JPH083403A - Hard vinyl chloride resin composition - Google Patents
Hard vinyl chloride resin compositionInfo
- Publication number
- JPH083403A JPH083403A JP6162614A JP16261494A JPH083403A JP H083403 A JPH083403 A JP H083403A JP 6162614 A JP6162614 A JP 6162614A JP 16261494 A JP16261494 A JP 16261494A JP H083403 A JPH083403 A JP H083403A
- Authority
- JP
- Japan
- Prior art keywords
- chloride resin
- vinyl chloride
- resin composition
- polyvinyl chloride
- impact resistance
- 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.)
- Pending
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ポリ塩化ビニル系樹脂
組成物、特にポリ塩化ビニル系樹脂と耐衝撃性向上剤を
含む組成物において、従来のポリ塩化ビニル系樹脂の特
性を損なわず、さらに耐衝撃性を改善した硬質塩化ビニ
ル系樹脂組成物に関する。FIELD OF THE INVENTION The present invention relates to a polyvinyl chloride resin composition, particularly a composition containing a polyvinyl chloride resin and an impact resistance improver, which does not impair the properties of conventional polyvinyl chloride resins. Further, the present invention relates to a hard vinyl chloride resin composition having improved impact resistance.
【０００２】[0002]
【発明の背景】一般に硬質塩化ビニル系樹脂は、剛性、
耐老化性、耐薬品性、耐油性、耐候性、難燃性等の物性
に優れたものであるが、反面可塑性が十分でなく、加工
性に劣り、耐衝撃性、耐寒性、耐熱性などの物性におい
て必ずしも優れたものでなく、成型加工上多くの問題が
ある。このため各種の改質方法が提案されているが、あ
る物性が改善されたとしても、他方塩化ビニル系樹脂の
特性を損なう場合が多く、満足すべきものはなかった。
特に耐衝撃性を改善する方法としては、例えばアクリロ
ニトリル−ブタジエン−スチレン共重合体（以下ＡＢＳ
樹脂という）、メチルメタクリレート−ブタジエン−ス
チレン共重合体（以下ＭＢＳ樹脂という）、エチレン−
酢酸ビニル共重合体（以下ＥＶＡ樹脂という）、アクリ
ロニトリル−アクリルゴム−スチレン共重合体（以下Ａ
ＡＳ樹脂という）、塩素化ポリエチレン（以下ＣＰＥ樹
脂という）等の異種の重合体をポリ塩化ビニル樹脂に配
合する方法がある。BACKGROUND OF THE INVENTION Generally, a rigid vinyl chloride resin has rigidity,
It has excellent physical properties such as aging resistance, chemical resistance, oil resistance, weather resistance, and flame retardancy, but on the other hand, it does not have sufficient plasticity and is poor in workability, impact resistance, cold resistance, heat resistance, etc. It is not always excellent in physical properties, and has many problems in molding. Therefore, various reforming methods have been proposed, but even if some physical properties are improved, on the other hand, the characteristics of the vinyl chloride resin are often impaired, and none of them is satisfactory.
In particular, as a method for improving impact resistance, for example, acrylonitrile-butadiene-styrene copolymer (hereinafter referred to as ABS
Resin), methyl methacrylate-butadiene-styrene copolymer (hereinafter referred to as MBS resin), ethylene-
Vinyl acetate copolymer (hereinafter referred to as EVA resin), acrylonitrile-acrylic rubber-styrene copolymer (hereinafter referred to as A
There is a method in which a different type of polymer such as AS resin) or chlorinated polyethylene (hereinafter referred to as CPE resin) is mixed with polyvinyl chloride resin.
