JPH11246732A - Thermoplastic resin composition and extruded molded article using it - Google Patents
Thermoplastic resin composition and extruded molded article using itInfo
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- JPH11246732A JPH11246732A JP4661698A JP4661698A JPH11246732A JP H11246732 A JPH11246732 A JP H11246732A JP 4661698 A JP4661698 A JP 4661698A JP 4661698 A JP4661698 A JP 4661698A JP H11246732 A JPH11246732 A JP H11246732A
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- thermoplastic resin
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は異形押出し時の外観
悪化の原因となっている加熱時の樹脂の熱劣化を抑制
し、かつ耐衝撃性、機械的特性、特に成形品外観、成形
加工性に優れた熱可塑性樹脂組成物であり、雨樋部品、
自動車関連部品、住宅関連部品、電柱銘板などに使用さ
れる押出し成形品に好適な材料を提供するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention suppresses thermal degradation of a resin during heating which causes deterioration in appearance during profile extrusion, and also provides impact resistance and mechanical properties, especially appearance of molded articles and moldability. Excellent thermoplastic resin composition, gutter parts,
An object of the present invention is to provide a material suitable for an extruded product used for an automobile-related part, a housing-related part, a telephone pole nameplate and the like.
【０００２】[0002]
【従来技術】成形品に好適な耐衝撃性熱可塑性樹脂とし
て、ＡＢＳ樹脂、ＡＥＳ樹脂、ＡＡＳ樹脂等の樹脂−ゴ
ム２相系の熱可塑性樹脂があり各種用途に用いられてい
る。押出し成形用材料としては汎用ＡＳ樹脂と高分子量
ＡＳ樹脂を混合した組成物等があるが、熱劣化に対する
対策が行われていないため、成形条件の幅が狭く、成形
品外観が優れず、またロングラン時の外観悪化、リサイ
クル時の着色等の問題もある。2. Description of the Related Art Two-phase resin-rubber thermoplastic resins such as ABS resin, AES resin and AAS resin have been used as impact-resistant thermoplastic resins suitable for molded articles, and are used for various purposes. Extrusion molding materials include compositions in which a general-purpose AS resin and a high-molecular-weight AS resin are mixed, but since measures against thermal deterioration have not been taken, the range of molding conditions is narrow, and the appearance of the molded product is not excellent. There are also problems such as deterioration in appearance during long runs and coloring during recycling.
【０００３】[0003]
【発明が解決しようとする課題】押出し成形時に成形機
内に樹脂溜まり等が発生し、押出し成形品表面外観が悪
化（肌荒れ、ダイラインの発生）する原因となってい
る。本発明は押出し成形時の外観悪化の原因となってい
る成形機内の樹脂溜まりを無くし、加熱時の樹脂の熱劣
化を抑制し、かつ耐衝撃性、機械的特性、特に成形品外
観、成形加工性に優れた熱可塑性樹脂組成物を提供する
ものである。[0005] During extrusion molding, resin pools and the like are generated in the molding machine, which causes the surface appearance of the extruded product to be deteriorated (rough skin and die lines). The present invention eliminates resin accumulation in a molding machine that causes deterioration in appearance during extrusion molding, suppresses thermal degradation of resin during heating, and provides impact resistance, mechanical properties, especially molded product appearance, molding processing. It is intended to provide a thermoplastic resin composition having excellent properties.
【０００４】[0004]
【課題を解決するための手段】本発明は、下記の（Ａ）
〜（Ｄ）よりなる熱可塑性樹脂組成物及びこれを用いて
得られる押出し成形品に関する。 （Ａ）ゴム状重合体の存在下に、芳香族ビニル化合物、
シアン化ビニル化合物及びこれらと共重合可能な単量体
混合物を重合して得られるグラフト共重合体、（Ｂ）芳
香族ビニル化合物、シアン化ビニル化合物及びこれらと
共重合可能な単量体混合物を重合して得られる共重合
体、（Ｃ）燐系加工安定剤、及び（Ｄ）可塑剤Means for Solving the Problems The present invention provides the following (A)
To (D) and an extruded product obtained using the same. (A) an aromatic vinyl compound in the presence of a rubbery polymer,
A graft copolymer obtained by polymerizing a vinyl cyanide compound and a monomer mixture copolymerizable therewith, (B) an aromatic vinyl compound, a vinyl cyanide compound and a monomer mixture copolymerizable therewith; Copolymer obtained by polymerization, (C) phosphorus-based processing stabilizer, and (D) plasticizer
【０００５】本発明においては、（Ｂ）共重合体の重量
平均分子量が１５万〜４０万である上記の熱可塑性樹脂
組成物であることが好ましい。In the present invention, it is preferable that the thermoplastic resin composition has a weight average molecular weight of the copolymer (B) of 150,000 to 400,000.
