JP2006117744A - Vibration-damping material - Google Patents
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この発明は、スチレン−ビニルイソプレンブロック共重合体の水素添加物を架橋成分に用いた制振材料に関し、ＯＡ機器、電気電子機器、精密機器、自動車、船舶、建築および土木など、軽量負荷部分を含む広い範囲の制振材として好適に使用される。 The present invention relates to a vibration damping material using a hydrogenated product of a styrene-vinylisoprene block copolymer as a crosslinking component, and a lightweight load portion such as OA equipment, electrical and electronic equipment, precision equipment, automobiles, ships, architecture, and civil engineering. It is suitably used as a wide range of damping materials.
スチレン−ビニルイソプレンブロック共重合体からなる熱可塑性エラストマーは、常温における制振性が高いので、制振材料として広く利用されている。例えば、下記の特許文献１には、有機過酸化物により架橋されたスチレン−ビニルイソプレン−スチレンブロック共重合体、熱可塑性材料および軟化剤を含み、ＪＩＳ−Ａ硬度が２５度以下の防振用熱可塑材料が開示されている。また、下記の特許文献２には、ビニル芳香族化合物から作られる少なくとも２つの重合体ブロックＡと、共役ジエン化合物から作られる少なくとも１つの重合体ブロックＢとからなるブロック重合体、非芳香族系ゴム用軟化剤、パーオキサイド架橋型オレフィン系樹脂等を含む熱可塑性エラストマー組成物が開示されている。
上記の特許文献１に記載された熱可塑性エラストマーは、軽量物の防振性、特にクリープ特性に優れ、低硬度である等の特性を備え、また上記特許文献２に記載された組成物は、柔軟性に富み、−６０℃から３０℃において優れた制振性を発現し、耐油性・成形加工性に優れ、かつ成形工程での加硫が不要であるため、バリが発生しない。そして、いずれも過酸化物架橋であって、硫黄架橋や樹脂架橋でないため、金属腐食や環境汚染を発生させずに圧縮永久歪を改善することができる。しかしながら、上記の特許文献１、２に記載された熱可塑性エラストマーは、いずれもパラフィンオイル等の軟化剤を大量に使用して柔軟性や低硬度を実現するので、制振材として使用中、上記の軟化剤が接触物へ移行し、色移りや接触物の性能低下等が生じるという問題があった。そして、特に特許文献１に記載された熱可塑性エラストマーは、架橋成分の使用量が２５％以下と少ないため、高温における圧縮永久歪の改善が不十分であった。 The thermoplastic elastomer described in the above-mentioned Patent Document 1 has characteristics such as excellent vibration-proofing properties of lightweight materials, in particular, creep properties and low hardness, and the composition described in the above-mentioned Patent Document 2, It is highly flexible, exhibits excellent vibration damping properties at -60 ° C. to 30 ° C., is excellent in oil resistance and molding processability, and does not require vulcanization in the molding process, so no burrs are generated. And since all are peroxide bridge | crosslinking and are not sulfur bridge | crosslinking and resin bridge | crosslinking, a compression set can be improved, without generating metal corrosion and environmental pollution. However, the thermoplastic elastomers described in Patent Documents 1 and 2 above all use a large amount of a softening agent such as paraffin oil to achieve flexibility and low hardness. There is a problem that the softening agent is transferred to the contact material, causing color transfer and performance deterioration of the contact material. In particular, the thermoplastic elastomer described in Patent Document 1 has an insufficient improvement in compression set at high temperatures because the amount of crosslinking component used is as low as 25% or less.
この発明は、上記のスチレン−ビニルイソプレンブロック共重合体からなる熱可塑性エラストマーを用いた制振材料において、軟化剤を用いないで柔軟性や低硬度を実現し、もって軽量負荷物を含む広い範囲での制振性を良好にすると共に、接触物への移行による色移りや性能低下を解消し、しかも硫黄架橋や樹脂架橋を用いず、過酸化物架橋を採用することにより、金属腐食や環境汚染を発生させずに圧縮永久歪を改善し、さらに成形工程での加硫を不要とし、リサイクルを可能にする。 The present invention provides a vibration damping material using a thermoplastic elastomer composed of the above styrene-vinyl isoprene block copolymer, which realizes flexibility and low hardness without using a softening agent, and thus has a wide range including a lightweight load. In addition to improving the vibration damping performance at the same time, eliminating color transfer and performance degradation due to transfer to contact materials, and using peroxide crosslinking instead of sulfur crosslinking or resin crosslinking, metal corrosion and the environment Improves compression set without causing contamination, eliminates the need for vulcanization in the molding process, and enables recycling.
