CN108165026A - Encapsulated composite thermoplastic elastic material is bonded for PC/PBT alloys - Google Patents
Encapsulated composite thermoplastic elastic material is bonded for PC/PBT alloys Download PDFInfo
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- CN108165026A CN108165026A CN201711460384.5A CN201711460384A CN108165026A CN 108165026 A CN108165026 A CN 108165026A CN 201711460384 A CN201711460384 A CN 201711460384A CN 108165026 A CN108165026 A CN 108165026A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The present invention relates to thermoplastic macromolecule material technical fields, solve at present with PC/PBT alloys made of plastic components surface adhesive it is very poor, it is easily peeled off after quadric injection mould, not the problem of not being suitable for the cover material of PC/PBT alloys, it is specially a kind of that encapsulated composite thermoplastic elastic material is bonded for PC/PBT alloys, including following raw material in parts by weight：10~60 parts of styrenic elastomer, 10~60 parts of filling oil, compound 10~60 parts of adhesive, 5~20 parts of compatilizer, 5~20 parts of mineral filler, 0.3~1.0 part of antioxidant, 0.3~1 part of light stabilizer and other auxiliary agents, the encapsulated thermoplastic elastomer (TPE) of the PC/PBT alloys of the present invention, preferable with the surface adhesive of PC/PBT alloy plastics, peeling force is higher than more than 8kgf, it can be directly molded in PC/PBT alloy plastics surface second encapsulated, mechanical property is good, and tensile strength reaches more than 8MPa, and tearing strength is more than 10kN/m；Flexibility is preferable, and shore hardness is up to 40~80A, and available for the encapsulated of PC/PBT alloy plastic products, this will will obtain larger popularization on the market.
Description
Technical field
The present invention relates to thermoplastic macromolecule material technical field, bonded particularly for PC/PBT alloys encapsulated compound
Thermoplastic elastomer (s).
Background technology
PC/PBT alloys are the very excellent thermoplastic alloy engineering plastics of comprehensive performance, have excellent mechanical property,
The advantages that corrosion resistance, high-fire resistance, workability, is widely used in auto industry, electronic enterprises and machine-building etc.
The plastic part of industry.But the surface of plastic components is harder made of PC/PBT alloys, in the plastic components for being contacted with hand
When, lack texture and sense of touch, usual industry uses the surface second in PC/PBT alloy plastic products to be molded one layer of soft thermoplastic
The mode of property elastomer is realized, is commonly called as encapsulated.
In recent years, applied to the encapsulated thermoplastic elastomer (TPE) of rigid plastics, faster development has been obtained.Number of patent application is
200810066132.9 disclose it is a kind of be used to ABS low temperature penetrate viscous thermoplastic elastomer (TPE), the purpose is to provide one kind to be used for
Viscous thermoplastic elastomer (TPE) is penetrated with ABS；Number of patent application is a kind of 201210197799.9 POM cover materials and its preparation side
Method discloses a kind of thermoplastic elastomer (TPE) encapsulated available for POM；Number of patent application discloses one for 201110100194.9
Thermoplastic elastomer (TPE) of the kind available for PCTG；These patents announced at present about encapsulated thermoplastic elastomer (TPE) can be used for PP,
The quadric injection mould of the plastic materials such as PE, ABS, POM, PCTG is encapsulated, but with PC/PBT alloys made of the surface of plastic components glue
Attached property is very poor, is easily peeled off after quadric injection mould, is not suitable for the encapsulated of PC/PBT alloys.
Invention content
The problem of for background technology, the present invention provides encapsulated composite thermoplastic is bonded for PC/PBT alloys
Property elastic material, it is desirable to provide it is a kind of can improve with PC/PBT alloys made of plastic components surface adhesive, quadric injection mould
It is not easy the encapsulated thermoplastic elastomer (TPE) being easily peeled off afterwards.
To achieve the above object, the present invention provides following technical solution and encapsulated composite thermoplastic is bonded for PC/PBT alloys
Property elastic material, including following raw material in parts by weight：10~60 parts of styrenic elastomer, 10~60 parts of filling oil are multiple
With 10~60 parts of adhesive, 5~20 parts of compatilizer, 5~20 parts of mineral filler, 0.3~1.0 part of antioxidant, light stabilizer 0.3~
1 part and other auxiliary agents.