【０００６】本発明においては、（Ｂ）共重合体の組成
比（重量）が、芳香族ビニル化合物：シアン化ビニル化
合物：共重合可能な単量体＝２０〜３５：８０〜６５：
０〜２０である上記の熱可塑性樹脂組成物であることが
好ましい。In the present invention, the composition ratio (weight) of the copolymer (B) is as follows: aromatic vinyl compound: vinyl cyanide compound: copolymerizable monomer = 20 to 35:80 to 65:
It is preferable that the above-mentioned thermoplastic resin composition is 0 to 20.
【０００７】本発明においては、（Ｃ）燐系加工安定剤
を０．０５〜５重量％及び（Ｄ）可塑剤を０．１〜５重
量％含有してなる上記の熱可塑性樹脂組成物であること
が好ましい。In the present invention, the thermoplastic resin composition comprises (C) 0.05 to 5% by weight of a phosphorus-based processing stabilizer and (D) 0.1 to 5% by weight of a plasticizer. Preferably, there is.
【０００８】[0008]
【発明の実施の形態】次に本発明を詳細に説明する。本
発明における（Ａ）グラフト重合体としては、ＡＢＳ樹
脂（アクリロニトリルーブタジエンースチレン三元共重
合体）、ＡＥＳ樹脂（アクリロニトリルーエチレンプロ
ピレンゴムースチレン三元共重合体）、ＡＡＳ樹脂（ア
クリロニトリルーアクリルゴムースチレン三元共重合
体）等が挙げられ、その中で好ましいものは、ＡＡＳ樹
脂である。Next, the present invention will be described in detail. As the graft polymer (A) in the present invention, ABS resin (acrylonitrile butadiene-styrene terpolymer), AES resin (acrylonitrile ethylene propylene rubber-styrene terpolymer), AAS resin (acrylonitrile acryl) Rubber-styrene terpolymer), among which AAS resin is preferable.
【０００９】本発明における（Ｂ）共重合体としては、
アクリロニトリルースチレン共重合体、アクリロニトリ
ルーαメチルスチレンースチレン共重合体、アクリロニ
トリルースチレンーメタクリル酸エステル共重合体、ア
クリロニトリルースチレンーメトフェニルマレイミド共
重合体等が挙げられ、その中で好ましいものは、アクリ
ロニトリルースチレン共重合体である。The (B) copolymer in the present invention includes:
Acrylonitrile styrene copolymer, acrylonitrile α-methylstyrene-styrene copolymer, acrylonitrile styrene-methacrylic acid ester copolymer, acrylonitrile styrene-methphenyl maleimide copolymer, and the like, among which preferred ones. And an acrylonitrile styrene copolymer.
【００１０】本発明は、（Ａ）グラフト共重合体及び
（Ｂ）共重合体を含有する熱可塑性樹脂組成物であり、
いわゆるグラフト・ブレンド型ＡＡＳ、ＡＢＳ、ＡＥＳ
樹脂において、共重合体（Ｂ）の重量平均分子量が１５
〜４０万であることが好ましい。 （Ａ）グラフト共重
合体と（Ｂ）共重合体の混合比率は、重量比で１０〜８
０：９０〜２０が好ましく、より好ましくは、２０〜８
０：８０〜２０とする。グラフト共重合体（Ａ）の添加
量が上記の混合比率で８０を越えると、耐熱性、流動
性、成形加工性、外観が低下する傾向があり、また共重
合体（Ｂ）の添加量が上記の混合比率で９０を越える
と、耐候性、耐衝撃性が低下する傾向がある。また、共
重合体（Ｂ）の重量平均分子量が１５万未満では溶融粘
度が低くなるため、成形機内に樹脂溜まり、樹脂焼けな
どが生じ、良好な成形品外観を得ることが出来ない傾向
があり、また、平均分子量が４０万を越えると樹脂の溶
融粘度が高くなりすぎるため異形押出し性が低下する傾
向がある。The present invention is a thermoplastic resin composition containing (A) a graft copolymer and (B) a copolymer,
So-called graft-blend type AAS, ABS, AES
In the resin, the weight average molecular weight of the copolymer (B) is 15
Preferably, it is up to 400,000. The mixing ratio of the (A) graft copolymer and (B) copolymer is 10 to 8 by weight.
