CN113106765B - Environment-friendly high-flame-retardance multilayer composite polyurethane synthetic leather and preparation method thereof - Google Patents

Environment-friendly high-flame-retardance multilayer composite polyurethane synthetic leather and preparation method thereof Download PDF

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CN113106765B
CN113106765B CN202110390398.4A CN202110390398A CN113106765B CN 113106765 B CN113106765 B CN 113106765B CN 202110390398 A CN202110390398 A CN 202110390398A CN 113106765 B CN113106765 B CN 113106765B
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flame retardant
synthetic leather
flame
parts
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CN113106765A (en
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韩建
曾繁超
苏娟娟
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Gongli New Materials Zhejiang Co ltd
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Gongli New Materials Zhejiang 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
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0013—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using multilayer webs
    • 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
    • D06N3/0086—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
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    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04—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 by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/042—Acrylic polymers
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    • 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
    • D06N2209/06—Properties of the materials having thermal properties
    • D06N2209/067—Flame resistant, fire resistant
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    • 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
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
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  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Abstract

The invention provides an environment-friendly high-flame-retardance multilayer composite polyurethane synthetic leather and a preparation method thereof; the polyurethane synthetic leather comprises a surface layer, an intermediate layer, a bonding layer, a base cloth, a composite layer, a base cloth and a finishing layer which are sequentially attached; the surface layer is made of polyurethane resin added with an organic flame retardant; the intermediate layer and the composite layer are respectively and independently prepared from polyurethane resin containing a flame retardant and a flame retardant synergist; the finishing layer is prepared from polyacrylate emulsion containing a flame retardant and a flame retardant synergist; the adhesive layer is made of polyurethane resin containing a flame retardant. The polyurethane synthetic leather disclosed by the invention has a good flame retardant effect, and keeps the appearance and the negotiation physical properties of the polyurethane synthetic leather on the basis of not affecting the color fastness of the polyurethane synthetic leather. According to the preparation method, a multi-layer composite design is adopted, and different flame retardants and auxiliary agents are added into different layer structures, so that the polyurethane synthetic leather can meet basic use and greatly improve the flame retardant property of the polyurethane synthetic leather.

Description

Environment-friendly high-flame-retardance multilayer composite polyurethane synthetic leather and preparation method thereof
Technical Field
The invention belongs to the technical field of synthetic leather manufacturing, in particular to flame-retardant polyurethane synthetic leather, and particularly relates to environment-friendly high-flame-retardant multilayer composite polyurethane synthetic leather and a preparation method thereof.
Background
The polyurethane synthetic leather has the excellent performances of good glossiness, leather handfeel, wear resistance, folding resistance, cold resistance, air permeability, moisture permeability, ageing resistance and the like, and replaces the best position of natural leather. Polyurethane synthetic leather is widely applied to industries such as automobiles, home furnishings, clothing, shoemaking, bags and the like because of similar appearance to natural leather and better performance.
Although polyurethane synthetic leather has excellent properties and wide uses, it is extremely easy to burn, and releases a large amount of heat and a large amount of smoke and toxic gases upon combustion, so that the application of polyurethane synthetic leather is limited. In order to improve the flame retardant property of polyurethane synthetic leather, it is necessary to flame-retardant the polyurethane synthetic leather with a flame retardant.
The polyurethane synthetic leather treated by the existing flame-retardant finishing technology has poor hand feeling, reduced mechanical property and insufficient flame retardant property, and can not meet the use requirement. Therefore, with the continuous development of the polyurethane synthetic leather market, research and development of polyurethane synthetic leather with high flame retardant property are important to the social and economic significance of the market for functional synthetic leather products.
Disclosure of Invention
The invention aims to solve the problems that the polyurethane synthetic leather has poor flame retardant property and the existing flame retardant finishing technology damages various properties of the polyurethane synthetic leather, and provides the environment-friendly high-flame-retardant multilayer composite polyurethane synthetic leather and the preparation method thereof.
