阅读说明：本技术 一种真皮革材料及其制备方法和应用 (Leather material and preparation method and application thereof ) 是由 周国祥 刘大卫 刘光闪 尹涛 段升准 于明东 唐淑田 冯殿清 于 2020-12-23 设计创作，主要内容包括：本发明提供了一种真皮革材料的处理方法,属于皮革材料技术领域。本发明以动物生皮为基础,先对动物生皮依次进行水浸和脱毛,得到脱毛皮,之后对所述脱毛皮依次进行第一酸处理、纯植鞣和陈化,得到纯植鞣毛皮；再对所述纯植鞣毛皮依次进行轻铬鞣、重植鞣和第二酸处理,得到铬/植结合鞣毛皮；随后在所述铬/植结合鞣毛皮表面依次涂覆防水防油防污聚合物、阻燃剂、清味剂和甲醛清除剂,之后进行真空绷板干燥,得到真皮革材料。本发明所得真皮革材料具有优异的三防性能、阻燃性能；具有良好的弹性、韧性、环保性以及良好的保温、隔音效果。(The invention provides a method for treating a real leather material, and belongs to the technical field of leather materials. The method is based on animal hides, firstly, the animal hides are sequentially subjected to water immersion and unhairing to obtain the unhaired skins, and then, the unhaired skins are sequentially subjected to first acid treatment, pure vegetable tanning and aging to obtain the pure vegetable tanned skins; sequentially carrying out light chrome tanning, heavy vegetable tanning and secondary acid treatment on the pure vegetable tanned fur to obtain chrome/vegetable combined tanned fur; and then sequentially coating a waterproof, oil-proof and antifouling polymer, a flame retardant, a smell cleaning agent and a formaldehyde scavenger on the surface of the chromium/vegetable combined tanned fur, and then carrying out vacuum toggling drying to obtain the leather material. The real leather material obtained by the invention has excellent three-proofing performance and flame retardant property; has good elasticity, toughness, environmental protection and good heat preservation and sound insulation effects.)

1. A preparation method of a leather material comprises the following steps:

(1) sequentially soaking and unhairing the animal hide to obtain a dehaired skin;

(2) sequentially carrying out first acid treatment, pure vegetable tanning and aging on the fur removed to obtain pure vegetable tanned fur;

(3) sequentially carrying out light chrome tanning, heavy vegetable tanning and secondary acid treatment on the pure vegetable tanned fur to obtain a chrome/vegetable combined tanned fur;

(4) retanning the chrome/vegetable combined tanned fur, adding a waterproof, oilproof and antifouling polymer, a flame retardant, a smell cleaning agent and a formaldehyde scavenger during retanning, and then drying by a vacuum toggling plate to obtain the leather material.

2. The method according to claim 1, wherein the soaking temperature in the step (1) is 24-26 ℃ and the time is 4-6 h;

the depilatory for depilation comprises liming auxiliary agent and Na₂S, NaHS, liming enzymes and lime; the liming auxiliary agent is a liming auxiliary agent containing amine and nitrogen;

liming auxiliary agent and Na in depilatory₂S, NaHS, and the mass percentage of the liming enzyme and the lime is 1.0-1.5%, 1.0-1.4%, 1.2-1.5%, 0.1-0.15% and 2.5-5.5% respectively.

3. The method of claim 1, wherein the first acid treatment is acid leaching, the pH value of acid leaching solution used for acid leaching is 4-4.5, the Baume value is 6.5-7.5, and the acid leaching time is 5-8 h.

4. The method according to claim 1, characterized in that the tanning material used for the pure vegetable tanning is one or more of quebracho extract, castanopsis mollissima extract, wattle bark extract, myrica extract, areca extract, kozi extract and tara extract; the mass of the pure vegetable tanning material is 30-50% of the mass of the de-furled skin; the pure vegetable tanning time is 14-16 h; the aging time is more than or equal to 3 days.