この発明は、スチレン−ビニルイソプレンブロック共重合体の水素添加物および未添加物を架橋成分とし、結晶性オレフィン系樹脂を樹脂成分とする混練物であり、上記架橋成分の配合量が架橋成分と樹脂成分の合計に対して４０〜９５重量％、好ましくは６０〜９０重量％であり、架橋成分における水素未添加物の含有量が０〜４０重量％であり、上記の架橋成分が有機過酸化物で部分架橋されていることを特徴とする制振材料である。 The present invention is a kneaded product in which a hydrogenated product and an unadded product of a styrene-vinylisoprene block copolymer are used as a crosslinking component, and a crystalline olefin resin is used as a resin component. 40 to 95% by weight, preferably 60 to 90% by weight, based on the total amount of the resin components, the content of hydrogen non-additive in the crosslinking component is 0 to 40% by weight, and the above crosslinking component is organic peroxidation It is a vibration damping material characterized in that it is partially crosslinked with a product.
上記のスチレン−ビニルイソプレンブロック共重合体は、スチレン単位をハードセグメントとし、ビニルイソプレン単位をソフトセグメントとする熱可塑性エラストマーである。ここで、上記の共重合体におけるスチレン単位の含有量は、５〜５０重量％、特に１０〜３５重量％が好ましく、５重量％未満ではハードセグメントが不足してゴム弾性が低下し、反対に５０重量％を超えると、得られる組成物が硬くなり過ぎて制振性が低下する。また、イソプレン単位のビニルイソプレン含有量によってブロック共重合体のガラス転移温度Ｔgが変化し、上記含有量が大きいほどＴgも高くなり、制振性は、このＴg付近で最大となるので、Ｔgは常温領域に近いことが好ましく、上記ブロック共重合体のＴgは−４０〜＋４０℃であることが好ましい。 The styrene-vinyl isoprene block copolymer is a thermoplastic elastomer having a styrene unit as a hard segment and a vinyl isoprene unit as a soft segment. Here, the content of the styrene unit in the copolymer is preferably 5 to 50% by weight, particularly preferably 10 to 35% by weight, and if it is less than 5% by weight, the hard segment is insufficient and the rubber elasticity is lowered. If it exceeds 50% by weight, the resulting composition becomes too hard and the vibration damping properties are reduced. In addition, the glass transition temperature Tg of the block copolymer changes depending on the vinylisoprene content of the isoprene unit, and the higher the content, the higher the Tg, and the damping performance is maximum near this Tg. It is preferable to be close to the normal temperature region, and the Tg of the block copolymer is preferably -40 to + 40 ° C.
また、この発明では、上記のスチレン−ビニルイソプレンブロック共重合体のイソプレン部分における二重結合の８０％以上を水素添加したブロック共重合体（水素添加物）および水素添加しないブロック共重合体（未添加物）が併用される。ただし、水素添加物のみを使用し、未添加物の使用を省略することができる。そして、未添加物の添加により、圧縮永久歪が改善されるが、その使用量が多くなると、耐オゾン性が低下するので、未添加物の使用量は、水素添加物および未添加物の合計の４０重量％以下に制限される。 In the present invention, a block copolymer (hydrogenated product) in which 80% or more of the double bonds in the isoprene portion of the styrene-vinylisoprene block copolymer are hydrogenated and a block copolymer that is not hydrogenated (not yet added) Additive). However, only the hydrogenated product can be used, and the use of the non-added product can be omitted. The compression set is improved by the addition of the non-additive, but the ozone resistance is lowered when the amount used is increased, so the amount of the non-additive used is the sum of the hydrogenated product and the non-added product. To 40% by weight or less.
また、樹脂成分として用いられる結晶性オレフィン系樹脂には、エチレン系、プロピレン系、ブテン−１系の単独重合体およびエチレン、プロピレンもしくはブテン−１と炭素数２〜８のα−オレフィンとの共重合体が例示され、軟質ポリプロピレン（ポリプロピレンとエチレン・プロピレンゴムとの混合物）および共重合ポリプロピレン（プロピレンとそれ以外のα−オレフィンとの共重合体）が含まれる。これらの中で、ポリプロピレン系樹脂、特に軟質ポリプロピレンおよび共重合ポリプロピレンは、組成物の硬度を低くできる点で好ましい。 The crystalline olefin resin used as the resin component includes ethylene, propylene and butene-1 homopolymers, and copolymers of ethylene, propylene or butene-1 and α-olefins having 2 to 8 carbon atoms. Examples of the polymer include soft polypropylene (a mixture of polypropylene and ethylene / propylene rubber) and copolymerized polypropylene (a copolymer of propylene and other α-olefin). Among these, polypropylene resins, particularly soft polypropylene and copolymer polypropylene, are preferable in that the hardness of the composition can be lowered.
