CN115519815A - Polyurethane and rubber synthetic pouring bottom process - Google Patents
Polyurethane and rubber synthetic pouring bottom process Download PDFInfo
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- CN115519815A CN115519815A CN202211069016.9A CN202211069016A CN115519815A CN 115519815 A CN115519815 A CN 115519815A CN 202211069016 A CN202211069016 A CN 202211069016A CN 115519815 A CN115519815 A CN 115519815A
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- polyurethane
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 244000043261 Hevea brasiliensis Species 0.000 description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 5
- -1 ester polyol Chemical class 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
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- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- FRPHFZCDPYBUAU-UHFFFAOYSA-N Bromocresolgreen Chemical compound CC1=C(Br)C(O)=C(Br)C=C1C1(C=2C(=C(Br)C(O)=C(Br)C=2)C)C2=CC=CC=C2S(=O)(=O)O1 FRPHFZCDPYBUAU-UHFFFAOYSA-N 0.000 description 3
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- 229920005906 polyester polyol Polymers 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical group CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 description 1
- MYRBYBROEFGOQV-UHFFFAOYSA-N C(C)(=O)OCCCC.C(CCC)NCCCC Chemical compound C(C)(=O)OCCCC.C(CCC)NCCCC MYRBYBROEFGOQV-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 241000028631 Microstomus pacificus Species 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- MRUXVMBOICABIU-UHFFFAOYSA-N [3,5-bis(methylsulfanyl)phenyl]methanediamine Chemical compound CSC1=CC(SC)=CC(C(N)N)=C1 MRUXVMBOICABIU-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D35/00—Producing footwear
- B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
- B29D35/122—Soles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D35/00—Producing footwear
- B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
- B29D35/128—Moulds or apparatus therefor
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
Abstract
The invention relates to a polyurethane and rubber synthetic pouring bottom process, which comprises the following steps: firstly, manufacturing a rubber bottom mold and producing a rubber bottom; secondly, manufacturing a polyurethane outsole mold and a cover plate, wherein the polyurethane outsole mold is arranged between the rubber outsole mold and the cover plate; putting the rubber bottom into the rubber bottom mould again; a layer of rubber suction mould sheet is added on the rubber bottom; and thirdly, preparing a polyurethane sole stock solution, injecting the polyurethane sole stock solution into a polyurethane outsole mold, melting the rubber suction mold piece through the temperatures of the polyurethane sole stock solution and the rubber sole, maintaining the temperature between 70 and 80 ℃, forming the polyurethane after 5 to 6 minutes, melting and crosslinking the polyurethane and the rubber sole together through the rubber suction mold piece, ensuring the firmness of the sole, and preparing the injection sole with the rubber sole as the sole bottom layer and the polyurethane sole as the upper layer.
Description
Technical Field
The invention relates to the technical field of sole production processes, in particular to a polyurethane and rubber synthetic pouring sole process.
Background
The shoes in daily life are various, such as formal, leisure, sports, slippers and the like. Different shoe styles use different materials and have different functions. Some shoes are heavy and some shoes are light, which are caused by different materials. Different materials have different special properties, such as the cowhells and the rubber materials are relatively wear-resistant; the foaming materials such as EVA and the like are lighter and are suitable for sports; the pu material is light, is suitable for various leisure shoes, but does not have the performances of wear resistance, skid resistance and the like; therefore, according to the wearing requirements of people, a novel filling and combining process needs to be developed, two or more materials are filled through processes such as a mold, temperature, a flow and the like, and then are combined together to form a sole, and the sole has various characteristics such as PU, rubber and the like.
Although the conventional polyurethane outsole is light, the conventional polyurethane outsole is not wear-resistant, non-skid and easy to hydrolyze, most importantly, the polyurethane outsole is easy to decompose in a closed environment and turns into powder under pressure, and in addition, the pu polyurethane outsole is easy to break off at low temperature, and the sole is broken off under the condition that the vamp of a pair of shoes is still intact.
Because the pu polyurethane outsole has the weakness, a rubber sheet is adhered to the lower surface of a plurality of sandals in the prior art, and the functions of skid resistance, wear resistance and the like are achieved. However, such rubber veneers are often adhered by glue, and are easy to fall off after a long time, so that the value of the pair of shoes is lost.
At present, most of common soles in life are rubber undersoles, common casual shoes and formal soles are rubber undersoles, but the rubber materials are heavy, so the comfort and the experience of the shoes are not good, and the soles are heavy, so the whole shoes look heavy.