An environment-friendly high-flame-retardance multilayer composite polyurethane synthetic leather comprises a surface layer, an intermediate layer, a bonding layer, base cloth, a composite layer, a base cloth and a finishing layer which are sequentially attached;
the surface layer is made of polyurethane resin added with an organic flame retardant; the intermediate layer and the composite layer are respectively and independently prepared from polyurethane resin containing a flame retardant and a flame retardant synergist;
the finishing layer is prepared from polyacrylate emulsion containing a flame retardant and a flame retardant synergist; the adhesive layer is made of polyurethane resin containing a flame retardant.
According to the technical scheme, through designing the structures of all layers of the polyurethane synthetic leather, different flame retardants and auxiliary agents are added into different hierarchical structures to perform different treatments, so that the polyurethane synthetic leather can meet basic use and achieve a higher flame retardant effect. And the appearance and the negotiation physical properties of the polyurethane synthetic leather are maintained to the maximum extent on the premise of not affecting the performances such as the color fastness of the synthetic leather.
According to the technical scheme, the polyacrylate emulsion with good weather resistance is selected as the finishing layer, so that the production cost can be reduced, and the polyacrylate emulsion is flexible and elastic after film formation, so that the polyacrylate emulsion can be firmly bonded with fabrics and flame retardants, the added flame retardants are not easy to fall off, and the service life is long.
Preferably, the polyurethane resin for preparing the surface layer, the middle layer and the adhesive layer is respectively and independently added with a bridging agent, butanone, color paste, a leveling agent and a light-resistant auxiliary agent.
Preferably, the organic flame retardant is one or a mixture of more of halogen-free phosphate flame retardants (including phosphate esters, substituted phosphonates and the like), phosphaphenanthrene flame retardants and phosphazene flame retardants.
In the technical scheme, the surface layer adopts the liquid phosphorus-containing organic flame retardant and the solid organic flame retardant with good compatibility with the solvent polyurethane resin, so that good wear resistance of the surface layer resin can be maintained, powder flame retardant in the lower layer structure can be prevented from falling off from the surface, and certain flame retardance can be improved.
As a further preferred aspect, the organic flame retardant is selected from one or a mixture of several of dimethyl methylphosphonate, DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), tricresyl phosphate, triethyl phosphate, trimethyl phosphate.
Preferably, in the intermediate layer: the flame retardant is one or a mixture of more of refined ammonium polyphosphate aluminum hypophosphite, alkyl aluminum hypophosphite (such as diethyl aluminum hypophosphite) and melamine polyphosphate, and the average grain diameter is 3-12 μm;
the intermediate layer is: the flame retardant synergist is one or a mixture of more of silicon dioxide, zinc borate, boron phosphate, hydrotalcite, organic montmorillonite, magnesium hydroxide and aluminum hydroxide.
According to the technical scheme, the powder flame retardant and the flame retardant synergist which are subjected to refining treatment are selected as the intermediate layer, so that powder settlement generated by long-time placement of the prepared flame retardant slurry can be slowed down, caking in a slurry tank in the processing process is reduced, and the flame retardant is uniformly dispersed in the intermediate layer. Compared with the low-valence organic P-containing flame retardant, the inorganic powder flame retardant has high valence of P, mainly plays a role in condensed phase flame retardance, can promote resin to form a compact carbon layer in the combustion process, covers the surface of the fabric, and reduces damage.
Preferably, in the adhesive layer, the flame retardant is one or a mixture of a plurality of halogen-free phosphate flame retardants, phosphaphenanthrene flame retardants and phosphazene flame retardants.
When the inorganic powder flame retardant is added into a polymer matrix, the inorganic powder flame retardant can gradually migrate out of the matrix under the change of external conditions (damp heat or external force action) due to poor compatibility, and the phenomena of white frost and the like are generated, so that the appearance and the performance of the product are influenced.
