JPH066638B2 - Rubber composition - Google Patents
Rubber compositionInfo
- Publication number
- JPH066638B2 JPH066638B2 JP29555485A JP29555485A JPH066638B2 JP H066638 B2 JPH066638 B2 JP H066638B2 JP 29555485 A JP29555485 A JP 29555485A JP 29555485 A JP29555485 A JP 29555485A JP H066638 B2 JPH066638 B2 JP H066638B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- weight
- butyl
- parts
- conjugated diene
- 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.)
- Expired - Lifetime
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- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は特にスチレン系耐衝撃性樹脂の製造に好適なゴ
ム組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a rubber composition particularly suitable for producing a styrene-based impact resistant resin.
（従来の技術） スチレン系耐衝撃性樹脂は従来からポリブタジエンゴム
あるいはスチレン−ブタジエン共重合ゴムをスチレンモ
ノマーに溶解し、塊状重合あるいは塊状−懸濁重合によ
り製造されている。該樹脂の製造工程中の熱履歴により
最終製品としての該樹脂の着色を防止するために使用す
るゴムにはＢＨＴ（2,6−ジ−ｔ−ブチル−ｐ−クレゾ
ール）が添加されているのが一般的であるが、完全には
着色防止されず改善が望まれている。(Prior Art) Styrenic impact-resistant resins have conventionally been produced by bulk polymerization or bulk-suspension polymerization by dissolving polybutadiene rubber or styrene-butadiene copolymer rubber in styrene monomer. BHT (2,6-di-t-butyl-p-cresol) is added to the rubber used to prevent coloration of the resin as a final product due to heat history during the manufacturing process of the resin. However, coloration is not completely prevented, and improvement is desired.
（発明が解決しようとする問題点） 本発明の目的は、製造工程の熱履歴による着色を生じな
いスチレン系耐衝撃性樹脂の製造に適したゴム組成物の
提供にある。(Problems to be Solved by the Invention) An object of the present invention is to provide a rubber composition suitable for producing a styrene-based impact resistant resin that does not cause coloration due to heat history in the production process.
（問題点を解決するための手段） 本発明のかかる目的は共役ジエン重合体ゴムまたは共役
ジエンと芳香族ビニル単量体との共重合ゴム１００重量
部当り一般式 （式中Ｒ1及びＲ2はＣ１〜４のアルキル基を表わす）で
表わされるフエノール系安定剤を0.001〜5.0重量部及び
螢光増白剤を0.0001〜１重量部添加して成るゴム組成物
を使用することによつて達成される。(Means for Solving the Problems) The object of the present invention is to provide a conjugated diene polymer rubber or a general formula per 100 parts by weight of a copolymerized rubber of a conjugated diene and an aromatic vinyl monomer. A rubber composition obtained by adding 0.001 to 5.0 parts by weight of a phenolic stabilizer represented by the formula (wherein R 1 and R 2 represent an alkyl group of C 1 to 4 ) and 0.0001 to 1 part by weight of a brightening agent. It is achieved by using a thing.
本発明で使用される共役ジエン重合体ゴム又は共役ジエ
ンと芳香族ビニル単量体との共重合体ゴムは、通常、乳
化重合法、リチウム基材触媒あるいはチーグラー触媒に
よる溶液重合法によつて得られるが、本発明の目的に最
適なゴムは溶液重合法によるゴムである。The conjugated diene polymer rubber or the copolymer rubber of the conjugated diene and the aromatic vinyl monomer used in the present invention is usually obtained by an emulsion polymerization method, a solution polymerization method using a lithium base catalyst or a Ziegler catalyst. However, the most suitable rubber for the purpose of the present invention is a solution polymerization rubber.
ゴムを構成する共役ジエンとしては1,3−ブタジエン、
イソブレン、1,3−ペンタジエンなどが挙げられる。1,3-butadiene as the conjugated diene that constitutes the rubber,
Isobrene, 1,3-pentadiene and the like can be mentioned.