Disclosure of Invention
The invention aims to provide a polyurethane and rubber synthetic pouring bottom process, which aims to solve the technical problems of at least how to pour two different materials and then form the materials to produce a novel special sole and finally obtain a sole product which has the double characteristics of wear resistance, skid resistance and the like of rubber and the light and portable effect of polyurethane.
In order to achieve the above object, the present invention provides a polyurethane and rubber synthetic pouring bottom process, comprising the following steps:
firstly, manufacturing a rubber bottom mold, and producing a rubber bottom by using the rubber bottom mold;
secondly, manufacturing a polyurethane outsole mold and a cover plate, and hinging the rubber outsole mold, the polyurethane outsole mold and the cover plate together through hinges to form a shoe mold; the polyurethane outsole mold is arranged between the rubber outsole mold and the cover plate; putting the rubber bottom produced in the first step back into the rubber bottom mould; a layer of rubber suction mold piece is added on the rubber bottom;
and thirdly, preparing a polyurethane sole stock solution, rotationally covering the polyurethane outsole mold on the rubber sole mold and a rubber sole arranged in the rubber sole mold, injecting the polyurethane sole stock solution into the polyurethane outsole mold, rotationally covering the cover plate on the polyurethane outsole mold and the polyurethane sole stock solution, clamping the rubber suction mold piece between the polyurethane sole stock solution and the rubber sole, enabling the rubber suction mold piece to melt through the temperatures of the polyurethane sole stock solution and the rubber sole, maintaining the temperature between 70 ℃ and 80 ℃ and forming the polyurethane after 5 to 6 minutes, and enabling the polyurethane suction mold piece to melt and crosslink the polyurethane and the rubber sole together to ensure the firmness of the sole, so that the sole bottom layer is made of rubber, and the upper layer of the sole is a poured sole of polyurethane.
Preferably, the specific steps of using the rubber bottom mold to produce the rubber bottom in the first step comprise cleaning the rubber bottom mold, adjusting the rubber bottom mold, spraying a release agent, placing a rubber raw material and placing the rubber raw material into a pressure device for molding.
Preferably, the second step of injecting the polyurethane sole solution into the polyurethane outsole mold comprises the specific steps of cleaning the polyurethane outsole mold, adjusting the polyurethane outsole mold, spraying a mold release agent, injecting a polyurethane raw material and performing in-mold molding.
Preferably, the step of preparing the polyurethane sole stock solution in the third step specifically comprises: the polyurethane sole stock solution comprises a component A, a component B and a component C, wherein the component A is obtained by fully and uniformly mixing polyether polyol, a chain extender, a foaming agent, a catalyst and a foam stabilizer in a mixer; the component B is modified isocyanate or liquefied MDI; the component C is a catalyst.
Preferably, the polyether polyol is a mixed polyol containing both an ether and an ester.
Preferably, the third step of injecting the polyurethane sole liquid into the polyurethane outsole mold comprises the specific steps of: the method comprises the steps of completely melting the component A and the component B of the polyurethane sole stock solution in a raw material preheating oven, respectively adding the melted components into a stock solution tank of a sole forming machine, respectively adjusting the rotating speeds of metering pumps of the component A and the component B according to the formula requirement and the pouring amount, injecting the component A and the component B of the polyurethane sole stock solution into a mixing device from the stock solution tank through the metering pumps, uniformly stirring and mixing the component A and the component B of the polyurethane sole stock solution in the mixing device at a high speed to generate a chemical reaction, pouring a mixture in the mixing device into a polyurethane outsole mold, adjusting the pouring time set by a computer program controller according to the size of a shoe mold cavity in the polyurethane outsole mold, rotationally covering the cover plate on the polyurethane outsole mold and the polyurethane sole stock solution to form a shoe mold, heating and curing the shoe mold, and obtaining a finished product after demolding, trimming, finishing and inspecting.
Preferably, before the component A and the component B of the polyurethane sole stock solution are injected into the mixing device from the stock solution tank through the metering pump, the component C and the color paste are added into the component A according to requirements.
Preferably, when the double-color sole is produced, the stock solution of the polyurethane sole needs to be poured on the sole after the first curing for the second time.
Preferably, the rubber used for producing the rubber sole in the first step is prepared by the following steps: weighing raw materials, mixing, open milling on a wheel table, discharging pieces on the wheel table, storing, weighing large materials and ingredients, open milling on the large materials and ingredients, discharging pieces on the large materials and ingredients on the wheel table, cutting, vulcanizing, secondarily vulcanizing a foamed base, roughening, cutting, trimming, finishing and discharging.
