CN101805475B - Formula of soles of PU-simulated foaming sneakers through injection and manufacturing method - Google Patents
Formula of soles of PU-simulated foaming sneakers through injection and manufacturing method Download PDFInfo
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Abstract
The invention relates to a formula of soles of PU-simulated foaming sneakers through injection, which comprises the following raw materials in percentage by mass: 40 percent of 21 percent ethylene-vinyl acetate copolymer (EVA 7360), 16.7 percent of styrene butadiene copolymer SBBSJT-83, 12.5 percent of ethylene octylene copolymer POE8130, 8.3 percent of ethylene-propylene-diene copolymer 3745P, 65.9 percent of wear-resisting agent A-18, 8.3 percent of talcpowder, 0.25 percent of stearic acid, 0.42 percent of zinc stearate, 0.9 percent of zinc oxide, 0.08 percent of bridging auxiliary agent ET-102, 0.75 percent of bridging agent DCP, 1.7 percent of high-temperature foaming agent AC-6000H, 2.5 percent of titanium white powder R-103 and 1.7 percent of master batch. The preparation method comprises the steps of banburying, mixing, granulation, injection molding, physical property tests and the like. Thus, in the research and development and application, the PU-simulated foaming soles not only have the physical and chemical properties of no crease marks, high elasticity, low compression and wear resistance of PU soles, and but also have the advantages of low production cost, light specific gravity, good limited-slip properties, no hydrolysis and long service life.
Description
Technical field
The present invention relates to a kind of special athletic shoe sole, especially relate to the foamed shoe sole prescription and the method for manufacture thereof of the texture of a kind of PU of having and on-slip again, long service life.
Background technology
China is maximum footwear production and export State of the whole world, and various footwear materials are complete, and wherein the polyurethane PU sole is fashionable for a time.Its wear-resisting good, good springiness, folding resistance is strong and peculiar texture obtains numerous human consumer's favorable comments and approval; But its unit price is high, density greatly, not on-slip, facile hydrolysis be short work-ing life, these weak points have made PU fewer and feweri in the occupation rate in market.Therefore, improve these weak points of PU material, the substitute of seeking and research and develop it is the direction and the inexorable trend of footwear material development.Our everyone life has been come in motion; Also make sports shoes use each environment of human lives; Special in the environment that grease and water are arranged, like oil field, market etc., when athletic shoe sole and wet ground or the ground that is attached with oil stain contact; Water, oil will be attached to sole surface and form moisture film, oil film, and the feasible unexpected danger that takes place of slipping happens occasionally.Like this, wear resistance, non-skid property, hydrolysis is directly to influence footwear work-ing life and safety, comfortable key factor.
In addition, more and more tighter to the requirement of sole function in the world after China's entry into the World Trade Organization, the outlet of the Chinese footwear of so big limitations.Yet, conventional P U expect not on-slip, can hydrolysis, work-ing life short, the high needs that can not satisfy market of cost.In order to increase shoes work-ing life, prevent the generation of the accident of falling down, increasing human consumer and importor; Focus onto on the over-all properties of sole; Like this, research and development PU-simulated foaming sneakers through injection sole guarantees human consumer's interests and security with the use value of further raising shoes; More help improving the quality of China's footwear; Make China in the competition of international overall situation quality awareness in 21 worlds and quality, establish oneself in an unassailable position, continue to keep China footwear outlet the world's strongest nation status.The PU-simulated foaming material for sole of shoe is by EVA, special rubber, plastic cement and multiple auxiliary agent synthetic high molecular polymer; Closely bound up with physics, the chemical property of the material of sole own; Therefore necessary selection and synthetic high abrasion, on-slip, long sole chemical materials of life-span just can be produced the footwear material that really exceeds the PU performance.It is injection molded that conventional P U sole directly passes through injection moulding machine with the urethane of different size, though urethane has its unique physical and chemical performance, can not satisfy the requirement of market to the footwear material.
Summary of the invention
The objective of the invention is almost do not have a difficult problem that non-skid property, density are big again, the life-span is short, a kind of both wear-resisting, good springiness are provided to present PU sole is existing; And on-slip, density is little, the life-span is longer imitative PU formula of soles and method of manufacture thereof.
