CN1544523A - Thermoplastic elastomeric foaming material and its preparation method - Google Patents
Thermoplastic elastomeric foaming material and its preparation method Download PDFInfo
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- CN1544523A CN1544523A CNA2003101167507A CN200310116750A CN1544523A CN 1544523 A CN1544523 A CN 1544523A CN A2003101167507 A CNA2003101167507 A CN A2003101167507A CN 200310116750 A CN200310116750 A CN 200310116750A CN 1544523 A CN1544523 A CN 1544523A
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Abstract
The invention relates to a phenylethene- butadiene segmented copolymer elastic body expanded material with modified bonding property and method for preparation, wherein the material is prepared from SBS, PS, acrylic acid copolymer, softening oil, filling material, foaming agent, foam core forming agent, anti-oxidant, releasing agent through weighing, mixing, blending, granulating, mixing foaming agent with granulate, then injection moulding, extrusion, die pressing or calendaring. The invention can be applied to the fields of sole, tubular product and sheet material.
Description
(1) technical field
The present invention relates to a kind of thermoplastic elastomer foaming material, especially a kind of adhesive property is able to elastomer foamed material of improved styrene-butadiene block copolymer (SBS) and preparation method thereof.
(2) background technology
SBS is a kind of novel thermoplastic elastomer macromolecular material that grows up the sixties, now has been widely used in fields such as shoemaking, tackiness agent, modifying plastics and asphalt modification.Sole with the SBS material preparation has characteristics such as forming process is convenient, wet-sliding resistant performance is good, with low cost, is a kind of application material for sole of shoe very widely.Along with the progress and the development of footwear art, lightweight, elastomeric material for sole of shoe are development main flows from now on.Yet, with the sole density of common SBS material preparation generally at 1.0g/cm
3About, preparation SBS foam material can alleviate product weight, economical with materials, lifting competition capability.
Interim in CN02114034.0 patent application and " elastomerics " 2002 the 12nd volumes the 3rd, people such as Wu Zhiyong and Liang Hongwen provides invention and the research that SBS (model YH-788) is foamed, in SBS, add Zinc Stearate, zinc oxide, polystyrene (PS), ethylene-vinyl acetate copolymer (EVA), naphthenic oil, lime carbonate and Cellmic C 121 (AC) whipping agent etc., be higher than at die head temperature under 180 ℃ the condition and prepare foamed shoe sole, its concrete prescription is as follows:
Prescription 15 parts of 65 parts of 1:SBS, PS, 5 parts of EVA, 15 parts of naphthenic oils, 1.2 parts of AC, 0.8 part of Zinc Stearate, 1.2 parts in zinc oxide.
Prescription 15 parts of 65 parts of 2:SBS, PS, 5 parts of EVA, 15 parts of naphthenic oils, 5 parts in lime carbonate, 1.2 parts of AC, 0.8 part of Zinc Stearate, 1.2 parts in zinc oxide.
The foamed shoe sole density that adopts above-mentioned prescription 1 and 2 to prepare respectively is respectively 0.66g/cm
3, 0.78g/cm
3Appoint Xiang in the CN96104514.4 patent application, to provide thermoplastic foaming composition to reach and prepare the method for sole with it, the vinylbenzene matrix high molecular elasticity triblock copolymer of employing anionoid polymerization, PS, activation azodicarbonamide whipping agent etc. are main raw material, be to penetrate under 170～200 ℃ the condition in temperature, preparation density is 0.69g/cm
3Foamed shoe sole, and itself and rubber soles made up.
Foregoing invention and research all adopt azo foaming agent to foam, because this class foaming agent decomposition temperature is higher, need to add foamed promoters such as zinc oxide and Zinic stearas, penetrate temperature up to 170～200 ℃.In addition, foregoing invention and research have the following disadvantages: 1) because SBS, PS are non-polar material, during with the sole of above-mentioned material preparation and vamp applying, must could obtain bond effect preferably after surface treatment; 2) because azo foaming agent generally is yellow, if it is not enough to penetrate temperature and time, then the whipping agent decomposition is often incomplete, and whipping agent residual in the goods is very big to the color influence of goods; 3) too much zinc oxide and Zinic stearas produce sometimes and tell white phenomenon, and products appearance is produced detrimentally affect; 4) there is the C=C unsaturated link(age) in the SBS material, at high temperature aging easily, thus influence work-ing life of product.
