CN102115556B - Formula and manufacturing method for light plastic last - Google Patents
Formula and manufacturing method for light plastic last Download PDFInfo
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- CN102115556B CN102115556B CN 200910247774 CN200910247774A CN102115556B CN 102115556 B CN102115556 B CN 102115556B CN 200910247774 CN200910247774 CN 200910247774 CN 200910247774 A CN200910247774 A CN 200910247774A CN 102115556 B CN102115556 B CN 102115556B
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Abstract
The invention relates to a formula and a manufacturing method for a light plastic last. The formula for the plastic last comprises 80 to 85 weight percent of high-density polyethylene, 5 to 7.4 weight percent of calcium carbonate, 5 to 7.4 weight percent of magnesium salt whisker, and the balance of trace elements. Therefore, materials can be saved, and the manufacture procedure is shortened; moreover, the finished product is lightened, manpower is saved, the production capacity of factories is improved, and the environmental protection requirement of recycling the product can be met.
Description
Technical field
The present invention system is about a kind of prescription and method for making thereof of plastics shoe last, and especially, the present invention is about a kind of light-weighted prescription of plastics shoe last and method for making thereof of making.
Background technology
The known pure high density polyethylene(HDPE) (being called for short HDPE) that utilizes foams, and promote foaming effect without adding other straight chain shape Low Density Polyethylene (LL-DPE) or ethylene-propylene rubber(EPR) (being called for short EPDM) etc., almost do not have, moreover, prior art requires the size specification in control bubble aperture very difficult to the little foaming technique of pure HDPE, also unstable, reason is that the fusing point of HDPE is higher, the restriction of fusing point is very narrow, and the intensity of melt is very low, processibility is quite harsh, be applicable to shoe last loss of weight foam material difficult.
In addition, existing HDPE+EVA foam material or EPDM or LL-DPE have plenty of the one step foaming method of employing or two steps foaming, produce micro-foaming material, except this material property can't be fit to produce the required shoe last of footwear next life, exist simultaneously following problem:
1, the cost of equipment is very high, and the secondary mould closing device need be arranged;
2, processing procedure is longer: mostly need to make master batch, and add whipping agent at the screw rod middle section position of ejaculator, not only processing procedure is long, and also inconvenient production operation, and its productive rate is lower;
3, operation and quality are unstable: when reason is that secondary mould closing fixedly, changes the outfit and calculate the size of secondary mould into the speed of fixed mould and foaming ratio, can cause the problem points of operation.Still uncontrollable bubble aperture is in the micron bubble size for one step foaming method or two steps foaming, and namely the aperture is 10 μ m～50 μ m, and cell density is 109～1012/cm
3, the aperture affects the steady quality degree of finished product;
4, the cost of conventional materials is high: if be light micro-foaming HDPE with micron order porous plastics particulate, this kind particulate system coats air with the high polymer of fusing point and mixes interpolation with HDPE, because the fusing point of polymeric membrane is higher than HDPE, therefore can not broken by melting, and reach light-weighted purpose, but expensive, except special engineering plastics are required, and do not meet the cost consideration of general general-using type product.
Therefore, all aforementioned disappearances of commonly using of going against have necessity that it work is further improved in fact.
The inventor still has improved place in view of commonly using at present, so just be engaged in for many years production and marketing experience of related products, and for the associated problem of present existence, the method that deep thinking improves, through after repeatedly improvement is tested, finally create a kind of prescription and method for making thereof of light-weighted plastics shoe last.
Summary of the invention
Main purpose of the present invention provides a kind of finished product and has equally distributed micropore, quality tool stability, and still have prescription and the method for making thereof of the light-weighted plastics shoe last of smoothness of the surface after the materials processing turning.
In order to realize above-mentioned purpose, the present invention system provides a kind of prescription of light-weighted plastics shoe last, comprising:
The high density polyethylene(HDPE) of 80 to 85 % by weight;
The calcium carbonate of 5 to 7.4 % by weight;
The magnesium salt whisker of 5 to 7.4 % by weight; And
The trace element of residue content.
Wherein, the content of this high density polyethylene(HDPE) is 83 to 85 % by weight.
Wherein, the content of this calcium carbonate is 6 to 7 % by weight.
Wherein, the content of this magnesium salt whisker is 6 to 7 % by weight.
Wherein, this trace element has the Di Iso Decyl Phthalate of 10～20CC.
