CN110343323B - Open-cell EVA (ethylene vinyl acetate) foaming composite shoe material and manufacturing method thereof - Google Patents
Open-cell EVA (ethylene vinyl acetate) foaming composite shoe material and manufacturing method thereof Download PDFInfo
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/0009—Footwear characterised by the material made at least partially of alveolar or honeycomb material
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/14—Footwear characterised by the material made of plastics
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
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- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/05—Open cells, i.e. more than 50% of the pores are open
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
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Abstract
An open-cell EVA foaming composite shoe material and a manufacturing method thereof relate to an EVA foaming shoe material. The open-cell EVA foaming composite shoe material comprises the following raw materials: ethylene-vinyl acetate copolymer-1, ethylene-vinyl acetate copolymer-2, ethylene olefin copolymer, thermoplastic elastomer SEPS, ethylene propylene diene monomer, stearic acid, di-tert-butylperoxyisopropyl benzene and modified dinitropentamethylene tetramine foaming agent. Is prepared by adopting an injection molding or secondary compression molding method. The foam holes formed by the foaming body are connected with the foam holes in series locally, the large air bag formed by the surface skin is communicated with the small air bag, and when the small air bag is subjected to external pressure and impact, the borne pressure can be dispersed and transferred relatively, so that the impact resistance is greatly improved; the foam skin formed by the foam is very thin and difficult to wrinkle, and the appearance structure is kept for a long time. Compared with the traditional EVA foaming shoe material, the elasticity, the shock absorption performance, the crease resistance, the formability and the like are obviously improved.
Description
Technical Field
The invention relates to an EVA (ethylene-vinyl acetate copolymer) foaming shoe material, in particular to an open-cell EVA foaming composite shoe material and a manufacturing method thereof.
Background
China is a large country for producing and consuming shoes, various shoes are fully available, and particularly, with the special army prominence of sports brands of lie and army, sports shoes are popular in daily life of people. Meanwhile, the living and consumption level of people is greatly improved, and consumers have paid attention to the appearance of the pair of shoes, namely the shoes have fashionable appearance and more comfortable foot feeling. Therefore, shoe material development engineers have become a popular occupation in recent years, and experts, professors, doctors and researchers in all colleges and universities have been in the industry of not seeing shoe materials, and nowadays, the shoe material development engineers are greatly introduced, and professional hardpowers are injected. The investment of shoe material enterprises on shoe material research and development is gradually strengthened, a special research and development center is established, and full-time research and development personnel make own contribution to the development of domestic shoe materials.
At present, a lot of reports on EVA foamed shoe materials are reported in the market, for example, Chenyonghua and Lin pine cypress disclose an EVA foamed shoe material between closed cells and open cells and a manufacturing method thereof in Chinese invention patent ZL201510221969.6, and the invention relates to an EVA foamed shoe material. The EVA foaming shoe material between the closed hole and the open hole comprises raw materials of ethylene-vinyl acetate copolymer, ethylene-octene copolymer, ethylene propylene diene monomer, stearic acid, zinc stearate, zinc oxide, dicumyl peroxide, foaming agent and color master batch. Mixing dicumyl peroxide and a foaming agent for later use, mixing the other raw materials, then carrying out first-stage banburying, adding a mixture of dicumyl peroxide and the foaming agent when the temperature reaches 105-110 ℃, carrying out second-stage banburying until the temperature is raised to 112-115 ℃ to obtain a mixture, thinning for 2 times, discharging, putting into a flat plate mold, and adding sulfur for foaming; standing, and carrying out surface peeling, slitting, oblique cutting, polishing, hot-press forming, trimming and other treatments to obtain the EVA foamed shoe material between closed pores and open pores. Liao shuqiong, Wu Shicheng and so on in Chinese invention patent CN201910018662.4 disclose a kind of sports shoes coarse hole composite foaming material, its preparation method and application, this material is made by foaming the composite material of the expandable elastomer, the composite material of said expandable elastomer includes the following component of part by mass: 15-25 parts of a polyolefin elastomer; 20-45 parts of ethylene-vinyl acetate copolymer; 15-35 parts of an olefin block copolymer; 5-10 parts of polyethylene; 2-8 parts of calcium carbonate; 0.6-1.5 parts of nano active zinc oxide; 0.5-0.8 parts of stearic acid; 0.5-0.8 part of a cross-linking agent; 3-5 parts of a coarse-pore foaming agent; the coarse-pore composite foam material for the sneakers has an open-pore spherical cell structure.
In recent years, EVA foamed shoe materials have been widely applied in the field of shoe materials, and the performance and comfort of the EVA foamed shoe materials are improved with the addition of more other foamed polymer materials.
Disclosure of Invention
The invention aims to provide an open-cell EVA (ethylene vinyl acetate) foamed composite shoe material which is suitable for injection molding and in-mold foaming secondary mold pressing and shaping and a manufacturing method thereof.
The open-cell EVA foaming composite shoe material comprises the following raw materials in percentage by mass:
the ethylene-vinyl acetate copolymer-1 has the vinyl acetate VA content of 33 percent and the melt index of 2g/10 min;
the ethylene-vinyl acetate copolymer-2 has 25 percent of vinyl acetate VA content and 2g/10min of melt index;
the ethylene olefin copolymer can be selected from ethylene butene or ethylene octene copolymer, and the hardness of the selected material is preferably 45-60A;
the thermoplastic elastomer SEPS is a linear triblock copolymer which takes polystyrene as a terminal segment and takes an ethylene-propylene copolymer obtained by hydrogenation of polyisoprene as a middle elastic block.
