JPH03269006A - New copolymer resin having excellent transparency - Google Patents
New copolymer resin having excellent transparencyInfo
- Publication number
- JPH03269006A JPH03269006A JP6680190A JP6680190A JPH03269006A JP H03269006 A JPH03269006 A JP H03269006A JP 6680190 A JP6680190 A JP 6680190A JP 6680190 A JP6680190 A JP 6680190A JP H03269006 A JPH03269006 A JP H03269006A
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- weight
- content
- unsaturated nitrile
- unit
- 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.)
- Granted
Links
- 229920006026 co-polymeric resin Polymers 0.000 title claims abstract description 11
- 229920001577 copolymer Polymers 0.000 claims abstract description 38
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000002560 nitrile group Chemical group 0.000 claims 5
- 150000002825 nitriles Chemical group 0.000 abstract description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 15
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract description 8
- 229920002554 vinyl polymer Polymers 0.000 abstract description 4
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- -1 aromatic vinyl compound Chemical class 0.000 abstract 2
- 239000000203 mixture Substances 0.000 description 18
- 238000001746 injection moulding Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 238000004383 yellowing Methods 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- PLFLGERUUOMAII-UHFFFAOYSA-N 1-(2-aminoethylamino)propan-1-ol Chemical compound CCC(O)NCCN PLFLGERUUOMAII-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical class NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229920006164 aromatic vinyl copolymer Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、新規な熱可塑性共重合体樹脂に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel thermoplastic copolymer resin.
さらに詳しく言えば、本発明は、滞留変色性が少なく、
機械的強度に優れた、無色透明な芳香族ビニル単位と不
飽和ニトリル単位を主体とした新規な共重合体樹脂に関
するものである。More specifically, the present invention has low retention discoloration,
The present invention relates to a colorless and transparent copolymer resin mainly composed of aromatic vinyl units and unsaturated nitrile units, which has excellent mechanical strength.
（従来の技術及び発明が解決しようとする課題）従来、
透明性、加工性がよく、安価に入手しうる樹脂としては
アクリロニトリルとスチレンの共重合体が知られている
。(Prior art and problems to be solved by the invention) Conventionally,
A copolymer of acrylonitrile and styrene is known as a resin that has good transparency and processability and is available at low cost.
しかしながら、この樹脂はアクリロニトリルとスチレン
の共重合反応性から、積分重合法である懸濁重合や乳化
重合では、モノマー・ポリマーのアゼオ組成であるスチ
レン／アクリロニトリル＝７５／２５重量％の組成を除
いては、広い組成範囲に亘って透明な樹脂を得ることが
困難であった。However, due to the copolymerization reactivity of acrylonitrile and styrene, this resin cannot be used in suspension polymerization or emulsion polymerization, which are integral polymerization methods, except for the monomer-polymer azeo composition of styrene/acrylonitrile = 75/25% by weight. However, it was difficult to obtain transparent resin over a wide composition range.
さらに、アクリロニトリル−スチレン共重合体は、射出
成形時に黄色に着色しやすく透明性が損なわれ、工業的
使用範囲が大きく制限されることは免れ得ない。Furthermore, acrylonitrile-styrene copolymers tend to be colored yellow during injection molding, resulting in loss of transparency, which inevitably greatly limits the scope of their industrial use.
スチレン−アクリロニトリル共重合体が射出成形時に熱
変色することを改良する技術としては、ヒンダードフェ
ノール等の酸化防止剤を添加することが行われている。As a technique for improving thermal discoloration of styrene-acrylonitrile copolymers during injection molding, addition of an antioxidant such as hindered phenol has been carried out.
しかし、熱変色に対する効果を発揮するために使用され
る酸化防止剤の使用量は、一般に０． ５〜２．０重量
％であり、このように酸化防止剤の使用量が多い場合に
は、射出成形時にメヤニ等のトラブルが発生し、工業的
利用範囲の制限を免れ得ない。However, the amount of antioxidant used to exert the effect against thermal discoloration is generally 0. It is 5 to 2.0% by weight, and if the amount of antioxidant used is large, troubles such as smearing will occur during injection molding, and the scope of industrial use will inevitably be restricted.
