JPS63156848A - Thermoplastic elastomer composition - Google Patents
Thermoplastic elastomer compositionInfo
- Publication number
- JPS63156848A JPS63156848A JP30343086A JP30343086A JPS63156848A JP S63156848 A JPS63156848 A JP S63156848A JP 30343086 A JP30343086 A JP 30343086A JP 30343086 A JP30343086 A JP 30343086A JP S63156848 A JPS63156848 A JP S63156848A
- Authority
- JP
- Japan
- Prior art keywords
- based polymer
- component
- weight
- butadiene
- rubber
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 18
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims description 5
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 229920001971 elastomer Polymers 0.000 claims abstract description 18
- 239000005060 rubber Substances 0.000 claims abstract description 16
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 6
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 4
- 229920000412 polyarylene Polymers 0.000 claims abstract description 4
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 3
- 239000004417 polycarbonate Substances 0.000 claims abstract description 3
- 229920006324 polyoxymethylene Polymers 0.000 claims abstract description 3
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 4
- -1 polyoxymethylene Polymers 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 abstract 2
- 229920006132 styrene block copolymer Polymers 0.000 abstract 2
- 229930040373 Paraformaldehyde Natural products 0.000 abstract 1
- 239000010690 paraffinic oil Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（１）発明の背景
本発明は、高耐熱、高ゴム弾性を有し、優れた成形加工
性を有する熱可塑性エラストマー組成物に関する。DETAILED DESCRIPTION OF THE INVENTION (1) Background of the Invention The present invention relates to a thermoplastic elastomer composition having high heat resistance, high rubber elasticity, and excellent moldability.
スチレン・ブタジェン・スチレンブロック共重合体の水
素添加物と、プロピレン系重合体と、ゴム用軟化剤を含
有するスチレン系熱可塑性エラストマー組成物は、特開
昭５８−２０６６４４、特開昭５８−２２２．１４２、
等で公知であり、各種熱可塑性ニジストマーの中では、
最も柔軟性に富み、ゴム弾性も優れていることから、各
種の工業用部品、自動車部品、建築・土木用部品、医療
、食品用部品等巾広い用途展開が成されている。A styrene thermoplastic elastomer composition containing a hydrogenated product of styrene-butadiene-styrene block copolymer, a propylene polymer, and a rubber softener is disclosed in JP-A-58-206644 and JP-A-58-222. .142,
Among various thermoplastic nidistomers,
Because it is the most flexible and has excellent rubber elasticity, it has been used in a wide range of applications, including various industrial parts, automobile parts, architectural and civil engineering parts, medical and food parts.
しかしながら、これら用途展開が拡大される中で、加硫
ゴム部品の代替、特に自動車部品用途等で、更に高耐熱
、高ゴム弾性を有するエラストマーが要望されている。However, as these applications expand, there is a demand for elastomers with even higher heat resistance and higher rubber elasticity as a substitute for vulcanized rubber parts, particularly for use in automobile parts.
（２）発明の概要
本発明者等は、鋭意検討した結果、従来の成分に加え、
特定の熱可塑性重合体を配合することにより初期の目的
を達成することができることを見出し本発明に到ったも
のでらり、本発明は、成分Ａ ポリオキシメチレン系重
合体、ポリカーボネート系重合体、ポリスルホン系重合
体、ポリフェニレンエーテル系重合体、ポリアリ−レン
スルフイド系重合体のうちから選ばれた少なくとも１種
の熱可塑性重合体５〜２５重量％
成分Ｂ スチレン・ブタジェン・スチレンブロック共重
合体の水素添加物重合体
２０〜４０重量％
成分Ｃプロピレン系重合体
５〜２０重量％
成分Ｄ ゴム用軟化剤
３５〜６０重量％
よりなる熱可塑性エラストマー組成物を提供するもので
ある。(2) Summary of the invention As a result of intensive study, the present inventors have discovered that in addition to conventional ingredients,
It was discovered that the initial objective could be achieved by blending a specific thermoplastic polymer, and this invention led to the present invention. , 5 to 25% by weight of at least one thermoplastic polymer selected from polysulfone polymers, polyphenylene ether polymers, and polyarylene sulfide polymers Component B Hydrogen of styrene-butadiene-styrene block copolymer The present invention provides a thermoplastic elastomer composition comprising: 20-40% by weight of an additive polymer; Component C: 5-20% by weight of a propylene polymer; and 35-60% by weight of component D: a rubber softener.
