CN101845196B - Thermoplastic elastomer for ABS jetting adhesion - Google Patents

Thermoplastic elastomer for ABS jetting adhesion Download PDF

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Publication number
CN101845196B
CN101845196B CN201010166524XA CN201010166524A CN101845196B CN 101845196 B CN101845196 B CN 101845196B CN 201010166524X A CN201010166524X A CN 201010166524XA CN 201010166524 A CN201010166524 A CN 201010166524A CN 101845196 B CN101845196 B CN 101845196B
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Prior art keywords
thermoplastic elastomer
abs
styrene
percent
oil
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CN101845196A (en
Inventor
廖时勇
黄志杰
安孝善
郑京连
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Cgn Juner New Materials Co ltd
SHANGHAI JUNER NEW MATERIALS CO Ltd
Zhejiang Juner New Materials Co ltd
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Shanghai Jun'er New Material Co Ltd
JUNER NEW MATERIALS CO Ltd ZHEJIANG
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders

Abstract

The invention discloses a thermoplastic elastomer for ABS jetting adhesion, which comprises the following raw materials in percentage by weight: 10 to 80 percent of thermoplastic matrix resin, 0 to 60 percent of filling oil, 0 to 30 percent of adhesives, 0 to 30 percent of mineral filler, 0 to 10 percent of polar compatibilizer, 0.1 to 2 percent of processing aid and 0.08 to 2 percent of stabilizer. The problem of bonding non-polar base material and ABS is solved by improving a blending formulation and process. The hardness of the jetting adhesion ABS thermoplastic elastomer can be freely adjusted through the formulation so as to obtain the thermoplastic elastomer with high elasticity, high bonding strength to ABS material and good surface effect.