芳香族ビニル単量体としてはスチレン、２−メチルスチ
レン、３−メチルスチレン、４−メチルスチレン、α−
メチルスチレン、2,4−ジメチルスチレン、3,5−ジメチ
ルスチレンなどが挙げられる。共役ジエンと芳香族ビニ
ル単量体とのランダム又はブロツク共重合体ゴム中の芳
香族ビニル単量体の含有量は３０重量％以下が好まし
く、３０重量％を超えると耐衝撃性樹脂の耐衝撃性が低
下する。共役ジエン重合体ゴム及び共重合ゴム中の共役
ジエン単位のシス含量あるいはビニル含量は特に限定さ
れず、耐衝撃性樹脂の用途、該樹脂の製造条件等に適つ
たものを使用すればよい。通常はシス1,4−結合量が９
０モル％以上の高シスポリブタジエンゴム、アルカリ金
属基材触媒を用いたアニオン重合による低シスポリブタ
ジエンゴム（ビニル含量５〜７０モル％）が使用され
る。As the aromatic vinyl monomer, styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-
Methylstyrene, 2,4-dimethylstyrene, 3,5-dimethylstyrene and the like can be mentioned. The content of the aromatic vinyl monomer in the random or block copolymer rubber of the conjugated diene and the aromatic vinyl monomer is preferably 30% by weight or less, and when it exceeds 30% by weight, the impact resistance of the impact resistant resin is high. Sex decreases. The cis content or vinyl content of the conjugated diene unit in the conjugated diene polymer rubber and the copolymerized rubber is not particularly limited, and those suitable for the application of the impact resistant resin, the production conditions of the resin, etc. may be used. Normally, the cis-1,4-bond amount is 9
0 mol% or more of high cis polybutadiene rubber and low cis polybutadiene rubber (vinyl content of 5 to 70 mol%) obtained by anionic polymerization using an alkali metal base catalyst are used.
これらのゴムに添加される前記の一般式で示される安定
剤の具体例としては、２−ｔ−ブチル−６−（3′−ｔ
−ブチル−5′−メチル−2′−ヒドロキシベンジル）−
４−メチルフエニルアクリレート、２−ｔ−ブチル−６
−（3′−ｔ−ブチル−5′−エチル−2′−ヒドロキシ
ベンジル）−４−エチルフエニルアクリレート、２−ｔ
−ブチル−６−（3′−ｔ−ブチル−5′−ｉ−ブチル−
2′−ヒドロキシベンジル）−４−ｉ−ブチルフエニル
アクリレート、２−ｔ−ブチル−６−（3′−ｔ−ブチ
ル−5′−ｔ−ブチル−2′−ヒドロキシベンジル）−４
−ｔ−ブチルフエニルアクリレートなどが挙げられる。
この安定剤の使用量は該ゴム１００重量部に対し0.001
〜５重量部である。0.001重量部未満では耐衝撃性樹脂
の着色性は改良されず、５重量部を超えると耐衝撃性樹
脂の物性上好ましくない。Specific examples of the stabilizer represented by the above general formula added to these rubbers include 2-t-butyl-6- (3'-t.
-Butyl-5'-methyl-2'-hydroxybenzyl)-
4-methylphenyl acrylate, 2-t-butyl-6
-(3'-t-butyl-5'-ethyl-2'-hydroxybenzyl) -4-ethylphenyl acrylate, 2-t
-Butyl-6- (3'-t-butyl-5'-i-butyl-
2'-hydroxybenzyl) -4-i-butylphenyl acrylate, 2-t-butyl-6- (3'-t-butyl-5'-t-butyl-2'-hydroxybenzyl) -4
-T-butyl phenyl acrylate etc. are mentioned.
The amount of this stabilizer used is 0.001 per 100 parts by weight of the rubber.
~ 5 parts by weight. If it is less than 0.001 part by weight, the coloring property of the impact resistant resin will not be improved, and if it exceeds 5 parts by weight, the physical properties of the impact resistant resin are not preferable.
本発明で使用される螢光増白剤は吸収した光エネルギー
の一部を螢光として輻射し得る物質であり、代表的化合
物としては4,4′−ジアミノスチルベン−2,2′−ジスル
ホン酸誘導体、ベンズオキサゾール系化合物、ベンズオ
キサゾリルチオフエン系化合物、クマリン系化合物、ピ
ラゾリン系化合物、ナフタルイミド系化合物などが例示
されるが、これらに限定されるものではない。The fluorescent brightening agent used in the present invention is a substance capable of emitting a part of absorbed light energy as fluorescent light, and a typical compound thereof is 4,4′-diaminostilbene-2,2′-disulfonic acid. Examples thereof include derivatives, benzoxazole-based compounds, benzoxazolylthiophene-based compounds, coumarin-based compounds, pyrazoline-based compounds, naphthalimide-based compounds, but are not limited thereto.
螢光増白剤の使用量は該ゴム１００重量部当り0.0001〜
１重量部であり、0.00001重量部未満では耐衝撃性樹脂
の着色は防止されず、１重量部を超えても、着色防止効
果は変らない。好ましくは０．５重量部以下である。The amount of the fluorescent whitening agent used is 0.0001 to 100 parts by weight of the rubber.