（！！題を解決するための手段）
このような、芳香族ビニルー不飽和ニトリル共重合体の
加熱変色安定性及び透明性が充分でないという欠点を克
服するために、本発明者らは、鋭意検討を重ねた結果、
特定の共重合体組成及び共重合体組成分布をもつ共重合
体を用いることにより、透明性が良好で、機械強度に優
れ、熱滞留着色のない新規な熱可塑性共重合体樹脂を見
出し、本発明を完成するに至った。(!!Means for Solving the Problem) In order to overcome the drawbacks that the aromatic vinyl-unsaturated nitrile copolymer does not have sufficient thermal discoloration stability and transparency, the present inventors have made efforts to solve the problem. As a result of repeated consideration,
By using a copolymer with a specific copolymer composition and copolymer composition distribution, we discovered a new thermoplastic copolymer resin with good transparency, excellent mechanical strength, and no heat retention coloring. The invention was completed.
すなわち、本発明は：
（Ａ）芳香族ビニル単位と（Ｂ）不飽和ニトリル単位と
からなり、メチルエチルケトンの１０％溶液中の２５℃
における溶液粘度が６．０〜１３ｃｐｓの範囲の共重合
体であって、
芳香族ビニル単位含有量の平均値がＸ重量％、不飽和ニ
トリル単位含有量の平均値がＹ重置％とした場合に、７
７≦Ｘ≦９０．１０≦Ｙ≦２３の関係が成り立っており
、
しかも、Ｙ±５重量％の不飽和ニトリル単位をもつ共重
合体の含有量が５重量％以下、Ｙ±１０重量％の不飽和
ニトリル単位をもつ共重合体の含有量が１重量％以下、
Ｙ±１５重量％以上の不飽和ニトリル単位をもつ共重合
体の含有量が０．１重量％以下であることを特徴とする
、新規な透明性に優れた共重合体樹脂に関する。That is, the present invention comprises: (A) an aromatic vinyl unit and (B) an unsaturated nitrile unit;
A copolymer having a solution viscosity in the range of 6.0 to 13 cps, where the average aromatic vinyl unit content is X weight % and the average unsaturated nitrile unit content is Y weight %. To, 7
The relationship 7≦X≦90.10≦Y≦23 holds, and in addition, the content of the copolymer having unsaturated nitrile units of Y±5% by weight is 5% by weight or less and Y±10% by weight. The content of a copolymer having unsaturated nitrile units is 1% by weight or less,
The present invention relates to a novel copolymer resin with excellent transparency, characterized in that the content of a copolymer having unsaturated nitrile units of Y±15% by weight or more is 0.1% by weight or less.
また、該新規な透明性に優れた共重合体樹脂に添加剤と
して、Ｎ−テトラキス（α−ハイドロキシプロピルエチ
レンジアミン）などのエチレンジアミンの誘導体を配合
した組成物にも特徴を有する。Another feature is a composition in which an ethylenediamine derivative such as N-tetrakis (α-hydroxypropylethylenediamine) is blended as an additive with the new copolymer resin having excellent transparency.
本発明において、芳香族ビニル単位含有量の平均値は７
７〜９０重量％の範囲にあることが重要である。芳香族
ビニル単位の含有量の平均値が７７重量％に満たない場
合には、溶融流動性が悪く、問題である。また、９０重
量％を越えた場合には、耐熱性の低下が起こり好ましく
ない。In the present invention, the average value of the aromatic vinyl unit content is 7
It is important that the content is in the range of 7 to 90% by weight. If the average content of aromatic vinyl units is less than 77% by weight, melt fluidity is poor, which is a problem. Moreover, if it exceeds 90% by weight, heat resistance may deteriorate, which is not preferable.