In the technical scheme, the bonding layer adopts organic liquid and solid flame retardants with good compatibility with solvent polyurethane resin, so that the contact between the water-soluble powder flame retardants in the middle layer and water vapor is greatly reduced, the phenomenon of white frost is reduced, and the flame retardance of the resin and the base cloth can be improved.
As a further preferable mode, the flame retardant used in the adhesive layer is one or a mixture of several of dimethyl methylphosphonate, DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), tricresyl phosphate, triethyl phosphate and trimethyl phosphate.
Preferably, the base fabric is a microfiber woven fabric (cloth) or a knitted fabric (cloth).
Preferably, in the composite layer and finishing layer: the flame retardant is respectively and independently selected from expandable graphite and one or more of refined ammonium polyphosphate, aluminum hypophosphite, aluminum alkyl hypophosphite (such as diethyl aluminum hypophosphite) and melamine polyphosphate, and has an average particle size of 3-12 μm;
the composite layer and the finishing layer are as follows: the flame retardant synergist is one or more of silicon dioxide, zinc borate, boron phosphate, hydrotalcite, organic montmorillonite, magnesium hydroxide and aluminum hydroxide.
Preferably, the base fabric is one of fiber braids (cloths).
Preferably, the polyurethane resin is used in an amount of 100 parts by weight: 15-25 parts by weight of a flame retardant in the surface layer; 15-35 parts of flame retardant and 1-5 parts of flame retardant synergist in the middle layer; 10-25 parts by weight of flame retardant in the adhesive layer; 10-40 parts of flame retardant and 1-5 parts of flame retardant synergist in the composite layer;
based on 100 parts by weight of the polyacrylate emulsion: the weight of the flame retardant in the finishing layer is 10-40 parts, and the weight of the flame retardant synergist is 1-5 parts.
As a specific preference, the formulation of the slurry for preparing the surface layer is as follows by mass: 100 parts of polyurethane resin, 3-15 parts of bridging agent, 100 parts of butanone, 15-25 parts of flame retardant, 2-8 parts of color paste, 0.1-2 parts of flatting agent and 1-2 parts of light-resistant auxiliary agent.
As a specific preference, the formulation of the slurry for preparing the intermediate layer comprises the following components in mass: 100 parts of polyurethane resin, 3-15 parts of bridging agent, 100 parts of butanone, 15-35 parts of flame retardant, 1-5 parts of flame retardant synergist, 2-8 parts of color paste, 0.1-2 parts of flatting agent and 1-2 parts of light-resistant auxiliary agent.
As a specific preference, the formulation of the slurry for preparing the adhesive layer is as follows by mass: 100 parts of polyurethane resin, 3-15 parts of bridging agent, 90 parts of butanone, 10-25 parts of flame retardant, 2-8 parts of color paste, 0.1-2 parts of flatting agent and 1-2 parts of light-resistant auxiliary agent.
In the invention, the bridging agent comprises isocyanate bridging agent (such as LA-75) and melamine bridging agent (such as bridging agent 619); the color paste is oily dry color paste; the leveling agent is an organosilicon leveling agent; the light-resistant auxiliary agent comprises a benzophenone light-resistant auxiliary agent and a hindered amine light-resistant auxiliary agent.
Preferably, the thickness of the surface layer is 10 to 20 μm; the thickness of the intermediate layer is 10-25 mu m; the thickness of the adhesive layer is 10-20 mu m; the thickness of the composite layer is 0.5-1 mm.
According to the technical scheme, the refined flame retardant and the flame retardant synergist are compounded for use, and meanwhile, the thickness (0.5-1 mm) of the composite layer is increased, so that the polyurethane synthetic leather can achieve a better flame retardant effect.
A method for preparing the multilayer composite polyurethane synthetic leather according to any one of the above, comprising:
(1) Sequentially coating the surface layer, the middle layer and the adhesive layer on the surface of the release paper, and respectively heating and drying after the surface layer and the middle layer are coated to obtain a coating layer;
(2) The adhesive layer of the coating layer obtained in the step (1) is bonded with the base cloth in a hot-pressing way, dried, stripped from the release paper and rolled to obtain a semi-finished product;
(3) Coating a finishing layer on the back surface of the base fabric; and (3) attaching the base cloth attached with the adhesive layer in the step (2) to the front surface of the base cloth by utilizing the composite layer, and then rolling, heating and curing to obtain the environment-friendly high-flame-retardance multilayer composite polyurethane synthetic leather.
As a further preferred aspect, the release paper is one of a plain paper and an embossed paper.
As a specific preferred aspect, a method for preparing a multilayer composite polyurethane synthetic leather includes:
(1) Spreading polyurethane surface layer slurry on the surface of release paper, heating and drying at 80-120 ℃;
(2) Spreading polyurethane intermediate layer slurry on the surface layer, and heating and drying at 80-120 ℃;
(3) The polyurethane adhesive layer sizing agent is coated on the middle layer in a scraping way to form an adhesive layer;
(4) The adhesive layer is bonded with the base cloth in a hot pressing mode at the temperature of 80-140 ℃, the drying speed is 5-30 m/min, the release paper is peeled off, and the semi-finished synthetic leather is obtained;
(5) Treating the back surface of the base fabric with the flame-retardant finishing layer slurry to form a flame-retardant finishing layer;
(6) And (3) using polyurethane resin added with a flame retardant and a flame retardant synergist, tightly combining the semi-finished product synthetic leather prepared in the step (4) with the surface of the base fabric through a composite process, and then rolling and curing at 80-130 ℃ for 8-16 hours to prepare the environment-friendly high-flame-retardant multilayer composite polyurethane synthetic leather.
According to the preparation method, on the basis of a common synthetic leather dry process, the flame retardant performance of the polyurethane synthetic leather is greatly improved by adding various halogen-free phosphate flame retardants, inorganic powder flame retardants and flame retardant synergists. On the premise of not affecting the performances such as color fastness and the like of the synthetic leather, the flame retardant property of the synthetic leather can meet the requirement of' BS 5852:2006, (source 0 and source 1) "requirements. In addition, the appearance and the negotiation physical properties of the polyurethane synthetic leather are maintained to the maximum extent.
Preferably, the compounding process in the step (6) is one of hot melt adhesive compounding and bi-component PU adhesive compounding.
Compared with the prior art, the invention has the beneficial effects that:
the environment-friendly high-flame-retardance multilayer composite polyurethane synthetic leather disclosed by the invention has a good flame retardance effect, and the appearance and the negotiation physical properties of the polyurethane synthetic leather are maintained to the greatest extent on the basis of not affecting the color fastness and other properties of the polyurethane synthetic leather.
According to the preparation method of the polyurethane synthetic leather, on the basis of a common synthetic leather dry process, a multi-layer composite design is adopted, and different flame retardants and auxiliary agents are added into different layer structures and are subjected to different treatments, so that the polyurethane synthetic leather can meet basic use and the flame retardant property of the polyurethane synthetic leather is greatly improved.
Drawings
FIG. 1 is a schematic diagram of the layered structure of an environment-friendly high-flame-retardance multilayer composite polyurethane synthetic leather fabric.
In the figure: 1. a polyurethane surface layer; 2. a polyurethane intermediate layer; 3. a polyurethane adhesive layer; 4. a base cloth; 5. a composite layer; 6. a base fabric; 7. and a flame retardant finishing layer.
Detailed Description
The following examples further illustrate the present invention, but the present invention is not limited to the following examples.
As shown in fig. 1, the environment-friendly high-flame-retardance multilayer composite polyurethane synthetic leather comprises a surface layer 1, a middle layer 2, a bonding layer 3, a base fabric 4, a composite layer 5, a base fabric 6 and a finishing layer 7 which are sequentially bonded.
The sources of the raw materials in the following examples are: polyurethane resin 0130, 595, color paste RX-851, organosilicon leveling agent 26G from Zhejiang Roxb industries, inc.;
isocyanate bridging agent LA-75 and hot melt adhesive JUR-628 are from Zhejiang maple ocean technologies Co., ltd;
melamine bridging agent 619 from shaoxing chemical industry limited;
polyacrylate emulsion 908 was from Hangzhou point wetting chemical Co., ltd;
ammonium polyphosphate TF-201S is from Shi Yu Shi TaiFeng novel flame retardant Limited liability company, aluminum hypophosphite and diethyl aluminum hypophosphite are from Souzhou alliance chemical technology, and melamine polyphosphate is from Zhenhui star flame retardant Limited company;
the light resistance auxiliary Tinuvin770 and C81 are from Basoff company of Germany;
the superfine fiber woven cloth and the knitted cloth are from Tung rural city Tudianyu short plush factory, the thickness is 0.4+/-0.05 mm, and the gram weight is 120g/m 2 ；
The base fabric was from Ming light warp knitting plant in the Haining city and had a thickness of 2.3.+ -. 0.10mm and a gram weight of 210g/m 2 ；
Example 1
(1) The polyurethane surface layer sizing agent is coated on the surface of the embossing release paper in a scraping way, and is heated and dried at 80 ℃ to form a surface layer of 15 mu m, wherein the sizing agent comprises the following components in percentage by mass: 100 parts of polyurethane resin (0130) (about 20 kg), 3 parts of isocyanate bridging agent (LA-75), 100 parts of butanone, 10 parts of dimethyl methylphosphonate, 5 parts of DOPO, 2 parts of color paste (RX-851), 0.1 part of organosilicon leveling agent (26G) and 2 parts of light resistance auxiliary agent (Tinuvin 770);
(2) The polyurethane intermediate layer slurry is coated on the surface layer in a scraping way, and then heated and dried at 85 ℃ to form a 25 mu m intermediate layer, wherein the slurry comprises the following components in percentage by mass: 100 parts of polyurethane resin (595) (about 20 kg), 4 parts of melamine bridging agent (619), 100 parts of butanone, 15 parts of ammonium polyphosphate (subjected to refining treatment, with the particle size of 12 mu m), 5 parts of aluminum hypophosphite (subjected to refining treatment, with the particle size of 3 mu m), 2 parts of zinc borate, 1 part of silicon dioxide, 3 parts of color paste (RX-851), 0.5 part of organosilicon leveling agent (26G) and 2 parts of light resistance auxiliary agent (Tinuvin 770);
(3) The polyurethane adhesive layer slurry is coated on the intermediate layer in a scraping way to form a 15 mu m adhesive layer, and the slurry comprises the following components in percentage by mass: 100 parts of polyurethane resin (0130) (about 20 kg), 5 parts of isocyanate bridging agent (LA-75), 90 parts of butanone, 20 parts of trimethyl phosphate, 5 parts of DOPO, 3 parts of color paste (RX-851), 2 parts of organosilicon leveling agent (26G) and 1 part of light-resistant auxiliary agent (C81);
(4) Hot-pressing and laminating the adhesive layer and the superfine fiber woven cloth at 100 ℃, drying, peeling off release paper at a speed of 8m/min, and rolling to obtain semi-finished synthetic leather;
(5) The back surface of the base fabric is treated by the flame-retardant finishing layer sizing agent to form a flame-retardant finishing layer, and the formula of the sizing agent comprises the following components in mass: 100 parts (about 30 kg) of polyacrylate emulsion (908), 10 parts of ammonium polyphosphate (refinement treatment, particle size of 12 μm), 5 parts of expandable graphite and 2 parts of zinc borate;
(6) The semi-finished synthetic leather prepared in the step (4) is tightly combined with the surface of the base fabric through a compounding process by using polyurethane resin (595) (about 30 kg) added with the same flame retardant and flame retardant synergist (the components and the dosage are the same) as those in the step (5), and then the semi-finished synthetic leather is rolled and cured for 12 hours at 80 ℃ to prepare the environment-friendly high-flame-retardant multilayer composite polyurethane synthetic leather; wherein the thickness of the composite layer is about 0.8mm.
Example 2
(1) The polyurethane surface layer sizing agent is coated on the surface of the embossing release paper in a scraping way, and is heated and dried at 115 ℃ to form a surface layer of 15 mu m, wherein the sizing agent comprises the following components in mass: 100 parts of polyurethane resin (0130) (about 20 kg), 10 parts of isocyanate bridging agent (LA-75), 100 parts of butanone, 15 parts of tricresyl phosphate, 5 parts of triethyl phosphate, 5 parts of color paste (RX-851), 1 part of organosilicon leveling agent (26G) and 1 part of light resistance auxiliary agent (Tinuvin 770);
(2) The polyurethane intermediate layer slurry is coated on the surface layer in a scraping way, and then heated and dried at 120 ℃ to form a 25 mu m intermediate layer, wherein the slurry comprises the following components in percentage by mass: 100 parts of polyurethane resin (595) (about 20 kg), 12 parts of melamine bridging agent (619), 100 parts of butanone, 5 parts of diethyl aluminum hypophosphite (refinement treatment, particle size of 3 mu m), 15 parts of melamine polyphosphate (refinement treatment, particle size of 5 mu m), 1 part of silicon dioxide, 1 part of magnesium hydroxide, 2 parts of aluminum hydroxide, 8 parts of color paste (RX-851), 2 parts of organosilicon leveling agent (26G) and 1 part of light resistance auxiliary agent (Tinuvin 770);
(3) The polyurethane adhesive layer slurry is coated on the intermediate layer to form a 10 mu m adhesive layer, and the slurry comprises the following components in mass: 100 parts of polyurethane resin (595) (about 20 kg), 10 parts of melamine bridging agent (619), 90 parts of butanone, 15 parts of tricresyl phosphate, 5 parts of DOPO, 2 parts of color paste (RX-851), 1 part of organosilicon leveling agent (26G) and 1 part of light-resistant auxiliary agent (C81);
(4) Hot-pressing and laminating the adhesive layer and the superfine fiber woven cloth at 120 ℃, drying, peeling off release paper at a speed of 10m/min, and rolling to obtain semi-finished synthetic leather;
(5) The back surface of the base fabric is treated by the flame-retardant finishing layer sizing agent to form a flame-retardant finishing layer, and the formula of the sizing agent comprises the following components in mass: 100 parts (about 30 kg) of polyacrylate emulsion (908), 8 parts of ammonium polyphosphate (refinement treatment, particle size of 12 μm), 2 parts of diethyl aluminum hypophosphite (refinement treatment, particle size of 3 μm), 2 parts of melamine polyphosphate (refinement treatment, particle size of 5 μm), 8 parts of expandable graphite and 2 parts of boron phosphate;
(6) The polyurethane resin (595) (about 30 kg) added with the same flame retardant and flame retardant synergist as in the step (5) is used for realizing the tight combination with the surface of the base fabric through a composite process, and then the base fabric is rolled and cured for 8 hours at 100 ℃ to prepare the environment-friendly high-flame-retardant multilayer composite polyurethane synthetic leather; wherein the thickness of the composite layer is about 0.7mm.
Comparative example 1 (addition of a gas phase flame retardant organic flame retardant alone in the middle layer)
This comparative example differs from example 1 in that:
in the step (2), the formula of the slurry of the middle layer comprises the following components in mass: 100 parts of polyurethane resin (595) (about 20 kg), 4 parts of melamine bridging agent (619), 100 parts of butanone, 10 parts of dimethyl methylphosphonate, 7 parts of tricresyl phosphate, 8 parts of triethyl phosphate, 3 parts of color paste (RX-851), 0.5 part of organosilicon leveling agent (26G) and 2 parts of light resistance auxiliary agent (Tinuvin 770);
comparative example 2 (addition of inorganic powder flame retardant alone and flame retardant synergist to surface layer resin)
This comparative example differs from example 1 in that:
in the step (1), the formula of the slurry of the surface layer comprises the following components in mass percent: 100 parts of polyurethane resin (0130) (about 20 kg), 3 parts of isocyanate bridging agent (LA-75), 100 parts of butanone, 12 parts of ammonium polyphosphate (refinement treatment, particle size of 12 mu m), 3 parts of melamine polyphosphate (refinement treatment, particle size of 5 mu m), 1 part of silicon dioxide, 2 parts of color paste (RX-851), 0.1 part of organosilicon leveling agent (26G) and 2 parts of light resistance auxiliary agent (Tinuvin 770);
comparative example 3 (composite layer not flame retardant)
This comparative example differs from example 2 in that:
and (6) using polyurethane resin (595) (about 30 kg) without adding flame retardant and flame retardant synergist, tightly combining the semi-finished synthetic leather prepared in the step (4) with the surface of the base fabric through a composite process, and then rolling and curing for 8 hours at 100 ℃ to prepare the environment-friendly high-flame-retardance multilayer composite polyurethane synthetic leather.
Comparative example 4 (non-flame finishing of base fabrics)
This comparative example differs from example 2 in that: and (5) performing no flame retardant treatment on the back surface of the base fabric.
The polyurethane synthetic leathers prepared in examples 1 to 2 and comparative examples 1 to 4 were subjected to the surface color fastness test (see GB/T8949-2008), the LOI (limiting oxygen index) test (see GB/T5455-1997), and the flammability evaluation test (see BS 5852-2006), respectively, and the test structures are shown in the following tables.
TABLE 1 results of Performance test of polyurethane synthetic leather obtained in examples 1 to 2 and comparative examples 1 to 4
Figure BDA0003016486700000091
As can be seen from Table 1, the polyurethane synthetic leather prepared in examples 1 to 2 and comparative examples 1 to 2 can pass through BS5852-2006: and (3) testing the Source0 and the Source1, wherein the examples 1-2 realize the environment-friendly and efficient flame retardance of the multilayer composite polyurethane synthetic leather under the combined action of various phosphate flame retardants, inorganic powder flame retardants and flame retardant synergists, and the limiting oxygen index reaches more than 28 percent, and the surface color fastness is more than or equal to grade 3.
Comparative example 1 flame retardant due to lack of condensed phase in the middle layer, the flame spread rate during combustion is relatively fast and the limiting oxygen index is low. Comparative example 2 the color fastness was affected by the fact that the powder particles partially detached from the matrix during the abrasion process because of the presence of the inorganic powder flame retardant on the surface layer. Comparative example 3 and comparative example 4 have a low limiting oxygen index, although having a certain flame retardancy, because of the presence of a non-flame retardant portion in the layer structure. Through the design of flame-retardant function of each structural layer of the synthetic leather, the environment-friendly high-flame-retardant multilayer composite polyurethane synthetic leather meeting the related test requirements can be prepared.
The present invention is not limited to the preferred embodiments, and any person skilled in the art should make some changes or modifications to the equivalent embodiments without departing from the scope of the present invention, but any simple modification, equivalent changes and modifications to the above embodiments according to the technical principles of the present invention shall fall within the scope of the present invention.

