CN103113733A - Composite material safety toe cap and manufacturing method thereof - Google Patents
Composite material safety toe cap and manufacturing method thereof Download PDFInfo
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- CN103113733A CN103113733A CN2013100337576A CN201310033757A CN103113733A CN 103113733 A CN103113733 A CN 103113733A CN 2013100337576 A CN2013100337576 A CN 2013100337576A CN 201310033757 A CN201310033757 A CN 201310033757A CN 103113733 A CN103113733 A CN 103113733A
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Abstract
The invention discloses a composite material safety toe cap which is formed by bonding and pressing multiple layers of glass fiber cloth coated with resin paste, wherein the resin paste comprises polyester resin, an initiator, a low-shrink additive, an inner release agent, a thickener and a crosslinking agent; and the invention also discloses a method for manufacturing the composite material safety toe cap. The formula of the composite material safety toe cap provided by the invention is scientific and reasonable in design, has good mechanical performance and high strength, greatly enhances the impact resistance, effectively avoids the phenomena that the foot of a user kicks a foreign object or is bruised by the falling foreign object and the toes are injured, and realizes high safety; the composite material safety toe cap has the advantages of corrosion resistance, high temperature resistance, cold resistance, acid resistance and the like, and the service life is greatly prolonged; and the composite material safety toe cap can pass the International test standards such as European Union EN12568-S, Canada CSA-Z195 and the United States ASTM-F2413 and the like. The method provided by the invention has a simple manufacturing technology, is easy to realize and can quickly produce a composite material safety toe cap.
Description
Technical field
The invention belongs to the toe-cap technical field, be specifically related to a kind of matrix material safety toes and preparation method thereof.
Background technology
Oneself becomes the problem that each laborer is concerned about conscientiously society labour protection, and thus, the labor protection facilities of each side are also corresponding a lot, and a kind of safety toes of the personnel safety for the protection of laborer is exactly one of them.Head at shoes is provided with the safety toes with certain physical strength exactly, with prevent from being expert at or working process in kick foreign object or the foreign object that fallen weighs, injures by a crashing object toe wounded.
The safety toes security of adopting metal to make is very high, also used a lot of years, but weight is heavier, easily makes wearer's action painstaking; And easily be subjected to the impact of moisture or chemical substance and corrosion exists potential safety hazard.In recent years terrorism is prevailing in addition, the airport, various countries, port and various momentous conference turnover sluice gate, all improve safety check and do not have metal locator, the steel toe-cap can cause alarm, causing much inconvenience of user, just arises at the historic moment to non-metal safety shoes (Non-metallic shoes) demand in various countries, and fiber reinforced plastic also begins to be applied to make safety toes.Yet the material mixture ratio of existing non-metal safety shoes and the problem of manufacture craft can't be made light mass and thin wall, and intensity is stable safety toes greatly again.
Therefore research and develop a kind of aesthetic in appearance, quality is light, intensity is large, and is and corrosion-resistant, long service life can be passed through the EN-12568-S of European Union, required for when generation of the safety toes of the international testing standards such as Canadian CSA-Z195 and U.S. ASTM-F2413.
Summary of the invention
For above-mentioned deficiency, one of the object of the invention is, provides that a kind of quality is light, intensity is large, and corrosion-resistant, the matrix material safety toes of long service life.
Two of the object of the invention is, a kind of method of making above-mentioned matrix material safety toes is provided, and the manufacture craft of the method is simple and easy, is easy to realize, can produce fast the matrix material safety toes, production efficiency is high.
For achieving the above object, technical scheme provided by the present invention is: a kind of matrix material safety toes, toe-cap has glasscloth bonding, the pressing of resin paste to form by multiple coating, this toe-cap is made of end face, side and base hook, the mass percent of described resin paste and glasscloth is: resin paste 65～80%, glasscloth 20～35%; Each component and the mass percent thereof of wherein said resin paste are as follows: alkyd resin 65～80%, initiator 0.2～2%, low shrinkage additive 10～30%, interior remover 1～2%, thickening material 1～5%, linking agent 1～2%.
