CN113243608A

CN113243608A - Waterproof shoe and processing technology thereof

Info

Publication number: CN113243608A
Application number: CN202110561181.5A
Authority: CN
Inventors: 张娇洁; 辛青红; 周环浩
Original assignee: Zhejiang Lichao Children's Products Co ltd
Current assignee: Zhejiang Lichao Children's Products Co ltd
Priority date: 2021-05-22
Filing date: 2021-05-22
Publication date: 2021-08-13
Anticipated expiration: 2041-05-22
Also published as: CN113243608B

Abstract

The application relates to the field of shoes, and particularly discloses a waterproof shoe and a processing technology thereof. The waterproof shoes include sole and vamp, and vamp surface covering has the waterproof layer, and the waterproof layer includes following raw materials: an ABS resin; polyethylene glycol succinate emulsions; lime; a film-forming aid; defoaming agents; leveling agent; the processing technology comprises the following steps: s1, preparing a waterproof layer; and S2, processing the shoes. The utility model provides a waterproof shoes adopts ABS resin, polyethylene glycol succinate emulsion and lime, ABS resin has better waterproof nature, polyethylene glycol succinate emulsion has good adhesion, the waterproof performance that enables the waterproof layer that makes after both mix is better, add the lime and mix the back, lime absorbs water and takes place the slaking, and then the bonding forms compact network structure, can make the inner structure of waterproof layer inseparabler, the infiltration of moisture to the waterproof layer has been inhibited, thereby the waterproof performance of shoes has further been improved.

Description

Waterproof shoe and processing technology thereof

Technical Field

The application relates to the field of shoes, in particular to waterproof shoes and a processing technology thereof.

Background

A shoe is an article of daily use that is worn on a foot to facilitate walking, and generally includes a sole and an upper. When walking outside in rainy days, the shoes are easily wetted by the falling rainwater and the rainwater splashed during walking, the wearing comfort of the shoes is reduced, bacteria are easily bred when the shoes are wet, the beriberi generated on feet of a human body is caused, the health of the human body is influenced, and the improvement is needed.

Disclosure of Invention

In order to improve the problem that the waterproofness of the shoes is poor, the application provides a waterproof shoe and a processing technology thereof.

In a first aspect, the present application provides a waterproof shoe, which adopts the following technical scheme:

the waterproof shoe comprises a sole and a vamp, wherein a waterproof layer covers the surface of the vamp, and the waterproof layer comprises the following raw materials in parts by weight:

40-60 parts of ABS resin;

20-30 parts of polyethylene glycol succinate emulsion;

5-10 parts of lime;

0.2-0.4 part of film-forming additive;

0.2-0.4 part of defoaming agent;

0.1-0.2 parts of flatting agent.

By adopting the technical scheme, the ABS resin has better waterproofness, the polyethylene glycol succinate emulsion has good adhesion, and the prepared waterproof coating can have good waterproofness and good adhesion after being mixed with the ABS resin, so that the firmness degree of the waterproof layer on the vamp is improved, and the waterproofness of the waterproof layer is indirectly improved.

After the mixture of the polyethylene glycol succinate emulsion and the ABS resin is mixed with lime, the lime absorbs the water of the polyethylene glycol succinate emulsion in the mixture to be cured, the polyethylene glycol succinate emulsion loses water to form an elastic film layer with adhesive property, the elastic film layer is distributed in the waterproof coating in a staggered way, and interpenetrates with the product after lime slaking, so that the elastic film layer with adhesive property is filled in the gap of the product after lime slaking, the product after lime slaking is filled in the elastic film layer, then the mixture is bonded to form a compact reticular structure, when the subsequent waterproof coating is coated on the surface of the vamp and is solidified and dehydrated, the molecules of the product after lime slaking are close to each other due to dehydration, and then make the inner structure of the waterproof layer after solidifying inseparabler, restrained the infiltration of moisture to the waterproof layer to the waterproof performance of waterproof layer has further been improved.

The film forming additive is added to improve the film forming performance of the waterproof coating, and is favorable for curing the waterproof coating on the surface of the vamp to form a film so as to form a waterproof layer.

The defoaming agent is added, so that the formation of foam in the preparation process of the waterproof coating can be reduced, the influence of foam generation to cracking on the internal network structure of the waterproof coating is further reduced, and the generation of internal gaps of the waterproof coating is reduced, so that the permeation of water is reduced, and the waterproof performance of the prepared waterproof layer is indirectly improved.

The addition of the leveling agent is favorable for forming a flat, smooth and uniform waterproof layer, so that the friction coefficient of the surface of the waterproof layer is reduced, the wear resistance of the waterproof layer is improved, and the waterproof layer is more durable.

