CN102532778A - Thermoplastic polyurethane elastomer (TPE) door seal for refrigerator and freezer and preparation method thereof - Google Patents
Thermoplastic polyurethane elastomer (TPE) door seal for refrigerator and freezer and preparation method thereof Download PDFInfo
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- CN102532778A CN102532778A CN2011100359133A CN201110035913A CN102532778A CN 102532778 A CN102532778 A CN 102532778A CN 2011100359133 A CN2011100359133 A CN 2011100359133A CN 201110035913 A CN201110035913 A CN 201110035913A CN 102532778 A CN102532778 A CN 102532778A
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Abstract
The invention discloses a thermoplastic polyurethane elastomer (TPE) door seal for a refrigerator and a freezer and a preparation method thereof. The TPE door seal is a TPE door seal rubber sleeve which is manufactured by adopting the following raw materials by mass: 15% to 50% of SEBS, 20% to 50% of white mineral oil, 10% to 48% of polypropylene, 10% to 45% of ethylene vinyl acetate (EVA), 5% to 25% of calcium carbonate, 0.1% to 0.6% of antioxygen and 0.1% to 0.6% of lubricant. The EVA material is introduced into a TPE door seal formula system, so that weather resistance, aging resistance and adhesiveness of the materials can be improved. The EVA material is added into a blending system of SEBS, white mineral oil, propene polymer and calcium carbonate, and low temperature resistance of products can be improved by utilizing good low temperature resistance of the EVA material. Compared with the polyvinyl chloride (PVC) material, the TPE material of the blending system of the SEBS, the white mineral oil, the propene polymer (PP), the EVA and the calcium carbonate has better low temperature resistance, and the problems of gap lighting, dropping and damage of the seal of the refrigerator and the freezer caused by the fact that the PVC material is poor in cold resistance and low temperature impact strength and the like can be resolved.
Description
Technical field
The present invention relates to the door encapsulation technique field that refrigerator, refrigerator are used, relate in particular to gasket of a kind of TPE material and preparation method thereof, TPE gasket material belongs to the thermoplastic elastomer of SEB S/PP blend.
Background technology
At present, the gasket that the refrigerator of selling on the market, refrigerator are used is most to adopt soft PVC material to form, and receives the Effect on Performance of PVC material own; In gasket use and installation process; Exist following weak point: the gasket resistance to low temperature of (1) PVC material is poor, receives the circumstance of temperature difference variable effect quite obvious, and the variation of summer and winter temperature is very big to the influence of PVC gasket hardness; Cause gasket sealing property variation, thereby make the energy consumption of product increase; (2) the anti-migration performance of gasket is relatively poor: because the PVC material has added softening agent in manufacturing processed, softening agent is prone to move on the ABS/PS plastic-absorbing component, corrodes the inner container of icebox material easily, and softening agent has certain carcinogenesis; (3) not environmental protection: PVC belongs to halide-containing, is divided into non-environmental protection material in the world, its not environmental protection in processing and use; And PVC performance in removal process can lose about 30%, is unfavorable for recycling; (4) its ageing resistance is poor: owing to flexible PVC is made up of polyvinyl chloride resin powder, multiple softening agent and auxiliary material, and along with the prolongation of duration of service, the hardening of PVC gasket, variable color, aging, thus influence its outward appearance and stopping property, reduction of service life.
For solving the problems of the technologies described above; The now existing correlation technique that the TPE material is applied to the gasket that refrigerator, refrigerator use; Existing TPE formula system mainly is made up of SEBS+ white mineral oil+PP+PE+ lime carbonate+auxiliary agent; The main effect that white mineral oil plays in formula system is the viscosity that reduces melt, improves the flowability of melt, regulates the hardness of product and the processing characteristics that improves SEBS; It is the hardness of regulating product, molten finger, the workability that improves whole formula system and the formability of gasket that another component PP (Vestolen PP 7052) material in the TPE formula system mainly acts on, if there is not adding SEBS+ white mineral oil+PE of PP to do the seal strip for refrigerator door difficult forming.