As a modification of the present invention, described alkyd resin is vinyl ester resin, described initiator is peroxidation-2-ethyl acetic acid tert-butyl ester, described low shrinkage additive is thermoplastic polymer, described interior remover is Zinic stearas, described thickening material is MgO, and described linking agent is peroxidized t-butyl perbenzoate.
As a modification of the present invention, described glasscloth is alkali-free glass fiber cloth.
A kind of method of making above-mentioned matrix material safety toes, it comprises the following steps: (1) preparing material, each component and the mass percent thereof of raw material are as follows: resin paste 65～80%, glasscloth 20～35%; Each component and the mass percent thereof of wherein said resin paste are as follows: alkyd resin 65～80%, initiator 0.2～2%, low shrinkage additive 10～30%, interior remover 1～2%, thickening material 1～5%, linking agent 1～2%; (2) first resin paste is coated on glasscloth, then posts respectively barrier film on the upper surface of this glasscloth and lower surface, and compacting; (3) glasscloth after compacting is dried, form felt; (4) according to the specification of the required toe-cap that makes, prepare the felt of respective numbers, and this felt is cut shaping, barrier film on felt is removed, and superpose successively, fit, then put into the toe-cap mould and heat, pressurize, make matrix material safety toes goods.
As a modification of the present invention, described step (1) specifically comprises the following steps: (1.1) preparation alkyd resin, initiator, low shrinkage additive, interior remover, thickening material, linking agent and glasscloth; (1.2) take out alkyd resin, initiator, low shrinkage additive, interior remover, thickening material and the linking agent of corresponding proportional quantity, then mix and stir, make resin paste.
As a modification of the present invention, described alkyd resin is vinyl ester resin, described initiator is peroxidation-2-ethyl acetic acid tert-butyl ester, described low shrinkage additive is thermoplastic polymer, described interior remover is Zinic stearas, described thickening material is MgO, and described linking agent is peroxidized t-butyl perbenzoate, and described glasscloth is alkali-free glass fiber cloth.
As a modification of the present invention, described step (2) specifically comprises the following steps: (2.1) preparation coating machine or adhesive applicator, draw glasscloth to this coating machine or adhesive applicator; (2.2) the preparation barrier film, draw this barrier film glasscloth to coating machine or adhesive applicator; (2.3) start coating machine or adhesive applicator, resin paste is coated on glasscloth, and then barrier film is fitted in upper surface and the lower surface of this glasscloth, and roll by the pressure roller of this coating machine or adhesive applicator, realize the purpose of compacting glasscloth.
As a modification of the present invention, described barrier film is polyethylene film.
As a modification of the present invention, described step (3) specifically comprises the following steps: (3.1) are transferred to the glasscloth after compacting in baking oven; (3.2) starting baking oven, is 20～50 degree with the Temperature Setting of this baking oven, and the time is set as 20～60 hours; (3.3) after to be dried, form felt.
As a modification of the present invention, described step (4) specifically comprises the following steps: (4.1) are prepared the felt of respective numbers, and this felt are cut shaping according to the specification of the required toe-cap that makes; (4.2) barrier film on felt is removed, and superposeed successively, fit, form tabular compound material; (4.3) preparation toe-cap mould, carry out preheating to this toe-cap mould;
(4.4) coat releasing agent on the die cavity of toe-cap mould; (4.5) tabular compound material is put into the die cavity of toe-cap mould; (4.6) control the toe-cap mould and carry out mould assembling action, when the punch of toe-cap mould did not touch tabular compound material, mold pressure was set as 1.5～3Mpa; When the punch of toe-cap mould touched tabular compound material, mold pressure was set as 15～30Mpa;
(4.7) etc. the toe-cap die venting complete after, toe-cap mould fully closes; (4.8) the toe-cap mould is heated, pressurizeed, until tabular compound material curing molding forms the matrix material safety toes; (4.9) open the toe-cap mould, the matrix material safety toes is ejected from die cavity, obtain matrix material safety toes goods.
