阅读说明：本技术 一种环保硫化鞋革及其制备方法 (Environment-friendly vulcanized shoe leather and preparation method thereof ) 是由 周志军 姜慧 陈倩 陈永 杜超 严雪峰 徐一剡 于 2020-12-30 设计创作，主要内容包括：本发明公布了一种环保硫化鞋革,以高密度针织布作为底布层,所述底布层上依次设置有粘结层、中间层和表皮层；所述粘结层为以下重量份的原料制备的无溶剂发泡层：无溶剂树脂A料HX-5002A：100份、无溶剂树脂B料HX-5002B：40～120份、助剂JN3-030：0.1～1份、助剂JN3-031：0.1～1份；所述中间层包括以下重量份的原料：水性树脂HG3-106：100份、流平剂JN3-052：0.1～1份、消泡剂JN3-095：0.1～0.5份、架桥剂JN3-105：1～5份、色浆：3-30份；所述表皮层包括以下重量份的原料：水性树脂HG3-066：100份、流平剂JN3-052：0.1～1份、消泡剂JN3-095：0.1～0.5份、架桥剂JN3-108：1～5份、色浆：3-20份。本发明采用水性涂层设计和无溶剂粘结层树脂,不添加有害溶剂,环保,成品DMF残留测试≤50ppm,且制得的鞋革手感饱满,高剥离、耐曲折性能优异。(The invention discloses environment-friendly vulcanized shoe leather, which takes high-density knitted fabric as a bottom fabric layer, wherein an adhesive layer, an intermediate layer and a surface layer are sequentially arranged on the bottom fabric layer; the bonding layer is a solvent-free foaming layer prepared from the following raw materials in parts by weight: solvent-free resin A material HX-5002A: 100 parts of solvent-free resin B material HX-5002B: 40-120 parts of an auxiliary agent JN 3-030: 0.1-1 part of assistant JN 3-031: 0.1-1 part; the middle layer comprises the following raw materials in parts by weight: waterborne resin HG 3-106: 100 parts of leveling agent JN 3-052: 0.1-1 part of defoaming agent JN 3-095: 0.1-0.5 parts of bridging agent JN 3-105: 1-5 parts of color paste: 3-30 parts; the skin layer comprises the following raw materials in parts by weight: waterborne resin HG 3-066: 100 parts of leveling agent JN 3-052: 0.1-1 part of defoaming agent JN 3-095: 0.1-0.5 parts of bridging agent JN 3-108: 1-5 parts of color paste: 3-20 parts. The invention adopts the water-based coating design and the solvent-free bonding layer resin, no harmful solvent is added, the environment is protected, the DMF residue test of the finished product is less than or equal to 50ppm, and the prepared shoe leather has full hand feeling, high peeling and excellent flexing resistance.)

1. The environment-friendly vulcanized shoe leather is characterized in that high-density knitted fabric is used as a base fabric layer, and an adhesive layer, an intermediate layer and a surface layer are sequentially arranged on the base fabric layer;

the bonding layer is a solvent-free foaming layer prepared from the following raw materials in parts by weight: solvent-free resin A material HX-5002A: 100 parts of solvent-free resin B material HX-5002B: 40-120 parts of an auxiliary agent JN 3-030: 0.1-1 part of assistant JN 3-031: 0.1-1 part;

the middle layer comprises the following raw materials in parts by weight: waterborne resin HG 3-106: 100 parts of leveling agent JN 3-052: 0.1-1 part of defoaming agent JN 3-095: 0.1-0.5 parts of bridging agent JN 3-105: 1-5 parts of color paste: 3-30 parts;

the skin layer comprises the following raw materials in parts by weight: waterborne resin HG 3-066: 100 parts of leveling agent JN 3-052: 0.1-1 part of defoaming agent JN 3-095: 0.1-0.5 parts of bridging agent JN 3-108: 1-5 parts of color paste: 3-20 parts of a solvent;

the water-based resin HG3-066 is aliphatic polyether water-based resin, the water-based resin HG3-106 is high-solid-content aliphatic polyether water-based resin, the solvent-free resin A material HX-5002A is polyether polyol mixture, and the solvent-free resin B material HX-5002B is polyether isocyanate prepolymer.

