JPH0234614A - Rubber-modified styrene resin - Google Patents
Rubber-modified styrene resinInfo
- Publication number
- JPH0234614A JPH0234614A JP18527288A JP18527288A JPH0234614A JP H0234614 A JPH0234614 A JP H0234614A JP 18527288 A JP18527288 A JP 18527288A JP 18527288 A JP18527288 A JP 18527288A JP H0234614 A JPH0234614 A JP H0234614A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- styrene
- weight
- resin
- butadiene
- 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
- 229920005989 resin Polymers 0.000 title claims abstract description 32
- 239000011347 resin Substances 0.000 title claims abstract description 32
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 title 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229920001971 elastomer Polymers 0.000 claims abstract description 54
- 239000005060 rubber Substances 0.000 claims abstract description 53
- 239000002245 particle Substances 0.000 claims abstract description 39
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 31
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 18
- 230000008961 swelling Effects 0.000 claims abstract description 13
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 claims abstract description 8
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 229920001890 Novodur Polymers 0.000 claims description 57
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 21
- -1 polysiloxane Polymers 0.000 claims description 15
- 229920001296 polysiloxane Polymers 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 abstract description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 15
- 229920001400 block copolymer Polymers 0.000 abstract description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 17
- 238000012662 bulk polymerization Methods 0.000 description 16
- 230000000704 physical effect Effects 0.000 description 15
- 238000003756 stirring Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 7
- 239000000178 monomer Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 238000010557 suspension polymerization reaction Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000003440 styrenes Chemical class 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000010558 suspension polymerization method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は、成形品表面の光沢および耐衝撃性に優れたゴ
ム変性スチレン系樹脂に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a rubber-modified styrenic resin that has excellent gloss on the surface of a molded product and excellent impact resistance.
［従来の技術］
ゴム状重合体の存在下にスチレン系単量体を重合させて
得られるゴム変性スチレン系樹脂は、比較的良好な物性
バランスに加え、優れた成形加工性を有しており、また
これらと製造法の異なるスチレン系樹脂であるＡＢＳ樹
脂に比べ安価であるため、汎用樹脂として、弱電機器分
野、事務機器分野、包装容器分野、雑貨分野等で広く使
用されているが、近年、成形品表面光沢等の外観の要求
される用途への適用が特に強く望まれている。[Prior art] Rubber-modified styrenic resins obtained by polymerizing styrenic monomers in the presence of rubbery polymers have a relatively good balance of physical properties and excellent moldability. In addition, it is cheaper than ABS resin, which is a styrene-based resin manufactured using a different manufacturing method, so it is widely used as a general-purpose resin in the fields of light electrical equipment, office equipment, packaging containers, and miscellaneous goods. It is particularly strongly desired to be applied to applications that require appearance such as surface gloss of molded products.
一般にゴム変性スチレン系樹脂は、ブタジェン系ゴムの
スチレン系中量体溶液を塊状重合または塊状−懸濁重合
することにより製造されており、要求物性に応じて原料
組成、重合条件等の調整が適宜なされている。しかし、
従来のゴム変性スチレン系樹脂は、成形品表面の光沢と
耐衝撃性のバランスが劣るという欠点を有していた。Rubber-modified styrenic resins are generally produced by bulk polymerization or bulk-suspension polymerization of a styrene intermediate solution of butadiene rubber, and the raw material composition, polymerization conditions, etc. are adjusted as appropriate depending on the required physical properties. being done. but,
Conventional rubber-modified styrene resins have had the disadvantage of poor balance between the gloss and impact resistance of the molded product surface.
ゴム変性スチレン系樹脂は、樹脂中の分散ゴム粒子相に
より耐衝撃性を発現させているが、この分散ゴム粒子が
成形品表面の光沢を低下させるため、光沢を向上させる
手段として分散ゴム粒子径を小さくする方法が従来より
一般的に検討されている。しかし、従来より用いられて
いる通常のブタジェン系ゴムを用いた場合、例えばミド
ルシスゴムでは満足できる光沢が得られるまで分散ゴム
粒子径を小さくすると耐衝撃性の低下が大きく、またハ
イシスゴムでは耐衝撃性は比較的良好であるが、光沢お
よび外観に問題があり、光沢と耐衝撃性のバランスを共
に満足するゴム変性スチレン系樹脂を得ることは困難で
あった。Rubber-modified styrenic resins exhibit impact resistance due to the dispersed rubber particle phase in the resin, but since these dispersed rubber particles reduce the gloss of the surface of the molded product, the diameter of the dispersed rubber particles can be adjusted as a means to improve the gloss. Conventionally, methods of reducing the size of However, when conventional butadiene-based rubbers are used, for example, with middle cis rubber, if the dispersed rubber particle size is reduced until a satisfactory gloss is obtained, the impact resistance decreases significantly, and with high cis rubber, the impact resistance decreases significantly. Although it is relatively good, there are problems with gloss and appearance, and it has been difficult to obtain a rubber-modified styrenic resin that satisfies the balance between gloss and impact resistance.
また、分散ゴム粒子径を比較的容易に小さくできるブタ
ジェン系ゴムとして、平均分子量を低下させることによ
り溶液粘度を低下させたブタジェン系ゴムも知られてい
るが、これらを使用した場合、耐衝撃性が不十分であっ
たり、得られるゴム変性スチレン系樹脂中に大粒径のゲ
ル化物が発生し易く、光沢の低下や外観不良を生じたり
する問題があり、満足できる光沢と耐衝撃性のバランス
を有するゴム変性スチレン系樹脂を得ることは困難であ
った。In addition, butadiene-based rubbers with lower solution viscosity by lowering the average molecular weight are known as butadiene-based rubbers that can relatively easily reduce the dispersed rubber particle size, but when these are used, impact resistance However, it is difficult to find a satisfactory balance between gloss and impact resistance. It was difficult to obtain a rubber-modified styrenic resin having the following properties.
［発明が解決しようとする課Ｈ
本発明の目的は、成形品表面の光沢、外観を向上させた
場合の耐衝撃性の低下を少なくすることにより、光沢と
耐衝撃性のバランスに優れたゴム変性スチレン系樹脂を
提供することにある。[Problem to be solved by the invention H The purpose of the present invention is to improve the gloss and appearance of the surface of a molded product while minimizing the drop in impact resistance, thereby creating a rubber with an excellent balance between gloss and impact resistance. An object of the present invention is to provide a modified styrenic resin.