Further embodiment, styrenic elastomer (the also known as styrene block copolymer Styreneic
Block Copolymers, abbreviation SBCs), it is currently world wide production maximum and a kind of the most similar thermoplasticity of rubber performance
Elastomer.At present, mainly there are 4 types in SBCs series of products, i.e.,：Styrene-Butadiene-Styrene Block Copolymer
(SBS)；Styrene-isoprene-styrene block copolymer (SIS)；Styrene-ethylene-butylene-styrene block copolymer
(SEBS)；Styrene-ethylene-propylene, Styrene type block copolymer (SEPS).SEBS and SEPS is SBS and SIS respectively
Hydrogenated copolymer.
Oil is filled described in further embodiment as one kind in aromatic naphtha, naphthenic oil, paraffin oil, preferably naphthenic oil.
Further embodiment, it is described compounding adhesive by polyester polyurethane elastomer, polyether polyurethane elastomer,
Thermoplastic poly ester type elastomer (including polyester polyether-type and pet copolyester type), thermoplastic polyamide elastomer (TPAE), ethylene-
Methyl acrylate copolymer (EMA), ethylene ethyl acrylate copolymer (EEA), ethylene-butyl acrylate copolymer (EBA), second
At least two or more in alkene-vinyl acetate co-polymer (EVA), ethylene methyl methacrylate copolymer (EMMA) are multiple
With into.
Further embodiment, the compatilizer is ethylene-octene copolymer grafted maleic anhydride, ethylene-octene copolymer
Object grafting grafted propylene acid glycidyl ester, ABS- grafted maleic anhydrides, styrene-acrylonitrile-maleic anhydride, ethylene-fourth two
One or more of alkene-polystyrene ternary segmented copolymer grafted maleic anhydride compounds.
Further embodiment, the mineral filler is talcum powder, calcium carbonate, land plaster, barium sulfate, mica powder, kaolinite
One or more of soil.
Further embodiment, the antioxidant are four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] Ji Wusi
Alcohol ester, N, N ' -1,6- inferior hexyls-bis- [3- (3,5- di-tert-butyl-hydroxy phenyls) propionamide], 3,5- di-t-butyl -4- hydroxyls
The positive octadecanol of base phenylpropionic acid, 1,3,5- tri- (4- tertiary butyl -3- hydroxyl -2,6- dimethyl benzyls) -1,3,5- triazine -2,4,
6- (1H, 3H, 5H) triketone, triethylene glycol bis- [3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionic esters], 2,2 '-methylene
Bis- (4- methyl-6-tert-butylphenols), phosphorous acid three (2,4- di-tert-butyl-phenyls) ester, bis- (2,4- di-tert-butyl-phenyls) seasons
Penta tetrol diphosphites, distearyl pentaerythritol diphosphite, four (2,4- di-tert-butyl-phenyls -4,4 '-biphenyl
Base) one or more antioxidant such as bisphosphonate compound.
Further embodiment, the light stabilizer include 2,4- dihydroxies benzophenone, 2- hydroxyl -4- n-octyloxy hexichol
Ketone, ESCALOL 567,2- acrylic acid 2- (4- benzoyl -3- hydroxyphenoxies) ethyl ester, 2- (2 '-hydroxyls
Base -5 '-aminomethyl phenyl) benzotriazole, 2'- (2'- hydroxyl -3'- tertiary butyl -5'- aminomethyl phenyls) -5- chlorobenzotriazoles, 2-
(bis- (a, the a- dimethyl benzyl) phenyl of 2'- hydroxyls -3', 5') benzotriazole, 2- (2 '-hydroxyl -3 ', 5 '-di-tert-butyl
Base) -5- chlorinated benzotriazoles, bis- (2,2,6,6- tetramethyl -4- piperidyls) sebacic acid esters, poly-succinic (4- hydroxyl -2,2,6,
6- tetramethyl -1- piperidine ethanols) ester, poly- { (6- morpholinyl -5- triazine -2,4- diyls) (2,2,6,6- tetramethyl-piperidyls) is sub-
Amido hexa-methylene [(2,2,6,6- tetramethyl-piperidyls)-imido grpup] }, in 2,2,6,6- tetramethyl -4- piperidines stearates
It is one or more of.
