TWI300423B - A thermoplastic elastomer foaming material and the manufacturing method thereof - Google Patents

Description

1300423 IX. Description of the Invention: [Technical Field] The present invention relates to a foamed material of a thermoplastic elastomer (TPE), and more particularly to a hydrogenated styrene/conjugated diene copolymerization A soft low specific gravity foamed material which is a substrate and a method for producing the same. [Prior Art] The application products of foamed rubber and plastics include: weatherproof sealing strips for automobiles, > cushioning boards, heat insulating materials for home appliances, anti-vibration materials, sports and leisure products, work clothes and sole materials, etc. widely. However, the materials used in these products are also very diverse, such as ethylene-vinyl acetate copolymer (EVA), styrene-butadiene rubber (SBR), natural rubber (NR), acrylonitrile-butadiene rubber (NBR). , ethylene-propylene-non-conjugated diene rubber (EPDM), butadiene rubber (BR), polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), polyurethane (PU), polypropylene _ - (PP), chloroprene rubber (CR), isoprene rubber (IR), and the well-known sole foaming material styrene-butadiene-styrene bomb-sex (SBS). In daily life, foamed materials are widely used because of their advantages of energy saving (heat insulation, light weight), safety, and comfort (cushionability). The foaming material based on rubber/plastic has a large amount of air bubbles, so the foamed rubber/plastic can also be said to be a composite material with gas as a filler. Foamed rubber/plastics are similar to general synthetic materials and can be modified to suit a variety of needs by modifying the formulation and molding techniques. 6 1300423 The raw materials of foamed rubber are generally mixed with various additives in the polymer. The polymer is the main component, and its properties will determine the basic characteristics of the foamed rubber. in accordance with. The purpose of adding fillers and various additives to the raw material formulation is to improve the molding properties of the polymer, improve the performance of the product, and improve the economical effect of the blood. Therefore, in the continuous production process, different additives and formulations will be required according to different requirements. The well-known closed-cell foaming materials are traditional thermosetting rubber kicks such as NR, SBR, CR, etc., which will cause air pollution to the environment during the manufacturing process and generate s〇x and other (four) gases during the vulcanization process, not only industrial The production is unfavorable 'and because the produced product is vulcanized foamed rubber, so it can not be recycled again, so the application range of its products is limited. Another closed-cell foamed material made of "ethylene-propylene copolymer" and "ethylene olefin" I (EQC) is also used in large quantities, but "ethylene propylene copolymer" and "ethylene glycol copolymerization". However, it is impossible to balance the soft touch that is attached to soft low-density products and the excellent low compression set. Although a certain proportion of "olefin copolymer rubber" is often added to industrial production to change its properties, it may result in poor compatibility of the two materials when added in a specific ratio, and there is "acetamidine-propylene copolymerization". The material and the material of the "ethylene_α_olefin copolymer" cannot be processed by oil filling, thus limiting its application to soft, low specific gravity foamed articles. In view of the fact that the above-mentioned conventional thermosetting rubber cannot be recovered, and the compatibility of the conventional rare copolymer with the processing oil is poor, the soft low specific gravity cannot be obtained. 7 1300423

Disadvantages of foam materials, etc., U.S. Patent No. 6,653,360, which is 2 to 15 wt% of a styrenic block copolymer, 6 to 90 wt% of a polyolefin, and a processing oil of 4 to 15 wt. And 〇〇 5 to 3 wt% of the additive are mixed with each other, and the styrenic block copolymer described above comprises styrene-ethylene-butylene-styrene copolymer (SEBS), by SEBS and processing oil The compatibility is good to improve the softness of the plastic. However, due to the low addition amount of SEBS and processing oil in the foamed material, and the main component thereof is a polyolefin plastic material, the hardness and specific gravity of the foamed material are still high, and in this case, a two-stage processing method is utilized. The process steps are cumbersome. - In order to overcome the above-mentioned shortcomings of the prior art, the inventor has carefully tested and researched, and has been persevering in the spirit of perseverance, and finally created the "hot = elastic elastomer foaming material and its manufacturing method", with the concept of innovation Provided - a soft low specific gravity heat (four) elastomer foaming material and a method of manufacturing the same. [Summary of the Invention] The concept of the Maoyue is a hydrogenated styrene/conjugated diene series copolymer:,, and a foamed elastomer of a low-specific gravity thermoplastic elastomer of the soil material: a weight of 16 to 5 inches. a percentage of a benzophenone plastic; a series of copolymers; a 7 to 50 weight percent olefin, and 16 to 45 weight percent of a plasticizer. Stupid B = a foaming material of a thermoplastic elastomer, wherein the molecular weight of the above hydrogenated diethyl n-copolymer is between 8 and 0 4 8 1300423, such as the foaming material of the thermoplastic elastomer, wherein the above-mentioned woman The furnace plastic comprises one or a combination of the following materials: ethylene-vinyl acetate co-polymer, ethyl butyl acrylate vinegar, and ethylene-Qj-enene copolymer. The foaming material of the thermoplastic elastomer further comprises a rubber, and the rubber comprises one or a combination of the following materials: ethylene-propylene-non-conjugated diene rubber, isoprene rubber, styrene· Butadiene rubber, acrylonitrile-butadiene rubber, and butadiene rubber.