5. The method according to claim 1, characterized in that the tanning material used for light chrome tanning comprises animal protein, acrylic acid polymer, styrene maleic anhydride, melamine, dicyandiamide, phenolic syntan and chrome powder; the content of the chromium powder is 24 wt%;

the weight of the light chrome tanning material is 6-8% of that of pure vegetable tanning fur; the light chrome tanning time is 12-15 h;

the tanning materials used in the re-vegetable tanning comprise un-saccharified castanea mollissima tannin extract, quebracho tannin extract, wattle bark tannin extract, acrylic resin tanning agent, formaldehyde-free melamine, dicyandiamide and replacement tannin, and the mass ratio of the re-vegetable tanning materials to pure vegetable tanning fur is 0.25-0.3: 1; and the time for retanning is 6-8 h.

6. The method of claim 1, wherein the second acid is treated by: adding acid into the retanning material for tanning; the pH value of the tanning material after the acid is added is 3.3-3.6, the temperature of the acid-added tanning is 45-50 ℃, and the time is 1-2 hours.

7. The process according to claim 1, characterized in that said water, oil and soil repellent polymer is a polyamide polymer; the mass ratio of the waterproof, oil-proof and antifouling polymer to the chromium/vegetable combined tanned fur is 6-10%;

the using amount of the flame retardant is 0.5-1% of the mass of the chromium/vegetable combined tanned fur;

the dosage of the smell removing agent is 0.2-0.5% of the mass of the chromium/vegetable combined tanned fur;

the dosage of the formaldehyde scavenger is 0.2-0.5% of the mass of the chromium/vegetable combined tanned fur.

8. The method according to claim 1, wherein the vacuum of the vacuum-stretched plate drying is 950 to 1000mbar, the temperature is 55 to 60 ℃, and the time is 4 to 5 min.

9. A leather material obtained by the method according to any one of claims 1 to 8.

10. Use of the genuine leather material of claim 9 as flooring leather or wall leather.

Technical Field

The invention relates to the technical field of leather materials, in particular to a real leather material and a preparation method and application thereof.

Background

The traditional floor leather is low in price, but the waterproof and antifouling properties are poor, and if the waterproof and antifouling properties and the flame retardant property of the vegetable tanned floor leather can be improved in a process optimization mode, the use value of the floor leather can be greatly improved.

Disclosure of Invention

In view of the above, the present invention aims to provide a real leather material, a preparation method and an application thereof, and the real leather material obtained by the present invention has good multi-prevention property, environmental protection property, toughness and elasticity.

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

the invention provides a preparation method of a leather material, which comprises the following steps:

(1) sequentially soaking and unhairing the animal hide to obtain a dehaired skin;

(2) sequentially carrying out first acid treatment, pure vegetable tanning and aging on the fur removed to obtain pure vegetable tanned fur;

(3) sequentially carrying out light chrome tanning, heavy vegetable tanning and secondary acid treatment on the pure vegetable tanned fur to obtain a chrome/vegetable combined tanned fur;

(4) retanning the chrome/vegetable combined tanned fur, adding a waterproof, oilproof and antifouling polymer, a flame retardant, a smell cleaning agent and a formaldehyde scavenger during retanning, and then drying by a vacuum toggling plate to obtain the leather material.

Preferably, the soaking temperature in the step (1) is 24-26 ℃, and the time is 4-6 h;

the depilatory for depilation comprises liming auxiliary agent and Na₂S, NaHS, liming enzymes and lime; the liming auxiliary agent is a liming auxiliary agent containing amine and nitrogen;

liming auxiliary agent and Na in depilatory₂S, NaHS, and the mass percentage of the liming enzyme and the lime is 1.0-1.5%, 1.0-1.4%, 1.2-1.5%, 0.1-0.15% and 2.5-5.5% respectively.

Preferably, the first acid treatment mode is acid leaching, the pH value of acid leaching liquid used for acid leaching is 4-4.5, the Baume value is 6.5-7.5, and the acid leaching time is 5-8 h.