［課題を解決するための手段］
本発明者らは、かかる問題点に鑑み、他のゴムに比べ比
較的良好な光沢、外観の得られ易いミドルシス系のブタ
ジェン系ゴムについて、鋭意検討した結果、特定の構造
を有するミドルシス系ブタジェン系重合体と特定の構造
を存するスチレンブタジェンブロック共重合体を特定の
比率で組合わせて用い、かつ特定の分散ゴム粒子構造を
とることにより、上記目的が有効に達成され、光沢と耐
衝撃性のバランスに優れたゴム変性スチレン系樹脂が得
られることを見出し、本発明に至った。[Means for Solving the Problems] In view of the above problems, the present inventors conducted extensive studies on middle cis-based butadiene rubbers, which tend to have relatively good gloss and appearance compared to other rubbers. The above purpose can be effectively achieved by using a combination of a middle-cis butadiene polymer having a specific structure and a styrene-butadiene block copolymer having a specific structure in a specific ratio, and by having a specific dispersed rubber particle structure. The present inventors have discovered that a rubber-modified styrenic resin with an excellent balance of gloss and impact resistance can be obtained, leading to the present invention.
即ち、本発明は、ブタジェン系ゴムの存在下にスチレン
系単量体を重合して得られるゴム変性スチレン系樹脂で
あって、
ａ）ブタジェン系ゴムがスチレン含有量が２５重量％未
満、シス−１，４結合金量が２５〜４５モル％、重量平
均分子量と数平均分子量との比が１．７以上、２５℃に
おける５重量％スチレン溶液の溶液粘度が５０〜３５０
ｃｐｓＳｔｏｏ℃におけるムーニー粘度が２５〜８０、
溶液粘度とムーニー粘度の比が２以上のブタジェン系重
合体（Ａ）およびスチレン含有量が２５〜５０重童％の
スチレン−ブタジェンブロック共重合体（Ｂ）からなり
、かつ該樹脂中の（Ａ）と（［３）の重量比が（Ａ）／
（Ｂ）−９５１５〜４５１５５であり、
ｂ）該樹脂中に分散しているゴム粒子相の重量平均粒径
が０．３〜１μであり、
Ｃ）該樹脂中のトルエン不溶分の膨潤度が７〜１３であ
る、
ことを特徴とするゴム変性スチレン系樹脂に関する。That is, the present invention provides a rubber-modified styrenic resin obtained by polymerizing a styrene monomer in the presence of a butadiene rubber, comprising: a) the butadiene rubber has a styrene content of less than 25% by weight; The amount of 1,4 bond is 25 to 45 mol%, the ratio of weight average molecular weight to number average molecular weight is 1.7 or more, and the solution viscosity of a 5 wt % styrene solution at 25°C is 50 to 350.
cpsStooo Mooney viscosity at ℃ 25-80,
It consists of a butadiene-based polymer (A) having a ratio of solution viscosity to Mooney viscosity of 2 or more and a styrene-butadiene block copolymer (B) having a styrene content of 25 to 50%, and ( The weight ratio of A) and ([3) is (A)/
(B) -9515 to 45155; b) the weight average particle size of the rubber particle phase dispersed in the resin is 0.3 to 1 μ; and C) the degree of swelling of toluene-insoluble components in the resin is 7 to 13. It relates to a rubber-modified styrenic resin characterized by the following.
また、本発明は、上記ゴム変性スチレン系樹脂中に有機
ポリシロキサンが０．０１〜０．５重量％含有されてい
るゴム変性スチレン系樹脂に関する。The present invention also relates to a rubber-modified styrenic resin containing 0.01 to 0.5% by weight of organic polysiloxane in the rubber-modified styrenic resin.
本発明に用いるブタジェン系重合体（Ａ）は、スチレン
含有量が２５重量％未満、シス−１，４結合金量が２５
〜４５モル％、重量平均分子量と数平均分子量との比が
１．７以上、２５℃における５重量％スチレン溶液の溶
液粘度（ＳＶ）が５０〜３５０ｃｐｓ。The butadiene polymer (A) used in the present invention has a styrene content of less than 25% by weight and a cis-1,4 bond amount of 25% by weight.
-45 mol%, the ratio of weight average molecular weight to number average molecular weight is 1.7 or more, and the solution viscosity (SV) of a 5 wt% styrene solution at 25°C is 50 to 350 cps.
１００℃におけるムーニー粘度（ＭＬ 、１００℃
）■＋４
が２５〜８０の範囲にあり、かつ溶液粘度とムーニ粘度
の比ＳＶ／ＭＬが２以上であることが必要である。Mooney viscosity at 100°C (ML, 100°C
)■+4 is in the range of 25 to 80, and the ratio SV/ML of solution viscosity to Mooney viscosity is required to be 2 or more.
このようなブタジェン系重合体（Ａ）は、エチルリチウ
ム、ｎ−ブチルリチウム、ステアリルリチウム等の有機
リチウム化合物触媒により、■、３−ブタジエンを主成
分とする１１２体を重合することにより得ることができ
る。ブタジェン系重合体（Ａ）の具体例としては、ポリ
ブタジェン、スチレン−ブタジェン共重合体があげられ
る。Such a butadiene-based polymer (A) can be obtained by polymerizing 112 polymers containing 1,3-butadiene as a main component using an organic lithium compound catalyst such as ethyllithium, n-butyllithium, or stearyllithium. can. Specific examples of the butadiene polymer (A) include polybutadiene and styrene-butadiene copolymer.
ブタジェン系重合体（Ａ）のスチレン含有量が２５重−
５以上では、耐衝撃性が劣り好ましくない。The styrene content of the butadiene polymer (A) is 25-
If it is 5 or more, the impact resistance will be poor, which is not preferable.
シス−１，４結合金２が２５モル％未満では、耐衝撃性
が劣り、一方シスー１，４結合金量が４５モル％を越え
る場合は、光沢が劣るので好ましくない。If the amount of cis-1,4 alloy 2 is less than 25 mol%, the impact resistance will be poor, while if the amount of cis-1,4 alloy 2 exceeds 45 mol%, the gloss will be poor, which is not preferable.
また、重量平均分子量と数平均分子量との比が１．７未
満では、耐衝撃性が劣るので好ましくない。Moreover, if the ratio of weight average molecular weight to number average molecular weight is less than 1.7, impact resistance will be poor, which is not preferable.
２５℃における５重−％スチレン溶液の溶液粘度が５０
ｃｐｓ未満では、耐衝撃性が劣り、また３５０ｃｐｓを
越える場合は、光沢が劣るので好ましくない。The solution viscosity of a 5% styrene solution at 25°C is 50
If it is less than cps, the impact resistance will be poor, and if it exceeds 350 cps, the gloss will be poor, which is not preferable.
１００°Ｃにおけるムーニー粘度が２５未満では、耐衝
撃性が劣り、また８０を越える場合は光沢が劣るので好
ましくない。If the Mooney viscosity at 100°C is less than 25, the impact resistance will be poor, and if it exceeds 80, the gloss will be poor, which is not preferred.
ＳＶ／ＭＬが２未満の場合は、光沢が不十分であり、ま
た得られるゴム変性スチレン系樹脂の成形品表面の外観
不良を生じることがあり好ましくない。When SV/ML is less than 2, the gloss is insufficient and the surface of the resulting rubber-modified styrenic resin molded product may have a poor appearance, which is not preferable.