The waterproof performance of the shoe covering the waterproof layer is better through the comprehensive action of the ABS resin, the polyethylene glycol succinate emulsion, the lime, the film forming additive, the defoaming agent and the flatting agent.

Preferably, the raw materials also comprise 4 to 6 parts of hydroxyl silicone oil and 0.1 to 0.2 part of zirconia according to parts by weight.

By adopting the technical scheme, the molecules of the polyethylene glycol succinate emulsion contain active carboxyl, and the carboxyl and the hydroxyl silicone oil are esterified under the catalytic action of zirconium oxide, so that the carboxyl is sealed, the hydrophobicity of the prepared waterproof coating is improved, and the hydroxyl silicone oil has better hydrophobicity and lubricity, when water drops on the waterproof layer, the water drops along the surface of the waterproof layer, the retention time of the water on the waterproof layer is reduced, the permeation of the water is further reduced, the waterproof performance of the waterproof layer is further improved, and the waterproof performance of the shoe prepared by adopting the waterproof layer is better.

Preferably, the raw materials also comprise 8-10 parts of glass fiber in parts by weight.

Through adopting above-mentioned technical scheme, glass fiber is the filament column structure, intertwine and cross distribution are inside waterproof coating after the mixing, and then form long and continuous, inseparable and crisscross space, and glass fiber has good waterproof nature, when water infiltration waterproof layer, the infiltration route of waterproof layer has been prolonged, be favorable to moisture to be consumed at the in-process of infiltration waterproof layer, and the diffusion of moisture has been suppressed, thereby the condition of moisture contact and soaking the vamp has been reduced, be favorable to promoting the waterproof performance of waterproof layer, make the waterproof performance of the shoes that make better.

Preferably, the raw material also comprises 2-5 parts of nano titanium dioxide by weight.

By adopting the technical scheme, the nano titanium dioxide has larger specific surface area, better mechanical strength and chemical stability, the glass fiber is reinforced after being compounded with the glass fiber, the brittleness of the compound glass fiber is reduced, the condition that the glass fiber is fractured in the preparation process of the waterproof coating is further reduced, and a long and continuous gap is formed in the waterproof layer, so that the waterproof property of the waterproof layer is indirectly improved, the waterproof performance of the prepared shoe is further improved, the nano titanium dioxide has good light stability and strong ultraviolet shielding effect, and after being compounded with the glass fiber and uniformly mixed in the waterproof coating, the influence of ultraviolet rays on the waterproof layer can be reduced, the aging of the waterproof layer is delayed, and the waterproof layer is more durable.

Preferably, the coalescing agent is a dodecanol ester.

By adopting the technical scheme, the lowest film forming temperature of the waterproof coating can be reduced by adding the dodecyl alcohol ester, the waterproof coating is favorably condensed into a film, the dodecyl alcohol ester and the polyethylene glycol succinate emulsion are good in compatibility, demulsification is not easy to cause, the film forming effect of the waterproof coating is favorably improved, and the waterproofness of the waterproof layer is indirectly improved.

Preferably, the preparation method of the polyethylene glycol succinate emulsion comprises the following steps based on 100 parts by weight of the polyethylene glycol succinate emulsion: adding 15-20 parts of polyethylene glycol succinate into 80-90 parts of water while stirring, heating to 80-90 ℃, cooling to 40-50 ℃ after the polyethylene glycol succinate is completely dissolved, adding 6-8 parts of emulsifier, stirring for reaction for 25-30min, and cooling to room temperature to obtain the polyethylene glycol succinate emulsion.

In a second aspect, the application provides a processing technology of waterproof shoes, which adopts the following technical scheme:

a processing technology of waterproof shoes comprises the following steps:

s1, preparing a waterproof layer: heating to 100-120 ℃, uniformly stirring and mixing the ABS resin, the polyethylene glycol succinate emulsion, the film forming aid, the defoaming agent and the flatting agent, adding lime, uniformly stirring and mixing, cooling to room temperature to prepare a waterproof coating, coating the waterproof coating on the surface of the cut vamp, drying at 40-50 ℃, and curing the waterproof coating on the surface of the vamp to form a waterproof layer to prepare a finished vamp;

s2, processing shoes; and adhering the finished vamp on the sole, pressing for 4-6s, and drying to obtain the finished shoe.

By adopting the technical scheme, the lime and other raw materials are separately mixed, so that the influence of slaked lime on the dispersibility of the other raw materials in the waterproof coating is reduced, and the uniform waterproof coating is favorably obtained.