2. The environmentally friendly vulcanized shoe leather of claim 1, wherein the base fabric layer is 0.5-1.2mm in thicknessHigh-density knitted fabric with the gram weight of 150-²。

3. The preparation method of the environment-friendly vulcanized shoe leather is characterized by comprising the following steps:

s1: preparing bonding layer slurry, preparing middle layer slurry, preparing epidermal layer slurry, and selecting base fabric and release paper;

s2: coating the prepared epidermal layer slurry on release paper, wherein the coating thickness is 0.03-0.15mm, drying at the temperature of 60-150 ℃ by controlling an oven, and cooling to form an epidermal layer;

s3: coating the prepared intermediate layer slurry on a dried surface layer, wherein the coating thickness is 0.05-0.2mm, controlling the temperature of an oven to be 60-150 ℃, drying, and cooling to form an intermediate layer;

s4: coating the prepared bonding layer slurry on the dried intermediate layer, wherein the coating thickness is 0.1-0.5mm, and controlling the temperature of the oven to be 60-130 ℃ for pre-drying to be semi-dry, namely, the retention time in the oven is 50-120 s;

s5: then adhering the leather to the front surface of the base fabric, drying, controlling the temperature of an oven to be 60-150 ℃, and finally stripping the release paper to obtain the environment-friendly vulcanized shoe leather.

4. The method for preparing environment-friendly vulcanized shoe leather as claimed in claim 3, wherein the skin layer slurry has a viscosity of 3000-10000cps/25 ℃ and a coating amount of 60-250 g/m.

5. The method for preparing environment-friendly vulcanized shoe leather as claimed in claim 3, wherein the viscosity of the middle layer slurry is 3000-10000cps/25 ℃, and the coating weight is 100-250 g/m.

6. The method for preparing environment-friendly vulcanized shoe leather as claimed in claim 3, wherein the coating amount of the bonding layer slurry is 100-500 g/m.

7. The method for preparing environment-friendly vulcanized shoe leather according to claim 3, wherein in step S2, the dried skin layer has a film thickness of 0.01-0.1 mm.

8. The method for preparing environment-friendly vulcanized shoe leather according to claim 3, wherein in the step S3, the dried middle layer has a film thickness of 0.03-0.1 mm.

9. The method for preparing environment-friendly vulcanized shoe leather according to claim 3, wherein in the step S5, the thickness of the bonding layer after bonding and drying is 0.08-0.5 mm.

Technical Field

The invention relates to the technical field of vulcanized shoe leather, in particular to environment-friendly vulcanized shoe leather and a preparation method thereof.

Background

Shoe upper leather is a raw material for manufacturing shoes, and on the surface of the shoes, the shoe upper leather is made of a plurality of raw materials, including genuine leather shoe upper leather, PU shoe upper leather, PVC shoe upper leather and the like; however, Dimethylformamide (DMF) solvent is usually added in the production process of shoe upper leather for preparing vulcanized shoes, so that the final product contains DMF solvent residue with high concentration or even exceeding the standard. Dimethylformamide (DMF), although an excellent organic solvent, is itself toxic and can be absorbed through the respiratory tract, skin and digestive tract, with irritation to the eyes, skin and respiratory tract. In 2017, 10, 27, a carcinogen list published by international cancer research institution of world health organization is preliminarily prepared for reference, and dimethylformamide is listed in a 2A class carcinogen list, so that if people often wear shoes containing high-concentration carcinogens, the shoe is extremely harmful to human health.

Based on the situation, the invention provides the environment-friendly vulcanized shoe leather and the preparation method thereof, and the existing problems can be effectively solved.

Disclosure of Invention

The invention aims to provide the environment-friendly vulcanized shoe leather and the preparation method thereof aiming at the defects in the prior art, the environment-friendly vulcanized shoe leather prepared by the invention is simple in preparation process and beneficial to human health, DMF residue detection is less than or equal to 50ppm, the safety standard is met, and the prepared shoe leather is full in hand feeling, high in stripping and excellent in flexing resistance and can adapt to a vulcanized shoe production process.