Preferably, said storage is for a minimum of 24 hours.
Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
the polyurethane and rubber synthetic pouring bottom process disclosed by the invention is characterized in that two materials with different properties, namely Polyurethane (PU) and rubber, are poured and combined, and the two different materials are poured and formed through mold change, process flow change, temperature change and the like, so that a novel special sole is produced.
According to the polyurethane and rubber synthetic pouring sole process, after the rubber outsole is formed, a layer of rubber suction mold piece is added on the rubber outsole, the rubber suction mold piece is placed and then injected with polyurethane materials, and the polyurethane is formed at the temperature of 70-80 ℃ for 5-6 minutes, so that the rubber suction mold piece can be better melted and crosslinked with the rubber and the polyurethane, the firmness of the sole is ensured, and the novel pouring sole with the rubber at the bottom layer and the polyurethane at the upper layer, which is wear-resistant, skid-resistant, light and soft, can be manufactured.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
Fig. 1 is a schematic structural diagram of a polyurethane outsole mold and a rubber outsole mold according to the present invention.
Detailed Description
The present invention is described in more detail below to facilitate an understanding of the present invention.
As shown in FIG. 1, the polyurethane and rubber synthetic pouring bottom process of the invention comprises the following steps:
firstly, manufacturing a rubber bottom mold 1, and producing a rubber bottom by using the rubber bottom mold;
secondly, manufacturing a polyurethane outsole mold 2 and a cover plate 3, and hinging the rubber outsole mold 1, the polyurethane outsole mold 2 and the cover plate 3 together through a hinge 4 to form a shoe mold; the polyurethane outsole mold 2 is arranged between the rubber outsole mold 1 and the cover plate 3; the rubber bottom produced in the first step is put back into the rubber bottom mould 1 again; a layer of rubber suction mold piece is added on the rubber bottom;
thirdly, preparing a polyurethane sole stock solution, rotationally covering the polyurethane outsole mold 2 on the rubber sole mold 1 and a rubber sole arranged in the rubber sole mold 1, injecting the polyurethane sole stock solution into the polyurethane outsole mold 2, rotationally covering the cover plate 3 on the polyurethane outsole mold 2 and the polyurethane sole stock solution, clamping the rubber suction mold piece between the polyurethane sole stock solution and the rubber sole, melting the rubber suction mold piece through the polyurethane sole stock solution and the rubber sole, maintaining the temperature between 70 ℃ and 80 ℃ and forming polyurethane after 5 to 6 minutes, melting and crosslinking the polyurethane and the rubber sole through the rubber suction mold piece, ensuring the firmness of the sole, manufacturing a novel sole which is made of rubber, and an upper layer of the sole is made of polyurethane, is skid-proof, is light and soft, and is wear-resistant.
Because the melting temperature of the conventional rubber is about 160 ℃, the temperature can enable the raw material of the rubber to be completely melted into the shape of a mold, namely, the rubber sole is made. When the rubber outsole is molded for the first time, the temperature for injecting polyurethane at the back is just about 80 ℃, so that the semi-dissolved state at the joint of the rubber outsole and the polyurethane outsole is just ensured, and the rubber outsole and the polyurethane are better combined together. Because the temperature is not well controlled, the problem that the two materials are broken when combined due to different materials and different fusion agents is also feared, a process is added at present, the process is also a new process, namely, after the rubber outsole is formed, a layer of rubber suction mold sheet is added on the rubber outsole, polyurethane material is injected after the rubber suction mold sheet is placed, and the polyurethane is formed at the temperature of between 70 and 80 ℃ for 5 to 6 minutes, so that the rubber suction mold sheet can be better melted with the rubber and the polyurethane, the firmness of the sole is ensured, and the novel injection sole with the rubber at the bottom layer and the polyurethane at the upper layer, which is wear-resistant, skid-resistant, light and soft, can be manufactured.
Preferably, the thickness of the rubber suction piece is one-thirtieth to one-tenth of the thickness of the rubber substrate, and the rubber suction piece is subjected to vulcanization treatment, so that the rubber suction piece can be melted at a temperature of between 70 and 80 ℃ and is crosslinked with the rubber substrate and the polyurethane.
In the experimental process, the thinner the thickness of the rubber suction mold piece is, the lower the temperature required for melting is. The thickness of the rubber suction piece is controlled to be one-thirtieth to one-tenth of that of the rubber substrate, and the rubber suction piece can be melted at the temperature of 70-80 ℃ by matching with vulcanization treatment.
