CN102634131B - Low-density PVC (Poly Vinyl Chloride) injection-molded shoe material and preparation method thereof - Google Patents
Low-density PVC (Poly Vinyl Chloride) injection-molded shoe material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a low-density PVC (Poly Vinyl Chloride) injection-molded shoe material and a preparation method thereof. The low-density PVC injection-molded shoe material comprises raw materials of poly vinyl chloride, a stabilizing agent, a plasticizer, a lubricant, a foaming agent and rubber powder. The preparation method provided by the invention comprises the following steps of: preparing a composite foaming agent; then mixing and pelleting the raw materials; and finally preparing the shoe material through injection molding. According to the low-density PVC injection-molded shoe material provided by the invention, the defect that the conventional PVC injection-molded shoe material cannot be efficiently foamed is overcome, so that the shoe material provided by the invention has the advantages of good foaming effect and low density.
Description
Technical field
The present invention relates to a kind of Foamed polyvinyl chloride material and preparation method thereof, relate in particular to a kind of injection molding low density polyvinyl-chloride footwear material and preparation method thereof.
Background technology
Polyvinyl chloride (PVC) material being widely used at home, because it is with low cost, PVC has irreplaceable status in footwear material field.But at present the density of PVC footwear material is higher, wear heavylier, and flexibility is inadequate, wears fatiguability.In order to reduce the density of pvc material, conventionally adopt foam polyvinyl chloride to reach the effect of light weight, conventional foaming method has chemical foaming and physical blowing.Physical blowing can make material have very little abscess, and density is low, but physical blowing requires equipment precision high, and technology control difficulty is large, and corresponding cost is also high; And adopt chemical foaming relative cost low, be the most suitable method of making foamed shoe sole.Common chemical foaming method is normally directly in material, to add chemical foaming agent, then produces pvc material by injection moulding or die press technology for forming.The foaming control ratio of PVC die press technology for forming is easier to, and therefore the PVC material of low-density compression molding is very common.But for injection molding process, it is larger that difficulty is controlled in foaming, foam structure, abscess density are difficult to control, often occur collapse hole and and hole, and abscess is inhomogeneous.Therefore, the injection molding footwear material of polyvinyl chloride density is in the market all at 1.2g/cm
3above.Rarely has the low density polyvinyl-chloride footwear material of injection foaming.
Summary of the invention
Therefore,, in order to solve the problems such as the density of injection moulding PVC footwear material in prior art is too high, and flexibility is poor, the invention provides the high-foaming polyvinyl chloride injection moulding footwear material of a kind of uniform in foaming, densification.
The present invention for the technical scheme that its technical problem of solution adopts is:
A kind of low density PVC injection molding footwear material, is characterized in that, described low density PVC injection molding footwear material comprises the raw material of following weight part:
Described whipping agent comprises endothermic blowing agent, heat release type whipping agent and linking agent.
Described rubber powder is ethylene-propylene rubber(EPR) or acrylonitrile-butadiene rubber powder.
Described rubber powder is full cross-linked rubber powder or half cross-linked rubber powder.
Described endothermic blowing agent is that sodium bicarbonate is or/and volatile salt.
Described heat release type whipping agent is azo foaming agent, nitroso group foaming agent or hydrazides class whipping agent.
Described linking agent is acrylic ester cross-linking agent or dicumyl peroxide.
Described softening agent is phthalate, dibutyl ester class and/or epoxy plasticiser.
Described stablizer is calcium zinc class stablizer; Described lubricant is stearic acid or stearic acid and polyethylene wax polymer compounded lubricant.
Described filler is hard calcium carbonate or nano-calcium carbonate.
The present invention also provides a kind of preparation method of low density PVC injection molding footwear material, comprises the following steps:
(1) first endothermic blowing agent, heat release type whipping agent and linking agent mechanically mixing are evenly prepared to composite foamable agent;
(2) batch mixing, granulation
First add PVC raw material and stablizer, rubber powder, mix lubricant even, then add part softening agent, below 80 DEG C, height is mixed even, then add another part softening agent until height is mixed even, after softening agent is absorbed by resin completely, add again 0-50 weight part filler and 0-10 weight part chlorinatedpolyethylene, finally add whipping agent to mix.Then send into twin screw extruder granulation, prilling temperature is 130-140 DEG C.
(3) injection moulding
Before injection moulding, first pellet is dried, drying temperature is 105-120 DEG C, time of drying 3-6h, in the moulding of 150-160 DEG C of temperature hemostasis.
The endothermic blowing agent of described step (1) is that sodium bicarbonate is or/and volatile salt; Described heat release type whipping agent is azo foaming agent, nitroso group foaming agent or hydrazides class whipping agent.
The linking agent of described step (1) is acrylic ester cross-linking agent or dicumyl peroxide.
The rubber powder of described step (2) is ethylene-propylene rubber(EPR) or acrylonitrile-butadiene rubber powder.
The rubber powder of described step (2) is full cross-linked rubber powder or half cross-linked rubber powder.
The softening agent of described step (2) is phthalate, dibutyl ester class and/or epoxy plasticiser.
Described step (2) stablizer be calcium zinc class stablizer; Described lubricant is stearic acid or stearic acid and polyethylene wax polymer compounded lubricant.
The filler of described step (2) is hard calcium carbonate or nano-calcium carbonate.
The present invention adds rubber powder, has greatly strengthened the intensity of PVC melt, thus the collapse hole of effectively having avoided bubble in high-foaming process to break causing and and hole; Moreover linking agent in whipping agent of the present invention makes PVC system be cross-linked to form network, improve to a certain extent melt strength, contribute to foam control in melt.In traditional foaming process, because the heat release of heat release type whipping agent acutely causes that abscess breaks, gas overflowing, not only in material, occur collapse hole and and hole, and the excessive foaming degree that causes of gas is not high, material heaviness.The present invention adopts the thermal equilibrium system of heat release type whipping agent and endothermic blowing agent composition effectively to control the heat effect in PVC foaming system, moreover rubber powder of the present invention and linking agent have strengthened melt strength greatly, thereby can more effectively gas be trapped in melt, successfully realize the high-foaming of PVC material.The present invention has overcome the high defect of injection molding footwear material density, and a kind of low density PVC injection molding footwear material is provided; And the abscess densification of PVC footwear material of the present invention, evenly, not only comfortable and easy to wear, soft, more can save starting material.
Embodiment
Whipping agent of the present invention comprises endothermic blowing agent, heat release type whipping agent and linking agent.Below the present invention's whipping agent used and preparation method thereof:
Whipping agent 1
Cellmic C 121 in whipping agent: sodium bicarbonate (NaHCO
3): trimethylolpropane trimethacrylate=1: 1: 1
Manufacturing processed: by Cellmic C 121, NaHCO
3first stir by standard machinery, then join in trimethylolpropane trimethacrylate and be uniformly mixed.
Whipping agent 2
N in whipping agent, N-dinitrosopentamethylene tetramine: NaHCO
3: dicumyl peroxide is 1: 1: 1
Manufacturing processed: by N, N-dinitrosopentamethylene tetramine and NaHCO
3first stir by standard machinery, then join in dicumyl peroxide and be uniformly mixed.
Whipping agent 3
In whipping agent 4,4 '-OBSH: NH
4hCO
3: trimethylolpropane trimethacrylate is 2: 1: 1
Manufacturing processed: by 4,4 '-OBSH and NH
4hCO
3first stir by standard machinery, then join in trimethylolpropane trimethacrylate and be uniformly mixed.
Embodiment
Embodiment 1
The preparation method of the low density PVC injection molding footwear material of the present embodiment is:
(1) first batch mixing, granulation: first that PVC raw material, calcium zinc stabilizer, rubber powder, stearic acid mix lubricant is even, then add 23 parts of dibutyl ester softening agent, below 80 DEG C, height is mixed even, then add remaining dibutyl ester softening agent until height is mixed evenly, treat that softening agent is absorbed by resin completely.Finally add whipping agent 1 to mix.Then send into twin screw extruder granulation, prilling temperature is 130 DEG C.
(2) injection moulding
Before injection moulding, first pellet is dried, drying temperature is 120 DEG C, time of drying 5h, in the moulding of 160 DEG C of temperature hemostasis.
Comparative example 1
Polyvinyl chloride 50 calcium zinc stabilizers 0.5
Dibutyl ester 45 stearic acid 2.0
Cellmic C 121 1.0
Comparative example 1 '
Polyvinyl chloride 50 calcium zinc stabilizers 0.5
Dibutyl ester 45 stearic acid 2.0
Whipping agent 1 1.0
Comparative example 1 with 1 ' preparation method except the different steps of composition of raw materials are with embodiment 1.
Embodiment 2
The preparation method of the low density PVC injection molding footwear material of the present embodiment is:
(1) first batch mixing, granulation: first the compounded lubricant of PVC raw material, calcium zinc stabilizer, rubber powder, stearic acid and polyethylene wax composition is mixed, then 23 parts of Plasticizer Epoxidized Soybean Oil, below 80 DEG C, height is mixed even, then add remaining epoxy soybean oil until height is mixed even, treat that softening agent is absorbed by resin completely, then add hard calcium carbonate to mix.Finally add whipping agent 1 to mix.Then send into twin screw extruder granulation, prilling temperature is 130 DEG C.
(2) injection moulding
Before injection moulding, first pellet is dried, drying temperature is 120 DEG C, time of drying 5h, in the moulding of 160 DEG C of temperature hemostasis.
Embodiment 3
Polyvinyl chloride 50 epoxy soybean oils 15
Calcium zinc stabilizer 2.0 stearic acid 0.5
The full crosslinking acrylonitrile butadiene powder 5 of whipping agent 2:1.0
The preparation method of the low density PVC injection molding footwear material of the present embodiment is:
(1) first batch mixing, granulation: first that PVC raw material, calcium zinc stabilizer, rubber powder, stearic acid mix lubricant is even, then add 5 parts of Plasticizer Epoxidized Soybean Oil, below 80 DEG C, height is mixed even, then add remaining epoxy soybean oil until height is mixed evenly, treat that softening agent is absorbed by resin completely.Finally add whipping agent 2 to mix.Then send into twin screw extruder granulation, prilling temperature is 130 DEG C.
(2) injection moulding
Before injection moulding, first pellet is dried, drying temperature is 120 DEG C, time of drying 5h, in the moulding of 160 DEG C of temperature hemostasis.
Embodiment 4
The preparation method of the low density PV of the present embodiment DEG C of injection molding footwear material is:
(1) first batch mixing, granulation: first that PVC raw material, calcium zinc stabilizer, rubber powder, stearic acid mix lubricant is even, then add 20 parts of epoxy soybean oils and dibutyl ester softening agent, below 80 DEG C, height is mixed even, then add remaining epoxy soybean oil and dibutyl ester until height is mixed even, treat that softening agent is absorbed by resin completely, then add hard calcium carbonate and chlorinatedpolyethylene to mix.Finally add whipping agent 3 to mix.Then send into twin screw extruder granulation, prilling temperature is 140 DEG C.
(2) injection moulding
Before injection moulding, first pellet is dried, drying temperature is 105 DEG C, time of drying 3h, in the moulding of 150 DEG C of temperature hemostasis.
Embodiment 5
The preparation method of the low density PVC injection molding footwear material of the present embodiment is:
(1) first batch mixing, granulation: first PVC raw material, calcium zinc stabilizer, rubber powder, stearic acid and polyethylene wax compounded lubricant are mixed, then add 5 parts of dibutyl esters, epoxy soybean oil and Plasticized with Dibutyl Phthalate agent, below 80 DEG C, height is mixed even, then add remaining softening agent until height is mixed even, treat that softening agent is absorbed by resin completely, then add nano-calcium carbonate to mix.Finally add whipping agent 1 to mix.Then send into twin screw extruder granulation, prilling temperature is 130 DEG C.
(2) injection moulding
Before injection moulding, first pellet is dried, drying temperature is 120 DEG C, time of drying 6h, in the moulding of 160 DEG C of temperature hemostasis.
Embodiment 6
The preparation method of the low density PVC injection molding footwear material of the present embodiment is:
(1) first batch mixing, granulation: first that PVC raw material, calcium zinc stabilizer, rubber powder, stearic acid mix lubricant is even, then add 10 parts of Plasticized with Dibutyl Phthalate agent, below 80 DEG C, height is mixed even, then add remaining dibutyl phthalate until height is mixed even, treat that softening agent is absorbed by resin completely, then add hard calcium carbonate and chlorinatedpolyethylene to mix.Finally add whipping agent 1 to mix.Then send into twin screw extruder granulation, prilling temperature is 140 DEG C.
(2) injection moulding
Before injection moulding, first pellet is dried, drying temperature is 105 DEG C, time of drying 3h, in the moulding of 150 DEG C of temperature hemostasis.