Summary of the invention
One of the object of the invention is the deficiency to above-mentioned prior art; Provide a kind of refrigerator, refrigerator with TPE elastomerics gasket; The present invention is used for the interior external door of refrigeration equipments such as refrigerator, refrigerator and seals up; Have that environmental protection, hardness are influenced under little, the low temperature by variation of ambient temperature to keep excellent sealing performance and elasticity, energy consumption is low and advantage such as long service life; And the present invention adds the EVA material in the co-mixing system of SEBS, white mineral oil, PP and lime carbonate, can improve weather-proof, ageing-resistant performance, the binding property of material; Secondly, in the co-mixing system of SEBS, white mineral oil, PP and lime carbonate, add the EVA material, utilize EVA material good low-temperature resistance performance, can improve the resistance to low temperature of product.The present invention also provides a kind of refrigerator, the refrigerator preparation method with TPE elastomerics gasket.
For solving the problems of the technologies described above, the present invention adopts following technical scheme to be achieved:
A kind of refrigerator, refrigerator are with TPE elastomerics gasket, and both TPE elastomerics door sealing cover is characterized in that, said TPE elastomerics door sealing cover adopts following each raw material by mass percentage to process:
SEBS 15-50％；
White mineral oil 20-50%;
Vestolen PP 7052 10-48%;
EVA 10-45％；
CaCO3 5-25％；
Oxidation inhibitor 0.1-0.6%;
Lubricant 0.1-0.6%.
Wherein, said oxidation inhibitor is Hinered phenols or phosphite ester kind antioxidant.
Lubricated and outer lubricated in said lubricant comprises, said lubricant is one or more of hydro carbons, fatty acid, fatty acid acyl amine, ester class, alcohols, metallic soap class, compounded lubricant.
Further, also include pigment in the raw material of said TPE elastomerics door sealing cover, the mass percent that said pigment accounts for the raw material total mass is 0.1-1%.
Wherein, said pigment be selected from pigment dyestuff, mineral dye, dyestuff, special tinting material one or more.
Further again, the present invention also provides a kind of method for preparing refrigerator, refrigerator with TPE elastomerics gasket, and this method may further comprise the steps:
1), each raw material of TPE elastomerics door sealing cover is weighed respectively by following mass percent:
SEBS 15-50％，
White mineral oil 20-50%,
Vestolen PP 7052 10-48%,
EVA 10-45％，
CaCO3 5-25％，
Oxidation inhibitor 0.1-0.6%,
Lubricant 0.1-0.6%,
Mix the formation material then, material is deposited certain hour after, put into the twin screw extruder of L/D >=48 again and extrude the TPE elastomer particles;
2), the TPE elastomer particles of above-mentioned preparation is extruded a sealing cover through single screw extrusion machine, cut behind the cooling and shaping, deposit certain hour again, process TPE elastomerics door sealing cover finished product;
3), with above-mentioned TPE elastomerics door sealing cover finished product by 45 degree corner cuts cuttings, external door sealing cover finished product penetrates magnetic stripe, after welding, processes TPE elastomerics gasket.
Wherein, Said oxidation inhibitor is Hinered phenols or phosphite ester kind antioxidant; Lubricated and outer lubricated in said lubricant comprises, said lubricant is one or more of hydro carbons, fatty acid, fatty acid acyl amine, ester class, alcohols, metallic soap class, compounded lubricant.
Further again, also comprise in pigment dyestuff, mineral dye, dyestuff, the special tinting material one or more in the raw material of said TPE elastomerics door sealing cover, the mass percent that said pigment accounts for the raw material total mass is 0.1-1%.
Further, said preparation refrigerator, refrigerator are with the method steps 1 of TPE elastomerics gasket) in certain hour be 2～24 hours; Said step 2) certain hour in is 12～24 hours.