また、本発明に用いるブタジェン系重合体（Ａ）は、１
，２結合金量が３０モル９６以下であることが好ましい
。 １，２結合金量が３０モル％を越える場合は、耐衝
撃性が劣り、また得られるゴム変性スチレン系樹脂中に
大粒径のゲル化物が発生し易く、成形品表面の外観不良
を生じることがあり好ましくない。Moreover, the butadiene-based polymer (A) used in the present invention has 1
, 2 bond amount is preferably 30 mol 96 or less. If the amount of 1,2 alloy exceeds 30 mol%, the impact resistance will be poor, and gelled substances with large particle sizes will easily occur in the resulting rubber-modified styrene resin, resulting in poor appearance on the surface of the molded product. There are some things that I don't like.
本発明に用いるスチレン−ブタジェンブロック共重合体
（Ｂ）は、リチウム系触媒により、１．３−ブタジェン
を主成分とする共役ジオレフィンとスチレンを主成分と
するスチレン系単量体とをブロック共重合することによ
り得られる共重合体であり、例えば−最大（Ｓ−Ｂ）
、Ｓ （Ｂ−Ｓ） 。The styrene-butadiene block copolymer (B) used in the present invention blocks a conjugated diolefin mainly composed of 1,3-butadiene and a styrene monomer mainly composed of styrene using a lithium-based catalyst. It is a copolymer obtained by copolymerizing, for example - maximum (S-B)
, S (B-S).
ｎ
（（Ｓ−Ｂ） ＞ Ｘ等（ただし°、Ｂはブタジェ
ンを主とするブロック、Ｓはスチレンを主とするブロッ
ク、ｎは１以上の整数、ｍは３以上の整数、Ｘはカップ
リング剤の残基である。）の配列、好ましくは、Ｓ−Ｂ
もしくは５−Ｂ−５の配列を有するブロック共重合体で
ある。また、本発明に用いるスチレン−ブタジェンブロ
ック共重合体は、一部ランダム部を含有してもよいが、
スチレンブロック部を構成するスチレン量は全スチレン
量に対して５０モル％以上、好ましくは７５モル％以上
であることが必要である。スチレンブロックを構成する
スチレン量が５０モル％未満の場合は、良好な光沢、外
観を与えるゴム変性スチレン系樹脂を得ることはできな
い。また、スチレン−ブタジェンブロック共重合体中の
スチレン含有量は、２５〜５０重量％、二部しくは３５
〜４５重量％で二部ことが必要である。スチレン含有量
が２５重量部未満の場合は、光沢の改良効果が劣り、ス
チレン含有量が５０重量部を越える場合は耐衝撃性が劣
るため、いずれの場合も改良された光沢と耐衝撃性のバ
ランスを有するゴム変性スチレン系樹脂を得ることはで
きない。n ((S-B) > ), preferably the sequence S-B
Alternatively, it is a block copolymer having a 5-B-5 sequence. Furthermore, the styrene-butadiene block copolymer used in the present invention may partially contain random parts, but
The amount of styrene constituting the styrene block portion needs to be at least 50 mol%, preferably at least 75 mol%, based on the total amount of styrene. If the amount of styrene constituting the styrene block is less than 50 mol%, it is impossible to obtain a rubber-modified styrenic resin that provides good gloss and appearance. In addition, the styrene content in the styrene-butadiene block copolymer is 25 to 50% by weight, 2 parts or 35% by weight.
Two parts at ~45% by weight are required. If the styrene content is less than 25 parts by weight, the gloss improvement effect will be poor, and if the styrene content exceeds 50 parts by weight, the impact resistance will be poor. It is not possible to obtain a rubber-modified styrenic resin with balance.
本発明に用いるブタジェン系ゴムは、ブタジェン系重合
体（Ａ）およびスチレン−ブタジェンブロック共重合体
（Ｂ）からなることが必要であり、（Ａ）と（Ｂ）の重
量比は（Ａ）／（Ｂ）−９５１５〜４５１５５、好まし
くは（八）／（Ｂ） −９０／１０〜ＧＯ／４０である
。（Ａ）の割合が重量比で９５を越える場合は、光沢、
外観が不十分であり、（Ａ）の割合が重量比で４５未満
の場合は耐衝撃性が劣るため、いずれの場合も改良され
た光沢と耐衝撃性を有するゴム変性スチレン系樹脂を得
ることはできない。The butadiene rubber used in the present invention needs to be composed of a butadiene polymer (A) and a styrene-butadiene block copolymer (B), and the weight ratio of (A) and (B) is (A). /(B)-9515 to 45155, preferably (8)/(B)-90/10 to GO/40. If the ratio of (A) exceeds 95 in weight ratio, gloss,
The appearance is unsatisfactory and impact resistance is poor when the proportion of (A) is less than 45 by weight, so in both cases to obtain a rubber-modified styrenic resin with improved gloss and impact resistance. I can't.
また、本発明のゴム変性スチレン系樹脂におけるブタジ
ェン系ゴムの含有量は特に限定されるものではないが、
得られるゴム変性スチレン系樹脂の光沢、耐衝撃性およ
び剛性等の物性バランスの点で３〜１２ｆｆｌＨ％の範
囲にあることが好ましい。Further, the content of butadiene rubber in the rubber-modified styrenic resin of the present invention is not particularly limited, but
In view of the balance of physical properties such as gloss, impact resistance, and rigidity of the resulting rubber-modified styrenic resin, the content is preferably in the range of 3 to 12 fflH%.
本発明のゴム変性スチレン系樹脂中に分散したゴム粒子
相の重量平均粒径は、０．３〜１μ、好ましくは０．４
〜０．８μであることが必要である。ゴム粒子相の重量
平均粒径が１μを越える場合は、得られるゴム変性スチ
レン系樹脂の光沢が劣り、また０、３μ未満では耐衝撃
性が劣るため、光沢と耐衝撃性を共に満足するゴム変性
スチレン系樹脂を得ることはできない。The weight average particle size of the rubber particle phase dispersed in the rubber modified styrenic resin of the present invention is 0.3 to 1μ, preferably 0.4μ.
~0.8μ is required. If the weight average particle size of the rubber particle phase exceeds 1μ, the gloss of the rubber-modified styrenic resin obtained will be poor, and if it is less than 0.3μ, the impact resistance will be poor, so a rubber that satisfies both gloss and impact resistance. Modified styrenic resin cannot be obtained.