0: 90-20 is preferable, and 20-20 is more preferable.
0: 80 to 20. When the addition amount of the graft copolymer (A) exceeds 80 in the above mixing ratio, heat resistance, fluidity, moldability, and appearance tend to decrease, and the addition amount of the copolymer (B) is reduced. If the mixing ratio exceeds 90, the weather resistance and impact resistance tend to decrease. If the weight average molecular weight of the copolymer (B) is less than 150,000, the melt viscosity is low, so that the resin is accumulated in the molding machine, the resin is burned, and the like, and there is a tendency that a good molded product appearance cannot be obtained. If the average molecular weight exceeds 400,000, the melt viscosity of the resin becomes too high, and the profile extrusion property tends to decrease.
【００１１】本発明における（Ｃ）燐系加工安定剤とし
ては、例えば、トリス（トリデシル）フォスフォナイ
ト、フェニールジイソシルフォスフォナイト、テトラキ
ス（２，４−ジ−ｔ−ブチルフェニル）４，４−ビフェ
ニレンジフォスフォナイト、トリス（２，４−ジ−ｔ−
ブチルフェニル）フォスフォナイト、トリス（２，４−
ジ−ｔ−ブチルフェニル）フォスフォナイト、９，１０
−ジヒドロ−９−ｘａ−１０−フォスフォ−１０−オキ
シド等が挙げられ、好ましくはテトラキス（２，４−ジ
−ｔ−ブチルフェニル）４，４−ビフェニレンジフォス
フォナイト、トリス（２，４−ジ−ｔ−ブチルフェニ
ル）フォスフォナイトまたは９，１０−ジヒドロ−９−
ｘａ−１０−フォスフォフェナンスレン−１０−オキシ
ドが挙げられ、より好ましくはテトラキス（２，４−ジ
−ｔ−ブチルフェニル）４，４−ビフェニレンジフォス
フォナイトが挙げられる。As the phosphorus-based processing stabilizer (C) in the present invention, for example, tris (tridecyl) phosphonite, phenyldiisosylphosphonite, tetrakis (2,4-di-t-butylphenyl) 4, 4-biphenylenediphosphonite, tris (2,4-di-t-
Butylphenyl) phosphonite, tris (2,4-
Di-t-butylphenyl) phosphonite, 9,10
-Dihydro-9-xa-10-phospho-10-oxide and the like, preferably tetrakis (2,4-di-t-butylphenyl) 4,4-biphenylenediphosphonite and tris (2,4- Di-tert-butylphenyl) phosphonite or 9,10-dihydro-9-
xa-10-phosphophenanthrene-10-oxide, more preferably, tetrakis (2,4-di-t-butylphenyl) 4,4-biphenylenediphosphonite.
【００１２】本発明における（Ｃ）燐系加工安定剤は、
熱可塑性樹脂組成物に対して０．０５〜５重量％添加す
ることが好ましく、０．１〜３重量％添加することがよ
り好ましい。添加量が０．０５重量％未満では加工安定
剤としての効果を得ることが難しい傾向があり、また、
５重量％を越えると、成形時に良好な成形品の外観を得
ることが出来ない傾向がある。また（Ｃ）燐系加工安定
剤の使用により、加工時の熱安定性が飛躍的に向上し、
押出し成形時の成形幅を大幅に広くすることが可能にな
る。The (C) phosphorus-based processing stabilizer in the present invention comprises:
It is preferably added in an amount of 0.05 to 5% by weight, more preferably 0.1 to 3% by weight, based on the thermoplastic resin composition. If the addition amount is less than 0.05% by weight, it tends to be difficult to obtain the effect as a processing stabilizer,
If it exceeds 5% by weight, it tends to be impossible to obtain a good appearance of a molded article during molding. In addition, the use of (C) a phosphorus-based processing stabilizer dramatically improves the thermal stability during processing,
It is possible to greatly increase the molding width during extrusion molding.