Preferably, in the step S1, 2 to 5 parts of nano titanium dioxide are added into 100 parts of 110 parts of water for ultrasonic dispersion to prepare nano titanium dioxide dispersion liquid;

ball-milling 8-10 parts of glass fiber and 4-8 parts of ethanol at the rotating speed of 300-350r/min for 24h, adding 4-8 parts of ethanol every 2h to enable the glass fiber to be viscous all the time, then drying at 80-90 ℃ for 12h, sieving by using a 80-mesh screen to obtain glass fiber fine powder, then adding 10-15 parts of water, stirring for 8-10min to obtain glass fiber suspension, then dropwise adding nano titanium dioxide dispersion while stirring, continuously stirring for 20-30min to obtain glass fiber mixed solution, then adding 0.5-0.8 part of sodium carboxymethylcellulose, stirring uniformly, then magnetically stirring at 80-90 ℃ until the water is completely evaporated, drying at 80-90 ℃, then melting and drawing at 1300-1400 ℃, and cooling at room temperature to obtain the composite glass fiber;

stirring 8-10 parts of polyethylene glycol succinate emulsion, 4-6 parts of hydroxyl silicone oil and 0.1-0.2 part of zirconium oxide at the temperature of 120-140 ℃ for reaction for 1.5-2h, and cooling to room temperature to obtain a mixture A;

heating to 100-120 ℃, taking the rest polyethylene glycol succinate emulsion, the mixture A, the composite glass fiber, 40-60 parts of ABS resin, 0.2-0.4 part of film-forming assistant, 0.2-0.4 part of defoaming agent and 0.1-0.2 part of flatting agent, stirring and mixing uniformly, then adding 5-10 parts of lime, stirring and mixing uniformly, cooling to room temperature to prepare a waterproof coating, coating the waterproof coating on the surface of the cut vamp, and drying at 40-50 ℃ to prepare the finished vamp covered with the waterproof layer.

By adopting the technical scheme, the reaction of the polyethylene glycol succinate emulsion and the hydroxyl silicone oil and the preparation of the composite glass fiber are separately carried out with the mixing of other raw materials, so that the influence of other components on the reaction of the polyethylene glycol succinate emulsion and the hydroxyl silicone oil and the influence on the preparation of the composite glass fiber are reduced, and the esterification product of the polyethylene glycol succinate emulsion and the hydroxyl silicone oil and the composite glass fiber are favorably obtained.

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

1. because this application adopts ABS resin, polyethylene glycol succinate emulsion and lime, ABS resin has better waterproof nature, polyethylene glycol succinate emulsion has good adhesion, the waterproof performance that can make the waterproof layer that makes after the two mix is better, add the lime and mix the back, the moisture in the polyethylene glycol succinate emulsion of lime absorption takes place the curing, and then the bonding forms compact network structure, can make the inner structure of the waterproof layer after the solidification inseparabler, the infiltration of moisture to the waterproof layer has been inhibited, thereby the waterproof performance of waterproof layer has further been improved, make the waterproof performance of the shoes that cover above-mentioned waterproof layer better.

2. Preferably adopt hydroxyl silicone oil and zirconia in this application, the polyethylene glycol succinate emulsion molecule takes place to esterify with hydroxyl silicone oil under zirconia's catalytic action to seal the carboxyl, improved the hydrophobicity of the waterproof coating who makes, and hydroxyl silicone oil has better hydrophobicity and lubricity, has reduced the infiltration of moisture to the waterproof layer, has further improved the waterproof performance of waterproof layer, makes the waterproof nature of the shoes that adopt above-mentioned waterproof layer to make better.

3. According to the method, lime and other raw materials are mixed separately, so that the influence of slaked lime on the dispersibility of the other raw materials in the waterproof coating is reduced, and the uniform waterproof coating is favorably obtained.

Detailed Description

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

ABS resin is purchased from Shanghai plastic Limited and has the brand name of PA-757; polyethylene glycol succinate is purchased from Beijing Heng Mitsui chemical Co., Ltd; the emulsifier is purchased from Shanghai Beike chemical Co., Ltd, and has the model of CO-436; the lime is purchased from a practical factory of the Changxing Qing calcium industry, the product number is 2210, and the packaging specification is 200 meshes; the defoaming agent is purchased from Guangdong New Material Co., Ltd, the type of which is DE-0570; the leveling agent is purchased from Foshan City minister trade Co., Ltd, and has the model of mlb-148; hydroxyl silicone oil is purchased from a source manufacturer of textile materials in south of the Yangtze river, and has the model of JF-M30-203; the glass fiber is purchased from Xinshengjia composite material Co., Ltd, Dongguan city, the product number is XSJ-31, and the specification is 6 mm; the nano titanium dioxide is purchased from Nanjing Baoke new material Co., Ltd, the product number is PTA, and the particle size is 20 nm; sodium carboxymethylcellulose was purchased from Henan Yingxue Biotech, Inc. under the product number 0685; the phenolic resin was purchased from Jiamai plastics Co., Ltd, Dongguan, and was model number 54325435.