この発明の制振材料は、架橋成分に上記スチレン−ビニルイソプレンブロック共重合体の水素添加物を単独で用いるか、または未添加物と併用し、樹脂成分に結晶性オレフィン系樹脂を用いて混練し、架橋成分を有機過酸化物で部分架橋したものであり、上記スチレン−ビニルイソプレンブロック共重合体の水素添加物を主体とする架橋成分を比較的大量に使用しているので、軟化剤を用いないにも拘わらず、柔軟性が得られ、常温での制振性が良好となり、かつ部分架橋がされることによって高温域での圧縮永久歪が改善される。そして、軟化剤を用いないので、接触物への色移りや接触物の性能低下が生じない。また、熱可塑性を有するので、成形工程での架橋が不要であり、そのためバリの発生がなく、リサイクルも可能である。ただし、架橋成分の配合量が架橋成分および樹脂成分の合計に対し４０重量％未満の場合は、組成物が硬くなり、制振性が低下する。反対に９５重量％を超えると、組成物が粉々となり、実用不可となる。なお、架橋成分中の水素未添加物が架橋成分全量の４０重量％を超えると、前記のとおり耐オゾン性が低下する。 The vibration damping material of the present invention uses the hydrogenated product of the styrene-vinylisoprene block copolymer alone as a crosslinking component, or is used in combination with an unadded material, and kneads using a crystalline olefin resin as a resin component The crosslinking component is partially crosslinked with an organic peroxide, and a relatively large amount of the crosslinking component mainly composed of the hydrogenated product of the styrene-vinylisoprene block copolymer is used. Although it is not used, flexibility is obtained, vibration damping properties at normal temperature are improved, and compression set at a high temperature range is improved by partial crosslinking. And since a softener is not used, the color transfer to a contact thing and the performance fall of a contact thing do not arise. In addition, since it has thermoplasticity, it is not necessary to crosslink in the molding process, so that no burrs are generated and it can be recycled. However, when the blending amount of the crosslinking component is less than 40% by weight with respect to the total of the crosslinking component and the resin component, the composition becomes hard and vibration damping properties are reduced. On the other hand, if it exceeds 95% by weight, the composition becomes shattered, making it impractical. In addition, when the hydrogen non-added substance in a crosslinking component exceeds 40 weight% of a crosslinking component whole quantity, as above-mentioned, ozone resistance will fall.
この発明では、上記の架橋成分および樹脂成分以外に第３成分として石油系炭化水素樹脂を添加配合することができる。この石油系炭化水素樹脂としては、ロジン系樹脂、テルペン系樹脂および脂環族飽和炭化水素樹脂が例示されるが、特に脂環族飽和炭化水素樹脂は、相溶性の面で好ましく、これを添加することにより、前記組成物の流動性、柔軟性、制振性が良好になる。ただし、その配合量は、架橋成分および樹脂成分の合計１００重量部に対し１００重量部以下、特に２０〜７０重量部以下が好ましく、１００重量部を超えると、組成物の粘着性が高くなり、加工性が低下する。 In the present invention, a petroleum hydrocarbon resin can be added and blended as the third component in addition to the above-mentioned crosslinking component and resin component. Examples of the petroleum hydrocarbon resins include rosin resins, terpene resins, and alicyclic saturated hydrocarbon resins. In particular, alicyclic saturated hydrocarbon resins are preferable in terms of compatibility, and are added to these. By doing so, the fluidity, flexibility, and vibration damping properties of the composition are improved. However, the blending amount is preferably 100 parts by weight or less, particularly preferably 20 to 70 parts by weight or less with respect to 100 parts by weight of the total of the crosslinking component and the resin component, and when it exceeds 100 parts by weight, the adhesiveness of the composition becomes high, Workability is reduced.
また、この発明では、過酸化物で架橋しない性質のブチルゴム、いわゆるレギュラー型ブチルゴムを、上記第３成分の石油系炭化水素樹脂とは別の第４成分として、または第３成分と共に併用して添加配合することができ、このブチルゴムの添加配合により、上記組成物の流動性および柔軟性を改良することができる。ただし、その配合量は、架橋成分および樹脂成分の合計１００重量部に対し１００重量部以下、特に５〜６０重量部が好ましく、１００重量部を超えると、組成物の強度が低下し、粘着性も高くなる。 In the present invention, a butyl rubber that does not crosslink with peroxide, so-called regular butyl rubber, is added as a fourth component separate from the third component petroleum hydrocarbon resin or in combination with the third component. The fluidity and flexibility of the composition can be improved by adding butyl rubber. However, the blending amount is preferably 100 parts by weight or less, particularly preferably 5 to 60 parts by weight with respect to 100 parts by weight of the total of the crosslinking component and the resin component. Also gets higher.
