CN117901502A - Multilayer composite material and forming method and application thereof - Google Patents
Multilayer composite material and forming method and application thereof Download PDFInfo
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- CN117901502A CN117901502A CN202410309076.6A CN202410309076A CN117901502A CN 117901502 A CN117901502 A CN 117901502A CN 202410309076 A CN202410309076 A CN 202410309076A CN 117901502 A CN117901502 A CN 117901502A
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- 239000011185 multilayer composite material Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 72
- 210000003423 ankle Anatomy 0.000 claims abstract description 29
- 210000002435 tendon Anatomy 0.000 claims abstract description 9
- 239000010410 layer Substances 0.000 claims description 65
- 229920002635 polyurethane Polymers 0.000 claims description 56
- 239000004814 polyurethane Substances 0.000 claims description 56
- 229920002755 poly(epichlorohydrin) Polymers 0.000 claims description 31
- 239000010985 leather Substances 0.000 claims description 22
- 239000002131 composite material Substances 0.000 claims description 17
- 238000005187 foaming Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 14
- 239000000853 adhesive Substances 0.000 claims description 12
- 230000001070 adhesive effect Effects 0.000 claims description 12
- 239000006260 foam Substances 0.000 claims description 11
- 239000012948 isocyanate Substances 0.000 claims description 11
- 150000002513 isocyanates Chemical class 0.000 claims description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 229920000570 polyether Polymers 0.000 claims description 9
- 229920005862 polyol Polymers 0.000 claims description 9
- 150000003077 polyols Chemical class 0.000 claims description 9
- 239000004359 castor oil Substances 0.000 claims description 8
- 235000019438 castor oil Nutrition 0.000 claims description 8
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 8
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 8
- 239000006261 foam material Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002649 leather substitute Substances 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229910015900 BF3 Inorganic materials 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000007767 bonding agent Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000012790 adhesive layer Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 2
- 210000002683 foot Anatomy 0.000 abstract description 10
- 238000013461 design Methods 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 230000006378 damage Effects 0.000 description 5
- 210000003205 muscle Anatomy 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000003139 buffering effect Effects 0.000 description 3
- 230000036544 posture Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- 208000008035 Back Pain Diseases 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 208000008930 Low Back Pain Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000009692 acute damage Effects 0.000 description 1
- 208000019804 backache Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000037237 body shape Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a multilayer composite material, a forming method and application thereof, and relates to the technical field of high polymer materials. In particular to an upper structure for protecting ankle tendons, which can stabilize high-heeled shoes of ankle. The invention better covers the foot through structural design and material upgrading, adjusts the movement form of the foot, and improves the movement stability so as to improve the comfort level of wearing the high-heeled shoes.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a multilayer composite material, a forming method and application thereof.
Background
High-heeled shoes are important women's shoes, and are dressing types with extremely high frequency in the society nowadays. The high-heeled shoes mainly comprise vamps, soles and heels, wherein the vamps are fixed on the soles in a gluing or sewing mode, and the heels are fixed at the positions, close to the rear sides, of the soles in a fixing nail or gluing mode. The utility model is characterized in that the heel is higher, the height of the heel can be utilized to achieve the effect of heightening, and the body shape can be better reflected by changing the standing posture.
However, as the height of the heel increases, the comfort and the comfort of wearing gradually decrease, and particularly, the user's legs become painful and lumbago due to long-time walking and standing. The important reason is that when the high-heeled shoes are worn, the center of gravity deviates to the front side of the body when the body is erected compared with the flat shoes, the supporting weight of the front sole is increased by 10-20%, particularly the high-heeled shoes with heels more than 8 cm, and the center of gravity mostly falls on the front sole; the requirements for the supporting force of the front sole of the user are high, and the requirements for the auxiliary stabilizing muscle groups around the ankle, the heel and the like are also high. Particularly in the exercise state, the foot stabilizing muscle group has insufficient strength, so that other muscle groups are compensated for stability, and the series of problems such as leg ache, waist ache, back ache and the like are caused.
In addition, the high-heeled shoes, in particular to the high-heeled shoes with heels more than 8 cm, bring bad wearing experience while improving the wearing aesthetic feeling and the air quality of the wearer, thereby limiting the use and the development of the high-heeled shoes.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a multilayer composite material, a forming method thereof and application thereof in high-heeled shoes, and the multilayer composite material better covers feet, adjusts the movement form of the feet, improves the movement stability, protects ankle tendons and improves the comfort degree of wearing the high-heeled shoes through material upgrading and upper structural design.