Wherein, this trace element has the azo two formyl ammoniums of 0.001 to 0.01 % by weight.
Wherein, this trace element has the toner of 0.0001 to 0.0005 % by weight.
In addition, the present invention also provides a kind of method for making of light-weighted plastics shoe last, comprises the following steps:
When " preparation packing material " step: first activated inorganic nanometer or micron packing material, and add high density polyethylene(HDPE) and activator, and carry out the high-speed mixing first time;
When " interpolation pigment " step: after first time high-speed mixing, carry out pigment dyestuff and add, and carry out the high-speed mixing second time, and the compound after the high-speed mixing is placed in the storing reactive tank of tool reliever;
When " injecting in the mould of matched moulds " step: behind the mould matched moulds, the Temperature Setting that utilizes injection moulding machine to keep, and penetrate pressure, and compound is injected in this mould, carry out ejection formation;
When " cooling " step: utilize the product to be formed in the water quench mould that circulates;
When " die sinking " step: this mould is separated, and forming composition is taken out;
When " surface working processing " step: this forming composition is carried out surface working process, so namely finish finished product of the present invention.
Wherein, this activator is titanate coupling agent, aluminate coupling agent, monomer coupling agent, silane coupling agent or dimerization di (isooctyl) phosphate magnesium stearate.
Wherein, for the first time during high-speed mixing, can add an amount of plasticizing auxiliary agent.
Wherein, this plasticizing auxiliary agent is Di Iso Decyl Phthalate.
Wherein, for the second time during high-speed mixing, can add an amount of whipping agent.
Wherein, this whipping agent is azo two formyl ammoniums.
Wherein, should remain between 8～13 ℃ in the water coolant water temperature of " cooling " step.
Wherein, the Temperature Setting of this injection moulding machine remains between 150～180 ℃.
Wherein, the ejaculation pressure of this injection moulding machine is 100～130kg/m
2
Wherein, this packing material is calcium carbonate, zinc oxide, opal, talcum powder, micro-crystal powder, magnesium hydroxide, glass fibre or powder magnesium salt whisker.
The present invention has following useful technique effect:
1, finished product has equally distributed micropore, quality tool stability, and still have smoothness of the surface after the materials processing turning;
2, save material, processing procedure shortening, traditional HDPE tool is lightened, and save artificial muscle power expenditure, increase factory production capacity can reach again the environmental protection demand of recycling;
3, realize that high density polyethylene(HDPE) (HDPE) Microcellular foam extrusion type comes production lightweight plastic H DPE shoe last material, and the cost that significantly reduces existing HDPE shoe last and material.
Description of drawings
What below hereby cooperate preferred embodiment of the present invention graphicly further specifies as followsly, and to making the personage who is familiar with correlation technique of the present invention, the statement of De Yiben specification sheets is implemented according to this.
Fig. 1 is manufacturing process schematic diagram of the present invention.
Fig. 2 is the impact strength test of finished product of the present invention.
Fig. 3 is another impact strength test of finished product of the present invention.
Fig. 4 is the bending strength test of finished product of the present invention.
Fig. 5 is the tensile strength test of finished product of the present invention.
Fig. 6 is another tensile strength test of finished product of the present invention.
Fig. 7 is the fracture tension test of finished product of the present invention.
Embodiment
Below be by particular specific embodiment explanation embodiments of the present invention, the personage who is familiar with this skill can understand other advantage of the present invention and effect by content disclosed in the present specification.
In this specification sheets, except as otherwise noted, otherwise the composition that the plastics shoe last comprises is all take the prescription gross weight of this plastics shoe last as benchmark, and represents with weight percent (wt%).
The present invention is a kind of prescription of light-weighted plastics shoe last, comprising:
The high density polyethylene(HDPE) of 80 to 85 % by weight (being called for short HDPE);
Calcium carbonate (the CaCO of 5 to 7.4 % by weight
3);
Magnesium salt whisker (the MgSO of 5 to 7.4 % by weight
4.5Mg (OH)
2.3H
2O); And
The trace element of residue content.
Wherein, the content of this high density polyethylene(HDPE) is 83 to 85 % by weight.
Wherein, the content of this calcium carbonate is 6 to 7 % by weight.
Wherein, the content of this magnesium salt whisker is 6 to 7 % by weight.