A foamed material of the thermoplastic elastomer, wherein the plasticizer comprises a processing oil. A foamed material of the thermoplastic elastomer, wherein the processing is selected from the group consisting of paraffin white &, cycloalkylated hydrocarbon oil, musk hydrocarbon oil, or a combination thereof. Wherein the processing oil, wherein the processing oil, such as the foaming material of the thermoplastic elastomer, has an aromatic hydrocarbon content of from 〇1% to 2%.

The foamed material of the thermoplastic elastomer may be free of aromatic hydrocarbons. The foaming material of the thermoplastic elastomer, wherein the above-mentioned splashing agent 3 or more of the following additives: a foaming agent, a bridge aid: a bridging promoter, a dispersing aid, and a filler.勹入士: 1 foaming material of thermoplastic elastomer, before foaming, 0 2~5^^ in 10~10 parts by weight of azobisguanamine foaming oxidized chain ^^ Base benzene bridging agent, 〇·5~6 weight, emulsified zinc foaming aid bridging accelerator, and n~L high molecular weight butyl female 酉1 and 〇·2~5 parts by weight of aliphatic stearic acid 1300423 Agent 0 is a foaming material of the thermoplastic elastomer, which further comprises a light calcium carbonate filler substantially equal to 1 to 120 parts by weight. Another concept of the present invention is to provide a foaming material of a thermoplastic elastomer comprising a fluorinated styrene-butadiene copolymer of a percentage of 16 to 5 〇f, 7 to 7% by weight a thin hydrocarbon plastic; and a 16 to 45 weight percent plasticizer, wherein the foamed material has a specific gravity of 0.1 to 0.25 and a hardness of 3 c to 3 〇c. Another concept of the present invention is to provide a thermoplastic elastomer material comprising a styrene_ethylene_butene_, ethylene (SEBS), 5 to 90 parts by weight of 1 〇 to 1 part by weight. An olefin plastic; and 5 to 1 part by weight of a plasticizer. This month's re-enactment is to provide a soft low-specific gravity thermoplastic elastomer (4) foaming material comprising 10 to 100 parts by weight of styrene-butene-styrene (SEBS) thermoplastic elastomer; 9 g parts by weight of the olefinic plastic; 5 to 9 parts by weight of the rubber; and 〜1 〇〇 by weight of the 堃J, wherein the above-mentioned foamed material has a specific gravity of 〇25 and a hardness of π to 30C. A further concept of the present invention is to provide a foaming material curing method for a soft low specific gravity thermoplastic early body, which comprises the following steps: a hydrogenated styrene/co-diene copolymer copolymer having a percentage of Μ 50 50 f Mixed with up to 45 weight percent of plasticizer and adsorbed; added 7 to 9 percent by weight of olefin plastic mixed with a mixture of deuterated styrene/conjugated diene series ▲ and plasticizer; kneaded and foamed into 10 1300423. The foaming material of the soft low specific gravity thermoplastic elastomer according to the above, wherein the soft low specific gravity thermoplastic elastomer foaming material has a specific gravity of 0.1 to 0.25 and a hardness of 3C to 30C. The foamed material of the soft low specific gravity thermoplastic elastomer is added as described above, wherein the hydrogenated styrene/conjugated diene series copolymer and the plasticizer are mixed at a temperature of 50 ° C to 70 ° C. a foamed material of a soft low specific gravity thermoplastic elastomer as described

The method of mixing, wherein the mixing step is carried out in an internal mixer or a twin screw extruder. A foaming material addition method of a soft low specific gravity thermoplastic elastomer as described above, wherein the above kneading step is carried out at a temperature of substantially 11. The above foam molding step in the foaming material processing method of the soft low specific gravity thermoplastic elastomer as described is an overmolding molding. The foaming material of the soft low specific gravity thermoplastic elastomer as described above is added to the method wherein the foaming step is at a temperature (10). C ~ 18 〇 C between. The strength of the foaming material of the soft low-specific gravity thermoplastic elastomer is 2, and the above-mentioned hydrogenated styrene/co-diester copolymer is divided into 80,000 to 500,000. Knife 1 [Embodiment] The present invention is further described and described in detail, however, the accompanying drawings merely provide 1300 423 for limiting the invention. Since the hydrogenated styrene/conjugated diene copolymer has the advantages of high compatibility with other raw materials and additives, and easy processing, the present invention provides a hydrogenated styrene/conjugated diene having a soft low specific gravity property. The copolymer is a foamed material of a substrate. Introduction of conjugated diene series copolymer materials: The decadiene-conjugated diene series copolymer used in the present invention includes 1,3-butadiene, isoprene, ι, and a common diene. 