The raw materials used in the following embodiments may be those conventionally commercially available unless otherwise specified.

Preparation example of polyethylene glycol succinate emulsion

Preparation example 1

Preparation of polyethylene glycol succinate emulsion: adding 15 parts of polyethylene glycol succinate into 85 parts of water while stirring, heating to 85 ℃, cooling to 50 ℃ after the polyethylene glycol succinate is completely dissolved, adding 6 parts of emulsifier, stirring for reacting for 30min, and cooling to room temperature to obtain 100 parts by weight of polyethylene glycol succinate emulsion.

Examples

Example 1

The application discloses waterproof shoes, waterproof shoes include sole and vamp, and vamp surface covering has the waterproof layer, and the waterproof layer includes following raw materials: ABS resin, poly (ethylene glycol succinate) emulsion, lime, a film forming aid, a defoaming agent and a flatting agent, wherein the poly (ethylene glycol succinate) emulsion is prepared by preparation example 1, the film forming aid is propylene glycol ethyl ether, and the content of each component is shown in the following table 1-1.

The processing technology of the waterproof shoe comprises the following steps:

s1, preparing a waterproof layer: heating to 100 ℃, uniformly stirring and mixing the ABS resin, the polyethylene glycol succinate emulsion, the film forming aid, the defoaming agent and the flatting agent, adding lime, uniformly stirring and mixing, cooling to room temperature to prepare a waterproof coating, coating the waterproof coating on the surface of the cut vamp, drying at 40 ℃, and curing the waterproof coating on the surface of the vamp to form a waterproof layer to prepare a finished vamp;

s2, processing shoes; and adhering the finished vamp on the sole, pressing for 4s, and drying to obtain the finished shoe.

Example 2

The processing technology of the waterproof shoe comprises the following steps:

s1, preparing a waterproof layer: heating to 120 ℃, uniformly stirring and mixing the ABS resin, the polyethylene glycol succinate emulsion, the film forming aid, the defoaming agent and the flatting agent, adding lime, uniformly stirring and mixing, cooling to room temperature to prepare a waterproof coating, coating the waterproof coating on the surface of the cut vamp, drying at 50 ℃, and curing the waterproof coating on the surface of the vamp to form a waterproof layer to prepare a finished vamp;

s2, processing shoes; and adhering the finished vamp on the sole, pressing for 6s, and drying to obtain the finished shoe.

Example 3

The processing technology of the waterproof shoe comprises the following steps:

s1, preparing a waterproof layer: heating to 110 ℃, uniformly stirring and mixing the ABS resin, the polyethylene glycol succinate emulsion, the film forming aid, the defoaming agent and the flatting agent, adding lime, uniformly stirring and mixing, cooling to room temperature to prepare a waterproof coating, coating the waterproof coating on the surface of the cut vamp, drying at 45 ℃, and curing the waterproof coating on the surface of the vamp to form a waterproof layer to prepare a finished vamp;

s2, processing shoes; and adhering the finished vamp on the sole, pressing for 5s, and drying to obtain the finished shoe.

Example 4

The difference from example 1 is that hydroxy silicone oil and zirconia were added to the raw materials of the waterproof layer, and the contents of the respective components are shown in the following table 1-1.

S1, preparing a waterproof layer: stirring 8 parts of polyethylene glycol succinate emulsion and hydroxyl silicone oil at 120 ℃ for reaction for 2 hours, and cooling to room temperature to obtain a mixture A;

heating to 100 ℃, taking the rest polyethylene glycol succinate emulsion, the mixture A, ABS resin, the film forming aid, the defoaming agent and the flatting agent, stirring and mixing uniformly, adding lime, stirring and mixing uniformly, cooling to room temperature to prepare the waterproof coating, coating the waterproof coating on the surface of the cut vamp, and drying at 40 ℃ to prepare the finished vamp covered with the waterproof layer.

Example 5

The difference from the example 1 is that the glass fiber is added into the raw material of the waterproof layer, and the content of each component is shown in the following table 1-1.

