CN100463942C - Thermoplastic elastomer for injection adhering nylon material - Google Patents
Thermoplastic elastomer for injection adhering nylon material Download PDFInfo
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- CN100463942C CN100463942C CNB2006100533393A CN200610053339A CN100463942C CN 100463942 C CN100463942 C CN 100463942C CN B2006100533393 A CNB2006100533393 A CN B2006100533393A CN 200610053339 A CN200610053339 A CN 200610053339A CN 100463942 C CN100463942 C CN 100463942C
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- thermoplastic elastomer
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- nylon
- tackifier
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Abstract
The thermoplastic elastomer for injection adhering nylon material used in electric tool handle, box handhold, etc. consists of matrix resin 10-60 wt%, filler oil 5-60 wt%, tackifier 5-50 wt%, mineral filler 0-25 wt%, coupling agent 0.1-0.8 wt%, machining assistant 0.1-2 wt%, and composite stabilizer 0.1-2 wt%. The thermoplastic elastomer has firm adhesion to nylon, excellent forming performance, capacity of raising the comfortability of the product and excellent stainability to beautify the product.
Description
Technical field
The present invention relates to polymeric material field, particularly a kind of and nylon material material secondary injection adhering thermoplastic elastomer, this material are mainly used in power tool handle, case and bag handle etc. needs thermoplastic elastomer to be coated with anti-skidding, raising comfort.
Background technology
Along with plastics quilt application and various household implements, toy and office appliance more and more widely.As handle, shaver, door handle of refrigerator, dishwasher, comb, the pen cap, screwdriver lever and power tool handle etc.Though these articles for daily use have various uses, all articles for use all need to guarantee firm hold and can not slip out from user's hand.For example: tablewares such as cutter that uses in the western-style food and fork, as hold the words that are not easy to hold and be easy to human body is damaged.
The equal rigid plastics of the daily necessities handle of the overwhelming majority is formed, and is therefore most important to the solution of the anti-skidding problem of handle.Particularly the apparatus of Chang Yushui such as toothbrush, shaver contact often is easy to skid off from user's hand after being got wet by water.Also can bring inconvenience to the user or reduce the comfortableness of use for other articles for daily use because of slick rigid plastic surface.
Present thermoplastic elastomer is widely used in the coating with some plastic parts such as polypropylene, polystyrene, polyethylene, polycarbonate, ABS.
Thermoplastic elastomer (Thermoplastic Elastomer-TPE) also claims that thermoplastic elastomer (Thermoplastic Rubber-TPR) is a kind of material that has rubber and thermoplastics characteristic concurrently, thermoplastic elastomer has multiple possible structure, the most basic one is to need at least two mutual dispersive polymer phases, under normal use temperature, one is fluid (making temperature be higher than its Tg-second-order transition temperature) mutually, another is solid (make temperature be lower than its Tg or equal Tg) mutually, and exists between the two-phase and interact.Promptly show caoutchouc elasticity at normal temperatures, macromolecular material that again can plasticizing forming under the high temperature has the mechanical property and the use properties that are similar to rubber, can process and reclaim by thermoplastics again, and it has erected a bridge block between plastics and rubber.Therefore, thermoplastic elastomer can resemble the thermoplastics fast and effectively, economic machine-shaping.With regard to processing, it is a kind of plastics; With regard to character, it is again a kind of rubber.Thermoplastic elastomer has many characteristics that are better than thermoset rubber.Domestic thermoplastic styrene-butadiene block copolymer then is referred to as SBS, thermoplasticity isoprene-styrene block copolymer is called SIS, hydrogenation saturation type SBS then is referred to as SEBS, be the abbreviation of Styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-butylene-styrene segmented copolymer just.Hydrogenation saturation type SIS then is referred to as SEPS.
Also there are some problems in TPE material and nylon material, particularly the secondary injection adhering coating with glass enhanced nylon material at present, at first are that the bond properties of thermoplastic elastomer and nylon material is bad.The TPE material that coats is easily from the nylon material sur-face peeling or come off.Moulding difficulty, goods were difficult for the demoulding when next was TPE and nylon material secondary injection molding.External is that head it off has been released with polar polymer as AES company, as: materials such as vinylformic acid, acrylate are that base material adopts dynamic vulcanization technology to produce the TPV associated materials.But this type of material cost height, production unit and complex process, domestic enterprise is difficult to produce at present.