また、本発明のゴム変性スチレン系樹脂中のトルエン不
溶分の膨潤度は７〜１３、好ましくは９〜１２であるこ
とが必要である。ゴム変性スチレン系樹脂中のトルエン
不溶分の膨潤度が７未満の場合は、得られるゴム変性ス
チレン系樹脂の耐衝撃性が劣り、また膨潤度が１３を越
える場合も得られるゴム変性スチレン系樹脂の耐衝撃性
が劣り好ましくない。また、膨潤度が１３を越える場合
、成形品表面の光沢が劣り、特に射出成形品においてゲ
ート近傍の表面に曇りが生じたり、流動末端表面の光沢
低下が著しい等の問題があり好ましくない。Further, the degree of swelling of toluene-insoluble components in the rubber-modified styrenic resin of the present invention needs to be 7 to 13, preferably 9 to 12. If the degree of swelling of toluene-insoluble components in the rubber-modified styrenic resin is less than 7, the resulting rubber-modified styrenic resin will have poor impact resistance, and if the swelling degree exceeds 13, the rubber-modified styrenic resin obtained will be poor. It is not preferable because of its poor impact resistance. If the degree of swelling exceeds 13, the gloss of the surface of the molded product will be poor, and problems such as clouding of the surface near the gate, especially in the case of injection molded products, and a significant decrease in the gloss of the flow end surface, are undesirable.
本発明のゴム変性スチレン系樹脂の重合方法としては、
従来より公知の塊状重合法、塊状−懸濁重合法等が用い
られる。例えば、塊状重合法による場合は、本発明に用
いられるブタジェン系ゴムのスチレン系単量体溶液、も
しくはこれにトルエン、エチルベンゼン等を希釈剤とし
て加えた溶液を撹拌下に加熱することにより所定の重合
率まで予備重合を行い、史に所定の重合率まで塊状重合
を実施した後、加熱、減圧条件下で未反応単量体、希釈
剤を除去し、重合を完結させる。The method for polymerizing the rubber-modified styrenic resin of the present invention includes:
Conventionally known bulk polymerization methods, bulk-suspension polymerization methods, etc. are used. For example, in the case of bulk polymerization, a styrene monomer solution of the butadiene rubber used in the present invention, or a solution prepared by adding toluene, ethylbenzene, etc. as a diluent, is heated with stirring to achieve the desired polymerization. After carrying out preliminary polymerization to a predetermined polymerization rate and carrying out bulk polymerization to a predetermined polymerization rate, unreacted monomers and diluent are removed under heating and reduced pressure conditions to complete the polymerization.
また、塊状−懸濁重合法による場合は、本発明に用いら
れるブタジェン系ゴムのスチレン系１１１２体溶液を子
ｆｉ重合工程として撹拌下に加熱することにより所定の
重合率まで塊状重合を実施した後、この重合溶液を懸濁
剤を含む水中に懸濁させ、重合開始剤の存在下で懸濁重
合を実施し、重合を完結させる。In the case of the bulk-suspension polymerization method, the styrene-based 1112 body solution of the butadiene-based rubber used in the present invention is heated under stirring as a child fi polymerization step to carry out bulk polymerization to a predetermined polymerization rate. This polymerization solution is suspended in water containing a suspending agent, suspension polymerization is carried out in the presence of a polymerization initiator, and the polymerization is completed.
これらの重合に際し、連鎖移動剤、重合開始剤、可塑剤
、酸化防止剤等の添加剤を必要に応じて適宜使用するこ
とができる。During these polymerizations, additives such as chain transfer agents, polymerization initiators, plasticizers, and antioxidants may be used as appropriate.
本発明のゴム変性スチレン系樹脂中の分散ゴム粒子相の
重量平均粒径は、用いるブタジェン系ゴムの溶液粘度、
ゴム溶液の濃度、ブタジェン系重合体（Ａ）とスチレン
−ブタジェンブロック共重合体（Ｂ）の使用比率、予備
重合時の撹拌強度、連鎖移動剤あるいは重合開始剤の種
類および添加量等の変更により調整される。The weight average particle size of the dispersed rubber particle phase in the rubber-modified styrenic resin of the present invention is determined by the solution viscosity of the butadiene rubber used,
Changes in the concentration of the rubber solution, the usage ratio of the butadiene polymer (A) and the styrene-butadiene block copolymer (B), the stirring intensity during prepolymerization, the type and amount of the chain transfer agent or polymerization initiator, etc. Adjusted by
また、ゴム変性スチレン系樹脂中のトルエン不溶分の膨
潤度は、塊状重合法では未反応単量体除去工程における
加熱、減圧条件等の変更により調整され、塊状−懸濁重
合法では懸濁重合時の重合温度および時間、重合開始剤
の種類および添加量等の変更により：Ａ整される。In addition, the degree of swelling of toluene-insoluble components in the rubber-modified styrene resin is adjusted by changing the heating and vacuum conditions in the unreacted monomer removal step in the bulk polymerization method, and in the bulk-suspension polymerization method, the degree of swelling of toluene-insoluble components is adjusted by By changing the polymerization temperature and time, the type and amount of the polymerization initiator added, etc., the: A is adjusted.
本発明のゴム変性スチレン系樹脂中の分散ゴム粒子相の
重量平均粒径は、重合条件の変更により２Ｉ整される以
外に、２種以上のゴム変性スチレン系樹脂のブレンドに
よっても調整することができる。The weight average particle size of the dispersed rubber particle phase in the rubber-modified styrenic resin of the present invention can be adjusted not only by changing the polymerization conditions but also by blending two or more rubber-modified styrenic resins. can.
また、本発明のゴム変性スチレン系樹脂のブタジェン系
ゴムの含有量は、重合時のブタジェン系ゴムの使用量の
変更による以外に、ブタジェン系ゴムを含有しないスチ
レン系樹脂とのブレンドによっても調整することができ
る。In addition, the content of butadiene rubber in the rubber-modified styrenic resin of the present invention can be adjusted not only by changing the amount of butadiene rubber used during polymerization but also by blending it with a styrene resin that does not contain butadiene rubber. be able to.
本発明におけるスチレン系単量体とは、スチレン、α−
メチルスチレン、ｐ−メチルスチレン、ビニルキシレン
等であり、これらは単独または混合して使用される。ま
た、これらのスチレン系単量体と共重合可能なアクリロ
ニトリル、メタクリル酸メチル等の単量体でスチレン系
単量体の一部を置換することができる。The styrenic monomer in the present invention refers to styrene, α-
These include methylstyrene, p-methylstyrene, vinylxylene, etc., and these may be used alone or in combination. Further, a part of the styrene monomer can be replaced with a monomer such as acrylonitrile or methyl methacrylate that can be copolymerized with these styrene monomers.
本発明のゴム変性スチレン系樹脂は、他の熱可塑性樹脂
、例えばポリフェニレンエーテル等を混合使用できる。The rubber-modified styrenic resin of the present invention can be mixed with other thermoplastic resins such as polyphenylene ether.
本発明のゴム変性スチレン系樹脂は、有機ポリシロキサ
ンを添加することにより耐衝撃性をさらに向上させるこ
とができる。ここで有機ポリシロキサンとは、ポリジメ
チルシロキサン、ポリメチルフェニルシロキサン等の有
機基とポリシロキサン結合を有するポリマーである。有
機ポリシロキサンの粘度（２５℃における粘度）は、１
０００〜２００００ｃｓＬが好ましい。The impact resistance of the rubber-modified styrenic resin of the present invention can be further improved by adding an organic polysiloxane. Here, the organic polysiloxane is a polymer having an organic group and a polysiloxane bond, such as polydimethylsiloxane and polymethylphenylsiloxane. The viscosity of the organic polysiloxane (viscosity at 25°C) is 1
000 to 20000 csL is preferable.