In order to achieve the purpose, the invention adopts the following technical scheme:

an environment-friendly vulcanized shoe leather takes high-density knitted fabric as a base fabric layer, and an adhesive layer, an intermediate layer and a surface layer are sequentially arranged on the base fabric layer;

the bonding layer is a solvent-free foaming layer prepared from the following raw materials in parts by weight: solvent-free resin A material HX-5002A: 100 parts of solvent-free resin B material HX-5002B: 40-120 parts of an auxiliary agent JN 3-030: 0.1-1 part of assistant JN 3-031: 0.1-1 part;

the middle layer comprises the following raw materials in parts by weight: waterborne resin HG 3-106: 100 parts of leveling agent JN 3-052: 0.1-1 part of defoaming agent JN 3-095: 0.1-0.5 parts of bridging agent JN 3-105: 1-5 parts of color paste: 3-30 parts;

the skin layer comprises the following raw materials in parts by weight: waterborne resin HG 3-066: 100 parts of leveling agent JN 3-052: 0.1-1 part of defoaming agent JN 3-095: 0.1-0.5 parts of bridging agent JN 3-108: 1-5 parts of color paste: 3-20 parts of a solvent;

the water-based resin HG3-066 is aliphatic polyether water-based resin, the water-based resin HG3-106 is high solid content (30% -60%) aliphatic polyether water-based resin, the solvent-free resin A material HX-5002A is polyether polyol mixture, and the solvent-free resin B material HX-5002B is polyether isocyanate prepolymer.

In the invention, the waterborne resin HG3-066 is used as the main raw material of the skin layer, so that the coating has excellent bending resistance; the aqueous resin HG3-106 is used as the main raw material of the intermediate layer slurry, so that the intermediate layer, the skin layer and the bonding layer can be excellently combined together;

in the invention, the solvent-free resin A material HX-5002A and the solvent-free resin B material HX-5002B are used as main raw materials of the bonding layer, so that the coating can be uniformly foamed and has excellent bonding property, and can be bonded with the base fabric;

in the invention, the adopted leveling agent JN3-052 is a high-solid surface tension adjusting aid, and can improve the leveling property of the surface of the water-based slurry in the coating process; if the addition amount of the leveling agent is small, the wetting and leveling effects cannot be achieved, and if the addition amount is large, the leveling agent can migrate to the surface of a coating layer to cause other series of problems, so that the inventor finds through a large number of experiments that the addition amount of the leveling agent is controlled to be 0.1-1 part, and the wetting and leveling effects are excellent;

in the invention, the adopted defoamer JN3-095 is an organic silicon assistant, so that surface bubbles of the aqueous slurry in the coating process can be reduced;

in the invention, the adopted bridging agent JN3-108 is a carbodiimide aqueous bridging agent, and can improve the binding force between aqueous slurry coatings;

in the invention, the adopted bridging agent JN3-105 is an isocyanate aqueous bridging agent, and can improve the binding force between a solvent-free foaming layer (bonding layer) and an aqueous coating;

in the invention, the adopted auxiliary JN3-030 is an organic silicon surfactant and is used for improving the opening property of the solvent-free foaming layer (bonding layer), controlling the uniformity of cells and ensuring the stability of the cells of the solvent-free foaming layer (bonding layer) in the vulcanization process;

in the invention, the adopted auxiliary JN3-031 is a heat-resistant auxiliary, which can improve the heat resistance of the bonding layer;

the color paste is used for adjusting color, and the using amount can be adjusted according to the color effect.

Preferably, the base fabric layer is a high-density knitted fabric with the weight of 0.5-1.2mm and the gram weight is 150-450g/m²。

The invention selects the high-density knitted fabric as the base fabric, is soft and elastic, and has comfortable foot feel.