Summary of the invention
The invention provides that a kind of the cost of material is low, the thermoplastic elastomer of using with nylon material secondary injection adhering that bond properties is good.
A kind of thermoplastic elastomer of using with nylon material secondary injection adhering, its raw material weight per-cent consists of:
Matrix resin 10%～60%
Extending oil 5%～60%
Tackifier 5%～50%
Mineral filler 0%～25%
Coupling agent 0.1%～0.8%
Processing aid 0.1%～2%
One package stabilizer 0.1%～2%
Described matrix resin is that described matrix resin is at least a in hydrogenation saturation type thermoplastic styrene-butadiene block copolymer (SEBS), the hydrogenation saturation type thermoplasticity isoprene-styrene block copolymer (SEPS).
Concrete as: the G-1651 of company (Kraton), G-1650 rise in U.S. section; The SEBS of Taiwan platform rubber company (Taipol) 3150,3151,3154; Ba Ling petrochemical industry Yueyang chemical general factory SEBS YH-503 etc.
Described extending oil is for having 200 ℃ of higher flash point (〉) saturated straight chain alkane oil, naphthenic oil at least a.Concrete as: Ni Nasi oil (NYNAS): Nplast220; U.S.'s Sunoco (SUNPAR): 150; The two dragons of Korea S: 150SN; Japan bright dipping (Idemitsu): PW-90; Kelamayi, Xinjiang refinery: KN4010, KN4020 etc.
Described tackifier are at least a in nylon-type polymkeric substance, the polar resin.
Described nylon-type polymkeric substance is at least a in nylon 6, nylon 66, Ni Long11, nylon 12, NYLON610, nylon 612, nylon 1010, nylon 46, nylon 7, nylon 9, the nylon 13, concrete as: PA6, the B3S of DSM N. V.; Yueyang petrochemical industry polyamide fibre section PA66; Dupont PA66 etc.
Described polar resin is the maleic anhydride class, acrylic acid esters co-polymer is as polypropylene-maleic anhydride grafts (PP-g-MAH), polyvinyl-maleic anhydride grafts (PE-g-MAH), terpolymer EP rubber-maleic anhydride grafts (EPDM-g-MAH), hydrogenation thermoplastic styrene butadiene rubber-maleic anhydride grafts (SEBS-g-MAH), polyacrylic ester, polyacrylic acid Racemic glycidol resin copolymer, styrene-maleic anhydride copolymer, the styrene-propene acid copolymer, copolymer in cinnamic acrylic ester, at least a in polyethylene-vinylformic acid-copolymer-maleic anhydride.The liter that Shanghai day is specifically arranged: 9801; Company is risen by U.S. section: SEBS-g-MAH; France Atofina: 1125AC, 4210,5500,9MA02 etc.
When adopting the nylon-type polymkeric substance to be tackifier, be again to carry out bondingly owing to contain the nylon-type polymkeric substance in the elastomerics with nylon, the two character is close, and effect is more outstanding.
Described coupling agent, as the compatilizer of matrix resin and inorganic mineral filler, at least a in titanate coupling agent, the silane coupling agent.Concrete as: the NDZ-101 of NanJing Shuguang Chemical Group Co., Ltd., NDZ-201, KH-550, KH-570; The KR-TTS of U.S. Kenrich petroleum chemistry company, KR-238 etc.
Described processing aid, at least a in fatty acid, fatty acid amide, the silicone material.As (Ciba companies) such as hard fat acid calcium, hard fat acid zinc, erucicamide, polydimethyl silicone.
Described one package stabilizer is at least a in benzophenone, phosphorous acid esters, Hinered phenols, the hindered amines.As: the UV-531 of Ciba company, Irganox1010, Irganox168, Irganox1076; The antioxygen that Li Anlong (Tianjin) Industrial Co., Ltd. produces, anti copper agent MD-1024 etc.
Described mineral filler is at least a in talcum powder, lime carbonate, barium sulfate, mica powder, the kaolin, and used filler does not have particular requirement, domesticly all can as many companies products such as Guilin Tian Cheng, Jiangsu Rieter, the inferior Thailands in Dalian.
Add man-hour, earlier SEBS is blotted components such as back adding tackifier, mineral filler, coupling agent, processing aid, one package stabilizer fully with even, the to be filled oil of extending oil thorough mixing by resin and in mixer, mix in proportion.Mixed material is sent in the twin screw extruder by feeder, through twin screw high speed shear, mixing, by head extrude, tie rod, air-cooled, pelletizing, drying and pack.Each section extruder temperature is controlled between 150～280 ℃ among the preparation method.