In order to achieve the above object, the present invention provides the following technical solutions:
In a first aspect, the invention provides a multilayer composite material, which comprises a substrate layer, a first bonding layer, a polyurethane micro-foam layer, a second bonding layer and an ankle contact layer, wherein the polyurethane micro-foam layer is made of polyurethane micro-foam material, the density of the polyurethane micro-foam material is 0.26-0.36 g/cm 3, and the hardness of ASKER C is 20-36; the first bonding layer and the second bonding layer adopt polyurethane bonding agents, the basal layer is natural leather and/or artificial leather, and the ankle contact layer is natural leather and/or artificial leather.
Further, the polyurethane micro-foam layer material is a polycondensation product of 100 parts by mass of hydroxyl-terminated polyepichlorohydrin and 50-70 parts by mass of PAPI isocyanate.
Further, the hydroxyl-terminated polyepichlorohydrin is a cross-linked ring-opening polymerization product of four-arm polyethylene glycol and epichlorohydrin under the catalysis of boron trifluoride.
Further, the hydroxyl-terminated polyepichlorohydrin has a structure as shown in a structural formula (I):
（I）
Wherein a, b, m and n represent the number of the repeating units in the polymer, and the number average molecular weight of the hydroxyl-terminated polyepichlorohydrin is 10500.
Further, the viscosity of the hydroxyl-terminated polyepichlorohydrin is 1.2 Pa.s.
Further, the preparation method of the polyurethane micro-foam layer material comprises the following steps: mixing 100 parts by mass of hydroxyl-terminated polyepichlorohydrin with 30-50 parts by mass of plasticizer, 20-40 parts by mass of 5613 polyether polyol and 0.1-0.15 part by mass of stannous octoate uniformly, and adding 50-70 parts by mass of PAPI isocyanate to obtain a precursor to be molded; adding a precursor to be formed into a grinding tool, and curing for 10-20 hours at the temperature of 50-80 ℃ to obtain a polyurethane micro-foaming material; the plasticizer is castor oil.
Further, the multi-layer composite material can also comprise other functional layers such as a protective layer, a breathable layer and the like, and has the effects of protecting, ventilating, reducing damage, prolonging the service life of products and the like.
In a second aspect, the present invention also provides a method for forming the above-mentioned multilayer composite material, including the steps of:
Mixing 100 parts by mass of hydroxyl-terminated polyepichlorohydrin with 30-50 parts by mass of plasticizer, 20-40 parts by mass of 5613 polyether polyol and 0.1-0.15 part by mass of stannous octoate uniformly, and adding 50-70 parts by mass of PAPI isocyanate to obtain a precursor to be molded;
Coating polyurethane adhesive on the surface of the substrate layer, and placing 30-180 s to form a first adhesive layer; coating the precursor to be formed on the surface of the first bonding layer, coating polyurethane adhesive on the surface of the precursor to be formed to form a second bonding layer, covering an ankle contact layer on the surface of the second bonding layer, and adding the second bonding layer into a die to form for 10-20 hours to obtain the multilayer composite material.
Further, before the polyurethane binder is coated on the surface of the substrate layer, the substrate layer is subjected to impregnation treatment by polyether polyol and/or polyester polyol.
Further, the molding temperature in the mold is 50-80 ℃.
In a third aspect, the invention also provides the use of a multi-layer composite according to any of the above in a high-heeled shoe.
In a fourth aspect, the present invention also provides an upper structure for protecting ankle tendons, the upper structure adopting the multilayer composite material of any one of the above, the upper structure adopting an arc shape, the thickness of the multilayer composite material being 1-3mm.
In a fifth aspect, the present invention also provides a high-heeled shoe, wherein the heel counter comprises the upper structure for protecting ankle tendons, the upper structure is arranged at a corresponding position contacted with the rear ankle, the upper structure extends upwards to a heel counter opening and is connected downwards to a heel end point of the upper, the height H between the heel end point of the upper and the horizontal line of the heel sole is 17-35mm, the included angle alpha between an arc tangent line of the heel sole at a position 2/3 of the tail end of the heel counter opening and a plumb line is 11-36 degrees, preferably 12-35 degrees, and the included angle beta between the arc tangent line of the heel counter opening and a horizontal plane is 58-76 degrees.