Description

A kind of being used for penetrated sticking thermoplastic elastomer with ABS
Technical field.
The present invention relates to polymeric material field, particularly a kind of being used for penetrated sticking thermoplastic elastomer with ABS.
Background technology
ABS (being acrylonitrile-butadiene-styrene copolymer) resin has shock-resistant, high rigidity, oil resistant, low temperature resistant, excellent properties such as dimensional stability good, molding shrinkage is little, is a kind of purposes thermoplastics extremely widely.But the product that adopts ABS resin to process; Its surface is often harder and smooth; In some product application, lack texture and feel; Therefore, often coat one deck flexible glue with intensifier booster texture and feel on ABS finished product top layer, usually industry is employed in ABS finished product surface and penetrates the mode of sticking one deck thermoplastic elastomer and realize.It is on the various injecting products of base material that the thermoplastic elastomer of penetrating sticking ABS is widely used in ABS; Make ABS finished product such as shaver shell, instrument material handle etc. have good texture and feel; Increase user's comfortableness, make product that better outer light arranged, improve the class of product.
Common and ABS penetrates the hardness of sticking thermoplastic elastomer generally between 50 degree-65 degree; And elongation at break is about 400; Elasticity is not high, often can not satisfy the needs that some needs snappiness, soft thermoplastic elastomer are used for penetrating with ABS sticking special occasions, therefore needs a kind of adjustable durometer level of exploitation wide; Adhesive effect is good, and be used for and the ABS that elasticity is high penetrates sticking thermoplastic elastomer (promptly penetrating sticking ABS material).
Summary of the invention
The present invention is directed to and existing penetrate the not high defective of elasticity that sticking thermoplastic elastomer exists with ABS, provide a kind of adjustable durometer level wide, penetrate sticking with ABS low temperature and cementability good, elastomeric being used for penetrated sticking thermoplastic elastomer with ABS.
A kind of being used for penetrated sticking thermoplastic elastomer with ABS, comprises following raw materials by weight percent:
The thermoplastic matrix resin 10%~80%
Extending oil 0~60%
Caking agent 0~30%
Mineral filler 0~30%
Polarity compatible agent 0~10%
Processing aid 0.1%~2%
Stablizer 0.08%~2%.
Described being used for penetrated sticking thermoplastic elastomer with ABS, preferably includes following raw materials by weight percent:
The thermoplastic matrix resin 15%~45%
Extending oil 15%~50%
Caking agent 0~30%
Mineral filler 0~30%
Polarity compatible agent 0~10%
Processing aid 0.1%~0.5%
Stablizer 0.08%~0.5%.
Described being used for penetrated sticking thermoplastic elastomer with ABS, further preferably includes following raw materials by weight percent:
The thermoplastic matrix resin 18%~40%
Extending oil 18%~50%
Caking agent 7%~30%
Mineral filler 0~30%
Polarity compatible agent 3%~10%
Processing aid 0.1%~0.5%
Stablizer 0.08%~0.5%.
As preferably:
Described thermoplastic matrix resin is selected from styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymers (SEBS), SIS (SIS), styrene-ethylene-propylene-styrene segmented copolymer (SEPS) or any two kinds mixture.For example; Can the section of selecting for use rise (KRATON): D-1102, D-1153, SIS-1160; Korea S LG chemistry: SBS LG-501, LG-502; Platform rubber (TAIPOL): SBS 4202, SEBS-6151 Ba Ling petrochemical industry: SBS YH-788, YH-792, YH-791, SIS-1105, SIS-1188, Taiwan English be chemistry entirely: one or more in the commercially available prod of SBS 685 trades mark such as grade.
Described extending oil be selected from flash-point greater than 200 ℃ saturated straight chain alkane oil, flash-point greater than in 200 ℃ the naphthenic oil one or both.For example, can select U.S.'s sun-stone (SUNPAR) for use: 150, the two dragons of Korea S: 150SN, Japanese bright dipping (Idemitsu): PW-90, one or more in the commercially available prod of the trades mark such as oily Kelamayi: KN4020, KN4010,32# white oil.
Described polarity compatible agent is selected from hydrogenated styrene-butadiene-styrene block copolymers-maleic anhydride grafts (SEBS-g-MAH); Terpolymer EP rubber-maleic anhydride grafts (EPDM-g-MAH); Polystyrene-maleic anhydride grafted thing (PS-g-MAH); Polyethylene oxide-maleic anhydride grafts (POE-g-MAH); Acrylic acid esters co-polymer; Terpolymer EP rubber (EPDM); Vinyl-vinyl acetate copolymer (EVA); At least a in the polyethylene oxide polymkeric substance such as (POE).For example; Optional liter with Shanghai day: 9801, company is risen by U.S. section: FG1901 (SEBS-g-MAH), E.I.Du Pont Company: EMA1125,1330; EEA2112; POE 8150, French Atofina: EVA 28-25 multipolymer, the liter of Shanghai day: at least a in the commercially available prod of the trades mark such as cmg9802.
Described caking agent is selected from least a in the polymkeric substance such as polyisobutene (PIB) (like BASF B10N, B150), PS-vinyl cyanide (SAN) (like BASF 358N, Japanese Asahi Chemical Industry 767), vinylbenzene-TEB 3K (SMMA) (like U.S. Nu Fake NAS30, the new MS-200 of anti-iron of Japan) or other styrene copolymers.