【００１３】本発明における（Ｄ）可塑剤としては、例
えば、アジピン酸ジ２エチルへキシル、アジピン酸ジイ
ソノニル、アジピン酸ジイソデシル、アジピン酸ジアル
キル等のアジピン酸系可塑剤、トリメリット酸トリ２エ
チルヘキシル、トリメリット酸トリアルキル等のトリメ
リット酸系可塑剤、フタル酸ジブチル、フタル酸２エチ
ルへキシル、フタル酸ジイソニル、フタル酸ジアルキ
ル、フタル酸ジウンデシル、フタル酸ブチルベンジル等
のフタル酸系可塑剤が挙げられるが、フタル酸系可塑剤
が好ましく、より好ましくはフタル酸ジアルキルであ
る。The plasticizer (D) in the present invention includes, for example, adipic acid-based plasticizers such as di-2-ethylhexyl adipate, diisononyl adipate, diisodecyl adipate and dialkyl adipate; tri-2-ethylhexyl trimellitate; Trimellitic plasticizers such as trialkyl trimellitate; and phthalic plasticizers such as dibutyl phthalate, 2-ethylhexyl phthalate, diisonyl phthalate, dialkyl phthalate, diundecyl phthalate, and butylbenzyl phthalate. However, a phthalic plasticizer is preferable, and a dialkyl phthalate is more preferable.
【００１４】本発明における（Ｄ）可塑剤は、熱可塑性
樹脂組成物に対して０．１〜５重量％添加することが好
ましく、０．３〜３重量％がより好ましい。添加量が１
重量％未満では可塑剤としての効果を得ることができな
い傾向があり、５重量％を越えると成形加工性が低下す
る傾向がある。In the present invention, the plasticizer (D) is preferably added in an amount of 0.1 to 5% by weight, more preferably 0.3 to 3% by weight, based on the thermoplastic resin composition. Addition amount is 1
If it is less than 5% by weight, the effect as a plasticizer tends not to be obtained, and if it exceeds 5% by weight, the moldability tends to decrease.
【００１５】本発明においては、着色剤、帯電防止剤、
滑剤等を樹脂の特性を阻害しない量で添加することがで
き、また、酸化防止剤、光安定剤、紫外線吸収剤等を所
定量添加することにより耐候性が向上される。In the present invention, a coloring agent, an antistatic agent,
A lubricant or the like can be added in an amount that does not inhibit the properties of the resin, and the weather resistance is improved by adding a predetermined amount of an antioxidant, a light stabilizer, an ultraviolet absorber or the like.
【００１６】本発明になる熱可塑性樹脂組成物は、耐衝
撃性、機械的特性、熱安定性に優れ、特に押出し成形時
の成形加工性、成形品の外観に優れる熱可塑性樹脂組成
物であり、例えば、雨樋部品、自動車関連部品、住宅関
連部品、電柱銘板などに使用される押出し成形品に好適
な材料である。The thermoplastic resin composition according to the present invention is excellent in impact resistance, mechanical properties, and thermal stability, and is particularly excellent in moldability during extrusion molding and appearance of a molded article. For example, it is a material suitable for extruded products used for gutter parts, automobile-related parts, house-related parts, telephone pole nameplates, and the like.
【００１７】[0017]
【実施例】次に、本発明を実施例により説明するが、本
発明はこれらにより制限されるものではない。Next, the present invention will be described by way of examples, which should not be construed as limiting the present invention.
【００１８】熱可塑性樹脂組成物の各種物性値は、以下
に記載の方法によって評価した。 耐衝撃強さ：ＪＩＳ Ｋ７１１０に準拠し、１／８イン
チの試験片によるアイゾット衝撃強さ（ノッチ付き）を意
味する（単位：kg・cm/cm）。 曲げ強さ：ＪＩＳ Ｋ７２０３に準拠した（単位：kg/c
m2）。 流動性（ＭＦＲ）：ＪＩＳ Ｋ７２１０の手法により、
温度２２０℃，荷重５ｋｇの条件下で１０分間の流量を
示す（単位：g/10min）。 また、共重合体（Ｂ）の重量平均分子量はゲル浸透クロ
マトグラフィー（ＧＰＣ）装置を用い測定した。Various physical properties of the thermoplastic resin composition were evaluated by the methods described below. Impact strength: In accordance with JIS K7110, means Izod impact strength (with notch) using a 1/8 inch test piece (unit: kg · cm / cm). Flexural strength: based on JIS K7203 (unit: kg / c
m 2). Fluidity (MFR): According to the method of JIS K7210,
Shows the flow rate for 10 minutes under the conditions of a temperature of 220 ° C. and a load of 5 kg (unit: g / 10 min). The weight average molecular weight of the copolymer (B) was measured using a gel permeation chromatography (GPC) device.
