CN114196134B

CN114196134B - Women's shoes with cold-resistant soles and preparation method thereof

Info

Publication number: CN114196134B
Application number: CN202111585343.5A
Authority: CN
Inventors: 冯虎; 赵延辉
Original assignee: Zhejiang Sanyi Shoes Trade Co ltd
Current assignee: Zhejiang Sanyi Shoes Trade Co ltd
Priority date: 2021-12-22
Filing date: 2021-12-22
Publication date: 2023-05-30
Anticipated expiration: 2041-12-22
Also published as: CN114196134A

Abstract

The application relates to the technical field of shoes, and particularly discloses a pair of shoes with cold-resistant soles and a preparation method thereof. The women's shoes with cold-resistant soles comprise soles and vamps, wherein the soles comprise the following raw materials in parts by weight: 80-100 parts of modified polyvinyl chloride, 18-22 parts of powdery 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 micropowder and carbon black. The women's shoes with cold-resistant soles have excellent cold-resistant performance, the soles of the women's shoes have lower hardness under the low-temperature condition, have lower embrittlement temperature and meet market demands.

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 pair of shoes with cold-resistant soles and a preparation method thereof.

Background

Shoes are a tool for protecting human feet from injury. At present, with the development of society, in order to meet different demands of people, shoes with more and more patterns and materials are developed. The shoe includes a sole and an upper. When the shoe is used, the sole is in direct contact with the ground, and friction is continuously received; in addition, the softness of the sole affects the comfort of people during walking, so that the material of the sole has obvious influence on the function and the comfort of the shoe.

The sole material can be divided into natural base materials and synthetic base materials. Wherein, the natural base material comprises bamboo, wood, natural leather and the like; synthetic class primer includes reclaimed leather, rubber and plastic materials, rubber, plastic, EVA (ethylene vinyl acetate), polyurethane, and the like. Wherein, the plastic sole has wide application in shoe manufacture due to low price. However, in cold winter, the air temperature is as low as-10 ℃ or even-20 ℃, so that the performances of the sole in all aspects are remarkably reduced, such as easy breakage, low comfort and the like. Accordingly, it is urgent to develop a shoe having a cold-resistant sole.

Disclosure of Invention

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

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

women's shoes with cold-resistant sole, the 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 powdery nitrile rubber, 5-7 parts of plasticizer and 8-10 parts of ethyl p-aminobenzoate, wherein the modified polyvinyl chloride is obtained by modifying an inorganic filler, and the inorganic filler is one of calcium powder, silicon carbide micro powder and carbon black.

By adopting the technical scheme, the women's shoes with cold-resistant soles have better cold-resistant performance. The sole of the women's shoes has lower embrittlement temperature and lower hardness at 22 ℃ and-40 ℃. The embrittlement temperature is (-113.4) - (-110.6) deg.C; the hardness range is 45-50 DEG A at 22 ℃; the hardness at-40 ℃ is in the range of 50-58 DEG A. It can be seen that the cold resistance of the sole is obviously improved through the mutual synergistic effect among the raw materials in the sole, the defects that the sole of the women's shoes is easy to break and has high hardness under the low-temperature condition are overcome, and the market demand is met.

The applicant has found that polyvinyl chloride (PVC) is a common material for plastic soles, from which soles are made, lightweight, inexpensive, and about one tenth of the price of polyurethane soles. Therefore, the cost of the women's shoes with cold-resistant soles can be reduced by adopting the polyvinyl chloride as the main raw material of the soles. However, the hardness of the sole prepared from the PVC material is high and the sole is easy to break, the defects of the sole can be improved by adding the high-toughness powder nitrile rubber into the sole, the service life of the sole is prolonged, and the cold resistance of the sole is still to be improved; the mechanical property and the wear resistance of the sole can be improved by adding the inorganic filler into the sole prepared from PVC, however, the hardness of the sole is generally increased and the cold resistance is reduced by adding the inorganic filler into the PVC through simple mixing. The applicant found that by modifying the polyvinyl chloride with an inorganic filler first, the inorganic filler can be interconnected with the polyvinyl chloride by van der waals force through a silane coupling agent, so that the interaction force between macromolecular chains is increased, and the low-temperature performance of the polyvinyl chloride is improved. And through adding cold-resistant plasticizer, the plasticizer can generate Van der Waals force with the modified polyvinyl chloride, so that the cold-resistant performance of the modified polyvinyl chloride is further improved. By adding ethyl p-aminobenzoate into the raw material of the sole, the amino group of the ethyl p-aminobenzoate can generate hydrogen bond interaction force with chlorine atoms in the polyvinyl chloride; the ester group and the benzene ring can generate Van der Waals force interaction with the powder nitrile rubber and the plasticizer, so that the compatibility between the sole raw materials can be obviously improved, the interaction force between the raw materials is increased, the degree of intertwining between macromolecular chains is improved, the cold resistance of the sole can be improved, the embrittlement temperature of the sole is reduced, and the hardness under normal temperature and low temperature conditions is reduced.