この発明で使用する架橋剤は有機過酸化物であり、２，５−ジメチル２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン、１，３−ビス（ｔ−ブチルパーオキシイソプロピル）ベンゼン、１，１−ビス（ｔ−ブチルパーオキシ）３，３，５−トリメチルシクロヘキサン、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン−３、ジクミルパーオキシド等が例示される。この中で特に２，５−ジメチル２，５−ジ（ｔ−ブチルパーオキシ）ヘキサンは、反応の均一性で好ましい。この有機過酸化物の配合量は、前記の架橋成分および樹脂成分の合計１００重量部に対し０．０５〜１０重量部、特に０．１〜３．０重量部が好ましく、０．０５重量部未満では架橋が不十分となって圧縮永久歪が低下し、反対に１０重量部を超えると組成物の流動性が低下し、成形困難になる。 The crosslinking agent used in the present invention is an organic peroxide, which is 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (t-butylperoxyisopropyl) benzene, 1 , 1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, dicumyl peroxide, etc. The Among these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane is particularly preferable in terms of reaction uniformity. The compounding amount of the organic peroxide is preferably 0.05 to 10 parts by weight, particularly preferably 0.1 to 3.0 parts by weight, and 0.05 parts by weight with respect to 100 parts by weight of the total of the crosslinking component and the resin component. If it is less than 1, the crosslinking is insufficient and the compression set is lowered. On the other hand, if it exceeds 10 parts by weight, the fluidity of the composition is lowered and molding becomes difficult.
また、均一架橋を実現するため、架橋助剤を添加することが好ましい。その好ましい添加量は、前記架橋成分および樹脂成分の合計１００重量部に対し０〜１０重量部、特に０．１〜３．０重量部である。なお、この架橋助剤としては、トリアリルイソシアヌレート、トリメチロールプロパントリメタクリレート、ジビニルベンゼン、エチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、Ｎ，Ｎ’−ｍ−フェニレンジマレイミド等が例示されるが、均一架橋の面から、特にトリメチロールプロパントリメタクリレートおよびトリエチレングリコールジメタクリレートが好ましい。 Moreover, in order to implement | achieve uniform bridge | crosslinking, it is preferable to add a crosslinking adjuvant. The preferable addition amount is 0 to 10 parts by weight, particularly 0.1 to 3.0 parts by weight, based on 100 parts by weight of the total of the crosslinking component and the resin component. Examples of the crosslinking aid include triallyl isocyanurate, trimethylolpropane trimethacrylate, divinylbenzene, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, N, N′-m-phenylene dimaleimide and the like. From the viewpoint of uniform crosslinking, trimethylolpropane trimethacrylate and triethylene glycol dimethacrylate are particularly preferable.
また、この発明では、一般に使用される充填剤、滑剤、老化防止剤、難燃剤、着色剤、耐光剤、抗菌剤、帯電防止剤等も、本発明の趣旨に反しない限り、添加することができる。充填剤としてはカーボンブラック、シリカ、タルク、微粒子状架橋ゴム、微粒子状樹脂、炭酸カルシウム、金属充填剤、木粉、中空粒子等が例示され、滑剤としてはステアリン酸、ステアリン酸カルシウム、ステアリン酸亜鉛、脂肪酸アミド、脂肪酸エステル、低分子量ポリオレフィン、シリコーン系滑剤等が例示され、老化防止剤にはフェノール系、リン系等が例示される。 Further, in the present invention, generally used fillers, lubricants, anti-aging agents, flame retardants, colorants, light proofing agents, antibacterial agents, antistatic agents, etc. may be added unless they are contrary to the spirit of the present invention. it can. Examples of the filler include carbon black, silica, talc, fine particle crosslinked rubber, fine particle resin, calcium carbonate, metal filler, wood powder, hollow particles, etc., and lubricants include stearic acid, calcium stearate, zinc stearate, Examples include fatty acid amides, fatty acid esters, low-molecular-weight polyolefins, silicone-based lubricants, and examples of anti-aging agents include phenol-based and phosphorus-based agents.
この発明の制振材料は、前記の架橋成分、樹脂成分および有機過酸化物を前記の特定割合で混練し、その際に架橋成分を動的架橋して製造される。その場合、前記の石油系炭化水素樹脂およびレギュラー型ブチルゴムの少なくとも一方を添加配合することができる。また、必要に応じて架橋助剤、充填剤、滑剤、老化防止剤、難燃剤、着色剤、耐光剤、抗菌剤、帯電防止剤等も添加配合することができる。混練装置としては、単軸押出し機や二軸押出し機等の連続式混練機およびニーダーやバンバリーミキサー等のバッチ式混練機など、公知の混練装置が用いられる。 The vibration damping material of the present invention is produced by kneading the cross-linking component, the resin component, and the organic peroxide at the specific ratio, and dynamically cross-linking the cross-linking component at that time. In that case, at least one of the petroleum hydrocarbon resin and the regular butyl rubber can be added and blended. Moreover, a crosslinking aid, a filler, a lubricant, an anti-aging agent, a flame retardant, a colorant, a light-resistant agent, an antibacterial agent, an antistatic agent and the like can be added and blended as necessary. As the kneading apparatus, a known kneading apparatus such as a continuous kneader such as a single screw extruder or a twin screw extruder and a batch kneader such as a kneader or a Banbury mixer is used.