芳香族ビニルとしては、スチレン、α−メチルスチレン
、ビニルトルエン、ジメチルスチレン、ｔ−ブチルスチ
レン、クロルスチレンなどを挙げることができるが、特
にスチレンが好ましい。Examples of the aromatic vinyl include styrene, α-methylstyrene, vinyltoluene, dimethylstyrene, t-butylstyrene, and chlorostyrene, with styrene being particularly preferred.
また、不飽和ニトリル単位は該共重合体の耐薬品性、機
械強度を向上させるのに重要である。Furthermore, unsaturated nitrile units are important for improving the chemical resistance and mechanical strength of the copolymer.
不飽和ニトリルとしては、アクリロニトリル、メタクリ
ロニトリルなどを挙げることができるが、特にアクリロ
ニトリルが好ましい。Examples of unsaturated nitriles include acrylonitrile and methacrylonitrile, with acrylonitrile being particularly preferred.
この不飽和ニトリル単位含有量平均値は、１０〜２３重
量％、特に好ましくは１５〜２２重置％の範囲にあるこ
とが重要である。不飽和ニトリルの含有量が１０重量％
に満たない場合には、耐薬品性が悪く、また、２３重量
％を越えた場合には、溶融流動性が悪く、射出成形等の
成形性が悪く問題である。It is important that the average content of unsaturated nitrile units is in the range of 10 to 23% by weight, particularly preferably 15 to 22% by weight. Content of unsaturated nitrile is 10% by weight
If it is less than 23% by weight, the chemical resistance is poor, and if it exceeds 23% by weight, the melt flowability is poor and moldability in injection molding etc. is poor, which is a problem.
本発明のランダム共重合体は、メチルエチルケトンの１
０％溶液中の２５℃における溶液粘度が６．０−１３ｃ
ｐｓの範囲の共重合体である。６０ｃｐｓに満たない場
合には機械強度が低く、１３を越えた場合には成形加工
性が不足し、工業的使用が制限され好ましくない。The random copolymer of the present invention comprises 1 of methyl ethyl ketone.
Solution viscosity at 25℃ in 0% solution is 6.0-13c
It is a copolymer in the ps range. If it is less than 60 cps, the mechanical strength is low, and if it exceeds 13, the moldability is insufficient, which limits industrial use, which is not preferable.
本発明の目的である透明性の良い共重合体を得るために
は、共重合体の組成分布が狭いことが重要である。In order to obtain a copolymer with good transparency, which is the object of the present invention, it is important that the composition distribution of the copolymer is narrow.
すなわち、共重合体における不飽和ニトリルの含有量の
平均値を７重量％とした場合に、Ｙ±５重量％の不飽和
ニトリル単位をもつ共重合体の含有量が５重量％以下、
Ｙ±１０重量％の不飽和ニトリル単位をもつ共重合体の
含有量が１重量％以下、Ｙ±１５重量％以上の不飽和ニ
トリル単位をもつ共重合体の含有量が０．１重量％以下
であることが重要である。That is, when the average content of unsaturated nitrile in the copolymer is 7% by weight, the content of the copolymer having Y±5% by weight of unsaturated nitrile units is 5% by weight or less,
The content of a copolymer having Y±10% by weight of unsaturated nitrile units is 1% by weight or less, and the content of a copolymer having Y±15% by weight or more of unsaturated nitrile units is 0.1% by weight or less. It is important that
共重合体の組成分布が広い場合には、透明性の低下が著
しく、本発明の目的を達成することができない。If the composition distribution of the copolymer is wide, the transparency will be significantly reduced, making it impossible to achieve the object of the present invention.
透明性の尺度としては、５０Ｘ９０Ｘ３■の射出成形試
験片を５オンスの射出成形機を用いて成形し、この試験
片をスガ試験機のヘーズメーターにセットし、測定した
透過率を用いることが出来る。As a measure of transparency, the transmittance can be used by molding a 50 x 90 x 3 cm injection molded test piece using a 5 oz injection molding machine, setting this test piece on the haze meter of Suga Test Machine, and measuring it. .