To achieve these goals, solution of the present invention is following:
Formula of soles of PU-simulated foaming sneakers through injection is EVA21% Injecatable EVA Copolymer 35%-45%, styrene-butadiene-copolymer SBBS JT-83 15%-20%, POE POE8130 10%-15%; Terpolymer EP rubber 3745P 7%-10%, anti-wear agent A-186 5%-7% talcum powder 8%-10%, Triple Pressed Stearic Acid 0.15%-0.35%; Zinic stearas 0.3%-0.5%, zinc oxide 0.6%-1.0%, bridge formation auxiliary agent ET-1020.06%-0.1%; Bridging agent DCP 0.65%-9%; High-temperature foaming agent AC-6000H 1.75%-2.0%, white titanium pigment R-103 2.0%-3.0%, Masterbatch 1.5%-3.0%.
The PU-simulated foaming sneakers through injection sole, its optimum formula is: EVA21% Injecatable EVA Copolymer 40%, styrene-butadiene-copolymer SBBS JT-8316.7%; POE POE8130 12.5%, terpolymer EP rubber 3745P 8.3%, anti-wear agent A-186 5.9% talcum powder 8.3%; Triple Pressed Stearic Acid 0.25%, Zinic stearas 0.42%, zinc oxide 0.9%; Bridge formation auxiliary agent ET-102 0.08%, bridging agent DCP 0.75%, high-temperature foaming agent AC-6000H 1.7%; White titanium pigment R-103 2.5%, Masterbatch 1.7%.
Prescription mainly makes sole have the texture of rubber by the foam introduction of compound footwear material, particularly SBBS of EVA and special rubber, plastic cement synthetic, and with POE, EPDM collocation use wear-resisting, on-slip is more excellent, has the physical and chemical performance of more optimizing than conventional P U.
PU-simulated foaming sneakers through injection preparation of soles method of the present invention may further comprise the steps:
1) pound material
By the prescription weighing raw materials of design, with the separately pack of bridging agent, high-temperature foaming agent, other materials mixes.
2) banburying
Confected materials except that DCP and AC-6000H, is poured in 75 liters of Banbury mixeies, started the Banbury mixer banburying, make mixing of materials even.Banburying time fs is 7-8 minute, and the stirring number of times is 4-5 time.When treating that temperature reaches 110 ℃-112 ℃, add DCP and AC-6000H, start the Banbury mixer banburying once more.The subordinate phase banburying time is 2-3 minute, and the stirring number of times is 2-3 time, and when temperature continued to be elevated to 115 ℃-118 ℃, all raw materials mixed, and pour out material and open refining.
3) open refining
The compound that banburying is good is moulded on 18 cun roller machines thin 2 times, moulds that slice thickness is the 1-1.5 millimeter when thin, and the roller temperature is set at 60 ± 5 ℃.
4) granulation
The compound that on roller, plasticate drops in the tablets press, is a granulated into the particle that diameter is the 2-3 millimeter.The tablets press die head temperature is set at 75 ± 5 ℃, and other three sections temperature are set at 70 ± 5 ℃.
5) injection moulding
The pellet of making prepares by the multiplying power of setting after static 24 hours, injects the footwear mould through computer numerical controlled injection moulding machine, is 180 ± 2 ℃ in die temperature, adds the sulphur time and be 300 ± 20 seconds condition compacted under.
6) thermostat container typing
The sole of gained in (5) is shaped into the foamed profile finished product through thermostat container, and thermostat container flow process condition is: 75 ℃-60 ℃-45 ℃-30 ℃ of temperature, and 200 rev/mins of revolutions, thermostat container length is 12 meters.
7) warehouse-in is taken a sample test, packed to the sole that thermostat container is come out through QC check, surface treatment, rerum natura, and shipment is perhaps waited to make up the big end of rubber.
The present invention compares with conventional P U and not only to have kept PU elasticity height, excellent wear resistance, characteristics that folding resistance is good, and density is little, cost is low, on-slip is good, can not hydrolysis, long service life.
Description of drawings
Do not have
Embodiment
Below in conjunction with embodiment the present invention is further specified.
Formula of soles of PU-simulated foaming sneakers through injection, EVA21% Injecatable EVA Copolymer 35%-45%, styrene-butadiene-copolymer SBBS JT-83 15%-20%; POE POE8130 10%-15%, terpolymer EP rubber 3745P 7%-10%, anti-wear agent A-186 5%-7% talcum powder 8%-10%; Triple Pressed Stearic Acid 0.15%-0.35%, Zinic stearas 0.3%-0.5%, zinc oxide 0.6%-1.0%; Bridge formation auxiliary agent ET-1020.06%-0.1%, bridging agent DCP 0.65%-9%, high-temperature foaming agent AC-6000H 1.75%-2.0%; White titanium pigment R-103 2.0%3.0%, Masterbatch 1.5%-3.0%.