Beneficial effect of the present invention is: the invention provides the formulating of recipe science of matrix material safety toes, rationally, has good mechanical property, intensity is large, greatly strengthened impact resistance, the phenomenon that the foreign object of effectively avoiding kicking in the process of walking foreign object or being fallen weighed, injured by a crashing object toe wounded occurs, safe, and possess the advantages such as corrosion-resistant, high temperature resistant, cold-resistant, antiacid, alkali resistant, anti-fuel oil, work-ing life greatly, can pass through the EN-12568-S of European Union, the international testing standards such as Canadian CSA-Z195 and U.S. ASTM-F2413; One-piece construction is simple in addition, is easy to realize, aesthetic in appearance, quality is light, is convenient to dress, is beneficial to wide popularization and application.The manufacture craft of method provided by the invention is simple and easy, is easy to realize, can produce fast the matrix material safety toes.
Below in conjunction with accompanying drawing and embodiment, the invention will be further described.
Description of drawings
Fig. 1 is plan structure schematic diagram of the present invention.
Fig. 2 is the structural representation of looking up of the present invention.
Fig. 3 is fabrication processing figure of the present invention.
Embodiment
Embodiment 1: referring to Fig. 1, Fig. 2 and Fig. 3, a kind of matrix material safety toes that the present embodiment provides, toe-cap has glasscloth bonding, the pressing of resin paste to form by multiple coating, this toe-cap is made of end face 1, side 2 and base hook 3, the mass percent of described resin paste and glasscloth is: resin paste 65～80%, glasscloth 20～35%; Each component and the mass percent thereof of wherein said resin paste are as follows: alkyd resin 65～80%, initiator 0.2～2%, low shrinkage additive 10～30%, interior remover 1～2%, thickening material 1～5%, linking agent 1～2%.
In the present embodiment, described alkyd resin is preferably vinyl ester resin, described initiator is peroxidation-2-ethyl acetic acid tert-butyl ester, described low shrinkage additive is preferably thermoplastic polymer, described interior remover is preferably Zinic stearas, described thickening material is preferably MgO, and described linking agent is preferably peroxidized t-butyl perbenzoate.Described glasscloth is preferably alkali-free glass fiber cloth.
A kind of method of making above-mentioned matrix material safety toes, it comprises the following steps: (1) preparing material, each component and the mass percent thereof of raw material are as follows: resin paste 65～80%, glasscloth 20～35%; Each component and the mass percent thereof of wherein said resin paste are as follows: alkyd resin 65～80%, initiator 0.2～2%, low shrinkage additive 10～30%, interior remover 1～2%, thickening material 1～5%, linking agent 1～2%; Described step (1) specifically comprises the following steps: (1.1) preparation alkyd resin, initiator, low shrinkage additive, interior remover, thickening material, linking agent and glasscloth; (1.2) take out alkyd resin, initiator, low shrinkage additive, interior remover, thickening material and the linking agent of corresponding proportional quantity, then mix and stir, make resin paste.
(2) first resin paste is coated on glasscloth, then posts respectively barrier film on the upper surface of this glasscloth and lower surface, and compacting; Described step (2) specifically comprises the following steps: (2.1) preparation coating machine or adhesive applicator, draw glasscloth to this coating machine or adhesive applicator; (2.2) the preparation barrier film, draw this barrier film glasscloth to coating machine or adhesive applicator; (2.3) start coating machine or adhesive applicator, resin paste is coated on glasscloth, and then barrier film is fitted in upper surface and the lower surface of this glasscloth, and roll by the pressure roller of this coating machine or adhesive applicator, realize the purpose of compacting glasscloth.
(3) glasscloth after compacting is dried, form felt; Described step (3) specifically comprises the following steps: (3.1) are transferred to the glasscloth after compacting in baking oven; (3.2) starting baking oven, is 20～50 degree with the Temperature Setting of this baking oven, and the time is set as 20～60 hours; (3.3) after to be dried, form felt.