【０００３】ＡＢＳ樹脂、ＭＢＳ樹脂は透明性を損なわ
ず塩化ビニル樹脂の耐衝撃性を改善することはできる
が、前記樹脂の分子内に二重結合を含むため耐候性が劣
る欠点がある。また、ＣＰＥ樹脂、ＥＶＡ樹脂等は耐候
性は優れているもののポリ塩化ビニル樹脂との相溶性が
悪く、耐衝撃性は改善されるものの引張強度が低下し好
ましくない等の、耐衝撃性向上剤を使用するとポリ塩化
ビニル樹脂の特性を損なう場合が多い。ABS resins and MBS resins can improve the impact resistance of vinyl chloride resins without impairing the transparency, but they have the drawback of poor weather resistance because they contain a double bond in the molecule. Further, CPE resins, EVA resins and the like have excellent weather resistance, but have poor compatibility with polyvinyl chloride resins, and impact resistance is improved but tensile strength is lowered, which is not preferable. When used, the properties of the polyvinyl chloride resin are often impaired.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、前述の耐衝
撃性向上剤の欠点を解決することを目的とするもので、
耐衝撃性向上剤の効果が大幅に向上された硬質塩化ビニ
ル樹脂組成物を提供することにある。SUMMARY OF THE INVENTION The present invention aims to solve the above-mentioned drawbacks of the impact resistance improver.
It is intended to provide a hard vinyl chloride resin composition in which the effect of the impact resistance improver is significantly improved.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、耐衝撃性
向上剤の効果をさらに向上させる添加剤を検討した結
果、ポリエステル、特に脂肪族ジカルボン酸、脂環族ジ
カルボン酸、芳香族ジカルボン酸から選ばれる一種以上
のジカルボン酸と、脂肪族ポリオールから得られるポリ
エステル（数平均分子量５００〜５００００）を配合す
ることで本発明を完成したものである。DISCLOSURE OF THE INVENTION The inventors of the present invention have investigated the additives that further improve the effect of the impact resistance improver, and as a result, have found that polyesters, particularly aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids. The present invention has been completed by blending one or more dicarboxylic acids selected from acids with polyesters (number average molecular weight 500 to 50,000) obtained from aliphatic polyols.
【０００６】即ち、本発明は、ポリ塩化ビニル系樹脂組
成物、特にポリ塩化ビニル系樹脂と耐衝撃性向上剤を含
む組成物において、従来のポリ塩化ビニル系樹脂の特性
を損なわず、さらに耐衝撃性を改善した硬質塩化ビニル
系樹脂組成物に関するものである。That is, the present invention provides a polyvinyl chloride resin composition, particularly a composition containing a polyvinyl chloride resin and an impact resistance improver, which does not impair the properties of conventional polyvinyl chloride resins and further The present invention relates to a hard vinyl chloride resin composition having improved impact resistance.
【０００７】本発明においてポリ塩化ビニル系樹脂と
は、ポリ塩化ビニルのほか、塩化ビニルが主成分（５０
％以上）を占める共重合体を含む。塩化ビニルと共重合
しうる単量体化合物としては、塩化ビニリデン、エチレ
ン、プロピレン、アクリロニトリル、マレイン酸、イタ
コン酸、アクリル酸、メタクリル酸、酢酸ビニル等が挙
げられる。これら塩化ビニル系樹脂は、乳化重合法、懸
濁重合法、溶液重合法、塊状重合法等の従来公知の製造
法のうち、いずれの方法によって製造されたものであっ
てもよい。In the present invention, the polyvinyl chloride resin is not only polyvinyl chloride but also vinyl chloride as a main component (50
%) Or more). Examples of the monomer compound copolymerizable with vinyl chloride include vinylidene chloride, ethylene, propylene, acrylonitrile, maleic acid, itaconic acid, acrylic acid, methacrylic acid and vinyl acetate. These vinyl chloride resins may be produced by any of conventionally known production methods such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, and a bulk polymerization method.
【０００８】本発明における耐衝撃性向上剤とは、ＡＢ
Ｓ樹脂、ＭＢＳ樹脂、ＥＶＡ樹脂、ＡＡＳ樹脂、ＣＰＥ
樹脂等である。The impact resistance improver in the present invention means AB
S resin, MBS resin, EVA resin, AAS resin, CPE
It is a resin or the like.
【０００９】又、ポリ塩化ビニル系樹脂の安定剤、滑剤
その他の添加剤には特に限定はない。There are no particular restrictions on the stabilizers, lubricants and other additives for the polyvinyl chloride resin.
