CN106835732B - Sewing-free hot melt adhesive TPU leather and preparation method thereof - Google Patents

Sewing-free hot melt adhesive TPU leather and preparation method thereof Download PDF

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CN106835732B
CN106835732B CN201710094594.0A CN201710094594A CN106835732B CN 106835732 B CN106835732 B CN 106835732B CN 201710094594 A CN201710094594 A CN 201710094594A CN 106835732 B CN106835732 B CN 106835732B
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parts
film
hot melt
melt adhesive
tpu
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CN106835732A (en
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何建雄
王一良
杨博
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DONGGUAN XIONGLIN NEW MATERIAL TECHNOLOGY CO LTD
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DONGGUAN XIONGLIN NEW MATERIAL TECHNOLOGY CO LTD
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, 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
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12Artificial 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
    • D06N3/14Artificial 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
    • D06N3/145Artificial 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
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, 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
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056Artificial 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
    • D06N3/0059Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, 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
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0086Artificial 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
    • D06N3/0095Artificial 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
    • D06N3/0097Release surface, e.g. separation sheets; Silicone papers
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, 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
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12Artificial 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
    • D06N3/14Artificial 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
    • D06N3/142Artificial 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 mixture of polyurethanes with other resins in the same layer
    • D06N3/144Artificial 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 mixture of polyurethanes with other resins in the same layer with polyurethane and polymerisation products, e.g. acrylics, PVC
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, 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
    • D06N2211/00Specially adapted uses
    • D06N2211/12Decorative or sun protection articles
    • D06N2211/28Artificial leather

Abstract

The invention provides a sewing-free hot melt adhesive TPU leather and a preparation method thereof. The bonding strength of the sewing-free hot melt adhesive TPU film is greatly improved; the comprehensive physical properties of the no-sewing hot melt adhesive TPU film can be further improved by using the specific PU film, the TPU film and the EVA foaming film, and PVC and PU artificial leather can be completely replaced; the cable does not change quality at the high temperature of 150 ℃, and has the performances of wear resistance, heat resistance and flexing resistance.

Description

Sewing-free hot melt adhesive TPU leather and preparation method thereof
Technical Field
The invention belongs to the technical field of leather, and relates to a sewing-free hot melt adhesive TPU leather and a preparation method thereof.
Background
In the production industries of clothes, shoes, bags, handbags, seats, military industry and the like, all fabrics attached to the products are connected in a traditional needle sewing mode. The production mode has the advantages of high labor intensity and high production cost, and the problems of easy breakage, tearing, peeling and the like of seams of the product under the action of external force seriously affect the service life and the quality of the product, and obviously increase the consumption cost. And because all the current product fabrics mostly adopt PVC leather, the PVC material contains PVC, ethylhexylamine and other toxic elements, has carcinogenic effect on human bodies and is extremely unsafe to use, most of the glue melting materials used in leather clothes in the prior art are industrial liquid glue, solid glue and PU glue, most of the glue melting materials have toxicity, and have certain defects in the aspects of elasticity, acid resistance, alkali resistance, water washing resistance, dry cleaning resistance, tensile force resistance, adhesion force and the like, and the PVC fabric belongs to an undesirable environment-friendly adhesive material.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a sewing-free hot melt adhesive TPU leather and a preparation method thereof, wherein the bonding strength of the contained TPU hot melt adhesive is greatly improved; the comprehensive physical properties of the no-sewing hot melt adhesive TPU film can be further improved by using the specific PU film, the TPU film and the EVA foaming film, and PVC and PU artificial leather can be completely replaced; the cable does not change quality at the high temperature of 150 ℃, and has the performances of wear resistance, heat resistance and flexing resistance.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the purposes of the invention is to provide a sewing-free hot melt adhesive TPU leather, which comprises at least one layer of PU film, at least one layer of TPU hot melt adhesive film and release paper or release film optionally matched with the TPU hot melt adhesive film, wherein the TPU hot melt adhesive film is arranged on one side of the PU film;
the PU film can be 1 layer, 2 layers, 3 layers, 4 layers, 5 layers, 6 layers, 7 layers or 10 layers and the like, and the TPU hot melt adhesive film can be 1 layer, 2 layers, 3 layers, 4 layers, 5 layers, 6 layers, 7 layers or 10 layers and the like;
the TPU hot melt adhesive film comprises the following raw material components in parts by weight:
30-40 parts of polyester polyol, such as 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts or 39 parts; 35-45 parts of polyether polyol, such as 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, 42 parts or 44 parts; 20-50 parts of diisocyanate, such as 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts or 46 parts; 0.5-2 parts of catalyst, such as 0.8 part, 1.0 part, 1.2 parts, 1.5 parts or 1.8 parts; 0.5-10 parts of chain extender, such as 0.8 part, 1 part, 2 parts, 3 parts, 5 parts, 8 parts or 9 parts and the like; 0-1 part of antioxidant, such as 0.1 part, 0.3 part, 0.5 part, 0.7 part or 0.9 part; 0-4 parts of flame retardant, such as 0.5 part, 1 part, 2 parts, 3 parts or 3.5 parts; 0-4 parts of toughening agent, such as 0.5 part, 1 part, 1.2 parts, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts or 3.8 parts; the polyester polyol is a hydroxyl-terminated polyester diol with the weight-average molecular weight of 500-1000, which is prepared by the polycondensation reaction of aliphatic diol and aliphatic dicarboxylic acid at 120-200 ℃, such as 600 parts, 700 parts, 800 parts, 900 parts or 950 parts of the weight-average molecular weight; the polyether polyol is tetrahydrofuran-propylene oxide copolymerization diol with the weight-average molecular weight of 600-900, such as 650 parts, 700 parts, 800 parts or 850 parts; the diisocyanate is a benzylidene diisocyanate.
The temperature of the polycondensation reaction can be 130 ℃, 150 ℃, 180 ℃, 190 ℃ or 195 ℃ and the like.