The decomposition temperature of the modified dinitroso pentamethylene tetramine foaming agent can be 135-140 ℃, and the gas forming amount is 140 +/-5 ml/g.
One of the manufacturing methods of the open-cell EVA foaming composite shoe material comprises the following steps:
1) soaking a thermoplastic elastomer SEPS and naphthenic oil, and granulating by using a double-screw granulator for later use;
in the step 1), the mass ratio of the thermoplastic elastomer SEPS to the naphthenic oil is 1: 1; the thermoplastic elastomer SEPS is a linear triblock copolymer which takes polystyrene as a terminal segment and takes an ethylene-propylene copolymer obtained by hydrogenation of polyisoprene as a middle elastic block.
2) Mixing di-tert-butylperoxyisopropyl benzene and a modified dinitrosopentamethylenetetramine foaming agent in proportion to obtain a mixture for later use, mixing ethylene-vinyl acetate copolymer-1, ethylene-vinyl acetate copolymer-2, ethylene olefin copolymer, thermoplastic elastomer SEPS granules, ethylene propylene diene monomer and stearic acid, and then pouring the mixture into an internal mixer for first-stage internal mixing to uniformly mix the materials, adding the mixture of di-tert-butylperoxyisopropyl benzene and the modified dinitrosopentamethylenetetramine foaming agent when the temperature reaches 100-105 ℃, and carrying out second-stage internal mixing to obtain an internally mixed mixture when the temperature is increased to 108-112 ℃;
in step 2), the ethylene-vinyl acetate copolymer-1, the ethylene-vinyl acetate copolymer-2, the ethylene olefin copolymer, the thermoplastic elastomer SEPS granules, the ethylene propylene diene monomer, the stearic acid, the di-tert-butylperoxyisopropyl benzene and the modified dinitrosopentamethylenetetramine foaming agent can be prepared from the following raw materials in percentage by mass: (30-40%) (20-33%) (10-18%) (5-10%) (10-18%) (0.3-0.6%) (0.48-0.6%) (2.7-3.3%);
the first-stage banburying time can be 6-8 min, and the material turning times can be 3-5; the banburying time of the second stage can be 3-5 min, and the material turning times can be 2-3.
3) Thinning and thickening the internally mixed mixture obtained in the step 2) on a roller machine, and then granulating to obtain granules;
in the step 3), the thinning and thickening can be performed on a roller machine for 2 times and then for 2 times; the thickness of the thinned sheet can be 1-2 mm; the thickness of the thickened output sheet can be 3-5 mm; the temperature of the roller machine is controlled to be 60 +/-5 ℃;
the length of the pellets may be 3-5 mm.
4) Standing the granules manufactured in the step 3), injecting the granules into a mould, adding sulfur, and forming to obtain a test piece;
in the step 4), the standing time can be 24 hours; the injection mold can inject the granules into a foaming ratio experiment mold by using an injection machine, and the specification of the foaming ratio experiment mold can be as follows: the length is 250mm, the width is 150mm, and the height is 10 mm; the temperature of the foaming ratio experiment mould can be 175 +/-3 ℃; the time for the sulfurization may be 420. + -.30 s.
5) Cooling the test piece obtained in the step 4) by a constant temperature box process, testing the length value and calculating the average foaming ratio;
in step 5), the test length value can adopt a transverse length value and a longitudinal length value of the test piece tested by a ruler; the foaming ratio is controlled to be 150 +/-2%.
6) The material particles confirmed by the foaming multiplying power are prepared according to the set foaming multiplying power and injected into a shoe mold through a computer numerical control injection molding machine, and the shoe sole is formed through high-temperature foaming to obtain a sole;
in the step 6), the temperature of the shoe mold can be 175 +/-3 ℃, the time of high-temperature foaming molding is 360 +/-20 s, and the vulcanizing time is adjusted according to the thickness of the molded keel.
7) Shaping the sole obtained in the step 6) by a constant temperature box, and carrying out QC inspection, surface treatment, physical property sampling, packaging and warehousing, shipment or synthesis of the sole shaped by the constant temperature box and a rubber outsole to obtain the perforated EVA foamed composite shoe material.
In step 7), the process conditions for the oven setting may be: the temperature is 85-80-70-60-40 ℃, the revolution is 120r/min, and the length of the constant temperature box is 8-10 m.
The second manufacturing method of the open-cell EVA foaming composite shoe material comprises the following steps:
1) soaking a thermoplastic elastomer SEPS and naphthenic oil, and granulating by using a double-screw granulator for later use;
in the step 1), the mass ratio of the thermoplastic elastomer SEPS to the naphthenic oil is 1: 1; the thermoplastic elastomer SEPS is a linear triblock copolymer which takes polystyrene as a terminal segment and takes an ethylene-propylene copolymer obtained by hydrogenation of polyisoprene as a middle elastic block.
