CN102051018B - Thermoplastic elastomer for being subjected to secondary injection adhesion with PBT (polybutylene terephthalate) material and composite molding product using same - Google Patents
Thermoplastic elastomer for being subjected to secondary injection adhesion with PBT (polybutylene terephthalate) material and composite molding product using same Download PDFInfo
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- CN102051018B CN102051018B CN2010105661021A CN201010566102A CN102051018B CN 102051018 B CN102051018 B CN 102051018B CN 2010105661021 A CN2010105661021 A CN 2010105661021A CN 201010566102 A CN201010566102 A CN 201010566102A CN 102051018 B CN102051018 B CN 102051018B
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Abstract
The invention relates to a thermoplastic elastomer for being subjected to secondary injection adhesion with a PBT (polybutylene terephthalate) material, which comprises the following components in percentage by weight: 18 to 45 percent of matrix resin, 5 to 10 percent of tackifying resin, 10 to 35 percent of polar resin, 15 to 40 percent of mineral oil and 0 to 35 percent of fillers. A coupling agent is not used in a composition formula of the thermoplastic elastomer for being subjected to secondary injection adhesion with the PBT material, so that compounding material components are reduced, the cost is reduced, the thermoplastic elastomer has high elasticity and high liquidity and is convenient to industrially produce and the performance of a product is more stable. Moreover, the thermoplastic elastomer in a prepared composite molding product is firmly adhered to the PBT material, is well molded, has lower hardness than the conventional product and has better handfeel.
Description
[technical field]
The present invention relates to polymeric material field, relate in particular to a kind of and thermoplastic elastomer that the PBT material secondary injection adhering is used and the composite molded article that uses this thermoplastic elastomer.
[background technology]
Polybutylene terephthalate (PBT) is the linear saturated polyester resin of a kind of crystal type, is by the one type thermoplast engineering plastics of U.S. Clanese company in the seventies in 20th century exploitation and suitability for industrialized production.It is fast that it has crystallization velocity, the electric property excellent characteristics, and with temperature, humidity changes little; Good weatherability is applicable to outdoor use, is the ideal material of electronics, electrical industry; Be widely used in electronics, electric, fields such as automobile, household electrical appliance, power tool, sports equipment.
Yet the PBT product surface is harder and smooth, lacks texture and feel in some application facet.The rubber and plastic alloy that therefore, often need coat one deck flexible touch at the PBT product surface is to strengthen relevance grade.Usually industry is employed in the PBT material surface and penetrates the mode of sticking one deck thermoplastic elastomer and realize.Thermoplastic elastomer is a kind of material that has rubber and thermoplastics characteristic concurrently; It shows the elasticity of rubber at normal temperatures; Macromolecular material that again can plasticizing forming during high temperature has the mechanical property and the use properties that are similar to rubber, can process and reclaim by thermoplastics again.Use thermoplastic elastomer to make the PBT coating material, easy to process, and feel is good, increases comfort.
Yet the material cost of existing thermoplastic elastomer as the PBT coating material is higher, and relatively poor with the binding property of PBT material.
[summary of the invention]
Based on this, be necessary to provide a kind of cost lower, binding property thermoplastic elastomer and use the composite molded article of this thermoplastic elastomer preferably during with the PBT material secondary injection adhering.
A kind of thermoplastic elastomer of using with the PBT material secondary injection adhering by weight percentage, comprising:
Matrix resin 18%～45%, said matrix resin are the mixture of a kind of in styrene-ethylene-butadiene-styrene block copolymer, the styrene-ethylene-propylene-styrene segmented copolymer or two kinds;
Tackifying resin 5%～10%, said tackifying resin are EVA;
Polar resin 10%～35%, described polar resin are SEBS-g-MAH, SEBS-g-NH
2, at least a among the EPDM-g-MAH;
MO 15%～40%, said MO are that flash-point is higher than 200 ℃ saturated straight chain alkane oil; And
Filler 0～35%.
In a preferred embodiment, said filler is at least a in lime carbonate, talcum powder, terra alba, potter's clay, permanent white, mica powder, the kaolin.
In a preferred embodiment, comprise that also mass percent is 0.1%～0.5% oxidation inhibitor.
In a preferred embodiment, said oxidation inhibitor is to contain in benzophenone, Hinered phenols, phosphorous acid esters, the suffocated amine antioxidant one or more.
In a preferred embodiment, comprise that also mass percent is 0.1%～0.3% processing aid.
In a preferred embodiment, described processing aid is at least a in lipid acid, fatty acid amide, the silicone.