Because adopt technical scheme of the present invention, the present invention has following beneficial effect: at first,, can improve weather-proof, the ageing-resistant performance of material, increase the service life owing to the no carbon-carbon double bond of EVA material itself; Secondly, add the EVA material and improve the elastomeric binding property of TPE; Once more, in the co-mixing system of SEBS, white mineral oil, PP and lime carbonate, add the EVA material, utilize EVA material good low-temperature resistance performance, can improve the resistance to low temperature of product.
Description of drawings
Fig. 1 is the making schema of the TPE elastomer particles in the one embodiment of the invention;
Fig. 2 is the making schema of the TPE elastomerics gasket in the one embodiment of the invention.
Embodiment
Through embodiment and accompanying drawing the present invention is done further elaboration below.
In following examples, (unit is g/cm to Zhou Midu respectively
3), 190 ℃ of 5kg of melt flow rate(MFR) (g/10min), hardness (Shore A), tensile strength (MPa) and elongation at break (%) be used as estimating the index of product.Wherein, the addition of TPE density of material and lime carbonate and the density of other raw materials itself are relevant, increase the add-on of lime carbonate, and density values is big more, and cost is low more; Melt flow rate(MFR) is product to be placed under 190 ℃ of temperature be added with the index that 5 kgfs recorded under 4 minutes; Hardness is relevant with the ratio of white mineral oil/PP.
SEBS is polystyrene-poly ethylene/butylene-polystyrene block copolymer, is a kind of multiduty novel thermoplastic elastomer, and SEBS not only has excellent ageing-resistant performance, and has good mechanical performance, chemicals-resistant corrosion and excellent lower temperature resistance.At normal temperatures; The PS of SEBS (PS) section is the section of moulding and intermediary ethylene/butylene (EB) elastomeric block firmly, and these two blocks are inconsistent on thermodynamics, are separated thereby produce two; Be the micron-scale phase separation state; The PS section of SEBS forms phase region, is scattered in the rubber phase of EB section formation, and forms physical cross-linked network with the EB section.SEBS had both been had a snappiness of rubber, at high temperature showed resin flow property, and processing characteristics is good.
Injecatable EVA Copolymer (being also referred to as ethene-vinyl acetate copolymer) is by ethene (E) and vinyl acetate (VA) copolymerization and make, and English name is: Ethylene Vinyl Acetate, abbreviate EVA as, or E/VAC.Polymerization method is with high pressure mass polymerization (plastics are used), solution polymerization (PVC processing aid), letex polymerization (tackiness agent), suspension polymerization.Vinyl acetate (VA) content is higher than 30% employing letex polymerization, and what vinyl acetate content was low just uses the high pressure mass polymerization.Just the polarity owing to acetate moiety in the EVA resin can make its elasticity and viscosity increase, and crystallinity and electrical property descend, and are dissolved in varsol and oils.
Fig. 1 shows the making schema of the TPE elastomer particles in the one embodiment of the invention, and Fig. 2 then is the making schema that the present invention prepares an embodiment of TPE elastomerics gasket.Below in conjunction with the making flow process of Fig. 1 and Fig. 2, specific embodiments of the invention is done concrete description.
Embodiment 1
Prepare TPE elastomerics gasket according to following method:
At first, preparation TPE elastomer particles:
Referring to shown in Figure 1, weigh according to each constituent mass among table 1 embodiment 1, various raw materials are put into high-speed mixer mix; After unloading material then and depositing 2 hours; Put into the twin screw extruder of L/D >=48 again, extruding pelletization is processed the TPE elastomer particles; Cooling back pelletizing, the packing warehouse-in is subsequent use.
Then, preparation TPE elastomerics gasket:
Referring to shown in Figure 2, at first,, extrude a sealing cover through single screw extrusion machine with the TPE elastomer particles of above-mentioned preparation, through behind the cooling and shaping, according to after the length requirement cutting, deposited 24 hours again, promptly process TPE elastomerics door sealing cover, subsequent use.