2) Mixing di-tert-butylperoxyisopropyl benzene and a modified dinitrosopentamethylenetetramine foaming agent in proportion to obtain a mixture for later use, mixing ethylene-vinyl acetate copolymer-1, ethylene-vinyl acetate copolymer-2, ethylene olefin copolymer, thermoplastic elastomer SEPS granules, ethylene propylene diene monomer and stearic acid, and then pouring the mixture into an internal mixer for first-stage internal mixing to uniformly mix the materials, adding the mixture of di-tert-butylperoxyisopropyl benzene and the modified dinitrosopentamethylenetetramine foaming agent when the temperature reaches 100-105 ℃, and carrying out second-stage internal mixing to obtain an internally mixed mixture when the temperature is increased to 108-112 ℃;
in step 2), the ethylene-vinyl acetate copolymer-1, the ethylene-vinyl acetate copolymer-2, the ethylene olefin copolymer, the thermoplastic elastomer SEPS granules, the ethylene propylene diene monomer, the stearic acid, the di-tert-butylperoxyisopropyl benzene and the modified dinitrosopentamethylenetetramine foaming agent can be prepared from the following raw materials in percentage by mass: (30-40%) (20-33%) (10-18%) (5-10%) (10-18%) (0.3-0.6%) (0.35-0.48%) (3.2-3.8%);
the first-stage banburying time can be 6-8 min, and the material turning times can be 3-5; the banburying time of the second stage can be 3-5 min, and the material turning times can be 2-3.
3) Thinning and thickening the internally mixed mixture obtained in the step 2) on a roller machine, and then granulating to obtain granules;
in the step 3), the thinning and thickening can be performed on a roller machine for 2 times and then for 2 times; the thickness of the thinned sheet can be 1-2 mm; the thickness of the thickened output sheet can be 3-5 mm; the temperature of the roller machine is controlled to be 60 +/-5 ℃;
the length of the pellets may be 3-5 mm.
4) Standing the granules manufactured in the step 3), pouring the granules into a small foaming mould for vulcanizing to obtain a blank semi-finished product, standing the blank semi-finished product in a natural environment for 4 hours, testing a multiplying power line on the blank semi-finished product to measure the foaming multiplying power, and controlling the foaming multiplying power to be 165 +/-3%;
in step 4), the condition of the sulfur addition may be: the temperature of the die is 170 +/-3 ℃, the vulcanizing time is 450 +/-30 s, the vulcanizing time is adjusted according to the thickness of the molded keel, and the molded keel is naturally cooled to the normal temperature;
5) and (3) cooling the blank semi-finished product after standing in the step 4) in a natural environment for 48h, trimming, cleaning by surface blowing, molding and shaping, and carrying out QC inspection, surface treatment, physical property extraction, packaging and warehousing, shipment or synthesis of the blank and a rubber outsole into a combined sole to obtain the perforated EVA foamed composite shoe material.
In step 5), the molding conditions may be: the temperature of the die is 170 +/-3 ℃, the heating time is 420 +/-30 s, the cooling time is 420 +/-30 s, and the heating and cooling time is adjusted according to the thickness of the molded keel.
In order to achieve the effects of large cells, open cell structures and series connection between the cells, powdery raw materials cannot be added into a formula system, such as: zinc oxide, talcum powder, calcium carbonate and the like, and powdery raw materials are filled among foam holes, so that the foam holes cannot be enlarged to reach an open-cell state. Meanwhile, due to the addition of the powdery raw materials, the foamed plate is not transparent or semi-transparent, and the visual effect of the appearance of the material is obviously reduced.
The open-cell EVA foaming composite shoe material can adopt injection molding (one manufacturing method) or secondary compression molding (the second manufacturing method), and the only difference of the two methods is that the dosages of the di-tert-butyl peroxy isopropyl benzene and the modified dinitroso pentamethine tetramine foaming agent are different. The same main rubber material formula, different production processes, different physical properties, secondary compression molding, and better compression, elasticity and thermal shrinkage than injection molding after two-time molding. The open-cell EVA foaming composite shoe material is prepared by using an injection molding or secondary die pressing and shaping method, and the main rubber materials are almost completely consistent except that the dosages of the foaming agent and the bridging agent are different. The finished product sole made of the shoe material not only meets different forming conditions, but also meets the requirements of designers on different processes of products. This shoes material has very big difference with traditional EVA foaming shoes material cell structure, and traditional EVA foaming shoes material is an even obturator foaming, and the formation bubble is even and fine and close, and independent rather than being connected between bubble and the bubble, the shortcoming is exactly that the foaming body top layer can form thicker skin structure, and pressure can not transmit between bubble and the bubble when receiving external force, and shock resistance is relatively poor, and the epidermis is wrinkled easily simultaneously and is difficult to the recovery. The foam holes formed by the foaming body of the shoe material are connected in series locally, namely the large air bag formed by the epidermis, the gas in the small air bag is communicated with the gas in the small air bag, when the shoe material is subjected to external pressure and impact, the borne pressure can be dispersed and transmitted relatively, and the impact resistance is greatly improved; meanwhile, the foam skin formed by the foam is very thin and difficult to wrinkle, and the appearance structure is kept for a long time. Because the cellular structure of the invention is different from the traditional EVA foaming cellular structure, when the same material is used, the elasticity, the shock absorption performance, the crease resistance, the formability and the like of the shoe material are obviously improved compared with the traditional EVA foaming shoe material.