The invention also provides a preparation method of the environment-friendly vulcanized shoe leather, which comprises the following steps:

s1: preparing bonding layer slurry, preparing middle layer slurry, preparing epidermal layer slurry, and selecting base fabric and release paper;

s2: coating the prepared epidermal layer slurry on release paper, wherein the coating thickness is 0.03-0.15mm, drying at the temperature of 60-150 ℃ by controlling an oven, and cooling to form an epidermal layer;

s3: coating the prepared intermediate layer slurry on a dried surface layer, wherein the coating thickness is 0.05-0.2mm, controlling the temperature of an oven to be 60-150 ℃, drying, and cooling to form an intermediate layer;

s4: coating the prepared bonding layer slurry on the dried intermediate layer, wherein the coating thickness is 0.1-0.5mm, and controlling the temperature of the oven to be 60-130 ℃ for pre-drying to be semi-dry, namely, the retention time in the oven is 50-120 s;

s5: then adhering the leather to the front surface of the base fabric, drying, controlling the temperature of an oven to be 60-150 ℃, and finally stripping the release paper to obtain the environment-friendly vulcanized shoe leather.

Preferably, the viscosity of the skin layer slurry is 3000-10000cps/25 ℃, and the coating weight is 60-250 g/m.

Preferably, the viscosity of the middle layer slurry is 3000-10000cps/25 ℃, and the coating weight is 100-250 g/m.

Preferably, the coating weight of the bonding layer slurry is 100-500 g/m.

Preferably, in step S2, the dried skin layer has a film thickness of 0.01 to 0.1 mm.

Preferably, in step S3, the dried intermediate layer has a film thickness of 0.03-0.1 mm.

Preferably, in step S5, the bonding layer after bonding and drying has a film thickness of 0.08-0.5 mm.

Compared with the prior art, the invention at least has the following beneficial effects:

1. according to the invention, the bridging agent is added into the water-based resin, so that the binding force between the water-based coatings in the vulcanization process can be improved, and the destructiveness of the vulcanization auxiliary agent on the water-based coatings can be prevented; the on-line reaction type material of the solvent-free resin A material and the solvent-free resin B material is used as the bonding layer, so that the coating has excellent temperature resistance and small physical property change under the condition of high vulcanization temperature; and the foam adjusting auxiliary agent is used in the bonding layer, so that the coating has uniform foam holes and certain openness, and the size of the foam holes can be kept unchanged under the conditions of high vulcanization temperature and high pressure.

2. In the production process, no harmful solvent is added, and the prepared shoe leather finished product has DMF residue of less than or equal to 50ppm, meets the safety standard and does not harm human health.

3. The use of the solvent-free bonding layer resin improves the binding force between the coating and the base fabric, so that the peeling and flexing resistance of the shoe leather material before and after vulcanization are not changed, and the prepared shoe leather finished product has full hand feeling and comfortable foot feeling.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The test methods or test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials, unless otherwise indicated, are conventionally obtained commercially or prepared by conventional methods.

Example 1

An environment-friendly vulcanized shoe leather takes high-density knitted fabric as a base fabric layer, and an adhesive layer, an intermediate layer and a surface layer are sequentially arranged on the base fabric layer;

the bonding layer is a solvent-free foaming layer prepared from the following raw materials in parts by weight: solvent-free resin A material HX-5002A: 100 parts of solvent-free resin B material HX-5002B: 40-120 parts of an auxiliary agent JN 3-030: 0.1-1 part of assistant JN 3-031: 0.1-1 part;

the middle layer comprises the following raw materials in parts by weight: waterborne resin HG 3-106: 100 parts of leveling agent JN 3-052: 0.1-1 part of defoaming agent JN 3-095: 0.1-0.5 parts of bridging agent JN 3-105: 1-5 parts of color paste: 3-30 parts;

the skin layer comprises the following raw materials in parts by weight: waterborne resin HG 3-066: 100 parts of leveling agent JN 3-052: 0.1-1 part of defoaming agent JN 3-095: 0.1-0.5 parts of bridging agent JN 3-108: 1-5 parts of color paste: 3-20 parts of a solvent;

the water-based resin HG3-066 is aliphatic polyether water-based resin, the water-based resin HG3-106 is high-solid-content aliphatic polyether water-based resin, the solvent-free resin A material HX-5002A is polyether polyol mixture, and the solvent-free resin B material HX-5002B is polyether isocyanate prepolymer.