The aliphatic diol is selected from any one or a combination of at least two of ethylene glycol, diethylene glycol, propylene glycol, methyl propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 3-butanediol, 1,5 pentanediol and dodecyl hexanediol, and is preferably a mixture of ethylene glycol and dodecyl hexanediol in a mass ratio of (1-5): 1, such as a mass ratio of 2:1, 3:1, 4:1 or 4.5: 1. Typical but non-limiting combinations are ethylene glycol and diethylene glycol, propylene glycol, methyl propylene glycol and 1, 4-butanediol, 1, 6-hexanediol and 1, 3-butanediol, 1, 5-pentanediol and dodecyl hexanediol.
Preferably, the aliphatic dicarboxylic acid is selected from any one or a combination of at least two of adipic acid, fumaric acid, maleic acid and suberic acid, and is preferably a mixture of adipic acid and suberic acid in a mass ratio of (2-6): 1, such as a mass ratio of 3:1, 4:1, 5:1 or 5.5: 1. Typical but non-limiting combinations are adipic acid and fumaric acid, maleic acid and suberic acid, adipic acid, fumaric acid and maleic acid.
Preferably, the catalyst is selected from any one of dibutyltin dilaurate, triethanolamine or dimorpholinodiethyl ether or a combination of at least two of the foregoing. Typical but non-limiting combinations are dibutyltin dilaurate with triethanolamine, triethanolamine with dimorpholinodiethyl ether.
Preferably, the chain extender is selected from any one of 1, 6-hexanediol, methyl propylene glycol or 1, 4-butanediol or a combination of at least two thereof. Typical but non-limiting combinations are 1, 6-hexanediol and methyl propanediol, 1, 6-hexanediol and 1, 4-butanediol, 1, 6-hexanediol, methyl propanediol and 1, 4-butanediol.
Preferably, the antioxidant is selected from 2, 6-tertiary butyl-4-methylphenol and/or pentaerythrityl tetrakis { β - (3, 5-tertiary butyl-4-hydroxyphenyl) propionate }.
Preferably, the flame retardant comprises the following components in percentage by mass: 18 to 80 percent of polypropylene with a melt index of 0.5 to 15.0g/10min, 1 to 50 percent of polyethylene with a melt index of 0.01 to 2.0g/10min, 15 to 60 percent of inorganic filler selected from one or the combination of at least two of powdery talc, kaolinite, sericite, silicon dioxide or diatomite, and 0.5 to 60 percent of organic halide selected from decabromodiphenyl ether and/or dodecachlorododeca-dihydrobenzene cyclooctene.
The polypropylene can be 20%, 30%, 35%, 40%, 45%, 50%, 60%, 70%, 75% or the like by mass, and the melt index of the polypropylene can be 0.6g/10min, 0.8g/10min, 1.0g/10min, 2.0g/10min, 3.0g/10min, 5.0g/10min, 7.0g/10min, 8.0g/10min, 9.0g/10min, 10.0g/10min, 12.0g/10min, 13.0g/10min, 14.0g/10min or the like; the mass percentage content of the polyethylene can be 3%, 5%, 10%, 20%, 30%, 40% or 45%, etc., and the melt index of the polyethylene can be 0.03g/10min, 0.05g/10min, 0.08g/10min, 0.1g/10min, 0.3g/10min, 0.5g/10min, 0.8g/10min, 1.2g/10min, 1.5g/10min or 1.8g/10min, etc.; the inorganic filler may be present in an amount of 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, etc., by weight, with typical, but non-limiting, combinations of inorganic fillers such as powdered talc and kaolinite, sericite and silica, silica and diatomaceous earth; the organic halide may be present in an amount of 1%, 3%, 5%, 10%, 20%, 30%, 40%, 50%, 55%, or the like, by mass.
Preferably, the toughening agent is obtained by mixing and extruding polyethylene elastomer, linear polyethylene, polypropylene and an anti-aging agent.
Preferably, the TPU hot melt adhesive film further comprises 1-10 parts of a tackifying resin, such as 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or 9 parts, and the tackifying resin is selected from any one or a combination of at least two of polyethylene-vinyl acetate copolymer, hydroxyl-terminated thermoplastic polyester or hydrogenated rosin resin. Typical but non-limiting combinations are polyethylene-vinyl acetate copolymers with hydroxyl terminated thermoplastic polyesters, polyethylene-vinyl acetate copolymers with hydrogenated rosin resins.
Preferably, the thickness of the TPU hot melt adhesive film is 0.01-1.0 mm, such as 0.02mm, 0.03mm, 0.05mm, 0.1mm, 0.3mm, 0.5mm, 0.7mm or 0.9 mm.
The thickness of the PU film is 0.01-3.0 mm, such as 0.02mm, 0.03mm, 0.05mm, 0.06mm, 0.08mm, 0.1mm, 0.2mm, 0.3mm, 0.5mm, 1.0mm, 2.0mm or 2.5 mm.
Preferably, the PU film comprises the following raw material components in parts by weight:
32-38 parts of poly propylene glycol adipate glycol with the weight-average molecular weight of 1000-2000, such as 33 parts, 34 parts, 35 parts, 36 parts or 37 parts; 30-35 parts of tetrahydrofuran-propylene oxide copolyol with the weight-average molecular weight of 1000-1500, such as 31 parts, 32 parts, 33 parts or 34 parts; 22-38 parts of isophorone diisocyanate, such as 23 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts or 37 parts; 0.5-2 parts of catalyst, such as 0.8 part, 1 part, 1.2 parts, 1.5 parts or 1.8 parts; 0.5-5 parts of chain extender, such as 0.8 part, 1.0 part, 2.0 parts, 3.0 parts, 4.0 parts or 4.5 parts and the like;
the weight average molecular weight of the poly (propylene adipate) glycol can be 1200-1300, 1350-1400, 1500-1600, 1700-1800 or 1800-1900, etc.; the weight average molecular weight of the tetrahydrofuran-propylene oxide copolymerized glycol can be 1100-1200, 1300-1400 or 1200-1300.