If the amount is less than 0.00001 parts by weight, the impact resistant resin is not prevented from being colored, and if the amount exceeds 1 part by weight, the effect of preventing coloration is not changed. It is preferably 0.5 parts by weight or less.
本発明の効果は該安定剤のみの使用でも、螢光増白剤の
みの使用でも達せられず、両者を併用することが必要で
ある。本発明においては更に他の安定剤を使用すること
は本発明の効果を妨げない。The effect of the present invention cannot be achieved either by using the stabilizer alone or by using the fluorescent brightening agent alone, and it is necessary to use both in combination. In the present invention, the use of other stabilizers does not impair the effects of the present invention.
以下実施例により本発明を具体的に説明する。The present invention will be specifically described below with reference to examples.
実施例１ 内容積４のステンレス製重合反応器を洗浄、乾燥し、
乾燥窒素で置換した後に、1,3−ブタジエン４４０ｇ、
ｎ−ヘキサン１７６０ｇを加え均一に混合した。次に−
ブチルリチウム４．４ミルモルを添加した。その後４０
℃で１２０分重合を行いメタノール５２mlを加え５分間
撹拌して重合反応を停止した。生成ゴム固形分１００重
量部あたり２−ｔ−ブチル−６（3′−ｔ−ブチル−5′
−メチル−2′−ヒドロキシベンジル）−４−メチルフ
エニルアクリレートを0.1重量部と2.5−ビス〔5′−ｔ
−ブチルベンゾオキサゾリン(2)〕チオフエンを0.001重
量部添加した。その後、スチールを吹込み生成ゴムを分
離凝固した。分離したゴムを６０℃で２４時間減圧乾燥
した。Example 1 A stainless steel polymerization reactor having an internal volume of 4 was washed and dried,
After purging with dry nitrogen, 440 g of 1,3-butadiene,
1760 g of n-hexane was added and mixed uniformly. Next-
Butyllithium 4.4 mmol was added. Then 40
Polymerization was carried out at 120 ° C. for 120 minutes, 52 ml of methanol was added, and the mixture was stirred for 5 minutes to terminate the polymerization reaction. 2-t-butyl-6 (3'-t-butyl-5 ') per 100 parts by weight of the produced rubber solid content.
-Methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate and 0.1 part by weight of 2.5-bis [5'-t
0.001 part by weight of -butylbenzoxazoline (2)] thiophene was added. Then, steel was blown to separate and solidify the produced rubber. The separated rubber was dried under reduced pressure at 60 ° C. for 24 hours.
生成ゴムのムーニー粘度（ML1+4，１００℃）は、３６
であり、５％スチレン溶液の粘度（３０℃）は１２２．
３ｃｓｔであつた。The Mooney viscosity (ML 1 + 4 , 100 ° C) of the produced rubber is 36
And the viscosity of a 5% styrene solution (30 ° C.) is 122.
It was 3 cst.
内容積５のポリエチレン製広口ビンに生成ゴム２３０
ｇ、スチレン２０７０ｇを入れ、室温で１６時間振とう
溶解した。Generated rubber 230 in a polyethylene wide-mouthed bottle with an internal volume of 5
g and 2070 g of styrene were added, and the mixture was shaken and dissolved at room temperature for 16 hours.
内容積４のステンレス製重合反応器を洗浄後、溶解液
を全量移した。その後、１４０℃で４０分間バルク重合
を行い、冷却後取り出した。After washing the stainless steel polymerization reactor having an inner volume of 4, the total amount of the solution was transferred. Then, bulk polymerization was performed at 140 ° C. for 40 minutes, and after cooling, it was taken out.
バルク重合溶液の全固形分は、４２．４％で、スチレン
モノマーの重合体への転化率は、３６．０％であつた。The total solid content of the bulk polymerization solution was 42.4%, and the conversion rate of the styrene monomer to the polymer was 36.0%.