3-Pentadiene, or a mixture thereof or the like, wherein the residual amount of the unsaturated double bond of the conjugated diene polymerized unit is less than 10%, preferably less than 5%. Of course, the deuterated styrene-co-diene series copolymers used in the present invention can also be provided from commercially available deuterated styrene-conjugated dilute thermoplastic elastomers. For example, Kraton's Kraton G series, Kuraray or Septon's Septon 6 or 8 series, Taiwan Rubber's SEBS series, Polymeri's SEBS 2 series, Dynasol's Calprene Η series, and Asahi's Tuftec Η series of styrene-ethylene - Butene-* Styrene (SEBS) Thermoplastic Elastomer, which can be used as a material of a 1,3-butadiene-based, diene-derived styrene-conjugated diene block series copolymer. In addition, 'JSR Dynaron series or a mixture of Dynaflex series of polystyrene-butadiene rubber (HSBR) thermoplastic elastomer, can be used as hydrogenated styrene-conjugated 1,3-butane difluorene as conjugated diene A material of an olefin partial block or disordered copolymer. Also, for example, Kuraray or Septon's Septon 2 series of stupid ethylene-ethylene-propylene-styrene (SEPS) thermoplastic elastomer can be used as argon styrene conjugated with isoprene as conjugated diene 12 1300423 material of diene block copolymer. Furthermore, for example, Kuraray or Septon's Septon 4 series styrene_[ethylene-(ethylene-propylene)]-styrene (SEEPS) thermoplastic elastomer can be used as isoprene and 1,3-butyl The olefin mixture is a material of a hydrogenated styrene copolymer of a conjugated diene. The synthetic or commercially available hydrogenated styrene/conjugated diene copolymer of the present invention has a molecular weight (MW) of from about 85,000 to 500,000 grams per mole without any processing oil (based on PS) GPC measurement) The rubber/plastic is blended with different types of raw rubber or mixed with filler I (filler), plasticizer, auxiliary agent and cross-linking (foaming agent) as a compound (formulation rubber) to meet The required function, processability and cost, and the process of plasticizing the raw material rubber, mixing other compounding agents, and uniformly dispersing it are called kneading. Processing mixers can be roughly divided into batch type and continuous type; batch type mixers have open mills (also called open mixers such as mill) and internal mixers (also known as closed mixers such as kneader). , banbury), etc.; continuous mixers have mixing extruders and continuous mixers. However, rubber has viscoelasticity and is mostly supplied in the form of solid pellets. In order to produce small batches in a variety of types, it is almost always mixed in a batch. _ The advantage of kneader (banbury) is that the mixing conditions such as kneading time and material mixing order are large. Therefore, it can be adapted to various requirements and is now widely used. The main mixing machine, the kneading device and the kneading method according to the present invention are all kneaded by such an internal mixer, and the material kneaded by the internal mixer is usually combined with a mill to formulate rubber. The thin plate is formed into a flat shape to facilitate the subsequent molding foaming operation. First, the hydrogenated styrene-conjugated diene series copolymer is mixed with a plasticizer. 13 1300423 The adsorption is complete, which is usually stirred using a stirring tank, and the temperature is set to 50 C to 70 C, followed by the addition of olefin plastic, rubber, and other additives. For example, a foaming agent, a bridging agent, an auxiliary agent, and the like are completely kneaded, and then kneaded by a mixer (a 10,000-mass mixer, a refiner) or a twin-screw extruder to form a colloidal particle. The colloidal particles can be foamed by adding different proportions of bridging agent and blowing agent in a heated and pressurized PRESS. The plasticizer added in the present invention is a processing oil, which may be, for example, oils such as Paraffinic Oil, Naphthenic 〇il, and Aromatic Oil, by preparing rubber. A large amount of processing oil is used in the foaming process of plastics to reduce the cost of the compound and improve the processing performance. However, the use of processing oil should also pay attention to the content of aromatic hydrocarbon components (Ca%) should not be too high (0~20%), otherwise it will affect the bridging efficiency, so it is recommended to make Paraffinic Oil better. The olefin plastic used in the present invention may be, for example, ethylene-ethylene acetate copolymer (EVA), ethylene butyl acrylate, or ethylene-α-olefin copolymer (E〇c). · ethylene-a-olefin