Preferably, the chain extender is selected from any one or a combination of at least two of 1, 6-hexanediol, methyl propanediol or 1, 4-butanediol, typical but not limiting combinations are 1, 6-hexanediol and methyl propanediol, 1, 6-hexanediol and 1, 4-butanediol, 1, 6-hexanediol, methyl propanediol and 1, 4-butanediol, preferably a mixture of 1, 6-hexanediol and 1, 4-butanediol with a mass ratio of (2-5): 1, such as 3:1, 4:1 or 4.5:1, etc.
Preferably, the raw material components of the PU film further include 1-3 parts by weight of a colorant, such as 1.0 part, 1.5 parts, 2 parts, 2.5 parts, or 2.8 parts.
The thickness of the release paper or the release film is 0.01-1.0 mm, such as 0.03mm, 0.05mm, 0.08mm, 0.1mm, 0.12mm, 0.15mm, 0.2mm, 0.3mm, 0.5mm or 0.8 mm.
Preferably, the material of the release paper or release film is selected from any one or a combination of at least two of PVC, EVA, PP or PE, such as, typically but not limited to, PVC and EVA, PP and PE, EVA, PP and PE.
Exempt from sewing hot melt adhesive TPU leather still includes at least one deck TPU membrane (like 2 layers, 3 layers, 4 layers, 5 layers, 6 layers, 7 layers or 10 layers etc.), the TPU membrane sets up between PU membrane and TPU hot melt adhesive membrane, the TPU membrane includes according to parts by weight: 86-98 parts of thermoplastic polyurethane particles, such as 87 parts, 88 parts, 89 parts, 90 parts, 92 parts, 93 parts or 95 parts; 0.1-3 parts of slipping agent, such as 0.1 part, 0.2 part, 0.3 part, 0.5 part, 1.0 part, 1.5 parts or 2.0 parts; 0.1-1 part of antioxidant, such as 0.2 part, 0.3 part, 0.5 part, 0.8 part or 0.9 part; 0.1-2 parts of anti-ultraviolet agent, such as 0.2 part, 0.5 part, 0.8 part, 1.2 parts, 1.5 parts or 1.8 parts; 0.1-3 parts of filler, such as 0.3 part, 0.5 part, 0.6 part, 0.8 part, 1.0 part, 1.2 parts, 1.8 parts, 2.1 parts, 2.5 parts or 2.8 parts;
the thermoplastic polyurethane particle comprises the following raw material components in parts by weight:
5-10 parts of poly propylene glycol adipate glycol with the weight-average molecular weight of 2200-3200, such as 6 parts, 7 parts, 8 parts, 9 parts or 9.5 parts; 20-25 parts of polyhexamethylene carbonate glycol with the weight-average molecular weight of 1000-2000, such as 21, 22, 23 or 24; 20-25 parts of polytetramethylene ether glycol with the weight-average molecular weight of 1000-1500, such as 21, 22, 23, 24 or 24.5; 12-18 parts of 1, 5-naphthalene diisocyanate, such as 13 parts, 14 parts, 15 parts, 16 parts, 17 parts or 17.5 parts; 18-25 parts of benzylidene diisocyanate, such as 19 parts, 20 parts, 21 parts, 22 parts, 23 parts or 24 parts; 4-6 parts of a chain extender, such as 4.5 parts, 5 parts, 5.5 parts and the like; 0.5-1 part of catalyst, such as 0.6 part, 0.7 part, 0.8 part or 0.9 part;
the weight average molecular weight of the poly (trimethylene adipate) glycol is 2200-3200, such as 2300-2400, 2500-2600 or 2800-3000; the weight average molecular weight of the poly hexamethylene carbonate diol is 1000-2000, such as 1100-1200, 1300-1400, 1600-1800 or 1700-1900, etc.; the weight average molecular weight of the polytetramethylene ether glycol is 1000-1500, such as 1100-1200, 1300-1400 or 1200-1450.
Preferably, the slipping agent is selected from any one of silicone oil, methyl silicone oil, water-soluble silicone oil or hydroxyl silicone oil or the combination of at least two of the silicone oil, the methyl silicone oil, the water-soluble silicone oil and the hydroxyl silicone oil. Typical but non-limiting combinations are silicone oils and methyl silicone oils, water soluble silicone oils and hydroxy silicone oils.
Preferably, the antioxidant is selected from any one of or a combination of at least two of tetrakis [ methylene-3, 3 ', 5- (di-tert-butyl-4-hydroxy-phenyl) propionate ] pentaerythritol ester, N' -bis [ [3- (3,5) -di-tert-butyl-4-hydroxyphenyl ] propionyl ] hexanediamine, tris [2, 4-di-tert-butylphenyl ] phosphite or pentaerythritol diphosphite stearyl ester. Typical but non-limiting combinations are tetra [ methylene-3, 3 ', 5- (di-tert-butyl-4-hydroxy-phenyl) propionate ] pentaerythritol ester with N, N' -bis [ [3- (3,5) -di-tert-butyl-4-hydroxyphenyl ] propanoyl ] hexanediamine, tris [2, 4-di-tert-butylphenyl ] phosphite with pentaerythritol diphosphite stearyl ester.
Preferably, the anti-ultraviolet agent is selected from any one of benzoic acid type anti-ultraviolet agents, xylene ketone type anti-ultraviolet agents or benzotriazole type anti-ultraviolet agents or a combination of at least two of the benzoic acid type anti-ultraviolet agents and the xylene ketone type anti-ultraviolet agents. Typical but non-limiting combinations are benzoic and xylene based UV blockers, xylene based UV blockers and benzotriazoles based UV blockers.