内容積４のステンレス製重合反応器を洗浄後、バルク
重合溶液６２５ｇ，ポリビニルアルコールの０．２％水
溶液１８７５ｇを加え、７０℃まで昇温した。次に、ベ
ンゾイルパーオキサイド１．２５ｇとジクミルパーオキ
サイド０．６３ｇを２０ｇのスチレンに溶解させ、添加
した。その後、７０℃で１時間、９０℃で１時間、１１
０℃で１時間、１３０℃で１時間、１４０℃で３時間懸
濁重合を行い、冷却後、生成耐衝撃性ポリスチレン樹脂
を過分離した。分離した該樹脂を水洗し、６０℃で６
時間減圧乾燥した。After washing the stainless steel polymerization reactor having an internal volume of 4, 625 g of the bulk polymerization solution and 1875 g of a 0.2% aqueous solution of polyvinyl alcohol were added, and the temperature was raised to 70 ° C. Next, 1.25 g of benzoyl peroxide and 0.63 g of dicumyl peroxide were dissolved in 20 g of styrene and added. Then, at 70 ℃ for 1 hour, 90 ℃ for 1 hour, 11
Suspension polymerization was carried out at 0 ° C. for 1 hour, at 130 ° C. for 1 hour, and at 140 ° C. for 3 hours, and after cooling, the resulting impact-resistant polystyrene resin was excessively separated. The separated resin is washed with water and kept at 60 ° C for 6
It was dried under reduced pressure for an hour.
生成耐衝撃性ポリスチレン樹脂４０ｇをPLASTI-CORDER
(BRABENDER社製)を用いて、１８０℃で４分間練つた
後、取出し、水冷した。練つた該樹脂４ｇを４０φ×３
m/mの金型に入れ２００℃、３５kg／cm2で１０分間ブレ
ス後、１０分間水冷し、試験片を作成した。40 g of impact-resistant polystyrene resin produced is PLASTI-CORDER
(Manufactured by BRABENDER) was kneaded at 180 ° C. for 4 minutes, then taken out and cooled with water. 40 g of 3 g of the resin kneaded
A test piece was prepared by placing it in a m / m mold and breathing at 200 ° C. and 35 kg / cm 2 for 10 minutes and then cooling with water for 10 minutes.
色相の評価は、第１表の条件に従い、Yellow Indexで行
つた。結果を第２表に示す。The hue was evaluated by the Yellow Index according to the conditions shown in Table 1. The results are shown in Table 2.
第２表の結果から、本発明の方法により得られた耐衝撃
性ポリスチレン系樹脂は、非常に色相が改良されること
がわかる。 From the results shown in Table 2, it can be seen that the impact-resistant polystyrene-based resin obtained by the method of the present invention has an extremely improved hue.
実施例２〜６，比較例１〜１４ ゴムの重合反応停止後、生成ゴム１００重量部に対して
第２表に示すフエノール系安定剤及び／他は螢光増白剤
と量を添加する以外は、実施例１と同様にして耐衝撃性
ポリスチレン樹脂を製造し、色相の評価を行つた。結果
を第２表に示す。Examples 2-6, Comparative Examples 1-14 After stopping the polymerization reaction of the rubber, a phenol-based stabilizer shown in Table 2 and / or other amounts of the fluorescent brightening agent are added to 100 parts by weight of the produced rubber. In the same manner as in Example 1, an impact-resistant polystyrene resin was produced, and the hue was evaluated. The results are shown in Table 2.
第２表の結果から、本発明の方法は非常に色相が改良さ
れることがわかる。From the results in Table 2, it can be seen that the method of the present invention is very improved in hue.
Claims (1)
芳香族ビニル単量体との共重合ゴム１００重量部当り一
般式 （式中Ｒ1及びＲ2はＣ１〜４のアルキル基を表わす）で
表わされるフエノール系安定剤を0.001〜５重量部及び
螢光増白剤を0.0001〜１重量部添加して成るゴム組成
物。1. A general formula per 100 parts by weight of a conjugated diene polymer rubber or a copolymer rubber of a conjugated diene and an aromatic vinyl monomer. A rubber composition obtained by adding 0.001 to 5 parts by weight of a phenolic stabilizer represented by the formula (wherein R 1 and R 2 represent an alkyl group of C 1 to 4 ) and 0.0001 to 1 part by weight of a fluorescent whitening agent. object.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29555485A JPH066638B2 (en) | 1985-12-27 | 1985-12-27 | Rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29555485A JPH066638B2 (en) | 1985-12-27 | 1985-12-27 | Rubber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62153329A JPS62153329A (en) | 1987-07-08 |
| JPH066638B2 true JPH066638B2 (en) | 1994-01-26 |
Family
ID=17822144
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29555485A Expired - Lifetime JPH066638B2 (en) | 1985-12-27 | 1985-12-27 | Rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH066638B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2961577B2 (en) * | 1991-09-24 | 1999-10-12 | 住友化学工業株式会社 | Method for producing thermoplastic resin with excellent impact resistance |
-
1985
- 1985-12-27 JP JP29555485A patent/JPH066638B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62153329A (en) | 1987-07-08 |
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