The polyurethane and rubber synthetic pouring bottom process is divided into two parts, one is a material proportioning part and the other is a mould part.
The first step of using the rubber bottom mold to produce the rubber bottom comprises the specific steps of cleaning the rubber bottom mold, adjusting the rubber bottom mold, spraying a release agent, placing raw materials and placing the raw materials into pressure equipment for molding.
And in the second step, the concrete steps of injecting the polyurethane sole stock solution into the polyurethane outsole mold comprise cleaning the polyurethane outsole mold, adjusting the polyurethane outsole mold, spraying a release agent, injecting a polyurethane raw material and performing in-mold molding.
The combination is that rubber is firstly molded, then a suction mold sheet is put in the rubber, and then polyurethane material is injected for molding. The material proportioning part mainly comprises the preparation of rubber and the preparation of polyurethane sole stock solution.
The polyurethane sole stock solution can be divided into polyester type and polyether type. Polypropylene glycol systems developed in the early years are mostly polyester-based systems, and the preparation methods are different due to different properties.
The polyester type PU sole stock solution is prepared by a prepolymer method or a semi-prepolymer method mostly and can be generally prepared into two components or three components, wherein the component A comprises partial polyester, a chain extender, a foam stabilizer, a foaming agent and the like, and is prepared by uniformly mixing, standing and degassing. In the all-water foam system, the foaming agent is water, and the amount of water in the A component must be measured, and the content thereof is generally about 0.4%. The component B is an isocyanate-terminated prepolymer prepared by reacting part of polyester polyol with isocyanate. The relative molecular mass of the polyester polyol is preferably from 1500 to 2000. Of the isocyanates, the ratio of pure MDI (4,4' diphenylmethane diisocyanate) to liquefied MDI was 19:1. in the reaction process, one ten thousandth of inhibitor of the mass of the raw materials is added to prevent the side reaction, and the temperature is kept for 2 to 3 hours, wherein the NCO percent is controlled to be about 19 percent. The component C is a catalyst (added into the component A to form a two-component stock solution). The three-component system is suitable for two-color, low-hardness sports shoes and low-density sandals. When in use, the component A and the component C are mixed uniformly and then mixed with the component B. Its advantages are low viscosity and reactivity, low hardness and size variation, and high stability.
In the present application, NCO means an aromatic polyisocyanate based on diphenylmethane diisocyanate, and NCO% means the NCO value. The NCO value is the mass of NCO groups contained in 100g of curing agent.
The NCO value was checked as follows:
unless otherwise specified, reagents used in the detection method are all reagents of above chemical purity, n-butyl acetate requires that the water content is less than or equal to 0.1 percent, the alcohol content is less than or equal to 0.15 percent, and the used distilled water meets the requirement of GB/T6682-1992 laboratory third-class water.
Preparing a solution:
di-n-butylamine-n-butyl acetate solution:
10mL of di-n-butylamine is weighed and added into 50mL of n-butyl acetate, the mixture is uniformly mixed and placed in a sealed container, and the solution is ready to use.
0.5mol/L HCl standard solution: prepared and calibrated according to the GB/T601-1988.
0.1% (m/V) bromocresol green indicator:
0.1g of bromocresol green is weighed out and dissolved in 100mL of absolute ethanol.
The operation method comprises the following steps:
adding 20ML butyl acetate into an Erlenmeyer flask, accurately weighing (1-1.5) g (accurately to 0.001 g) of a curing agent, placing the curing agent into the Erlenmeyer flask with a ground opening and a plug, accurately transferring 20mL of di-n-butylamine butyl ester solution into the Erlenmeyer flask by using a transfer pipette, tightly covering the Erlenmeyer flask by using a bottle plug, slightly shaking to dissolve and mix the curing agent uniformly, standing for 20min, adding 20mL of absolute ethyl alcohol, shaking uniformly, dripping (3-5) of 0.1% bromocresol green indicator, titrating by using 0.5mol/L of HCl standard solution until the curing agent just becomes yellow to be a titration endpoint, and simultaneously carrying out a blank test.
And (3) calculating:
the NCO value is calculated according to equation (1).
NCO value (%) = (V0-V1). Times.CHCl 4.2/m (1)
In formula (1), V0-the volume of HCl standard solution consumed in the blank test, mL;
v1-volume of HCl standard solution consumed by the sample, mL;
CHCl-HCl standard solution concentration, mol/L;
m is the sample mass, g.