Preferably, the tanning materials used in the pure vegetable tanning are one or more of quebracho tannin extract, chestnut tannin extract, wattle tannin extract, waxberry tannin extract, areca tannin extract, kozi tannin extract and tara tannin extract; the mass of the pure vegetable tanning material is 30-50% of the mass of the de-furled skin; the pure vegetable tanning time is 14-16 h; the aging time is more than or equal to 3 days.

Preferably, the tanning materials used for light chrome tanning comprise animal protein, acrylic acid polymer, styrene maleic anhydride, melamine, dicyandiamide, phenolic synthetic tanning agent and chrome powder; the content of the chromium powder is 24 wt%;

the weight of the light chrome tanning material is 6-8% of that of pure vegetable tanning fur; the light chrome tanning time is 12-15 h;

the tanning materials used in the re-vegetable tanning comprise un-saccharified castanea mollissima tannin extract, quebracho tannin extract, wattle bark tannin extract, acrylic resin tanning agent, formaldehyde-free melamine, dicyandiamide and replacement tannin, and the mass ratio of the re-vegetable tanning materials to pure vegetable tanning fur is 0.25-0.3: 1; and the time for retanning is 6-8 h.

Preferably, the second acid treatment mode is as follows: adding acid into the retanning material for tanning; the pH value of the tanning material after the acid is added is 3.3-3.6, the temperature of the acid-added tanning is 45-50 ℃, and the time is 1-2 hours.

Preferably, the water, oil and soil repellent polymer comprises truptosis D water repellent oil or PM4700 water repellent agent; the mass ratio of the waterproof, oil-proof and antifouling polymer to the chromium/vegetable combined tanned fur is 6-10%;

the using amount of the flame retardant is 0.5-1% of the mass of the chromium/vegetable combined tanned fur;

the dosage of the smell removing agent is 0.2-0.5% of the mass of the chromium/vegetable combined tanned fur;

the dosage of the formaldehyde scavenger is 0.2-0.5% of the mass of the chromium/vegetable combined tanned fur.

Preferably, the vacuum degree of the vacuum toggling plate drying is 950-1000 mbar, the temperature is 55-60 ℃, and the time is 4-5 min.

The invention provides a leather material obtained by the method.

The invention provides application of the real leather material as floor leather or wall leather.

The invention provides a method for treating a leather material, which is based on animal hides and is subjected to first acid treatment after water immersion and unhairing, so that the combination of leather fibers and tanning materials can be promoted; according to the invention, pure vegetable tanning is carried out, so that the obtained leather matrix is more environment-friendly and healthy on the basis of ensuring the toughness and elasticity of the real leather matrix; according to the invention, the leather material obtained by chrome tanning is endowed with basic heat resistance and machining resistance after pure vegetable tanning; then performing vegetable tanning, wherein vegetable tanning materials can physically fill the dermal fibers, and after the second acid treatment, the vegetable tanning materials physically filled among the dermal fibers can chemically react with active groups of the dermal fibers to chemically characterize the dermal fibers so as to obtain stable shape, and the dermal fibers do not shrink and bulge in the using process; according to the invention, the surface of the obtained chrome/vegetable combined tanned fur is coated with the waterproof, oil-proof and antifouling polymer, so that the leather material can be endowed with good waterproof, oil-proof and antifouling properties; the flame retardant is coated on the surface of the leather material, so that the leather material has good fireproof performance and is safe to use; by coating the surface with the odor removing agent and the formaldehyde removing agent, an extremely low VOC value can be obtained, zero formaldehyde emission can be realized, and the leather material has good environmental protection performance; according to the invention, through vacuum toggling drying, the leather material can obtain ultralow elongation, no shrinkage and no deformation are ensured in the use process, and the complete release of volatile substances is ensured. The functional polyamide polymer is used for treating the leather matrix, amino groups in the functional polyamide polymer are connected with carboxyl groups in the leather fibers through hydrogen bonds, ionic bonds, covalent bonds and Edwardsies force, a densely-woven staggered and rowed ordered net-shaped structure is formed among the leather fiber layers, the toughness, elasticity and wear resistance of the leather material are obviously improved, and the leather material has good comfort, environmental protection and good heat preservation and sound insulation effects when being used for floor leather or wall leather.