Preferably, the filler is selected from any one or a combination of at least two of talc, diatomaceous earth, calcium carbonate or titanium dioxide. Typical but non-limiting combinations are talc with diatomaceous earth, calcium carbonate with titanium dioxide.
Preferably, the TPU film further comprises 0.01 to 50 parts by weight of a color modifier, such as 0.02 part, 0.05 part, 0.08 part, 0.1 part, 0.3 part, 0.5 part, 1 part, 2 parts, 5 parts, 8 parts, 10 parts, 20 parts, 30 parts, 40 parts or 45 parts, and the like, wherein the color modifier is selected from any one of color master batch, carbon black or toner or a combination of at least two of color master batch, carbon black and toner.
Preferably, the thickness of the TPU film is 0.01 to 5.0mm, such as 0.1mm, 0.2mm, 0.3mm, 0.5mm, 0.8mm, 1.0mm, 2.0mm, 3.0mm, 4.0mm, or 4.5mm, and the like.
The sewing-free hot melt adhesive TPU leather further comprises at least one layer of non-TPU film (such as 2 layers, 3 layers, 4 layers, 5 layers, 6 layers, 7 layers or 10 layers and the like), the non-TPU film is arranged between the PU film and the TPU hot melt adhesive film, and the non-TPU film comprises any one or combination of at least two of PU foaming film, EVA foaming film or PVC foaming film. Typical but non-limiting non-TPU films can be PU foam films and EVA foam films, PU foam films and PVC foam films.
The non-TPU film may be 2, 3, 4, 5, 6, or 10 layers, etc.
Preferably, the non-TPU film has a thickness of 0.01 to 3.0mm, such as 0.05mm, 0.08mm, 0.1mm, 0.2mm, 0.5mm, 1.0mm, 1.5mm, 2mm, or 2.5mm, and the like.
The sewing-free hot melt adhesive TPU leather further comprises at least one layer of non-TPU film (such as 2 layers, 3 layers, 4 layers, 5 layers, 6 layers, 7 layers or 10 layers and the like), the non-TPU film is arranged between the TPU film and the TPU hot melt adhesive film, and the non-TPU film comprises any one or combination of at least two of a PU foaming film, an EVA foaming film or a PVC foaming film. Typical but non-limiting non-TPU films can be PU foam films and EVA foam films, PU foam films and PVC foam films.
The non-TPU film may be 2, 3, 4, 5, 6, or 10 layers, etc.
Preferably, the non-TPU film has a thickness of 0.01 to 3.0mm, such as 0.05mm, 0.08mm, 0.1mm, 0.2mm, 0.5mm, 1.0mm, 1.5mm, 2mm, or 2.5mm, and the like.
The EVA foaming film comprises the following components in parts by weight: 30 to 90 parts of main materials, such as 35 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts or 85 parts, etc., 0.1 to 30 parts of fillers, such as 0.5 part, 1 part, 3 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 20 parts or 25 parts, etc., 1 to 20 parts of foaming agents, such as 2 parts, 3 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts or 18 parts, etc., 0.01 to 5 parts of foaming promoters, such as 0.03 parts, 0.05 parts, 0.1 parts, 0.3 parts, 0.5 parts, 1 part, 2 parts, 3 parts or 4 parts, etc., 0.01 to 5 parts of lubricants, such as 0.03 parts, 0.05 parts, 0.1 part, 0.3 parts, 0.5 parts, 0.8 parts, 1 part, 2 parts, 3 parts or 4 parts, etc., 0.01 to 10 parts of antistatic agents, such as 0.5 parts, 1 part, 2 parts, 3 parts, 5 parts, or 4 parts of flame retardants, etc.; the main material comprises an ethylene-vinyl acetate copolymer, a thermoplastic polyurethane elastomer and a polyolefin thermoplastic elastomer in a mass ratio of 50 (1-3) to (5-10), wherein the mass ratio is 50:2:7, 50:2.5:8 or 50:1.5: 9.
Preferably, the thickness of the EVA foaming film is 0.1-10.0 mm, such as 0.2mm, 0.5mm, 1.0mm, 2.0mm, 4.0mm, 5.0mm, 6.0mm, 7.0mm, 8.0mm, or 9.0 mm.
Preferably, the filler is selected from calcium carbonate and/or talcum powder with a particle size of 50-1000 meshes, such as 60-100 meshes, 200-300 meshes, 400-500 meshes, 600-800 meshes or 700-900 meshes.
Preferably, the blowing agent is AC-3000H.
Preferably, the foaming promoter is zinc oxide powder.
Preferably, the lubricant is stearic acid.
Preferably, the flame retardant is an organic flame retardant and/or an inorganic flame retardant.
Preferably, the raw material components of the EVA foaming film further include 0.1-10 parts by weight of a color modifier, such as 0.1 part, 0.5 part, 1 part, 3 parts, 5 parts, 7 parts, 9 parts or 10 parts, and the color modifier is selected from any one of color master batch, color glue or toner or a combination of at least two of the color master batch, the color glue or the toner.
One of the purposes of the invention is also to provide a preparation method of the sewing-free hot melt adhesive TPU leather, which comprises the following steps:
(1) carrying out opposite-pressing compounding on the TPU hot melt adhesive film obtained by casting and the TPU film or the non-TPU film obtained by casting optionally to form a first composite film;
(2) the first composite film and the PU film are oppositely pressed and compounded to form a second composite film;
(3) and optionally bonding a release paper or a release film on the second composite film to form the sewing-free hot melt adhesive TPU leather.
The pressing and compounding in the step (1) and the step (2) are carried out by adopting at least two rollers, such as 2 rollers, 3 rollers, 4 rollers, 5 rollers, 8 rollers or 10 rollers.
Preferably, the surface of the roller is provided with a pattern.
The skilled in the art can prepare each film by a tape casting method according to the raw material components of the TPU hot melt adhesive film, the TPU film, the non-TPU film or the PU film, and can obtain a proper preparation method only according to practical operation experience and limited tests. Therefore, the present invention is not described in detail with respect to the preparation process of each film.