It is a kind of prepare the present invention for the method that PC/PBT alloys bond encapsulated composite thermoplastic elastic material include with
Lower step：
(1)：According to parts by weight, styrenic elastomer and filling oil are first weighed, 0.5 is stood after high-speed mixer stirring
Hour；
(2)：It weighs remaining raw material respectively according still further to parts by weight, is put into step (1), then in high-speed mixer
It remixes 5 minutes；
(3)：The mixture formed in step (2) is put into extruding pelletization in twin-screw extrusion, extruder temperature is set as：
One 0 DEG C of area's temperature, 190 DEG C of two area's temperature, 210 DEG C of three area's temperature, 210 DEG C of four area's temperature, 210 DEG C of five area's temperature, six area's temperature
210 DEG C, 210 DEG C of head, after material squeezes out, pelletizing air blast under water is dried.
Compared with prior art, the beneficial effects of the invention are as follows：The encapsulated thermoplastic elastic of PC/PBT alloys in the present invention
Body, preferable with the surface adhesive of PC/PBT alloy plastics, peeling force is higher than more than 8kgf, can directly be moulded in PC/PBT alloys
Expect that surface second injection is encapsulated；Mechanical property is good, and tensile strength reaches more than 8MPa, and tearing strength is more than 10kN/m；Flexibility
Preferably, shore hardness is up to 40~80A.Available for the encapsulated of PC/PBT alloy plastic products, this will will obtain on the market compared with
Big popularization.
Specific embodiment
Below in conjunction with the embodiment of the present invention, the technical solution in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, those of ordinary skill in the art's all other embodiments obtained without making creative work, all
Belong to the scope of protection of the invention.
Embodiment 1：
39 parts of styrenic elastomers and 39.8 parts of naphthenic oils are weighed, 0.5hr is stood after high-speed stirred, then weighs 5 parts
TPU, 5 parts of EMA, 5 parts of POE-g-MAH, 5 parts of CaCO3, 0.3 part of antioxidant 1010,0.3 part of irgasfos 168,0.6 part
Tinuvin770 is remixed 5 minutes in high-speed mixer；
By uniformly mixed material in twin-screw extrusion extruding pelletization.Extruder temperature is set as：0 DEG C of I areas, II areas
190 DEG C, 210 DEG C of III areas, 210 DEG C of IV areas, 210 DEG C of V areas, 210 DEG C of VI areas, 210 DEG C of head, material squeeze out after, pelletizing under water
Air blast is dried.Gained composite elastic body material property is shown in Table 1.
Embodiment 2：
27 parts of styrenic elastomers and 28.8 parts of naphthenic oils are weighed, 0.5hr is stood after high-speed stirred, then weighs 5 parts
TPU, 5 parts of EMA, 3 parts of POE-g-MAH, 5 parts of CaCO3, 0.3 part of antioxidant 1010,0.3 part of irgasfos 168,0.6 part
Tinuvin770 is remixed 5 minutes in high-speed mixer；
By uniformly mixed material in twin-screw extrusion extruding pelletization.Extruder temperature is set as：0 DEG C of I areas, II areas
190 DEG C, 210 DEG C of III areas, 210 DEG C of IV areas, 210 DEG C of V areas, 210 DEG C of VI areas, 210 DEG C of head, material squeeze out after, pelletizing under water
Air blast is dried.Gained composite elastic body material property is shown in Table 1.
Embodiment 3：
16.8 parts of styrenic elastomers and 18 parts of naphthenic oils are weighed, 0.5hr is stood after high-speed stirred, then weighs 5 parts
TPU, 5 parts of EMA, 3 parts of POE-g-MAH, 0.3 part of antioxidant 1010,0.3 part of irgasfos 168,0.6 part of Tinuvin770 is at a high speed
It is remixed in mixing machine 5 minutes；
By uniformly mixed material in twin-screw extrusion extruding pelletization.Extruder temperature is set as：0 DEG C of I areas, II areas
190 DEG C, 210 DEG C of III areas, 210 DEG C of IV areas, 210 DEG C of V areas, 210 DEG C of VI areas, 210 DEG C of head, material squeeze out after, pelletizing under water
Air blast is dried.