The application provides a coarse porous composite foamed material has excellent resilience performance and compression resistance to density is lower, can also realize high light transmittance, and the outward appearance effect is unique, does benefit to the sole of preparation high-quality sports shoes. The invention breaks through the process from the physical property, the formula structure and the production process of the material, optimizes the formula structure and changes the foaming cell structure on the basis of the traditional EVA foaming shoe material, so that the better physical property is achieved, and different experiences are brought to consumers.
The open-cell EVA foaming composite shoe material can be subjected to physical property test: and (3) placing the prepared finished sole product in a laboratory (23 ℃) for 24 hours, testing physical properties such as hardness, specific gravity, elasticity, compression deflection, fatigue resistance test, shrinkage rate, light transmittance and the like, recording the physical property test values, comparing the test result with a set standard, correspondingly adjusting the formula according to the comparison result, and obtaining the optimal formula mass percentage range.
The main physical properties of the open-cell EVA foaming composite shoe material comprise (injection molding): hardness: 50 +/-3C; density: not more than 0.25g/cm3(ii) a Elasticity: more than or equal to 60 percent; tensile strength: not less than 3 MPa; compression distortion: less than or equal to 35 percent; thermal shrinkage: less than or equal to 1.5 percent (70 ℃ for 40 min); damping performance: less than or equal to 10 percent; light transmittance: not less than 20 percent.
And (3) secondary compression molding: hardness: 50 +/-3C; density: not more than 0.25g/cm3(ii) a Elasticity: more than or equal to 65 percent; tensile strength: not less than 3 MPa; compression distortion: less than or equal to 30 percent; thermal shrinkage: less than or equal to 1.5 percent (70 ℃ for 40 min); damping performance: less than or equal to 10 percent; transparent filmLight rate: not less than 20 percent.
Drawings
FIG. 1 is a surface view of a foamed material.
FIG. 2 is a diagram of the cells inside the foamed material.
Fig. 3 is a diagram of the light transmission effect of the material.
Detailed Description
The following examples will further illustrate the present invention with reference to the accompanying drawings.
The open-cell EVA foaming composite shoe material comprises the following raw materials in percentage by mass as shown in Table 1:
TABLE 1
The invention aims to achieve the foaming and opening structure of the EVA foaming shoe material, the cells are large, the pore diameter distribution structure is formed by locally connecting the cells in series, and the preset physical index is also achieved, and the final result is obtained through numerous tests on the selection of raw materials. To further illustrate the experimental runs, experiments were conducted using chemical materials manufactured by the following companies to obtain specific experimental data: the ethylene-vinyl acetate copolymer is prepared from EVA UE3302 and EVA UE659 produced by Taiwan Taiji corporation, wherein the VA (vinyl acetate) content of the EVA UE3302 is 33%, the Melt Index (MI) is 2g/10min, and the ethylene-vinyl acetate copolymer has good flexibility, elasticity, molecular weight, support property and contractibility; the VA (vinyl acetate) content of the EVA UE659 is 25%, the Melt Index (MI) is 2g/10min, the tensile strength and the tearing strength are good, the compression distortion is good, the molecular weights of the two EVA are large enough, and the generation and the stable formation of large cells are facilitated; the ethylene-olefin copolymer can be POE LC168 produced by Korean LG company, and the POE belongs to a copolymer with four carbon atoms, and has soft hardness, good glue feeling, strong toughness and good elasticity; the SEPS can be selected from SEPS powder produced by medium petrochemical industry, and the SEPS powder is beneficial to the post-processing after oil-filling processing; the SEPS is mainly used in the formula, and the toughness, elasticity, thermal shrinkage, weather resistance and the like of the SEBS are much better than those of the SEBS; the ethylene propylene diene monomer can be EPDM2032 produced by Mitsui corporation of Japan, the ENB content of the third monomer of the brand is 1.2 percent, the ethylene propylene diene monomer is suitable for production and processing of shoe material industry, the performance of the ethylene propylene diene monomer can be comparable to that of American Dow products, and the price is advantageous; the di-tert-butyl peroxy isopropyl) benzene BIBP is a product produced by Acksonobel company; CAP produced by Kunzhou Jinlang company is selected as a modified dinitroso pentamethine tetramine foaming agent, the main component of the modified foaming agent is a mixture of dinitroso pentamethine tetramine (DPT/H) and other active auxiliary agents, wherein the dinitroso pentamethine tetramine (DPT/H) is used as an open-cell foaming agent, the decomposition temperature of the dinitroso pentamethine tetramine (DPT/H) is about 200 ℃, in order to enable the size of cells to be uniform and meet the requirement of production conditions, the active auxiliary agents are added into the DPT/H, the decomposition temperature is controlled to be 135-140 ℃, and stearic acid is a common chemical material in the market.