In this embodiment, the bottom fabric layer is a high-density knitted fabric with a weight of 0.5-1.2mm and a gram weight of 150-²。

In this embodiment, the preparation method of the environment-friendly vulcanized shoe leather comprises the following steps:

s1: preparing bonding layer slurry, preparing middle layer slurry, preparing epidermal layer slurry, and selecting base fabric and release paper;

s2: coating the prepared epidermal layer slurry on release paper, wherein the coating thickness is 0.03-0.15mm, drying at the temperature of 60-150 ℃ by controlling an oven, and cooling to form an epidermal layer;

s3: coating the prepared intermediate layer slurry on a dried surface layer, wherein the coating thickness is 0.05-0.2mm, controlling the temperature of an oven to be 60-150 ℃, drying, and cooling to form an intermediate layer;

s4: coating the prepared bonding layer slurry on the dried intermediate layer, wherein the coating thickness is 0.1-0.5mm, and controlling the temperature of the oven to be 60-130 ℃ for pre-drying to be semi-dry, namely, the retention time in the oven is 50-120 s;

s5: then adhering the leather to the front surface of the base fabric, drying, controlling the temperature of an oven to be 60-150 ℃, and finally stripping the release paper to obtain the environment-friendly vulcanized shoe leather.

In the embodiment, the viscosity of the skin layer slurry is 3000-10000cps/25 ℃, and the coating weight is 60-250 g/m; the viscosity of the middle layer slurry is 3000-10000cps/25 ℃, and the coating weight is 100-250 g/m; the coating weight of the bonding layer slurry is 100-500 g/m.

In this embodiment, in step S2, the thickness of the dried skin layer is 0.01 to 0.1 mm; in step S3, the thickness of the dried intermediate layer film is 0.03-0.1 mm; in step S5, the thickness of the bonding layer after bonding and drying is 0.08-0.5 mm.

Example 2

An environment-friendly vulcanized shoe leather takes high-density knitted fabric as a base fabric layer, and an adhesive layer, an intermediate layer and a surface layer are sequentially arranged on the base fabric layer;

the bonding layer is a solvent-free foaming layer prepared from the following raw materials in parts by weight: solvent-free resin A material HX-5002A: 100 parts of solvent-free resin B material HX-5002B: 40 parts of auxiliary agent JN 3-030: 0.1 part of auxiliary agent JN 3-031: 0.1 part;

the middle layer comprises the following raw materials in parts by weight: waterborne resin HG 3-106: 100 parts of leveling agent JN 3-052: 0.1 part of defoaming agent JN 3-095: 0.1 part of bridging agent JN 3-105: 1 part of color paste: 3 parts of a mixture;

the skin layer comprises the following raw materials in parts by weight: waterborne resin HG 3-066: 100 parts of leveling agent JN 3-052: 0.1 part of defoaming agent JN 3-095: 0.1 part of bridging agent JN 3-108: 1 part of color paste: 3 parts of a mixture;

the water-based resin HG3-066 is aliphatic polyether water-based resin, the water-based resin HG3-106 is high-solid-content aliphatic polyether water-based resin, the solvent-free resin A material HX-5002A is polyether polyol mixture, and the solvent-free resin B material HX-5002B is polyether isocyanate prepolymer.

In this embodiment, the bottom fabric layer is a high-density knitted fabric with a 0.5mm weight of 150g/m²。

In this embodiment, the preparation method of the environment-friendly vulcanized shoe leather comprises the following steps:

s1: preparing bonding layer slurry, preparing middle layer slurry, preparing epidermal layer slurry, and selecting base fabric and release paper;

s2: coating the prepared epidermal layer slurry on release paper, wherein the coating thickness is 0.03mm, controlling the temperature of an oven to dry at 60 ℃, and cooling to form an epidermal layer;

s3: coating the prepared intermediate layer slurry on a dried surface layer, wherein the coating thickness is 0.05mm, controlling the temperature of an oven to dry at 60 ℃, and cooling to form an intermediate layer;

s4: coating the prepared bonding layer slurry on a dried intermediate layer, wherein the coating thickness is 0.1mm, and controlling the temperature of an oven to be pre-dried to be semi-dry under the condition of 60 ℃, namely, the retention time in the oven is 50 s;

s5: then bonding the vulcanized rubber with the front surface of the base fabric, drying, controlling the temperature of an oven to be 60 ℃, and finally stripping the release paper to obtain the environment-friendly vulcanized shoe leather.