上記Ｙ±５重置％の不飽和ニトリル単位をもつ共重合体
の含有量が５重量％を越えた場合には、透明性は８５％
以下となり、透明性は著しく損なわれ、本発明の透明性
の範囲から外れ好ましくない。If the content of the copolymer having unsaturated nitrile units of Y±5% by weight exceeds 5% by weight, the transparency will be 85%.
As a result, transparency is significantly impaired, which is outside the scope of transparency of the present invention and is not preferable.
本発明の共重合体の射出成形品の好ましい透明性の範囲
は、透明性が８８％以上である。The preferable range of transparency of the injection molded product of the copolymer of the present invention is 88% or more.
組成分布を狭くする方法としては、共重合反応性比から
推定されるアゼオ組成に匹敵するモノマー組成で重合す
るか、あるいは共重合反応を微分重合タイプの反応形式
で実施する必要がある。不飽和ニトリル−芳香族ビニル
共重合体におけるアゼオ組成は、不飽和ニトリル／芳香
族ビニルが２５重置％である。また、乳化重合、懸濁重
合タイプの重合によって得られたポリマーは、積分重合
タイプの反応形式を反映し、透明なポリマーは得られに
くい。In order to narrow the composition distribution, it is necessary to perform polymerization with a monomer composition comparable to the azeo composition estimated from the copolymerization reactivity ratio, or to carry out the copolymerization reaction in a differential polymerization type reaction format. The azeo composition of the unsaturated nitrile-aromatic vinyl copolymer is 25% by weight of unsaturated nitrile/aromatic vinyl. Furthermore, polymers obtained by emulsion polymerization and suspension polymerization type polymerization reflect the reaction format of integral polymerization type, and it is difficult to obtain transparent polymers.
本発明の共重合体を得る方法としては、完全撹拌混合槽
に、モノマー、開始剤、溶媒等を連続的にフィードし、
連続的に反応槽から抜き出し、熱時、脱揮系で揮発分を
除去することにより得られる。脱揮系でのポリマー滞留
は極力少なくする必要がある。As a method for obtaining the copolymer of the present invention, monomers, initiators, solvents, etc. are continuously fed into a completely stirred mixing tank,
It is obtained by continuously extracting it from the reaction tank and removing volatile components in a devolatilizing system when heated. It is necessary to minimize polymer retention in the devolatilizing system.
本発明においては、射出成形時の着色を防止する目的で
、エチレンジアミンの誘導体、特に好ましくはＮ−テト
ラキス（α−ハイドロキシプロピルエチレンジアミン）
を酸化防止剤として用いることが出来る。In the present invention, for the purpose of preventing coloration during injection molding, a derivative of ethylenediamine, particularly preferably N-tetrakis (α-hydroxypropylethylenediamine), is used.
can be used as an antioxidant.
前記添加剤の使用量としては、０．０５重量％以上０．
３重量％以下が好ましく、特に好ましくは、０．１〜０
．２ｇ量％の範囲で使用することが好ましい。The amount of the additive used is 0.05% by weight or more and 0.05% by weight or more.
It is preferably 3% by weight or less, particularly preferably 0.1 to 0
．． It is preferable to use it within a range of 2g%.
添加剤は、重合、脱揮後にポリマーミキサーを設置して
混練しても良いし、あるいは得られた共重合体を押出機
で溶融混練することによっても得られる。The additive may be obtained by kneading by installing a polymer mixer after polymerization and devolatilization, or by melt-kneading the obtained copolymer using an extruder.
樹脂の着色性の評価方法としては、黄化度（Ｙｌ）で表
すことができる０本発明の共重合体樹脂の射出成形機内
の熱時滞留後の黄化度は５以下であった。As a method for evaluating the coloring property of the resin, the yellowing degree, which can be expressed as the yellowing degree (Yl), was 0. The yellowing degree of the copolymer resin of the present invention after hot residence in the injection molding machine was 5 or less.
本発明の共重合体樹脂を製造するには、連続塊状重合法
、連続溶液重合方法などを用いることができる。In order to produce the copolymer resin of the present invention, a continuous bulk polymerization method, a continuous solution polymerization method, etc. can be used.