Drawings

FIG. 1 is a schematic representation of the real leather material obtained in example 1.

Detailed Description

The invention provides a preparation method of a leather material, which comprises the following steps:

(1) sequentially soaking and unhairing the animal hide to obtain a dehaired skin;

(2) sequentially carrying out first acid treatment, pure vegetable tanning and aging on the fur removed to obtain pure vegetable tanned fur;

(3) sequentially carrying out light chrome tanning, heavy vegetable tanning and secondary acid treatment on the pure vegetable tanned fur to obtain a chrome/vegetable combined tanned fur;

(4) retanning the chrome/vegetable combined tanned fur, adding a waterproof, oilproof and antifouling polymer, a flame retardant, a smell cleaning agent and a formaldehyde scavenger during retanning, and then drying by a vacuum toggling plate to obtain the leather material.

The invention sequentially immerses and unhaires the animal hides to obtain the unhaired skins. The present invention does not require a particular source and type of animal hide, and animal hides well known to those skilled in the art can be used; in the invention, preferably, a soaking solution is added with a surfactant type soaking auxiliary agent, a degreasing agent, a bactericide and a soaking enzyme to restore the original leather to a fresh leather state, remove impurities on the surface of the original leather and prepare for liming and unhairing. In the invention, the soaking temperature is preferably 24-26 ℃, and more preferably 25 ℃; the total soaking time is preferably 4-6 hours, and more preferably 5 hours.

In the invention, the depilatory used for depilating comprises liming auxiliary agent and Na₂S, NaHS, liming enzymes and lime; the liming auxiliary agent and Na₂S, NaHS, liming enzymes, and lime. In the invention, the liming auxiliary agent is a liming auxiliary agent containing amine and nitrogen; in the invention, liming auxiliary agent and Na are contained in the depilatory₂S, NaHS, the liming enzyme and the lime are preferably 1.0-1.5%, 1.0-1.4%, 1.2-1.5%, 0.1-0.15% and 2.5-5.5% respectively in percentage by mass. The invention uses liming auxiliary agent and Na₂S, NaHS, liming enzyme and lime are used as depilatory, which can prevent fiber from excessive decomposition, achieve the purpose of protecting the compact structure of the fiber, and lay the foundation for obtaining smooth, compact, flexible and elastic real leather material.

After the fur is removed, the method carries out first acid treatment, pure vegetable tanning and aging on the removed fur in sequence to obtain the pure vegetable tanned fur. In the invention, the first acid treatment mode is preferably acid leaching, the acid leaching solution used in the acid leaching is preferably a mixed solution of sodium chloride, formic acid and sulfuric acid, the mass content of the sodium chloride in the acid leaching solution is preferably 6-8%, the pH value of the acid leaching solution is preferably 4-4.5, and the Baume value is preferably 7; the acid leaching temperature is preferably room temperature, and the time is preferably 3-4 h.

In the invention, the tanning material used for pure vegetable tanning is preferably one or more of quebracho tannin extract, chestnut tannin extract, wattle tannin extract, waxberry tannin extract, areca tannin extract, kozi tannin extract and tara tannin extract; the mass of the pure vegetable tanning material is preferably 30-50% of the mass of the de-fur, and more preferably 35-45%; . According to the invention, the pure vegetable tanning is preferably carried out in a rotary drum, the rotating speed of the pure vegetable tanning is preferably 6 revolutions per minute, and the time is preferably 14-16 hours.