(3) summary of the invention
The present invention is directed to the shortcoming of existing SBS foam material, aim to provide that a kind of adhesive property is good, blowing temperature is low, the thermoplastic elastomer foaming material of color control stabilization and preparation method thereof.
The composition (by mass ratio) of the said thermoplastic elastomer foaming material of the present invention is: 5～40 parts of 100 parts of SBS, PS, 5～40 parts of acrylic copolymer, 5～40 parts of softening oils, 0～20 part of filler, 0.1～5 part of whipping agent, 0～2 part of foam nucleator, 0～5 part in oxidation inhibitor, 0～2 part of releasing agent.
The styrene-butadiene block copolymer that the present invention adopts is styrene-butadiene-styrene triblock copolymer (SBS), the SBS that the preferred molten index is higher is as the product of the high mountain YH-788 (being produced by Yueyang general petrochemicals factory) or strange U.S. 5302 trades mark such as (being produced by Taiwan Qi Mei company).
The acrylic copolymer that the present invention adopts can be ethylene-acrylic acid copolymer (EAA) or ethylene-methacrylic acid copolymer (EMA), perhaps its composition.
The preferred sulfohydrazide type blowing agent of whipping agent that the present invention adopts, or inorganic foaming agent, perhaps its composition.Sulfohydrazide type blowing agent can be selected OBSH for use, and inorganic foaming agent can be selected sodium bicarbonate for use, perhaps its modifier, and as DNA (produced by Zhejiang marine rainbow stock company, major ingredient is a sodium bicarbonate) etc., perhaps its composition.
The filler that the present invention adopts can be selected lime carbonate for use, kaolin, at least a in the inorganic materials such as wollastonite or silicon-dioxide.Said softening oil can adopt naphthenic oil.Said releasing agent can adopt Zinic stearas, calcium stearate or Magnesium Stearate etc.
But said foam nucleator optimization citric acid sodium.
Said oxidation inhibitor is antioxidant 264 preferably.
The present invention can also add this area other processing aids commonly used, as photostabilizer, pigment etc.
The step of the said thermoplastic elastomer foaming material preparation method of the present invention is:
1, except that whipping agent, according to said ratio scale material, the employing mixing machine carries out blend, granulation after being pre-mixed evenly;
2, whipping agent is mixed with above-mentioned pellet, injection moulding under 150～170 ℃ of conditions, extrude, mold pressing or calendering, the preparation foam material.
Because its flowing property of styrene-butadiene block copolymer that adopts is better, very favourable to forming process and quick mold filling, the density of the foam material of preparation is relatively low.Acrylic copolymer contains a large amount of carboxyls (COOH) active group, improved the polarity of foam material, if employing urethane etc. has the tackiness agent with carboxyl generation chemical reaction, will between two-phase, produce chemical bonding in the applying process, significantly improve its adhesive property.In addition, acrylic copolymer has higher melt viscosity, can suppress gas to a certain extent and overflow, and is favourable to stable foam.
The whipping agent that adopts is that decomposition temperature is lower, color is white in color, decompose residues influences very little low-temp foaming agent to color, this class whipping agent belongs to chemical foaming agent, is to decomposite gas under 150～170 ℃ of conditions and be evenly distributed in the polymer melt in temperature.
The present invention can adopt mill, Banbury mixer, forcing machine etc. to carry out blend, granulation.Adopt injection moulding, extrude, method processing such as mold pressing, calendering, its Application Areas relates to sole, tubing and sheet material etc.
(4) embodiment
Embodiment 1:
Forming (mass ratio) is: 23 parts of 100 parts of SBS, PS, 10 parts of EAA, 23 parts of naphthenic oils, 2.5 parts of OBSH, 0.5 part of foam nucleator, 0.3 part of Zinic stearas.