次に、実施例により本発明をさらに詳細に説明するが、
本発明はこれらにより制限されない。Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited by these.
なお、実施例中の各物性は、次に示す方法により求めた
。In addition, each physical property in an Example was calculated|required by the method shown below.
■ 溶液粘度： 試料３．０ｇをメチルエチルケトン５０ｍに熔解する。■ Solution viscosity: 3.0 g of sample is dissolved in 50 m of methyl ethyl ketone.
２５℃で＄３００の粘度針を用いて測定した。Measured using a $300 viscosity needle at 25°C.
■ 共重合体の組成分布の測定：
試料０．０５ｇを４０ｄのＴＨＦ （テトラヒドロフラ
ン）に溶解し、高速液体クロマトグラフを用いて共重合
体中のＡＮ＆ｕ成分布を測定した。(2) Measurement of the composition distribution of the copolymer: 0.05 g of the sample was dissolved in 40 d of THF (tetrahydrofuran), and the AN&U composition distribution in the copolymer was measured using a high performance liquid chromatograph.
なお、カラム充填材として島津製作所製ゾルパックＣＮ
を用いた。In addition, Solpack CN manufactured by Shimadzu Corporation is used as a column packing material.
was used.
■ 光線透過率、黄化度（Ｙｌ）の測定：下記条件にて
射出成形を行い、得られた成形品をスガ試験機の３Ｍカ
ラーコンピューター ５Ｍ３型を用いて、黄化度（Ｙｌ
）を測定した。■ Measurement of light transmittance and yellowing degree (Yl): Injection molding was performed under the following conditions, and the yellowing degree (Yl
) was measured.
射出成形機；東芝ｌ５８０
金型 ；５０Ｘ９０Ｘ３■、１５Ｘ２２．５Ｘ３朧
シリンダー温度；２２０．２３０．２４０°Ｃ金型温度
；４０℃
射出圧力；ショート シ町ント＋５ｋｇ／ｃ射出成形機
滞留時間；２分
また、光線透過率はＨＧＭ−２ヘーズメーターにより測
定した。Injection molding machine; Toshiba l580 Mold; 50X90X3, 15X22.5X3 Oboro Cylinder temperature: 220.230.240°C Mold temperature: 40°C Injection pressure: Short cylinder mount + 5kg/c Injection molding machine residence time: 2 minutes Moreover, the light transmittance was measured using an HGM-2 haze meter.
実施例１
完全攪拌槽にスチレン７２重量％、アクリロニトリル１
３重量％、エチルベンガフ１５重量％からなる単量体混
合物を連続的にフィードし、１５０°Ｃ，滞留時間２時
間で重合反応を行った０反応生成物を定量ポンプにより
定常的に取り出して、予熱器で２６０″Ｃに加熱し、脱
揮タンクに流延落下せしめる。脱揮タンクは真空度３０
トール、２２０℃で揮発分を除去した。Example 1 72% by weight of styrene and 1% of acrylonitrile in a completely stirred tank
A monomer mixture consisting of 3% by weight and 15% by weight of ethyl bengaf was continuously fed, and the polymerization reaction was carried out at 150°C for a residence time of 2 hours. The reaction product was constantly taken out using a metering pump and preheated. Heat it to 260"C in a container and drop it into a devolatilization tank.The devolatilization tank has a vacuum level of 30
Volatiles were removed at 220°C.
得られた共重合体の溶液粘度は８゜０ｃｐｓ、残留揮発
分は０，１１％であった。The solution viscosity of the obtained copolymer was 8°0 cps, and the residual volatile content was 0.11%.
