CN114196134A - Women's shoes with cold-resistant soles and preparation method thereof - Google Patents

Abstract

The application relates to the technical field of shoes, and particularly discloses a women's shoe with a cold-resistant sole and a preparation method thereof. The women's shoes with cold-resistant sole include sole and vamp, the sole includes the raw materials of following parts by weight: 80-100 parts of modified polyvinyl chloride, 18-22 parts of powdered nitrile rubber, 5-7 parts of plasticizer and 8-10 parts of ethyl p-aminobenzoate, wherein the modified polyvinyl chloride is obtained by modifying inorganic filler, and the inorganic filler is one or more of calcium powder, silicon carbide micro powder and carbon black. The application has the woman's shoe cold-resistant excellent performance of cold-resistant sole, and its sole hardness is lower under the low temperature condition to have lower brittle temperature, accord with the market demand.

Description

Women's shoes with cold-resistant soles and preparation method thereof

Technical Field

The application relates to the technical field of shoes, in particular to a women's shoe with a cold-resistant sole and a preparation method thereof.

Background

Shoes are a tool to protect the human foot from injury. At present, with the development of society, in order to satisfy different requirements of people, shoes with more and more styles and materials are developed. The shoe comprises a sole and an upper. When the shoe is used, the sole is in direct contact with the ground and is continuously rubbed; furthermore, the softness of the sole affects the comfort of the user when walking, and therefore the material of the sole significantly affects the function and comfort of the shoe.

The material of the sole can be divided into natural bottom materials and synthetic bottom materials. Wherein, the natural base materials comprise bamboo, wood, natural bottom leather and the like; synthetic primers include recycled leather, rubber and plastic materials, rubber, plastics, EVA (ethylene-vinyl acetate copolymer), polyurethane, and the like. The plastic sole has low price, so that the plastic sole is widely applied to the manufacturing of shoes. However, in cold winter, the temperature is as low as-10 ℃ or even-20 ℃, so that the sole has significantly reduced properties, such as easy breakage, low comfort, and the like. Therefore, the development of shoes with cold-resistant soles is urgent.

Disclosure of Invention

In order to improve the cold resistance of shoes, the application provides a woman's shoe with cold-resistant sole and preparation method thereof.

First aspect, the application provides a woman's shoe with cold-resistant sole adopts following technical scheme:

the utility model provides a woman's shoe with cold-resistant sole, woman's shoe includes sole and vamp, the sole includes the raw materials of following parts by weight: 80-100 parts of modified polyvinyl chloride, 18-22 parts of powdered nitrile rubber, 5-7 parts of plasticizer and 8-10 parts of ethyl p-aminobenzoate, wherein the modified polyvinyl chloride is obtained by modifying inorganic filler, and the inorganic filler is one of calcium powder, silicon carbide micro powder and carbon black.

Through adopting above-mentioned technical scheme for the woman's shoe that has cold-resistant sole has better cold-resistant performance. The soles of the shoes for women have lower brittle temperature and lower hardness at 22 ℃ and-40 ℃. The brittle temperature range is (-113.4) - (-110.6) DEG C; the hardness range is 45-50 DEG A at 22 ℃; the hardness range at-40 ℃ is 50-58 DEG A. The cold resistance of the sole is obviously improved through the mutual synergistic effect of the raw materials in the sole, the defects that the sole of the woman's shoe is easy to break and has high hardness under the low-temperature condition are overcome, and the sole meets the market demand.

The applicant has found that polyvinyl chloride (PVC) is a common material for plastic soles, and that soles made therefrom are lightweight and inexpensive, being about one-tenth the price of polyurethane soles. Therefore, the polyvinyl chloride is used as the main raw material of the sole, and the cost of the women's shoes with cold-resistant soles can be reduced. However, the sole prepared from the PVC material has higher hardness and is easy to break, the defects can be improved and the service life of the sole can be prolonged by adding the high-toughness powdered nitrile rubber into the sole, but the cold resistance of the sole is to be improved; the addition of inorganic filler to soles made from PVC improves the mechanical properties and wear resistance of the soles, however, the addition of inorganic filler to PVC by simple compounding generally increases the hardness of the soles and reduces cold resistance. The applicant found that by modifying polyvinyl chloride with an inorganic filler first, the inorganic filler can be linked to polyvinyl chloride by van der waals force via a silane coupling agent, so that the interaction force between macromolecular chains is increased, and the low-temperature performance thereof is improved. And through adding cold-resistant plasticizer, the plasticizer can generate Van der Waals force with the modified polyvinyl chloride, thereby further improving the cold-resistant performance of the modified polyvinyl chloride. By adding ethyl p-aminobenzoate into the raw materials of the sole, the amino group of the ethyl p-aminobenzoate can generate hydrogen bond interaction force with chlorine atoms in polyvinyl chloride; the ester group and the benzene ring of the shoe sole can generate van der Waals force interaction with the powdery nitrile rubber and the plasticizer, so that the compatibility among the raw materials of the shoe sole can be obviously improved, the interaction force among the raw materials is increased, the improvement of the mutual winding degree among macromolecular chains is facilitated, the cold resistance of the shoe sole can be improved, the embrittlement temperature of the shoe sole is reduced, and the hardness of the shoe sole under the conditions of normal temperature and low temperature is reduced.