The present invention is further illustrated by the following examples and comparative examples, wherein in the testing process of the examples and comparative examples, almost the same main rubber formulation is adopted, and the used amount of di-tert-butylperoxyisopropyl) benzene (BIBP) and modified dinitroso pentamethylene tetramine foaming agent (CAP) is different in the injection and secondary molding process, so as to facilitate the more intuitive comparison effect, and the implementation process is as follows:
example 1: the open-cell EVA foaming composite shoe material comprises the following raw materials in percentage by mass:
TABLE 2
| Name of raw materials | Injection mass percent (%) | MD percent by mass (%) |
| EVA UE3302 | 34 | 34 |
| EVA UE659 | 27 | 27 |
| LC-168 | 14 | 14 |
| SEPS | 7 | 7 |
| EPDM2032 | 14 | 14 |
| ST | 0.5 | 0.3 |
| BIBP | 0.5 | 0.4 |
| CAP | 3 | 3.3 |
The manufacturing method of the open-cell EVA foaming composite shoe material adopts the following steps of an injection process flow:
1) firstly, soaking SEPS and naphthenic oil Kunlun 4008# according to a ratio of 1: 1, and then granulating by using a double-screw granulator for later use.
2) Mixing di-tert-butylperoxyisopropyl benzene and a modified dinitrosopentamethylenetetramine foaming agent for later use, mixing other raw materials of EVA, POE, SEPS, EPDM and ST, pouring the mixture into an internal mixer for first-stage internal mixing to uniformly mix the materials, adding the mixture of the di-tert-butylperoxyisopropyl benzene and the modified dinitrosopentamethylenetetramine foaming agent when the temperature reaches 100-105 ℃, starting the internal mixer again for second-stage internal mixing until the temperature is increased to 108-112 ℃, and mixing all the raw materials to obtain an internally mixed mixture; the first-stage banburying time is 6-8 min, the material turning times are 3-5 times, the second-stage banburying time is 3-5 min, and the material turning times are 2-3 times.
3) The banburying mixture obtained in the step 1) is thinned for 2 times and thickened for 2 times on a roller; the thickness of the output sheet is 1-2 mm during thinning; the thickness of the output sheet is 3-5 mm during the thickening; the temperature of the roller of the second stage is controlled at 60 +/-5 ℃.
4) Conveying the uniformly mixed materials of the roller machine into a granulator for granulation to obtain granules; the length of the granules is 3-5 mm.
5) After the manufactured granules are stood, injecting the granules into a mould, adding sulfur, and forming to obtain a test piece; the standing time is 24 hours; the granule injection mold can inject granules into a foaming ratio experiment mold by using an injection machine, and the specification of the mold is as follows: the length is 250mm, the width is 150mm, and the height is 10 mm; the temperature of the die is 175 +/-3 ℃, and the time for adding sulfur is 420 +/-30 s.
6) The test piece obtained in the step 5) is processed by a constant temperature box flow, after being cooled, the length value is tested, and the average foaming ratio is calculated; the test length value uses a ruler to test the transverse length value and the longitudinal length value of the test piece; the foaming ratio is controlled to be 150% +/-2%.
7) The material particles confirmed by the foaming multiplying power are mixed according to the set foaming multiplying power and injected into a shoe mold through a computer numerical control injection molding machine to be molded, and a sole is obtained; the temperature of the shoe mold is 175 +/-3 ℃, the vulcanizing time is 360 +/-20 s, and the vulcanizing time is adjusted according to the thickness of the molded keel.
8) Shaping the sole obtained in the step 6) by a constant temperature box, and carrying out QC inspection, surface treatment, physical property sampling, packaging and warehousing, shipment or waiting for synthesizing a combined sole with a rubber outsole on the sole shaped by the constant temperature box to obtain the perforated EVA foamed composite shoe material.
9) The process conditions for the setting of the constant temperature box in the step 7) are as follows: the temperature is 85-80-70-60-40 ℃, the revolution is 120r/min, and the length of the constant temperature box is 8-10 m.
The manufacturing method of the open-cell EVA foaming composite shoe material adopts a secondary compression molding process flow and comprises the following steps:
1) firstly, soaking SEPS and naphthenic oil Kunlun 4008# according to a ratio of 1: 1, and then granulating by using a double-screw granulator for later use.
2) Mixing di-tert-butylperoxyisopropyl benzene and a modified dinitrosopentamethylenetetramine foaming agent for later use, mixing other raw materials of EVA, POE, SEPS, EPDM and ST, pouring the mixture into an internal mixer for first-stage internal mixing to uniformly mix the materials, adding the mixture of the di-tert-butylperoxyisopropyl benzene and the modified dinitrosopentamethylenetetramine foaming agent when the temperature reaches 100-105 ℃, starting the internal mixer again for second-stage internal mixing until the temperature is increased to 108-112 ℃, and mixing all the raw materials to obtain an internally mixed mixture; the first-stage banburying time is 6-8 min, the material turning times are 3-5 times, the second-stage banburying time is 3-5 min, and the material turning times are 2-3 times.
3) The banburying mixture obtained in the step 1) is thinned for 2 times and thickened for 2 times on a roller; the thickness of the output sheet is 1-2 mm during thinning; the thickness of the output sheet is 3-5 mm during the thickening; the temperature of the roller of the second stage is controlled at 60 +/-5 ℃.
4) Conveying the uniformly mixed materials of the roller machine into a granulator for granulation to obtain granules; the length of the granules is 3-5 mm.
5) And after the manufactured granules are stood, pouring the granules into a small foaming mould for vulcanizing to obtain a blank semi-finished product, standing the blank semi-finished product in a natural environment for 4 hours, and testing a multiplying power line on the blank semi-finished product to measure the foaming multiplying power, wherein the foaming multiplying power is controlled to be 165 +/-3%.
