JP2001139748A - Chlorinated vinyl chloride-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a chlorinated vinyl chloride-based resin composition having strong tensile strength at high temperature and strong impact strength at low temperature. SOLUTION: This chlorinated vinyl chloride-based resin composition comprises 100 pts.wt. chlorinated vinyl chloride-based resin having 600-1,500 polymerization degree before chlorination and 62-70 wt.% chlorination degree, 1-9 pts.wt. MBS resin having >60 wt.% butadiene content in whole particles and 1-4 pts.wt. vinyl chloride-based resin having 600-1,900 polymerization degree.

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、特に高温での引張強度が強く、低温での
耐衝撃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 for molding having high tensile strength at high temperatures and high impact strength at low temperatures.

【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。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。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. 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.
In the chlorinated vinyl chloride resin composition, ABS and / or
Alternatively, it has been proposed to mix MBS and chlorinated polyethylene. 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.

【０００３】[0003]

【発明が解決しようとする課題】本発明の目的は、低温
での耐衝撃性に優れると同時に、高温での引張強度も高
く、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。SUMMARY OF THE INVENTION It is an object of the present invention to provide a chlorinated vinyl chloride resin composition which is excellent in impact resistance at low temperatures and high in tensile strength at high temperatures.

【０００４】[0004]

【課題を解決するための手段】本発明は、上記の目的を
達成するために、塩素化前の重合度が６００〜１５００
であり、塩素化度が６２〜７０重量％である塩素化塩化
ビニル系樹脂１００重量部と粒子全体中のブタジエン含
有量が６０重量％より大きいＭＢＳ粒子１〜９重量部お
よび重合度が６００〜１９００の塩化ビニル系樹脂１〜
４重量部を含んでなる塩素化塩化ビニル系樹脂組成物と
する。According to the present invention, in order to achieve the above object, the degree of polymerization before chlorination is from 600 to 1500.
100 parts by weight of a chlorinated vinyl chloride resin having a chlorination degree of 62 to 70% by weight, 1 to 9 parts by weight of MBS particles having a butadiene content of more than 60% by weight in the whole particles, and a polymerization degree of 600 to 1900 vinyl chloride resin 1
A chlorinated vinyl chloride resin composition containing 4 parts by weight.

【０００５】[0005]

【発明の実施の形態】本発明で用いられる塩素化塩化ビ
ニル系樹脂の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、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６２〜７０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原料で
ある塩化ビニル系樹脂の平均重合度が６００未満であれ
ば、十分な機械的強度が得られず、一方、その重合度が
１５００を越えると、樹脂組成物の加工が容易でないの
で好ましくない。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。本発明において「塩化ビニ
ル系樹脂」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。ＭＢＳとしては、ブタジエン含有
量が６０重量％より大きいＭＢＳ１〜９重量部を用い
る。ここでＭＢＳとは、メチルメタクリレートとブタジ
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ＭＢＳとして鐘淵化学工業社製の
Ｂ５６あるいはクレハ社製ＢＴＡIIIＮＸ等が知られて
いる。ここで、ブタジエン含有量が６０重量％以下であ
ると、低温での耐衝撃強度が低下する。また、ＭＢＳの
配合量が１重量部未満だと成形品の耐衝撃物性が低下
し、９重量部を越えると塩素化塩化ビニル系樹脂の持つ
特性である耐熱性が低下する。本発明の塩素化塩化ビニ
ル系樹脂は、上記ＭＢＳに加えて塩化ビニル系樹脂１〜
４重量部を含んでなることを特徴とする。ＭＢＳ単独で
は、上記の低温での耐衝撃強度が十分満足できない。BEST MODE FOR CARRYING OUT THE INVENTION The average degree of polymerization of a vinyl chloride resin before chlorination, which is a raw material of the chlorinated vinyl chloride resin used in the present invention, is from 600 to 1500, preferably from 600.
~ 1300, more preferably from 600 to 1200,
The chlorination degree of the chlorinated vinyl chloride resin is 62 to 70% by weight, preferably 63 to 70% by weight, more preferably 64 to 70% by weight.
７０70% by weight. If the average degree of polymerization of the vinyl chloride resin as a raw material of the chlorinated vinyl chloride resin is less than 600, sufficient mechanical strength cannot be obtained, while if the degree of polymerization exceeds 1500, It is not preferable because processing is not easy. 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,
It is not preferable because the melt viscosity becomes high and processing of the resin composition involves technical difficulties. In the present invention, "vinyl chloride resin" is a homopolymer of vinyl chloride, and other copolymerizable monomers with vinyl chloride, for example, ethylene, propylene, vinyl acetate, allyl chloride, allyl glycidyl ether, acrylic acid Includes copolymers with esters, vinyl ethers and the like. As MBS, 1 to 9 parts by weight of MBS having a butadiene content of more than 60% by weight is used. Here, MBS is a copolymer of methyl methacrylate, butadiene and styrene, and MBS having a butadiene content of more than 60% by weight, such as B56 manufactured by Kaneka Chemical Industry Co., Ltd. or BTAIIINX manufactured by Kureha Corporation, is known. Here, when the butadiene content is 60% by weight or less, the impact resistance at low temperatures is reduced. On the other hand, if the amount of MBS is less than 1 part by weight, the impact resistance of the molded article is reduced. The chlorinated vinyl chloride resin of the present invention is a vinyl chloride resin 1 to 5 in addition to the MBS.
It is characterized by comprising 4 parts by weight. MBS alone cannot sufficiently satisfy the above-mentioned impact resistance at low temperatures.