According to said ratio scale material, the employing mixing machine carries out blend, granulation after being pre-mixed evenly in Banbury mixer, adopts injection moulding machine to penetrate sole then under 160 ℃ of conditions, and recording sole density is 0.65g/cm
3Polyurethane adhesive is evenly coated on sole and corium surface, stops 6 minutes in 60 ℃ thermostat container, and sole and corium are fitted, pressurizeed, and naturally cooling was measured stripping strength after 24 hours, and the result is 70N/cm.
Embodiment 2:
Forming (mass ratio) is: 25 parts of 100 parts of SBS, PS, 10 parts of EMA, 25 parts of naphthenic oils, 2 parts of DNA, 0.5 part of foam nucleator, 0.3 part of Zinic stearas, 0.5 part of antioxidant 264.
According to said ratio scale material, the employing mixing machine carries out blend, granulation after being pre-mixed evenly in screw extrusion press, adopts injection moulding machine to penetrate sheet material then under 150 ℃ of conditions.Similar to Example 1 with the attaching process of corium, wherein, the temperature of thermostat container is 70 ℃, and the residence time is 7 minutes.The density that records product is 0.66g/cm
3, stripping strength is 63N/cm.
Embodiment 3～6:
The component of desired raw material and content and comparative example see Table 1, and its manufacturing process and embodiment 1,2 are similar.
Table 1
| Material | Example 3 | Example 4 | Example 5 | Example 6 | Comparative example 1 | Comparative example 2 |
| ?SBS | ?100 | ?100 | ?100 | ?100 | ????65 | ????150 |
| ?PS | ?5 | ?30 | ?10 | ?40 | ????15 | ????10 |
| ?EAA | ?5 | ?15 | ||||
| ?EMA | ?10 | ?20 | ||||
| ?EVA | ????5 | |||||
| Naphthenic oil | ?5 | ?25 | ?15 | ?40 | ????15 | ????15 |
| ?OBSH | ?1.5 | ?3 |
| DNA | ?1.5 | ?4 | ||||
| AC | ????1.2 | ????1.2 | ||||
| The foam nucleator | 0.5 | ?1.0 | ?0.5 | ?1.0 | ||
| Lime carbonate | 10 | ?20 | ?0 | ?15 | ????5 | |
| Zinc Stearate | 0 | ?0.3 | ?1.0 | ?2.0 | ????0.8 | ????0.5 |
| Zinc oxide | ????1.2 | ????1.0 | ||||
| Oxidation inhibitor | 0.5 | ?0 | ?0.5 | ?0.5 | ????0.5 | ????0.5 |
| Density (g/cm 3) | 0.81 | ?0.68 | ?0.63 | ?0.60 | ????0.78 | ????0.69 |
| Stripping strength (N/cm) | 55 | ?75 | ?67 | ?82 | ????22 | ????18 |
From The above results as can be known, under not surface treated situation, the cohesive force of comparative example 1,2 and corium is lower, the foam material of the present invention's preparation and the cohesive force of corium are able to obvious raising, reason is to contain among EAA and the EMA carboxyl (COOH) active group, in the applying process can with polyurethane adhesive generation chemical reaction, two-phase interface combines with chemical bond, improves the cohesive force of itself and corium greatly.When the applying vamp, can save surface treatment step with the foamed shoe sole of novel material preparation, simplify production technique, enhance productivity, reduce production costs.
With embodiment 1 and comparative example 1 injection moulding sole under different temperature, test-results sees Table 2.
Table 2
| Temperature (℃) | ?????????165 | ??????????175 | ??????????190 | |||
| Sample | Embodiment 1 | Comparative example 1 | Embodiment 1 | Comparative example 1 | Embodiment 1 | Comparative example 1 |
| Density (g/cm 3) | ????0.76 | ????0.92 | ????0.65 | ????0.83 | ????0.63 | ????0.78 |
| Color | White | Yellow | White | Slightly yellow | White | White |
As known from Table 2, little, the colour stable of the sole density variation for preparing in the time of 165～190 ℃ of the present invention, production control are convenient.And comparative example 1, when temperature during at 165-175 ℃ whipping agent decompose not exclusively, the density of sole is big, color is wayward.