copolymer, etc., may also comprise a combination of one or more of the above olefin plastics. The rubber which can be optionally added is, for example, ethylene-propylene-non-co-light diene rubber (EPDM), isoprene rubber (IR), stupid ethylene, butadiene rubber (SBR), acrylonitrile butadiene rubber ( NBR), butadiene rubber (br) Winter may also comprise one or more of the above rubbers. Material foaming can be achieved by the addition of a blowing agent or by the supercritical fluid technology currently being developed. The blowing agent which can be used in the present invention is 1300423, which comprises a physical foaming agent and a chemical foaming agent, or a combination of the two. Wherein, the physical blowing agent may comprise an aliphatic carbon hydrocarbon (such as propane, isobutyl, pentane, hexane, etc.), fluorinated hydrocarbon, nitrogen or other gases. Etc., and the chemical blowing agent may contain azo (AZO, such as azobisguanamine; Azoicarbonamide; AC), Nitroso, Hydrazide or Hydrazo, sodium bicarbonate ( Sodium bicarbinate), ammonium carbonate, and the like. If azobiscarbamide (AC) is used as the blowing agent, it may be added in an amount of from 1 to 10 parts by weight. The present invention can also be added to a preferred embodiment such as a bridging agent, a bridging promoter, a foaming aid, a dispersing aid, and a filler to adjust its properties. In the preferred embodiment of the present invention, an organic peroxide, such as Dicumyl peroxide, is used as a bridging agent, and the amount thereof is added in an amount of about 2 to 5 parts by weight. between. ® The ratio of the above blowing agent / bridging agent (such as AC / DCP) can be between 〇 2~5 / -1~10. - In a preferred embodiment of the invention, a metal oxide such as active oxidized (ZnO) or magnesium oxide (MgQ) foaming is used in an amount of between 5 and 6 parts by weight. In the preferred embodiment of the invention, aliphatic stearic acid SA (CnH35CO〇H) is used as a dispersing aid, and the dazzle point is between 59. 〇 ~ hunger white solid, and the amount added is between 0.2 and 5 parts by weight. 15 K00423 is one. Its _2===^ molecular formula is added to the lighter carbon _ (cacw_ _iler), which can be added in an amount of 1 to m parts by weight. For the purpose of filling, for convenience, the present invention will enumerate and compare the examples to specifically describe the example formulation ratio as shown in h and Table 2: Marriage 0 (DuPo_ 7 〇 eva (10) containing ^ - co-located (5) coffee secret blending shot at the touch temperature of the mix, J / dish degree up to the surgery, then add other additives such as 23 parts by weight

And (4) parts by weight of (10) _, u parts by weight of active zinc oxide foaming and Μ by weight of PL__ bridging promoter, G 5 parts by weight of stearic acid SA, bulk additives and the like. Continue to mix to Qing _, move to the temperature step = machine mix in the machine, the fine electronic balance is difficult _, placed in the temperature ^ C thank you. The size of the mold is (10) drying _mm> < 12 coffee (long X under the service _ pressure, and the hot pressing time is released after 18 minutes to release the pressure. Hardness it: foaming of the elastomer) Comparative Example 2: 16 1300423 The mixing tank will be 3 weight percent of styrene_ethylene-butylene-ethyl acetamide copolymer (SEBS) of Taipol SEBS-3151 and 4 weight percent

The PW_32 paraffin white oil produced by Idemitsu was mixed and fully adsorbed, and the temperature was set to 50C. Then, together with 90% by weight of EVA (VA content of 18%), it is mixed in a closed mixer at an initial temperature of 80 ° C. When the temperature is increased to 100 C, other additives such as 1 are added. Parts by weight of AC foaming agent, 0.7 parts by weight of DCP_agent, ()·7 parts by weight of foaming aid for active zinc oxide, and 〇·3 • Hole for heavy wounds &quot;400 bridge promoter, 〇·3 weight Part of the dispersing aid of stearic acid SA. When the performance is mixed to ll〇°C, the material is discharged, and the temperature is transferred to the temperature of the thief. The mixture is thinned out and the _ electronic balance is weighed and placed at a temperature of 16 () χ: / In the package. The mold size was 14 〇mm x 1 〇〇 χ 12mm (long father wide 〆 high), under 15 〇 kg / cm pressure ' while the marrow time 18 minutes after release pressure to form. The foamed material of the thermoplastic elastomer obtained above had a hardness of 60 C and a specific gravity of 0.33. Example 1: ‘Use a mixing tank to mix 50 parts by weight of SEBS thermoplastic elastomer of Taip〇1 SEBS_3151 with 20 parts of pW_32 paraffin oil and complete it, and set the temperature to 5 °C. Then, together with 30 parts by weight of EpDM, 3 parts by weight of the intestine, 〇·5 parts by weight of the