(4) according to the specification of the required toe-cap that makes, prepare the felt of respective numbers, and this felt is cut shaping, barrier film on felt is removed, and superpose successively, fit, then put into the toe-cap mould and heat, pressurize, make matrix material safety toes goods.Described step (4) specifically comprises the following steps: (4.1) are prepared the felt of respective numbers, and this felt are cut shaping according to the specification of the required toe-cap that makes; (4.2) barrier film on felt is removed, and superposeed successively, fit, form tabular compound material; (4.3) preparation toe-cap mould, carry out preheating to this toe-cap mould; (4.4) coat releasing agent on the die cavity of toe-cap mould; (4.5) tabular compound material is put into the die cavity of toe-cap mould; (4.6) control the toe-cap mould and carry out mould assembling action, when the punch of toe-cap mould did not touch tabular compound material, mold pressure was set as 1.5～3Mpa; When the punch of toe-cap mould touched tabular compound material, mold pressure was set as 15～30Mpa; (4.7) etc. the toe-cap die venting complete after, toe-cap mould fully closes; (4.8) the toe-cap mould is heated, pressurizeed, until tabular compound material curing molding forms the matrix material safety toes; (4.9) open the toe-cap mould, the matrix material safety toes is ejected from die cavity, obtain matrix material safety toes goods.
In the present embodiment, described alkyd resin is preferably vinyl ester resin, described initiator is peroxidation-2-ethyl acetic acid tert-butyl ester, described low shrinkage additive is preferably thermoplastic polymer, described interior remover is preferably Zinic stearas, described thickening material is preferably MgO, and described linking agent is preferably peroxidized t-butyl perbenzoate.Described glasscloth is preferably alkali-free glass fiber cloth.Described barrier film is preferably polyethylene film.
Embodiment 2: its difference from embodiment 1 be in the matrix material safety toes component with and mass percent different.Its each component and mass percent thereof are as follows: resin paste 65%, glasscloth 35%; Each component and the mass percent thereof of wherein said resin paste are as follows: alkyd resin 75%, initiator 0.2%, low shrinkage additive 20.3%, interior remover 1.5%, thickening material 1.2%, linking agent 1.8%.
Embodiment 3: its difference from embodiment 1 be in the matrix material safety toes component with and mass percent different.Its each component and mass percent thereof are as follows: resin paste 80%, glasscloth 20%; Each component and the mass percent thereof of wherein said resin paste are as follows: alkyd resin 65%, initiator 2%, low shrinkage additive 30%, interior remover 1%, thickening material 1%, linking agent 1%.
Embodiment 4: its difference from embodiment 1 be in the matrix material safety toes component with and mass percent different.Its each component and mass percent thereof are as follows: resin paste 70.5%, glasscloth 29.5%; Each component and the mass percent thereof of wherein said resin paste are as follows: alkyd resin 80%, initiator 1%, low shrinkage additive 10%, interior remover 2%, thickening material 5%, linking agent 2%.
Above-described embodiment only is the present invention's embodiment preferably, and the present invention can not enumerate out whole embodiments, and the technical scheme of one of all employing above-described embodiments, or the equivalent variations of doing according to above-described embodiment are all in protection domain of the present invention.
When making, the tolerance range of feeding quantity can directly affect size and the close end of goods, and is should be strictly in addition quantitative, material is added to equably in the die cavity of toe-cap mould, and the quantifying feed method has a: weighting method b: counting process c: volumetry.The preferred weight method of feeding in raw material.
Be divided into for two steps during matched moulds: before punch does not contact tabular compound material, need low pressure (1.5MPa～3.0MPa)) fast, can shorten like this cycle and avoid plastics to change; After the tabular compound material of punch contact, should begin to slow down toold closing speed, (15～30MPa) at a slow speed, in order to avoid damage inserts, and makes Bas Discharged in mould to use high pressure instead.