S1, preparing a waterproof layer: heating to 100 ℃, uniformly stirring and mixing the ABS resin, the polyethylene glycol succinate emulsion, the glass fiber, the film forming auxiliary agent, the defoaming agent and the flatting agent, adding lime, uniformly stirring and mixing, cooling to room temperature to prepare a waterproof coating, coating the waterproof coating on the surface of the cut vamp, drying at 40 ℃, and curing the waterproof coating on the surface of the vamp to form a waterproof layer to prepare a finished vamp;

example 6

The difference from the example 5 is that the nano titanium dioxide is added into the raw material of the waterproof layer, and the content of each component is shown in the following table 1-1.

S1, preparing a waterproof layer: adding 100 parts of water into nano titanium dioxide, and performing ultrasonic dispersion to prepare nano titanium dioxide dispersion liquid;

ball-milling glass fiber and 4 parts of ethanol at the rotating speed of 300r/min for 24h, adding 4 parts of ethanol every 2h to enable the glass fiber to be viscous all the time, then drying at 80 ℃ for 12h, sieving by using a 80-mesh screen to obtain glass fiber fine powder, adding 10 parts of water, stirring for 8min to obtain glass fiber suspension, then dropwise adding nano titanium dioxide dispersion while stirring, continuing stirring for 20min to obtain glass fiber mixed solution, adding 0.5 part of sodium carboxymethylcellulose, stirring uniformly, then magnetically stirring at 80 ℃ until the water is completely evaporated, drying at 80 ℃, then melting and drawing at 1300 ℃, and cooling at room temperature to obtain composite glass fiber;

heating to 100 ℃, taking the polyethylene glycol succinate emulsion, the composite glass fiber, the ABS resin, the film forming additive, the defoaming agent and the flatting agent, stirring and mixing uniformly, then adding lime, stirring and mixing uniformly, cooling to room temperature to prepare the waterproof coating, coating the waterproof coating on the surface of the cut vamp, and drying at 40 ℃ to prepare the finished vamp covered with the waterproof layer.

Example 7

The application discloses waterproof shoes, waterproof shoes include sole and vamp, and vamp surface covering has the waterproof layer, and the waterproof layer includes following raw materials: the ABS resin, the polyethylene glycol succinate emulsion, lime, a film forming aid, a defoaming agent, a leveling agent, hydroxyl silicone oil, zirconium oxide, glass fiber and nano titanium dioxide, wherein the polyethylene glycol succinate emulsion is prepared by the preparation example 1, the film forming aid is dodecyl alcohol ester, and the content of each component is shown in the following table 1-1.

The processing technology of the waterproof shoe comprises the following steps:

stirring 8 parts of polyethylene glycol succinate emulsion, hydroxyl silicone oil and zirconium oxide at 120 ℃ for reacting for 2 hours, and cooling to room temperature to obtain a mixture A;

heating to 100 ℃, taking the rest polyethylene glycol succinate emulsion, the mixture A, the composite glass fiber, the ABS resin, the film forming aid, the defoaming agent and the flatting agent, stirring and mixing uniformly, adding lime, stirring and mixing uniformly, cooling to room temperature to prepare a waterproof coating, coating the waterproof coating on the surface of the cut vamp, and drying at 40 ℃ to prepare a finished vamp covered with a waterproof layer;

Example 8

The processing technology of the waterproof shoe comprises the following steps:

s1, preparing a waterproof layer: adding 110 parts of water into nano titanium dioxide, and performing ultrasonic dispersion to prepare nano titanium dioxide dispersion liquid;

ball-milling glass fiber and 8 parts of ethanol at the rotating speed of 350r/min for 24h, adding 4-8 parts of ethanol every 2h to enable the glass fiber to be viscous all the time, then drying at 90 ℃ for 12h, sieving by using a 80-mesh screen to obtain glass fiber fine powder, adding 15 parts of water, stirring for 10min to obtain glass fiber suspension, then dropwise adding nano titanium dioxide dispersion while stirring, continuing stirring for 30min to obtain glass fiber mixed solution, adding 0.8 part of sodium carboxymethylcellulose, stirring uniformly, then magnetically stirring at 90 ℃ until the water is completely evaporated, drying at 90 ℃, then melting and drawing at 1400 ℃, and cooling at room temperature to obtain composite glass fiber;

stirring 10 parts of polyethylene glycol succinate emulsion, hydroxyl silicone oil and zirconium oxide at 140 ℃ for reaction for 1.5h, and cooling to room temperature to obtain a mixture A;

heating to 120 ℃, taking the rest polyethylene glycol succinate emulsion, the mixture A, the composite glass fiber, the ABS resin, the film forming aid, the defoaming agent and the flatting agent, stirring and mixing uniformly, adding lime, stirring and mixing uniformly, cooling to room temperature to prepare a waterproof coating, coating the waterproof coating on the surface of the cut vamp, and drying at 50 ℃ to prepare a finished vamp covered with a waterproof layer;