guillotine SA auxiliaries, and 5 parts by weight of the light carbonic acid lining agent, the eadea closed scale The towel is kneaded at the temperature of the thief. When the temperature is increased to 100 C%, other additives such as 6 parts by weight of ac foaming agent, u 17 1300423 parts by weight of DCP bridging agent, and 1 part by weight of active zinc oxide are added. Auxiliary, and 0.5 parts by weight of PL-400 bridging promoter. The mixture was continuously mixed to 110 ° C, and the mixture was transferred to a temperature of 80 ° C. The mixture was thinly passed out, and 260 g was weighed by an electronic balance, and placed in a foaming machine at a temperature of 160 ° C. . The mold size is 140 legs X 100 legs X 12 legs (length X width X height), under a pressure of 150 kg/cm 2 , and the hot pressing time is released after 18 minutes to form a pressure. As shown in Table 1, the processing conditions and composition components of Examples 2, 3, and 4 were the same as those in Example 1, except that the proportion of the rubber component and the processing oil was 30 parts by weight of SBR, IR, NBR, respectively. 40, 60, 100 parts by weight of processing oil, respectively. 18 1300423 Table 1: (except hardness and specific gravity) The remaining values are in parts by weight)

In Example 1, the hardness of the foamed material of the SEBS block polymer was 30 C, and the specific gravity was 2. By comparison of Examples 1 to 4, it is found that changing the ratio of the processing oil can be used to adjust the hardness and specific gravity of the foamed material, and the obtained foam of the SEBS composite is a micro-closed with a touch-sensitive feeling. Porous material In the above-mentioned example, the foamed special 19 1300423 material of the sebs block polymer obtained by the present invention has a hardness of 5C to 30C and a specific gravity of between 〇1 and 〇25. Example 5: Eight use of the spoiler bucket will be Kuraray's ¥ 〇 11-4 〇 55 of 51 weight hundred knives = styrene [ethylene _ (ethylene propylene)] _ benzene women (ship (9) and 17 · 2 里 里 里 里 匕 P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P The mixture is placed together in a closed mixer at a temperature of (10).C, and the mixture is heated. When the temperature rises to a bribe, other additives such as an AC foaming agent of a weight of one part, and a weight of DCp bridging agent are added. , u parts by weight of active oxygen foaming auxiliary, and 5 parts by weight of 4 (8) bridging promoter, 〇·5 weight = month ISA dispersing aid, etc.. Continuous mixing to 峨 when discharging, moving to temperature In the mill open mill, the mixture is thinned out, and the electronic balance is used to weigh %叱, and placed in a foaming machine with a ft of 16 °C. The mold size is 140 awake&gt;&lt;1〇〇X 12 1 force 'at 15G kg / (10) 2 pressure, and hot pressing day after 8 minutes release (4) The foamed material of the thermoplastic elastomer obtained has a hardness of 25c and a specific gravity of 0.21. : Mixing 17.2 wt% of methotrexate-ethylene-butylene-benzene (10) copolymer (8 coffee) of Taipol SEBS-3151 with 21,5 wt% of PW-32 stone moon white oil mixed with a mixing tank Adsorption is complete, and the temperature is compared with 47.3 weight percent ΕγΑ and 1〇 parts by weight of the carbonated filler in a 1300423 ^kn▲ closed mixer at the initial temperature of the step, when the temperature = 100 In the case of C, other additives such as 3 parts by weight of Ac foaming agent, 0.45 parts of DCP bridging agent, h2 parts by weight of zinc oxide foaming _, and 0.5 parts of PL-400 bridging promoter, 〇 5 parts by weight are added. The dispersing aid 2 of stearic acid sa is continuously kneaded to 11 叱, and moved to a temperature of 8 〇t. The mixture is thinned out and the moon is weighed and weighed by the electronic balance, and placed at temperature (10) The foaming machine of c. The size of the mold is 140 legs x 100 coffee X η coffee (length X width x height), which is formed under the force of 150 kg/cni and the dust is released after 18 minutes of hot pressing time. The foamed material of the obtained thermoplastic elastomer was measured to have a hardness of 20 C' and a specific gravity of 〇 13. Example 7: Using Kuraray's Sept with a mixing tank N-4〇55 of 15 9 weight percent styrene-[ethylene-(ethylene·propylene)]-styrene (SEEps) mixed with 19.8 weight 1% pw_32 paraffin white oil and adsorbed completely, and the temperature • Set to 5 ° C. Next with 43. 