Wherein, this trace element has the Di Iso Decyl Phthalate (being called for short DIDP) of 10～20CC.
Wherein, this trace element has the azo two formyl ammoniums (being called for short ADC) of 0.001 to 0.01 % by weight.
Wherein, this trace element has the toner of 0.0001 to 0.0005 % by weight.
This case contriver finds, when with the calcium carbonate of known high-content and magnesium salt whisker (being all more than the 6wt%) when being added into high density polyethylene(HDPE), on microcosmic, be easy to realize that high density polyethylene(HDPE) Microcellular foam extrusion type comes production lightweight plastic last head material, it can significantly reduce the material cost of existing high density polyethylene(HDPE) shoe last, and the physical property that then significantly exceeds pure high-density polyethylene material for the physical property of demand, realize the advantage of product, not only can solve the shortcoming that known plastic material derives, and for commercial production and the upper very advantageous of application.
In addition, according to the prescription of the light-weighted plastics shoe last of the present invention, the material after foaming, the former solid material loss of weight of its weight ratio reaches light-weighted demand more than at least 20% really.Therefore, will be conducive to make shoe tree according to plastics shoe last prescription of the present invention.
Please cooperate that to consult shown in Figure 1 be plastic shoe tree processing procedure of the present invention, the present invention is a kind of light-weighted plastics shoe last method for making, comprises the following steps:
When " preparation packing material " step: first activated inorganic nanometer or micron packing material, and add high density polyethylene(HDPE) and activator, and carry out the high-speed mixing first time;
When " interpolation pigment " step: after first time high-speed mixing, carry out pigment dyestuff and add, and carry out the high-speed mixing second time, and the compound after the high-speed mixing is placed in the storing reactive tank of tool reliever;
When " injecting in the mould of matched moulds " step: behind the mould matched moulds, the Temperature Setting that utilizes injection moulding machine to keep, and penetrate pressure, and compound is injected in this mould, carry out ejection formation;
When " cooling " step: utilize the product to be formed in the water quench mould that circulates;
When " die sinking " step: this mould is separated, and forming composition is taken out;
When " surface working processing " step: this forming composition is carried out surface working process, so namely finish finished product of the present invention.
Wherein, this activator is titanate coupling agent, aluminate coupling agent, monomer coupling agent, silane coupling agent or dimerization di (isooctyl) phosphate magnesium stearate.
Wherein, for the first time during high-speed mixing, can add an amount of plasticizing auxiliary agent.The three-dimensional high-speed mixer of high-speed mixing system's employing three-D of the present invention, come abundant mixed plastic HDPE and packing material, played bridging action in inorganic fill nanometer or micron grain with the interface of HDPE at this activator, being combined closely adds approximately 0.5% plasticity auxiliary agent again, i.e. plasticizer phthalic acid two isodecyl esters (DIDP).To promote plasticizing fully.Also can take before this twin screw or single screw extruder and extruding granulator to connect to make master batch; its effect is better; can obtain mixing more uniformly; but this law is because of the problem of cost; only take the three-dimensional high-speed mixing cylinder of three-D and transform the ejaculator injection moulding apparatus, can reach shoe last material required standard.
Wherein, this plasticizing auxiliary agent is Di Iso Decyl Phthalate.
Wherein, for the second time during high-speed mixing, can add an amount of whipping agent.
Wherein, this whipping agent is azo two formyl ammoniums.
Wherein, should remain between 8～13 ℃ in the water coolant water temperature of " cooling " step.
Wherein, the Temperature Setting of this injection moulding machine remains between 150～180 ℃.
Wherein, the about 100～130kg/m of the ejaculation pressure of this injection moulding machine
2
Wherein, this packing material is calcium carbonate, zinc oxide, opal, talcum powder, micro-crystal powder, magnesium hydroxide, glass fibre or powder magnesium salt whisker.
In embodiment, the prescription of the light-weighted plastics shoe last of the present invention comprises the high density polyethylene(HDPE) (be called for short HDPE) of 80 to 85 % by weight; Calcium carbonate (the CaCO of 5 to 7.4 % by weight
3); Magnesium salt whisker (the MgSO of 5 to 7.4 % by weight
4.5Mg (OH)
2.3H
2O); And the trace element of residue content.
Below, will elaborate the present invention with exemplary embodiments.