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

Through adopting above-mentioned technical scheme, have 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 toluene diphenyl phosphate and butyl phthalate, and the mass ratio of toluene diphenyl phosphate to butyl phthalate is 1 (5-6).

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

Optionally, the inorganic filler is silicon carbide micropowder.

By adopting the technical scheme, the embrittlement temperature and hardness of the sole of the women's shoes can be further reduced, and the cold resistance of the sole of the women's shoes is improved.

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

Through adopting above-mentioned technical scheme, the particle diameter of carborundum miropowder is too big, causes hardness, the brittleness increase of polyvinyl chloride easily, reduces its cold-resistant performance, and when the particle diameter was 30-60nm continuous level, can improve the cold-resistant performance of woman's shoe sole.

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

By adopting the technical scheme, the inorganic filler is coupled to the polyvinyl chloride through the silane coupling agent, the modification method is simple, and the raw materials are easy to obtain. Further, 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 an expected range.

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

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

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

1) Preparation of the sole: uniformly mixing the raw materials of the sole, carrying out melt extrusion to obtain a mixture, then coating a release agent on the outer surface of a sole die, drying, pouring the mixture, closing the die, carrying out heat preservation for 4-6min, carrying out demoulding, and cooling to 22+/-3 ℃ to obtain the sole;

2) Preparation of women's shoes: and sewing and forming the vamp and the sole to obtain the women's shoes with cold-resistant soles.

By adopting the technical scheme, the preparation method of the women's shoes is simple and convenient to operate. Also, when the operating conditions lie within the above-described range, the influence on the performance detection result is within an predictable range.

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

firstly, through the mutual synergistic effect among the raw materials in the sole of the women's shoes, the embrittlement temperature of the sole of the women's shoes and the hardness at 22 ℃ are obviously reduced, the cold resistance is improved, the embrittlement temperature is reduced to minus 110.9 ℃, the hardness at 22 ℃ is reduced to 49 DEG A, and the hardness at minus 40 ℃ is reduced to 56 DEG A;

secondly, the cold resistance of the sole of the women's shoes is further improved by taking toluene diphenyl ester and butyl phthalate with the mass ratio of 1:5 as plasticizers, so that the embrittlement temperature of the sole of the women's shoes 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 is described in further detail below with reference to examples.

Raw materials

Polyvinyl chloride selected from Kaiyin chemical Co., ltd; the silane coupling agent is gamma-methacryloxypropyl trimethoxysilane, the model is KH-570, and is selected from Shandong Yilong chemical Co., ltd; a release agent, model 369, selected from Shenzhen Longwei cleaner company; the powdered nitrile rubber is selected from Dongguan Ming Yuan Plastic Co.

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, adding 70kg of polyvinyl chloride, stirring until the inorganic filler and the silane coupling agent are uniformly mixed, and 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 was different from preparation example 1 in that the inorganic filler was an equivalent amount of calcium powder, and the rest was the same as preparation example 1.

Preparation example 3

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

Preparation example 4

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

Preparation example 5

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

Preparation example 6

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

Examples

Table 1 contents (kg) of the respective raw materials for 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(s)	5	6	6.5	7
Para aminobenzoic acid ethyl ester	10	9	9.5	8

Example 1

A pair of shoes with cold-resistant soles, which comprises soles and vamps, wherein the raw materials of the soles are shown in table 1;

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

the plasticizer is dioctyl adipate.

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

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

Examples 2 to 4

The women's shoes with cold-resistant soles of examples 2-4 were different from example 1 in that the raw material contents of the soles were different, and the raw material contents are shown in table 1.

Example 5

A women's shoe with a cold-resistant sole differs from example 3 in that the plasticizer is an equivalent amount of tricresyl phosphate, the remainder being the same as in example 3.