有機ポリシロキサンの添加量は０．ＯＩ〜０．５重量％
が好ましい。有機ポリシロキサンの添加量が０．０１重
量％未満ては、耐衝撃性の改良効果が十分でなく、また
有機ポリシロキサンの添加量が０．５重量％を越える場
合は、成形品表面にベトッキが生じて好ましくない。The amount of organic polysiloxane added is 0. OI~0.5% by weight
is preferred. If the amount of organic polysiloxane added is less than 0.01% by weight, the effect of improving impact resistance will not be sufficient, and if the amount of organic polysiloxane added exceeds 0.5% by weight, stickiness may appear on the surface of the molded product. This is not desirable.
有機ポリシロキサンを含有するゴム変性スチレン系樹脂
は、スチレン系単量体に有機ポリシロキサンを添加して
重合を行なってもよいし、ゴム変性スチレン系樹脂と有
機ポリシロキサンを押出機等を用いて溶融混合して製造
することができる。Rubber-modified styrenic resin containing organic polysiloxane may be polymerized by adding organic polysiloxane to styrene monomer, or polymerization may be performed by adding rubber-modified styrenic resin and organic polysiloxane using an extruder or the like. It can be manufactured by melt-mixing.
また、本発明のゴム変性スチレン系樹脂は加工に際して
、必要に応じて酸化防止剤、紫外線吸収剤、離型剤、滑
剤、充填剤、耐衝撃性改良剤、色剤等を添加混合使用で
きる。Furthermore, when processing the rubber-modified styrenic resin of the present invention, antioxidants, ultraviolet absorbers, mold release agents, lubricants, fillers, impact modifiers, coloring agents, etc. can be added and mixed as necessary.
［実 施 例］ 以下、実施例をあげて本発明をさらに詳細に説明する。[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.
なお、実施例および比較例におけるブタジェン系ゴムの
構造解析は、以下の方法で実施した。Note that the structural analysis of the butadiene rubber in the Examples and Comparative Examples was carried out by the following method.
（１） シス−１，４結合金量、１．２結合金量赤外
吸収スペクトル分光法により算出した。(1) Cis-1,4 bond amount and 1.2 bond amount Calculated by infrared absorption spectroscopy.
（２） スチレン含有量 紫外吸収スペクトル分光法により算出した。(2) Styrene content Calculated by ultraviolet absorption spectroscopy.
（３）重量平均分子ｆｆｌ（Ｍν）と数平均分子量（Ｍ
ｎ）との比（Ｍｙ／Ｍｎ）
ＧＰＣ（東洋曹達型、ＨＬＣ−８０２ＵＲ）を使用し、
屈折計を検出器として用い、展開溶媒としてテトラヒド
ロフラン（ＴＨＦ）を用いてＭｙ／＠ｎを測定した。(3) Weight average molecular weight ffl (Mν) and number average molecular weight (M
n) ratio (My/Mn) using GPC (Toyo Soda type, HLC-802UR),
My/@n was measured using a refractometer as a detector and tetrahydrofuran (THF) as a developing solvent.
（４）溶液粘度（ＳＶ）
キャノンフェンスケ型粘度計を用いて、２５℃にて５重
量％スチレン溶液の粘度を測定した。(4) Solution viscosity (SV) The viscosity of a 5% by weight styrene solution was measured at 25°C using a Cannon-Fenske viscometer.
（５）ムーニー粘度（ＭＬ 、１００℃）１００℃
に設定したムーニー粘度を用いて、１分間予熱し、更に
４分後のトルク値を測定した。(5) Mooney viscosity (ML, 100℃) 100℃
Using Mooney viscosity set to , preheating was performed for 1 minute, and the torque value was measured after another 4 minutes.
また、実施例および比較例におけるゴム変性スチレン系
樹脂の物性測定は、以下の方法で実施した。In addition, physical properties of the rubber-modified styrenic resins in Examples and Comparative Examples were measured by the following method.
（１）ゴム粒子相のｆｆ１ｆｆｉ平均拉径樹脂の超薄切
片法による透過型電子顕微鏡写真により、 ２００〜７
００個のゴム粒子径を測定し、次式により算出した。(1) A transmission electron micrograph of the rubber particle phase with an average diameter of ff1ffi of 200 to 7
The diameter of 00 rubber particles was measured and calculated using the following formula.
匝ｆｆｉ平均粒径−ΣＮ１Ｄｉ’／ ΣＮ１Ｄｉ３ここ
で、Ｎ１は粒径１］のゴム粒子の個数であり、粒径Ｄ＋
はゴム粒子の長径と短径の平均値である。匝ffi Average particle size - ΣN1Di'/ ΣN1Di3 Here, N1 is the number of rubber particles with particle size 1], and particle size D+
is the average value of the long axis and short axis of the rubber particles.
（２）トルエン不溶分の膨潤度
樹脂をトルエンに溶解し、常温で２４時間放置した後、
遠心分離、デカンテーション操作により膨潤状態のトル
エン不溶分型Ｗ（Ｗｓ）を測定した。(2) Swelling degree of toluene-insoluble content After dissolving the resin in toluene and leaving it at room temperature for 24 hours,
The toluene-insoluble form W (Ws) in a swollen state was measured by centrifugation and decantation.
ついで減圧乾燥を行い、乾燥状態のトルエン不溶分重量
（Ｗｄ）を測定し、次式により算出した。Subsequently, drying was performed under reduced pressure, and the weight (Wd) of toluene insoluble matter in the dry state was measured and calculated using the following formula.
トルエン不溶分膨潤度＝Ｗｓ ／Ｗｄ
（３）光沢
射出成形により２■厚の平板を成形し、ＪＩＳＫ７１０
５により、６０度鏡面光沢度をｎ１定した。Swelling degree of toluene insoluble matter = Ws / Wd (3) A 2-inch thick flat plate was formed by gloss injection molding, and JISK710
5, the 60 degree specular gloss was determined as n1.
（４）成形品表面の外観
射出成形により２ｍｍ厚の平板を成形し、表面外観に異
状の無いものを○、ゲート付近に若干の曇りを生じたも
のを△、傷、曇り、光沢ムラ等の外観不良を生じたもの
を×とした。(4) Appearance of the surface of the molded product A flat plate with a thickness of 2 mm is molded by injection molding, and those with no abnormalities on the surface appearance are ○, those with slight clouding near the gate are △, and those with scratches, cloudiness, uneven gloss, etc. Those with poor appearance were rated x.
（５）アイゾツト衝撃値
射出成形により試験片を成形し、ＪＩＳ Ｋ８８７１に
より測定した。(5) Izot impact value A test piece was molded by injection molding and measured according to JIS K8871.