In this preferred embodiment, the composition of plastic shoe tree of the present invention (unit is weight percentage) is as follows:
High density polyethylene(HDPE): approximately 84.8%
Calcium carbonate: approximately 6.7%
Magnesium salt whisker: approximately 6.7%
Trace element comprises following:
Di Iso Decyl Phthalate DIDP is 15cc approximately,
Azo two formyl ammonium ADC approximately 0.006%, and
Toner approximately 0.0003%.
Proportioning by preferred embodiment of the present invention, and the plastic shoe tree that manufactures of the aforesaid processing procedure of the present invention, further carry out shock strength, flexural strength, tension force and fracture tension test, met set demand to guarantee the present invention, in order to reach the set effect of the present invention and purpose.
Please continue to cooperate and consult Fig. 2 to shown in Figure 7, be every test that plastic shoe tree cost that the present invention produces is done, wherein:
The impact strength test part, as shown in Figure 2, it is to show shock strength to the impact of calcium carbonate content, and relatively passes through the impact strength after the stearic acid surface treatment.Clearly, can clearly learn in graphic by this, through the impact strength after the stearic acid surface treatment, better before specific surface is processed, also provable impact strength of the present invention is good than known techniques really.
Please cooperate shown in Figure 3, it is for surface treatment agent (SMA1000+ titanate coupling agent) content impact strength to be tested, this SMA1000 (macromolecular coupling agent) and titanate coupling agent, these two kinds are mixed use, make inorganic filler play bridging action by these auxiliary agents, and make inorganic filling material and HDPE combine closely, whole toughness, shock strength, hardness so that mixture is increased, and increasing dispersiveness, the physical propertiess such as the hot melt flowability of mixture strengthen.Wherein, the formula rate of test substrate is HDPE:84%; CaCO
3: 8%; Magnesium salt whisker: 8%.
Carry out bending strength test for finished product of the present invention in addition, please cooperate consult shown in Figure 4, the flexural strength of HDPE is 29.89MPA, its surface treatment agent (SMA1000+ titanate coupling agent) is 2%, change the flexural strength test that calcium carbonate content is done among the HDPE, it can reach the set flexural strength of the present invention really.
Moreover, carry out tensile strength test for finished product of the present invention, please cooperate consult shown in Figure 5, by in graphic obviously as can be known, the tensile strength of HDPE of the present invention is 22.8MPA, it is to compare HDPE+CaCO
3With HDPE+CaCO
3+ surface treatment agent (2%) comparison on tensile strength when different calcium carbonate content; Wherein:
The A line segment is HDPE+CaCO
3
The B line segment is HDPE+CaCO
3+ surface treatment agent (2%).
Very clear can learning, adding 2% surface treatment agent can be so that tensile strength improves, and can reach the effect that the present invention is scheduled to.
The person of advancing, as shown in Figure 6, it is comparison HDPE+ magnesium salt whisker+surface treatment agent (2%), HDPE+CaCO
3+ surface treatment agent (2%), HDPE:84%+ (magnesium salt whisker+CaCO
3) 16%+ surface treatment agent (2%) (magnesium salt whisker, CaCO under the different content weighting material
3, magnesium salt whisker+CaCO
3) tensile strength performance; Wherein:
The A line segment is HDPE+ magnesium salt whisker+surface treatment agent (2%);
The B line segment is HDPE+CaCO
3+ surface treatment agent (2%);
The C line segment is HDPE:84%+ (magnesium salt whisker+CaCO
3) 16%+ surface treatment agent (2%).
In addition, please continue to cooperate and consult shown in Figure 7ly, be the fracture tension test of finished product of the present invention; By can obviously learning in graphic, the elongation at break of HDPE is 28.5%, and through the HDPE after magnesium salt whisker (16%) processing, its elongation at break is 23.9%;
And use the surface treatment agent (SMA1000+ titanate coupling agent) of various dose as shown in the drawing on the impact of elongation at break; Wherein:
The A line segment is CaCO
3: 16%+HDPE:84% is with surface treatment agent (SMA1000+ titanate coupling agent) generation of the Different Weight per-cent impact on elongation at break;
The B line segment is CaCO
3: 8%+ magnesium salt whisker: 8%+HDPE:84% is with surface treatment agent (SMA1000+ titanate coupling agent) generation of the Different Weight per-cent impact on elongation at break.