【０００６】上記の塩化ビニル系樹脂としては、重合度
６００〜１９００の塩化ビニル系樹脂を用いる。重合度
が６００未満だと十分な機械的強度が得られず、一方で
その重合度が１５００を越えると、樹脂組成物の加工が
容易でないので好ましくない。また、用いる塩化ビニル
系樹脂の配合量が１重量部未満であると、成形品の目的
とする低温での耐衝撃生が満足されない。また、用いる
塩化ビニル系樹脂の配合量が４重量部未満であると、成
形品の高温での引張強度が不十分となる。As the vinyl chloride resin, a vinyl chloride resin having a degree of polymerization of 600 to 1900 is used. If the degree of polymerization is less than 600, sufficient mechanical strength cannot be obtained, while if the degree of polymerization exceeds 1500, processing of the resin composition is not easy, which is not preferable. If the amount of the vinyl chloride resin used is less than 1 part by weight, the intended low-temperature impact resistance of the molded product is not satisfied. If the amount of the vinyl chloride resin used is less than 4 parts by weight, the tensile strength of the molded product at high temperatures becomes insufficient.

【０００７】[0007]

【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に限
定されるものではない。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 to the following examples. In Examples and Comparative Examples,
“Parts” or “%” are “parts by weight” unless otherwise specified.
Or "% by weight".

【０００８】（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
ル樹脂を得た。この塩素化塩化ビニル樹脂１００部に、
衝撃吸収剤としてブタジエン含有量７０％のＢ５６（鐘
淵化学工業株式会社製のＭＢＳ樹脂）６部と重合度１３
００の塩化ビニル樹脂Ｓ１００３（鐘淵化学工業株式会
社製の塩化ビニル樹脂）３部および安定剤としてオクチ
ル錫メルカプト２部、滑剤を２部、充填剤として二酸化
チタン５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 degree of polymerization of 1000 was post-chlorinated to obtain a chlorinated vinyl chloride resin having a degree of chlorination of 67%. 100 parts of this chlorinated vinyl chloride resin
6 parts of B56 (MBS resin manufactured by Kaneka Chemical Co., Ltd.) having a butadiene content of 70% as a shock absorber and a degree of polymerization of 13
3 parts of vinyl chloride resin S1003 (vinyl chloride resin manufactured by Kanegafuchi Chemical Industry Co., Ltd.), 2 parts of octyltin mercapto as a stabilizer, 2 parts of a lubricant, and 5 parts of titanium dioxide as a filler were added. The blend was hand blended to obtain a uniform blend.

【０００９】このブレンド配合物を、１９５℃の８イン
チのロールにて３分間混練し、２００℃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１０．５ｋｇ・
ｃｍ／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２６３ｋｇ／ｃｍ ²であった。また、ＪＩＳ Ｋ
７２０６に準じた５ｋｇ荷重でのＶｉｃａｔ軟化点は１
１６．９℃だった。 （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を得
た。この塩素化塩化ビニル樹脂１００部に、衝撃吸収剤
としてブタジエン含有量７０％のＢ５６（鐘淵工業株式
会社製のＭＢＳ樹脂）６部と重合度１３００の塩化ビニ
ル樹脂Ｓ１００３（鐘淵化学工業株式会社製の塩化ビニ
ル樹脂）２部および塩素含有量３５％の塩素化ポリエチ
レンＨ１３５（ダイソー社製）１部、安定剤としてオク
チル錫メルカプト２部、滑剤を２部、充填剤として二酸
化チタン５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。[0009] The blend formulation was added at 195 ° C for 8 inches.
And kneaded for 3 minutes with a roll of
A test piece was obtained by cutting after pressing for 10 minutes. JIS K
 Izod impact test at -7 ° C according to 7110
At this point, the Izod impact test value was 10.5 kg
cm / cm^TwoMet. In addition, JIS K 7113
When a tensile test was conducted at 82 ° C.
The degree is 263kg / cm ^TwoMet. Also, JIS K
Vicat softening point at 5 kg load according to 7206 is 1
16.9 ° C. (Example 2) A vinyl chloride resin having a polymerization degree of 1000 was post-chlorinated.
To obtain a chlorinated vinyl chloride resin with a chlorination degree of 67%
Was. 100 parts of the chlorinated vinyl chloride resin is added to a shock absorber
With a butadiene content of 70%
6 parts of MBS resin manufactured by the company and vinyl chloride with a polymerization degree of 1300
Resin S1003 (Kanebuchi Chemical Industry Co., Ltd.
Chlorinated polyethylene with 2 parts and 35% chlorine content
1 part of Ren H135 (manufactured by Daiso), octane as a stabilizer
2 parts of chill tin mercapto, 2 parts of lubricant, diacid as filler
5 parts of titanium oxide were added. Hand blend this formulation
A uniform formulation was obtained.