Compared with the prior art, the invention has the beneficial effects that:
(1) the hot melt adhesive TPU film without sewing provided by the invention adopts a new TPU hot melt adhesive film, so that the bonding strength is greatly improved and can reach 10.0Kg/25mm at most.
(2) The comprehensive physical properties of the non-sewing hot melt adhesive TPU film can be further improved by using the specific PU film, the TPU film and the EVA foaming film, and PVC and PU artificial leather can be completely replaced.
(3) The sewing-free hot melt adhesive TPU leather provided by the invention does not undergo quality change at a high temperature of 150 ℃, is easy to adhere to the surfaces of materials such as cloth, rubber (plastic) leather, wood and the like, can be widely applied to the production and manufacturing industries such as clothing, shoes, handbags, bags, seats, architectural decorations and the like, and the adhered product is resistant to water washing and dry cleaning and has the performances of wear resistance, heat resistance and flexing resistance.
Drawings
Fig. 1 is a schematic structural diagram of a no-sewing hot melt adhesive TPU leather provided in embodiment 2, which does not include a release film.
Fig. 2 is a schematic structural diagram of the no-sewing hot melt adhesive TPU leather provided in embodiment 2, which includes a release film.
Fig. 3 is a schematic structural diagram of the no-sewing hot melt adhesive TPU leather provided in embodiment 3, which does not include a release film.
Fig. 4 is a schematic structural diagram of the no-sewing hot melt adhesive TPU leather provided in embodiment 3, which includes a release film.
Fig. 5 is a schematic structural diagram of the no-sewing hot melt adhesive TPU leather provided in embodiment 4, which includes a release film.
Fig. 6 is a schematic structural diagram of the no-sewing hot melt adhesive TPU leather provided in example 10, which does not include a release film.
Fig. 7 is a schematic structural diagram of the no-sewing hot melt adhesive TPU leather provided in example 11, which does not include a release film.
Wherein: 1, PU film; 2, TPU hot melt adhesive film; 3, release film; 4, a TPU film; 5, non-TPU film.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Example 1
The sewing-free hot melt adhesive TPU leather comprises a PU film layer, a TPU hot melt adhesive film layer and release paper or a release film which is optionally matched with the TPU hot melt adhesive film, wherein the TPU hot melt adhesive film is arranged on one side of the PU film; the thickness of the TPU hot melt adhesive film is 0.01 mm; the thickness of the PU film is 0.01 mm; the thickness of the release paper or the release film is 0.01 mm;
the material of the release paper or the release film is selected from any one or the combination of at least two of PVC, EVA, PP or PE;
the TPU hot melt adhesive film comprises the following raw material components in parts by weight:
30 parts of polyester polyol; 35 parts of polyether polyol; 20 parts of diisocyanate; 0.5 part of a catalyst; 0.5 part of a chain extender; the polyester polyol is a hydroxyl-terminated polyester diol with the weight-average molecular weight of 500-800, which is prepared by the polycondensation reaction of aliphatic diol and aliphatic dicarboxylic acid at 120-200 ℃; the polyether polyol is tetrahydrofuran-propylene oxide copolymerization diol with the weight-average molecular weight of 600-900; the diisocyanate is a benzylidene diisocyanate.
The aliphatic diol is selected from a mixture of ethylene glycol and dodecyl hexanediol with a mass ratio of 4: 1.
The aliphatic dicarboxylic acid is selected from a mixture of adipic acid and suberic acid in a mass ratio of 5: 1.
The catalyst is selected from dibutyltin dilaurate.
The chain extender is selected from 1, 6-hexanediol.
The TPU hot melt adhesive film also comprises 1 part of tackifying resin, wherein the tackifying resin is selected from polyethylene-vinyl acetate copolymer.
The preparation method of the sewing-free hot melt adhesive TPU leather comprises the following steps:
and (3) oppositely pressing and compounding the TPU hot melt adhesive film and the PU film by using a roller, and then optionally bonding a release paper or a release film on the TPU hot melt adhesive film to form the sewing-free hot melt adhesive TPU leather.
Example 1'
The sewing-free hot melt adhesive TPU leather comprises a PU film layer, a TPU hot melt adhesive film layer and release paper or a release film which is optionally matched with the TPU hot melt adhesive film, wherein the TPU hot melt adhesive film is arranged on one side of the PU film; the thickness of the TPU hot melt adhesive film is 0.3 mm; the thickness of the PU film is 3.0 mm; the thickness of the release paper or the release film is 1.0 mm;
the material of the release paper or the release film is selected from any one or the combination of at least two of PVC, EVA, PP or PE;
the TPU hot melt adhesive film comprises the following raw material components in parts by weight:
40 parts of polyester polyol; 45 parts of polyether polyol; 50 parts of diisocyanate; 2 parts of a catalyst; 10 parts of a chain extender; 1 part of antioxidant; 4 parts of a flame retardant; 4 parts of a toughening agent; the polyester polyol is a hydroxyl-terminated polyester diol with the weight-average molecular weight of 700-1000, which is prepared by the polycondensation reaction of aliphatic diol and aliphatic dicarboxylic acid at 120-200 ℃; the polyether polyol is tetrahydrofuran-propylene oxide copolymerization diol with the weight-average molecular weight of 600-900; the diisocyanate is a benzylidene diisocyanate.
The aliphatic diol is selected from a mixture of ethylene glycol and dodecyl hexanediol with a mass ratio of 1: 1.
The aliphatic dicarboxylic acid is selected from a mixture of adipic acid and suberic acid in a mass ratio of 2: 1.
The catalyst is selected from triethanolamine.
The chain extender is selected from methyl propylene glycol.
The antioxidant is selected from pentaerythritol tetrakis { β - (3, 5-tertiary butyl-4-hydroxyphenyl) propionate }.