Optionally, the plasticizer is one or more of tricresyl phosphate, butyl phthalate and toluene diphenyl phosphate.

Through adopting above-mentioned technical scheme, there is better compatibility between above-mentioned plasticizer and the polyvinyl chloride, can effectively improve the cold-resistant performance of woman's shoe sole.

Optionally, the plasticizer is a mixture of diphenyl cresyl phosphate and butyl phthalate, and the mass ratio of diphenyl cresyl phosphate to butyl phthalate is 1 (5-6).

Through adopting above-mentioned technical scheme, mutual cooperation between diphenyl toluene phosphate, the butyl phthalate can further improve the compatibility between plasticizer and the polyvinyl chloride to further improve the cold resistance of woman's shoe sole.

Optionally, the inorganic filler is silicon carbide micropowder.

Through adopting above-mentioned technical scheme, can further reduce the brittle temperature, the hardness of woman's shoe sole, improve its cold-resistant performance.

Optionally, the particle size of the silicon carbide micro powder is 30-60nm continuous gradation.

Through adopting above-mentioned technical scheme, the particle diameter of carborundum miropowder is too big, causes hardness, the fragility increase of polyvinyl chloride easily, reduces its cold resistance, when the particle diameter is 30-60nm continuous grade timing, can improve the cold resistance of woman's shoe sole.

Optionally, the modified polyvinyl chloride comprises, by weight, 60-80 parts of polyvinyl chloride, 5-7 parts of a silane coupling agent, and 5-6 parts of an inorganic filler.

By adopting the technical scheme, the inorganic filler is coupled on the polyvinyl chloride through the silane coupling agent, the modification method is simple, and the raw materials are easy to obtain. When the content of each raw material of the modified polyethylene is within the above range, the influence on the performance test result is within a predictable range.

Optionally, the polyvinyl chloride has an average degree of polymerization of 1700-1900.

Through adopting above-mentioned technical scheme, polyvinyl chloride's viscosity is great for its cold-resistant performance is more excellent, can further improve the cold-resistant performance of woman's shoe sole.

The second aspect, the application provides a preparation method of woman's shoe with cold-resistant sole, adopts following technical scheme: the preparation method of the women's shoes with the cold-resistant soles comprises the following steps:

1) preparing a sole: uniformly mixing the raw materials of the sole, melting and extruding to obtain a mixture, then coating a release agent on the outer surface of a sole mold, drying, pouring the mixture, closing the mold, carrying out heat preservation treatment for 4-6min, demolding, and cooling to 22 +/-3 ℃ to obtain the sole;

2) preparation of women's shoes: and sewing the vamp and the sole to form the cold-resistant sole for the women.

By adopting the technical scheme, the preparation method of the women's shoes is simple and convenient to operate. Also, when the operating conditions are within the above range, the influence on the performance test results is within the expected range.

In summary, the present application has at least the following beneficial effects:

firstly, the embrittlement temperature of the sole of the woman shoe, the hardness at the temperature of 22 ℃ and the hardness at the temperature of-40 ℃ are obviously reduced through the mutual synergistic effect of the raw materials in the sole of the woman shoe, and the cold resistance of the sole of the woman shoe is improved, so that the embrittlement temperature is reduced to-110.9 ℃, the hardness at the temperature of 22 ℃ is reduced to 49 degrees A, and the hardness at the temperature of-40 ℃ is reduced to 56 degrees A;

secondly, the cold resistance of the sole of the women's shoes is further improved by taking the diphenyl toluate and the butyl phthalate with the mass ratio of 1:5 as the plasticizer, so that the brittle temperature of the sole is reduced to-112.3 ℃, the hardness at 22 ℃ is reduced to 47 DEG A, and the hardness at-40 ℃ is reduced to 52 DEG A.

Detailed Description

The present application will be described in further detail with reference to examples.