6) In the step 5), the vulcanizing conditions of the primary blank semi-finished product are as follows: the temperature of the die is 170 +/-3 ℃, the vulcanizing time is 450 +/-30 s, the vulcanizing time is adjusted according to the thickness of the molded keel, and the molded keel is naturally cooled to the normal temperature.
7) And (3) cooling the semifinished blank in the step 6) in a natural environment for more than 48 hours, trimming, cleaning by surface blowing, and molding.
8) The die pressing and shaping conditions in the step 7) are as follows: the temperature of the die is 170 +/-3 ℃, the heating time is 420 +/-30 s, the cooling time is 420 +/-30 s, and the heating and cooling time is adjusted according to the thickness of the molded keel.
The product prepared by the formula and the process can be subjected to physical property test: and (3) placing the prepared finished sole product in a laboratory (23 ℃) for 24 hours, testing physical properties such as hardness, specific gravity, elasticity, compression deflection, fatigue resistance test, shrinkage rate, light transmittance and the like, recording the physical property test values, comparing the test result with a set standard, correspondingly adjusting the formula according to the comparison result, and obtaining the optimal formula mass percentage.
The main physical properties of the open-cell EVA foaming composite shoe material comprise (injection molding): hardness: 50 +/-3C; density: not more than 0.25g/cm3(ii) a Elasticity: more than or equal to 60 percent; tensile strength: not less than 2 MPa; compression distortion: less than or equal to 35 percent; thermal shrinkage: less than or equal to 1.5 percent (70 ℃ for 40 min); damping performance: less than or equal to 10 percent; light transmittance: not less than 20 percent.
The main physical properties of the secondary compression molding include: hardness: 50 +/-3C; density: not more than 0.25g/cm3(ii) a Elasticity: more than or equal to 65 percent; tensile strength: not less than 3 MPa; compression distortion: less than or equal to 30 percent; thermal shrinkage: less than or equal to 1.5 percent (70 ℃ for 40 min); damping performance: less than or equal to 10 percent; light transmittance: not less than 20 percent.
Example 2: the amounts of the starting materials were adjusted on the basis of example 1, the starting material formulation of which is given in table 3:
TABLE 3
| Name of raw materials | Injection mass percent (%) | MD percent by mass (%) |
| EVA UE3302 | 40 | 40 |
| EVA UE659 | 20 | 20 |
| LC-168 | 10 | 10 |
| SEPS | 8 | 7.3 |
| EPDM2032 | 18 | 18 |
| ST | 0.55 | 0.55 |
| BIBP | 0.55 | 0.35 |
| CAP | 2.9 | 3.8 |
Example 3: continuously adjusting the dosage of the raw materials in the formula on the basis of the example 2 to control the dosage within a set dosage range, wherein the formula comprises the raw materials in percentage by mass as shown in the table 4;
TABLE 4
Example 4: continuously adjusting the dosage of the raw materials on the basis of the example 3 to control the dosage within a set dosage range, wherein the formula comprises the raw materials according to the mass percentage shown in the table 5;
TABLE 5
| Name of raw materials | Injection mass percent (%) | MD percent by mass (%) |
| EVA UE3302 | 38 | 38 |
| EVA UE659 | 25 | 25 |
| LC-168 | 10 | 10 |
| SEPS | 10 | 10 |
| EPDM2032 | 12.7 | 12.6 |
| ST | 0.4 | 0.5 |
| BIBP | 0.6 | 0.4 |
| CAP | 3.3 | 3.5 |
To better illustrate the results of the study, the formulation does not use a mixed blowing agent for the blowing agent, comparative example 1 is prepared by replacing the CAP open-cell blowing agent with an Azo (AC) blowing agent on the basis of example 1, comparative example 2 is prepared by replacing part of the raw materials with a percentage by mass outside the set range of the formulation on the basis of example 2, and comparative example 1 (damping performance is reduced, elasticity is reduced, and light transmittance is no longer allowed): the formula of the raw materials is shown in the following table 6 in percentage by mass:
TABLE 6
| Name of raw materials | Injection mass percent (%) | MD percent by mass (%) |
| EVA UE3302 | 34 | 34 |
| EVA UE659 | 27 | 27 |
| LC-168 | 14 | 14 |
| SEPS | 7 | 7 |
| EPDM2032 | 14 | 14 |
| ST | 0.5 | 0.3 |
| BIBP | 0.5 | 0.4 |
| AC-6000H | 2 | 2.3 |
Comparative example 2 (property deterioration): the formula comprises the following raw materials in percentage by mass as shown in Table 7:
TABLE 7
Injection formulation examples 1 to 4 and comparative examples 1 to 2 were sampled and subjected to physical property tests, and the test results thereof are shown in Table 8:
TABLE 8
Two-shot molding formulations examples 1 to 4 and comparative examples 1 to 2 were sampled and subjected to physical property tests, and the test results are shown in Table 9.