【００１９】異形押出し性樹脂組成物からパイプ押出し
機（ＩＫＧ製、ＥＡ２１−ＢＮＤ）によって直径３０m
m、厚さ２mmのパイプ成形品を成形温度２１０℃、スク
リュウ回転数３０回転／分で成形した。 （１）成形する際のパイプ引き取り速度の測定は引き取
り機により測定を行った。パイプ引き取り速度が速いほ
ど生産性が良いことを示す。 （２）得られた成形品の表面の外観（ダイライン）の深
さを表面粗さ計で測定した。ダイラインが深いほど外観
が悪いことを示す。 （３）樹脂の熱安定性は、ダイスに付着する劣化物を肉
眼で観察し、付着のないものを「熱安定性」○、少量付
着しているものを「熱安定性」△、多量に付着している
ものを「熱安定性」×としてそれぞれ表示した。 （４）ロングランテストでの外観変化は、ロングランテ
ストを２時間行った時のダイライン深さの変化を表面粗
さ計で測定した。ロングランテストはパイプ押出し機に
よって直径３０ｍｍ、厚さ２ｍｍのパイプ成形品を成形
温度２１０℃、スクリュウ回転数３０回転／分で測定し
た。 （５）押出し成形機内の樹脂溜まりは、成形機ダイスを
はずし樹脂を取り出すことにより樹脂の付着具合を観察
した。樹脂がきれいにとれるものを「樹脂溜まり」○、
樹脂が残ってしまうものを「樹脂溜まり」×とした。From the deformable extrudable resin composition, a pipe extruder (manufactured by IKG, EA21-BND) has a diameter of 30 m.
A molded pipe having a thickness of 2 mm and a thickness of 2 mm was molded at a molding temperature of 210 ° C. and a screw rotation speed of 30 rotations / minute. (1) The pipe take-up speed during molding was measured by a take-up machine. The higher the pipe take-up speed, the better the productivity. (2) The depth of the appearance (die line) of the surface of the obtained molded article was measured by a surface roughness meter. The deeper the die line, the worse the appearance. (3) The thermal stability of the resin is determined by observing the degraded material adhering to the die with the naked eye. Those that adhered were indicated as "thermal stability" x. (4) The change in appearance in the long run test was measured by measuring the change in die line depth when the long run test was performed for 2 hours with a surface roughness meter. In the long run test, a pipe molded product having a diameter of 30 mm and a thickness of 2 mm was measured by a pipe extruder at a molding temperature of 210 ° C. and a screw rotation speed of 30 rotations / minute. (5) The resin pool in the extrusion molding machine was observed by removing the molding machine dies and taking out the resin. If the resin can be removed neatly, "resin pool" ○,
What left the resin was designated as "resin pool".
【００２０】１.グラフト共重合体（Ａ）の製造 １−１ グラフト共重合体ゴムラテックスの製造 ［配合組成］ 成分(1)：ポリブタジエンラテックス（住友ダウ、SNX80
04）３００重量部 成分(2)：アクリル酸ブチル ７００重量 アリルメタクリレート ０．６８９重量部 成分(3)：過硫酸カリウム ０．０４重量部 亜硫酸ナトリウム ０．０４重量部 乳化剤（花王製、ＫＳソープ） ９．２重量部 脱イオン水 １４２０重量部 ［重合操作］反応容器に成分(1)及び均一に溶融した成
分(3)を仕込んで混合撹拌した後、均一に溶解した成分
(2)を添加し、６０〜６５℃で約４．５時間重合させた
後冷却して重合を停止させた。この時の重合率は６５％
であった。1. Production of Graft Copolymer (A) 1-1 Production of Graft Copolymer Rubber Latex [Blending Composition] Component (1): Polybutadiene latex (Sumitomo Dow, SNX80)
04) 300 parts by weight Component (2): butyl acrylate 700 parts by weight Allyl methacrylate 0.689 part by weight Component (3): potassium persulfate 0.04 parts by weight sodium sulfite 0.04 parts by weight Emulsifier (KAO, KS soap) 9.2 parts by weight Deionized water 1420 parts by weight [Polymerization operation] Ingredient (1) and homogeneously melted ingredient (3) are charged into a reaction vessel, mixed and stirred, and then uniformly dissolved.