Embodiment 7
The preparation method of the low density PVC injection molding footwear material of the present embodiment is:
(1) first batch mixing, granulation: first that PVC raw material, calcium zinc stabilizer, rubber powder, stearic acid mix lubricant is even, then add 20 parts of dibutyl esters and Plasticizer Epoxidized Soybean Oil, below 80 DEG C, height is mixed even, then add remaining dibutyl ester and epoxy soybean oil until height is mixed even, treat that softening agent is absorbed by resin completely, then add hard calcium carbonate to mix.Finally add whipping agent 2 to mix.Then send into twin screw extruder granulation, prilling temperature is 130 DEG C.
(2) injection moulding
Before injection moulding, first pellet is dried, drying temperature is 120 DEG C, time of drying 5h, in the moulding of 160 DEG C of temperature hemostasis.
Comparative example 7
The preparation method of the low density PVC injection molding footwear material of the present embodiment is: step, with embodiment 7, changes raw material into the raw material of above-mentioned formula.
Embodiment 8
The preparation method of the low density PVC injection molding footwear material of the present embodiment is: step, with embodiment 1, changes raw material into the raw material of above-mentioned formula.
The preparation method of the low density PVC injection molding footwear material of the present embodiment is:
(1) first batch mixing, granulation: first that PVC raw material, calcium zinc stabilizer, rubber powder, stearic acid mix lubricant is even, then add 20 parts of dibutyl esters and Plasticizer Epoxidized Soybean Oil, below 80 DEG C, height is mixed even, then add remaining dibutyl ester and epoxy soybean oil until height is mixed even, treat that softening agent is absorbed by resin completely, then add hard calcium carbonate to mix.Finally add whipping agent 1 to mix.Then send into twin screw extruder granulation, prilling temperature is 130 DEG C.
(2) injection moulding
Before injection moulding, first pellet is dried, drying temperature is 120 DEG C, time of drying 5h, in the moulding of 160 DEG C of temperature hemostasis.
Comparative example 8
The preparation method of the low density PVC injection molding footwear material of the present embodiment is: step, with embodiment 8, changes raw material into the raw material of above-mentioned formula.
The present invention also can add the composition such as static inhibitor, toughner.Rubber powder is divided into full cross-linked rubber powder, half cross-linked rubber powder or non-crosslinked type rubber powder according to the difference of virgin rubber degree of crosslinking, and degree of crosslinking characterizes with gel content.Rubber powder and PVC consistency are not good, and part embodiment of the present invention adds chlorinatedpolyethylene to improve.
| Embodiment | Density (g/cm 3) |
| Comparative example 1 | 1.31 |
| Comparative example 1 ' | 1.10 |
| Embodiment 1 | 0.67 |
| Embodiment 2 | 0.80 |
| Embodiment 3 | 0.76 |
| Embodiment 4 | 0.75 |
| Embodiment 5 | 0.80 |
| Embodiment 6 | 0.90 |
| Embodiment 7 | 0.75 |
| Comparative example 7 | 1.20 |
| Embodiment 8 | 0.82 |
| Comparative example 8 ' | 1.02 |
As can be seen from the above table, the foaming effect of whipping agent of the present invention (endothermic blowing agent, heat release type whipping agent and linking agent) is obviously good than the foaming effect of heat release type whipping agent or endothermic blowing agent.And rubber powder (especially full cross-linked rubber powder) is conducive to improve the foaming of PVC injection molding footwear material.
Claims (9)
1. a low density PVC injection molding footwear material, is characterized in that, described low density PVC injection molding footwear material comprises the raw material of following weight part:
Described whipping agent comprises endothermic blowing agent, heat release type whipping agent and linking agent; Described rubber powder is full cross-linked rubber powder or half cross-linked rubber powder.
2. low density PVC injection molding footwear material as claimed in claim 1, is characterized in that, described rubber powder is ethylene-propylene rubber(EPR) or acrylonitrile-butadiene rubber powder.
3. low density PVC injection molding footwear material as claimed in claim 1, is characterized in that, described endothermic blowing agent is that sodium bicarbonate is or/and volatile salt; Described heat release type whipping agent is azo foaming agent, nitroso group foaming agent or hydrazides class whipping agent.
4. low density PVC injection molding footwear material as claimed in claim 1, is characterized in that, described linking agent is acrylic ester cross-linking agent or dicumyl peroxide.
5. low density PVC injection molding footwear material as claimed in claim 1, is characterized in that, described softening agent is phthalate, dibutyl ester class and/or epoxy plasticiser.