Embodiment 7
Forming (mass ratio) is: 25 parts of 100 parts of SBS, PS, 10 parts of EAA, 20 parts of naphthenic oils, 5.0 parts of sodium bicarbonates, 0.5 part of foam nucleator, 8 parts of kaolin, 0.3 part of Zinic stearas.Its preparation technology is identical with embodiment 1.
Embodiment 8
Forming (mass ratio) is: 35 parts of 100 parts of SBS, PS, 15 parts of EAA, 30 parts of naphthenic oils, 2.0 parts of sodium bicarbonates, 0.5 part of foam nucleator, 0 part of silica 1,0.3 part of Zinic stearas.Its preparation technology is identical with embodiment 2.
Claims (10)
1, thermoplastic elastomer foaming material is characterized in that its composition (mass ratio) is: 5～40 parts of 100 parts of SBS, PS, 5～40 parts of acrylic copolymer, 5～40 parts of softening oils, 0～20 part of filler, 0.1～5 part of whipping agent, 0～2 part of foam nucleator, 0～5 part in oxidation inhibitor, 0～2 part of releasing agent.
2, thermoplastic elastomer foaming material as claimed in claim 1 is characterized in that preferred high mountain YH-788 of the SB that adopts or strange U.S. 5302 products.
3, thermoplastic elastomer foaming material as claimed in claim 1 is characterized in that acrylic copolymer optimal ethylene-acrylic copolymer (EAA) or ethylene-methacrylic acid copolymer (EMA), perhaps its composition of adopting.
4, thermoplastic elastomer foaming material as claimed in claim 1 is characterized in that the whipping agent that adopts is selected from sulfohydrazide type blowing agent, or inorganic foaming agent, perhaps its composition.
5, thermoplastic elastomer foaming material as claimed in claim 4 is characterized in that the preferred OBSH of the sulfohydrazide type blowing agent that adopts, and inorganic foaming agent is selected sodium bicarbonate or its modifier for use.
6, thermoplastic elastomer foaming material as claimed in claim 1 is characterized in that the filler that adopts is selected from lime carbonate, kaolin, at least a in wollastonite or the silicon-dioxide.
7, thermoplastic elastomer foaming material as claimed in claim 1 is characterized in that said softening oil adopts naphthenic oil.
8, thermoplastic elastomer foaming material as claimed in claim 1 is characterized in that said releasing agent adopts Zinic stearas, calcium stearate or Magnesium Stearate.
9, thermoplastic elastomer foaming material as claimed in claim 1 is characterized in that said foam nucleator optimization citric acid sodium; The preferred antioxidant 264 of said oxidation inhibitor.
10, thermoplastic elastomer foaming material preparation method is characterized in that the steps include:
1), except that whipping agent, according to proportioning scale material, adopt mixing machine to be pre-mixed evenly after, carry out blend, granulation;
2), whipping agent is mixed with above-mentioned pellet, injection moulding under 150～170 ℃ of conditions, extrude, mold pressing or calendering, the preparation foam material:
3), said proportioning is 5～40 parts of 100 parts of SBS, PS, 5～40 parts of acrylic copolymer, 5～40 parts of softening oils, 0～20 part of filler, 0.1～5 part of whipping agent, 0～2 part of foam nucleator, 0～5 part in oxidation inhibitor, 0～2 part of releasing agent.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100425677C (en) * | 2006-08-31 | 2008-10-15 | 无锡惠源高级润滑油有限公司 | Processing method of softening oil (paraffin base) |
| CN100430202C (en) * | 2004-12-15 | 2008-11-05 | 微细科技股份有限公司 | Normal pressure continuous foaming production method for heat-plastic elastomer composite material |
| JP2010254860A (en) * | 2009-04-27 | 2010-11-11 | Bridgestone Corp | Rubber composition, vulcanized rubber, and tire |
| CN101245170B (en) * | 2007-02-14 | 2012-03-21 | 宏玮协志(中国)有限公司 | Thermoplastic elastic body shoe material and production method |