Representation of the results:
taking the arithmetic mean value of the parallel measurement results as the measurement results, and the absolute error of the parallel measurement results is not more than 0.2%.
The polyether type polyurethane sole stock solution is prepared by adopting a one-step method. The polyether type polyurethane sole stock solution also comprises a component A, a component B and a component C, wherein the component A is prepared by fully and uniformly mixing polyether polyol, a chain extender, a foaming agent, a foam stabilizer and the like in a mixer: the component B is modified isocyanate or liquefied MDI. The component C is a catalyst. The polyether polyol can endow the sole with the characteristics of high strength, wear resistance, strong adhesion with a vamp and the like, the polyether polyurethane sole overcomes the defects of poor water resistance and poor low-temperature elasticity of the polyester polyurethane sole, the formability is good, and the physical and mechanical properties of the sole can be kept basically unchanged while the excellent low-temperature flexibility and elasticity are endowed. Under the condition of low density, the dimensional stability of the polyester sole is poor, while the dimensional stability of the polyether sole is good but the mechanical property is low under the same density, so that in a water foaming system, the mechanical strength and the wear resistance of the product can be improved by mixing two alcohols according to a certain proportion. For example, polyether 2 ester polyol is a mixed polyol containing both ether and ester, and the performance of the sole material is between that of polyester type and polyether type. The domestic polyether is used as the main raw material to be blended with a specific amount of polyester polyol for improvement, so that the polyester 2 ether type foaming shoe sole material is synthesized, the physical and mechanical properties of the shoe sole material are superior to indexes GB10508289, and the cost of the shoe sole material is 10 to 15 percent lower than that of a pure polyester type PU sole material.
Preferably, the chain extender is diethyltoluenediamine or 3,5-dimethylthiotoluenediamine.
Chain extenders are usually diols and diamines low molecular compounds, mainly diamines.
Preferably, the foaming agent is polyether or isocyanate.
Preferably, the foam stabilizer is a silicone surfactant or a polysiloxane-alkylene oxide block copolymer.
The foam stabilizer is one of the essential raw materials in the foaming process of polyurethane foam plastics and plays a key role in foaming. Silicone surfactants (Silicone surfactants), also known as foam leveling agents and foam stabilizers.
Polyether-modified foam stabilizers for polyurethane foams are mostly polyether-grafted or block-type structures (both hydrophilic and hydrophobic groups are in the main chain), such as block copolymers of polysiloxane-alkylene oxides. The polysiloxane chain segment is hydrophobic, the polyoxyalkylene chain segment is hydrophilic, the coexistence of the polysiloxane chain segment and the polyoxyalkylene chain segment has the function of interface orientation, the compatibility of various raw materials is improved, and the dispersed particle size can be reduced to be in a microemulsion state, so that the raw materials can be emulsified into a uniform system, which is called as solubilization and emulsification in the field.
Preferably, the catalyst is a solution of Triethylenediamine (TEDA).
The catalyst used in the present application is a strong gel type tertiary amine catalyst that can be used to catalyze urethane (polyol-isocyanate) reactions in flexible foams.
The forming process of the polyurethane sole comprises the following specific steps: the method comprises the steps of completely melting the component A and the component B of the polyurethane sole stock solution in a raw material preheating oven, respectively adding the completely melted components into a stock solution tank of a sole forming machine, respectively adjusting the rotating speeds of metering pumps of the two components (the component A and the component B) according to the formula requirement and the pouring amount, injecting the component A and the component B of the polyurethane sole stock solution into a mixing device through the stock solution tank through the metering pumps, uniformly stirring and mixing the component A and the component B of the polyurethane sole stock solution in the mixing device at a high speed to generate a chemical reaction, pouring a mixture in the mixing device into a polyurethane outsole mold 2, adjusting the pouring time set by a computer program controller according to the size of a shoe mold cavity in the polyurethane outsole mold 2, conveying a capped shoe mold (namely, covering the cover plate 3 on the polyurethane outsole mold 2 and the polyurethane sole stock solution in a rotating manner) to an annular production line to heat and cure the shoe mold (the shoe sole is cured and then is subjected to secondary curing), and obtaining a cured PU, trimming, finishing, inspecting and spraying the finished product, and adjusting the pouring speed of the shoe mold release agent according to the whole production line.
Preferably, before the component A and the component B of the polyurethane sole stock solution are injected into the mixing device from the stock solution tank through the metering pump, the component C (catalyst) and the color paste are added into the component A according to requirements.