In order to get rid of air in mould, aqueous vapor and volatile matter, after toe-cap mould closure, what have also needed toe-cap mold open for some time, and this process is called exhaust, and it is rapid that bleeding should be made every effort to, must when not yet plastifying, complete material, otherwise material hardens and loses plasticity-, even open the toe-cap mould and also do not arrange gas this moment, also can not obtain desirable goods even improve temperature and pressure.Exhaust can be shortened set time, and can improve mechanical property and the electrical property of goods.For fear of the demixing phenomenon of goods, exhaust is too early or all bad after late, does not reach too early the order ground of exhaust, and solidify on slow material surface excessively, and gas is arranged not out.
When pressurize is solidified, the speed of curing speed directly has influence on production efficiency, in order to accelerate the curing of thermosetting resin, preferably add some solidifying agent when moulding, just can add the muriate of hexamethylenetetramine, magnesium or oxyhydroxide can accelerate the sclerosis of phenol formaldehyde moulding powder as the Thermocurable phenol formaldehyde moulding powder.Dwell time is preferably between 60～150 seconds.
When the demoulding, can take out by push rod or other special tool, preferably add releasing agent when reinforced.To obtain easily and fast matrix material safety toes goods.
In order further to improve the quality of goods, after the goods demoulding, often need to process under higher temperatures, the height of post-processing temperature is looked the kind of plastics and different, and the purpose of aftertreatment is: a: the assurance plastics solidify to be completed; B: reduce the moisture and volatile matter content of goods, to improve its electrical property; C: eliminate the internal stress of goods etc.Because volatile matter is further discharged, also can make shrink of product generation dimensional change during the aftertreatment oven dry, sometimes even produce warpage and crack, therefore must strictly control post-treatment condition.
When carrying out new round production, need carry out clean to the toe-cap mould.Because may leave some remaining materials and fall into overlap in the toe-cap mould during mold pressing, so must the toe-cap mold cleaning is clean after each mold pressing, can clear up with copper sheet if on the toe-cap mould, dirt settling is sacrifices consisting of an ox, a sheep and a pig, also can wipe away brush etc. by rumbling compound, coat releasing agent after inventory in order to carry out mold pressing next time.
In other embodiments, can also be according to color and the performance index of required matrix material safety toes, add pigment and the filler of corresponding proportional quantity in the resin paste.
Adopt the matrix material safety toes of producing of technology provided by the invention that following advantage is arranged: (1) safety toes characteristic of matrix material, light weight is high-strength, alleviates the deadweight of footwear body and structure.(2) anti-air and acidity is aging.(3) designability is good, can carry out material laying and optimized design of structure according to the requirement of footwear structure.(4) moulding is simple, than steel, and aluminium matter toe-cap saving of labor, the batch production performance is good especially, and the potentiality that reduce cost are very large.(5) has good toughness, impact-absorbing load.(6) has the erosion of good uvioresistant and salt thing.(7) surperficial beautiful gloss, be particularly suitable for making safety toes.
Can find out by above-mentioned advantage, the invention provides matrix material safety toes formulating of recipe science, reasonable, has good mechanical property, intensity is large, greatly strengthen impact resistance, effectively avoided kicking in the process of walking foreign object or phenomenon that the foreign object that fallen weighed, injured by a crashing object toe wounded occurs, safe, and possesses the advantages such as corrosion-resistant, high temperature resistant, cold-resistant, antiacid, alkali resistant, anti-fuel oil, work-ing life greatly; One-piece construction is simple in addition, is easy to realize, aesthetic in appearance, quality is light, is convenient to dress.
The manufacture craft of method provided by the invention is simple and easy, is easy to realize, can produce fast the matrix material safety toes.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also change and revise above-mentioned embodiment.Therefore, the embodiment that discloses and describe above the present invention is not limited to also should fall in the protection domain of claim of the present invention modifications and changes more of the present invention.In addition, although used some specific terms in this specification sheets, these terms do not consist of any restriction to the present invention just for convenience of description.As described in the above embodiment of the present invention, adopt method same or similar with it and component and other toe-cap of obtaining and preparation method thereof, all in protection domain of the present invention.