Example 9

The processing technology of the waterproof shoe comprises the following steps:

s1, preparing a waterproof layer: adding 105 parts of water into nano titanium dioxide, and performing ultrasonic dispersion to prepare nano titanium dioxide dispersion liquid;

ball-milling glass fiber and 6 parts of ethanol at the rotating speed of 325r/min for 24h, adding 6 parts of ethanol every 2h to enable the glass fiber to be viscous all the time, then drying at 85 ℃ for 12h, sieving by using a 80-mesh screen to obtain glass fiber fine powder, adding 13 parts of water, stirring for 9min to obtain glass fiber suspension, then dropwise adding nano titanium dioxide dispersion while stirring, continuing stirring for 25min to obtain glass fiber mixed solution, adding 0.6 part of sodium carboxymethylcellulose, stirring uniformly, then magnetically stirring at 85 ℃ until the water is completely evaporated, drying at 85 ℃, then melting and drawing at 1350 ℃, and cooling at room temperature to obtain composite glass fiber;

stirring 9 parts of polyethylene glycol succinate emulsion, hydroxyl silicone oil and zirconium oxide at 130 ℃ for reaction for 1.5h, and cooling to room temperature to obtain a mixture A;

heating to 110 ℃, taking the rest polyethylene glycol succinate emulsion, the mixture A, the composite glass fiber, the ABS resin, the film forming aid, the defoaming agent and the flatting agent, stirring and mixing uniformly, adding lime, stirring and mixing uniformly, cooling to room temperature to prepare a waterproof coating, coating the waterproof coating on the surface of the cut vamp, and drying at 45 ℃ to prepare a finished vamp covered with a waterproof layer;

Example 10

The difference from example 4 is that the hydroxy silicone oil is replaced by methyl silicone oil, and the contents of the components are shown in the following tables 1-2.

Example 11

The difference from example 5 is that the glass fiber is replaced by talc, and the contents of the components are shown in tables 1 to 2 below.

Example 12

The difference from the embodiment 6 is that the nano titanium dioxide is replaced by the talcum powder, and the content of each component is shown in the following tables 1-2.

Example 13

The difference from example 1 is that the coalescing agent used was a dodecane alcohol ester, and the contents of the respective components are shown in tables 1 to 2 below.

Comparative example

Comparative example 1

The difference from example 1 is that the shoe upper, which is not coated with the waterproof coating of the present application, is used as a blank control.

Comparative example 2

The difference from example 1 is that the ABS resin is replaced with a phenolic resin, and the contents of the respective components are shown in the following tables 1-2.

Comparative example 3

The difference from example 1 is that polyethylene glycol succinate emulsion was replaced with polyethylene glycol, and the contents of each component are shown in tables 1 to 2 below.

Comparative example 4

The difference from example 1 is that the lime is replaced by talc, and the contents of the components are shown in tables 1 to 2 below.

Comparative example 5

The difference from example 3 is that the lime is replaced by talc, and the contents of the components are shown in tables 1-2 below.

TABLE 1-1 ingredient content Table

	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6	Example 7	Example 8	Example 9
										ABS resin/phenolic resin	40	60	50	40	40	40	40	60	50
Polyethylene glycol succinate emulsion/polyethylene glycol	20	30	25	20	20	20	20	30	25
										Lime/talcum powder	5	10	7	5	5	5	5	10	7
Film forming aid	0.2	0.4	0.3	0.2	0.2	0.2	0.2	0.4	0.3
										Defoaming agent	0.2	0.4	0.3	0.2	0.2	0.2	0.2	0.4	0.3
Leveling agent	0.1	0.2	0.2	0.1	0.1	0.1	0.1	0.2	0.2
										Hydroxy silicone oil/methyl silicone oil	/	/	/	4	/	/	4	6	5
Zirconium oxide	/	/	/	0.1	/	/	0.1	0.2	0.1
										Glass fiber/talcum powder	/	/	/	/	8	8	8	10	9
Nano titanium dioxide/talcum powder	/	/	/	/	/	2	2	5	4