The flame retardant comprises the following components in percentage by mass: 80% of polypropylene with a melt index of 0.5-15.0 g/10min, 4.5% of polyethylene with a melt index of 0.01-2.0 g/10min, 15% of powdered talc and 0.5% of decabromodiphenyl ether;
the toughening agent is obtained by mixing and extruding polyethylene elastomer, linear polyethylene, polypropylene and an anti-aging agent;
the TPU hot melt adhesive film also comprises 10 parts of tackifying resin, wherein the tackifying resin is selected from hydroxyl-terminated thermoplastic polyester.
The preparation method of the sewing-free hot melt adhesive TPU leather is the same as that of the embodiment 1.
Example 1 "
The sewing-free hot melt adhesive TPU leather comprises a PU film layer, a TPU hot melt adhesive film layer and release paper or a release film which is optionally matched with the TPU hot melt adhesive film, wherein the TPU hot melt adhesive film is arranged on one side of the PU film; the thickness of the TPU hot melt adhesive film is 0.2 mm; the thickness of the PU film is 1.0 mm; the thickness of the release paper or the release film is 0.5 mm;
the material of the release paper or the release film is selected from any one or the combination of at least two of PVC, EVA, PP or PE;
the TPU hot melt adhesive film comprises the following raw material components in parts by weight:
32 parts of polyester polyol; 38 parts of polyether polyol; 20-50 parts of diisocyanate; 1 part of a catalyst; 2 parts of a chain extender; 0.5 part of antioxidant; 2 parts of a flame retardant; 1.5 parts of a toughening agent; the polyester polyol is hydroxyl-terminated polyester diol with the weight-average molecular weight of 700-900, which is prepared by the polycondensation reaction of aliphatic diol and aliphatic dicarboxylic acid at 120-200 ℃; the polyether polyol is tetrahydrofuran-propylene oxide copolymerization diol with the weight-average molecular weight of 600-900; the diisocyanate is a benzylidene diisocyanate.
The aliphatic diol is selected from a mixture of ethylene glycol and dodecyl hexanediol with a mass ratio of 5: 1.
The aliphatic dicarboxylic acid is selected from a mixture of adipic acid and suberic acid in a mass ratio of 6: 1.
The catalyst is selected from any one or a combination of at least two of dibutyltin dilaurate, triethanolamine or dimorpholinyl diethyl ether.
The chain extender is selected from methyl propylene glycol.
The antioxidant is selected from 2, 6-tertiary butyl-4-methylphenol and tetra { β - (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid } pentaerythritol ester in a mass ratio of 1: 1.
The flame retardant comprises the following components in percentage by mass: 18% of polypropylene with a melt index of 0.5-15.0 g/10min, 50% of polyethylene with a melt index of 0.01-2.0 g/10min, 15% of kaolinite and 17% of dodecachlorododeca-dihydro-bridged-benzene-cyclooctene.
The toughening agent is obtained by mixing and extruding polyethylene elastomer, linear polyethylene, polypropylene and an anti-aging agent;
the TPU hot melt adhesive film also comprises 5 parts of tackifying resin, wherein the tackifying resin is selected from hydrogenated rosin resin.
The preparation method of the sewing-free hot melt adhesive TPU leather is the same as that of the embodiment 1.
Example 2
The utility model provides a exempt from to sew hot melt adhesive TPU leather, as shown in figure 1 or figure 2, the only difference of structure of exempting from to sew hot melt adhesive TPU leather with embodiment 1 exempt from to sew hot melt adhesive TPU leather's structure is:
the PU film comprises the following raw material components in parts by weight:
32 parts of poly (propylene glycol adipate) glycol with the weight-average molecular weight of 1000-1400; 30 parts of tetrahydrofuran-propylene oxide copolyol with the weight-average molecular weight of 1000-1300; 22 parts of isophorone diisocyanate; 0.5 part of a catalyst; and 0.5 part of chain extender.
The chain extender is selected from a mixture of 1, 6-hexanediol and 1, 4-butanediol in a mass ratio of 2: 1.
The PU film comprises the raw material components of 1 part by weight of colorant.
The preparation method of the sewing-free hot melt adhesive TPU leather is the same as that of the embodiment 1.
Example 2'
The utility model provides a exempt from to sew hot melt adhesive TPU leather, exempt from to sew hot melt adhesive TPU leather's structure and embodiment 1 ' exempt from to sew hot melt adhesive TPU leather's the only difference of structure is:
the PU film comprises the following raw material components in parts by weight:
38 parts of poly propylene glycol adipate glycol with the weight-average molecular weight of 1700-2000; 35 parts of tetrahydrofuran-propylene oxide copolymerized glycol with the weight-average molecular weight of 1200-1500; 38 parts of isophorone diisocyanate; 2 parts of a catalyst; and 5 parts of a chain extender.
The chain extender is preferably selected from a mixture of 1, 6-hexanediol and 1, 4-butanediol in a mass ratio of 5: 1.
The PU film comprises the raw material components of 3 parts by weight of colorant.
The preparation method of the sewing-free hot melt adhesive TPU leather is the same as that of the embodiment 1.
Example 2 "
The utility model provides a exempt from sewing hot melt adhesive TPU leather, exempt from sewing hot melt adhesive TPU leather's structure and embodiment 1 "exempt from sewing hot melt adhesive TPU leather's the only difference of structure be:
the PU film comprises the following raw material components in parts by weight:
35 parts of poly propylene glycol adipate glycol with the weight-average molecular weight of 1300-1600; 33 parts of tetrahydrofuran-propylene oxide copolymerized glycol with the weight-average molecular weight of 1100-1400; 30 parts of isophorone diisocyanate; 1.0 part of a catalyst; and 2 parts of a chain extender.
The chain extender is selected from a mixture of 1, 6-hexanediol and 1, 4-butanediol in a mass ratio of 3: 1.
The PU film comprises 2 parts of colorant according to the parts by weight.