Preferably, the rubber preparation process is: weighing raw materials, mixing, open milling on a wheel table, discharging pieces on the wheel table, storing (at least 24 hours), weighing large materials and ingredients, open milling on the large materials and the ingredient wheel table, discharging pieces on the large materials and the ingredient wheel table, cutting, vulcanizing for the second time of a foamed base, roughing, cutting, trimming, finishing and discharging.
The basic formulation materials used in the preparation of the rubber include:
(1) Rubber (natural Rubber, synthetic Rubber);
(2) A promoting agent;
(3) Curing agents, also known as bridging agents;
(4) An activator, active agent;
(5) And others: additives (fillers, processing aids, protectants, colorants, etc.).
Wherein, the natural rubber comprises the following components: the mass fraction of the liquid gum is 80 percent and the mass fraction of the solid gum is 20 percent.
The natural rubber has the characteristics that: a. the viscosity is very high; b. easier to process than synthetic rubbers; c. good tearing force, tensile force, heat bearing property and high elasticity, has a better structure, but has unstable physical properties.
The types of natural rubber include: raw rubber No. 3 and standard rubber;
the production area of natural rubber comprises: produced in subtropical and tropical rainforest regions (Malaysia, thailand, brazil, etc.).
Preferably, as shown in fig. 1, the hinge 4 may be provided at both the top of the rubber sole mold 1, the polyurethane outsole mold 2, and the cover plate 3 (i.e., at the position of the toe cap) and the side of the rubber sole mold 1, the polyurethane outsole mold 2, and the cover plate 3 (i.e., at the position of the arch). Rubber end mould 1, polyurethane outsole mould 2 and apron 3 form the shoe mold through hinge 4 is articulated together, polyurethane outsole mould 2 places in the centre, mould 1 places in one side of polyurethane outsole mould 2 through the hinge 4 of side at the bottom of the rubber, perhaps places in front of polyurethane outsole mould 2 through the hinge 4 at top, namely mould 1 can rotate through flip's mode at the bottom of the rubber, both sides flip about can be, flip around also can be.
In a whole and simple way, the polyurethane and rubber synthetic pouring bottom process is a novel production process for combining two materials, namely a novel process for perfectly combining the two materials together by combining the rubber and the polyurethane, combining a plurality of dies, combining a plurality of process flows, combining temperature difference and the like.
The foregoing describes preferred embodiments of the present invention, but is not intended to limit the invention thereto. Modifications and variations of the embodiments disclosed herein may be made by those skilled in the art without departing from the scope and spirit of the invention.
Claims (10)
1. The polyurethane and rubber synthetic pouring bottom process is characterized by comprising the following steps of:
firstly, manufacturing a rubber bottom mold, and producing a rubber bottom by using the rubber bottom mold;
secondly, manufacturing a polyurethane outsole mold and a cover plate, and hinging the rubber outsole mold, the polyurethane outsole mold and the cover plate together through hinges to form a shoe mold; the polyurethane outsole mold is arranged between the rubber outsole mold and the cover plate; putting the rubber bottom produced in the first step back into the rubber bottom mould; a layer of rubber suction mold piece is added on the rubber bottom;
and thirdly, preparing a polyurethane sole stock solution, rotationally covering the polyurethane outsole mold on the rubber sole mold and a rubber sole arranged in the rubber sole mold, injecting the polyurethane sole stock solution into the polyurethane outsole mold, rotationally covering the cover plate on the polyurethane outsole mold and the polyurethane sole stock solution, clamping the rubber suction mold piece between the polyurethane sole stock solution and the rubber sole, enabling the rubber suction mold piece to melt through the temperatures of the polyurethane sole stock solution and the rubber sole, maintaining the temperature between 70 ℃ and 80 ℃ and forming the polyurethane after 5 to 6 minutes, and enabling the polyurethane suction mold piece to melt and crosslink the polyurethane and the rubber sole together to ensure the firmness of the sole, so that the sole bottom layer is made of rubber, and the upper layer of the sole is a poured sole of polyurethane.
2. The process for preparing a polyurethane and rubber composite injection bottom according to claim 1, wherein the specific steps of using the rubber bottom mold to produce the rubber bottom in the first step comprise cleaning the rubber bottom mold, adjusting the rubber bottom mold, spraying a release agent, placing rubber raw materials and placing the rubber raw materials into a pressure device for molding.
3. The process for preparing a polyurethane and rubber synthetic insole according to claim 1, wherein the specific steps of injecting the polyurethane sole dope into the polyurethane outsole mold in the second step include cleaning the polyurethane outsole mold, adjusting the polyurethane outsole mold, spraying a mold release agent, injecting a polyurethane raw material, and in-mold forming.