The present invention compares with using SBS, SIS based on the thermoplastic elastomer of SEBS, SEPS, because the cause that the carbon-carbon double bond in the polymkeric substance is hydrogenated, so the thermoplastic elastomer (TPE) that with this type of material is base-material be the weather resistance that the TPE product of base material has excellence than SBS, SIS etc., the corrodibility of pharmaceutical chemicalss such as its thermostability, acid-and base-resisting etc. also improves a lot.Therefore in fields such as automobile, building, medicine equipment, packing, household electrical appliance and the consumer's goods, obtain to use widely.
The plastics that adopt TPE of the present invention to coat are coated with the soft elastomerics of one deck because of the surface, so the user only needs less power just can hold firmly, and the pen of the pushing time grasping of this kind coated prod particularly suitable needs, screwdriver, power tool etc.The application of elastomerics coating material alleviated greatly the user fatigue, improved the comfortableness that product uses.Simultaneously because the tint permanence of thermoplastic elastomer excellence makes product more attractive in appearance.
The method that twin screw extruder is extruded after the employing blending is to the body material modification, and is firm with nylon adhesive, forming.The present invention is low simple with technology to equipment requirements, and the equipment of numerous domestic producer all can be produced at present.
Embodiment
Embodiment 1
SEBS and even, the to be filled oil of extending oil thorough mixing are blotted the back fully by resin to add components such as tackifier, mineral filler, coupling agent, processing aid, one package stabilizer and mixes in mixer in following parts by weight ratio.Mixed material is sent in the twin screw extruder by feeder, and the twin screw extruder temperature is set in 240 ℃, 25 hertz of feeding frequencies, 20 hertz of engine speeds.Starting material are through twin screw high speed shear, mixing, by head extrude, tie rod, air-cooled, pelletizing, drying and packing.
SEBS (Kraton) G-1651:100 part
Extending oil (Nplast220): 150 parts
Tackifier (nylon 6): 250 parts
Mineral filler (talcum powder): 50 parts
Coupling agent (NDZ-101): 4 parts
Processing aid (calcium stearate): 5 parts
One package stabilizer (UV-531): 5 parts
The thermoplastic elastomer that makes by above-mentioned prescription is carried out performance test, adopt the commercial like product to be contrast, every index of product of the present invention all is better than currently available products as can be seen, result such as following table:
| Performance | Unit | Testing method | Test value | Contrast product |
| Shore hardness | Shore?A | ASTM?D-2240 | 70 | 75 |
| Melting index (190 ℃, 2.16kg) | g/10min | ASTM?D-1238 | 35 | 20 |
| 100% tensile strength | Mpa | ASTM?D-412 | 1.0 | 0.8 |
| Tensile break strength | Mpa | ASTM?D-412 | 4.0 | 3.5 |
| Tension fracture elongation rate | ％ | ASTM?D-412 | 400 | 300 |
| Tear strength | KN/m | ASTM?D-1922 | 10 | 9 |
| Proportion | - | ASTM?D-792 | 0.975 | 1.15 |
Embodiment 2
Prepare thermoplastic elastomer according to technology among the embodiment 1 and following parts by weight proportioning.
SEBS (Kraton) G-1650:150 part
Extending oil (Nplast220): 150 parts
Tackifier (nylon 66): 250 parts
Mineral filler (lime carbonate): 50 parts
Coupling agent (KR-TTS): 4 parts
Processing aid (hard ester acid): 5 parts
One package stabilizer (Irganox1076): 5 parts
Embodiment 3
Prepare thermoplastic elastomer according to technology among the embodiment 1 and following parts by weight proportioning.
SEBS (Taipol) 3151:100 part
Extending oil (Nplast220): 150 parts
Tackifier (nylon 1010): 250 parts
Mineral filler (kaolin): 50 parts
Coupling agent (KH-570): 4 parts
Processing aid (Zinc Stearate): 5 parts
One package stabilizer (MD-1024): 5 parts
Embodiment 4
Prepare thermoplastic elastomer according to technology among the embodiment 1 and following parts by weight proportioning.
SEBS (Ba Ling petrochemical industry) 503:400 part
Extending oil (Nplast220): 150 parts
Tackifier (Ni Long11): 250 parts
Mineral filler (kaolin): 50 parts
Coupling agent (KH-550): 5 parts
Processing aid (erucicamide): 5 parts
One package stabilizer (Irganox1076): 5 parts
Embodiment 5
Prepare thermoplastic elastomer according to technology among the embodiment 1 and following parts by weight proportioning.