A kind of composite molded article is formed by above-mentioned thermoplastic elastomer and PBT material secondary injection adhering.
The above-mentioned thermoplastic elastomer of using with the PBT material secondary injection adhering has reduced the compounding ingredient component owing to do not use coupling agent on the compositing formula, has reduced cost, possesses snappiness simultaneously, and high workability is convenient to suitability for industrialized production and product performance are more stable.In addition, thermoplastic elastomer in the composite molded article that makes and PBT material adhesive are firm, forming, and existing relatively product hardness is lower, has preferable feel.
[embodiment]
The thermoplastic elastomer that will combine embodiment pair and PBT material secondary injection adhering to use is below done further to specify.
The thermoplastic elastomer of using with the PBT material secondary injection adhering of one embodiment by weight percentage, comprising:
Matrix resin 18%～45%;
Tackifying resin 5%～10%;
Polar resin 10%～35%;
MO 15%～40%;
Filler 0～35%.
Wherein, matrix resin is preferably the mixture of a kind of in styrene-ethylene-butadiene-styrene block copolymer (SEBS), the styrene-ethylene-propylene-styrene segmented copolymer (SEEPS) or two kinds.The effect of matrix resin is to make material to have good hand feeling and excellent weathering resistance.
SEBS specifically can be: SEBS1641, SEBS1654, SEBS1535, SEBS1536, the SEBS6924 of U.S. Kraton company.SEEPS specifically can be SEEPS4077, the SEEPS4055 of Japanese Kuraray company.
Wherein, tackifying resin is preferably at least a in EVA, alpha-methyl styrene resin, propenoate (for example vinylbenzene-TEB 3K) and the styrene copolymer.Tackifying resin is usually used in the hot melt adhesive field, has the function that improves tack of materials.Add the cohesiveness that tackifying resin can improve thermoplastic elastomer and PBT effectively in this embodiment.
Tackifying resin specifically can be U.S. Nu Fake NAS30, French A Kema 4260, Taiwan polymerization EU630, U.S. Yi Shiman 5140.
Wherein, polar resin is preferably SEBS-g-MAH (hydrogenation thermoplastic styrene butadiene rubber-maleic anhydride grafts), SEBS-g-NH
2At least a among (hydrogenation thermoplastic styrene butadiene rubber-imido grpup grafts), PP-g-MAH (Vestolen PP 7052-maleic anhydride grafts), HDPE-g-MAH (high density polyethylene(HDPE)-maleic anhydride grafts), EPDM-g-MAH (terpolymer EP rubber-maleic anhydride grafts), the POE-g-MAH (POE-maleic anhydride grafts).Because PBT is a kind of strong polar material that has; And matrix resin, tackifying resin do not possess polarity; Therefore according to the principle of similar compatibility, in material, adding polar resin can further increase thermoplastic elastomer and have the adhesive capacity of strong polar PBT.
Polar resin specifically can be: the FG of U.S. Kraton company series 1901,1924, the Japanese M1913 of Asahi Chemical Industry, MP-10, U.S. Chemtura Chemtura company 3109,3029,3002,1001,3150.
Wherein, MO is preferably flash-point and is higher than 200 ℃ saturated straight chain alkane oil and in the naphthenic oil one or both.The MO of high flash point can improve the heat resistance of material, the flowability of increase material, can adjust addition according to practical situation again simultaneously, to obtain the material of various hardness, satisfies more clients' demand.
MO specifically can be naphthenic oil such as the KN4006, KN4010 of Kelamayi refinery, the 500N saturated straight chain alkane oil of the two dragon oil refining of Korea S (S-Oil), or the PW90 saturated straight chain alkane of Japanese bright dipping oil.
Wherein, filler is preferably at least a in lime carbonate, talcum powder, terra alba, potter's clay, permanent white, mica powder, the kaolin.The corresponding product that can use many companies such as domestic production producer such as Guilin Tian Cheng, Jiangsu Rieter, the inferior Thailand in Dalian to produce.Suitably add the cost that mineral filler not only can suitably reduce product, can also reduce the molding shrinkage of product, be reduced in and penetrate the probability that occurs defective products in the sticking process.
In addition, the above-mentioned thermoplastic elastomer that uses with the PBT material secondary injection adhering can comprise that also mass percent is 0.1%～0.5% oxidation inhibitor.
Wherein, oxidation inhibitor is preferably and contains in benzophenone, Hinered phenols, phosphorous acid esters, the suffocated amine antioxidant one or more.It is oxidized in the process of processing and use that oxidation inhibitor can prevent or slow down thermoplastic elastomer effectively, prolongs the work-ing life of thermoplastic elastomer.
