JP2001200122A - Chlorinated vinyl chloride-based resin composition - Google Patents
Chlorinated vinyl chloride-based resin compositionInfo
- Publication number
- JP2001200122A JP2001200122A JP2000008257A JP2000008257A JP2001200122A JP 2001200122 A JP2001200122 A JP 2001200122A JP 2000008257 A JP2000008257 A JP 2000008257A JP 2000008257 A JP2000008257 A JP 2000008257A JP 2001200122 A JP2001200122 A JP 2001200122A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- chloride resin
- chlorinated vinyl
- weight
- chlorination
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【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)
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.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000008257A JP2001200122A (en) | 2000-01-17 | 2000-01-17 | Chlorinated vinyl chloride-based resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000008257A JP2001200122A (en) | 2000-01-17 | 2000-01-17 | Chlorinated vinyl chloride-based resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JP2001200122A true JP2001200122A (en) | 2001-07-24 |
Family
ID=18536562
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP2000008257A Pending JP2001200122A (en) | 2000-01-17 | 2000-01-17 | Chlorinated vinyl chloride-based resin composition |
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