4. The polyurethane and rubber synthetic pouring sole process according to claim 1, wherein the step of preparing the polyurethane sole stock solution in the third step is specifically: the polyurethane sole stock solution comprises a component A, a component B and a component C, wherein the component A is obtained by fully and uniformly mixing polyether polyol, a chain extender, a foaming agent, a catalyst and a foam stabilizer in a mixer; the component B is modified isocyanate or liquefied MDI; the component C is a catalyst.
5. The polyurethane and rubber synthetic casting base process of claim 4, wherein the polyether polyol is a mixed polyol containing both ether and ester.
6. The process for preparing a polyurethane and rubber synthetic insole according to claim 4, wherein said third step of injecting said polyurethane sole liquid into said polyurethane outsole mold comprises the steps of: the method comprises the steps of completely melting the component A and the component B of the polyurethane sole stock solution in a raw material preheating oven, respectively adding the melted components into a stock solution tank of a sole forming machine, respectively adjusting the rotating speeds of metering pumps of the component A and the component B according to the formula requirement and the pouring amount, injecting the component A and the component B of the polyurethane sole stock solution into a mixing device from the stock solution tank through the metering pumps, uniformly stirring and mixing the component A and the component B of the polyurethane sole stock solution in the mixing device at a high speed to generate a chemical reaction, pouring a mixture in the mixing device into a polyurethane outsole mold, adjusting the pouring time set by a computer program controller according to the size of a shoe mold cavity in the polyurethane outsole mold, rotationally covering the cover plate on the polyurethane outsole mold and the polyurethane sole stock solution to form a shoe mold, heating and curing the shoe mold, and obtaining a finished product after demolding, trimming, finishing and inspecting.
7. The process for preparing a synthetic pouring sole of polyurethane and rubber according to claim 6, wherein the component A and the component B are added to the component A as required before the component A and the component B are injected into the mixing device from the stock solution tank through the metering pump.
8. The process for preparing a synthetic injection sole of polyurethane and rubber as claimed in claim 6, wherein when producing a two-color sole, the primary polyurethane sole liquid is poured on the primary cured sole for the second time.
9. The polyurethane and rubber synthetic potting base process of claim 1, wherein the rubber used in the first step to produce the rubber base is prepared by the following steps: weighing raw materials, mixing, open milling on a wheel table, discharging pieces on the wheel table, storing, weighing large materials and ingredients, open milling on the large materials and ingredients, discharging pieces on the large materials and ingredients on the wheel table, cutting, vulcanizing, secondarily vulcanizing a foamed base, roughening, cutting, trimming, finishing and discharging.
10. The polyurethane and rubber synthetic casting base process of claim 9, wherein said storing is for a minimum of 24 hours.
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Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2241493A1 (en) * | 1972-08-23 | 1974-03-14 | Desma Werke Gmbh | METHOD AND DEVICE FOR MANUFACTURING MULTI-LAYERED SOLES FROM LOW VISCOSITY MATERIALS, IN PARTICULAR POLYURETHANE OR RUBBER |
JPH06113902A (en) * | 1992-09-30 | 1994-04-26 | Achilles Corp | Manufacture of shoes |
JPH10323850A (en) * | 1997-05-23 | 1998-12-08 | Nippon Mektron Ltd | Mold for urethane rubber molding and molding method using the same |
JP2002028002A (en) * | 2000-07-18 | 2002-01-29 | Mizuno Corp | Shoe sole |