The PU-simulated foaming sneakers through injection sole, optimum formula is: EVA21% Injecatable EVA Copolymer 40%, styrene-butadiene-copolymer SBBS JT-83 16.7%; POE POE8130 12.5%, terpolymer EP rubber 3745P 8.3%, anti-wear agent A-1865.9% talcum powder 8.3%; Triple Pressed Stearic Acid 0.25%, Zinic stearas 0.42%, zinc oxide 0.9%; Bridge formation auxiliary agent ET-102 0.08%, bridging agent DCP 0.75%, high-temperature foaming agent AC-6000H 1.7%; White titanium pigment R-1032.5%, Masterbatch 1.7%.
PU-simulated foaming sneakers through injection preparation of soles method, it mainly may further comprise the steps:
1) pound material
By the prescription weighing raw materials of design, with the separately pack of bridging agent, high-temperature foaming agent, other materials mixes.
2) banburying
Confected materials except that DCP and AC-6000H, is poured in 75 liters of Banbury mixeies, started the Banbury mixer banburying, make mixing of materials even.Banburying time fs is 7-8 minute, and the stirring number of times is 4-5 time.When treating that temperature reaches 110 ℃-112 ℃, add DCP and AC-6000H, start the Banbury mixer banburying once more.The subordinate phase banburying time is 2-3 minute, and the stirring number of times is 2-3 time, and when temperature continued to be elevated to 115 ℃-118 ℃, all raw materials mixed, and pour out material and open refining.
3) open refining
The compound that banburying is good is moulded on 18 cun roller machines thin 2 times, moulds that slice thickness is the 1-1.5 millimeter when thin, and the roller temperature is set at 60 ± 5 ℃.
4) granulation
The compound that on roller, plasticate drops in the tablets press, is a granulated into the particle that diameter is the 2-3 millimeter.The tablets press die head temperature is set at 75 ± 5 ℃, and other three sections temperature are set at 70 ± 5 ℃.
5) injection moulding
The pellet of making prepares by the multiplying power of setting after static 24 hours, injects the footwear mould through computer numerical controlled injection moulding machine, is 180 ± 2 ℃ in die temperature, adds the sulphur time and be 300 ± 20 seconds condition compacted under.
6) thermostat container typing
The sole of gained in (5) is shaped into the foamed profile finished product through thermostat container, and thermostat container flow process condition is: 75 ℃-60 ℃-45 ℃-30 ℃ of temperature, and 200 rev/mins of revolutions, thermostat container length is 12 meters.
7) warehouse-in is taken a sample test, packed to the sole that thermostat container is come out through QC check, surface treatment, rerum natura, and shipment is perhaps waited to make up the big end of rubber.
The product that prescription of the present invention and technology are processed can carry out the test of rerum natura: the imitative PU sole product that will process is after lining, laboratory (23 ℃) is placed 24 hours; Can carry out the test of rerum naturas such as (DIN) is wear-resisting, hardness, density, write down wear-resisting and test value and on-slip experiments such as hardness number, density.Imitative PU shoe soles slip stopping test is with the SAFVA STM-603 of European Union standard on-slip test machine.
Concrete, the formula material scope and the usage ratio of ejaculation PU-simulated foaming sole according to the invention see the following form:
Table 1
Make sample (implement appearance) by following prescription, and measure in inspection center that hardness, density, DIN are wear-resisting, dry type/wet type on-slip coefficient, tear, physical indexs (annotate: it is in order to confirm the production formula of this material of research and development that listed sample is implemented) such as tension, unit elongation.
Embodiment 1: be the experimental formula that designs by traditional thinking mode, its consumption is the research and development samples, with the gram metering.
Table 2
Embodiment 2: similar with embodiment 1, its difference is that composition of raw materials sees table 3.
Table 3
Embodiment 3: similar with embodiment 2, its difference is that composition of raw materials sees table 4.
Table 4
Embodiment 4: on the basis of embodiment 3, change POE8130 into 8003,
EPDM3745P changes 3722P into, and its composition of raw materials is seen table 5.