In the embodiment, the viscosity of the skin layer slurry is 3000cps/25 ℃, and the coating weight is 60 g/m; the viscosity of the middle layer slurry is 3000cps/25 ℃, and the coating weight is 100 g/m; the coating weight of the bonding layer slurry is 100 g/m.

In this embodiment, in step S2, the thickness of the dried skin layer is 0.01 mm; in step S3, the dried film thickness of the middle layer is 0.03 mm; in step S5, the thickness of the adhesive layer after bonding and drying is 0.08 mm.

Example 3

An environment-friendly vulcanized shoe leather takes high-density knitted fabric as a base fabric layer, and an adhesive layer, an intermediate layer and a surface layer are sequentially arranged on the base fabric layer;

the bonding layer is a solvent-free foaming layer prepared from the following raw materials in parts by weight: solvent-free resin A material HX-5002A: 100 parts of solvent-free resin B material HX-5002B: 120 parts of auxiliary agent JN 3-030: 1 part, auxiliary agent JN 3-031: 1 part;

the middle layer comprises the following raw materials in parts by weight: waterborne resin HG 3-106: 100 parts of leveling agent JN 3-052: 1 part, defoaming agent JN 3-095: 0.5 part of bridging agent JN 3-105: 5 parts of color paste: 30 parts of (1);

the skin layer comprises the following raw materials in parts by weight: waterborne resin HG 3-066: 100 parts of leveling agent JN 3-052: 1 part, defoaming agent JN 3-095: 0.5 part of bridging agent JN 3-108: 5 parts of color paste: 20 parts of (1);

the water-based resin HG3-066 is aliphatic polyether water-based resin, the water-based resin HG3-106 is high-solid-content aliphatic polyether water-based resin, the solvent-free resin A material HX-5002A is polyether polyol mixture, and the solvent-free resin B material HX-5002B is polyether isocyanate prepolymer.

In this embodiment, the base fabric layer is a high-density knitted fabric with a thickness of 1.2mm and a grammage of 450g/m²。

In this embodiment, the preparation method of the environment-friendly vulcanized shoe leather comprises the following steps:

s1: preparing bonding layer slurry, preparing middle layer slurry, preparing epidermal layer slurry, and selecting base fabric and release paper;

s2: coating the prepared epidermal layer slurry on release paper, wherein the coating thickness is 0.15mm, controlling the temperature of an oven to dry at 150 ℃, and cooling to form an epidermal layer;

s3: coating the prepared intermediate layer slurry on a dried surface layer, wherein the coating thickness is 0.2mm, controlling the temperature of an oven to dry at 150 ℃, and cooling to form an intermediate layer;

s4: coating the prepared bonding layer slurry on the dried intermediate layer, wherein the coating thickness is 0.5mm, and controlling the temperature of an oven to be pre-dried to be semi-dry under the condition of 130 ℃, namely, the retention time in the oven is 120 s;

s5: then adhering the leather to the front surface of the base fabric, drying, controlling the temperature of an oven to be 150 ℃, and finally stripping the release paper to obtain the environment-friendly vulcanized shoe leather.

In the embodiment, the viscosity of the skin layer slurry is 10000cps/25 ℃, and the coating weight is 250 g/m; the viscosity of the middle layer slurry is 10000cps/25 ℃, and the coating weight is 250 g/m; the coating weight of the bonding layer slurry is 500 g/m.

In this embodiment, in step S2, the thickness of the dried skin layer is 0.1 mm; in step S3, the dried intermediate layer has a film-forming thickness of 0.1 mm; in step S5, the thickness of the adhesive layer after bonding and drying is 0.5 mm.