The preparation method of the sewing-free hot melt adhesive TPU leather is the same as that of the embodiment 1.
Example 3
A no-sewing hot melt adhesive TPU leather, as shown in figure 3 or figure 4. The only difference between the structure and the composition of the TPU leather without the sewing hot melt adhesive in the embodiment 2 is as follows: the sewing-free hot melt adhesive TPU leather also comprises a TPU film, and the thickness of the TPU film is 0.01 mm; the TPU film is arranged between the PU film and the TPU hot melt adhesive film.
The TPU film comprises the following components in parts by weight: 86 parts of thermoplastic polyurethane particles; slipping agent; 0.1 part of antioxidant; 0.1 part of an anti-ultraviolet agent; 0.1 part of a filler;
the thermoplastic polyurethane particle comprises the following raw material components in parts by weight:
5 parts of poly propylene glycol adipate glycol with the weight-average molecular weight of 2200-2500; 20 parts of polyhexamethylene carbonate glycol with the weight-average molecular weight of 1000-1300; 20 parts of polytetramethylene ether glycol with the weight-average molecular weight of 1000-1200; 12 parts of 1, 5-naphthalene diisocyanate; 18 parts of benzylidene diisocyanate; 4 parts of a chain extender; 0.5 part of catalyst.
The slipping agent is selected from silicone oil.
The antioxidant is selected from the group consisting of tetrakis [ methylene-3, 3', 5- (di-tert-butyl-4-hydroxy-phenyl) propionate ] pentaerythritol ester.
The uvioresistant agent is selected from benzoic acid uvioresistant agents.
The filler is selected from talc powder.
The TPU film also comprises 0.01 part of color modifier by weight, and the color modifier is selected from color master batches.
The preparation method of the sewing-free hot melt adhesive TPU leather comprises the following steps:
(1) utilizing a roller to perform opposite pressing compounding on the TPU hot melt adhesive film obtained by casting and the TPU film obtained by casting to form a first composite film;
(2) pressing and compounding the first composite film and the PU film by using a roller to form a second composite film; wherein the surface of the roller is provided with patterns;
(3) and optionally bonding a release paper or a release film on the second composite film to form the sewing-free hot melt adhesive TPU leather.
Example 3'
The utility model provides a exempt from sewing hot melt adhesive TPU leather, its structure and constitution and embodiment 2 exempt from sewing hot melt adhesive TPU leather only difference is: the sewing-free hot melt adhesive TPU leather also comprises a TPU film, and the thickness of the TPU film is 5.0 mm; the TPU film is arranged between the PU film and the TPU hot melt adhesive film.
The TPU film comprises the following components in parts by weight: 98 parts of thermoplastic polyurethane particles; 8 parts of a slipping agent; 1 part of antioxidant; 2 parts of an anti-ultraviolet agent; 3 parts of a filling agent;
the thermoplastic polyurethane particle comprises the following raw material components in parts by weight:
10 parts of poly propylene glycol adipate glycol with the weight-average molecular weight of 2200-3200; 25 parts of polyhexamethylene carbonate glycol with the weight-average molecular weight of 1700-2000; 25 parts of polytetramethylene ether glycol with the weight-average molecular weight of 1200-1500; 18 parts of 1, 5-naphthalene diisocyanate; 25 parts of benzylidene diisocyanate; 6 parts of a chain extender; 1 part of catalyst.
The slipping agent is selected from methyl silicone oil.
The antioxidant is selected from N, N' -bis [ [3- (3,5) -di-tert-butyl-4-hydroxyphenyl ] propionyl ] hexanediamine.
The uvioresistant agent is selected from xylene ketone uvioresistant agents.
The filler is selected from carbon black.
The TPU film also comprises 0.5 part of color modifier according to the parts by weight, and the color modifier is selected from carbon black.
The preparation method of the sewing-free hot melt adhesive TPU leather is the same as that of the embodiment 3.
Example 3 "
The utility model provides a exempt from sewing hot melt adhesive TPU leather, its structure and constitution and embodiment 2 exempt from sewing hot melt adhesive TPU leather only difference is: the sewing-free hot melt adhesive TPU leather also comprises a TPU film, and the thickness of the TPU film is 1.0 mm; the TPU film is arranged between the PU film and the TPU hot melt adhesive film.
The TPU film comprises the following components in parts by weight: 90 parts of thermoplastic polyurethane particles; 7 parts of a slipping agent; 0.5 part of antioxidant; 1 part of an anti-ultraviolet agent; 1 part of a filling agent;
the thermoplastic polyurethane particle comprises the following raw material components in parts by weight:
8 parts of poly propylene glycol adipate glycol with the weight-average molecular weight of 2500-2800; 22 parts of polyhexamethylene carbonate glycol with the weight-average molecular weight of 1300-1500; 23 parts of polytetramethylene ether glycol with the weight-average molecular weight of 1200-1400; 16 parts of 1, 5-naphthalene diisocyanate; 20 parts of benzylidene diisocyanate; 5 parts of a chain extender; 0.7 part of catalyst.
The slipping agent is selected from the combination of water-soluble silicone oil and hydroxyl silicone oil with the mass ratio of 1: 1.
The antioxidant is selected from the combination of tris [2, 4-di-tert-butylphenyl ] phosphite or pentaerythritol diphosphite stearyl ester in a mass ratio of 2: 1.
The anti-ultraviolet agent is selected from benzotriazole anti-ultraviolet agents.
The filler is selected from titanium dioxide.
The TPU film also comprises 1.0 part of color modifier according to parts by weight, and the color modifier is selected from toner.
The preparation method of the sewing-free hot melt adhesive TPU leather is the same as that of the embodiment 3.