実施例 １
■、２結合金量が１１モル％、シス−１，４結合金量が
３７モル％、１ｌｄｖ／Ｍｎが１．８、ムーニー粘度（
ＭＬ）が３８、溶液粘度（ＳＶ）が９５ｃｐｓ、ＳＶ／
ＭＬが２．５であるポリブタジェンゴム（Ａ）６．４重
量部およびスチレン含有量が４０重量％である、Ｓ（ス
チレン）−Ｂ（ブタジェン）配列を有するスチレン−ブ
タジェンブロック共重合ゴム（Ｂ）１．ｆ３重量部をス
チレン９９重量部および白色鉱油１重量部に溶解したゴ
ム溶液を内容積５ｇの撹拌機付オートクレーブに仕込み
、塊状重合開始時にｔ−ドデシルメルカプタン０．０２
重量部、重合開始２時間後にｎ−ドデシルメルカプタン
０．０５重量部を加え、１１５℃で５時間、撹拌機の回
転数が２２０ｒｐｍの撹拌下で塊状重合した後冷却し、
予備重合液を得た。次いで、内容積１０ｊ１１の撹拌機
付オートクレーブに水１００重量部、第３リン酸カルシ
ウム１重量部、ドデシルベンゼンスルホン酸ソーダ０．
００１重量部を仕込み、次に、前記予備重合液１００重
量部、重合開始剤としてベンゾイルパーオキサイド０．
２重量部、ｔ−ブチルパーオキシベンゾエート０．３５
重量部を加え、９０℃で４時間、１４０℃で３時間、撹
拌下で懸濁重合を行った。得られた懸濁重合液に塩酸を
加え、ン戸別、水洗、乾燥した後、２．８−ジ−ｔ−ブ
チル−ｐ−クレゾール０．１重量％、ジンクステアレー
ト０．３重量％を混合し、押出機によりベレット化する
ことによりゴム変性スチレン系樹脂を得た。得られた樹
脂の物性を第１表に示す。Example 1 ■, 2 bond amount is 11 mol%, cis-1,4 bond amount is 37 mol%, 1ldv/Mn is 1.8, Mooney viscosity (
ML) is 38, solution viscosity (SV) is 95 cps, SV/
A styrene-butadiene block copolymer rubber having an S (styrene)-B (butadiene) arrangement, which has 6.4 parts by weight of polybutadiene rubber (A) having an ML of 2.5 and a styrene content of 40% by weight. (B)1. A rubber solution in which parts by weight of f3 were dissolved in 99 parts by weight of styrene and 1 part by weight of white mineral oil was charged into an autoclave with an internal volume of 5 g equipped with a stirrer, and at the start of bulk polymerization, 0.02 parts by weight of t-dodecyl mercaptan was added.
Part by weight, 0.05 part by weight of n-dodecylmercaptan was added 2 hours after the start of polymerization, bulk polymerization was carried out at 115° C. for 5 hours with stirring at a stirrer rotation speed of 220 rpm, and then cooled.
A preliminary polymerization solution was obtained. Next, 100 parts by weight of water, 1 part by weight of tertiary calcium phosphate, and 0.0 parts by weight of sodium dodecylbenzenesulfonate were placed in an autoclave with an internal volume of 10j11 equipped with a stirrer.
Next, 100 parts by weight of the prepolymerization solution and 0.001 parts by weight of benzoyl peroxide as a polymerization initiator were added.
2 parts by weight, t-butyl peroxybenzoate 0.35
Parts by weight were added, and suspension polymerization was carried out under stirring at 90°C for 4 hours and at 140°C for 3 hours. Hydrochloric acid was added to the resulting suspension polymerization solution, washed with water, dried, and mixed with 0.1% by weight of 2.8-di-t-butyl-p-cresol and 0.3% by weight of zinc stearate. A rubber-modified styrenic resin was obtained by pelletizing with an extruder. Table 1 shows the physical properties of the obtained resin.
実施例２および３
実施例１において、ポリブタジェンゴム（Ａ）を第１表
に示すシス−１，４結合金量、Ｕ７ｉｖ／Ｍｎ。Examples 2 and 3 In Example 1, the polybutadiene rubber (A) had the cis-1,4 bond amount and U7iv/Mn shown in Table 1.
ＭＬ、ＳＶ、ＳＶ／ＭＬであるポリブタジェンゴムに変
更し、ゴム粒子径調整のため塊状重合時の撹拌回転数を
変更した以外は、実施例１と同様にしてゴム変性スチレ
ン系樹脂を得た。得られた樹脂の物性を第１表に示す。A rubber-modified styrenic resin was obtained in the same manner as in Example 1, except that the polybutadiene rubbers were changed to ML, SV, and SV/ML, and the stirring rotation speed during bulk polymerization was changed to adjust the rubber particle size. Ta. Table 1 shows the physical properties of the obtained resin.
実施例 ４
実施例１において、スチレン−ブタジェンブロック共重
合ゴム（Ｂ）をスチレン含有量３０重量％のスチレン−
ブタジェンブロック共重合ゴム（Ｓ−Ｂ配列）に変更し
、ゴム粒子径調整のため塊状重合時の撹拌回転数を変更
した以外は、実施例１と同様にしてゴム変性スチレン系
樹脂を得た。Example 4 In Example 1, the styrene-butadiene block copolymer rubber (B) was replaced with styrene-butadiene block copolymer rubber (B) having a styrene content of 30% by weight.
A rubber-modified styrenic resin was obtained in the same manner as in Example 1, except that the butadiene block copolymer rubber (S-B arrangement) was used and the stirring rotation speed during bulk polymerization was changed to adjust the rubber particle size. .
得られた樹脂の物性を第１表に示す。The physical properties of the obtained resin are shown in Table 1.
比較例 １
ブタジェン系ゴムとして、実施例１で用いたポリブタジ
ェンゴム（＾）７．０１二部のみを用い、ゴム粒子径調
整のため塊状重合時の撹拌回転数を変更した以外は、実
施例１と同様にしてゴム変性スチレン系樹脂を得た。得
られた樹脂の物性を第１表に示す。Comparative Example 1 The same procedure was carried out except that only 7.01 parts of the polybutadiene rubber (^) used in Example 1 was used as the butadiene rubber, and the stirring rotation speed during bulk polymerization was changed to adjust the rubber particle size. A rubber-modified styrenic resin was obtained in the same manner as in Example 1. Table 1 shows the physical properties of the obtained resin.
比較例 ２
実施例１において、ポリブタジェンゴム（Ａ）とスチレ
ン−ブタジェンブロック共重合ゴム（Ｂ）の比率を第１
表に示す比率に変更し、ゴム粒子径調整のため塊状重合
時の撹拌回転数を変更した以外は、実施例１と同様にし
てゴム変性スチレン系樹脂を得た。得られた樹脂の物性
を第１表に示す。Comparative Example 2 In Example 1, the ratio of polybutadiene rubber (A) and styrene-butadiene block copolymer rubber (B) was changed to the first
A rubber-modified styrenic resin was obtained in the same manner as in Example 1, except that the ratio was changed to the one shown in the table and the stirring rotation speed during bulk polymerization was changed to adjust the rubber particle size. Table 1 shows the physical properties of the obtained resin.