KR200304929Y1 (en) * | 2002-08-26 | 2003-02-19 | 진재학 | The manufacturing mold for outsole attached none-forming material |
EP1356919A1 (en) * | 2002-04-24 | 2003-10-29 | KLÖCKNER DESMA SCHUHMASCHINEN GmbH | Method for the production of shoe soles |
CN1470201A (en) * | 2002-06-26 | 2004-01-28 | ���ȿ���ͨ�Źɷ�����˾ | Method for producing shoe sole composed of external sole of rubber sulfide jointed on middle sole of polyurethane and composition thereof |
CN203305306U (en) * | 2013-06-17 | 2013-11-27 | 徐玉冰 | Novel rubber composite punching die |
CN104013157A (en) * | 2014-06-19 | 2014-09-03 | 方柏明 | PU elastic environment-friendly shoe sole and production method and manufacturing mold thereof |
CN104972667A (en) * | 2015-06-08 | 2015-10-14 | 佛山市南方鞋材有限公司 | Manufacturing technology and equipment of shoe outsole |
CN105774009A (en) * | 2016-04-29 | 2016-07-20 | 广州润凯实业股份有限公司 | Production method for shoe sole with metal texture, shoe sole and pair of shoes |
CN106393543A (en) * | 2016-09-14 | 2017-02-15 | 佛山市南海创意鞋材有限公司 | Integrated forming technology for combined shoe sole |
CN206579041U (en) * | 2017-02-15 | 2017-10-24 | 广州市邦尔福鞋材有限公司 | A kind of rubber capsule heel and footwear sole construction |
CN107868205A (en) * | 2017-12-14 | 2018-04-03 | 山东诺威聚氨酯股份有限公司 | Cold-resistant polyurethane shoe-sole stoste and preparation method |
CN109608681A (en) * | 2018-11-07 | 2019-04-12 | 高邮市强杰塑料制品有限公司 | A kind of production technology of polyurethane foam sole |
-
2022
- 2022-09-02 CN CN202211069016.9A patent/CN115519815A/en active Pending
Patent Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2241493A1 (en) * | 1972-08-23 | 1974-03-14 | Desma Werke Gmbh | METHOD AND DEVICE FOR MANUFACTURING MULTI-LAYERED SOLES FROM LOW VISCOSITY MATERIALS, IN PARTICULAR POLYURETHANE OR RUBBER |
JPH06113902A (en) * | 1992-09-30 | 1994-04-26 | Achilles Corp | Manufacture of shoes |
JPH10323850A (en) * | 1997-05-23 | 1998-12-08 | Nippon Mektron Ltd | Mold for urethane rubber molding and molding method using the same |
JP2002028002A (en) * | 2000-07-18 | 2002-01-29 | Mizuno Corp | Shoe sole |
EP1356919A1 (en) * | 2002-04-24 | 2003-10-29 | KLÖCKNER DESMA SCHUHMASCHINEN GmbH | Method for the production of shoe soles |
CN1453123A (en) * | 2002-04-24 | 2003-11-05 | 克勒克纳-德斯马制鞋设备有限公司 | Method for producing especially soles in mechanical shoes-production |
CN1470201A (en) * | 2002-06-26 | 2004-01-28 | ���ȿ���ͨ�Źɷ�����˾ | Method for producing shoe sole composed of external sole of rubber sulfide jointed on middle sole of polyurethane and composition thereof |
KR200304929Y1 (en) * | 2002-08-26 | 2003-02-19 | 진재학 | The manufacturing mold for outsole attached none-forming material |
CN203305306U (en) * | 2013-06-17 | 2013-11-27 | 徐玉冰 | Novel rubber composite punching die |
CN104013157A (en) * | 2014-06-19 | 2014-09-03 | 方柏明 | PU elastic environment-friendly shoe sole and production method and manufacturing mold thereof |
CN104972667A (en) * | 2015-06-08 | 2015-10-14 | 佛山市南方鞋材有限公司 | Manufacturing technology and equipment of shoe outsole |
CN105774009A (en) * | 2016-04-29 | 2016-07-20 | 广州润凯实业股份有限公司 | Production method for shoe sole with metal texture, shoe sole and pair of shoes |
CN106393543A (en) * | 2016-09-14 | 2017-02-15 | 佛山市南海创意鞋材有限公司 | Integrated forming technology for combined shoe sole |
CN206579041U (en) * | 2017-02-15 | 2017-10-24 | 广州市邦尔福鞋材有限公司 | A kind of rubber capsule heel and footwear sole construction |
CN107868205A (en) * | 2017-12-14 | 2018-04-03 | 山东诺威聚氨酯股份有限公司 | Cold-resistant polyurethane shoe-sole stoste and preparation method |
CN109608681A (en) * | 2018-11-07 | 2019-04-12 | 高邮市强杰塑料制品有限公司 | A kind of production technology of polyurethane foam sole |
Non-Patent Citations (4)
Title |
---|
吴培熙: "《塑料制品生产工艺手册》", 28 February 1991, 化学工业出版社, pages: 290 - 291 * |
林仕明: "《时装女鞋制作工程 工艺技术篇》", 31 March 2009, 中国轻工业出版社, pages: 130 - 131 * |
欧国荣: "《高分子科学与工程实验》", 31 December 1997, 华东理工大学出版社, pages: 150 - 151 * |
童幸生: "《材料成形工艺基础》", 31 August 2010, 华中科技大学出版社, pages: 174 - 175 * |
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