（３）発明の詳細な説明
本発明に使用する成分Ａは、ポリオキシメチレン系重合
体、ポリカーボネート系重合体、ポリスルホン系重合体
、ポリフェニレンエーテル系重合体、ポリアリ−レンス
ルフイド系重合体のうちから選ばれた少なくとも１種の
熱可塑性重合体であり、一般にエンジニアリング樹脂と
呼ばれているものである。(3) Detailed description of the invention Component A used in the present invention is selected from polyoxymethylene polymers, polycarbonate polymers, polysulfone polymers, polyphenylene ether polymers, and polyarylene sulfide polymers. It is at least one type of thermoplastic polymer generally referred to as an engineering resin.
これらの中では、成分Ｂとの相溶性を考慮して、ポリフ
ェニレンエーテル系重合体が最も好ましい。Among these, in consideration of compatibility with component B, polyphenylene ether polymers are most preferred.
成分Ａの全組成物中の割合としては、５〜２５重量％、
好ましくは７〜２０重世％、更に好ましくは１０〜１８
重量％であり、５重量％より少ない場合には、高温耐熱
セット特ＩＩ（ＪＩＳ Ｋ６３０１．１００℃に於け
る圧縮永久歪特性）の改良効果が少なく、２５重量％よ
り多くなった場合には、全組成物の硬度（ＪＩＳ Ｋ
６３０１）が高くなり、ゴム弾性の特性が劣ることとな
る。The proportion of component A in the total composition is 5 to 25% by weight,
Preferably 7-20%, more preferably 10-18%
If it is less than 5% by weight, the effect of improving high temperature heat resistance set special II (JIS K6301. Compression set property at 100°C) is small, and if it is more than 25% by weight, Hardness of the entire composition (JIS K
6301) becomes high, resulting in poor rubber elastic properties.
本発明に使用する成分Ｂは、物性の優れたニジストマー
組成物を得る上で重要な成分である。Component B used in the present invention is an important component in obtaining a nidistomer composition with excellent physical properties.
スチレン・ブタジェン・スチレンブロックコポリマーは
、柔軟性に富み、常温では良好なゴム弾性を有している
が、分子内の共役ジエンブロック部に不飽和結合を有し
ているため、耐熱老化性、熱安定性、耐候性等に多くの
問題を有している。Styrene-butadiene-styrene block copolymer is highly flexible and has good rubber elasticity at room temperature, but because it has unsaturated bonds in the conjugated diene block part of the molecule, it has poor heat aging resistance and It has many problems with stability, weather resistance, etc.
しかるに、スチレンと共役ジエンのブロック共重合体の
分子内二重結合に水素を添加することによって熱安定性
の向上したエラストマーを得ることができる。However, by adding hydrogen to the intramolecular double bonds of a block copolymer of styrene and a conjugated diene, an elastomer with improved thermal stability can be obtained.
水素添加は、ブタジェン由来の二重結合が元の重合体の
１５％以下、好ましくは１０％以下となるように行なわ
れる。このような水素添加されたブロック共重合体の製
造は、例えば特公昭４２−８７０４号、特公昭４３−６
６３６号、特公昭４５−２０５０４号等の各明細書に記
載されている。The hydrogenation is carried out such that the double bonds derived from butadiene account for 15% or less of the original polymer, preferably 10% or less. The production of such hydrogenated block copolymers is described, for example, in Japanese Patent Publication Nos. 42-8704 and 43-6.
It is described in various specifications such as No. 636 and Japanese Patent Publication No. 45-20504.
この成分Ｂの共重合体としては、例えばシェル・ケミカ
ル社よりｒＫＲＡＴＯＮ−ＧＪという商品名で市販され
ている。This copolymer of component B is commercially available, for example, from Shell Chemical Company under the trade name rKRATON-GJ.
成分Ｂの配合割合としては、２０〜４０重量％、好まし
くは２３〜３８重量％、更に好ましくは２５〜３５重量
％である。４０重量％より多くなるとあまりに柔軟にな
りすぎ、造粒時にストランド切れをおこしたり、ペレッ
ト同志のブロッキングをきたし、２０重量％よ抄少なく
なると柔軟性が低下し、ゴム弾性の特性が低下する。The blending ratio of component B is 20 to 40% by weight, preferably 23 to 38% by weight, and more preferably 25 to 35% by weight. When the amount is more than 40% by weight, it becomes too flexible, causing strand breakage during granulation or blocking of pellets together, and when the amount is less than 20% by weight, the flexibility decreases and the rubber elastic properties decrease.