Claims (10)
1. a matrix material safety toes, is characterized in that, toe-cap has glasscloth bonding, the pressing of resin paste to form by multiple coating, and this toe-cap is made of end face, side and base hook, and the mass percent of described resin paste and glasscloth is:
Resin paste 65～80%,
Glasscloth 20～35%;
Each component and the mass percent thereof of wherein said resin paste are as follows:
Alkyd resin 65～80%,
Initiator 0.2～2%,
Low shrinkage additive 10～30%,
Interior remover 1～2%,
Thickening material 1～5%,
Linking agent 1～2%.
2. matrix material safety toes according to claim 1, it is characterized in that, described alkyd resin is vinyl ester resin, described initiator is peroxidation-2-ethyl acetic acid tert-butyl ester, described low shrinkage additive is thermoplastic polymer, described interior remover is Zinic stearas, and described thickening material is MgO, and described linking agent is peroxidized t-butyl perbenzoate.
3. matrix material safety toes according to claim 1, is characterized in that, described glasscloth is alkali-free glass fiber cloth.
4. a method of making the described matrix material safety toes of claim 1, is characterized in that, it comprises the following steps:
(1) preparing material, each component and the mass percent thereof of raw material are as follows:
Resin paste 65～80%,
Glasscloth 20～35%;
Each component and the mass percent thereof of wherein said resin paste are as follows:
Alkyd resin 65～80%,
Initiator 0.2～2%,
Low shrinkage additive 10～30%,
Interior remover 1～2%,
Thickening material 1～5%,
Linking agent 1～2%;
(2) first resin paste is coated on glasscloth, then posts respectively barrier film on the upper surface of this glasscloth and lower surface, and compacting;
(3) glasscloth after compacting is dried, form felt;
(4) according to the specification of the required toe-cap that makes, prepare the felt of respective numbers, and this felt is cut shaping, barrier film on felt is removed, and superpose successively, fit, then put into the toe-cap mould and heat, pressurize, make matrix material safety toes goods.
5. method according to claim 4, is characterized in that, described step (1) specifically comprises the following steps:
(1.1) preparation alkyd resin, initiator, low shrinkage additive, interior remover, thickening material, linking agent and glasscloth;
(1.2) take out alkyd resin, initiator, low shrinkage additive, interior remover, thickening material and the linking agent of corresponding proportional quantity, then mix and stir, make resin paste.
6. according to claim 4 or 5 described methods, it is characterized in that, described alkyd resin is vinyl ester resin, described initiator is peroxidation-2-ethyl acetic acid tert-butyl ester, described low shrinkage additive is thermoplastic polymer, and described interior remover is Zinic stearas, and described thickening material is MgO, described linking agent is peroxidized t-butyl perbenzoate, and described glasscloth is alkali-free glass fiber cloth.
7. method according to claim 4, is characterized in that, described step (2) specifically comprises the following steps:
(2.1) preparation coating machine or adhesive applicator draw glasscloth to this coating machine or adhesive applicator;
(2.2) the preparation barrier film, draw this barrier film glasscloth to coating machine or adhesive applicator;
(2.3) start coating machine or adhesive applicator, resin paste is coated on glasscloth, and then barrier film is fitted in upper surface and the lower surface of this glasscloth, and roll by the pressure roller of this coating machine or adhesive applicator, realize the purpose of compacting glasscloth.
8. according to claim 4 or 7 described methods, is characterized in that, described barrier film is polyethylene film.
9. method according to claim 4, is characterized in that, described step (3) specifically comprises the following steps:
(3.1) glasscloth after compacting is transferred in baking oven;
(3.2) starting baking oven, is 20～50 degree with the Temperature Setting of this baking oven, and the time is set as 20～60 hours;
(3.3) after to be dried, form felt.
10. method according to claim 4, is characterized in that, described step (4) specifically comprises the following steps:
(4.1) according to the specification of the required toe-cap that makes, prepare the felt of respective numbers, and this felt is cut shaping;
(4.2) barrier film on felt is removed, and superposeed successively, fit, form tabular compound material;
(4.3) preparation toe-cap mould, carry out preheating to this toe-cap mould;
(4.4) coat releasing agent on the die cavity of toe-cap mould;
(4.5) tabular compound material is put into the die cavity of toe-cap mould;
(4.6) control the toe-cap mould and carry out mould assembling action, when the punch of toe-cap mould did not touch tabular compound material, mold pressure was set as 1.5～3Mpa; When the punch of toe-cap mould touched tabular compound material, mold pressure was set as 15～30Mpa;
(4.7) etc. the toe-cap die venting complete after, toe-cap mould fully closes;
(4.8) the toe-cap mould is heated, pressurizeed, until tabular compound material curing molding forms the matrix material safety toes;
(4.9) open the toe-cap mould, the matrix material safety toes is ejected from die cavity, obtain matrix material safety toes goods.
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| CN2013100337576A CN103113733A (en) | 2013-01-30 | 2013-01-30 | Composite material safety toe cap and manufacturing method thereof |
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| CN103405002A (en) * | 2013-06-28 | 2013-11-27 | 句容市百事特复合材料有限公司 | Composite glass fiber material with mixed reinforced form and safety toe cap made of composite glass fiber material |
| CN104260366A (en) * | 2013-09-03 | 2015-01-07 | 徐振寰 | Manufacturing method of middle sole and middle sole |
| CN104382284A (en) * | 2014-11-25 | 2015-03-04 | 东莞华固复合材料科技有限公司 | New type nanocomposite safety shoe cap manufacturing method and shoe cap product thereof |
| CN105212435A (en) * | 2014-05-28 | 2016-01-06 | 淮安可宾复合材料有限公司 | A kind of nano composite material safety toes and preparation method thereof |
| CN105903172A (en) * | 2016-04-22 | 2016-08-31 | 广州市勇源日用品工业有限公司 | Ice skate titanium alloy toe cap and molding method thereof |
| CN106617477A (en) * | 2016-10-13 | 2017-05-10 | 东莞联欣运动器材有限公司 | Shoe body structure, production methods therefor and sports shoes product |
| CN106751638A (en) * | 2016-12-30 | 2017-05-31 | 华缘新材料股份有限公司 | A kind of fiber reinforced thermoset plastics and preparation method thereof |
| CN109008075A (en) * | 2018-07-03 | 2018-12-18 | 东莞华和复合材料科技有限公司 | The production method and its toe-cap of novel graphene Composite material safety toe cap |
| CN115926488A (en) * | 2022-10-28 | 2023-04-07 | 永康市赛复特工贸有限公司 | Labor protection shoe toe cap formula |
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| CN105212435A (en) * | 2014-05-28 | 2016-01-06 | 淮安可宾复合材料有限公司 | A kind of nano composite material safety toes and preparation method thereof |
| CN105212435B (en) * | 2014-05-28 | 2017-05-24 | 淮安可宾复合材料有限公司 | Safety toe cap of nano-composite material and preparation method of safety toe cap |
| CN104382284A (en) * | 2014-11-25 | 2015-03-04 | 东莞华固复合材料科技有限公司 | New type nanocomposite safety shoe cap manufacturing method and shoe cap product thereof |
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| CN106617477A (en) * | 2016-10-13 | 2017-05-10 | 东莞联欣运动器材有限公司 | Shoe body structure, production methods therefor and sports shoes product |
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| CN109008075A (en) * | 2018-07-03 | 2018-12-18 | 东莞华和复合材料科技有限公司 | The production method and its toe-cap of novel graphene Composite material safety toe cap |
| CN115926488A (en) * | 2022-10-28 | 2023-04-07 | 永康市赛复特工贸有限公司 | Labor protection shoe toe cap formula |
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