After the pure vegetable tanning, the pH value of the pure vegetable tanning material is preferably adjusted to 3.0-3.5, preferably to 3.2-3.3; the invention has no special requirement on the regulator for regulating the pH value of the pure vegetable tanning material, and the acid regulator which is well known to the technical personnel in the field can be used, such as formic acid. According to the method, the pH value of the pure vegetable tanning material is adjusted to 3.0-3.5, so that the vegetable tanning material can be fully fixed.

After the pure vegetable tanning is finished, the fur is taken out and aged. In the invention, the aging mode is preferably the hasty aging, and the aging time is preferably more than or equal to 3 days.

After the pure vegetable tanned fur is obtained, the invention sequentially performs chrome tanning and vegetable tanning on the pure vegetable tanned fur to obtain the chrome/vegetable combined tanned fur. The light chrome tanning and the heavy vegetable tanning are preferably carried out in a rotating drum. In the present invention, the tanning material used for the chrome tanning preferably comprises: animal protein, acrylic polymer, styrene maleic anhydride, melamine, dicyandiamide, phenol synthetic tanning agent and chromium powder, wherein the content of the chromium powder in the tanning material is preferably 24 wt%; the mass ratio of the chrome tanning material to the pure vegetable tanning fur is preferably 6-8%, and more preferably 7%. In the present invention, the rotation speed of the light chrome tanning is preferably 8 revolutions per minute; the light chrome tanning time is preferably 12-15 hours, and is preferably 13-14 hours. The light chrome tanning can endow the leather material with basic heat resistance and machining resistance.

In the present invention, the tannages used in the retanning include unglycated castanea mollissima extract, quebracho extract, wattle bark extract, acrylic resin tanning agent, formaldehyde-free melamine, dicyandiamide and substituted tannin. In the invention, the mass ratio of the re-vegetable tanning material to the pure vegetable tanning fur is preferably 0.25-0.3: 1, and more preferably 0.28: 1; the time for the retanning is preferably 6-8 h, and more preferably 7 h. In the invention, the rotation speed of the re-vegetable tanning is preferably 6-8 r/min. During the retanning process, the tanning material is able to physically fill the dermal fibers.

In the present invention, the second acid treatment mode is preferably: adding acid to the retanning material for tanning. In the invention, the pH value of the acid-added tanning material is preferably 3.3-3.6, more preferably 3.5, the tanning temperature is preferably 45-50 ℃, the tanning time is preferably 1-2 h, and the tanning rotating speed is preferably 6-8 r/min. The present invention can chemically determine the dermis fibers by chemically reacting the active groups of the dermis fibers with the vegetable tanning material physically filled between the dermis fibers by the second acid treatment. The leather material after chemical qualitative analysis has stable qualitative performance, and does not shrink, wing edges and bulge in the using process.

After the chrome/vegetable combined tanned fur is obtained, the chrome/vegetable combined tanned fur is retanned, a waterproof, oil-proof and antifouling polymer, a flame retardant, a cleaning agent and a formaldehyde scavenger are added during retanning, and then vacuum toggling drying is carried out to obtain the leather material. The present invention does not require any particular manner of coating, and may be applied using any manner known to those skilled in the art.

In the present invention, the water, oil and soil repellent polymer preferably comprises TRUPOSIST D water repellent oil, preferably TRUPOSIST D water repellent oil from thopler, germany, or PM4700 water repellent agent, preferably PM4700 water repellent agent produced by 3M company, usa. In the invention, the mass ratio of the waterproof, oil-proof and antifouling polymer to the chromium/vegetable combined tanned fur is preferably 6-10%, and more preferably 8-9%.

In the invention, the flame retardant is preferably a flame retardant of RESISTOL PFS (RESISTOL PFS) produced by Germany Thompler company, and the dosage of the flame retardant is 0.5-1% of the mass of the chrome/vegetable combined tanned fur.

In the invention, the smell removing agent is preferably a DISOL smell removing agent produced by Toyo chemical industry of Korea, and the dosage of the smell removing agent is preferably 0.2-0.5%, more preferably 0.3% of the mass of the chrome/vegetable combined tanned fur.