TABLE 1-2 ingredient content table

	Example 10	Example 11	Example 12	Example 13	Comparative example 2	Comparative example3	Comparative example 4	Comparative example 5
									ABS resin/phenolic resin	40	40	40	40	40	40	40	40
Polyethylene glycol succinate emulsion/polyethylene glycol	20	20	20	20	20	20	20	20
									Lime/talcum powder	5	5	5	5	5	5	5	5
Film forming aid	0.2	0.2	0.2	0.2	0.2	0.2	0.2	0.2
									Defoaming agent	0.2	0.2	0.2	0.2	0.2	0.2	0.2	0.2
Leveling agent	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1
									Hydroxy silicone oil/methyl silicone oil	4	/	/	/	/	/	/	/
Zirconium oxide	0.1	/	/	/	/	/	/	/
									Glass fiber/talcum powder	/	8	8	/	/	/	/	/
Nano titanium dioxide/talcum powder	/	/	2	/	/	/	/	/

Performance test

The waterproof coatings prepared according to the methods of examples 1 to 13 and comparative examples 2 to 5 were respectively applied to the surfaces of the vamps of 10cm × 10cm, and dried at 45 ℃ to prepare vamp samples, and the vamps of comparative example 1 were cut into a size of 10cm × 10cm as vamp samples of comparative example 1.

(1) Water resistance test (Water absorption for Water resistance): placing the vamp sample in a container containing water, maintaining the water temperature at 20 + -5 deg.C and the water surface 5mm higher than the surface of the sample, soaking for 12 hr, taking out the vamp sample, wiping off the surface water of the vamp sample, and weighing (m)₁) Then the sample is placed in an oven at 105 +/-5 ℃ to be dried to constant weight, then taken out and placed in a container with a cover to be cooled for 1h, and weighed again (m₂) And calculating the water absorption according to the following formula:

water absorption (%) = [ (m)₁-m₂）/ m₂]×100%

The lower the water absorption, the better the water repellency, and the test results are shown in table 2 below.

(2) And (3) testing the adhesion: for the vamp samples prepared in the embodiment 1 and the comparative example 3, the adhesive fastness of the coating layer is tested by using a self-adhesive tape, and the sample is prepared by 5 minutes, preferably 5 minutes; the test results are shown in table 2 below.

(3) And (3) ultraviolet ray resistance test: the vamp samples prepared in the examples 1, 4 to 5 are irradiated at an irradiance of 0.73 mu W/cm²The test result is shown in the following table 2, and the phenomenon of the surface of the vamp sample is recorded after the vamp sample is irradiated for 300 hours under the ultraviolet light.

TABLE 2 test results of examples and comparative examples

	Water absorption/%)	Adhesion test structure	Ultraviolet-resistant test structure
				Example 1	22.8	5	A large number of cracks appear on the waterproof layer on the surface of the sample
Example 2	21.3	/	/
				Example 3	21.9	/	/
Example 4	20.5	/	A large number of cracks appear on the waterproof layer on the surface of the sample
				Example 5	19.9	/	A small amount of cracks appear on the waterproof layer on the surface of the sample
Example 6	18.2	/	/
				Example 7	17.0	/	/
Example 8	15.6	/	/
				Example 9	16.7	/	/
Example 10	21.7	/	/
				Example 11	22.4	/	/
Example 12	19.7	/	/
				Example 13	22.1	/	/
Comparative example 1	35.5	/	/
				Comparative example 2	28.3	/	/
Comparative example 3	25.9	3	/
				Comparative example 4	24.6	/	/
Comparative example 5	26.3	/	/

In summary, the following conclusions can be drawn:

1. combining example 1 and comparative examples 1-3 with table 2, it can be seen that the addition of ABS resin and polyethylene succinate emulsion can improve the waterproof performance of the shoe upper, probably because: the ABS resin has good waterproofness, the polyethylene glycol succinate emulsion has good adhesion, and after being mixed with the ABS resin, the prepared waterproof coating has good waterproofness and good adhesion, so that the firmness degree of the waterproof layer on the vamp is improved, and the waterproof performance of the vamp is indirectly improved.

2. Combining example 1 and comparative examples 3-5 with table 2, it can be seen that the co-addition of lime and polyethylene succinate latex improves the waterproof properties of the shoe upper, probably because: after the mixture of the polyethylene glycol succinate emulsion and the ABS resin is mixed with lime, the lime absorbs the water of the polyethylene glycol succinate emulsion in the mixture and slakes, the polyethylene glycol succinate emulsion loses water to form an elastic film layer with adhesiveness, the elastic film layer is distributed in the waterproof coating in a staggered manner and penetrates through the slaked product of the lime, and then the elastic film layer and the slaked product of the lime are bonded to form a compact net structure.