(2) was added, and the mixture was polymerized at 60 to 65 ° C. for about 4.5 hours, and then cooled to stop the polymerization. The polymerization rate at this time is 65%
Met.
【００２１】１−２ グラフト共重合体ゴムラテックス
存在下での乳化重合 成分(4)：脱イオン水 １４２５重量部 乳化剤（ＫＳソープ） １０．６重量部 ロンガリット（住友化学製） ２．８重量部 成分(5)：スチレン ６１．６重量部 アクリロニトリル ２０．６重量部 アリルメタクリレート １．９０５重量部 ジビニルベンゼン ０．５９６重量部 キュメンハイドロパーオキサイド ０．１４８重量部 ｔ−ドデシルメルカプタン ０．３７重量部 成分(6)：スチレン ４６３．３重量部 アクリロニトリル １５４．５重量部 キュメンハイドロパーオキサイド ０．４９４重量部 ｔ−ドデシルメルカプタン ２．７８８重量部 ［重合操作］均一に溶解した成分(4)及び(5)を反応容器
に仕込み、均一に撹拌混合した後、上記で得たグラフト
共重合体ゴムラテックスを添加し、窒素置換しながら更
に３０分撹拌混合した。その後、約７０℃にて２．５時
間重合し、重合率が５５％以上に達していることを確認
した後、更にピロリン酸ソーダ５．８３部、硫化第一鉄
０．１１２重量部を各々添加溶解し、続いて、成分(6)
をを約３．５時間かけて連続的に滴下した。滴下終了
後、同温度で約一時間保温した後８０℃に昇温し３０分
保温した後樹脂ラテックスを得た。最終重合率は９０％
であった。この樹脂ラテックスを硫酸アルミを溶解した
熱水中で塩析し、析出した粉体を乾燥脱水して樹脂粉末
を得た。1-2 Emulsion polymerization in the presence of graft copolymer rubber latex Component (4): 1425 parts by weight of deionized water Emulsifier (KS soap) 10.6 parts by weight Rongalit (manufactured by Sumitomo Chemical) 2.8 parts by weight Component (5): 61.6 parts by weight of styrene 20.6 parts by weight of acrylonitrile 1.905 parts by weight of allyl methacrylate 0.596 parts by weight of divinylbenzene 0.148 parts by weight of cumene hydroperoxide 0.37 parts by weight of t-dodecyl mercaptan (6): 463.3 parts by weight of styrene 154.5 parts by weight of acrylonitrile 0.494 parts by weight of cumene hydroperoxide 2.788 parts by weight of t-dodecylmercaptan [Polymerization operation] Uniformly dissolved components (4) and (5) Into a reaction vessel, and uniformly stirred and mixed.Then, the graft copolymer rubber latex obtained above was mixed. The mixture was added and stirred and mixed for another 30 minutes while replacing with nitrogen. Thereafter, polymerization was carried out at about 70 ° C. for 2.5 hours, and after confirming that the polymerization rate had reached 55% or more, 5.83 parts of sodium pyrophosphate and 0.112 parts by weight of ferrous sulfide were further added. Addition and dissolution, followed by ingredient (6)
Was continuously added dropwise over about 3.5 hours. After completion of the dropwise addition, the mixture was kept at the same temperature for about 1 hour, then heated to 80 ° C. and kept for 30 minutes to obtain a resin latex. Final polymerization rate is 90%
Met. The resin latex was salted out in hot water in which aluminum sulfate was dissolved, and the precipitated powder was dried and dehydrated to obtain a resin powder.