By the aforesaid every test of the present invention as can be known, it is in demand this law packing material calcium carbonate (CaCO of shoe last material
3) mix the interpolation use with each ratio of 50% of magnesium salt whisker, it is former because the rigidity of calcium carbonate is high, microporous foam HDPE material hardness is high and reduce along with the density of bubble, and with the calcium carbonate-filled material hardness of strengthening microporous foam HDPE, but its shortcoming is the increase along with calcium carbonate content, the flexural strength of microporous foam HDPE material, tensile strength and elongation at break all descend to some extent, wherein, descend with elongation at break again too many, and make the above-listed shortcomings such as enhancing tensile strength of microporous foam HDPE of magnesium salt whisker, namely supply the shortcoming of calcium carbonate-filled material, it can reach desired effects of the present invention and purpose really.
By the allotment of the invention described above prescription and process design, really can reach following predetermined effect:
One, realize that HDPE Microcellular foam extrusion type comes production lightweight plastic H DPE shoe last material, and the cost that significantly reduces existing HDPE shoe last and material.
Two, realize HDPE micro foaming composite material physical property, certain part is little or equal the physical property of pure HDPE material, but then significantly exceeds the physical property of pure HDPE material for the physical property of demand, to realize the advantage of product.
Three, shorten processing procedure and can realize producing required target, and significantly reduce equipment and production cost.
Four, finished product has equally distributed micropore, and after the materials processing turning, still has smoothness of the surface.
Five, the light-weighted microporous foam technology of combining nano material modification technology and HDPE, fully overcoming the HDPE microporous foam, to be subject to the fusing point of HDPE high, and molten limit is narrow, and melt strength is low, be processed as the shortcomings such as microporous foam difficult, and realize saving material, processing procedure shortening, reduction cost, and traditional HDPE tool is lightened, save artificial muscle power and pay, increase factory's production capacity, can reach again the environmental protection demand of recycling, and according to the characteristic demand of product, but weight reduction approximately about 20%～50%.
In sum, the present invention system is used for the production technology of shoe last and material thereof, but the light material of a kind of quality of output, and with this usefulness as the tool of material produce; Not only be easy to user's operation, saving manpower burden, production capacity is further promoted, and this material thermal diffusivity is good, processing procedure is short, and the Effective Raise product yield is so that the steady quality of finished product, simultaneously can save in a large number material, effectively reduce production costs, for commercial production and the upper very advantageous of application, dark tool economic and practical.
Above-described embodiment is prescription and the method for making thereof of the light-weighted plastics shoe last of illustrative the present invention only, but not is used for restriction the present invention.Any personage who is familiar with this skill all can be under spirit of the present invention and category, and above-described embodiment is modified and changed.Therefore, claim is contained as described for the scope of the present invention.
Claims (15)
1. a light-weighted plastics shoe last is characterized in that, comprising:
The high density polyethylene(HDPE) of 80 to 85 % by weight;
The calcium carbonate of 5 to 7.4 % by weight;
The magnesium salt whisker of 5 to 7.4 % by weight; And
The trace element of residue content, this trace element comprises the toner of 0.0001 to 0.0005 % by weight.
2. light-weighted plastics shoe last as claimed in claim 1 is characterized in that, the content of this high density polyethylene(HDPE) is 83 to 85 % by weight.
3. light-weighted plastics shoe last as claimed in claim 1 is characterized in that, the content of this calcium carbonate is 6 to 7 % by weight.
4. light-weighted plastics shoe last as claimed in claim 1 is characterized in that, the content of this magnesium salt whisker is 6 to 7 % by weight.
5. light-weighted plastics shoe last as claimed in claim 1 is characterized in that, this trace element also comprises 10 ~ 20 cubic centimetres Di Iso Decyl Phthalate.
6. light-weighted plastics shoe last as claimed in claim 1 is characterized in that, this trace element also comprises the azo two formyl ammoniums of 0.001 to 0.01 % by weight.
