℃での引張試験をおこなったところ、引張強度
は２５２ｋｇ／ｃｍ²であった。また、ＪＩＳ Ｋ ７
２０６に準じた５ｋｇ荷重でのＶｉｃａｔ軟化点は１１
６．３℃だった。This blend was kneaded with an 8-inch roll at 200 ° C. for 3 minutes, pressed with a press machine at 205 ° C. for 10 minutes, and then cut to obtain a test piece. JIS K
When an Izod impact test at -7 ° C. was performed according to 7110, the Izod impact test value was 7.1 kg · c.
m / cm ² . A tensile test at 82 ° C. according to JIS K 7113 revealed a tensile strength of 252 kg / cm ² . In addition, JIS K7
The Vicat softening point at 5 kg load according to 206 is 11
6.3 ° C.

【００１７】上記の実施例および比較例の結果を表１に
まとめた。The results of the above Examples and Comparative Examples are summarized in Table 1.

【００１８】[0018]

【表１】 [Table 1]

【００１９】[0019]

【発明の効果】実施例１〜２の結果から明らかなよう
に、塩素化塩化ビニル系樹脂（I）１００重量部に対し
て、粒子中のブタジエン含有量が６０重量％より大きい
ＡＢＳ粒子（II）５〜１２重量部、および塩素化度が５
８〜６２重量％である塩素化塩化ビニル系樹脂（III)
０．５〜４重量部からなる塩素化塩化ビニル系樹脂組成
物を用いることにより、低温での耐衝撃強度を犠牲にせ
ずに成形体の耐熱性を向上し、高温での引張強度を向上
することができる。As is apparent from the results of Examples 1 and 2, ABS particles (II) having a butadiene content of more than 60% by weight based on 100 parts by weight of the chlorinated vinyl chloride resin (I). ) 5 to 12 parts by weight and a chlorination degree of 5
8 to 62% by weight of chlorinated vinyl chloride resin (III)
By using a chlorinated vinyl chloride-based resin composition consisting of 0.5 to 4 parts by weight, the heat resistance of the molded body is improved without sacrificing the impact strength at low temperatures, and the tensile strength at high temperatures is improved. be able to.

Claims (1)

【特許請求の範囲】[Claims] 【請求項１】 塩素化度が６２〜７０重量％である塩素
化塩化ビニル系樹脂（I）１００重量部、粒子中のブタ
ジエン含有量が６０重量％より大きいＡＢＳ粒子（II）
５〜１２重量部、および塩素化度が５８〜６２重量％で
ある塩素化塩化ビニル系樹脂（III)０．５〜４重量部か
らなる塩素化塩化ビニル系樹脂組成物。1. A chlorinated vinyl chloride resin (I) having a degree of chlorination of 62 to 70% by weight, and ABS particles (II) having a butadiene content of more than 60% by weight in the particles.
A chlorinated vinyl chloride resin composition comprising 5 to 12 parts by weight and 0.5 to 4 parts by weight of a chlorinated vinyl chloride resin (III) having a chlorination degree of 58 to 62% by weight.