Oxidation inhibitor specifically can be antioxidant 1076, antioxidant 1010, oxidation inhibitor 168, oxidation inhibitor 1024 of Ciba company etc.
In addition, the above-mentioned thermoplastic elastomer that uses with the PBT material secondary injection adhering can comprise that also mass percent is 0.1%～0.3% processing aid.
Wherein, processing aid is preferably at least a in lipid acid, fatty acid amide, the silicone.Processing aid can suitably improve the feel and the processing characteristics of material.
Processing aid specifically can be hard ester acid, favourable triumphant agate 1753 (erucicamide) etc.
Above-mentioned thermoplastic elastomer can have multiple moulding (processing) mode; For example can or extrude moulding methodes such as extrusion molding, injection forming, blow molding, blowing, press molding, calendaring molding, fusion stacking shaping, compression molding, vacuum forming, foaming and molding such as thin slice shaping, form the molding of random shapes such as Powdered, particulate state, tabular, film or laminar, tubulose, hollow form, case shape through special-shaped extrusion molding.
Preferably, the above-mentioned thermoplastic elastomer of using with the PBT material secondary injection adhering can prepare according to following method:
With thermoplastic matrix resin and MO thorough mixing; After treating that MO is sucked by matrix resin fully; Adding tackifying resin, polar resin, MO, filler, oxidation inhibitor etc. stirs; Send into twin screw extruder again, through the Couble screw rod high-temp shear-mixed extrude, granulation, make the thermoplastic elastomer that is used for the PBT material secondary injection adhering.
Aforesaid method is simple to operate, be suitable for suitability for industrialized production.
Because above-mentioned thermoplastic elastomer and PBT material have good cohesiveness, therefore can carry out secondary injection adhering and form composite molded article with the PBT material.For example slipmat is ridden pad, indoor carpet, ground panel; Comb, watchband, cosmetic container, suitcase, toothbrush handles, the knife rest that shaves, torch light, table and serving coasters and mats, case and bag base and accessory thereof; Products such as various kitchen tools, tableware, cutter, sanitary equipment and household electrical appliance; Stationery products such as the pen cap, rubber, stapler, paper-cutter, tapping and plugging machine; Toy car tire, bearing circle and accessory thereof, game pad, yo-yo, toy products such as pet toy; Baby bottles, nipple, sting articles for children such as ring.
Above-mentioned thermoplastic elastomer is a base material with SEBS, SEEPS, than traditional SBS, and the SIS base material, anti-xanthochromia, ageing-resistant performance significantly improve.Owing to do not use coupling agent on the compositing formula, reduced the compounding ingredient component, reduced cost, possess snappiness simultaneously, high workability is convenient to suitability for industrialized production and product performance are more stable.Thermoplastic elastomer in the composite molded article that makes and PBT material adhesive are firm, forming.The thermoplastic elastomer that is used for the PBT material secondary injection adhering provided by the invention can be through changing the massfraction of MO, the hardness of regulating coating material effectively.This thermoplastic elastomer mechanical property good and hand feel and drape has ideally solved the problem that PBT goods texture is hard and be smooth to the touch.
Below be specific embodiment, yet the following example does not limit the present invention in any way.
1. proportioning raw materials
2. extrude processing
The raw material of above-mentioned each embodiment is mixed by proportioning, send into twin screw extruder then, setting and extruding processing temperature is 200 ℃, through mixingly extrude, water-cooled, pelletizing and dryly make and can be packaged to be finished product in penetrating sticking thermoplastic elastomer with PBT.
3. performance test
Thermoplastic elastomer to making by above-mentioned each prescription carries out performance test, result such as following table:
Remarks: fusing exponential test condition is: 190 ℃ of temperature, pressure 5KG.
Can know that by the foregoing description and test performance thereof above-mentioned thermoplastic elastomer is compared to prior art, cancel the use of coupling agent, reduce matching component, reduce cost, be convenient to suitability for industrialized production, make quality product more stable; Simultaneously, the thermoplastic elastomer prescription that is used for the PBT secondary injection adhering provided by the invention is through changing the component of MO; Just the hardness of conveniently adjusted thermoplastic elastomer; Under the identical situation of other component, the content of MO is high more, and the shore hardness of final finished is low more; The minimum 45ShoreA that reaches has than the better feel of like product.