TABLE 9
From the test results, the physical property results of the samples of the examples can reach the set physical property standard; however, the comparative examples do not satisfy the set physical property targets, and particularly, the elasticity, shock absorption performance, light transmittance, heat shrinkage, and the like of the comparative examples are remarkably reduced. Compared with the traditional EVA foaming, the open-cell EVA foaming composite shoe material changes the cellular structure of the foaming shoe material from closed cell structure to open cell structure, so that the skin of the foaming shoe material becomes thin and is easy to carry out secondary forming. Meanwhile, compared with the traditional EVA foaming shoe material, the elasticity, the shock absorption performance, the crease resistance, the durability, the formability and the like are obviously improved. FIG. 1 shows a surface view of the foam of the present invention; FIG. 2 shows a diagram of the cells inside the foamed material; fig. 3 shows the light transmission effect of the material.
Claims (9)
1. The open-cell EVA foaming composite shoe material is characterized by comprising the following raw materials in percentage by mass:
the ethylene-vinyl acetate copolymer-1 has the vinyl acetate VA content of 33 percent and the melt index of 2g/10 min;
the ethylene-vinyl acetate copolymer-2 has 25 percent of vinyl acetate VA content and 2g/10min of melt index;
the ethylene olefin copolymer is selected from an ethylene butene copolymer or an ethylene octene copolymer, and the hardness is 45-60A;
the thermoplastic elastomer SEPS is a linear triblock copolymer which takes polystyrene as a terminal segment and takes an ethylene-propylene copolymer obtained by hydrogenation of polyisoprene as a middle elastic block;
the modified dinitroso pentamethylene tetramine foaming agent has the decomposition temperature of 135-140 ℃ and the gas forming amount of 140 +/-5 ml/g.
2. The method for manufacturing the open-cell EVA foaming composite shoe material of claim 1, which comprises the following steps:
1) soaking a thermoplastic elastomer SEPS and naphthenic oil, and granulating by using a double-screw granulator for later use;
2) mixing di-tert-butylperoxyisopropyl benzene and a modified dinitrosopentamethylenetetramine foaming agent in proportion to obtain a mixture for later use, mixing ethylene-vinyl acetate copolymer-1, ethylene-vinyl acetate copolymer-2, ethylene olefin copolymer, thermoplastic elastomer SEPS granules, ethylene propylene diene monomer and stearic acid, and then pouring the mixture into an internal mixer for first-stage internal mixing to uniformly mix the materials, adding the mixture of di-tert-butylperoxyisopropyl benzene and the modified dinitrosopentamethylenetetramine foaming agent when the temperature reaches 100-105 ℃, and carrying out second-stage internal mixing to obtain an internally mixed mixture when the temperature is increased to 108-112 ℃;
3) thinning and thickening the internally mixed mixture obtained in the step 2) on a roller machine, and then granulating to obtain granules;
4) standing the granules manufactured in the step 3), injecting the granules into a mould, adding sulfur, and forming to obtain a test piece;
5) cooling the test piece obtained in the step 4) by a constant temperature box process, testing the length value and calculating the average foaming ratio;
6) the material particles confirmed by the foaming multiplying power are prepared according to the set foaming multiplying power and injected into a shoe mold through a computer numerical control injection molding machine, and the shoe sole is formed through high-temperature foaming to obtain a sole;
7) shaping the sole obtained in the step 6) by a constant temperature box, and carrying out QC inspection, surface treatment, physical property sampling, packaging and warehousing, shipment or synthesis of the sole shaped by the constant temperature box and a rubber outsole to obtain the perforated EVA foamed composite shoe material.
3. The method for manufacturing the open-cell EVA foam composite shoe material of claim 2, wherein in the step 1), the mass ratio of the SEPS to the naphthenic oil is 1: 1; the thermoplastic elastomer SEPS is a linear triblock copolymer which takes polystyrene as a terminal segment and takes an ethylene-propylene copolymer obtained by hydrogenation of polyisoprene as a middle elastic block;
in step 2), the ethylene-vinyl acetate copolymer-1, the ethylene-vinyl acetate copolymer-2, the ethylene olefin copolymer, the thermoplastic elastomer SEPS granules, the ethylene propylene diene monomer, the stearic acid, the di-tert-butylperoxyisopropyl benzene and the modified dinitrosopentamethyl tetramine foaming agent comprise the following raw materials in percentage by mass: (30-40%) (20-33%) (10-18%) (5-10%) (10-18%) (0.3-0.6%) (0.48-0.6%) (2.7-3.3%); the modified dinitroso pentamethylene tetramine foaming agent has the decomposition temperature of 135-140 ℃ and the gas forming amount of 140 +/-5 ml/g; the first-stage banburying time is 6-8 min, and the material turning times are 3-5; and the banburying time of the second stage is 3-5 min, and the material turning times are 2-3.
4. The method of manufacturing the open-cell EVA foam composite shoe material according to claim 2, wherein in step 3), the thinning and re-thickening are performed 2 times on a roller machine and 2 times; the thickness of the thinned output sheet is 1-2 mm; the thickness of the thickened output sheet is 3-5 mm; the temperature of the roller machine is controlled to be 60 +/-5 ℃;
the length of the granules is 3-5 mm.
5. The method for manufacturing the open-cell EVA foam composite shoe material of claim 2, wherein in the step 4), the standing time is 24 h; the injection mold is used for injecting the granules into a foaming ratio experiment mold by using an injection machine, and the foaming ratio experiment mold has the following specifications: the length is 250mm, the width is 150mm, and the height is 10 mm; the temperature of the foaming ratio experiment mould is 175 +/-3 ℃; the time for adding sulfur is 420 +/-30 s;
in the step 5), the test length value adopts a ruler to test the transverse length value and the longitudinal length value of the test piece; the foaming ratio is controlled to be 150 +/-2%.