Table 5
Embodiment 5: on the basis of embodiment 4 prescriptions, change SEBS 1515 into SBBSJT-83, its composition of raw materials is seen table 6.
Table 6
Embodiment 6: on the basis of embodiment 5, change EVA3212 into EVA7360, POE8003 changes POE8130 into, and EPDM3722P changes 3745P into, and its composition of raw materials is seen table 7.
Table 7
Embodiment 7: all material is finely tuned, obtain final prescription, its composition of raw materials is seen table 8.
Table 8
For result of study can better be described; The ratio that changes EVA, POE, SBBS, EPDM respectively makes it not meet or exceed the optimized proportion scope; Comparative example 1 is that the POE ratio is not in the optimized proportion scope; Comparative example 2 be SBBS not in the optimized proportion scope, comparative example 3EPDM has surpassed the optimized proportion scope, comparative example 4 is POE, SBBS, EPDM, all less than in the optimized proportion scope.Make sample (comparative example) according to the following table prescription, and the physical index of testing by the requirement of surveying embodiment in inspection center, its result does a comparison at other in next table.
Comparative example 1 (rerum natura is defective): composition of raw materials is seen table 9.
Table 9
Comparative example 2 (rerum natura is defective): composition of raw materials is seen table 10.
Table 10
Comparative example 3 (rerum natura is defective): composition of raw materials is seen table 11
Table 11
Comparative example 4 (rerum natura is defective): composition of raw materials is seen table 12
Table 12
Embodiment 1-7 and comparative example 1-4 physical property measurement result see: table 13
| Test result examination example | Hardness Asker.C | Proportion g/mm 3 | Tension Mpa | Unit elongation % | Tear N/mm | The wear-resisting mm of DIN 3 | Compression ratio % | The on-slip test |
| Standard | 60±3 | 0.3±0.02 | ≥3.0 | ≥300 | ≥4.0 | ≤120 | ≤35 | Dry type: >=0.55 wet type: >=045 |
| Implement examination example 1 | 63 | 0.3 | 3.2 | 320 | 4.2 | 123 | 35.8 | Dry type: 0.51 wet type: 0.35 |
| Implement examination example 2 | 63 | 0.285 | 3.3 | 325 | 4.3 | 125 | 36 | Dry type: 0.49 wet type: 0.38 |
| Implement examination example 3 | 63 | 0.301 | 3.1 | 280 | 3.8 | 124 | 34.8 | Dry type: 0.52 wet type: 0.41 |
| Implement examination example 4 | 64 | 0.298 | 3.3 | 295 | 4.2 | 131 | 37.2 | Dry type: 0.48 wet type: 0.4 |
| Implement examination example 5 | 65 | 0.31 | 3.0 | 330 | 3.95 | 135 | 36.1 | Dry type: 0.53 wet type: 0.41 |
| Implement examination example 6 | 64 | 0.306 | 3.5 | 345 | 4.25 | 108 | 33 | Dry type: 0.52 wet type: 0.46 |
| Implement examination example 7 | 61 | 0.29 | 3.3 | 350 | 4.5 | 101 | 31 | Dry type: 0.585 wet type: 0.485 |
| Comparative example 1 | 62 | 0.31 | 3.2 | 315 | 3.9 | 115 | 33 | Dry type: 0.52 wet type: 0.40 |
| Comparative example 2 | 65 | 0.3 | 3.4 | 285 | 4.1 | 121 | 37 | Dry type: 0.41 wet type: 0.31 |
| Comparative example 3 | 63 | 0.32 | 2.9 | 325 | 3.8 | 123 | 36 | Dry type: 0.48 wet type: 0.36 |
| Comparative example 4 | 64 | 0.3 | 3.5 | 345 | 4.6 | 132 | 38 | Dry type: 0.40 wet type: 0.29 |
From above physical property measurement result, the whole rerum natura of embodiment is better than comparative example, and particularly anti-slip effect embodiment is greatly improved than comparative example.
At the bottom of the PU-simulated foaming sneakers through injection by our company invention, characteristics such as elasticity is high at the bottom of the conventional P U, compression ratio is little, folding resistance is good have not only been kept; And density is little, anti-slip effect is good, and not hydrolysis long service life will become the upgrading products of conventional P U sole at the bottom of this sports shoes.