【００１０】本発明によるポリエステルは、脂肪族ジカ
ルボン酸、脂環族ジカルボン酸、芳香族ジカルボン酸
と、脂肪族ポリオールとを脱水し縮合により合成され
る。このときチェーンストッパー（中、高級アルコール
又は脂肪酸）を使用してもよい。The polyester according to the present invention is synthesized by dehydrating and condensing an aliphatic dicarboxylic acid, an alicyclic dicarboxylic acid, an aromatic dicarboxylic acid and an aliphatic polyol. At this time, a chain stopper (medium, higher alcohol or fatty acid) may be used.
【００１１】本発明に用いられるジカルボン酸には、例
えばシュウ酸、マロン酸、コハク酸、アジピン酸、マレ
イン酸、フマル酸、ダイマー酸、テレフタル酸、イソフ
タル酸、フタル酸、ナフタレンジカルボン酸、トリメリ
ット酸等およびこれらの無水物が挙げられる。Examples of the dicarboxylic acid used in the present invention include oxalic acid, malonic acid, succinic acid, adipic acid, maleic acid, fumaric acid, dimer acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and trimellitic acid. Examples thereof include acids and their anhydrides.
【００１２】脂肪族ポリオールとしては、例えばエチレ
ングリコール、プロピレングリコール、１，３−ブタン
ジオール、１，４−ブタンジオール、ジエチレングリコ
ール、ジプロピレングリコール、グリセリン、トリメチ
ロールプロパン、ペンタエリスリトール等が挙げられ
る。Examples of the aliphatic polyol include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane and pentaerythritol.
【００１３】ポリエステル重合方法は通常の方法が利用
できる。例えばジカルボン酸のジメチルエステルと脂肪
族ポリオールのエステル交換反応を行いメタノールを留
出せしめた後、徐々に減圧し高真空下重縮合を行う方法
等がある。エステル交換触媒としては酢酸カルシウム、
酢酸亜鉛等を、重縮合触媒としてはジブチル錫オキシ
ド、チタンテトラブトキシ等公知のものを使用できる。
しかし重合方法、触媒等の種々の条件は上述の例に限定
されるものではない。As the polyester polymerization method, a usual method can be used. For example, there is a method in which dimethyl ester of dicarboxylic acid and an aliphatic polyol are subjected to transesterification reaction to distill off methanol, and then the pressure is gradually reduced to carry out polycondensation under high vacuum. Calcium acetate as a transesterification catalyst,
Zinc acetate or the like can be used as the polycondensation catalyst, and known ones such as dibutyltin oxide and titanium tetrabutoxy can be used.
However, various conditions such as the polymerization method and the catalyst are not limited to the above examples.
【００１４】本発明によるポリエステルは、ゲル・パー
ミエーション・クロマトグラフィーで決定される数平均
分子量５００〜５００００の範囲であることが好まし
い。数平均分子量５００未満では、ゲル化促進効果（可
塑剤と同様の性能）は有するが耐衝撃性向上効果はわず
かしかないか又は全くない。一方、数平均分子量５００
００を越えるとポリ塩化ビニル系樹脂との相溶性が悪
く、透明性の低下、引張強度の低下等ポリ塩化ビニル系
樹脂のもつ物性が損なわれる結果となる。ポリエステル
の添加量については、ポリ塩化ビニル系樹脂１００重量
部に対して０．１重量部から２０重量部の範囲で用いる
のが望ましく、これより少ないと上記の効果がなく、こ
れより多量に用いるとポリ塩化ビニル系樹脂のもつ物性
を損なうため好ましくない。The polyester according to the present invention preferably has a number average molecular weight of 500 to 50,000 as determined by gel permeation chromatography. When the number average molecular weight is less than 500, the gelation-promoting effect (performance similar to that of a plasticizer) is obtained, but the impact resistance-improving effect is little or no. On the other hand, the number average molecular weight is 500
If it exceeds 00, the compatibility with the polyvinyl chloride resin is poor, and the physical properties of the polyvinyl chloride resin are impaired, such as a decrease in transparency and a decrease in tensile strength. The amount of polyester added is preferably in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin. If it is less than this, the above effect is not obtained, and if it is used in a larger amount. And the physical properties of the polyvinyl chloride resin are impaired, which is not preferable.