Described mineral filler is selected from least a in lime carbonate, talcum powder, terra alba, asbestos powder, potter's clay, permanent white, mica powder, kaolin, the white carbon black.Do not have particular requirement, the product that many companies such as domestic production producer such as Guilin Tian Cheng, Jiangsu Rieter, the inferior Thailand in Dalian produce all can.
Described processing aid is selected from least a in lipid acid, soap, fatty acid amide, the silicone material.For example, can select at least a in (Ciba Company products) such as hard ester acid, calcium stearate, Zinc Stearate, erucicamides for use, as to converge the erucicamide trade mark of general chemistry be 1753.
Described stablizer is selected from and contains in UVNUL MS-40 functional compounds stablizer (being the benzophenone stablizer), Hinered phenols stablizer, phosphorous acid esters stablizer, the hindered amines stablizer one or more.For example, can select at least a in UV-531,1010,168,1076, (Ciba Company products) trade mark commercially available prod such as 1024 for use.
The present invention also provides a kind of being used for to penetrate sticking process for preparation of thermoplastic elastomer with ABS, has advantage simple to operate, as to be suitable for suitability for industrialized production.
Described being used for penetrated sticking process for preparation of thermoplastic elastomer with ABS, comprises step:
Thermoplastic matrix resin and extending oil thorough mixing is even; Oil to be filled is blotted the back fully by resin and adds caking agent, mineral filler, polarity compatible agent, processing aid and stablizer; Send into extruding pelletization in the twin screw extruder after mixing, make and be used for penetrating sticking thermoplastic elastomer with ABS.
Each section extruder temperature is controlled at 150 ℃~250 ℃ in the described twin screw extruder.
Described thermoplastic elastomer can be used as with ABS penetrates sticking elastomerics, mainly is to be coated on starting material ABS to go up to be used to prepare power tool shell related prodss such as (like the shaver shells)
Beneficial effect of the present invention is embodied in:
The present invention is used for penetrating sticking thermoplastic elastomer with ABS, is to be base material with the styrene copolymer, cooperates process Couble screw rod high-temp high shear mixing such as polarity compatible agent, sticker, extending oil, mineral filler, processing aid and stablizer to form.The adjustable durometer level of this thermoplastic elastomer is wide, low processing temperature and processing temperature are wide; Snappiness, high workability, from 150 spend to 190 the degree any injection temperature under all can produce excellent adhesion performance with ABS; And surperficial texture and feel are good, can satisfy different clients' demand
Embodiment
Embodiment 1-8
1. proportioning raw materials:
Figure GSA00000113997500041
Figure GSA00000113997500051
In the above-mentioned raw materials, styrene resin: 6151 (the platform rubber, SEBS), 791 and 792 (the Ba Ling petrochemical industry, SBS), 685 (Taiwan English is complete, SBS);
Extending oil: 32# white oil (Kelamayi, Xinjiang, white oil (be flash-point greater than 200 ℃ saturated straight chain alkane oil)), 4010 (Kelamayi, Xinjiang, flash-point is greater than 200 ℃ NO), 150SN (the two dragons of Korea S, flash-point is greater than 200 ℃ saturated straight chain alkane oil);
Caking agent: B10N (BASF, polyisobutene), 358N (BASF, PS-vinyl cyanide), MS-200 (U.S. Nu Fake, styrene-methylmethacrylate copolymer);
Compatilizer: fg1901 (section rises, SEBS-g-MAH), cmg9802 (liter of Shanghai day, EPDM-g-MAH);
Processing aid: 1753 (converge general, erucicamide);
Stablizer: 1076 (vapour crust, hindered phenol antioxygens);
Mineral filler: CaCO 3(Jiangsu Rieter, 1250 orders).
2. injection moulding processing
Take by weighing raw material by above-mentioned each proportioning respectively; Styrene resin and extending oil thorough mixing is even, and oil to be filled is blotted the back fully by resin and adds caking agent, mineral filler, polarity compatible agent, processing aid and stablizer, sends in the twin screw extruder after mixing; The processing temperature of setting twin screw extruder is 200 ℃; Through twin screw high speed shear (400r/min), mixing 15 seconds, extrude by head, through tie rod, air-cooled, pelletizing and drying; Make and be used for penetrating sticking thermoplastic elastomer, be packaged to be finished product with ABS.
3. performance test
Thermoplastic elastomer to making by above-mentioned each prescription carries out performance test, result such as following table:
Test event Testing method Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8
Shore hardness ASTM D-2240 58 40 60 70 65 50 80 55
With the ABS bonding effect 160 degree re-pack, and hand tears Better Better The jail Fine Fine The jail Better Generally
Proportion (g/cm3) ASTM D-792 1.15 0.93 1.08 1.1 1.05 1.07 1.04 0.96
Melting index ASTM D-1238 7 14 9 6 7.5 10 5 11
Tensile strength, MPa ASTM D-412 4.8 3 4.5 6 5 4 10 3.7
Elongation at break, % ASTM D-412 650 800 700 560 600 750 320 770
Remarks: the test condition of melting index is: temperature 190 degree, pressure 2.16KG.
The above embodiment has only expressed several kinds of embodiments of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art under the prerequisite that does not break away from the present invention's design, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with accompanying claims.