Compared with the prior art, the invention has the beneficial effects that:
The multilayer composite material provided by the invention, the preferable polyurethane material provides an optimized performance interval, ensures the buffering performance and the wear resistance, simultaneously exerts enough holding force on the ankle, improves the stability of the ankle, and reduces the shake of the ankle during walking, thereby reducing the compensation of body stable muscle groups and reducing the fatigue. Reduces the damage caused by the high-heeled shoes. The performance is superior to that of elastic materials and cushioning materials which are commonly represented by sponges in the market.
The forming method of the multilayer composite material provided by the invention can be used for rapidly adding the buffer protection layer on the upper, the obtained product has good stability, the forming can be completed at room temperature, and the influence damage to vamp materials is reduced.
According to the upper structure for protecting ankle tendons, provided by the invention, the foot postures during standing and walking are adjusted by optimizing the upper design, so that compensation of body stabilizing muscle groups is reduced. The acute injury or accumulated injury to the body caused by the wrong walking posture is reduced.
According to the high-heeled shoe provided by the invention, the heel angle design of the high-heeled shoe is adjusted, so that the wrapping effect of the upper on the foot is improved, the shoe is more fit with the foot, the stability of the shoe during walking is improved, and the fatigue caused by wearing the high-heeled shoe is reduced.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings may be obtained according to these drawings for a person having ordinary skill in the art.
Fig. 1 is a schematic structural diagram of a multi-layer composite material according to an embodiment of the present invention.
Fig. 2 is a schematic structural view of a high-heeled shoe according to an embodiment of the present invention.
FIG. 3 is an enlarged view of a portion of a heel counter according to an embodiment of the present invention.
FIG. 4 is a synthetic route for 4aPEG-PECH provided in an embodiment of the invention.
Reference numerals illustrate:
1. Heel upper 2, heel opening 3, heel end point 4, heel sole 5, upper structure 6, included angle alpha, 7, included angle beta, 5-1 a basal layer, 5-2 a first bonding layer, 5-3 a polyurethane micro foam layer, 5-4 a second bonding layer, 5-5 an ankle contact layer.
Detailed Description
In order to make the technical scheme of the present application better understood by those skilled in the art, the present application will be further described in detail with reference to the accompanying drawings. The embodiments described below are only specific embodiments of the present application, which are intended to illustrate the technical aspects of the present application, but not to limit the scope of the present application. In the description of the present application, it should be noted that the azimuth or positional relationship indicated by the terms "inner", "outer", etc. are based on the azimuth or positional relationship shown in the drawings, and are merely for convenience of describing the present application and simplifying the description, and are not indicative or implying that the apparatus or element in question must have a specific azimuth, be constructed and operated in a specific azimuth, and thus should not be construed as limiting the present application.
The multilayer composite material provided by the invention, as shown in fig. 1, comprises a substrate layer 5-1, a first bonding layer 5-2, a polyurethane micro-foam layer 5-3, a second bonding layer 5-4 and an ankle contact layer 5-5, wherein the polyurethane micro-foam layer 5-3 is made of polyurethane micro-foam material, and has the functions of buffering, reducing friction and coating the ankle. Wherein the density of the polyurethane micro-foam material is 0.2-0.4 g/cm 3, and the hardness of ASKER C is 15-40; the first bonding layer 5-2 and the second bonding layer 5-4 are made of polyurethane bonding agents, the basal layer 5-1 is made of natural leather and/or artificial leather, and the ankle contact layer 5-5 is made of natural leather and/or artificial leather.
The invention also provides application of the multilayer composite material in high-heeled shoes.
In particular, the invention also provides an upper structure 5 for protecting ankle tendons, which adopts the multi-layer composite material and is arc-shaped.