成分Ｃは、プロピレン系重合体であり、ポリプロピレン
又は、過半量のプロピレンを含有するプロピレン共重合
体が使用される。プロピレン共重合体に使用されるコモ
ノマーとしては、プロピレン以外のα−オレフィン、例
えば、エチレン、ｌ−フテン、１−ヘキセン、４−メチ
ル−１−ペンテン等の共重合体を挙げることができる。Component C is a propylene-based polymer, and polypropylene or a propylene copolymer containing the majority of propylene is used. Comonomers used in the propylene copolymer include copolymers of α-olefins other than propylene, such as ethylene, l-phthene, 1-hexene, and 4-methyl-1-pentene.
メルトフローレート（ＡＳＴＭ Ｄ−１２３８、Ｌ条
件、２３０℃）は、０．１〜５０ ｆ／１０分、好まし
くは１〜３０ ｒ／ｌ ０分の範囲のものである。The melt flow rate (ASTM D-1238, L conditions, 230°C) is in the range of 0.1 to 50 f/10 min, preferably 1 to 30 r/l 0 min.
成分Ｃの配合割合は、成分Ａと関連し、成分人の配合割
合が多いときは成分Ｃを少なく設定するのが一般的であ
るが、成分Ｃの配合割合は、５〜２０重量％、好ましく
は７〜１７重量％、更に好ましくは、８〜１５重量％で
ある。The blending ratio of component C is related to component A, and when the blending ratio of component A is large, it is common to set a small amount of component C, but the blending ratio of component C is preferably 5 to 20% by weight. is 7 to 17% by weight, more preferably 8 to 15% by weight.
成分Ｃが２０重量％を越えると組成物の硬度が高くなり
ゴム弾性の特性が低下し、５重量えより少ないときは高
温特性が低下する。When component C exceeds 20% by weight, the hardness of the composition increases and the rubber elastic properties deteriorate, and when it is less than 5% by weight, the high temperature properties deteriorate.
本発明組成物に於いて成分Ｃを配合しない場合には、本
組成物の柔軟性のコントロールは、成分Ａと成分Ｂ１及
び成分りにのみ決定されることとなるが、この場合には
、流動性が大巾に劣り、各種の成形法によって成形をす
る場合、ショートショット、ヒケ等の外観不良をきたす
こととなり、本発明組成物に於いて重要な成分である。When component C is not blended in the composition of the present invention, the flexibility of the composition is determined only by component A, component B1, and the composition. It is an important component in the composition of the present invention because its properties are inferior to the width, and when molded by various molding methods, it causes poor appearance such as short shots and sink marks.
成分りは、ゴム用軟化剤である。成分りとして好ましい
ものは、非芳香族系の鉱物油または、液状もしくは低分
子量の合成軟化剤が適している。The ingredient is a rubber softener. Preferred ingredients include non-aromatic mineral oil and liquid or low molecular weight synthetic softeners.
非芳香族系軟化剤としては、パラフィン系、ナフテン系
のものが好ましく、性状としては、３７．８℃における
動粘度が２０〜５００ ｃｓｔ （センチストークス）
、流動点が−１０〜−１５℃、および引火点が１７０〜
３００℃を示す。合成軟化剤としては、ポリブテン、低
分子量ポリブタジェン等がある。As the non-aromatic softener, paraffinic and naphthenic softeners are preferred, and the properties include a kinematic viscosity of 20 to 500 cst (centistokes) at 37.8°C.
, a pour point of -10 to -15°C, and a flash point of 170 to
Indicates 300°C. Examples of synthetic softeners include polybutene and low molecular weight polybutadiene.
成分りの配合割合は、全組成物の流動性と柔軟性の観点
よし決定される。一般には、３５〜６０重量％、好まし
くは３８〜５５重量％、更に好ましくは４０〜５２重量
％の範囲である。３５重量％より少ないときは、柔軟性
が劣り、特に流動性が低下する。また、６０重敬％を越
えるときは、機械的強度の低下をまねく。The proportions of the ingredients are determined from the viewpoint of fluidity and flexibility of the entire composition. Generally, it ranges from 35 to 60% by weight, preferably from 38 to 55%, more preferably from 40 to 52%. When the amount is less than 35% by weight, flexibility is poor, especially fluidity is reduced. Moreover, when it exceeds 60%, mechanical strength decreases.
本発明組成物に於いて、成分Ａ、Ｂ、Ｃ，Ｄ以外に、通
常目的に応じて常用されている一般の顔料、熱安定剤、
抗酸化剤、紫外線吸収剤等の各種助剤を添加することが
できる。In the composition of the present invention, in addition to components A, B, C, and D, general pigments, heat stabilizers,
Various auxiliary agents such as antioxidants and ultraviolet absorbers can be added.