Claims (6)

1. one kind is used for penetrating sticking thermoplastic elastomer with ABS, comprises following raw materials by weight percent:
Figure FSB00000603036800011
Described thermoplastic matrix resin is selected from a kind of or any two kinds mixture in styrene-butadiene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymers, SIS, the styrene-ethylene-propylene-styrene segmented copolymer;
Described extending oil be selected from flash-point greater than 200 ℃ saturated straight chain alkane oil, flash-point greater than in 200 ℃ the naphthenic oil one or both;
Described polarity compatible agent is selected from least a in hydrogenated styrene-butadiene-styrene block copolymers-maleic anhydride grafts, terpolymer EP rubber-maleic anhydride grafts, polystyrene-maleic anhydride grafted thing, polyethylene oxide-maleic anhydride grafts, Yodo Sol GH 28, terpolymer EP rubber, vinyl-vinyl acetate copolymer, the polyethylene oxide;
Described caking agent is selected from least a in polyisobutene, PS-vinyl cyanide, vinylbenzene-TEB 3K or other styrene copolymers.
2. thermoplastic elastomer as claimed in claim 1 is characterized in that: described mineral filler is selected from least a in lime carbonate, talcum powder, terra alba, asbestos powder, potter's clay, permanent white, mica powder, kaolin, the white carbon black.
3. thermoplastic elastomer as claimed in claim 1 is characterized in that: described processing aid is selected from least a in lipid acid, soap, fatty acid amide, the silicone.
4. thermoplastic elastomer as claimed in claim 1 is characterized in that: described stablizer is selected from and contains in UVNUL MS-40 functional compounds stablizer, hindered phenol stabilizer, phosphite ester stabilizer, the hindered amine stabilizer one or more.
5. like each described process for preparation of thermoplastic elastomer of claim 1~4, comprise step:
Thermoplastic matrix resin and extending oil thorough mixing is even; Oil to be filled is blotted the back fully by resin and adds caking agent, mineral filler, polarity compatible agent, processing aid and stablizer; Send into extruding pelletization in the twin screw extruder after mixing, make and be used for penetrating sticking thermoplastic elastomer with ABS.
6. preparation method as claimed in claim 5 is characterized in that: each section extruder temperature is 150 ℃~250 ℃ in the described twin screw extruder.
CN201010166524XA 2010-05-07 2010-05-07 Thermoplastic elastomer for ABS jetting adhesion Expired - Fee Related CN101845196B (en)

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CN102295817A (en) * 2010-06-23 2011-12-28 苏州市苏晨化工塑料有限公司 Mixture of thermoplastic elastomer for secondary overmolding coating with polypropylene material and preparation method thereof
CN102304267A (en) * 2011-07-25 2012-01-04 宁波市青湖弹性体科技有限公司 Thermoplastic elastomer shot sticky with ABS (acrylonitrile butadiene styrene)
CN102344603B (en) * 2011-10-24 2013-07-10 浙江俊尔新材料有限公司 Rubber and plastic sealing material in stable size at high and low temperatures and preparation method thereof
CN103172962A (en) * 2011-12-22 2013-06-26 中纺投资发展股份有限公司 Thermoplastic elastomer composition for injection molding and injection adhering
CN103897325A (en) * 2012-12-27 2014-07-02 中纺投资发展股份有限公司 Thermoplastic elastomer used for injection overmolding of POM (polyformaldehyde) and POM-modified hard plastics and its preparation method
CN103122119A (en) * 2013-02-05 2013-05-29 保定宝轶塑料有限公司 ABS (Acrylonitrile-Butadiene-Styrene) highlight packing master batch and preparation method thereof
CN107383851A (en) * 2017-08-29 2017-11-24 江阴市洸洋塑业有限公司 A kind of elastomer ABS claddings material and preparation method thereof
CN110669307A (en) * 2018-07-02 2020-01-10 苏州长振新材料科技有限公司 Thermoplastic elastomer for encapsulating PC/ABS and preparation method thereof
CN109796731B (en) * 2019-01-28 2021-04-13 盛嘉伦橡塑(深圳)股份有限公司 Thermoplastic elastomer material and preparation method thereof

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CN1765984A (en) * 2004-10-29 2006-05-03 上海日之升新技术发展有限公司 Thermoplastic elastomer material and its preparation method
CN101245183B (en) * 2008-03-21 2011-06-22 深圳市盛嘉伦橡塑工业有限公司 Thermoplastic elastic body for jetting and adhibiting with ABS at low-temperature

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