バッチ式の場合は、上記の架橋成分および樹脂成分を、その溶融する温度で混練しながら、必要に応じて石油系炭化水素樹脂、レギュラー型ブチルゴムおよびその他の添加剤を添加し、架橋剤の反応温度で動的架橋を行なう。ただし、石油系炭化水素樹脂、レギュラー型ブチルゴムおよびその他の添加剤は、その一部を最初の反応時に投入し、残りを反応終了後に投入することができる。また、連続式の場合は、架橋成分および樹脂成分を混練してペレット化し、このペレットに架橋剤および架橋助剤を付着した後、上記の反応温度で混練して動的架橋を施し、次いで再びペレット化し、しかるのち必要に応じて石油系炭化水素樹脂、レギュラー型ブチルゴムおよびその他を加えて混練し、所望の組成物を製造する。ただし、全成分を一括して混練りすることもできる。なお、ペレットに架橋剤等を付着する際、付着剤としてプロセスオイルを少量、好ましくは５重量％以下使用することができる。 In the case of the batch type, the above-mentioned crosslinking component and resin component are kneaded at the melting temperature, and petroleum-based hydrocarbon resin, regular butyl rubber and other additives are added as necessary to react the crosslinking agent. Perform dynamic crosslinking at temperature. However, a part of petroleum-based hydrocarbon resin, regular butyl rubber and other additives can be added at the time of the first reaction, and the rest can be added after the end of the reaction. In the case of the continuous type, the crosslinking component and the resin component are kneaded and pelletized, and after the crosslinking agent and the crosslinking aid are attached to the pellet, kneading is performed at the above reaction temperature to perform dynamic crosslinking, and then again. Pelletize, and then, if necessary, add petroleum-based hydrocarbon resin, regular butyl rubber and others and knead to produce the desired composition. However, all the components can be kneaded together. In addition, when attaching a crosslinking agent etc. to a pellet, a small amount of process oil can be used as the adhesive, preferably 5% by weight or less.
得られた制振材料は、通常の熱可塑性樹脂で用いられている押出成形、カレンダー成形および射出成形等の成形方法で任意の形状に成形することができる。そして、成形品の硬度、制振性、圧縮永久歪等は、架橋成分のスチレン−ビニルイソプレン共重合体、樹脂成分の結晶性オレフィン系樹脂および第３成分の脂環族飽和炭化水素樹脂もしくはレギュラー型ブチルゴムの種類や配合量の選択により、広い範囲で種々に設定することができる。 The obtained vibration damping material can be molded into an arbitrary shape by a molding method such as extrusion molding, calendar molding, and injection molding that is used for ordinary thermoplastic resins. Further, the hardness, vibration damping property, compression set, etc. of the molded product are determined by the styrene-vinyl isoprene copolymer as the crosslinking component, the crystalline olefin resin as the resin component, and the alicyclic saturated hydrocarbon resin as the third component or regular. Various types can be set within a wide range by selecting the type and blending amount of the type butyl rubber.
上記のとおり、この発明の制振材料は、軟化剤を用いないので、使用中に接触物への色移りや接触物の性能低下が生じることがなく、しかも配合比率の選択により、硬度を広い範囲で任意に設定することができ、かつ成形性、制振性および圧縮永久歪に優れている。特に請求項２に記載された発明は、架橋成分であるスチレン−ビニルイソプレンブロック共重合体におけるスチレン単位の含有量を限定したものであるから、制振性の制御が容易となる。また、請求項３に記載した発明は、第３成分として脂環族飽和炭化水素樹脂またはレギュラー型ブチルゴムを添加配合したものであるから、硬度がさらに低下し、物性が一層向上する。 As described above, since the vibration damping material of the present invention does not use a softening agent, there is no color transfer to the contact object or performance deterioration of the contact object during use, and the hardness is wide by selecting the blending ratio. It can be set arbitrarily within the range, and is excellent in moldability, vibration damping and compression set. In particular, the invention described in claim 2 limits the content of styrene units in the styrene-vinylisoprene block copolymer which is a cross-linking component, and therefore vibration damping can be easily controlled. In the invention described in claim 3, since the alicyclic saturated hydrocarbon resin or regular butyl rubber is added and blended as the third component, the hardness is further lowered and the physical properties are further improved.