SEBS (Kraton) G-1651:300 part
Extending oil (150SN): 150 parts
Tackifier (NYLON610): 250 parts
Mineral filler (lime carbonate): 50 parts
Coupling agent (NDZ-201): 5 parts
Processing aid (calcium stearate): 5 parts
One package stabilizer (Irganox1076): 5 parts
Embodiment 6
Prepare thermoplastic elastomer according to technology among the embodiment 1 and following parts by weight proportioning.
SEBS (Kraton) G-1651:100 part
Extending oil (KN4010): 150 parts
Tackifier (nylon 612): 250 parts
Mineral filler (talcum powder): 50 parts
Coupling agent (KR-238): 4 parts
Processing aid (calcium stearate): 5 parts
One package stabilizer (Irganox1010): 5 parts
Embodiment 7
Prepare thermoplastic elastomer according to technology among the embodiment 1 and following parts by weight proportioning.
SEBS (Kraton) G-1651:100 part
Extending oil (KN4010): 150 parts
Tackifier (PP-g-MAH): 250 parts
Mineral filler (talcum powder): 50 parts
Coupling agent (KH-570): 4 parts
Processing aid (lime carbonate): 5 parts
One package stabilizer (Irganox168): 5 parts
Embodiment 8
Prepare thermoplastic elastomer according to technology among the embodiment 1 and following parts by weight proportioning.
SEBS (Kraton) G-1651:100 part
Extending oil (KN4010): 250 parts
Tackifier (vinylbenzene-acrylic copolymer): 250 parts
Mineral filler (lime carbonate): 50 parts
Coupling agent (KR-TTS): 5 parts
Processing aid (Zinc Stearate): 5 parts
One package stabilizer (Irganox168): 5 parts
Embodiment 9
Prepare thermoplastic elastomer according to technology among the embodiment 1 and following parts by weight proportioning.
SEBS (Kraton) G-1651:100 part
Extending oil (KN4010): 350 parts
Tackifier (vinylformic acid Racemic glycidol resin copolymer): 250 parts
Mineral filler (lime carbonate): 50 parts
Coupling agent (KR-TTS): 5 parts
Processing aid (Zinc Stearate): 5 parts
One package stabilizer (Irganox1076): 5 parts
Embodiment 10
Prepare thermoplastic elastomer according to technology among the embodiment 1 and following parts by weight proportioning.
SEBS (Kraton) G-1651:100 part
Extending oil (KN4010): 150 parts
Tackifier (vinylbenzene-acrylate copolymer): 250 parts
Mineral filler (mica powder): 50 parts
Coupling agent (KH-550): 4 parts
Processing aid (calcium stearate): 5 parts
One package stabilizer (UV-531): 5 parts
Embodiment 11
Prepare thermoplastic elastomer according to technology among the embodiment 1 and following parts by weight proportioning.
SEPS (Kraton) 1650:100 part
Extending oil (KN4010): 150 parts
Tackifier (SEBS-g-MAH): 50 parts
Coupling agent (KH-550): 3 parts
Processing aid (calcium stearate): 5 parts
One package stabilizer (UV-531): 5 parts
Embodiment 12
Prepare thermoplastic elastomer according to technology among the embodiment 1 and following parts by weight proportioning.
SEPS (Kraton) 1651:100 part
Extending oil (KN4010): 150 parts
Tackifier (PE-g-MAH): 150 parts
Mineral filler (talcum powder): 50 parts
Coupling agent (KH-550): 3 parts
Processing aid (hard ester acid): 5 parts
One package stabilizer (UV-531): 5 parts
Embodiment 13
Prepare thermoplastic elastomer according to technology among the embodiment 1 and following parts by weight proportioning.