7 weight percent LDPE, 0.5 part by weight stearic acid SA dispersing aid, and rhodium parts by weight of antioxidant and 2 parts by weight of light carbon calcium carbonate The filler is placed in a kneader closed mixer at 8 (the initial temperature of rc - kneading, when the temperature rises to 10 ° C, then other additives such as 2 · 5 ° ^ AC foaming Agent, 丨 part by weight of DCP bridging agent, 丨 part by weight of active zinc oxide: auxiliaries, and 5 parts by weight of PL_400 bridging promoter, 〇 · 5 parts by weight of stearic acid SA dispersing aid. Continue to mix to 11〇t: when discharging, move to the temperature of 8 〇 之 mill mill mixing material thin through the film, and use the electronic balance to weigh 26 〇 g, placed at a temperature of 160 ° C In the bubble machine. The mold size is 140 legs X l〇〇mm χ 12 coffee (length 21 1300423 x width x height), under pressure of 150kg/cm2, and the pressure is released after 18 minutes of hot pressing time. The foamed material of the thermoplastic elastomer obtained above had a hardness of 28 C and a specific gravity of 0.11. Example 8: 19.9 wt% of a stupid ethylene-butylene-styrene-styrene copolymer of Taipol SEBS-3151 using a spoiler bucket (3£^幻与15.9% by weight of 222u produced by Nynas) Ring:): The oil is mixed and adsorbed completely, and the temperature is set to 50 C. Then, with 43.8 weight percent EVA and 20 parts by weight of light calcium carbonate filler - in the kneader _ type mixer, mix under _ when the temperature rises to 1 () 叱 _ add others to add fine Such as 2 5 ° heavy plate amount; AC foam i parts by weight DCP bridging agent, i parts by weight of active oxidation of the foaming aid, and 0.5 parts by weight of PL, bridging promoter, 〇 5 parts by weight of stearic acid SA dispersing aids, etc. When the mixture is continuously mixed to 11 〇t, the material is discharged, and the temperature is moved to the temperature of _ mm, and the refining mixture is thinned out, and is used in the foaming machine of the electronic balance weighing field. The size of the mold is 14〇_χ刚_χ XIX咼), under the pressure of 150kg/cm2, and the shape is formed at the time of η. Release pressure after 18 minutes between , , , and W The thermoplastic elastomer 髀 obtained by the above has a hardness of (10) and a specific gravity of 〇.13. Example 9: 21.6 weight percent of the foamed material was used to ferment Taipol SEBS-3151 22 1300423 styrene-ethylene-butylene-styrene copolymer (SEBS) with 43. 2 weight percent PW -32 paraffin white oil was mixed and adsorbed completely, and the temperature was set to 5 ° ° c. Then, together with 21.6% by weight of EVA and 1 part by weight of light calcium carbonate filler, =kneader Lai Shou refining at the initial temperature of _, when the temperature rises to loot: then add other additives such as 2 · 5 parts by weight of AC foaming d 1 part by weight of DCP bridging J, 1 part by weight of active oxidizing foaming aid, by weight of PL__ _ _, Q 5 parts by weight of stearic acid SA dispersion ^ When holding the secret to the boot, the material is 'moved to the temperature_the mill opener#, and the balance of the b-balance is weighed 26Gg and placed at a temperature of 160. 〇 in / in. 2 The mold size is 140 jobs X _ delete x 12fflm (length x width X height), g em moves, and the hot pressing time releases the pressure after 18 minutes to form. The hardness measured by the foaming material of the hot-spinning body of Shuosheng is far from 4C, and the specific gravity is 〇11. 』伃之23 1300423

Table 2: (except for hardness and specific gravity, the value is followed by %, which is expressed as weight percent, if not indicated, is part by weight) Example 5 6 7 8 9 Taipol-3151 (SEBS) — 17,2% — 19.9 % 21.6% Septon-4055 (SEEPS) 51% - 15.9% - - Paraffin white oil (processing oil) 17.2% 21.5% 19.8% - 43.2% Naphthenic oil (processing oil) ~ - - 15.9% - EVA (olefin Plastic) 17.2% 47.3% 43.8% 21.6% LDPE (olefin plastics) — — 43.7% — — CaC〇3 (Filler) 10 10 20 20 10 ZnO (foaming aid) 1.2 1.2 1 1 1 SA (dispersing aid) 0.5 0.5 1 0.5 0.5 PL-400 (Bridge Accelerator) 0.5 0.5 0.5 0.5 0.5 DCP (Bracement Agent) 1 1 1 1 1 AC (Blowing Agent) 3 3 2.5 2.5 2.5 Hardness 25C 20C 28C 24C 4C Sp. Rr (specific gravity) 0.21 0.13 0.11 0.13 0.11 Although the present invention has been disclosed above in several preferred embodiments, it is not intended to limit the invention, and the spirit and scope of the invention, when;;::=: The changes and retouchings attached to the scope of the invention are not subject to the scope of protection of the present invention. The scope defined by the application for patent is

25

Claims (1)