6. low density PVC injection molding footwear material as claimed in claim 1, is characterized in that, described stablizer is calcium zinc class stablizer; Described lubricant is stearic acid or stearic acid and polyethylene wax polymer compounded lubricant.
7. low density PVC injection molding footwear material as claimed in claim 1, is characterized in that, described filler is hard calcium carbonate or nano-calcium carbonate.
8. a preparation method for low density PVC injection molding footwear material claimed in claim 1, is characterized in that, said method comprising the steps of:
(1) first endothermic blowing agent, heat release type whipping agent and linking agent mechanically mixing are evenly prepared to composite foamable agent;
(2) batch mixing, granulation
First that PVC raw material and stablizer, rubber powder, mix lubricant is even, then add part softening agent, below 80 DEG C, height is mixed even, then add another part softening agent until height is mixed even, after softening agent is absorbed by resin completely, add again 0-50 weight part filler and 0-10 weight part chlorinatedpolyethylene mixes, finally add whipping agent to mix.Then send into twin screw extruder granulation, prilling temperature is 130-140 DEG C.
(3) injection moulding
Before injection moulding, first pellet is dried, drying temperature is 105-120 DEG C, time of drying 3-6h, in the moulding of 150-160 DEG C of temperature hemostasis.
9. the preparation method of low density PVC injection molding footwear material as claimed in claim 8, is characterized in that, the endothermic blowing agent of described step (1) is that sodium bicarbonate is or/and volatile salt; Described heat release type whipping agent is azo foaming agent, nitroso group foaming agent or hydrazides class whipping agent; The rubber powder of described step (2) is ethylene-propylene rubber(EPR) or acrylonitrile-butadiene rubber powder.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210105361.3A CN102634131B (en) | 2012-04-11 | 2012-04-11 | Low-density PVC (Poly Vinyl Chloride) injection-molded shoe material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210105361.3A CN102634131B (en) | 2012-04-11 | 2012-04-11 | Low-density PVC (Poly Vinyl Chloride) injection-molded shoe material and preparation method thereof |
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| CN102634131A CN102634131A (en) | 2012-08-15 |
| CN102634131B true CN102634131B (en) | 2014-06-18 |
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| CN103483736A (en) * | 2013-09-24 | 2014-01-01 | 吴江市董鑫塑料包装厂 | Soft PVC foaming shoe sole plastic |
| KR20150125523A (en) * | 2014-04-30 | 2015-11-09 | 주식회사 동진쎄미켐 | Foaming agent composition and method for foaming resin using the same |
| CN104262825A (en) * | 2014-09-04 | 2015-01-07 | 苏州市景荣科技有限公司 | PVC (polyvinyl chloride) foamed shoe sole material with high folding resistance and manufacturing method thereof |
| CN104262862A (en) * | 2014-10-22 | 2015-01-07 | 苏州市景荣科技有限公司 | Highly bending-resistant PVC (Polyvinyl Chloride) shoe material and manufacturing method thereof |
| CN104558967A (en) * | 2015-01-16 | 2015-04-29 | 江苏美誉虹新材料科技有限公司 | Novel functional food shoes |
| CN104672714A (en) * | 2015-03-09 | 2015-06-03 | 苏州市景荣科技有限公司 | PVC (polyvinyl chloride) sole material with high wear resistance and preparation method of PVC sole material |
| CN104974447A (en) * | 2015-06-30 | 2015-10-14 | 苏州博利迈新材料科技有限公司 | Polyvinyl chloride foam plastic and preparation method thereof |
| CN105440505A (en) * | 2015-12-31 | 2016-03-30 | 东莞市祺龙电业有限公司 | PVC (polyvinyl chloride) foam material for sole and preparation method of PVC foam material |
| CN106490753B (en) * | 2016-12-05 | 2018-08-10 | 天津丽泰鞋业科技股份有限公司 | Working boot production method |
| CN113174112A (en) * | 2020-01-24 | 2021-07-27 | 卢立娒 | Novel PVC injection-molded sole foaming agent |
| CN113201194B (en) * | 2021-06-07 | 2023-02-03 | 长春联塑实业有限公司 | Low-foaming high-impact PVC product and preparation method and application thereof |
| CN114044990A (en) * | 2021-11-24 | 2022-02-15 | 河南君源塑业有限公司 | High-strength polyvinyl chloride foam board and preparation method thereof |
| CN114634681A (en) * | 2022-03-16 | 2022-06-17 | 达州市嘉源体育用品有限公司 | High-elastic anti-static sole and preparation method thereof |
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