共重合体の組成分布を測定したところ、ＡＮ／５Ｔ＝２
４重量％が０．１
ＡＮ／５Ｔ＝２２重量％が０．２
ＡＮ／５Ｔ＝２０重量％が９９
ＡＮ／５Ｔ＝１８重量％が０．１以下
ＡＮ／５Ｔ＝１６重量％が０．１以下
５オンス射出成形機で試験片を作成し、熱着色試験を行
った。外観は無色透明であった。成形温度とＹｌ値の関
係は下記第１表の如くであった。When the composition distribution of the copolymer was measured, AN/5T=2
4% by weight is 0.1 AN/5T = 22% by weight is 0.2 AN/5T = 20% by weight is 99 AN/5T = 18% by weight is 0.1 or less AN/5T = 16% by weight is 0.1 Test pieces were prepared using a 5-ounce injection molding machine and subjected to a thermal coloring test. The appearance was colorless and transparent. The relationship between molding temperature and Yl value was as shown in Table 1 below.
第１表
比較例１
攪拌機付き反応器６０２に２４ｋｇの蒸留水を仕込み、
さらに懸濁安定剤として部分ケン化ポリビニルアルコー
ルの１２０ｇおよびラウリル硫酸ナトリウムの０．６ｇ
を加えて溶解させ、次いでスチレン９． ６ｋｇ、アク
リロニトリル２． ４ｋｇ、ジ−ｔ−ブチルパーオキシ
ヘキサノエート２４ｇオクチルメルカプタン２０ｇを順
次仕込んで、回転数１８Ｏｒｐｍで回転しながら８０℃
で８時間反応させた。更に、９５℃で２時間反応させた
。得られた共重合体を洗浄、脱水、乾燥して共重合体を
得た。Table 1 Comparative Example 1 24 kg of distilled water was charged into a reactor 602 equipped with a stirrer,
In addition, 120 g of partially saponified polyvinyl alcohol and 0.6 g of sodium lauryl sulfate as suspension stabilizers.
Add and dissolve styrene 9. 6 kg, acrylonitrile 2. 4kg of di-t-butyl peroxyhexanoate, 24g of octyl mercaptan, and 20g of octyl mercaptan were charged in sequence, and heated to 80°C while rotating at a rotational speed of 18Orpm.
The mixture was allowed to react for 8 hours. Further, the reaction was carried out at 95°C for 2 hours. The obtained copolymer was washed, dehydrated, and dried to obtain a copolymer.
得られた共重合体の組成分布の溶液粘度は１１ｃｐｓ、
残留揮発分は０．５１％であった。The solution viscosity of the composition distribution of the obtained copolymer was 11 cps,
The residual volatile content was 0.51%.
共重合体の組成分布を測定したところ、ＡＮ／５Ｔ＝２
４重量％が０． Ｉ
Ａ、Ｎ／５Ｔ＝２２重置％が０．５
ＡＮ／５Ｔ＝２０重量％が９５
ＡＮ／５Ｔ＝１８重量％が０．５
ＡＮ／５Ｔ＝１３重量％が０．５
ＡＮ／５Ｔ＝１１重量％が６．０
ＡＮ／ＳＴ＝ ９重置％が０．５
５オンス射出成形機で試験片を作成し、熱着色試験を行
った。試験片はクモリが発生し、成形温度とＹＩ値の関
係は下記第２表の如くであった。When the composition distribution of the copolymer was measured, AN/5T=2
4% by weight is 0. I A, N/5T=22 weight% is 0.5 AN/5T=20 weight% is 95 AN/5T=18 weight% is 0.5 AN/5T=13 weight% is 0.5 AN/5T= 11% by weight is 6.0 AN/ST = 9% by weight is 0.5 A test piece was prepared using a 5-ounce injection molding machine and subjected to a thermal coloring test. The test piece had cloudiness, and the relationship between molding temperature and YI value was as shown in Table 2 below.
第２表
（発明の効果）
本発明の不飽和ニトリル−芳香族ビニル系透明な耐熱樹
脂は新規なものであって、耐熱変形性、熱安定性、加工
性に優れ、高い機械強度を有しかつ無色透明であり、自
動車部品、家電部品などとして用いることができる。Table 2 (Effects of the Invention) The unsaturated nitrile-aromatic vinyl transparent heat-resistant resin of the present invention is novel and has excellent heat deformation resistance, thermal stability, processability, and high mechanical strength. It is also colorless and transparent, and can be used as automobile parts, home appliance parts, etc.