Raw materials

Polyvinyl chloride selected from Shanghai Kahn chemical Co., Ltd; the silane coupling agent is gamma-methacryloxypropyltrimethoxysilane with the model number of KH-570 and is selected from Shandong Yilong chemical company Limited; the mold release agent has the model number of 369 and is selected from Shenzhen Longwei detergent Limited; the powdered nitrile rubber is selected from Yuanyuan plastic Co., Ltd.

Preparation example

Preparation example 1

The modified polyvinyl chloride is prepared by the following method:

stirring 5kg of inorganic filler and 6kg of silane coupling agent in a stirrer until the inorganic filler and the silane coupling agent are uniformly mixed, then adding 70kg of polyvinyl chloride, stirring until the polyvinyl chloride is uniformly mixed, and then carrying out ultrasonic treatment on the uniformly mixed materials for 15min to obtain modified polyvinyl chloride;

the silane coupling agent is gamma-methacryloxypropyl trimethoxy silane;

the polymerization degree of the polyvinyl chloride is 1450 +/-50;

the inorganic filler is carbon black.

Preparation example 2

A modified polyvinyl chloride which is different from that of preparation example 1 in that an inorganic filler is calcium powder in an equal amount, and the rest is the same as that of preparation example 1.

Preparation example 3

The modified polyvinyl chloride is different from the modified polyvinyl chloride in preparation example 1 in that the inorganic filler is equal silicon carbide micro powder, the grain diameter of the silicon carbide micro powder is 60-100nm in continuous gradation, and the rest is the same as that of the modified polyvinyl chloride in preparation example 1.

Preparation example 4

A modified polyvinyl chloride is different from that of preparation example 3 in that the particle size of silicon carbide fine powder is 30-60nm in continuous gradation, and the rest is the same as that of preparation example 3.

Preparation example 5

A modified polyvinyl chloride which is different from preparation example 4 in that the degree of polymerization of polyvinyl chloride is 1850. + -. 50 and the rest is the same as preparation example 4.

Preparation example 6

A modified polyvinyl chloride which is different from that of production example 5 in that the degree of polymerization of polyvinyl chloride is 2500. + -. 200, and the rest is the same as that of production example 5.

Examples

Table 1 contents (kg) of raw materials of soles of women's shoes having cold-resistant soles in examples 1 to 4

Raw materials	Example 1	Example 2	Example 3	Example 4
					Modified polyvinyl chloride	80	90	95	100
Powdered nitrile rubber	22	21	20	18
					Plasticizer	5	6	6.5	7
P-aminobenzoic acid ethyl ester	10	9	9.5	8

Example 1

The women's shoes with cold-resistant soles comprise soles and vamps, wherein the raw material content of the soles is shown in table 1;

wherein, the modified polyvinyl chloride is prepared from the preparation example 1;

the plasticizer is dioctyl adipate.

A preparation method of women's shoes with cold-resistant soles comprises the following steps:

1) preparing a sole: adding the raw materials of the sole into a high-speed stirrer, stirring until the raw materials are uniformly mixed, adding the raw materials into a double-screw extruder, melting and extruding to obtain a mixture, coating a release agent on the outer surface of a sole mold, drying, pouring the mixture, closing the mold, carrying out heat preservation treatment for 6min, demolding, and cooling to 22 ℃ to obtain the sole;

2) preparation of women's shoes: and sewing the vamp and the sole to form the cold-resistant sole for the women.

Examples 2 to 4

The women's shoes having cold-resistant soles of examples 2 to 4 are different from example 1 in that the contents of raw materials for the soles are different and are shown in table 1.

Example 5

A women's shoes having cold-resistant soles, which are different from example 3 in that the plasticizer is tricresyl phosphate in an equal amount, and the rest is the same as example 3.

Example 6

A women's shoes having cold-resistant soles, which are different from example 5 in that the plasticizer is tolyldiphenyl phosphate in an amount equal to that of example 5, and the rest is the same as example 5.

Example 7

A women's shoe having a cold-resistant sole, which is different from example 6 in that the plasticizer is butyl phthalate in an equal amount, and the rest is the same as example 6.

Example 8

A women's shoes having cold-resistant soles, which is different from example 7 in that the plasticizer is a mixture of cresyldiphenyl phosphate and butyl phthalate, and the mass ratio of cresyldiphenyl phosphate to butyl phthalate is 1:5, and the rest is the same as example 7.

Examples 9 to 13

Examples 9 to 13 women's shoes having cold-resistant soles are different from example 8 in that modified polyvinyl chloride was prepared from preparation examples 2 to 6 in this order, respectively, and the rest was the same as example 8.