実施形態１スチレン−ビニルイソプレンブロック共重合体において、スチレン単位の含有量が５〜５０重量％、好ましくは１０〜３５重量％のスチレン−ビニルイソプレンブロック共重合体の水素添加物を架橋成分に用い、共重合ポリプロピレンを樹脂成分に用い、上記の架橋成分および樹脂成分を重量比率９５／５〜４０／６０、好ましくは９０／１０〜６０／４０で混練機に投入し、さらに架橋剤として有機過酸化物を上記架橋成分および樹脂成分の合計１００重量部当たり０．０５〜１０重量部添加し、温度１８０〜２３０℃で１〜３０分間混練する。得られた熱可塑性エラストマー組成物からなる制振材料を押出成形、カレンダー成形および射出成形等で任意の形状に成形し、制振の用途に利用する。 Embodiment 1 In the styrene-vinylisoprene block copolymer, a hydrogenated styrene-vinylisoprene block copolymer having a styrene unit content of 5 to 50% by weight, preferably 10 to 35% by weight, is used as a crosslinking component. Copolymer polypropylene is used as a resin component, and the above-mentioned crosslinking component and resin component are introduced into a kneader at a weight ratio of 95/5 to 40/60, preferably 90/10 to 60/40, and an organic solvent is used as a crosslinking agent. The oxide is added in an amount of 0.05 to 10 parts by weight per 100 parts by weight of the total of the crosslinking component and the resin component, and kneaded at a temperature of 180 to 230 ° C. for 1 to 30 minutes. The obtained vibration damping material comprising the thermoplastic elastomer composition is molded into an arbitrary shape by extrusion molding, calender molding, injection molding or the like, and used for vibration damping purposes.
実施形態２
上記の実施形態１において、スチレン−ビニルイソプレンブロック共重合体の水素添加物の一部、１０〜４０重量％を水素の未添加物で置換し、上記共重合体の水素添加物および未添加物を架橋成分として用い、その他は実施形態１と同様にして熱可塑性エラストマー組成物からなる制振材料を製造し、この制振材料を任意の形状に成形し、制振の用途に利用する。
Embodiment 2
In the first embodiment, a part of the hydrogenated product of the styrene-vinylisoprene block copolymer, 10 to 40% by weight, is replaced with an unadded product of hydrogen, and the hydrogenated product and the unadded product of the copolymer are replaced with each other. Is used as a cross-linking component, and the others are manufactured in the same manner as in the first embodiment, and a vibration damping material made of a thermoplastic elastomer composition is manufactured. The vibration damping material is molded into an arbitrary shape and used for vibration damping.
実施形態３
上記の実施形態１または２において、その架橋成分および樹脂成分の合計１００重量部当たり２０〜７０重量部の脂環族飽和炭化水素樹脂を添加配合し、その他は実施形態１または２と同様にして熱可塑性エラストマー組成物からなる制振材料を製造し、この制振材料を任意の形状に成形し、制振の用途に利用する。
Embodiment 3
In the above Embodiment 1 or 2, 20 to 70 parts by weight of the alicyclic saturated hydrocarbon resin is added and blended per 100 parts by weight of the total of the crosslinking component and the resin component, and the others are the same as in Embodiment 1 or 2. A damping material made of a thermoplastic elastomer composition is manufactured, and the damping material is molded into an arbitrary shape and used for damping purposes.
実施形態４
上記の実施形態３において、脂環族飽和炭化水素樹脂以外にレギュラー型ブチルゴムを、上記の架橋成分および樹脂成分の合計１００重量部に付き５〜６０重量部添加配合し、その他は実施形態３と同様にして熱可塑性エラストマー組成物からなる制振材料を製造し、この制振材料を任意の形状に成形し、制振の用途に利用する。
Embodiment 4
In the third embodiment, in addition to the alicyclic saturated hydrocarbon resin, a regular butyl rubber is added and blended in an amount of 5 to 60 parts by weight per 100 parts by weight of the total of the crosslinking component and the resin component. Similarly, a vibration damping material made of a thermoplastic elastomer composition is manufactured, and the vibration damping material is molded into an arbitrary shape and used for vibration damping.
架橋成分、樹脂成分、有機過酸化物およびその他として下記の材料を用意した。
１．架橋成分Ａ：スチレン−ビニルイソプレンブロック共重合体の水素添加物（スチレン含有量１２％、Ｔg：−３２℃、クラレ社製「ハイブラー７３１１」）
２．架橋成分Ｂ：スチレン−ビニルイソプレンブロック共重合体の水素添加物（スチレン含有量２０％、Ｔg：−１５℃、クラレ社製「ハイブラー７１２５」）
３．架橋成分Ｃ：スチレン−ビニルイソプレンブロック共重合体の水素未添加物（スチレン含有量２０％、Ｔg：−１３℃、クラレ社製「ハイブラー５１２５」）
４．架橋成分Ｄ：スチレン−ビニルイソプレンブロック共重合体の水素未添加物（スチレン含有量２０％、Ｔg：８℃、クラレ社製「ハイブラー５１２７」）
５．架橋成分Ｅ：スチレン・イソプレンブロック共重合体（１，４結合）の水素添加物（クラレ社製「セプトン２０６３」）
６．樹脂成分：共重合ポリプロピレン（住友化学社製「エクセレンＥＰ３７２５」）
７．ブチルゴム：レギュラー型ブチルゴム、バイエル社製「ブチル３０１」）
８．脂環族樹脂：脂環族飽和炭化水素樹脂（荒川化学工業社製「アルコンＰ−１００」）
９．軟化剤：パラフィンオイル（出光興産社製「ダイアナプロセスＰＷ−９０」）
１０．架橋剤：２，５−ジメチル２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン（日本油脂社製「パーヘキサ２５Ｂ−４０」）
１１．架橋助剤：トリメチロール・プロパン・トリメタクリレート（三新化学社製「サンエステルＴＭＰ」）
The following materials were prepared as a crosslinking component, a resin component, an organic peroxide, and others.