7. a manufacturing contains light-weighted plastics shoe last method for making as claimed in claim 1, it is characterized in that, comprises the following steps:
When " preparation packing material " step: first activated calcium carbonate and magnesium salt whisker, and add high density polyethylene(HDPE) and activator, and carry out the high-speed mixing first time;
When " interpolation pigment " step: after first time high-speed mixing, carry out toner and add, and carry out the high-speed mixing second time, and the compound after the high-speed mixing is placed in the storing reactive tank of tool reliever;
When " injecting in the mould of matched moulds " step: behind the mould matched moulds, the Temperature Setting that utilizes injection moulding machine to keep, and penetrate pressure, and compound is injected in this mould, carry out ejection formation;
When " cooling " step: utilize the product to be formed in the water quench mould that circulates;
When " die sinking " step: this mould is separated, and forming composition is taken out;
When " surface working processing " step: this forming composition is carried out surface working process, so namely finish finished product.
8. method for making as claimed in claim 7 is characterized in that, this activator is titanate coupling agent, aluminate coupling agent, monomer coupling agent, silane coupling agent or dimerization di (isooctyl) phosphate magnesium stearate.
9. method for making as claimed in claim 7 is characterized in that, for the first time during high-speed mixing, can add an amount of plasticizing auxiliary agent.
10. method for making as claimed in claim 9 is characterized in that, this plasticizing auxiliary agent is Di Iso Decyl Phthalate.
11. method for making as claimed in claim 7 is characterized in that, for the second time during high-speed mixing, can add an amount of whipping agent.
12. method for making as claimed in claim 11 is characterized in that, this whipping agent is azo two formyl ammoniums.
13. method for making as claimed in claim 7 is characterized in that, should remain between 8 ~ 13 ℃ in the water coolant water temperature of " cooling " step.
14. method for making as claimed in claim 7 is characterized in that, the Temperature Setting of this injection moulding machine remains between 150 ~ 180 ℃.
15. method for making as claimed in claim 7 is characterized in that, the ejaculation pressure of this injection moulding machine is 100 ~ 130kg/m
2
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910247774 CN102115556B (en) | 2009-12-30 | 2009-12-30 | Formula and manufacturing method for light plastic last |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910247774 CN102115556B (en) | 2009-12-30 | 2009-12-30 | Formula and manufacturing method for light plastic last |
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| CN102115556A CN102115556A (en) | 2011-07-06 |
| CN102115556B true CN102115556B (en) | 2013-01-23 |
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| CN 200910247774 Expired - Fee Related CN102115556B (en) | 2009-12-30 | 2009-12-30 | Formula and manufacturing method for light plastic last |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109181077A (en) * | 2018-09-21 | 2019-01-11 | 温州市华炜鞋材科技有限公司 | A kind of moulding process for the shoe tree that foams |
| CN109717551A (en) * | 2018-12-13 | 2019-05-07 | 温州明创科技有限公司 | A kind of precision positioning shoe tree processing method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87103391A (en) * | 1987-05-06 | 1987-12-23 | 廊坊市鞋楦厂 | Wooden-plastic shoe tree and manufacture method thereof |
| CN1065234A (en) * | 1992-04-16 | 1992-10-14 | 永嘉县塑木楦头厂 | The manufacture method of Wooden-plastic shoe tree and goods thereof |
| CN1090992A (en) * | 1993-02-12 | 1994-08-24 | 孙长松 | Compound glass fibre reinforced plastics molded shoe tree and preparation method thereof |
| CN1422576A (en) * | 2001-12-07 | 2003-06-11 | 张进荣 | PU shoe last and making technology |
-
2009
- 2009-12-30 CN CN 200910247774 patent/CN102115556B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87103391A (en) * | 1987-05-06 | 1987-12-23 | 廊坊市鞋楦厂 | Wooden-plastic shoe tree and manufacture method thereof |
| CN1065234A (en) * | 1992-04-16 | 1992-10-14 | 永嘉县塑木楦头厂 | The manufacture method of Wooden-plastic shoe tree and goods thereof |
| CN1090992A (en) * | 1993-02-12 | 1994-08-24 | 孙长松 | Compound glass fibre reinforced plastics molded shoe tree and preparation method thereof |
| CN1422576A (en) * | 2001-12-07 | 2003-06-11 | 张进荣 | PU shoe last and making technology |
Non-Patent Citations (2)
| Title |
|---|
| 化学工业部合成树脂及塑料工业科技情报中心站.聚烯烃无机酸钙填充塑料.《化工产品手册 合成树脂与塑料》.化学工业出版社,1985,第34-37页. * |
| 杨大全.塑料鞋楦在制鞋工业中的应用.《西部皮革》.1983,(第1期),第29-30,4页. * |
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| CN102115556A (en) | 2011-07-06 |
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