Example 14

A women's shoes having cold-resistant soles, which are different from example 12 in that a silane coupling agent is not added to the raw material of modified polyvinyl chloride, and the rest is the same as example 12.

Comparative example

Comparative example 1

A women's shoes having cold-resistant soles, which are different from example 1 in that ethyl p-aminobenzoate is not added to the raw materials of the soles, and the rest is the same as example 1.

Comparative example 2

A women's shoes having cold-resistant soles, which is different from example 1 in that the modified polyvinyl chloride is replaced with the same amount of polyvinyl chloride in the raw materials of the soles, and the rest is the same as example 1.

Performance test

The 16 women's shoes with cold-resistant soles prepared in examples 1-14 and comparative examples 1-2 were subjected to the following property tests:

detecting the embrittlement temperature of soles of 16 women shoes according to 'determination of embrittlement temperature by plastic impact method' GB/T5470-2008; according to the hardness of the whole shoe test method for shoes GB/T3903.4-2017, the hardness of the soles of 16 women's shoes after 1h at normal temperature (22 ℃) and freezing (-40 ℃) is detected, and the detection results are shown in Table 2.

TABLE 2 test results

As can be seen from the table 2, the women's shoes with the cold-resistant soles have the advantage of excellent cold resistance, the soles of the women's shoes have lower brittle temperature, and the brittle temperature range is (-113.4) - (-110.6) DEG C; the hardness is lower at 22 ℃ and-40 ℃, wherein the hardness range is 45-50 DEG A at 22 ℃; the hardness range at-40 ℃ is 50-58 DEG A. In this application, through the mutual synergism between each raw materials of woman's shoe sole, show to have improved its cold-resistant performance for the woman's shoe that has cold-resistant sole also has higher comfort level and security under the low temperature condition, accords with the market demand.

By comparing example 3 with examples 5 to 8, the plasticizer in example 3 was dioctyl adipate, and the sole of the woman's shoe had an embrittlement temperature of-110.9 ℃, a hardness of 49 ° a at 22 ℃ and a hardness of 56 ° a at-40 ℃; the plasticizer in the embodiment 5 adopts tricresyl phosphate, the brittle temperature of the sole of the women's shoes is-111.4 ℃, the hardness at 22 ℃ is 49 DEG A, and the hardness at 40 ℃ is 55 DEG A; the plasticizer in the embodiment 6 adopts diphenyl cresyl phosphate, the brittle temperature of the soles of the women's shoes is-111.6 ℃, the hardness at 22 ℃ is 49 degrees A, and the hardness at 40 ℃ is 54 degrees A; the plasticizer in the embodiment 7 adopts butyl phthalate, and the brittle temperature of the soles of the women's shoes is-111.9 ℃, the hardness at 22 ℃ is 48 DEG A, and the hardness at 40 ℃ is 54 DEG A; the plasticizer in example 8 was a mixture of cresyldiphenyl phosphate and butyl phthalate in a mass ratio of 1:5, and the soles of women's shoes had an embrittlement temperature of-112.3 ℃, a hardness of 47 ° a at 22 ℃ and a hardness of 52 ° a at-40 ℃. It can be seen that the plasticizer adopts one or more of tricresyl phosphate, butyl phthalate and cresyldiphenyl phosphate, so that the cold resistance of the sole of the women's shoes can be further improved. And moreover, the mutual synergistic effect exists between the diphenyl cresyl phosphate and the butyl phthalate, van der Waals force interaction can be generated between the diphenyl cresyl phosphate and the polyvinyl chloride, the cold resistance of the diphenyl cresyl phosphate and the polyvinyl chloride is improved, and meanwhile, the compatibility between the plasticizer and the polyvinyl chloride can be improved, so that the cold resistance of soles of the women's shoes is further improved.

By comparing example 12 with example 14, the shoe sole of the woman's shoe in example 12 had an embrittlement temperature of-113.4 ℃, a hardness of 45 ° A at 22 ℃ and a hardness of 50 ° A at-40 ℃; the shoe sole of the woman's shoe in example 14 had an embrittlement temperature of-110.6 ℃ and a hardness of 50 ° A at 22 ℃ and a hardness of 57 ° A at-40 ℃. Compared with example 12, the silane coupling agent is not added to the raw material of the modified polyvinyl chloride in example 14, so that the cold resistance of the sole is reduced. The silane coupling agent can generate Van der Waals force with the inorganic filler and the polyvinyl chloride at the same time, so that inorganic filler particles are attached to a polyvinyl chloride molecular chain, polyvinyl chloride molecules with large molecular weight are easier to move mutually, and the cold resistance of the polyvinyl chloride is improved. When the silane coupling agent is not added, Van der Waals force is difficult to generate between the inorganic filler and the polyvinyl chloride, and only simple mixing is adopted, so that the hardness and the brittle temperature of the shoe sole are improved by adding the inorganic filler, and the cold resistance of the shoe sole for women is reduced.