In the invention, the formaldehyde scavenger is preferably a formaldehyde scavenger which is produced by German Thompler and has a model number of TRUPOFIX FST, and the dosage of the formaldehyde scavenger is preferably 0.2-0.5 percent of the mass of the chrome/vegetable combined tanned fur, and more preferably 0.3-0.4 percent. The odor eliminating agent and the formaldehyde scavenging agent are used together, so that the odor and free formaldehyde in the real leather material can be removed, and zero formaldehyde emission is realized.

In the invention, the vacuum degree of the vacuum toggling drying is preferably 950-1000 mbar, more preferably 960-980 mbar, the temperature of the vacuum toggling drying is preferably 55-60 ℃, and the time is preferably 4-5 min. According to the invention, through vacuum toggling drying, the leather material can obtain ultralow elongation, no shrinkage and no deformation are ensured in the use process, and the complete release of volatile substances is ensured.

The invention provides a leather material prepared by the method. In the invention, the real leather material has excellent three-proofing performance (water resistance, oil resistance and stain resistance) and flame retardant performance; the material has good elasticity and toughness, so that the material has good comfort when in use; has good environmental protection, fresh and elegant natural plant tannin extract smell, has no adverse effect on human bodies and living room environment, and is suitable for home floor and wall board decoration. Meanwhile, the real leather material provided by the invention has low thermal conductivity and good heat preservation and insulation functions.

The invention provides application of the real leather material as floor leather or wall leather. In the present invention, the method of application is preferably: combining the dermal leather material with a substrate.

In the present invention, the substrate is preferably a metal material such as plywood, density board, particle board, stone, or aluminum alloy. In the present invention, the bonding is preferably performed by adhesion. The present invention does not require any particular bonding means, as would be known to one skilled in the art of floor panels.

In the invention, when the real leather material is used as the wall leather of the floor leather, the real leather material has good human affinity; is suitable for geothermal environment; heat preservation, heat insulation and sound insulation effects; also has good wear resistance.

The present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.

Example 1

(1) Soaking animal hide in water at 25 deg.C for 5 hr, and depilating with 1.5 wt% of liming assistant and 1.4 wt% of Na₂S, 1.5 wt% NaHS, 0.15 wt% liming enzyme and 5 wt% lime;

(2) acid-treating the dehaired skins with a pickle liquor with a pH value of 4 and a Baume value of 6.5 for 5h, and performing pure vegetable tanning for 15h by using quebracho tannin extract, chestnut tannin extract and wattle bark tannin extract, wherein the mass of the pure vegetable tanning material is 40% of the dehaired skins, and then aging for 3 days;

(3) performing light chrome tanning on the pure vegetable tanned fur for 12h by using a tanning material with 24 percent of chrome powder content, performing heavy vegetable tanning for 8h by using unsaponified castanea mollissima tannin extract, quebracho tannin extract, wattle bark tannin extract, acrylic resin tanning agent, formaldehyde-free melamine, dicyandiamide and substituted tannin, and then adding acid to a pH value of 3.3 for tanning for 2h to obtain chrome/vegetable combined tanned fur;

(4) adding 6% of TRUPOSIST D waterproof oil, 1% of flame retardant, 0.5% of smell cleaning agent and 0.5% of formaldehyde scavenger by weight of chromium/vegetable combined tanned fur for retanning, and then performing toggling drying at 1000mbar and 60 ℃ for 5min to obtain the leather material.

The obtained leather material was tested for formaldehyde content, water resistance, and flame retardancy, the test methods are shown in table 1.

TABLE 1 test methods and results

As can be seen from Table 1, the leather material provided by the invention has good waterproofness, flame retardancy and environmental protection.

The real figure of the obtained real leather material is shown in figure 1 as floor leather. The floor leather has comfortable foot feel and good sound insulation performance.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.