比較例３および４
実施例１において、ポリブタジェンゴム（Ａ）を第１表
に示すシス−１，４結合金量、ｐ／ｌ ｗ ／ Ｍ ｎ
。Comparative Examples 3 and 4 In Example 1, the polybutadiene rubber (A) had the amount of cis-1,4 bond shown in Table 1, p/l w/M n
.
ＭＬ、ＳＶ、ＳＶ／ＭＬであるポリブタジェンゴムに変
更し、ゴム粒子径調整のため塊状重合時の撹拌回転数を
変更した以外は実施例１と同様にしてゴム変性スチレン
系樹脂を得た。得られた樹脂の物性を第１表に示す。A rubber-modified styrenic resin was obtained in the same manner as in Example 1, except that the polybutadiene rubbers were changed to ML, SV, and SV/ML, and the stirring rotation speed during bulk polymerization was changed to adjust the rubber particle size. . Table 1 shows the physical properties of the obtained resin.
比較例 ５
実施例１において、スチレン−ブタジェンブロック共重
合ゴム（Ｂ）をスチレン含有ｆｆ１２０重量％のスチレ
ン−ブタジェンブロック共重合ゴム（Ｓ−Ｂ配列）に変
更し、ゴム粒子径調整のため塊状重合時の撹拌回転数を
変更した以外は、実施例１と同様にしてゴム変性スチレ
ン系樹脂を得た。Comparative Example 5 In Example 1, the styrene-butadiene block copolymer rubber (B) was changed to a styrene-butadiene block copolymer rubber (S-B arrangement) containing 120% by weight of styrene to adjust the rubber particle size. A rubber-modified styrenic resin was obtained in the same manner as in Example 1, except that the stirring rotation speed during bulk polymerization was changed.
得られた樹脂の物性を第１表に示す。The physical properties of the obtained resin are shown in Table 1.
比較例 ６
実施例１において、スチレン−ブタジェンブロック共重
合ゴム（Ｂ）をスチレン含ａ；２５二部％のスチレン−
ブタジェンランダム共重合ゴムに変更し、ゴム粒子径調
整のため塊状重合時の撹拌回転数を変更した以外は、実
施例１と同様にしてゴム変性スチレン系樹脂を得た。得
られた樹脂の物性を第１表に示す。Comparative Example 6 In Example 1, the styrene-butadiene block copolymer rubber (B) was mixed with styrene-containing a;
A rubber-modified styrenic resin was obtained in the same manner as in Example 1, except that butadiene random copolymer rubber was used and the stirring rotation speed during bulk polymerization was changed to adjust the rubber particle size. Table 1 shows the physical properties of the obtained resin.
比較例 ７
実施例１において、ポリブタジェンゴム（Ａ）とスチレ
ン−ブタジェンブロック共重合ゴム（Ｂ）の比率を第１
表に示す比率に変更し、実施例１における塊状重合時の
撹拌回転数を小さくした以外は、実施例１と同様にして
ゴム変性スチレン系樹脂を得た。得られた樹脂の物性を
第１表に示す。Comparative Example 7 In Example 1, the ratio of polybutadiene rubber (A) and styrene-butadiene block copolymer rubber (B) was changed to the first
A rubber-modified styrenic resin was obtained in the same manner as in Example 1, except that the ratios were changed to those shown in the table and the stirring rotation speed during bulk polymerization in Example 1 was lowered. Table 1 shows the physical properties of the obtained resin.
比較例 ８
実施例１において、懸濁重合時の重合開始剤の使用量を
ベンゾイルパーオキサイド０．２５重量部、ｔ−ブチル
パーオキシベンゾエート０．１重量部に変更した以外は
、実施例１と同様にしてゴム変性スチレン系樹脂を得た
。得られた樹脂の物性を第１表に示す。Comparative Example 8 Same as Example 1 except that the amount of polymerization initiator used during suspension polymerization was changed to 0.25 parts by weight of benzoyl peroxide and 0.1 part by weight of t-butyl peroxybenzoate. A rubber-modified styrenic resin was obtained in the same manner. Table 1 shows the physical properties of the obtained resin.
比較例 ９
実施例１において、懸濁重合時の重合開始剤としてｔ−
ブチルパーオキシベンゾニー） ０．１ｆｆｉ１部、ジ
−ｔ−ブチルパーオキサイド０．２５ｆｆｉｆｆｉ部を
使用し、重合条件を１２０℃で３時間、１４５℃で２時
間に変更した以外は、実施例２と同様にしてゴム変性ス
チレン系樹脂を得た。得られた樹脂の物性を第１表に示
す。Comparative Example 9 In Example 1, t-
Same as Example 2 except that 0.1 part of butylperoxybenzony) and 0.25 part of di-t-butyl peroxide were used, and the polymerization conditions were changed to 120°C for 3 hours and 145°C for 2 hours. A rubber-modified styrenic resin was obtained in the same manner. Table 1 shows the physical properties of the obtained resin.
（以下余白）
第１表に見られるとおり、実施例１〜４における本発明
のゴム変性スチレン系樹脂は、光沢と耐衝撃性のバラン
スに優れ、成形品の外観も良好であるが、比較例１の如
くポリブタジェンゴム（Ａ）を単独で使用した場合、あ
るいは比較例２の如くポリブタジェンゴム（Ａ）とスチ
レン−ブタジェンブロック共重合ゴム（Ｂ）の比率が本
発明における比率の範囲以外の場合、あるいは比較例３
および４の如＜ＳＶ／ＭＬが２未満の本発明における構
造以外のミドルシスポリブタジェンゴム（Ａ）を用いた
場合、あるいは比較例５の如く本発明における構造以外
のスチレン−ブタジェンブロック共重合ゴム（Ｂ）を用
いた場合、あるいは比較例６の如くスチレン−ブタジェ
ンブロック共重合ゴム（Ｂ）の代わりにスチレン−ブタ
ジェンランダム共重合ゴムを用いた場合、いずれの場合
も光沢と耐衝撃性のバランスが劣っており、しかも比較
例６では外観不良も生じており好ましくない。(The following is a blank space) As shown in Table 1, the rubber-modified styrenic resins of the present invention in Examples 1 to 4 have an excellent balance of gloss and impact resistance, and the appearance of molded products is also good. When polybutadiene rubber (A) is used alone as in Example 1, or as in Comparative Example 2, the ratio of polybutadiene rubber (A) and styrene-butadiene block copolymer rubber (B) is the same as in the present invention. Cases outside the range or comparative example 3
and 4 when a middle cis polybutadiene rubber (A) having a structure other than the structure of the present invention with SV/ML of less than 2 is used, or a styrene-butadiene block having a structure other than the structure of the present invention as in Comparative Example 5 is used. When polymer rubber (B) is used, or when styrene-butadiene random copolymer rubber is used instead of styrene-butadiene block copolymer rubber (B) as in Comparative Example 6, gloss and durability are improved in both cases. The balance of impact resistance is poor, and Comparative Example 6 also has poor appearance, which is not preferable.