| TWI385069B (en) * | 2009-11-06 | 2013-02-11 | ||
| CN103079788A (en) * | 2010-08-06 | 2013-05-01 | 综研化学株式会社 | Resin mold, production method thereof, and use thereof |
| CN104926351A (en) * | 2015-06-04 | 2015-09-23 | 合肥和安机械制造有限公司 | Compound modified nano wollastonite-carbonized foam phenolic resin based thermal insulation material for forklift engine exhaust pipe, and preparation method of thermal insulation material |
| CN102051003B (en) * | 2009-11-05 | 2016-03-02 | 晋江成昌鞋业有限公司 | Shock-absorbing rubber-plastic composite material |
| CN105670198A (en) * | 2016-01-21 | 2016-06-15 | 苏州市景荣科技有限公司 | Waterproof SBS foaming sole material and preparation method thereof |
| CN109370146A (en) * | 2018-11-23 | 2019-02-22 | 常州大学 | A kind of ABS foamed material of blending and modifying and preparation method thereof |
| TWI659833B (en) * | 2015-04-01 | 2019-05-21 | 李永騰 | Multi-layered thermoplastic elastomer foam and process for manufacturing the same |
| CN109912877A (en) * | 2019-03-08 | 2019-06-21 | 安踏（中国）有限公司 | A kind of anti-aging EVA foamed material of high temperature resistant and its preparation method and application |
| CN110204790A (en) * | 2019-07-04 | 2019-09-06 | 福建省卓睿新材料科技有限公司 | A kind of composite assistant being readily transported with storage |
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- 2003-11-20 CN CN 200310116750 patent/CN1244632C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100430202C (en) * | 2004-12-15 | 2008-11-05 | 微细科技股份有限公司 | Normal pressure continuous foaming production method for heat-plastic elastomer composite material |
| CN100425677C (en) * | 2006-08-31 | 2008-10-15 | 无锡惠源高级润滑油有限公司 | Processing method of softening oil (paraffin base) |
| CN101245170B (en) * | 2007-02-14 | 2012-03-21 | 宏玮协志(中国)有限公司 | Thermoplastic elastic body shoe material and production method |
| JP2010254860A (en) * | 2009-04-27 | 2010-11-11 | Bridgestone Corp | Rubber composition, vulcanized rubber, and tire |
| CN102051003B (en) * | 2009-11-05 | 2016-03-02 | 晋江成昌鞋业有限公司 | Shock-absorbing rubber-plastic composite material |
| TWI385069B (en) * | 2009-11-06 | 2013-02-11 | ||
| CN103079788B (en) * | 2010-08-06 | 2015-06-10 | 综研化学株式会社 | Resin mold, production method thereof, and use thereof |
| CN103079788A (en) * | 2010-08-06 | 2013-05-01 | 综研化学株式会社 | Resin mold, production method thereof, and use thereof |
| US9511535B2 (en) | 2010-08-06 | 2016-12-06 | Soken Chemical & Engineering Co., Ltd. | Resin mold, production method thereof, and use thereof |
| TWI659833B (en) * | 2015-04-01 | 2019-05-21 | 李永騰 | Multi-layered thermoplastic elastomer foam and process for manufacturing the same |
| CN104926351A (en) * | 2015-06-04 | 2015-09-23 | 合肥和安机械制造有限公司 | Compound modified nano wollastonite-carbonized foam phenolic resin based thermal insulation material for forklift engine exhaust pipe, and preparation method of thermal insulation material |
| CN105670198A (en) * | 2016-01-21 | 2016-06-15 | 苏州市景荣科技有限公司 | Waterproof SBS foaming sole material and preparation method thereof |
| CN105670198B (en) * | 2016-01-21 | 2019-01-11 | 苏州市景荣科技有限公司 | A kind of water-resistant type SBS foaming sole material and preparation method thereof |
| CN109370146A (en) * | 2018-11-23 | 2019-02-22 | 常州大学 | A kind of ABS foamed material of blending and modifying and preparation method thereof |
| CN109912877A (en) * | 2019-03-08 | 2019-06-21 | 安踏（中国）有限公司 | A kind of anti-aging EVA foamed material of high temperature resistant and its preparation method and application |
| CN110204790A (en) * | 2019-07-04 | 2019-09-06 | 福建省卓睿新材料科技有限公司 | A kind of composite assistant being readily transported with storage |
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