【００２２】２. 共重合体（Ｂ）の製造 ２ー１ 共重合体（Ｂー１）の製造 ［配合組成］ 成分(1)：イオン交換水 １５００重量部 リン酸カルシウム水溶液 ３０重量部（１０重量％水溶
液） ドデシルベンゼンスルホン酸ナトリウム水溶液 ０．４
重量部（１２．５重量％水溶液） 成分(2)：スチレン １１４０重量部 成分(3)：アクリロニトリル ３６０重量部 成分(4)：ターシャリドシルメルカプタン ３．６重量部 成分(5)：ジラウロイルパーオキサイド ７．５重量部 1,1-ヒ゛ス(t-フ゛チルハ゜ーオキシ)3,3,5トリメチルシクロヘキサン ０．７５重
量部 ［重合操作］反応容器に成分(1)を仕込んで、混合撹拌
した後、成分(2),(3),(4)及び(5)を混合し均一に溶解し
て添加し、窒素置換後に昇温して、６５℃で８時間縣濁
重合し、ついで１１０℃に昇温した後、２時間重合して
冷却した。この縣濁物を脱水乾燥し、スチレン−アクリ
ロニトリル共重合体（ＡＳ樹脂）を得た。得られた樹脂
の重量平均分子量は１６万であった。2. Preparation of copolymer (B) 2-1 Preparation of copolymer (B-1) [Blending composition] Component (1): 1500 parts by weight of ion-exchanged water 30 parts by weight of calcium phosphate aqueous solution (10% by weight) Aqueous solution) Sodium dodecylbenzenesulfonate aqueous solution 0.4
Part by weight (12.5% by weight aqueous solution) Component (2): 1140 parts by weight of styrene Component (3): 360 parts by weight of acrylonitrile Component (4): 3.6 parts by weight of tertiary syl mercaptan Component (5): dilauroyl par Oxide 7.5 parts by weight 1,1-bis (t-butylperoxy) 3,3,5 trimethylcyclohexane 0.75 parts by weight [Polymerization operation] Ingredient (1) is charged into a reaction vessel, and mixed and stirred. Components (2), (3), (4) and (5) are mixed and uniformly dissolved and added. The temperature is raised after purging with nitrogen, suspension polymerization is carried out at 65 ° C for 8 hours, and then the temperature is raised to 110 ° C. After warming, it was polymerized for 2 hours and cooled. The suspension was dehydrated and dried to obtain a styrene-acrylonitrile copolymer (AS resin). The weight average molecular weight of the obtained resin was 160,000.
【００２３】２ー２ 共重合体（Ｂー２）の製造 ターシャリドデシルメルカプタンを配合しないこと以外
は共重合体（Ｂー１）と同様にＡＳ樹脂を製造した。得
られた樹脂の重量平均分子量は４０万であった。2-2 Preparation of copolymer (B-2) An AS resin was prepared in the same manner as the copolymer (B-1) except that tertiary decyl mercaptan was not blended. The weight average molecular weight of the obtained resin was 400,000.
【００２４】２ー３ 共重合体（Ｂー３）の製造 ターシャリドデシルメルカプタンを４．５重量％添加し
たこと以外は共重合体（Ｂー１）と同様にＡＳ樹脂を製
造した。得られた樹脂の重量平均分子量は１２万であっ
た。2-3 Preparation of Copolymer (B-3) An AS resin was prepared in the same manner as for the copolymer (B-1), except that 4.5% by weight of tertiary decyl mercaptan was added. The weight average molecular weight of the obtained resin was 120,000.