The test method of peeling force is：In the encapsulated encapsulated thermoplastic elastomer (TPE)s of plate quadric injection mould of PC/PBT, encapsulated plate thickness
2mm, encapsulated stripping width 50mm carry out peel test, test stripping maximal force using tensilon；The survey of shore hardness
Amount requires to be tested according to ASTM D2240；Tensile strength, elongation at break are tested according to ASTM D412 standards；It tears
Resistance to spalling is tested according to ASTM D624 standards.
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Shao's A hardness | 50A | 80A | 85A |
| Tensile strength | 5.4MPa | 8.3MPa | 9.1MPa |
| Elongation at break | 610% | 650% | 450% |
| Tearing strength | 18kN/m | 25kN/m | 20kN/m |
| Peeling force | 8.0kgf | 9.3kgf | 10.1kgf |
Table 1
The encapsulated thermoplastic elastomer (TPE) of PC/PBT alloys as can be seen from Table 1, the surface adhesion with PC/PBT alloy plastics
Property it is preferable, peeling force be higher than more than 8kgf, can directly PC/PBT alloy plastics surface second be molded it is encapsulated；Mechanical property is good,
In addition to the tensile strength of embodiment 1 is less than 8Mpa, the tensile strength of remaining embodiment reaches more than 8MPa, and tearing strength is more than
10kN/m；Flexibility is preferable, and shore hardness is up to 40~80A.
Based on above-mentioned, present invention has the advantage that：The encapsulated thermoplastic elastomer (TPE) of PC/PBT alloys in the present invention, with
The surface adhesive of PC/PBT alloy plastics is preferable, and peeling force is higher than more than 8kgf, can be directly on PC/PBT alloy plastics surface
Quadric injection mould is encapsulated；Mechanical property is good, and tensile strength reaches more than 8MPa, and tearing strength is more than 10kN/m；Flexibility is preferable,
Shore hardness is up to 40~80A, and available for the encapsulated of PC/PBT alloy plastic products, this will will obtain larger push away on the market
Extensively.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should all be included in the protection scope of the present invention.
Claims (7)
1. bond encapsulated composite thermoplastic elastic material for PC/PBT alloys, which is characterized in that including it is following by weight
Several raw materials：10~60 parts of styrenic elastomer, 10~60 parts of filling oil, compounds 10~60 parts of adhesive, compatilizer 5~20
Part, 5~20 parts of mineral filler, 0.3~1.0 part of antioxidant, 0.3~1 part of light stabilizer and other auxiliary agents.
2. according to claim 1 bond encapsulated composite thermoplastic elastic material for PC/PBT alloys, feature exists
In：The filling oil is aromatic naphtha, one kind in naphthenic oil, paraffin oil.
3. according to claim 1 bond encapsulated composite thermoplastic elastic material for PC/PBT alloys, feature exists
In：The compounding adhesive is by polyester polyurethane elastomer, polyether polyurethane elastomer, thermoplastic poly ester type elastomer
(including polyester polyether-type and pet copolyester type), thermoplastic polyamide elastomer (TPAE), ethylene-methyl acrylate copolymer
(EMA), ethylene ethyl acrylate copolymer (EEA), ethylene-butyl acrylate copolymer (EBA), ethylene-vinyl acetate are common
At least two or more in polymers (EVA), ethylene methyl methacrylate copolymer (EMMA) compound.
4. according to claim 1 bond encapsulated composite thermoplastic elastic material for PC/PBT alloys, feature exists
In：The compatilizer is ethylene-octene copolymer grafted maleic anhydride, ethylene-octene copolymer is grafted grafted propylene acid and shrinks
Glyceride, ABS- grafted maleic anhydrides, styrene-acrylonitrile-maleic anhydride, the copolymerization of ethylene-butadiene-styrene tri-block
One or more of object grafted maleic anhydride compounds.