Example 6

A women's shoe with cold-resistant sole is different from example 5 in that the plasticizer is equal amount of toluene diphenyl phosphate, and the rest is the same as example 5.

Example 7

A women's shoe with cold-resistant sole is distinguished from example 6 in that the plasticizer is an equal amount of butyl phthalate, the remainder being the same as in example 6.

Example 8

The difference between the cold-resistant sole and the example 7 is that the plasticizer is a mixture of toluene diphenyl phosphate and butyl phthalate, the mass ratio of toluene diphenyl phosphate to butyl phthalate is 1:5, and the rest is the same as the example 7.

Examples 9 to 13

The women's shoes with cold-resistant soles of examples 9-13 were different from example 8 in that modified polyvinyl chloride was prepared from preparation examples 2-6, respectively, in this order, and the remainder was the same as example 8.

Example 14

A women's shoe with cold-resistant sole is different from example 12 in that a silane coupling agent is not added into the raw material of modified polyvinyl chloride, and the rest is the same as example 12.

Comparative example

Comparative example 1

A kind of shoes with cold-resistant sole is different from example 1 in that ethyl p-aminobenzoate is not added into the raw material of sole, and the rest is the same as example 1.

Comparative example 2

A kind of shoes with cold-resistant sole is different from example 1 in that the raw material of sole is replaced by equivalent polyvinyl chloride modified polyvinyl chloride, and the rest is the same as example 1.

Performance test

The following performance tests were carried out on 16 types of women's shoes with cold-resistant soles prepared in examples 1 to 14 and comparative examples 1 to 2:

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

TABLE 2 detection results

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

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

By comparing example 12 with example 14, the sole embrittlement temperature of the women's shoes in example 12 was-113.4 ℃, the hardness at 22 ℃ was 45 ° a, and the hardness at 40 ℃ was 50 ° a; the sole embrittlement temperature of the women's shoes in example 14 was-110.6 ℃, the hardness at 22 ℃ was 50°a, -the hardness at 40 ℃ was 57°a. Compared with example 12, the modified polyvinyl chloride in example 14 has no silane coupling agent added to the raw material, 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 polyvinyl chloride molecular chains, the polyvinyl chloride molecules with large molecular weight are easier to move mutually, and the cold resistance of the polyvinyl chloride molecules 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 addition of the inorganic filler improves the hardness and the embrittlement temperature of the inorganic filler, and the cold resistance of the sole of the women's shoes is reduced.

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

By comparing example 1 with comparative example 2, the sole embrittlement temperature of the women's shoes in example 1 was-110.7 ℃, the hardness at 22 ℃ was 49 ° a, and the hardness at 40 ℃ was 57 ° a; the sole embrittlement temperature of the women's shoes in comparative example 2 was-101.2 ℃, the hardness at 22 ℃ was 56 ° a, -the hardness at 40 ℃ was 69 ° a. Compared with the example 1, the comparative example 2 has the advantages that the raw materials of the sole of the women's shoes are replaced by equivalent polyvinyl chloride, so that the cold resistance of the sole of the women's shoes is obviously reduced, and the embrittlement temperature and the hardness are both increased. The inorganic filler is used for modifying the polyvinyl chloride, so that polyvinyl chloride macromolecules are easy to move mutually, the cold resistance of the polyvinyl chloride macromolecules is improved, the hardness of the polyvinyl chloride macromolecules is low under the low-temperature condition, the embrittlement temperature is low, and the market demand is met.

The present embodiment is only for explanation of the present invention and is not to be construed as limiting the present invention, and modifications to the present embodiment, which may not creatively contribute to the present invention as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present invention.

Claims

1. Women's shoes with cold-resistant sole, the 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 an inorganic filler, and the inorganic filler is one of calcium powder, silicon carbide micropowder and carbon black;

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

2. The shoe with cold-resistant sole according to claim 1, wherein the inorganic filler is silicon carbide micropowder.

3. The shoe with cold-resistant sole according to claim 2, wherein the silicon carbide micro powder has a particle size of 30-60nm continuous gradation.

4. The women's shoes with cold-resistant soles according to claim 1, characterized in that 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.

5. The shoe according to claim 4, wherein the polyvinyl chloride has an average degree of polymerization of 1700-1900.

6. A method of preparing a women's shoe with cold-resistant sole according to any one of claims 1-5, characterized in that it comprises the following steps: