CN108301224B - A kind of preparation method of environmental protection crystal leather - Google Patents

A kind of preparation method of environmental protection crystal leather Download PDF

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CN108301224B
CN108301224B CN201810127269.4A CN201810127269A CN108301224B CN 108301224 B CN108301224 B CN 108301224B CN 201810127269 A CN201810127269 A CN 201810127269A CN 108301224 B CN108301224 B CN 108301224B
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polyurethane
semi
finished product
colorless
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CN108301224A (en
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王鑫
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Fujian Xinlongshang Super Fiber Co ltd
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Fujian Longshang Microfiber Co ltd
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/145—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes two or more layers of polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
    • D06N3/0045—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by applying a ready-made foam layer; obtained by compressing, crinkling or crushing a foam layer, e.g. Kaschierverfahren für Schaumschicht
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
    • D06N3/0075—Napping, teasing, raising or abrading of the resin coating
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
    • D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
    • D06N3/0097—Release surface, e.g. separation sheets; Silicone papers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/08—Properties of the materials having optical properties
    • D06N2209/0838—Bright, glossy, shiny surface
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/14—Properties of the materials having chemical properties
    • D06N2209/146—Soilproof, soil repellent
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties
    • D06N2209/1685—Wear resistance
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Abstract

本发明涉及皮革领域，提供一种环保水晶革的制备方法,包括步骤1)涂布发泡树脂；2)涂布中间层聚氨酯浆料；3)流延无色面层聚氨酯；4)涂布无色透明聚氨酯热熔胶层；5)贴合；解决了现有水晶革制备过程中的有机溶剂污染问题及革表面易受污染的问题。The invention relates to the field of leather, and provides a method for preparing an environmental-friendly crystal leather, comprising the steps of 1) coating foamed resin; 2) coating an intermediate layer polyurethane slurry; 3) casting a colorless surface layer polyurethane; 4) coating The colorless and transparent polyurethane hot-melt adhesive layer; 5) lamination; solves the problem of organic solvent pollution in the preparation process of the existing crystal leather and the problem that the leather surface is easily polluted.

Description

Preparation method of environment-friendly crystal leather
Technical Field
The invention relates to the field of leather, in particular to a preparation method of environment-friendly crystal leather.
Background
The crystal synthetic leather in the market at present mainly adopts solvent type polyurethane, and when the solvent type polyurethane is used as interlayer resin for bonding, the crystal synthetic leather has the advantage of high bonding strength, but the solvent type polyurethane has the characteristics of low solid content and high solvent content, so that the problems of large patterns, difficult filling of deep patterns, easy generation of bubbles, large DMF residual quantity and the like exist; in addition, in actual use, the surface of the existing crystal leather cannot be cleaned up after being polluted by oil such as ball-point pen oil and pigment, so that subsequent use is influenced, and therefore, an environment-friendly antifouling crystal leather needs to be developed to meet the needs of people.
Patent document CN201710713825 discloses a preparation method of environment-friendly double-process mirror-finished crystal leather, wherein polyester-polyether copolymerized polyurethane resin, pearl powder, pigment and dimethylformamide are selected as surface layers and bonding layers of a first dry process to be bonded with a non-crease elastic wet-process synthetic leather semi-finished product, a cold pressing process is adopted to press the dry-process semi-finished product into pearl three-dimensional grains, a polyester-polyether copolymerized high-modulus polyurethane surface layer colorless slurry and a high-solid two-liquid type polyurethane colorless slurry are adopted, a secondary dry full-dry bonding process is carried out on mirror-finished release paper, and the pearl embossed semi-finished product is bonded to obtain the environment-friendly double-process mirror-finished crystal leather.
Disclosure of Invention
Therefore, aiming at the above content, the invention provides a preparation method of environment-friendly crystal leather, which solves the problems of organic solvent pollution and easy pollution on the leather surface in the existing crystal leather preparation process.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the preparation method of the environment-friendly crystal leather comprises the following steps:
1) coating foaming resin, namely coating a polyurethane foaming material on the base cloth, carrying out hot-pressing foaming and curing, standing for 4-6h, grinding the back surface by a leather grinding machine, and removing dust to obtain a semi-finished product a;
2) coating middle layer polyurethane slurry, namely coating the colored middle layer polyurethane slurry with the thickness of 10-30 threads on the foaming layer of the semi-finished product a, drying at the temperature of 100-140 ℃, and brightening the surface after being pressed by a hot pressing plate or a hot pressing roller to obtain a semi-finished product b;
3) casting colorless surface layer polyurethane, namely casting and compounding a layer of colorless surface layer polyurethane with the thickness of 10-20 filaments on the high-gloss mirror surface film, and drying at the temperature of 100-120 ℃ to obtain a semi-finished product c;
4) coating a colorless transparent polyurethane hot-melt adhesive layer, namely coating the colorless transparent polyurethane hot-melt adhesive layer on the surface of the colorless surface layer polyurethane of the semi-finished product c, and drying at the temperature of 100-:
5) and (3) gluing, namely thermally bonding the colorless polyurethane sol layer of the semi-finished product d and the mirror surface interlayer of the semi-finished product b under the pressure of 1-2MPa, cooling for 10-15min, standing for 3-5h, and stripping the highlight mirror surface film to obtain the environment-friendly crystal leather.
The further improvement is that: the middle layer polyurethane slurry consists of the following raw materials in parts by weight: 60-70 parts of aqueous polyurethane emulsion (with 35% of solid content), 10-20 parts of acrylic resin emulsion (with 35% of solid content), 5-10 parts of pigment paste, 5-10 parts of wax-separating agent (with 30% of solid content) and 5-10 parts of casein.
The further improvement is that: the colorless surface layer polyurethane slurry in the step 3 is prepared from the following raw materials in parts by weight: 0.5-1.0 part of POSS-based fluorine-containing polymer, 80-90 parts of thermoplastic elastomer TPU, 5-15 parts of thermoplastic elastomer POE, 0.1-0.5 part of defoaming agent and 1-5 parts of dispersing agent.
The further improvement is that: the preparation method of the POSS-based fluorine-containing polymer comprises the following steps: the raw materials comprise, by weight, 90-97 parts of perfluorohexylethanol, 2-7 parts of octavinyl POSS and 0.5-3 parts of Azobisisobutyronitrile (AIBN), and the raw materials are stirred and react for 3-4 hours at the temperature of 65-80 ℃ to obtain the POSS-based fluorine-containing polymer.
The further improvement is that: and 3, during the tape casting compounding, stirring the raw material components of the colorless surface layer polyurethane slurry by using a high-speed stirrer for 10-15 minutes, drying at the temperature of 80-90 ℃, and then putting into a feeding port of an extrusion tape casting compounding machine for melt blending, wherein the temperature of a melt blending stage is 200-250 ℃.
By adopting the technical scheme, the invention has the beneficial effects that:
1. the preparation method of the environment-friendly crystal leather provided by the invention does not use solvents in the production process, does not cause pollution to the environment, and replaces a dry method part in the traditional crystal leather production, so that the problems of high energy consumption, labor saving and no pollution are thoroughly solved.
2. In the colorless surface layer polyurethane slurry formula adopted by the invention, POSS-based fluorine-containing polymer is combined with TPU and POE polar bonds, and POSS-based fluorine atoms and fluorine atoms are gathered on the surface of the membrane, so that the water contact angle and the oil contact angle of the membrane can be increased to about 130 degrees, and effective antifouling is realized.
3. The polyurethane foaming material is coated on the base cloth, after hot-pressing foaming and curing, because polyurethane can be unevenly distributed at different parts of base cloth fibers, the whole thickness is different, the subsequent crystal effect of uneven feeding images can be caused when crystal leather is manufactured, and the polyurethane foaming base cloth with even thickness can be obtained after the back surface is ground by a leather grinding machine.
4. The acrylic resin emulsion in the raw material composition of the polyurethane slurry of the middle layer increases the hot adhesiveness of the middle layer and the upper and lower layers, the plate-separating wax can prevent the roller from being stuck when the smooth roller is subjected to hot pressing, and the casein can improve the brightness of the middle layer when the smooth roller is subjected to hot pressing, so that the crystal leather has natural bottom light to be transmitted.
Detailed Description
The following detailed description will be provided for the embodiments of the present invention with reference to specific embodiments, so that how to apply the technical means to solve the technical problems and achieve the technical effects can be fully understood and implemented.
Unless otherwise indicated, the techniques employed in the examples are conventional and well known to those skilled in the art, and the reagents and products employed are also commercially available. The source, trade name and if necessary the constituents of the reagents used are indicated at the first appearance.
The first embodiment of the invention is as follows:
the preparation method of the environment-friendly crystal leather comprises the following steps:
1) coating foaming resin, namely coating a polyurethane foaming material on the base cloth, carrying out hot-pressing foaming and curing, standing for 4 hours, grinding the back surface of the base cloth by using 800-mesh abrasive cloth through a leather grinder, and removing dust to obtain a semi-finished product a; the back surface is ground flat, so that the local uneven thickness of the base cloth after the polyurethane foam material is coated, foamed and cured can be avoided;
2) coating middle layer polyurethane slurry, namely coating color middle layer polyurethane slurry with the thickness of 30 threads on a foaming layer of the semi-finished product a, drying at 100 ℃, and hot-pressing at 100 ℃ and 10MPa by a smooth roller to obtain a mirror surface semi-finished product b;
3) casting colorless surface layer polyurethane, namely casting and compounding a layer of colorless surface layer polyurethane with the thickness of 10 silks on the highlight mirror surface film, and drying at 100 ℃ to obtain a semi-finished product c;
4) coating a colorless transparent polyurethane hot-melt adhesive layer, namely coating the colorless transparent polyurethane hot-melt adhesive layer on the colorless surface layer polyurethane surface of the semi-finished product d, and drying at 100 ℃ to obtain the semi-finished product d;
5) and (3) bonding the colorless polyurethane sol layer of the semi-finished product d and the mirror surface interlayer of the semi-finished product b at the temperature of 120 ℃ under the pressure of 1MPa, cooling for 10min, standing for 3h, and stripping the highlight mirror surface film to obtain the environment-friendly crystal leather.
The middle layer polyurethane slurry consists of the following raw materials in parts by weight: 60 parts of waterborne polyurethane emulsion (with the solid content of 35%), 10 parts of acrylic resin emulsion (with the solid content of 35%), 10 parts of pigment paste, 10 parts of wax-separating (with the solid content of 30%), 10 parts of casein, wherein the acrylic resin provides hot adhesiveness between the middle layer and the upper layer and the lower layer, the wax-separating avoids roller sticking, the casein improves the natural luster of the middle layer, and the bottom light of a finished product can be more natural.
The colorless surface layer polyurethane slurry in the step 3) is prepared from the following raw materials in parts by weight: 1 part of POSS-based fluorine-containing polymer, 90 parts of thermoplastic elastomer TPU, 5 parts of thermoplastic elastomer POE, 0.5 part of defoaming agent and 3.5 parts of dispersing agent; the TPU has good elasticity, so that the synthetic leather has the hand feeling of real leather; POE has excellent fluidity and toughness, and can improve the flexibility of the film; POSS group and fluorine atom are gathered on the surface of the formed film, and the water contact angle is 133 +/-2 degrees and the oil contact angle is 135 +/-2 degrees through actual measurement, so that the antifouling effect can be realized.
The preparation method of the POSS-based fluorine-containing polymer comprises the following steps: 90 parts of perfluorohexyl ethanol, 7 parts of octavinyl POSS and 3 parts of Azobisisobutyronitrile (AIBN), and stirring and reacting at 65 ℃ for 4 hours to obtain the POSS-based fluorine-containing polymer; azobisisobutyronitrile acts as an initiator.
3, during the tape casting compounding, all the raw material components of the colorless surface layer polyurethane slurry are firstly stirred by a high-speed stirrer for 10 minutes and uniformly stirred, so that the uniform dispersion of all the components is facilitated, the components are dried at the temperature of 80 ℃ to remove water so as to avoid the generation of bubbles during the tape casting, and then the components are put into a material inlet of an extrusion tape casting compounding machine for melt blending, wherein the temperature of the melt blending stage is 200-250 ℃.
The second embodiment of the invention is as follows:
the preparation method of the environment-friendly crystal leather comprises the following steps:
1) coating a polyurethane foaming material on a base cloth, carrying out hot-pressing foaming and curing at 110 ℃ under 10MPa, standing for 6h, grinding the back surface of the base cloth by using 600-mesh abrasive cloth through a leather grinder, and removing dust to obtain a semi-finished product a;
2) coating color middle layer polyurethane slurry with the thickness of 10 threads on the foaming layer of the semi-finished product a, drying at 140 ℃, and carrying out hot pressing at 100 ℃ and 10MPa by using a litchi pattern roller to obtain a mirror surface semi-finished product b;
3) casting and compounding a colorless surface layer polyurethane layer with the thickness of 10 silks on the highlight mirror surface film, and drying at 120 ℃ to obtain a semi-finished product c;
4) coating a colorless transparent polyurethane hot-melt adhesive layer on the colorless surface layer polyurethane surface of the semi-finished product d, and drying at 140 ℃ to obtain a semi-finished product d;
5) and (3) thermally bonding the colorless polyurethane sol layer of the semi-finished product d and the mirror surface interlayer of the semi-finished product b at the temperature of 150 ℃ under the pressure of 2MPa, cooling for 15min, standing for 5h, and stripping the highlight mirror surface film to obtain the environment-friendly crystal leather.
The middle layer polyurethane slurry consists of the following raw materials in parts by weight: 70 parts of aqueous polyurethane emulsion (with 35% of solid content), 15 parts of acrylic resin emulsion (with 35% of solid content), 5 parts of pigment paste, 5 parts of wax-separating agent (with 30% of solid content) and 5 parts of casein.
The colorless surface layer polyurethane slurry in the step 3) is prepared from the following raw materials in parts by weight: 0.5 part of POSS-based fluorine-containing polymer, 80 parts of thermoplastic elastomer TPU, 15 parts of thermoplastic elastomer POE, 0.1 part of defoaming agent, 4.4 parts of dispersing agent, and the POSS-based fluorine atoms are gathered on the surface of a formed film, and the water contact angle is 123 +/-3 degrees and the oil contact angle is 120 +/-5 degrees through actual measurement.
The preparation method of the POSS-based fluorine-containing polymer comprises the following steps: 97 parts of perfluorohexyl ethanol, 2 parts of octavinyl POSS and 1 part of Azobisisobutyronitrile (AIBN), and stirring and reacting at 80 ℃ for 4 hours to obtain the POSS-based fluorine-containing polymer.
And 3, during tape casting compounding, stirring all the raw material components of the colorless surface layer polyurethane slurry by using a high-speed stirrer for 10 minutes, uniformly stirring, facilitating the uniform dispersion of all the components, drying at the temperature of 90 ℃, and then putting into a material inlet of an extrusion tape casting compounding machine for melt blending at the temperature of 200-250 ℃ in the melt blending stage.
The third embodiment of the invention is as follows:
the preparation method of the environment-friendly crystal leather comprises the following steps:
1) coating a polyurethane foaming material on a base cloth, carrying out hot-pressing foaming and curing at 110 ℃ under 10MPa, standing for 5h, grinding the back surface of the base cloth by using 600-mesh abrasive cloth through a leather grinder, and removing dust to obtain a semi-finished product a;
2) coating 10-filament-thickness polyurethane slurry of a color intermediate layer on a foaming layer of the semi-finished product a, drying at 120 ℃, and hot-pressing at 120 ℃ and 10MPa through a smooth roller to obtain a mirror-surface semi-finished product b;
3) casting and compounding a layer of colorless surface layer polyurethane with the thickness of 10 silks on the highlight mirror surface film, and drying at 110 ℃ to obtain a semi-finished product c;
4) coating a colorless transparent polyurethane hot-melt adhesive layer on the colorless surface layer polyurethane surface of the semi-finished product d, and drying at 130 ℃ to obtain a semi-finished product d;
5) and (3) thermally bonding the colorless polyurethane sol layer of the semi-finished product d and the mirror surface interlayer of the semi-finished product b at the temperature of 120 ℃ under the pressure of 1MPa, cooling for 10min, standing for 5h, and stripping the highlight mirror surface film to obtain the environment-friendly crystal leather.
The middle layer polyurethane slurry consists of the following raw materials in parts by weight: 65 parts of aqueous polyurethane emulsion (35% solid content), 15 parts of acrylic resin emulsion (35% solid content), 7 parts of pigment paste, 7 parts of wax-separating agent (30% solid content) and 6 parts of casein.
The colorless surface layer polyurethane slurry in the step 3) is prepared from the following raw materials in parts by weight: 1 part of POSS-based fluorine-containing polymer, 85 parts of thermoplastic elastomer TPU, 10 parts of thermoplastic elastomer POE, 0.5 part of defoaming agent, 1 part of dispersing agent, POSS-based fluorine atoms gathered on the surface of a formed film, and the measured water contact angle is about 128 +/-5 degrees and the measured oil contact angle is about 125 +/-5 degrees.
The preparation method of the POSS-based fluorine-containing polymer comprises the following steps: 97 parts of perfluorohexyl ethanol, 2 parts of octavinyl POSS and 1 part of Azobisisobutyronitrile (AIBN), and stirring and reacting at 70 ℃ for 3 hours to obtain the POSS-based fluorine-containing polymer.
And 3, during tape casting compounding, stirring all the raw material components of the colorless surface layer polyurethane slurry by using a high-speed stirrer for 10 minutes, uniformly stirring, facilitating the uniform dispersion of all the components, drying at the temperature of 90 ℃, and then putting into a material inlet of an extrusion tape casting compounding machine for melt blending at the temperature of 200-250 ℃ in the melt blending stage.
The above description is only an embodiment utilizing the technical content of the present disclosure, and any modification and variation made by those skilled in the art can be covered by the claims of the present disclosure, and not limited to the embodiments disclosed.

Claims (4)

1.一种环保水晶革的制备方法,包括以下步骤:1. a preparation method of environmental protection crystal leather, comprises the following steps: 1)涂布发泡树脂:在基布上涂布聚氨酯发泡材料,热压发泡固化,静置4-6h，经磨革机磨平背面，除尘得到半成品a；1) Coating foaming resin: coating polyurethane foam material on the base cloth, hot-pressing foaming and curing, standing for 4-6 hours, smoothing the back side by a leather grinder, and dusting to obtain a semi-finished product a; 2)涂布中间层聚氨酯浆料:在半成品a的发泡层上涂布10-30丝厚度的有色中间层聚氨酯浆料,在100-140℃下烘干，经热压板或热压辊压制后表面发亮，得到半成品b；2) Coating the polyurethane slurry for the intermediate layer: Coat the colored intermediate layer polyurethane slurry with a thickness of 10-30 filaments on the foam layer of the semi-finished product a, dry it at 100-140 °C, and pass it through a hot pressing plate or a hot pressing roller. After pressing, the surface is shiny, and the semi-finished product b is obtained; 3)流延无色面层聚氨酯:在高光镜面膜上流延复合一层厚度10-20丝的无色面层聚氨酯浆料，在100-120℃下烘干，得到半成品c；3) cast colorless surface layer polyurethane: cast a layer of colorless surface layer polyurethane slurry with a thickness of 10-20 filaments on the high-gloss mirror film, and dry at 100-120 ° C to obtain semi-finished product c; 4)涂布无色透明聚氨酯热熔胶层:在半成品c的表面涂布无色透明聚氨酯热熔胶层,在100-140℃下烘干，得到半成品d:4) Coating a colorless and transparent polyurethane hot-melt adhesive layer: coat a colorless and transparent polyurethane hot-melt adhesive layer on the surface of the semi-finished product c, and dry it at 100-140 ° C to obtain a semi-finished product d: 5)贴合:将半成品d的无色聚氨酯熔胶层与半成品b的镜面中间层在1-2MPa压力下热粘合、冷却10-15min，静置3-5h,将高光镜面膜剥离制得环保水晶革；5) Lamination: thermally bond the colorless polyurethane melt adhesive layer of the semi-finished product d and the mirror surface intermediate layer of the semi-finished product b under the pressure of 1-2MPa, cool for 10-15min, stand for 3-5h, and peel off the high-gloss mirror mask to obtain Environmental protection crystal leather; 所述中间层聚氨酯浆料由以下重量份的各原料组成：质量百分比为35％固含量水性聚氨酯乳液60-70份，质量百分比为35％固含量丙烯酸树脂乳液10-20份,颜料膏5-10份,质量百分比为30％固含量离板蜡5-10份,酪素5-10份；The intermediate layer polyurethane slurry is composed of the following raw materials in parts by weight: 60-70 parts by mass of 35% solid content aqueous polyurethane emulsion, 10-20 parts by mass of 35% solid content acrylic resin emulsion, and 5-20 parts by mass of pigment paste. 10 parts, the mass percentage is 30%, and the solid content is 5-10 parts of slate wax and 5-10 parts of casein; 所述步骤3)的无色面层聚氨酯浆料由以下重量份的各原料组成：POSS基含氟聚合物0.5-1.0份,热塑性弹性体TPU 80-90份，热塑性弹性体POE 5-15份，消泡剂0.1-0.5份，分散剂1-5份。The colorless surface layer polyurethane slurry of the step 3) is composed of the following raw materials in parts by weight: 0.5-1.0 parts of POSS-based fluoropolymer, 80-90 parts of thermoplastic elastomer TPU, and 5-15 parts of thermoplastic elastomer POE , 0.1-0.5 parts of defoamer, 1-5 parts of dispersant. 2.根据权利要求1所述的一种环保水晶革的制备方法,其特征在于：所述POSS基含氟聚合物的制备方法是：POSS基含氟聚合物由全氟己基乙醇90-97重量份，八乙烯基POSS 2-7重量份，偶氮二异丁腈(AIBN)0.5-3重量份组成，在65-80℃下将上述组分搅拌反应3-4h，得到POSS基含氟聚合物。2. the preparation method of a kind of environment-friendly crystal leather according to claim 1, is characterized in that: the preparation method of described POSS-based fluoropolymer is: POSS-based fluoropolymer is composed of 90-97 weight perfluorohexyl ethanol parts, 2-7 parts by weight of octavinyl POSS, and 0.5-3 parts by weight of azobisisobutyronitrile (AIBN), and the above components are stirred and reacted at 65-80 ° C for 3-4 h to obtain a POSS-based fluorine-containing polymer thing. 3.根据权利要求1所述的一种环保水晶革的制备方法,其特征在于：步骤3)流延复合时，所述无色面层聚氨酯浆料各原料组分先用高速搅拌机搅拌10-15分钟，在温度80-90℃下烘干，再投入挤出流延复合机入料口熔融共混，熔融共混阶段温度200-250℃。3. the preparation method of a kind of environment-friendly crystal leather according to claim 1 is characterized in that: when step 3) casting compound, each raw material component of described colorless surface layer polyurethane slurry is first stirred with a high-speed mixer for 10- 15 minutes, drying at a temperature of 80-90 ℃, and then put into the feed port of the extrusion casting compound machine to melt and blend, and the temperature of the melt-blending stage is 200-250 ℃. 4.根据权利要求1至3任一权利要求所述的一种环保水晶革的制备方法,其特征在于：所述热压板或热压辊表面设有花纹。4. The preparation method of a kind of environmental protection crystal leather according to any one of claims 1 to 3, characterized in that: the surface of the hot pressing plate or the hot pressing roller is provided with patterns.
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