The invention also provides a high-heeled shoe, as shown in fig. 2 and 3, wherein the heel counter 1 comprises the upper structure 5 for protecting ankle tendons, the upper structure 5 is arranged at a corresponding position contacted with the rear ankle, the upper structure 5 extends upwards to a heel counter opening 2 and is connected downwards to a heel end point 3 of the upper, the height H between the heel end point 3 of the upper and the horizontal line of the heel sole 4 is 17-35 mm, the included angle alpha 6 between an arc tangent line of the heel sole 4 at a position 2/3 from the top end of the heel counter opening 2 and a plumb line is 11-36 degrees, preferably 12-35 degrees, and the included angle beta 7 between the arc tangent line of the heel counter opening 2 and the horizontal plane is 58-76 degrees.
Example 1 preparation of polyurethane micro-foaming Material
10 Parts by mass of a commercially available four-arm polyethylene glycol (4 aPEG) was completely dissolved in methylene chloride, and boron trifluoride (4% by mass in an amount of 4% by mass of 4: 4 aPEG) as a catalyst diluted with 1, 2-dichloroethane was added thereto, and the mixture was uniformly mixed at a catalyst concentration of 1g/1mL of 1, 2-dichloroethane. After fully mixing, slowly dripping 40-450 parts by mass of epichlorohydrin, and stopping the reaction after the reaction is completed. Washing the reaction mixture with saturated NaHCO 3 solution for three times, washing with deionized water to neutrality, extracting the organic phase, dissolving the extracted organic phase in N, N-Dimethylformamide (DMF), and filtering to remove insoluble substances; washing the filtrate with a large amount of water to remove DMF, settling to obtain a crude product of hydroxyl-terminated polyepichlorohydrin, and distilling the crude product at 110 ℃ under reduced pressure to obtain a final product with a yield of more than 80%, wherein the product is light yellow viscous liquid, namely the hydroxyl-terminated polyepichlorohydrin. The synthetic route for the hydroxyl terminated polyepichlorohydrin (4 aPEG-PECH) is shown in figure 4.
100 G hydroxyl-terminated polyepichlorohydrin PECH was mixed with 30g castor oil and added: 5613 polyether polyol 30g and stannous octoate 0.12 g are mixed uniformly, then 60 g PAPI isocyanate is added, the mixture is mixed uniformly, and the mixture is added into a mould to be cured for 10 hours at 60 ℃ to obtain the polyurethane micro-foaming material A.
Example 2 preparation of polyurethane micro-foaming Material
The hydroxyl terminated polyepichlorohydrin PECH was prepared as in example 1.
100 G hydroxyl-terminated polyepichlorohydrin PECH was mixed with 50g castor oil and added: 5613 polyether polyol 40 g and stannous octoate 0.15 g are mixed uniformly, then 70 gPAPI isocyanate is added, the mixture is mixed uniformly, and the mixed solution is injected into a mould to be solidified for 10 hours at 80 ℃ to obtain the polyurethane micro-foaming material B.
Example 3 preparation of polyurethane micro-foaming Material
The hydroxyl terminated polyepichlorohydrin PECH was prepared as in example 1.
100G hydroxyl-terminated polyepichlorohydrin PECH was mixed with 30g castor oil and added: 5613 polyether polyol 20g and stannous octoate 0.10 g are mixed uniformly, 50g PAPI isocyanate is added, the mixture is mixed uniformly, and the mixed solution is injected into a die to be cured for 20 hours at 50 ℃ to obtain the polyurethane micro-foaming material C.
Comparative example 1 preparation of a general foam Material
100 G polypropylene glycol and 20 g castor oil are mixed, toluene diisocyanate 75 g is added, the mixture is stirred uniformly, and the mixture is injected into a die and cured for 15 hours at 60 ℃ to obtain polyurethane material D.
Comparative example 2 preparation of elastomeric Material
100 G polypropylene glycol and 20g castor oil are mixed, PAPI isocyanate 75 g is added, the mixture is stirred uniformly, and the mixture is injected into a mould to be cured for 15 hours at 60 ℃ to obtain polyurethane material E.
The results of the density (g/cm 3), ASKER C hardness, strength (MPa), and elongation at break (%) of the above polyurethane micro-foaming materials A to C and polyurethane materials D to E are shown in Table 1.
TABLE 1 results of Performance test of materials A-E
The results show that the polyurethane micro-foaming materials A-C successfully synthesized by the invention are different from the polyurethane materials D and E in the aspects of density, ASKER C hardness, strength, elongation at break and the like, and particularly, compared with the common foaming material D and the sex material E, the polyurethane micro-foaming material disclosed by the invention is moderate in density, softer and higher in strength. The following is optimized for high-heeled shoe needs.
Example 4
100 G hydroxyl-terminated polyepichlorohydrin PECH was mixed with 30 g castor oil and added: 5613 polyether polyol 30 g,0.12 g stannous octoate are mixed uniformly, and then 60 g PAPI isocyanate is added, and the mixture is mixed uniformly to obtain polyurethane precursor pre-A.
The inner layer of leather material is used as a base material, polypropylene glycol is coated on the surface of the base material, the base material is immersed for 10 minutes, a polyurethane adhesive (prepolymer) is coated on the surface of the treated leather, and the base material is placed for 20 seconds. Uniformly coating the polyurethane precursor pre-A. And attaching a leather layer which is the same as the base material, placing the leather layer on a clamp for compaction, and keeping the temperature of the clamp at 60 ℃ for 5 hours to obtain the composite material.
The material keeps the original leather, no deformation and wrinkling occur, and no cracking is found when the material is rubbed for 1000 times at 40 ℃.
Example 5
The inside of the heel of the shoe was used as a base material, polypropylene glycol was applied to the surface of the shoe, the shoe was immersed for 10 minutes, a polyurethane adhesive (prepolymer) was applied to the treated leather surface, and the shoe was left for 30 seconds. Uniformly coating the polyurethane precursor pre-A. The same leather layer as the base material is taken, polypropylene glycol is coated on the surface of the leather layer, the leather layer is immersed for 10 minutes, polyurethane adhesive (prepolymer) is coated on the inner surface of the treated leather, the leather layer attached with the polyurethane adhesive (prepolymer) is covered on a polyurethane precursor pre-A layer, the leather layer is placed on a clamp for pressing, the temperature of the clamp is 50 ℃, and the temperature is kept for 10 hours, so that the shoe with the composite material is obtained.
The surface of the shoe keeps the original shape of the leather, deformation and wrinkling are not seen, and manual tearing does not cause glue opening.
Example 6
And taking the prepared polyurethane micro-foaming materials A-C and polyurethane materials D-E out of the mould to prepare the required crescent shape.
The inside of the heel of the shoe was used as a base material, polypropylene glycol was applied to the surface of the shoe, the shoe was immersed for 10 minutes, a polyurethane adhesive (prepolymer) was applied to the treated leather surface, and the shoe was left for 30 seconds. Crescent polyurethane micro foaming materials A-C and polyurethane materials D-E are respectively placed on the leather surface with the adhesive, and the crescent materials A-E are respectively and tightly covered by the leather material with the adhesive (ankle contact layer). And curing the adhesive to obtain the multilayer composite material.
The multi-layer composite material is directly made into the high-heeled shoes, and the positions with the multi-layer composite material correspond to the ankle positions.
The upper cladding effects of different heel heights, different included angles alpha, different included angles beta, different heights H, different composite material types and different composite material thicknesses are tested by the following steps: sample shoes were provided to the testers for 1 hour, and comfort and fatigue were evaluated, with scoring criteria 1-5,5 being comfortable and 1 being uncomfortable. The test results are shown in Table 2. The composite material is not adopted, and the discomfort is mainly caused by the grinding of the upper.
Table 2 upper wrapping effect test results
| Numbering device | Heel height (cm) | Included angle alpha (degree) | Included angle beta (degree) | Height H (mm) | Material type | Thickness of composite material (mm) | Comfort rating |
| 1 | 9.5 | 35-36 | 58-60 | 34-35 | -- | 0 | 2 |
| 2 | 9.5 | 35-36 | 58-60 | 34-35 | Material A | 1 | 4 |
| 3 | 9.5 | 35-36 | 58-60 | 34-35 | Material B | 3 | 4 |
| 4 | 9.5 | 35-36 | 58-60 | 34-35 | Material C | 1 | 4 |
| 5 | 9.5 | 35-36 | 58-60 | 34-35 | Material D | 3 | 2+ |
| 6 | 9.5 | 35-36 | 58-60 | 34-35 | Material E | 3 | 2+ |
| 7 | 9 | 26-28 | 63-66 | 29-31 | -- | 0 | 2 |
| 8 | 9 | 26-28 | 63-66 | 29-31 | Material A | 1 | 4 |
| 9 | 9 | 26-28 | 63-66 | 29-31 | Material B | 3 | 4 |
| 10 | 9 | 26-28 | 63-66 | 29-31 | Material C | 1 | 4 |
| 11 | 9 | 26-28 | 63-66 | 29-31 | Material D | 3 | 2+ |
| 12 | 9 | 26-28 | 63-66 | 29-31 | Material E | 3 | 2+ |
| 13 | 8.5 | 16-19 | 70-72 | 24-26 | -- | 0 | 3 |
| 14 | 8.5 | 16-19 | 70-72 | 24-26 | Material A | 1 | 4+ |
| 15 | 8.5 | 16-19 | 70-72 | 24-26 | Material B | 3 | 4+ |
| 16 | 8.5 | 16-19 | 70-72 | 24-26 | Material C | 1 | 4+ |
| 17 | 8.5 | 16-19 | 70-72 | 24-26 | Material D | 3 | 3 |
| 18 | 8.5 | 16-19 | 70-72 | 24-26 | Material E | 3 | 3 |
| 19 | 8 | 11-14 | 74-76 | 17-19 | -- | 0 | 3 |
| 20 | 8 | 11-14 | 74-76 | 17-19 | Material A | 1 | 5 |
| 21 | 8 | 11-14 | 74-76 | 17-19 | Material B | 3 | 5 |
| 22 | 8 | 11-14 | 74-76 | 17-19 | Material C | 1 | 5 |
| 23 | 8 | 11-14 | 74-76 | 17-19 | Material D | 3 | 4 |
| 24 | 8 | 11-14 | 74-76 | 17-19 | Material E | 3 | 4 |
| 25 | 8 | 8-10 | 80-82 | 10-12 | -- | 0 | 2 |
| 26 | 8 | 42-43 | 45-48 | 42-45 | -- | 0 | 1 |
The results showed that overall, the heel was raised and the feel of wear was deteriorated. For the same heel height, as follows: table 2 test nos. 1-6, the addition of cushioning material reduced the friction of the heel to some extent, thereby improving comfort. Experiment nos. 5, 6 add cushioning material, but do not significantly improve comfort. For analysis reasons, the cushioning material needs comprehensive consideration of various properties, is not required to simply cushion and prevent friction, and cannot provide effective support due to elasticity and strength, so that the degree of wrapping of the shoes is insufficient and the comfort degree is reduced, so that the comprehensive statistics of wearing feeling can only obtain a fraction of 2+. Similar scoring results are felt when the heel is 9cm high, and even the comfort level of the wearing feeling of the buffer material is not great along with the reduction of the heel height.
Comparing test numbers 1, 7, 13, 19 with test numbers 25, 26 in table 2, it can be seen that the influence of the shoe design on the wearing comfort level exists, and that the specific changes of the included angle alpha, the included angle beta and the height H have influence on the wearing comfort level, so that the better wearing feeling can be obtained only in the preferred range. It is emphasized that the included angle α, the included angle β, and the height H are the result of the integrated adjustment, and the expected effect cannot be achieved if only one element meets the requirement.
Also comparing table 2, test numbers 19-24 and 25, 26, it was found that the selection of composite materials at the foot and heel openings also had an effect on the comfort of wear, while the differences in the effect of the different materials on comfort were greater. Firstly, the friction is required to have certain buffering performance, so that friction is reduced; but the hardness and the elasticity cannot be too low, so that the fit between the upper and the foot is poor due to the low hardness and the elasticity, and the shoes shake and are easy to fall off, so that the wearing is uncomfortable and even damage is caused. The polyurethane micro-foaming material A, B, C provided by the invention provides better wearing feeling due to the comprehensive properties of foaming degree, hardness, elasticity and the like, and is better than the common polyurethane material and is better than the common sponge material.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The above examples are only specific embodiments of the present application, and are not intended to limit the scope of the present application, but it should be understood by those skilled in the art that the present application is not limited thereto, and that the present application is described in detail with reference to the foregoing examples: any person skilled in the art may modify or easily conceive of the technical solution described in the foregoing embodiments or make equivalent substitutions for some of the technical details within the technical scope of the present disclosure; such modifications, changes or substitutions do not depart from the spirit and scope of the corresponding technical solutions. Are intended to be encompassed within the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (10)
1. The multilayer composite material is characterized by comprising a substrate layer, a first bonding layer, a polyurethane micro-foam layer, a second bonding layer and an ankle contact layer, wherein the polyurethane micro-foam layer is made of polyurethane micro-foam material, the density of the polyurethane micro-foam material is 0.26-0.36 g/cm 3, and the hardness of ASKER C is 20-36; the first bonding layer and the second bonding layer adopt polyurethane bonding agents, the basal layer is natural leather and/or artificial leather, and the ankle contact layer is natural leather and/or artificial leather.