Then, by 45 degree corner cut cuttings, inside door sealing cover need not to penetrate magnetic stripe with the above-mentioned TPE elastomerics door sealing cover that makes; External door sealing cover penetrates magnetic stripe, after welding, promptly processes TPE elastomerics gasket; With the TPE elastomerics gasket finished product packing that makes, warehouse-in stores.Measure density of product, melt flow rate(MFR), tensile strength, elongation at break and hardness respectively according to examination criteria ASTMD792, ASTMD 1238, ASTMD412, ASTMD412 and ASTMD2240.
Oxidation inhibitor described in the present embodiment is Hinered phenols or phosphite ester kind antioxidant, and it is oxidation inhibitor that present embodiment is chosen four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Certainly oxidation inhibitor also can be selected from following one or more, specific as follows, for example β (3; 5-di-t-butyl-4-hydroxybenzene) propionic acid octadecanol ester, three (2.4-di-tert-butyl-phenyl) phosphorous acid ester, two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites; Lubricated and outer lubricated in two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites etc., said lubricant comprise, can be selected from hydro carbons, fatty acid, fatty acid acyl amine, ester class, alcohols, metallic soap class, compounded lubricant etc.; Present embodiment is chosen stearylamide, erucicamide, ethylene bis stearamide, Triple Pressed Stearic Acid; Calcium stearate, the optional pigment dyestuff of said pigment, mineral dye, dyestuff, special tinting material, present embodiment is chosen phthalocyanine green; Phthalocyanine blue, white titanium pigment, carbon black.
As scheme more specifically; The raw material of above-mentioned preparation TPE elastomerics door sealing cover also includes pigment; The mass percent that the pigment that is added accounts for the raw material total mass is 0.1-1%, after pigment and other raw materials mix, so that process the TPE elastomerics door sealing cover of required color.Shelf-time in the said step 1) is 2～24 hours, said step 2) in shelf-time be 12～24 hours.
Embodiment 2
According to the method like embodiment 1, the quality of embodiment 2 each component is weighed and is prepared TPE elastomerics gasket in the according to the form below 1.And according to measuring its index with embodiment 1 identical method.
Present embodiment and embodiment 1 difference are that said oxidation inhibitor is two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites, and be lubricated and outer lubricated in said lubricant comprises, and is selected from stearylamide; Ethylene bis stearamide, erucicamide, Triple Pressed Stearic Acid; Calcium stearate; Said pigment is phthalocyanine green, phthalocyanine blue, white titanium pigment, carbon black etc.
Embodiment 3
According to the method like embodiment 1, the quality of embodiment 3 each component is weighed and is prepared TPE elastomerics gasket in the according to the form below 1.And according to measuring its index with embodiment 1 identical method.Present embodiment and embodiment 1 difference are that said oxidation inhibitor is β (3,5-di-t-butyl-4-hydroxybenzene) propionic acid octadecanol ester, and be lubricated and outer lubricated in said lubricant comprises; Be selected from stearylamide, ethylene bis stearamide, erucicamide; Triple Pressed Stearic Acid, calcium stearate, said pigment are phthalocyanine green; Phthalocyanine blue, white titanium pigment, carbon black etc.