Example 4

An environment-friendly vulcanized shoe leather takes high-density knitted fabric as a base fabric layer, and an adhesive layer, an intermediate layer and a surface layer are sequentially arranged on the base fabric layer;

the bonding layer is a solvent-free foaming layer prepared from the following raw materials in parts by weight: solvent-free resin A material HX-5002A: 100 parts of solvent-free resin B material HX-5002B: 100 parts of auxiliary agent JN 3-030: 0.5 part of auxiliary agent JN 3-031: 0.6 part;

the middle layer comprises the following raw materials in parts by weight: waterborne resin HG 3-106: 100 parts of leveling agent JN 3-052: 0.4 part of defoaming agent JN 3-095: 0.3 part of bridging agent JN 3-105: 3 parts of color paste: 15 parts of (1);

the skin layer comprises the following raw materials in parts by weight: waterborne resin HG 3-066: 100 parts of leveling agent JN 3-052: 0.4 part of defoaming agent JN 3-095: 0.3 part of bridging agent JN 3-108: 3 parts of color paste: 10 parts of (A);

the water-based resin HG3-066 is aliphatic polyether water-based resin, the water-based resin HG3-106 is high-solid-content aliphatic polyether water-based resin, the solvent-free resin A material HX-5002A is polyether polyol mixture, and the solvent-free resin B material HX-5002B is polyether isocyanate prepolymer.

In this embodiment, the bottom fabric layer is a high-density knitted fabric with a weight of 300g/m and a thickness of 0.8mm²。

In this embodiment, the preparation method of the environment-friendly vulcanized shoe leather comprises the following steps:

s1: preparing bonding layer slurry, preparing middle layer slurry, preparing epidermal layer slurry, and selecting base fabric and release paper;

s2: coating the prepared epidermal layer slurry on release paper, wherein the coating thickness is 0.1mm, controlling the temperature of an oven to dry at 100 ℃, and cooling to form an epidermal layer;

s3: coating the prepared intermediate layer slurry on a dried surface layer, wherein the coating thickness is 0.15mm, controlling the temperature of an oven to dry at 100 ℃, and cooling to form an intermediate layer;

s4: coating the prepared bonding layer slurry on a dried intermediate layer, wherein the coating thickness is 0.3mm, and controlling the temperature of an oven to be pre-dried to be semi-dry under the condition of 90 ℃, namely, the retention time in the oven is 80 s;

s5: then adhering the leather to the front surface of the base fabric, drying, controlling the temperature of an oven to be 100 ℃, and finally stripping the release paper to obtain the environment-friendly vulcanized shoe leather.

In the embodiment, the viscosity of the skin layer slurry is 6500cps/25 ℃, and the coating weight is 180 g/m; the viscosity of the middle layer slurry is 7000cps/25 ℃, and the coating weight is 160 g/m; the coating weight of the bonding layer slurry is 300 g/m.

In this embodiment, in step S2, the thickness of the dried skin layer is 0.05 mm; in step S3, the dried film forming thickness of the middle layer is 0.06 mm; in step S5, the thickness of the adhesive layer after bonding and drying is 0.2 mm.

Example 5

An environment-friendly vulcanized shoe leather takes high-density knitted fabric as a base fabric layer, and an adhesive layer, an intermediate layer and a surface layer are sequentially arranged on the base fabric layer;

the bonding layer is a solvent-free foaming layer prepared from the following raw materials in parts by weight: solvent-free resin A material HX-5002A: 100 parts of solvent-free resin B material HX-5002B: 80 parts of auxiliary agent JN 3-030: 0.6 part of auxiliary agent JN 3-031: 0.7 part;

the middle layer comprises the following raw materials in parts by weight: waterborne resin HG 3-106: 100 parts of leveling agent JN 3-052: 0.6 part of defoaming agent JN 3-095: 0.2 part of bridging agent JN 3-105: 2.5 parts of color paste: 20 parts of (1);

the skin layer comprises the following raw materials in parts by weight: waterborne resin HG 3-066: 100 parts of leveling agent JN 3-052: 0.8 part of defoaming agent JN 3-095: 0.4 part of bridging agent JN 3-108: 3.5 parts of color paste: 16 parts of a mixture;

the water-based resin HG3-066 is aliphatic polyether water-based resin, the water-based resin HG3-106 is high-solid-content aliphatic polyether water-based resin, the solvent-free resin A material HX-5002A is polyether polyol mixture, and the solvent-free resin B material HX-5002B is polyether isocyanate prepolymer.