5. according to claim 1 bond encapsulated composite thermoplastic elastic material for PC/PBT alloys, feature exists
In：The mineral filler is one or more of talcum powder, calcium carbonate, land plaster, barium sulfate, mica powder, kaolin.
6. according to claim 1 bond encapsulated composite thermoplastic elastic material for PC/PBT alloys, feature exists
In：The antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters, N, N ' -1,6- inferior hexyls -
Bis- [3- (3,5- di-tert-butyl-hydroxy phenyls) propionamides], the positive octadecanol of 3,5- di-tert-butyl-hydroxy phenyl propionic acid,
It is 1,3,5- tri- (4- tertiary butyl -3- hydroxyl -2,6- dimethyl benzyls) -1,3,5- triazines -2,4,6- (1H, 3H, 5H) triketone, three sweet
Alcohol bis- [3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionic esters], 2,2 '-di-2-ethylhexylphosphine oxide (4- methyl-6-tert butyl benzene
Phenol), phosphorous acid three (2,4- di-tert-butyl-phenyls) ester, bis- (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites, double ten
Eight alkyl pentaerythritol bis-phosphites, four (2,4- di-tert-butyl-phenyls -4,4 '-xenyl) bisphosphonates etc. are one or more
Antioxidant compounds.
7. according to claim 1 bond encapsulated composite thermoplastic elastic material for PC/PBT alloys, feature exists
In：The light stabilizer includes 2,4- dihydroxies benzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- hydroxyl -4- methoxyl groups
Benzophenone, 2- acrylic acid 2- (4- benzoyl -3- hydroxyphenoxies) ethyl ester, 2- (2 '-hydroxyl -5 '-aminomethyl phenyl) benzo
Triazole, 2'- (2'- hydroxyl -3'- tertiary butyl -5'- aminomethyl phenyls) -5- chlorobenzotriazoles, 2- (2'- hydroxyls -3', 5' bis- (a, a-
Dimethyl benzyl) phenyl) benzotriazole, 2- (2 '-hydroxyl -3 ', 5 '-di-tert-butyl-phenyl) -5- chlorinated benzotriazoles, it is bis- (2,
2,6,6- tetramethyl -4- piperidyls) sebacic acid ester, poly-succinic (4- hydroxyl -2,2,6,6- tetramethyl -1- piperidine ethanols) ester,
Poly- { (6- morpholinyl -5- triazine -2,4- diyls) (2,2,6,6- tetramethyl-piperidyls) imido grpup hexa-methylene [(2,2,6,6- tetra-
Methyl piperidine base)-imido grpup], it is one or more of in 2,2,6,6- tetramethyl -4- piperidines stearates.
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| CN109017499A (en) * | 2018-07-02 | 2018-12-18 | 宁波帅特龙集团有限公司 | A kind of Automobile cup supporter liner support button and preparation method thereof |
| CN109320895A (en) * | 2018-09-21 | 2019-02-12 | 南京京锦元科技实业有限公司 | Encapsulated material of a kind of TPE for PBT plastic and preparation method thereof |
| CN109851977A (en) * | 2019-02-13 | 2019-06-07 | 苏州长振新材料科技有限公司 | The conductive thermoplastic elastomer and preparation method thereof of encapsulated polycarbonate |
| CN114621551A (en) * | 2022-03-31 | 2022-06-14 | 宁波市青湖弹性体科技有限公司 | Transparent flame-retardant thermoplastic elastomer for encapsulating PC material and preparation method thereof |
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| CN109017499A (en) * | 2018-07-02 | 2018-12-18 | 宁波帅特龙集团有限公司 | A kind of Automobile cup supporter liner support button and preparation method thereof |
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| CN114621551A (en) * | 2022-03-31 | 2022-06-14 | 宁波市青湖弹性体科技有限公司 | Transparent flame-retardant thermoplastic elastomer for encapsulating PC material and preparation method thereof |
| CN114621551B (en) * | 2022-03-31 | 2023-12-08 | 宁波市青湖弹性体科技有限公司 | Thermoplastic elastomer of transparent flame-retardant encapsulated PC material and preparation method thereof |
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Application publication date: 20180615 |