更に、大巾な品質低下をまねかない範囲で炭酸カルシウ
ム、カーボンブラック、タルク、クレー等の無機充填剤
も添加することができる。Furthermore, inorganic fillers such as calcium carbonate, carbon black, talc, and clay can also be added within a range that does not cause a significant deterioration in quality.
本発明樹脂組成物の混合方法は、パンツ＜ ＩＪ −ミ
キサー、ニーダ−１あるいは、１軸押出機、２軸押出機
等の汎用の混練機が何ら問題なく使用できる。For the mixing method of the resin composition of the present invention, a general-purpose kneading machine such as a pant mixer, a kneader 1, a single-screw extruder, a twin-screw extruder, etc. can be used without any problem.
次に実施例によって、本発明を具体的に説明する。Next, the present invention will be specifically explained with reference to Examples.
（４）実施例
表１に示す割合の原材料を２軸押出機（３０戸、池貝鉄
工製）にて、２７０℃にて混線、造粒し、得られたペレ
ットを２７０℃の温度条件、射出圧５００ｋｇ／ｃＩｉ
の条件下で、１２０Ｘ８０Ｘ２ｍの平板成形品を得た。(4) Raw materials in the proportions shown in Example Table 1 were mixed and granulated at 270°C using a twin-screw extruder (30 units, manufactured by Ikegai Iron Works), and the resulting pellets were injected at a temperature of 270°C. Pressure 500kg/cIi
A flat plate molded product measuring 120 x 80 x 2 m was obtained under these conditions.
この平板を利用して、Ｊ工５Ｋ６３０１の方法に従がい
、硬度、機械的強度ゴム弾性（圧縮永久歪）、成形外観
性（デラミ、平滑性、ベタツキ性等）等を評価した。Using this flat plate, hardness, mechanical strength, rubber elasticity (compression set), molded appearance (delami, smoothness, stickiness, etc.), etc., were evaluated according to the method of J.K. 5K6301.
これら実施例により、本発明組成物は、優れた機械的強
度、ゴム弾性のバランスが優れていることが判る。These Examples show that the composition of the present invention has an excellent balance of mechanical strength and rubber elasticity.
（以下余白）(Margin below)
Claims (1)
系重合体、ポリスルホン系重合体、ポリフェニレンエー
テル系重合体、ポリアリ−レンスルフイド系重合体のう
ちから選ばれた少なくとも１種の熱可塑性重合体 ５〜
２５重量％ 成分Ｂスチレン・ブタジエン・スチレンブロック共重合
体の水素添加物重合体 ２０〜４０重量％ 成分Ｃプロピレン系重合体 ５〜２０重量％ 成分Ｄゴム用軟化剤 ３５〜６０重量％[Claims] A thermoplastic elastomer composition comprising the following components A to D. Component A At least one thermoplastic polymer selected from polyoxymethylene polymers, polycarbonate polymers, polysulfone polymers, polyphenylene ether polymers, and polyarylene sulfide polymers 5-
25% by weight Component B Hydrogenated polymer of styrene-butadiene-styrene block copolymer 20-40% by weight Component C Propylene polymer 5-20% by weight Component D Rubber softener 35-60% by weight
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30343086A JPS63156848A (en) | 1986-12-19 | 1986-12-19 | Thermoplastic elastomer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30343086A JPS63156848A (en) | 1986-12-19 | 1986-12-19 | Thermoplastic elastomer composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63156848A true JPS63156848A (en) | 1988-06-29 |
Family
ID=17920913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30343086A Pending JPS63156848A (en) | 1986-12-19 | 1986-12-19 | Thermoplastic elastomer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63156848A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007169656A (en) * | 2007-01-25 | 2007-07-05 | Riken Technos Corp | Composite molded article |
| CN109593361A (en) * | 2018-11-09 | 2019-04-09 | 姜希猛 | One kind is to mould Dai Gangyong high intensity polyaryl thioether sulfone composite material |
-
1986
- 1986-12-19 JP JP30343086A patent/JPS63156848A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007169656A (en) * | 2007-01-25 | 2007-07-05 | Riken Technos Corp | Composite molded article |
| CN109593361A (en) * | 2018-11-09 | 2019-04-09 | 姜希猛 | One kind is to mould Dai Gangyong high intensity polyaryl thioether sulfone composite material |
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