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 (7)
1. a thermoplastic elastomer of using with the PBT material secondary injection adhering is characterized in that, by weight percentage, comprising:
Matrix resin 18%～45%, said matrix resin are the mixture of a kind of in styrene-ethylene-butadiene-styrene block copolymer, the styrene-ethylene-propylene-styrene segmented copolymer or two kinds;
Tackifying resin 5%～10%, said tackifying resin are EVA;
Polar resin 10%～35%, described polar resin are SEBS-g-MAH, SEBS-g-NH
2, at least a among the EPDM-g-MAH;
MO 15%～40%, said MO are that flash-point is higher than 200 ℃ saturated straight chain alkane oil; And
Filler 0～35%.
2. the thermoplastic elastomer that according to claim 1 and PBT material secondary injection adhering are used is characterized in that: said filler is at least a in lime carbonate, talcum powder, terra alba, potter's clay, permanent white, mica powder, the kaolin.
3. the thermoplastic elastomer of using with the PBT material secondary injection adhering according to claim 1 is characterized in that: comprise that also mass percent is 0.1%～0.5% oxidation inhibitor.
4. the thermoplastic elastomer that according to claim 3 and PBT material secondary injection adhering are used is characterized in that: said oxidation inhibitor is to contain in benzophenone, Hinered phenols, phosphorous acid esters, the suffocated amine antioxidant one or more.
5. the thermoplastic elastomer of using with the PBT material secondary injection adhering according to claim 1 is characterized in that: comprise that also mass percent is 0.1%～0.3% processing aid.
6. the thermoplastic elastomer that according to claim 5 and PBT material secondary injection adhering are used is characterized in that: described processing aid is at least a in lipid acid, fatty acid amide, the silicone.
7. composite molded article that forms according to any described thermoplastic elastomer of claim 1～6 and PBT material secondary injection adhering.
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| CN2010105661021A CN102051018B (en) | 2010-11-30 | 2010-11-30 | Thermoplastic elastomer for being subjected to secondary injection adhesion with PBT (polybutylene terephthalate) material and composite molding product using same |
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| CN2010105661021A CN102051018B (en) | 2010-11-30 | 2010-11-30 | Thermoplastic elastomer for being subjected to secondary injection adhesion with PBT (polybutylene terephthalate) material and composite molding product using same |
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| CN102051018B true CN102051018B (en) | 2012-06-13 |
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| CN103897321A (en) * | 2012-12-27 | 2014-07-02 | 中纺投资发展股份有限公司 | Thermoplastic elastomer composition capable of using in low temperature coated nylon and its preparation method |
| 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 |
| CN103524979B (en) * | 2013-10-18 | 2016-10-12 | 武汉工程大学 | A kind of SEBS thermoplastic elastomer bra liner material and preparation method thereof and use |
| CN104945827B (en) * | 2015-06-26 | 2017-11-03 | 台橡（上海）实业有限公司 | A kind of case and bag overlay film thermoplastic elastic material |
| CN104893227A (en) * | 2015-06-29 | 2015-09-09 | 房小明 | Thermoplastic elastomer used with PC (polycarbonate) material by means of secondary shot sticking and preparation method of thermoplastic elastomer |
| CN106519635A (en) * | 2016-10-13 | 2017-03-22 | 广东省石油化工研究院 | Surface scratch-resistant TPV composition capable of achieving secondary coating forming with ABS base material and preparation method thereof |
| CN106496971A (en) * | 2016-11-18 | 2017-03-15 | 无锡明盛纺织机械有限公司 | A kind of engineering plastic materials containing bamboo fibre and preparation method |
| CN106633409A (en) * | 2016-12-30 | 2017-05-10 | 慈溪市山今高分子塑料有限公司 | Thermoplastic elastomer for pet toy and preparation method thereof |
| CN107033524B (en) * | 2017-06-01 | 2019-07-02 | 厦门港沅塑胶工业有限公司 | A kind of thermoplastic elastomer (TPE) and preparation method thereof with PETG secondary injection adhering |
| FR3068975B1 (en) * | 2017-07-12 | 2020-07-17 | Urgo Recherche Innovation Et Developpement | COMPOSITION FOR INTERFACE DRESSING |
| CN109517392A (en) * | 2018-11-02 | 2019-03-26 | 浙江耀隆塑业有限公司 | A kind of thermoplastic elastomer (TPE) and preparation method thereof suitable for kitchen article |
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Address after: Sightseeing road rich industrial park in Baoan District Guanlan street of Shenzhen of Guangdong province 518109 City Guifeng No. 1 Patentee after: Sheng Jialun rubber (Shenzhen) Limited by Share Ltd Address before: Sightseeing road rich industrial park in Baoan District Guanlan street of Shenzhen of Guangdong province 518109 City Guifeng No. 1 Patentee before: Shenzhen Sungallon Rubber & Plastic Industry Co., Ltd. |