6. The method for manufacturing the open-cell EVA foaming composite shoe material of claim 2, wherein in step 6), the temperature of the shoe mold is 175 + -3 ℃, the time of high-temperature foaming molding is 360 + -20 s, and the vulcanizing time is adjusted according to the thickness of the molded keel;
in step 7), the process conditions for the setting of the incubator are as follows: the temperature is 85-80-70-60-40 ℃, the revolution is 120r/min, and the length of the constant temperature box is 8-10 m.
7. The method for manufacturing the open-cell EVA foaming composite shoe material of claim 1, which comprises the following steps:
1) soaking a thermoplastic elastomer SEPS and naphthenic oil, and granulating by using a double-screw granulator for later use;
2) mixing di-tert-butylperoxyisopropyl benzene and a modified dinitrosopentamethylenetetramine foaming agent in proportion to obtain a mixture for later use, mixing ethylene-vinyl acetate copolymer-1, ethylene-vinyl acetate copolymer-2, ethylene olefin copolymer, thermoplastic elastomer SEPS granules, ethylene propylene diene monomer and stearic acid, and then pouring the mixture into an internal mixer for first-stage internal mixing to uniformly mix the materials, adding the mixture of di-tert-butylperoxyisopropyl benzene and the modified dinitrosopentamethylenetetramine foaming agent when the temperature reaches 100-105 ℃, and carrying out second-stage internal mixing to obtain an internally mixed mixture when the temperature is increased to 108-112 ℃;
3) thinning and thickening the internally mixed mixture obtained in the step 2) on a roller machine, and then granulating to obtain granules;
4) standing the granules manufactured in the step 3), pouring the granules into a small foaming mould for vulcanizing to obtain a blank semi-finished product, standing the blank semi-finished product in a natural environment for 4 hours, testing a multiplying power line on the blank semi-finished product to measure the foaming multiplying power, and controlling the foaming multiplying power to be 165 +/-3%;
5) and (3) cooling the blank semi-finished product after standing in the step 4) in a natural environment for 48h, trimming, cleaning by surface blowing, molding and shaping, and carrying out QC inspection, surface treatment, physical property extraction, packaging and warehousing, shipment or synthesis of the blank and a rubber outsole into a combined sole to obtain the perforated EVA foamed composite shoe material.
8. The method for manufacturing the open-cell EVA foaming composite shoe material of claim 7, wherein in the step 1), the mass ratio of the SEPS to the naphthenic oil is 1: 1; the thermoplastic elastomer SEPS is a linear triblock copolymer which takes polystyrene as a terminal segment and takes an ethylene-propylene copolymer obtained by hydrogenation of polyisoprene as a middle elastic block;
in step 2), the ethylene-vinyl acetate copolymer-1, the ethylene-vinyl acetate copolymer-2, the ethylene olefin copolymer, the thermoplastic elastomer SEPS granules, the ethylene propylene diene monomer, the stearic acid, the di-tert-butylperoxyisopropyl benzene and the modified dinitrosopentamethyl tetramine foaming agent comprise the following raw materials in percentage by mass: (30-40%) (20-33%) (10-18%) (5-10%) (10-18%) (0.3-0.6%) (0.35-0.48%) (3.2-3.8%); the first-stage banburying time is 6-8 min, and the material turning times are 3-5; the banburying time of the second stage is 3-5 min, and the material turning times are 2-3;
in the step 3), thinning and thickening are performed on a roller machine for 2 times and thickening is performed for 2 times; the thickness of the thinned output sheet is 1-2 mm; the thickness of the thickened output sheet is 3-5 mm; the temperature of the roller machine is controlled to be 60 +/-5 ℃;
the length of the granules is 3-5 mm.
9. The method for manufacturing the open-cell EVA foaming composite shoe material of claim 7, wherein in the step 4), the vulcanizing conditions are as follows: the temperature of the die is 170 +/-3 ℃, the vulcanizing time is 450 +/-30 s, the vulcanizing time is adjusted according to the thickness of the molded keel, and the molded keel is naturally cooled to the normal temperature;
in the step 5), the molding and shaping conditions are as follows: the temperature of the die is 170 +/-3 ℃, the heating time is 420 +/-30 s, the cooling time is 420 +/-30 s, and the heating and cooling time is adjusted according to the thickness of the molded keel.
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| TWI746386B (en) * | 2021-03-08 | 2021-11-11 | 臺灣塑膠工業股份有限公司 | Antimicrobial foaming composition, antimicrobial foaming material including the same and method of manufacturing the same |
| CN113831631A (en) * | 2021-11-03 | 2021-12-24 | 福建康茂鞋材有限公司 | Leather shoe sole and production process thereof |
| CN114685885B (en) * | 2022-05-06 | 2023-11-24 | 北京中景橙石科技股份有限公司 | Elastic expansion joint plate and preparation method thereof |
| CN114874535A (en) * | 2022-06-24 | 2022-08-09 | 厦门冠颜塑化科技有限公司 | Healthy shoe material with far infrared emission function and preparation method thereof |
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