.1300423 丨公! 傪正97· 4, 2 丄, MU 1· A foaming material of a thermoplastic elastomer comprising: 16 to 50% by weight of a hydrogenated styrene/conjugated diene series copolymer; /, to 7 to 50 And 8% by weight of the olefin plastic; and 16 to 45 weight percent of the processing oil, wherein the olefin plastic is selected from the group consisting of ethylene-vinyl acetate copolymer, ethylene butyl acrylate, ethylene olefin copolymer, and combinations thereof. 2. The foaming material of the thermoplastic elastomer according to the first aspect of the invention, wherein the hydrogenated stupid ethylene/conjugated diene series copolymer has a molecular weight of between 80,000 and 500,000. 3. The hair thermoplastic elastomer according to claim 1, wherein the rubber material is selected from the group consisting of a rubber, and the rubber is selected from the group consisting of a woman's propylene/a non-carbon, a diene rubber, and an isoprene. One of the two rubbers, styrene-butadiene rubber knee, acrylonitrile-butadiene rubber, butadiene rubber and combinations thereof. = If you apply for a patent! The foamed material of the thermoplastic elastomer is selected from the group consisting of sarcophagus white oil, aquarium hydrocarbon oil, and aromatic oil, and a combination thereof. &quot; ^ As claimed in the scope of patent application, item i: Thermoplastic Γ. The addition: the oil has a fragrant material with a burying content of 〇.=: material 'the first item of plasticity bomb (4) + which Process oils may be free of aromatic hydrocarbons. ^ A foaming agent, bridging agent, foaming aid for a thermoplastic elastomer as described in the first paragraph of the patent scope;;;; a lower jaw, a beech bridge accelerator, a dispersing aid, and a 26 1300423 filler. The foam material of the thermoplastic elastomer described in the seventh paragraph of the patent 干 专利 枓 枓 枓 枓 枓 枓 枓 枓 枓 枓 枓 枓 枓 枓 枓 枓 枓 枓 枓 枓 发泡 发泡 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热Amine foaming agent, 0 Λ . ^ ^ ^ 2~5 by weight of 1 part of bismuth oxide isopropyl bridging agent, 2 parts by weight of zinc oxide foaming aid, 0.1~1.5 parts by weight a butyrate bridge builder and 0.2 to 5 parts by weight of an aliphatic stearic acid dispersing aid. 9. The foaming calcium carbonate filling material of the thermoplastic elastomer according to claim 8 of the patent scope, which further comprises foaming of a soft agent of a low-specific gravity thermoplastic elastomer in a weight fraction of 0 10 The material processing method 'includes the following steps: ^ (a) mixing 16 to 50 weight percent of the hydrogenated styrene/conjugated diene series copolymer with a 16 to 45 weight percent of processing oil and adsorbing to form a mixture; To a weight percentage of the olefin plastic mixed with the mixture to form a kneaded product, wherein the olefin plastic is selected from the group consisting of ethylene-vinyl acetate copolymer, ethylene butyl acrylate, ethylene-a. olefin, copolymer One of them and a combination thereof; and (c) a very pressure batch foaming molding of the kneaded material. The method for processing a foamed material of a soft low-specific gravity thermoplastic elastomer according to the first aspect of the invention, wherein the soft low-specific gravity thermoplastic elastomer foaming material has a specific gravity of 〇" to 〇·25 , hardness 3C to 30C. 27 1300423 12. If you apply for a foaming material processing method for sexual elastomers that are difficult to target, the μ +, low ratio 垔", 5叱~ thief is carried out. ^The above step U) is a patent The soft low-specific gravity thermoplastic material twisting method according to the item 10, wherein the step (1) is carried out in a machine or a twin-screw extruder. The method for processing a specific gravity heat-mouldable foam material, wherein the above step (1) is performed at a temperature of 110 ° C. The soft low-specific gravity heat-sensitive plastic material according to claim 10 of the patent scope, wherein the foaming material processing method is the above The step (C) is a foaming molding method for the outer ring of the soft, low-specific gravity thermoplastic/sexual body according to the tenth item of the patent scope, wherein the above step (c) is / The degree of the dish is between 160 C and 180 C. : The raw 7 wave 7: The soft low specific gravity hot plastic ▲ limb foaming material processing method described in the patent face 10, wherein the above hydrogenated styrene / eight vehicles The molecular weight of the copolymer is between 80,000 and 50,000. The soft low-specific gravity thermoplastic foaming material processing method according to Item 10 further comprises adding-rubber, and the speed rubber is selected from the group consisting of a mother-wife-wife-non-co-gelatin-Z-enene rubber and propylene. One of nitrile-butadiene rubber and butadiene rubber and its combination. 19·If you apply for special (4) ig, item soft low-specific gravity thermoplastic 28 1300423 flexible foam processing method, 苴Wax white oil, naphthenic oil, aromatic hydrocarbon oil "Processing oil is selected from the group consisting of stone 2〇κ., one of and a combination thereof. Second = please refer to the soft low ratio described in item 1G of the patent scope _ plastic processing modified foaming material processing method, complex &amp; U- A, A processing oil is right 芸 cigarette content is between 0.01% ~ 20%. ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, /, the processing oil can be free of aromatic _ please patent 帛 1G item soft low specific gravity elastic foam processing method, which includes addition; less one of the following additives: foaming agent, bridging agent, hair Foaming aids, bridging accelerators, dispersing aids, and fillers. The method for processing a foamed material of a soft f low specific gravity thermoplastic elastomer according to Item 22 of the patent scope includes the addition of a part by weight of the azobisformamide foaming agent, and 0.2 to 5 parts by weight. Isopropyl epoxide scavenger, 0,5~6 parts by weight of oxidized speech foaming aid, 〇1·7 parts by weight of high molecular weight methacrylate bridge promoter, and 〇2 2 5 ·· parts by weight The aliphatic stearic acid dispersing aid is mixed together. 〜24. The foaming material of the soft low specific gravity 埶 弹性 elastic elastomer according to claim 23, which further comprises a light calcium carbonate filler in an amount of 2 parts by weight. 25· a foaming material of a thermoplastic elastomer comprising: 16 to 50% by weight of a hydrogenated stupid ethylene/conjugated diene series copolymer; 29 1300423 7 to 50% by weight of olefin plastic; and 16 to 45 a processing oil of a weight percentage, wherein the olefin plastic is selected from the group consisting of ethylene vinyl acetate copolymer, acetamyl butyl acrylate, ethylene olefin copolymer, and combinations thereof, and the specific gravity of the foaming material is up to 0 25 Hardness 3c, to - 30C. 26. 30. The thermoplastic elastomer = material as described in claim 25, wherein the fraction of the hydrogenated styrene/conjugated diene copolymer is between 80,000 and 500,000. The hair of the thermodynamic elastomer described in item 25 of the material occupation includes - rubber' and the rubber is selected from the group consisting of ethylene-acrylic-acrylic-acrylic-di-rubber rubber, isoprene rubber, and styrene. Ding dilute rubber ^ know nitrile u rubber, Ding Ergui rubber among them - and combinations thereof. One of the aroma oils of the thermoplastic elastomer described in Item 25 of the Lei Wai Wai, and the group thereof: "oil, hospital hydrocarbon oil, aromatic foam material such as material: thermoplastic elastomer according to the scope of item 25. The hair is 0.01~20%/, and the processing oil has an aromatic hydrocarbon content of the foam material: the thermoplastic elastomer of the above-mentioned item 25, and the processing oil may not contain aromatic hydrocarbons. The force of the thermoplastic elastomer mentioned in Item 25: The foaming gas contains more than one or more of the following additives, foaming aids, bridging promoters, dispersion 30 31 1300423 And fillers. Foaming Qi 1, 0.2~5 ϋ: azo carbamide in U~1G parts by weight, diazonium bisulphate bridging agent, 0.5~6 = zinc oxide foaming Auxiliary agent, 01 to 15 parts by weight of high molecular weight acid =: bridge accelerator, ... by weight of aliphatic hard-feel as described in claim 32 of the thermoplastic elastomer of the hair / package material' Containing from 1 to 12 G parts by weight of a light carbonic acid hydrazine. VIII 34. A kind of thermoplastic elastomer a material comprising: 10 to 100 parts by weight of styrene-ethylene-butylene styrene (SEBS); 5 to 90 parts by weight of an olefin plastic; and 5 to 100 parts by weight of a processing oil, wherein the olefin plastic is selected From one of ethylene-vinyl acetate copolymer, ethylene butyl butyl acrylate, acetamidine-α-glycol copolymer, and combinations thereof. • Test 35. The thermoplastic elastomer as described in claim 34 The foaming material further comprises 5 to 90 parts by weight of rubber. 36. A foaming material of a soft low specific gravity thermoplastic elastomer comprising: 10 to 100 parts by weight of styrene-ethylene-butylene-benzene Ethylene (SEBS) thermoplastic elastomer; 5 to 90 parts by weight of roasted hydrocarbon plastic; 31 1300423 5 to 90 parts by weight of rubber; and 5 to 100 parts by weight of processing oil; ~, cut, ethylene butyl acrylate, ethylene One of the _α-olefin copolymers and the combination thereof, and the above-mentioned foaming material has a specific gravity of 〇·1 to 〇·25, and a hardness of 3C′ = 30 C. ^ 37. If the patent application scope is the first item, the first item , in the 25th styrene·co-diene series copolymer The olefin is selected from the group consisting of diene's; ene' 1,3-pentadiene and combinations thereof, wherein the residual amount of unsaturated double bonds of the conjugated diene polymerized unit is less than 1%. The hydrogenated styrene-co-binder series copolymer of the item 37, wherein the terpene polymerized unit has a low residual double bond residue 32