【００２５】実施例１〜６及び比較例１〜３ 上記の実施例により得られた（Ａ）グラフト共重合体と
（Ｂ）アクリロニトリルの含有量が２４重量％であり、
重量平均分子量（Ｍw）が異なる各種のスチレン−アク
リロニトリル共重合体（Ｂ−１，２及び３）と燐系加工
安定剤と可塑剤をそれぞれ表１の通り配合して二軸押出
し機により溶融混練し、ペレット化した。このペレット
を用い射出成形機によって物性測定用のテストピースを
成形し、前記の評価法によって物性を評価した。又、こ
のペレットを用いて押出し成形を行い、前記した評価方
法によって成形品の引き取り速度、ダイライン深さ、熱
安定性、ロングランテストでの外観変化及び樹脂溜まり
を評価した結果を表１に示す。Examples 1 to 6 and Comparative Examples 1 to 3 The content of (A) the graft copolymer and (B) acrylonitrile obtained in the above Examples was 24% by weight,
Various styrene-acrylonitrile copolymers (B-1, 2, and 3) having different weight average molecular weights (M w ), a phosphorus-based processing stabilizer and a plasticizer are blended as shown in Table 1, and melted by a twin-screw extruder. It was kneaded and pelletized. Using the pellets, a test piece for measuring physical properties was molded by an injection molding machine, and the physical properties were evaluated by the above-described evaluation methods. Extrusion molding was performed using the pellets, and the results of evaluation of the take-up speed, die line depth, thermal stability, change in appearance in a long run test, and resin accumulation by the evaluation method described above are shown in Table 1.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【発明の効果】本発明の熱可塑性樹脂組成物は、耐衝撃
性、機械的強度に優れ、押出し成形時の成形性加工性、
成形品外観、熱安定性に更に優れる樹脂組成物であり、
雨樋部品、自動車関連部品、住宅関連部品、電柱銘板な
どに幅広く使用できる材料を提供する。The thermoplastic resin composition of the present invention has excellent impact resistance and mechanical strength, and has excellent moldability and processability during extrusion molding.
It is a resin composition that is more excellent in molded product appearance and thermal stability,
Provide materials that can be widely used for gutter parts, automobile-related parts, housing-related parts, telephone pole nameplates, etc.
Claims (5)
樹脂組成物。 （Ａ）ゴム状重合体の存在下に、芳香族ビニル化合物、
シアン化ビニル化合物及びこれらと共重合可能な単量体
混合物を重合して得られるグラフト共重合体、（Ｂ）芳
香族ビニル化合物、シアン化ビニル化合物及びこれらと
共重合可能な単量体混合物を重合して得られる共重合
体、（Ｃ）燐系加工安定剤、及び（Ｄ）可塑剤1. A thermoplastic resin composition comprising the following (A) to (D). (A) an aromatic vinyl compound in the presence of a rubbery polymer,
A graft copolymer obtained by polymerizing a vinyl cyanide compound and a monomer mixture copolymerizable therewith, (B) an aromatic vinyl compound, a vinyl cyanide compound and a monomer mixture copolymerizable therewith; Copolymer obtained by polymerization, (C) phosphorus-based processing stabilizer, and (D) plasticizer
〜４０万である請求項１記載の熱可塑性樹脂組成物。2. The thermoplastic resin composition according to claim 1, wherein the weight average molecular weight of the copolymer (B) is 150,000 to 400,000.
族ビニル化合物：シアン化ビニル化合物：共重合可能な
単量体＝２０〜３５：８０〜６５：０〜２０である請求
項１または２記載の熱可塑性樹脂組成物。3. The composition ratio (weight) of the copolymer (B) is aromatic vinyl compound: vinyl cyanide compound: copolymerizable monomer = 20-35: 80-65: 0-20. The thermoplastic resin composition according to claim 1.
％及び（Ｄ）可塑剤を０．１〜５重量％含有してなる請
求項１〜３のいずれか１項記載の熱可塑性樹脂組成物。4. The method according to claim 1, which comprises (C) 0.05 to 5% by weight of a phosphorus-based processing stabilizer and (D) 0.1 to 5% by weight of a plasticizer. Thermoplastic resin composition.
塑性樹脂組成物を用いて得られる押出し成形品。5. An extruded product obtained by using the thermoplastic resin composition according to claim 1. Description:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04661698A JP4722237B2 (en) | 1998-02-27 | 1998-02-27 | Thermoplastic resin composition and profile extrusion product using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04661698A JP4722237B2 (en) | 1998-02-27 | 1998-02-27 | Thermoplastic resin composition and profile extrusion product using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11246732A true JPH11246732A (en) | 1999-09-14 |
| JP4722237B2 JP4722237B2 (en) | 2011-07-13 |
Family
ID=12752242
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2004041678A1 (en) * | 2002-11-06 | 2006-03-09 | 冨士ベークライト株式会社 | Clean room container |
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1998
- 1998-02-27 JP JP04661698A patent/JP4722237B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2004041678A1 (en) * | 2002-11-06 | 2006-03-09 | 冨士ベークライト株式会社 | Clean room container |
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| Publication number | Publication date |
|---|---|
| JP4722237B2 (en) | 2011-07-13 |
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