1. Cross-linking component A: Hydrogenated styrene-vinyl isoprene block copolymer (styrene content 12%, Tg: -32 ° C., "Hibler 7311" manufactured by Kuraray Co., Ltd.)
2. Cross-linking component B: Hydrogenated product of styrene-vinylisoprene block copolymer (styrene content 20%, Tg: -15 ° C., “Hibler 7125” manufactured by Kuraray Co., Ltd.)
3. Cross-linking component C: Hydrogen-free product of styrene-vinylisoprene block copolymer (styrene content 20%, Tg: -13 ° C., “Kyura 5125” manufactured by Kuraray Co., Ltd.)
4). Cross-linking component D: Hydrogen-free product of styrene-vinylisoprene block copolymer (styrene content 20%, Tg: 8 ° C., “Hybler 5127” manufactured by Kuraray Co., Ltd.)
5. Crosslinking component E: Hydrogenated product of styrene / isoprene block copolymer (1,4 bond) (“Septon 2063” manufactured by Kuraray Co., Ltd.)
6). Resin component: Copolymerized polypropylene ("Excellen EP3725" manufactured by Sumitomo Chemical Co., Ltd.)
7). Butyl rubber: Regular butyl rubber, “Butyl 301” manufactured by Bayer
8). Alicyclic resin: Alicyclic saturated hydrocarbon resin ("Arcon P-100" manufactured by Arakawa Chemical Industries)
9. Softener: Paraffin oil (“Diana Process PW-90” manufactured by Idemitsu Kosan Co., Ltd.)
10. Crosslinking agent: 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (“Perhexa 25B-40” manufactured by NOF Corporation)
11. Crosslinking aid: trimethylol, propane, trimethacrylate ("Sanester TMP" manufactured by Sanshin Chemical Co., Ltd.)
上記の「１」ないし「１１」の材料を種々の割合で配合し、混練して実施例１〜８および比較例１〜５の熱可塑性エラストマー組成物を製造した。混練機としてはブラベンダー型混練機（東洋精機社製「ラボプラストミルＲ−５００」）を用い、温度を１８０℃に設定した後、架橋成分を投入して２分間混練し、次いで樹脂成分その他（ただし、架橋剤を除く）を投入して３分間混練し、これらを均一に混合した後、有機過酸化物を投入して混練することにより動的架橋し、トルクが極大値を示してから更に２分間混練した。しかるのち、温度１８０℃のプレス機を用い、上記の混練で得られた組成物に熱プレスを施して厚さ約１mmのシートを作り、各種の物性を測定した。 The thermoplastic elastomer compositions of Examples 1 to 8 and Comparative Examples 1 to 5 were produced by blending the above materials “1” to “11” in various proportions and kneading. As a kneading machine, a Brabender type kneading machine ("Laboplast Mill R-500" manufactured by Toyo Seiki Co., Ltd.) was used. (However, the cross-linking agent is excluded) is added and kneaded for 3 minutes. After these are uniformly mixed, the organic peroxide is added and kneaded to dynamically crosslink, after the torque shows the maximum value. The mixture was further kneaded for 2 minutes. Thereafter, using a press machine at a temperature of 180 ° C., the composition obtained by the above kneading was hot-pressed to produce a sheet having a thickness of about 1 mm, and various physical properties were measured.
物性試験は下記により行った。
１．成形性：射出成形をして良好を○、流動不良のものを×とした。
２．制振性：粘弾性スペクトロメータを用い、周波数１０Ｈzで測定し、常温域でtanδが０．２以上を良好○とした。
３．硬度（ＪＩＳ−Ａ）：ＪＩＳ−Ｋ６２５３に基づいて押針を押付け、１０秒後の数値を読みとる。
４．圧縮永久歪：ＪＩＳ−Ｋ６２６２に基づき、２５％の圧縮で７０℃のギヤーオーブンに２４時間放置し、取出して３０分後に測定した。
５．移行性：厚紙の上にシートサンプルを置き、荷重２５０ｇ／cm2 を加え、温度５０℃のギヤーオーブン中に２４時間放置し、移行性なしを○、移行性ありを×とした。
The physical property test was conducted as follows.