2. The multilayer composite of claim 1, wherein the polyurethane micro-foam is a polycondensation product of 100 parts by mass of hydroxyl-terminated polyepichlorohydrin and 50 to 70 parts by mass of PAPI isocyanate.
3. The multilayer composite according to claim 2, wherein the hydroxyl-terminated polyepichlorohydrin is a crosslinked ring-opening polymerization product of a tetra-arm polyethylene glycol and epichlorohydrin under boron trifluoride catalysis.
4. The multilayer composite of claim 2, wherein the hydroxyl-terminated polyepichlorohydrin structure is of formula (I):
（I）
Wherein a, b, m and n represent the number of the repeating units in the polymer, and the number average molecular weight of the hydroxyl-terminated polyepichlorohydrin is 10500.
5. The multilayer composite of claim 2, wherein the hydroxyl terminated polyepichlorohydrin has a viscosity of 1.2 pa.s.
6. The multilayer composite of claim 2, wherein the polyurethane micro-foam layer material is prepared by a method comprising: mixing 100 parts by mass of hydroxyl-terminated polyepichlorohydrin with 30-50 parts by mass of plasticizer, 20-40 parts by mass of 5613 polyether polyol and 0.1-0.15 part by mass of stannous octoate uniformly, and adding 50-70 parts by mass of PAPI isocyanate to obtain a precursor to be molded; adding a precursor to be formed into a grinding tool, and curing for 10-20 hours at the temperature of 50-80 ℃ to obtain a polyurethane micro-foaming material; the plasticizer is castor oil.
7. A method of forming a multilayer composite according to any one of claims 1 to 6, comprising the steps of:
Mixing 100 parts by mass of hydroxyl-terminated polyepichlorohydrin with 30-50 parts by mass of plasticizer, 20-40 parts by mass of 5613 polyether polyol and 0.1-0.15 part by mass of stannous octoate uniformly, and adding 50-70 parts by mass of PAPI isocyanate to obtain a precursor to be molded;
Coating polyurethane adhesive on the surface of the substrate layer, and placing 30-180 s to form a first adhesive layer; coating the precursor to be formed on the surface of the first bonding layer, coating polyurethane adhesive on the surface of the precursor to be formed to form a second bonding layer, covering an ankle contact layer on the surface of the second bonding layer, and adding the second bonding layer into a die to form for 10-20 hours to obtain the multilayer composite material.
8. Use of a multilayer composite according to any one of claims 1-6 in high-heeled shoes.
9. An upper structure for protecting ankle tendons, wherein the upper structure is arc-shaped and the thickness of the multilayer composite is 1-3mm, and the multilayer composite is any one of claims 1-6.
10. A high-heeled shoe characterized in that the heel counter comprises an upper structure for protecting ankle tendons according to claim 9, the upper structure is arranged at a corresponding position contacted with the rear ankle, the upper structure extends upwards to a counter opening and is connected to a heel end point of the upper downwards, the height H between the heel end point of the upper and the horizontal line of the heel sole is 17-35 mm, an included angle alpha between an arc tangent line of the heel sole at a position 2/3 of the tail end of the counter opening and a plumb line is 11-36 degrees, and an included angle beta between the arc tangent line of the counter opening and the horizontal plane is 58-76 degrees.
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| CN202410109789.8A CN117621552A (en) | 2024-01-26 | 2024-01-26 | Multilayer composite material and forming method and application thereof |
| CN2024101097898 | 2024-01-26 |
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| CN117901502A true CN117901502A (en) | 2024-04-19 |
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| CN202410309076.6A Pending CN117901502A (en) | 2024-01-26 | 2024-03-19 | Multilayer composite material and forming method and application thereof |
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