By comparing example 1 with comparative example 1, the shoe sole of the woman's shoe in example 1 had an embrittlement temperature of-110.7 ℃, a hardness of 49 ° a at 22 ℃ and a hardness of 57 ° a at-40 ℃; the shoe sole of the woman's shoe in comparative example 1 had an embrittlement temperature of-104.6 deg.C, a hardness of 53A at 22 deg.C and a hardness of 66A at-40 deg.C. In comparison with example 1, the raw material of the sole of the women's shoe in comparative example 1 was not added with ethyl p-aminobenzoate, so that its embrittlement temperature was increased and hardness was increased under the conditions of 22 ℃ and-40 ℃. The ethyl p-aminobenzoate can generate van der waals force interaction with polyvinyl chloride, so that polyvinyl chloride molecules can move easily to each other even under a low-temperature condition, the hardness of the polyvinyl chloride molecules under the low-temperature condition is reduced, and the embrittlement temperature of the polyvinyl chloride molecules is reduced, so that the cold resistance of soles of women's shoes is improved.

By comparing example 1 with comparative example 2, the shoe sole of the woman's shoe in example 1 had an embrittlement temperature of-110.7 ℃, a hardness of 49 ° a at 22 ℃ and a hardness of 57 ° a at-40 ℃; the shoe sole of the woman's shoe in comparative example 2 had an embrittlement temperature of-101.2 deg.C, a hardness of 56 ° A at 22 deg.C and a hardness of 69 ° A at 40 deg.C. Compare in embodiment 1, replace modified polyvinyl chloride with equivalent polyvinyl chloride in the raw materials of woman's shoe sole in comparative example 2 for woman's shoe sole's cold resistance can show and reduce, and brittle temperature, hardness all increase. The inorganic filler is used for modifying the polyvinyl chloride, so that the polyvinyl chloride macromolecules are easy to move mutually, the cold resistance of the polyvinyl chloride is improved, the hardness of the polyvinyl chloride is lower under the low-temperature condition, the brittleness temperature of the polyvinyl chloride is lower, and the market demand is met.

The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.

Claims (8)

1. The utility model provides a woman's shoe with cold-resistant sole, woman's shoe includes sole and vamp, its characterized in that, the sole includes the raw materials of following parts by weight: 80-100 parts of modified polyvinyl chloride, 18-22 parts of powdered nitrile rubber, 5-7 parts of plasticizer and 8-10 parts of ethyl p-aminobenzoate, wherein the modified polyvinyl chloride is obtained by modifying inorganic filler, and the inorganic filler is one of calcium powder, silicon carbide micro powder and carbon black.

2. The women's shoes with cold-resistant soles according to claim 1, wherein said plasticizer is one or more of tricresyl phosphate, butyl phthalate, cresyl diphenyl phosphate.

3. The women's shoes with cold-resistant soles according to claim 2, wherein the plasticizer is a mixture of diphenyl cresyl phosphate and butyl phthalate, and the mass ratio of diphenyl cresyl phosphate to butyl phthalate is 1 (5-6).

4. The women's shoes with cold-resistant soles according to claim 1, characterized in that said inorganic filler is silicon carbide micropowder.

5. The women's shoes with cold-resistant soles according to claim 4, wherein the grain size of the silicon carbide micro powder is 30-60nm continuous gradation.

6. The women's shoes with cold-resistant soles according to claim 1, wherein the modified polyvinyl chloride comprises the following raw materials in parts by weight: 60-80 parts of polyvinyl chloride, 5-7 parts of silane coupling agent and 5-6 parts of inorganic filler.

7. The women's shoes with cold-resistant soles according to claim 6, wherein the average degree of polymerization of said polyvinyl chloride is 1700-1900.

8. A method for preparing women's shoes with cold-resistant soles according to any one of claims 1 to 7, characterized in that it comprises the following steps:

1) preparing a sole: uniformly mixing the raw materials of the sole, melting and extruding to obtain a mixture, then coating a release agent on the outer surface of a sole mold, drying, pouring the mixture, closing the mold, carrying out heat preservation treatment for 4-6min, demolding, and cooling to 22 +/-3 ℃ to obtain the sole;

2) preparation of women's shoes: and sewing the vamp and the sole to form the cold-resistant sole for the women.