1. Moldability: Good and good by injection molding, and poor flow.
2. Damping property: Measured at a frequency of 10 Hz using a viscoelastic spectrometer, and a tan δ of 0.2 or more in a normal temperature range was considered good.
3. Hardness (JIS-A): A push needle is pressed according to JIS-K6253, and the value after 10 seconds is read.
4). Compression set: Based on JIS-K6262, the sample was left in a gear oven at 70 ° C. for 24 hours at 25% compression, and measured 30 minutes after removal.
5. Transferability: A sheet sample was placed on cardboard, a load of 250 g / cm 2 was added, and the plate was left in a gear oven at a temperature of 50 ° C. for 24 hours.
上記の測定結果を材料の配合比率と共に下記の表１、２に示す。ただし、「実施例」は「実」と、「比較例」は「比」とそれぞれ略記した。 The above measurement results are shown in Tables 1 and 2 below together with the blending ratio of the materials. However, “Example” is abbreviated as “Real”, and “Comparative Example” is abbreviated as “Ratio”.
上記の表１、２に示すように、実施例１〜８は、成形性、制振性、移行性の全てが良好で、圧縮永久歪は５０％以下、硬度は８０度以下であり、特に実施例１、２、３、５、６は、硬度５０度以下を達成しており、電子機器における冷却ファンや小型モーター等の軽量負荷物における制振・防振材として好適に使用可能である。また、硫黄フリー、ハロゲンフリーであり、腐食性や環境負荷性も無いクリーンな材料が得られた。 As shown in Tables 1 and 2 above, Examples 1 to 8 are all good in formability, vibration damping and migration, have a compression set of 50% or less, and a hardness of 80 degrees or less. Examples 1, 2, 3, 5, and 6 have achieved a hardness of 50 degrees or less, and can be suitably used as vibration damping and vibration isolating materials for lightweight loads such as cooling fans and small motors in electronic devices. . In addition, a clean material free of sulfur and halogen and free from corrosiveness and environmental impact was obtained.
これに対して比較例１は、架橋成分Ａのみを用い、かつ架橋しなかったため、圧縮永久歪が１００％になった。また、比較例２は、架橋成分Ａのみを用い、かつ架橋したので、粉々となり、成形できなかった。また、比較例３は、架橋成分としてイソプレン部分にビニル結合のない架橋成分Ｅ（スチレン−イソプレンブロック共重合体の水素添加物）を用いたので、制振性が劣り、０．２未満であった。また、比較例４は、樹脂成分の配合量を６５％と過剰に用いたので、硬度が９０度以上と過大になった。また、比較例５は、軟化剤としてパラフィンオイルを５０重量部配合したので、移行性が生じた。 On the other hand, Comparative Example 1 used only the crosslinking component A and did not crosslink, so the compression set was 100%. Moreover, since the comparative example 2 used only the bridge | crosslinking component A and bridge | crosslinked, it shattered and it was not able to shape | mold. In Comparative Example 3, since the crosslinking component E (hydrogenated product of styrene-isoprene block copolymer) having no vinyl bond in the isoprene portion was used as the crosslinking component, the vibration damping property was inferior and less than 0.2. It was. Moreover, since the comparative example 4 used the compounding quantity of the resin component excessively with 65%, hardness became excessive with 90 degree | times or more. Further, in Comparative Example 5, 50 parts by weight of paraffin oil was blended as a softening agent, and thus migration occurred.
Claims (3)
3. The vibration damping according to claim 1, wherein a petroleum hydrocarbon resin and a regular butyl rubber are added and blended, and each blending amount is 100 parts by weight or less with respect to a total of 100 parts by weight of the crosslinking component and the resin component. material.
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| JP2009243614A (en) * | 2008-03-31 | 2009-10-22 | Sekisui Chem Co Ltd | Damping sheet for automobile |
| JP2009256467A (en) * | 2008-04-16 | 2009-11-05 | Asahi Kasei Chemicals Corp | Dynamically crosslinked composition |
| JP2012251661A (en) * | 2012-07-09 | 2012-12-20 | Sekisui Chem Co Ltd | Damping sheet for automobile |
| KR20180087866A (en) * | 2017-01-25 | 2018-08-02 | 티에스알시 코포레이션 | Thermoplastic elastomer composition for crosslinked foam and use thereof |
| JP2018119145A (en) * | 2017-01-25 | 2018-08-02 | ティエスアールシー・コーポレイションＴＳＲＣ Ｃｏｒｐｏｒａｔｉｏｎ | Thermoplastic elastomer composition for crosslinked foam and use thereof |
| KR102205060B1 (en) | 2017-01-25 | 2021-01-21 | 티에스알시 코포레이션 | Thermoplastic elastomer composition for crosslinked foam and use thereof |
| JP2020152810A (en) * | 2019-03-20 | 2020-09-24 | Jsr株式会社 | Thermoplastic polymer composition, fiber and vibration-damping material |
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