【００１５】本発明の硬質塩化ビニル系樹脂組成物の成
形方法については特に限定されず、ポリ塩化ビニル系樹
脂、耐衝撃性向上剤、安定剤、滑剤、加工助剤とポリエ
ステルとを配合し、二本ロール（カレンダー）、一軸押
し出し機、二軸押し出し機等によって直接成形品を得る
か、あらかじめペレットを作成し、射出成形機、吹き込
み成形、押し出し成形、カレンダー成形等により成形品
を得てもよい。The method for molding the hard vinyl chloride resin composition of the present invention is not particularly limited, and a polyvinyl chloride resin, an impact resistance improver, a stabilizer, a lubricant, a processing aid and polyester are blended. Even if a molded product is directly obtained by a twin roll (calender), a single-screw extruder, a twin-screw extruder, etc., or a pellet is prepared in advance and a molded product is obtained by an injection molding machine, blow molding, extrusion molding, calender molding, etc. Good.
【００１６】以上のようにして得られる硬質塩化ビニル
系樹脂組成物は耐衝撃性がさらに向上し、耐衝撃性向上
剤の使用量を減少させることができポリ塩化ビニル系樹
脂の特性を損なうことがない。The hard vinyl chloride resin composition thus obtained has further improved impact resistance, the amount of impact resistance improver used can be reduced, and the properties of the polyvinyl chloride resin are impaired. There is no.
【００１７】[0017]
【実施例】以下に実施例を挙げて本発明を更に具体的に
説明する。尚、「部」は「重量部」を意味する。無水フ
タル酸、無水コハク酸、アジピン酸、プロピレングリコ
ール、エチレングリコール、トリメチロールプロパンを
下記モル比で反応したポリエステルを表１に示す。EXAMPLES The present invention will be described in more detail with reference to the following examples. In addition, "part" means "part by weight". Table 1 shows polyesters obtained by reacting phthalic anhydride, succinic anhydride, adipic acid, propylene glycol, ethylene glycol, and trimethylolpropane at the following molar ratios.
【００１８】そして表１に示す各ポリエステルをポリ塩
化ビニル樹脂に配合（表２）し、ヘンシェルミキサーに
より混合、単軸押し出し機により混練りペレット化後、
射出成形機ＩＳ５５ＥＰＮ型（商品名、東芝機械製）に
より、シリンダー温度１８０℃、金型温度５０℃および
射出圧（ゲージ圧）８０Ｋｇ／ｃｍ2 の条件で射出成形
し、物性測定用試験片を得た。この試験片で、各物性値
を測定した。Then, each polyester shown in Table 1 was blended with polyvinyl chloride resin (Table 2), mixed with a Henschel mixer, kneaded with a single screw extruder to form pellets,
An injection molding machine IS55EPN (trade name, manufactured by Toshiba Machine) was used for injection molding under the conditions of a cylinder temperature of 180 ° C., a mold temperature of 50 ° C. and an injection pressure (gauge pressure) of 80 kg / cm 2 to obtain a test piece for measuring physical properties. It was Each physical property value was measured with this test piece.
【００１９】 引張強さ、伸び ：ＪＩＳ Ｋ ７１１３ 曲げ強さ、曲げ弾性率 ：ＪＩＳ Ｋ ７２０３ アイゾット衝撃強さ（ノッチ付き）：ＪＩＳ Ｋ ７１１０Tensile Strength, Elongation: JIS K 7113 Bending Strength, Bending Elastic Modulus: JIS K 7203 Izod Impact Strength (with Notch): JIS K 7110
【００２０】[0020]
【表１】 [Table 1]
【００２１】[0021]
【表２】 [Table 2]
【００２２】[0022]
【表３】 [Table 3]
【００２３】[0023]
【発明の効果】試験結果を表３に示した。The test results are shown in Table 3.