In this embodiment, the base fabric layer is a 1mm high-density knitted fabric with a grammage of 350g/m²。

In this embodiment, the preparation method of the environment-friendly vulcanized shoe leather comprises the following steps:

s1: preparing bonding layer slurry, preparing middle layer slurry, preparing epidermal layer slurry, and selecting base fabric and release paper;

s2: coating the prepared epidermal layer slurry on release paper, wherein the coating thickness is 0.08mm, controlling the temperature of an oven to dry at 120 ℃, and cooling to form an epidermal layer;

s3: coating the prepared intermediate layer slurry on a dried surface layer, wherein the coating thickness is 0.1mm, controlling the temperature of an oven to dry at 110 ℃, and cooling to form an intermediate layer;

s4: coating the prepared bonding layer slurry on a dried intermediate layer, wherein the coating thickness is 0.35mm, and controlling the temperature of an oven to be pre-dried to be semi-dry under the condition of 100 ℃, namely, the retention time in the oven is 100 s;

s5: then bonding the vulcanized rubber with the front surface of the base fabric, drying, controlling the temperature of an oven to be 120 ℃, and finally stripping the release paper to obtain the environment-friendly vulcanized shoe leather.

In the embodiment, the viscosity of the skin layer slurry is 8000cps/25 ℃, and the coating weight is 200 g/m; the viscosity of the middle layer slurry is 8000cps/25 ℃, and the coating weight is 180 g/m; the coating weight of the bonding layer slurry is 200 g/m.

In this embodiment, in step S2, the thickness of the dried skin layer is 0.06 mm; in step S3, the dried film thickness of the middle layer is 0.05 mm; in step S5, the thickness of the adhesive layer after bonding and drying is 0.3 mm.

Comparative example 1

The skin layer and the intermediate layer slurry were prepared in the same manner as in example 5 except that the aqueous resin was replaced with a non-aqueous urethane resin as compared with example 5.

Comparative example 2

The adhesive layer slurry was similar to example 5 except that the solvent-based resin was used instead of the solvent-free resin in example 5.

The invention carries out performance test on examples 2-5 and comparative examples 1-2, and the test results are shown in Table 1:

TABLE 1

	DMF content	Delamination of the layers	Comfortable feeling
				Example 2	48ppm	Without delamination	Soft and comfortable
Example 3	46ppm	Without delamination	Soft and comfortable
				Example 4	46ppm	Without delamination	Soft and comfortable
Example 5	45ppm	Without delamination	Soft and comfortable
				Comparative example 1	80ppm	Slight delamination	Is slightly rough
Comparative example 2	100ppm	Significant delamination	Rough hand feeling

As can be seen from Table 1, the invention adopts the design of the water-based coating, and the water-based resin is used for the process formula design of the surface layer and the middle layer, thereby avoiding the use of harmful solvents; the aqueous epidermal layer coating has skin-friendly property and can be adhered at high frequency; the water-based middle layer is excellently combined with the surface layer and the bonding layer by selecting high-solid content (30-60%) aliphatic polyether type water-based resin and adjusting the using amounts of a defoaming agent, a bridging agent and a flatting agent; the bonding layer is made of solvent-free resin, so that the coating is excellent in temperature resistance, the physical property change is small under the high-temperature vulcanization condition, the bubble adjusting aid is used in the bonding layer, the bubbles of the coating are uniform and have certain openness, the size of the bubbles can be kept unchanged under the high-temperature and high-pressure vulcanization condition, and the solvent-free foaming coating is designed to have obvious soft hand feeling improvement compared with a non-foaming coating.

The invention adopts the water-based coating design and the solvent-free bonding layer resin, avoids the use of harmful solvents, is green and environment-friendly, has the finished product DMF residue test of less than or equal to 50ppm, and is beneficial to human health.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.