また、比較例７〜９の如く、使用するブタジェン系ゴム
が本発明の範囲内であっても、得られるゴム変性スチレ
ン系樹脂中のゴム粒子相の重量平均粒径またはトルエン
不溶分の膨潤度が本発明の範囲外の場合は、光沢と耐衝
撃性のバランスが劣っており、しかも比較例７および８
では外観不良も生じており好ましくない。In addition, as in Comparative Examples 7 to 9, even if the butadiene rubber used is within the range of the present invention, the weight average particle diameter of the rubber particle phase or the degree of swelling of toluene-insoluble components in the rubber-modified styrenic resin obtained is outside the scope of the present invention, the balance between gloss and impact resistance is poor, and Comparative Examples 7 and 8
This is not preferable since it also causes poor appearance.
これらの結果から、特定のブタジェン系ゴム２種類を特
定の範囲で組合わせて用い、かつ分散ゴム粒子相を特定
の構造にコントロールすることにより、はじめて外観、
光沢、耐衝撃性を共に満足するゴム変性スチレン系樹脂
が得られることがわかる。These results show that by using two specific butadiene rubbers in combination within a specific range and controlling the dispersed rubber particle phase to have a specific structure, it is possible to improve the appearance,
It can be seen that a rubber-modified styrenic resin that satisfies both gloss and impact resistance can be obtained.
実施例 ５
実施例１で得られたゴム変性スチレン系樹脂に、２５℃
における粘度が１０００ｃｓｔのポリジメチルシロキサ
ン０．１重量％を押出機に混練り添加することによりゴ
ム変性スチレン系樹脂を得た。得られた樹脂の光沢は１
吋％、アイゾツト衝撃値は９．２ｋｇｃｍ／ｃ＋ｎであ
り、良好な光沢と耐衝撃性を示した。Example 5 The rubber-modified styrenic resin obtained in Example 1 was heated at 25°C.
A rubber-modified styrenic resin was obtained by kneading and adding 0.1% by weight of polydimethylsiloxane having a viscosity of 1000 cst to an extruder. The gloss of the obtained resin is 1
The Izot impact value was 9.2 kgcm/c+n, indicating good gloss and impact resistance.
［発明の効果］
以上の説明で示したように、本発明によるゴム変性スチ
レン系樹脂は、成形品表面の光沢等の外観と耐衝撃性の
バランスに優れているため、従来のゴム変性スチレン系
樹脂では不満足であった外観の要求される用途に適用す
ることができる。[Effects of the Invention] As shown in the above explanation, the rubber-modified styrenic resin according to the present invention has an excellent balance between appearance such as gloss on the surface of molded products and impact resistance, so it is superior to conventional rubber-modified styrene-based resins. It can be applied to applications that require an appearance that is unsatisfactory with resins.
Claims (2)
重合して得られるゴム変性スチレン系樹脂であって、 ａ）ブタジエン系ゴムがスチレン含有量が２５重量％未
満、シス−１，４結合金量が２５〜４５モル％、重量平
均分子量と数平均分子量との比が１．７以上、２５℃に
おける５重量％スチレン溶液の溶液粘度が５０〜３５０
ｃｐｓ、１００℃におけるムーニー粘度が２５〜８０、
溶液粘度とムーニー粘度の比が２以上のブタジエン重合
体（Ａ）およびスチレン含有量が２５〜５０重量％のス
チレン−ブタジエンブロック共重合体（Ｂ）からなり、
かつ該樹脂中の（Ａ）と（Ｂ）の重量比が（Ａ）／（Ｂ
）＝９５／５〜４５／５５であり、 ｂ）該樹脂中に分散しているゴム粒子相の重量平均粒径
が０．３〜１μであり、 ｃ）該樹脂中のトルエン不溶分の膨潤度が７〜１３であ
る、 ことを特徴とするゴム変性スチレン系樹脂。(1) A rubber-modified styrenic resin obtained by polymerizing a styrene monomer in the presence of a butadiene rubber, wherein a) the butadiene rubber has a styrene content of less than 25% by weight, cis-1,4 The amount of bond is 25 to 45 mol%, the ratio of weight average molecular weight to number average molecular weight is 1.7 or more, and the solution viscosity of a 5 weight % styrene solution at 25°C is 50 to 350.
cps, Mooney viscosity at 100°C is 25-80,
Consisting of a butadiene polymer (A) having a ratio of solution viscosity to Mooney viscosity of 2 or more and a styrene-butadiene block copolymer (B) having a styrene content of 25 to 50% by weight,
and the weight ratio of (A) and (B) in the resin is (A)/(B).
)=95/5 to 45/55, b) the weight average particle size of the rubber particle phase dispersed in the resin is 0.3 to 1μ, and c) swelling of toluene-insoluble components in the resin A rubber-modified styrenic resin characterized by having a degree of strength of 7 to 13.
が０．０１〜０．５重量％含有されていることを特徴と
する請求項（１）記載のゴム変性スチレン系樹脂。(2) The rubber-modified styrenic resin according to claim (1), wherein the rubber-modified styrenic resin contains 0.01 to 0.5% by weight of organic polysiloxane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18527288A JPH0234614A (en) | 1988-07-25 | 1988-07-25 | Rubber-modified styrene resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18527288A JPH0234614A (en) | 1988-07-25 | 1988-07-25 | Rubber-modified styrene resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0234614A true JPH0234614A (en) | 1990-02-05 |
Family
ID=16167924
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18527288A Pending JPH0234614A (en) | 1988-07-25 | 1988-07-25 | Rubber-modified styrene resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0234614A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0590965A1 (en) * | 1992-09-30 | 1994-04-06 | Nippon Zeon Co., Ltd. | Impact-resistant styrenic polymer resin composition and process for making same |
| US8074489B2 (en) | 2008-04-02 | 2011-12-13 | Ricoh Company, Limited | Impact detecting apparatus and packaging system |
-
1988
- 1988-07-25 JP JP18527288A patent/JPH0234614A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0590965A1 (en) * | 1992-09-30 | 1994-04-06 | Nippon Zeon Co., Ltd. | Impact-resistant styrenic polymer resin composition and process for making same |
| US5380798A (en) * | 1992-09-30 | 1995-01-10 | Nippon Zeon Co., Ltd. | Impact-resistant styrenic polymer resin composition and process for making same |
| US8074489B2 (en) | 2008-04-02 | 2011-12-13 | Ricoh Company, Limited | Impact detecting apparatus and packaging system |
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