Claims (6)
1. the PU-simulated foaming sneakers through injection sole is characterized in that: EVA21% Injecatable EVA Copolymer 35%-45%, styrene-butadiene-copolymer SBBS JT-83 15%-20%; POE POE8130 10%-15%, terpolymer EP rubber 3745P 7%-10%, anti-wear agent A-186 5%-7%; Talcum powder 8%-10%, Triple Pressed Stearic Acid 0.15%-0.35%, Zinic stearas 0.3%-0.5%; Zinc oxide 0.6%-1.0%, bridge formation auxiliary agent ET-102 0.06%-0.1%, bridging agent DCP 0.65%-9%; High-temperature foaming agent AC-6000H1.75%-2.0%, white titanium pigment R-103 2.0%-3.0%, Masterbatch 1.5%-3.0%.
2. the PU-simulated foaming sneakers through injection sole is characterized in that: EVA21% Injecatable EVA Copolymer 40%, styrene-butadiene-copolymer SBBS JT-83 16.7%; POE POE8130 12.5%, terpolymer EP rubber 3745P 8.3%, anti-wear agent A-1865.9%; Talcum powder 8.3%, Triple Pressed Stearic Acid 0.25%, Zinic stearas 0.42%; Zinc oxide 0.9%, bridge formation auxiliary agent ET-102 0.08%, bridging agent DCP 0.75%; High-temperature foaming agent AC-6000H 1.7%, white titanium pigment R-103 2.5%, Masterbatch 1.7%.
3. like the method for manufacture of right 1 or 2 described PU-simulated foaming sneakers through injection soles, it is characterized in that may further comprise the steps:
1) pound material
By the design the prescription weighing raw materials and mix, except that DCP and AC-6000H;
2) banburying
Confected materials except that DCP and AC-6000H, is poured in 75 liters of Banbury mixeies, started the Banbury mixer banburying; Make mixing of materials even, when treating that temperature reaches 110 ℃-112 ℃, add DCP and AC-6000H; Start the Banbury mixer banburying once more; When temperature continued to be elevated to 115 ℃-118 ℃, all raw materials mixed, and pour out material and open refining;
3) open refining
The compound that banburying is good is moulded on 18 cun roller machines thin 2 times, moulds that slice thickness is the 1-1.5 millimeter when thin;
4) granulation
The compound that on roller, plasticate drops in the tablets press, is a granulated into the particle that diameter is the 2-3 millimeter;
5) injection moulding
The pellet of making prepares through computer numerical controlled injection moulding machine by the multiplying power of setting and injects the footwear mould, is 180 ± 2 ℃ in die temperature, adds the sulphur time and be 300 ± 20 seconds condition compacted under;
6) thermostat container typing
The sole of gained in (5) is shaped into the foamed profile finished product through thermostat container, and thermostat container flow process condition is: 75 ℃-60 ℃-45 ℃-30 ℃ of temperature, and 200 rev/mins of revolutions, thermostat container length is 12 meters;
7) warehouse-in is taken a sample test, packed to the sole that thermostat container is come out through QC check, surface treatment, rerum natura, and shipment is perhaps waited to make up the big end of rubber.
4. the method for manufacture of PU-simulated foaming sneakers through injection sole according to claim 3 is characterized in that: in the said step (2), banburying time fs is 7 minutes, and the banburying mixing temperature is 110 ℃-112 ℃.
5. the method for manufacture of PU-simulated foaming sneakers through injection sole according to claim 3 is characterized in that: in the said step (2), add DCP and AC-6000H banburying 3 minutes again, banburying blended blanking temperature is 115-118 ℃.
6. the method for manufacture of PU-simulated foaming sneakers through injection sole according to claim 3 is characterized in that: the mould multiplying power is 140% sole wear resisting property DIN≤120mm in the said step (5)
3
Non-skid property: dry type>=0.55, wet type>=0.45; Density is: 0.3 ± 0.03g/cm
3
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| JPH09180689A (en) * | 1995-12-27 | 1997-07-11 | Idemitsu Petrochem Co Ltd | Battery jar material for sealed secondary battery and battery jar for sealed secondary battery with the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101148528A (en) * | 2007-11-02 | 2008-03-26 | 上海金发科技发展有限公司 | Method for preparing low-contraction high-fluidity high-toughness polypropylene |
| CN101575434A (en) * | 2009-06-23 | 2009-11-11 | 安徽纵横高科电缆股份有限公司 | Oilproof cabtyre insulation material |
Non-Patent Citations (1)
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| JP特开平9-180689A 1997.07.11 |
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