3. As can be seen by combining examples 1, 4 and 10 with table 2, the addition of the hydroxy silicone oil and the zirconium oxide is advantageous for improving the waterproof performance of the shoe upper, probably because: the molecules of the polyethylene glycol succinate emulsion contain active carboxyl, and the carboxyl is esterified with hydroxyl silicone oil under the catalytic action of zirconia, so that the carboxyl is sealed, the hydrophobicity of the prepared waterproof coating is improved, the hydroxyl silicone oil has better hydrophobicity and lubricity, the retention time of moisture on a waterproof layer is reduced, and the moisture permeation is further reduced, so that the waterproof performance of the waterproof layer is further improved, and the waterproof performance of a vamp prepared by the waterproof layer is better.

4. As can be seen from the combination of examples 1, 5 and 11 and table 2, the addition of the glass fibers can improve the waterproof performance of the shoe upper, which may be due to: glass fiber is fine thread column structure, intertwine and cross distribution are inside waterproof coating after the mixing, and then form long and continuous, inseparable and crisscross space, and glass fiber has good waterproof nature, when water infiltration waterproof layer, the infiltration route of waterproof layer has been prolonged, be favorable to moisture to be consumed at the in-process of infiltration waterproof layer, and the diffusion of moisture has been suppressed, thereby the condition of moisture contact and soaking the vamp has been reduced, be favorable to promoting the waterproof performance of waterproof layer, make the waterproof performance of the shoes that make better.

5. As can be seen from the combination of examples 1, 5-6, 11-12 and table 2, the co-addition of glass fibers and nano titanium dioxide can improve the waterproof and uv-resistant properties of the shoe upper, which may be due to: nanometer titanium dioxide has great specific surface area, better mechanical strength and chemical stability, strengthen glass fiber after compounding with glass fiber, the brittleness of compound glass fiber has been reduced, and then the condition that glass fiber breaks off in the water proof coating preparation process has been reduced, be favorable to forming long and continuous space in the waterproof layer, thereby indirectly improved the waterproof nature of waterproof layer, and then improved the waterproof performance of vamp, and nanometer titanium dioxide has good light stability, it is strong to shield ultraviolet effect, compound and mix in water proof coating after taking place with glass fiber, can reduce the influence of ultraviolet ray to the waterproof layer, thereby the ultraviolet resistance performance of vamp has been improved.

6. As can be seen by combining examples 1 and 13 with Table 2, the use of dodecanol ester as a film-forming aid is beneficial for improving the waterproof performance of the shoe upper, which may be due to the following reasons: the emulsion breaking agent has good compatibility with the polyethylene glycol succinate emulsion, is not easy to cause emulsion breaking, is beneficial to improving the film forming effect of the waterproof coating, and further indirectly improves the waterproofness of the waterproof layer.

The present embodiment is only for explaining the present application, and it is not limited to the present application, 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 application.

Claims

1. The utility model provides a waterproof shoes, includes sole and vamp, its characterized in that: the vamp surface is covered with a waterproof layer, and the waterproof layer comprises the following raw materials in parts by weight:

40-60 parts of ABS resin;

20-30 parts of polyethylene glycol succinate emulsion;

5-10 parts of lime;

0.2-0.4 part of film-forming additive;

0.2-0.4 part of defoaming agent;

0.1-0.2 parts of flatting agent.

2. The waterproof footwear of claim 1, wherein: the raw materials also comprise 4 to 6 parts of hydroxyl silicone oil and 0.1 to 0.2 part of zirconia according to parts by weight.

3. The waterproof footwear of claim 1, wherein: the raw materials also comprise 8-10 parts of glass fiber according to parts by weight.

4. The waterproof footwear of claim 3, wherein: the raw material also comprises 2-5 parts of nano titanium dioxide by weight.

5. The waterproof footwear of claim 1, wherein: the film-forming assistant is dodecyl alcohol ester.

6. The waterproof footwear of claim 1, wherein: the preparation method of the polyethylene glycol succinate emulsion comprises the following steps of (by weight) 100 parts of the polyethylene glycol succinate emulsion: adding 15-20 parts of polyethylene glycol succinate into 80-90 parts of water while stirring, heating to 80-90 ℃, cooling to 40-50 ℃ after the polyethylene glycol succinate is completely dissolved, adding 6-8 parts of emulsifier, stirring for reaction for 25-30min, and cooling to room temperature to obtain the polyethylene glycol succinate emulsion.

7. A manufacturing process for preparing the waterproof shoe of claim 1, comprising the steps of:

8. The waterproof shoe processing technology according to claim 7, characterized in that:

in the S1, 2-5 parts of nano titanium dioxide is added into 100-110 parts of water for ultrasonic dispersion to prepare nano titanium dioxide dispersion liquid;