The main performance index of the content of each raw material and the TPE elastomerics gasket processed among the table 1 embodiment 1-3
The standard of the main performance index of table 2TPE elastomerics gasket
| Test item | Unit | Technical indicator | Examination criteria |
| Density | g/cm 3 | 0.89-1.2 | ASTMD792 |
| 190 ℃ of 5kg of melt flow rate(MFR) | g/10min | 1-26 | ASTMD1238 |
| Tensile strength | MPa | ≥8 | ASTMD412 |
| Elongation at break | ％ | ≥400 | ASTMD412 |
| Hardness | Shore?A | 60-75 | ASTMD2240 |
Table 1 is each material content of the TPE elastomerics gasket that makes among the foregoing description 1-3 and each item performance index that record; Table 2 is each item index standards of hardness in the table 1, melt flow rate(MFR), tensile strength, elongation at break and density; Table 1 and table 2 are compared and can know; The content of each raw material meets the requirement of each component concentration of TPE formula system among the present invention among the embodiment 1-3; And the index of the evaluation product performance such as density, melt flow rate(MFR), hardness, tensile strength and elongation at break of the TPE elastomerics gasket that it makes also meets the standard of each item index, and the TPE elastomerics gasket excellent property that makes is described.
The changes in hardness rate of the TPE elastomerics gasket that mensuration makes by each Example formulations in the table 1; Measure gasket earlier and put into refrigerator hardness before; Measure then and place the hardness of-30 ℃ of refrigerators after 6 hours, calculate the velocity of variation of gasket hardness, experiment shows that the TPE elastomerics gasket velocity of variation that embodiment 1-3 makes is less; As shown in table 3, explain that its resistance to low temperature is good.The welding force of the TPE elastomerics gasket that mensuration makes according to each Example formulations in the table 1; The welding force of the TPE elastomerics gasket that embodiment 1-3 makes is bigger; Gasket is not easy to tear; And its smooth surface, do not have overlap, explain that the adding of EVA material can improve the bond properties of TPE elastomerics gasket.
The low temperature resistant experiment correlation data of the TPE elastomerics gasket that table 3 embodiment 1-3 makes
Adopt technical scheme of the present invention not only can improve the resistance to low temperature of gasket product, and, can improve weathering resistance, the ageing-resistant performance of material, increase the service life, improve the binding property of material owing to the no carbon-carbon double bond of EVA material itself.
The above only is preferred embodiment of the present invention, is not to be the restriction of the present invention being made other form, and any professional and technical personnel of being familiar with possibly utilize the technology contents of above-mentioned announcement to change or be modified as the equivalent embodiment of equivalent variations.But everyly do not break away from technical scheme content of the present invention, to any simple modification, equivalent variations and remodeling that above embodiment did, still belong to the protection domain of technical scheme of the present invention according to technical spirit of the present invention.
Claims (10)
1. a refrigerator, refrigerator comprise TPE elastomerics door sealing cover with TPE elastomerics gasket, it is characterized in that, said TPE elastomerics door sealing cover adopts following each raw material by mass percentage to process:
SEBS 15-50％；
White mineral oil 20-50%;
Vestolen PP 7052 10-48%;
EVA 10-45％；
CaCO
3 5-25％；
Oxidation inhibitor 0.1-0.6%;
Lubricant 0.1-0.6%.
2. a kind of refrigerator according to claim 1, refrigerator is characterized in that with TPE elastomerics gasket said oxidation inhibitor is Hinered phenols or phosphite ester kind antioxidant.
3. a kind of refrigerator according to claim 1, refrigerator are with TPE elastomerics gasket; It is characterized in that; Lubricated and outer lubricated in said lubricant comprises, said lubricant is one or more of hydro carbons, fatty acid, fatty acid acyl amine, ester class, alcohols, metallic soap class, compounded lubricant.
4. a kind of refrigerator according to claim 1, refrigerator is characterized in that with TPE elastomerics gasket, also include pigment in the raw material of said TPE elastomerics door sealing cover, and the mass percent that said pigment accounts for the raw material total mass is 0.1-1%.
5. a kind of refrigerator according to claim 4, refrigerator is characterized in that with TPE elastomerics gasket said pigment is one or more in pigment dyestuff, mineral dye, dyestuff, the special tinting material.