Claims (5)

1. The environment-friendly high-flame-retardance multilayer composite polyurethane synthetic leather is characterized by comprising a surface layer, an intermediate layer, a bonding layer, base cloth, a composite layer, a base cloth and a finishing layer which are sequentially attached;
the surface layer is made of polyurethane resin added with an organic flame retardant; the intermediate layer and the composite layer are respectively and independently prepared from polyurethane resin containing a flame retardant and a flame retardant synergist;
the finishing layer is prepared from polyacrylate emulsion containing a flame retardant and a flame retardant synergist; the adhesive layer is made of polyurethane resin containing a flame retardant;
the organic flame retardant is one or a mixture of a plurality of halogen-free phosphate flame retardant, phosphaphenanthrene flame retardant and phosphazene flame retardant;
the intermediate layer is: the flame retardant is one or a mixture of more of ammonium polyphosphate, aluminum hypophosphite, aluminum alkyl hypophosphite and melamine polyphosphate after refining treatment, and the average grain diameter is 3-5 mu m; the flame retardant synergist is one or a mixture of more of silicon dioxide, zinc borate, boron phosphate, hydrotalcite, organic montmorillonite, magnesium hydroxide and aluminum hydroxide;
in the bonding layer, the flame retardant is one or a mixture of a plurality of halogen-free phosphate flame retardants, phosphaphenanthrene flame retardants and phosphazene flame retardants;
the composite layer and the finishing layer are as follows: the flame retardants are respectively and independently selected from one or a mixture of more of expandable graphite, refined ammonium polyphosphate, aluminum hypophosphite, aluminum alkyl hypophosphite and melamine polyphosphate, and the average grain diameter is 3-12 mu m; the flame retardant synergist is one or a mixture of several of silicon dioxide, zinc borate, boron phosphate, hydrotalcite, organic montmorillonite, magnesium hydroxide and aluminum hydroxide;
the polyurethane resin for preparing the surface layer, the middle layer and the adhesive layer is respectively and independently added with a bridging agent, butanone, color paste, a leveling agent and a light-resistant auxiliary agent.
2. The multilayer composite polyurethane synthetic leather according to claim 1, wherein the weight of the polyurethane resin is 100 parts: 15-25 parts by weight of a flame retardant in the surface layer; 15-35 parts of flame retardant and 1-5 parts of flame retardant synergist in the middle layer; 10-25 parts by weight of flame retardant in the adhesive layer; 10-40 parts of flame retardant and 1-5 parts of flame retardant synergist in the composite layer;
based on 100 parts by weight of the polyacrylate emulsion: the weight of the flame retardant in the finishing layer is 10-40 parts, and the weight of the flame retardant synergist is 1-5 parts.
3. The multilayer composite polyurethane synthetic leather according to claim 1, wherein the thickness of the surface layer is 10 to 20 μm; the thickness of the intermediate layer is 10-25 mu m; the thickness of the adhesive layer is 10-20 mu m.
4. A method for producing the multilayer composite polyurethane synthetic leather according to any one of claims 1 to 3, comprising:
(1) Sequentially coating the surface layer, the middle layer and the adhesive layer on the surface of the release paper, and respectively heating and drying after the surface layer and the middle layer are coated to obtain a coating layer;
(2) The adhesive layer of the coating layer obtained in the step (1) is bonded with the base cloth in a hot-pressing way, dried, stripped from the release paper and rolled to obtain a semi-finished product;
(3) Coating a finishing layer on the back surface of the base fabric; and (3) attaching the semi-finished product in the step (2) to the front surface of the base fabric by utilizing a composite layer, and then rolling, heating and curing to obtain the environment-friendly high-flame-retardance multilayer composite polyurethane synthetic leather.
5. The method for preparing a multilayer composite polyurethane synthetic leather according to claim 4, comprising:
(1) Spreading polyurethane surface layer slurry on the surface of release paper, heating and drying at 80-120 ℃;
(2) Spreading polyurethane intermediate layer slurry on the surface layer, and heating and drying at 80-120 ℃;
(3) The polyurethane bonding layer sizing agent is coated on the middle layer in a scraping way to form a coating layer with a bonding layer;
(4) Hot-pressing and laminating the adhesive layer of the coating layer with the base cloth at 80-140 ℃, drying at a speed of 5-30 m/min, stripping the release paper and rolling to obtain semi-finished synthetic leather;
(5) Treating the back surface of the base fabric with the flame-retardant finishing layer slurry to form a flame-retardant finishing layer;
(6) And (3) taking polyurethane resin added with a flame retardant and a flame retardant synergist as composite layer slurry, tightly combining the semi-finished product synthetic leather prepared in the step (4) with the front surface of the base fabric through a composite process, and then rolling and curing at 80-130 ℃ for 8-16 hours to prepare the environment-friendly high-flame-retardant multilayer composite polyurethane synthetic leather.
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