【００１０】このブレンド配合物を、１９５℃の８イン
チのロールにて３分間混練し、２００℃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１１．１ｋｇ・
ｃｍ／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２６１ｋｇ／ｃｍ ²であった。また、ＪＩＳ Ｋ
７２０６に準じた５ｋｇ荷重でのＶｉｃａｔ軟化点は１
１６．６℃だった。 （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を得
た。この塩素化塩化ビニル樹脂１００部に、衝撃吸収剤
としてブタジエン含有量４６％のＢ２２（鐘淵化学工業
株式会社製のＭＢＳ）６部と塩素含有量３５％の塩素化
ポリエチレンＨ１３５（ダイソー社製）２部および安定
剤としてオクチル錫メルカプト２部、滑剤を２部、充填
剤として二酸化チタン５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。[0010] This blend formulation was added at 195 ° C for 8 inches.
And kneaded for 3 minutes with a roll of
A test piece was obtained by cutting after pressing for 10 minutes. JIS K
 Izod impact test at -7 ° C according to 7110
The Izod impact test value was 11.1 kg.
cm / cm^TwoMet. In addition, JIS K 7113
When a tensile test was conducted at 82 ° C.
The degree is 261kg / cm ^TwoMet. Also, JIS K
Vicat softening point at 5 kg load according to 7206 is 1
16.6 ° C. (Comparative Example 1) A vinyl chloride resin having a polymerization degree of 1000 was post-chlorinated.
To obtain a chlorinated vinyl chloride resin with a chlorination degree of 67%
Was. 100 parts of the chlorinated vinyl chloride resin is added to a shock absorber
With a butadiene content of 46%
Chlorination with 6 parts and 35% chlorine content
2 parts of polyethylene H135 (manufactured by Daiso) and stable
Octyltin mercapto 2 parts, lubricant 2 parts, filling agent
5 parts of titanium dioxide was added as an agent. Han of this compound
The mixture was blended to obtain a uniform composition.

【００１１】このブレンド配合物を、１９５℃の８イン
チのロールにて３分間混練し、２００℃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８．４ｋｇ・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２６０ｋｇ／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
５．２℃だった。上記の実施例および比較例の結果を表
１にまとめた。This blend was kneaded with an 8-inch roll at 195 ° C. for 3 minutes, pressed with a press machine at 200 ° 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 8.4 kg · c.
m / cm ² . Further, when a tensile test was conducted at 82 ° C. according to JIS K 7113, the tensile strength was 260 kg / cm ² . In addition, JIS K7
The Vicat softening point at 5 kg load according to 206 is 11
5.2 ° C. Table 1 summarizes the results of the above Examples and Comparative Examples.

【００１２】[0012]

【表１】 [Table 1]

【００１３】[0013]

【発明の効果】実施例１〜３の結果から明らかなよう
に、粒子全体中のブタジエン含有量が６０重量％より大
きいＭＢＳ樹脂１〜９重量部および重合度６００〜１９
００の塩化ビニル系樹脂１〜４重量部を含んでなる塩素
化塩化ビニル系樹脂組成物を用いると、成形体の高温で
の引張強度を向上するとともに低温での耐衝撃強度を向
上でき、また耐熱性も向上できる。As is clear from the results of Examples 1 to 3, 1 to 9 parts by weight of MBS resin having a butadiene content of more than 60% by weight in the whole particles and a polymerization degree of 600 to 19 are provided.
By using a chlorinated vinyl chloride resin composition containing 1 to 4 parts by weight of the vinyl chloride resin of No. 00, it is possible to improve the high-temperature tensile strength and the low-temperature impact strength of the molded article, and Heat resistance can also be improved.

Claims (1)

【特許請求の範囲】[Claims] 【請求項１】 塩素化前の重合度が６００〜１５００で
あり、塩素化度が６２〜７０重量％である塩素化塩化ビ
ニル系樹脂１００重量部と粒子全体中のブタジエン含有
量が６０重量％より大きいＭＢＳ粒子１〜９重量部およ
び重合度が６００〜１９００の塩化ビニル系樹脂１〜４
重量部を含んでなる塩素化塩化ビニル系樹脂組成物。1. A polymerization degree before chlorination is 600 to 1500, and 100 parts by weight of a chlorinated vinyl chloride resin having a chlorination degree of 62 to 70% by weight and a butadiene content in the whole particles are 60% by weight. 1 to 9 parts by weight of larger MBS particles and 1 to 4 vinyl chloride resins having a polymerization degree of 600 to 1900
A chlorinated vinyl chloride resin composition comprising parts by weight.