6. method for preparing the described refrigerator of claim 1, refrigerator with TPE elastomerics gasket is characterized in that this method may further comprise the steps:
1), each raw material of TPE elastomerics door sealing cover is weighed respectively by following mass percent:
SEBS 15-50％，
White mineral oil 20-50%,
Vestolen PP 7052 10-48%,
EVA 10-45％，
CaCO3 5-25％，
Oxidation inhibitor 0.1-0.6%,
Lubricant 0.1-0.6%,
Mix the formation material then, material is deposited certain hour after, put into the twin screw extruder of L/D >=48 again and extrude the TPE elastomer particles;
2), the TPE elastomer particles of above-mentioned preparation is extruded a sealing cover through single screw extrusion machine, cut behind the cooling and shaping, deposit certain hour again, process TPE elastomerics door sealing cover finished product;
3), with above-mentioned TPE elastomerics door sealing cover finished product by 45 degree corner cuts cuttings, external door sealing cover finished product penetrates magnetic stripe, after welding, processes TPE elastomerics gasket.
7. method according to claim 6 is characterized in that, said oxidation inhibitor is Hinered phenols or phosphite ester kind antioxidant; Said lubricant is one or several in hydro carbons, fatty acid, fatty acid acyl amine, ester class, alcohols, metallic soap class, the compounded lubricant.
8. method according to claim 6 is characterized in that, also includes pigment in the raw material of said TPE elastomerics door sealing cover, and the mass percent that said pigment accounts for the raw material total mass is 0.1-1%.
9. method according to claim 8 is characterized in that, said pigment is one or more of pigment dyestuff, mineral dye, dyestuff, special tinting material.
10. according to each described method in the claim 6 to 8, it is characterized in that the certain hour in the said step 1) is 2～24 hours; Said step 2) certain hour in is 12～24 hours.
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| CN2011100359133A CN102532778A (en) | 2010-12-31 | 2011-01-25 | Thermoplastic polyurethane elastomer (TPE) door seal for refrigerator and freezer and preparation method thereof |
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| CN2011100359133A CN102532778A (en) | 2010-12-31 | 2011-01-25 | Thermoplastic polyurethane elastomer (TPE) door seal for refrigerator and freezer and preparation method thereof |
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| CN104774417A (en) * | 2015-03-17 | 2015-07-15 | 宁波日樱电器有限公司 | Refrigerator sealing strip material and preparation method thereof |
| CN104774417B (en) * | 2015-03-17 | 2018-10-26 | 宁波日樱电器有限公司 | A kind of refrigerator sealing strip material and preparation method thereof |
| CN106589763A (en) * | 2016-12-30 | 2017-04-26 | 台橡（上海）实业有限公司 | Thermoplastic elastomer low density extrusion foam sealing strip material and preparation method |
| EP3360660B1 (en) * | 2017-02-14 | 2023-10-04 | Nitto Belgium N.V | Sound and vibration damping sealing member based on thermoplastic elastomers or thermosetting resins |
| CN108795065A (en) * | 2018-06-12 | 2018-11-13 | 安徽万朗磁塑股份有限公司 | One kind being used for dish-washing machine thermoplastic elastomer (TPE) pellet and preparation method |
| CN109535745A (en) * | 2018-11-22 | 2019-03-29 | 袁进 | A kind of refrigerator sealing strip thermoplastic elastic material and preparation method thereof |
| CN110218459A (en) * | 2019-05-29 | 2019-09-10 | 江苏中利集团股份有限公司 | A kind of TPE insulating materials |
| CN111978648A (en) * | 2020-08-25 | 2020-11-24 | 南通大学 | Environment-friendly elastomer material for refrigerator sealing strip and preparation method thereof |
| CN115304859A (en) * | 2022-08-30 | 2022-11-08 | 昆山浩恩高分子材料有限公司 | Environment-friendly TPE composite material and preparation method thereof |
| CN115304859B (en) * | 2022-08-30 | 2023-08-29 | 昆山浩恩高分子材料有限公司 | Environment-friendly TPE composite material and preparation method thereof |
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Application publication date: 20120704 |