SEPS (Kraton) 1651:100 part
Extending oil (KN4010): 150 parts
Tackifier (SEBS-g-MAH): 350 parts
Mineral filler (talcum powder): 50 parts
Coupling agent (NDZ-101): 2 parts
Processing aid (hard ester acid): 2 parts
One package stabilizer (UV-531): 2 parts
Claims (5)
1. thermoplastic elastomer of using with nylon material secondary injection adhering, the weight percent of its raw material consists of:
Matrix resin 10%～60%
Extending oil 5%～60%
Tackifier 5%～50%
Mineral filler 0%～25%
Coupling agent 0.1%～0.8%
Processing aid 0.1%～2%
One package stabilizer 0.1%～2%
Wherein, described matrix resin is at least a in hydrogenation saturation type thermoplastic styrene-butadiene block copolymer, the hydrogenation saturation type thermoplasticity isoprene-styrene block copolymer; Described tackifier are the nylon-type polymkeric substance; What described extending oil was flash-point greater than in 200 ℃ saturated straight chain alkane oil, the naphthenic oil is at least a.
2. thermoplastic elastomer as claimed in claim 1 is characterized in that: described mineral filler is at least a in talcum powder, lime carbonate, kaolin, mica powder, the white carbon black.
3. thermoplastic elastomer as claimed in claim 1 is characterized in that: described coupling agent is at least a in titanate coupling agent, the silane coupling agent.
4. thermoplastic elastomer as claimed in claim 1 is characterized in that: described processing aid is at least a in fatty acid, fatty acid salt, fatty acid acyl amine, the silicone material.
5. thermoplastic elastomer as claimed in claim 1 is characterized in that: described one package stabilizer is at least a in benzophenone, Hinered phenols, phosphorous acid esters, the hindered amines stablizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100533393A CN100463942C (en) | 2006-09-07 | 2006-09-07 | Thermoplastic elastomer for injection adhering nylon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100533393A CN100463942C (en) | 2006-09-07 | 2006-09-07 | Thermoplastic elastomer for injection adhering nylon material |
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| CN1931919A CN1931919A (en) | 2007-03-21 |
| CN100463942C true CN100463942C (en) | 2009-02-25 |
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| CNB2006100533393A Expired - Fee Related CN100463942C (en) | 2006-09-07 | 2006-09-07 | Thermoplastic elastomer for injection adhering nylon material |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102094328B (en) * | 2009-12-15 | 2012-12-19 | 银禧工程塑料（东莞）有限公司 | Thermoplastic elastomer material for replacing PVC coated polyester yarns and preparation method thereof |
| CN102140225A (en) * | 2010-12-29 | 2011-08-03 | 东莞市迅创实业有限公司 | Transparent thermoplastic elastomer in injection adhering with polypropylene |
| 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 |
| CN102876052A (en) * | 2012-09-28 | 2013-01-16 | 新昌县绿泰塑胶有限公司 | Printable thermoplastic elastomer composition |
| CN104139578B (en) * | 2014-08-05 | 2016-08-24 | 昆山同昌汽车新材料有限公司 | A kind of PP/PET is blended environment-friendly waterproof anti-petrol car wheelhouse and manufacture method thereof |
| CN105199299B (en) * | 2015-10-18 | 2018-02-02 | 温州市赢创新材料技术有限公司 | A kind of secondary injection adhering thermoplastic elastomer (TPE) |
| CN105199404B (en) * | 2015-10-26 | 2016-10-12 | 深圳达普林科技有限公司 | A kind of composition for thermoplastic elastomer for covered with nylon material |
| CN105694334A (en) * | 2016-03-08 | 2016-06-22 | 安徽韧达高分子材料有限公司 | TPE (thermal plastic elastomer) material for coating nylon and preparation method of TPE material |
| CN106928626A (en) * | 2017-02-28 | 2017-07-07 | 盛嘉伦橡塑(深圳）股份有限公司 | Thermoplastic elastic material for secondary injection adhering and preparation method thereof |
| CN107513263B (en) * | 2017-10-19 | 2020-08-04 | 威海联桥新材料科技股份有限公司 | Thermoplastic elastomer gasket material and production method thereof |
| CN109762349B (en) * | 2019-01-21 | 2021-11-09 | 盛嘉伦橡塑(深圳）股份有限公司 | Thermoplastic elastomer material and preparation method thereof |
| CN112011130A (en) * | 2020-08-28 | 2020-12-01 | 东风商用车有限公司 | Thermoplastic elastomer material and preparation method and application thereof |
| CN114736482A (en) * | 2022-03-09 | 2022-07-12 | 金发科技股份有限公司 | Thermoplastic elastomer composite material and preparation and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050197447A1 (en) * | 2004-03-05 | 2005-09-08 | Jiren Gu | Block copolymer composition for overmolding any nylon |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050197447A1 (en) * | 2004-03-05 | 2005-09-08 | Jiren Gu | Block copolymer composition for overmolding any nylon |
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