【００２４】試験結果から明らかなように、本発明の実
施例のものはいずれも耐衝撃性が向上しており、成形品
の引張強さ、伸び等の物性面でも優れていることが分か
る。As is apparent from the test results, all of the examples of the present invention have improved impact resistance and are excellent in physical properties such as tensile strength and elongation of the molded product.
【００２５】したがって、本発明の硬質塩化ビニル系樹
脂組成物は、ハウジング、パイプ継ぎ手、バルブ等の射
出成形品、工業用板、パイプ、雨樋、窓枠等の押し出し
成形品及び成形品用材料として好適に使用される。Therefore, the hard vinyl chloride resin composition of the present invention is used as an injection molded product such as a housing, a pipe joint, a valve, an extrusion molded product such as an industrial plate, a pipe, a gutter and a window frame, and a material for the molded product. Is preferably used as.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｌ 55:02 23:08 67:02） ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display area C08L 55:02 23:08 67:02)
Claims (2)
撃性向上剤０．１重量部から５０重量部を含む組成物に
おいて、ポリ塩化ビニル系樹脂１００重量部に対して
０．１重量部から２０重量部のポリエステルを含有して
なる硬質塩化ビニル系樹脂組成物。1. A composition containing 100 parts by weight of a polyvinyl chloride resin and 0.1 to 50 parts by weight of an impact resistance improver, and 0.1 parts by weight per 100 parts by weight of the polyvinyl chloride resin. To 20 parts by weight of polyester, a hard vinyl chloride resin composition.
ルボン酸、脂環族ジカルボン酸、芳香族ジカルボン酸か
ら選ばれる一種以上のジカルボン酸と、脂肪族ポリオー
ルから脱水縮合により得られたポリエステル（数平均分
子量５００〜５００００）であること特徴とする硬質塩
化ビニル系樹脂組成物。2. A polyester obtained by dehydration condensation of one or more dicarboxylic acids selected from an aliphatic dicarboxylic acid, an alicyclic dicarboxylic acid and an aromatic dicarboxylic acid, and an aliphatic polyol. A hard vinyl chloride resin composition having an average molecular weight of 500 to 50,000).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6162614A JPH083403A (en) | 1994-06-21 | 1994-06-21 | Hard vinyl chloride resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6162614A JPH083403A (en) | 1994-06-21 | 1994-06-21 | Hard vinyl chloride resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH083403A true JPH083403A (en) | 1996-01-09 |
Family
ID=15757953
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6162614A Pending JPH083403A (en) | 1994-06-21 | 1994-06-21 | Hard vinyl chloride resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH083403A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008144095A (en) * | 2006-12-13 | 2008-06-26 | Denki Kagaku Kogyo Kk | Resin composition and fiber comprising the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4937573B1 (en) * | 1970-12-03 | 1974-10-09 | ||
| JPS5117944A (en) * | 1974-05-09 | 1976-02-13 | Sumitomo Chemical Co | ENKABINIRUJUSHISHOKETSUTAI NO MOROSAKAIRYOHOHO |
| JPS532556A (en) * | 1976-06-29 | 1978-01-11 | Dainippon Ink & Chem Inc | Vinyl chloride resin compositions |
| JPS60186553A (en) * | 1984-03-05 | 1985-09-24 | Sekisui Chem Co Ltd | Vinyl chloride resin composition |
-
1994
- 1994-06-21 JP JP6162614A patent/JPH083403A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4937573B1 (en) * | 1970-12-03 | 1974-10-09 | ||
| JPS5117944A (en) * | 1974-05-09 | 1976-02-13 | Sumitomo Chemical Co | ENKABINIRUJUSHISHOKETSUTAI NO MOROSAKAIRYOHOHO |
| JPS532556A (en) * | 1976-06-29 | 1978-01-11 | Dainippon Ink & Chem Inc | Vinyl chloride resin compositions |
| JPS60186553A (en) * | 1984-03-05 | 1985-09-24 | Sekisui Chem Co Ltd | Vinyl chloride resin composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008144095A (en) * | 2006-12-13 | 2008-06-26 | Denki Kagaku Kogyo Kk | Resin composition and fiber comprising the same |
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