Claims (1)
からなり、メチルエチルケトンの１０％溶液中の２５℃
における溶液粘度が６．０〜１３ｃｐｓの範囲の共重合
体であって、 芳香族ビニル単位含有量の平均値がＸ重量％、不飽和ニ
トリル単位含有量の平均値がＹ重量％とした場合に、７
７≦Ｘ≦９０、１０≦Ｙ≦２３の関係が成り立っており
、 しかも、Ｙ±５重量％の不飽和ニトリル単位をもつ共重
合体の含有量が５重量％以下、Ｙ±１０重量％の不飽和
ニトリル単位をもつ共重合体の含有量が１重量％以下、
Ｙ±１５重量％以上の不飽和ニトリル単位をもつ共重合
体の含有量が０．１重量％以下であることを特徴とする
、新規な透明性に優れた共重合体樹脂。[Scope of Claims] Consisting of (A) aromatic vinyl units and (B) unsaturated nitrile units, at 25°C in a 10% solution of methyl ethyl ketone.
A copolymer having a solution viscosity in the range of 6.0 to 13 cps, where the average aromatic vinyl unit content is X weight % and the average unsaturated nitrile unit content is Y weight %. ,7
The relationships 7≦X≦90, 10≦Y≦23 are established, and the content of the copolymer having unsaturated nitrile units of Y±5% by weight is 5% by weight or less and Y±10% by weight. The content of a copolymer having unsaturated nitrile units is 1% by weight or less,
A novel copolymer resin with excellent transparency, characterized in that the content of a copolymer having unsaturated nitrile units of Y±15% by weight or more is 0.1% by weight or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02066801A JP3141293B2 (en) | 1990-03-19 | 1990-03-19 | New transparent copolymer resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02066801A JP3141293B2 (en) | 1990-03-19 | 1990-03-19 | New transparent copolymer resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03269006A true JPH03269006A (en) | 1991-11-29 |
| JP3141293B2 JP3141293B2 (en) | 2001-03-05 |
Family
ID=13326342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02066801A Expired - Fee Related JP3141293B2 (en) | 1990-03-19 | 1990-03-19 | New transparent copolymer resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3141293B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007106991A (en) * | 2005-09-15 | 2007-04-26 | Asahi Kasei Chemicals Corp | Styrenic thermoplastic resin for optical component and thermoplastic resin composition |
| JP2008222932A (en) * | 2007-03-14 | 2008-09-25 | Asahi Kasei Chemicals Corp | Thermoplastic resin, thermoplastic resin composition and optical component |
| JP2011518917A (en) * | 2008-04-25 | 2011-06-30 | ダウ グローバル テクノロジーズ リミティド ライアビリティ カンパニー | Positive skew styrene-acrylonitrile copolymer foam |
| JP2014517134A (en) * | 2011-06-20 | 2014-07-17 | タイ エイビーエス カンパニー リミテッド | Styrene-acrylonitrile resin having improved transparency and method for producing the same |
-
1990
- 1990-03-19 JP JP02066801A patent/JP3141293B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007106991A (en) * | 2005-09-15 | 2007-04-26 | Asahi Kasei Chemicals Corp | Styrenic thermoplastic resin for optical component and thermoplastic resin composition |
| JP2008222932A (en) * | 2007-03-14 | 2008-09-25 | Asahi Kasei Chemicals Corp | Thermoplastic resin, thermoplastic resin composition and optical component |
| JP2011518917A (en) * | 2008-04-25 | 2011-06-30 | ダウ グローバル テクノロジーズ リミティド ライアビリティ カンパニー | Positive skew styrene-acrylonitrile copolymer foam |
| JP2014517134A (en) * | 2011-06-20 | 2014-07-17 | タイ エイビーエス カンパニー リミテッド | Styrene-acrylonitrile resin having improved transparency and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3141293B2 (en) | 2001-03-05 |
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