Example 4
The only difference between the structure and the composition of the sewing-free hot melt adhesive TPU leather shown in the figure 5 and the sewing-free hot melt adhesive TPU leather described in the embodiment 2 is as follows: the sewing-free hot melt adhesive TPU leather also comprises a non-TPU film, wherein the non-TPU film is arranged between the PU film and the TPU hot melt adhesive film, and the thickness of the non-TPU film is 0.01 mm; the non-TPU film is an EVA foaming film;
the EVA foaming film comprises the following components in parts by weight: 30 parts of main materials, 0.1 part of filling agent, 1 part of foaming agent, 0.01 part of foaming accelerant, 0.01 part of lubricant, 0.01 part of antistatic agent and 0.01 part of flame retardant; the main material comprises ethylene-vinyl acetate copolymer, thermoplastic polyurethane elastomer and polyolefin thermoplastic elastomer in a mass ratio of 50:1: 5.
The filler is selected from calcium carbonate with the particle size of 500-1000 meshes.
The foaming agent is AC-3000H.
The foaming accelerant is zinc oxide powder.
The lubricant is stearic acid.
The flame retardant is an organic flame retardant.
The EVA foaming film comprises raw material components and 0.1 part by weight of color modifier, wherein the color modifier is selected from color master batches.
The preparation method of the sewing-free hot melt adhesive TPU leather comprises the following steps:
(1) utilizing a roller to perform opposite pressing compounding on a TPU hot melt adhesive film obtained by casting and a non-TPU film obtained by casting to form a first composite film;
(2) pressing and compounding the first composite film and the PU film by using a roller to form a second composite film; wherein the surface of the roller is provided with patterns;
(3) and optionally bonding a release paper or a release film on the second composite film to form the sewing-free hot melt adhesive TPU leather.
Example 4'
The utility model provides a exempt from sewing hot melt adhesive TPU leather, its structure and constitution and embodiment 2 exempt from sewing hot melt adhesive TPU leather only difference is: the sewing-free hot melt adhesive TPU leather also comprises a non-TPU film, wherein the non-TPU film is arranged between the PU film and the TPU hot melt adhesive film, and the thickness of the non-TPU film is 3.0 mm; the non-TPU film is an EVA foaming film;
the EVA foaming film comprises the following components in parts by weight: 90 parts of main material, 30 parts of filler, 20 parts of foaming agent, 5 parts of foaming promoter, 5 parts of lubricant, 10 parts of antistatic agent and 5 parts of flame retardant; the main material comprises ethylene-vinyl acetate copolymer, thermoplastic polyurethane elastomer and polyolefin thermoplastic elastomer in a mass ratio of 50:3: 10.
The filler is selected from talc powder with the particle size of 800-1000 meshes.
The foaming agent is AC-3000H.
The foaming accelerant is zinc oxide powder.
The lubricant is stearic acid.
The flame retardant is an organic flame retardant and/or an inorganic flame retardant.
The EVA foaming film comprises raw material components and 1.0 part by weight of color changing agent, wherein the color changing agent is selected from color glue.
The preparation method of the sewing-free hot melt adhesive TPU leather is the same as that described in example 4.
Example 4 "
The utility model provides a exempt from sewing hot melt adhesive TPU leather, its structure and constitution and embodiment 2 exempt from sewing hot melt adhesive TPU leather only difference is: the sewing-free hot melt adhesive TPU leather also comprises a non-TPU film, wherein the non-TPU film is arranged between the PU film and the TPU hot melt adhesive film, and the thickness of the non-TPU film is 1.0 mm; the non-TPU film is an EVA foaming film;
the EVA foaming film comprises the following components in parts by weight: 60 parts of main materials, 10 parts of filling agents, 10 parts of foaming agents, 1 part of foaming promoters, 2 parts of lubricating agents, 2 parts of antistatic agents and 3 parts of flame retardants; the main material comprises ethylene-vinyl acetate copolymer, thermoplastic polyurethane elastomer and polyolefin thermoplastic elastomer in a mass ratio of 50:2: 7.
The filler is selected from a mixture of calcium carbonate and talcum powder with the particle size of 50-100 meshes and the mass ratio of 3: 1.
The foaming agent is AC-3000H.
The foaming accelerant is zinc oxide powder.
The lubricant is stearic acid.
The flame retardant is an organic flame retardant and an inorganic flame retardant in a mass ratio of 1: 1.
The EVA foaming film comprises raw material components and 0.5 part by weight of color modifier, wherein the color modifier is selected from toner.
The preparation method of the sewing-free hot melt adhesive TPU leather is the same as that described in example 4.
Example 5
The utility model provides a exempt from sewing hot melt adhesive TPU leather, its structure and constitution and embodiment 3 exempt from sewing hot melt adhesive TPU leather only difference is: the sewing-free hot melt adhesive TPU leather further comprises a non-TPU film, the non-TPU film is arranged between the TPU film and the TPU hot melt adhesive film, and the non-TPU film is the EVA foaming film described in embodiment 4.
The preparation method of the sewing-free hot melt adhesive TPU leather comprises the following steps:
(1) utilizing a roller to perform counter-pressing compounding on the TPU hot melt adhesive film obtained by casting and the TPU film and the non-TPU film obtained by casting to form a first composite film;
(2) pressing and compounding the first composite film and the PU film by using a roller to form a second composite film; wherein the surface of the roller is provided with patterns;
(3) and optionally bonding a release paper or a release film on the second composite film to form the sewing-free hot melt adhesive TPU leather.
Example 5'
The utility model provides a exempt from sewing hot melt adhesive TPU leather, its structure and constitution and embodiment 3 exempt from sewing hot melt adhesive TPU leather only difference is: the sewing-free hot melt adhesive TPU leather further comprises a non-TPU film, the non-TPU film is arranged between the TPU film and the TPU hot melt adhesive film, and the non-TPU film is the EVA foaming film in the embodiment 4'.
The preparation method of the sewing-free hot melt adhesive TPU leather is the same as that of the embodiment 5.
Example 5 "
The utility model provides a exempt from sewing hot melt adhesive TPU leather, its structure and constitution and embodiment 3 exempt from sewing hot melt adhesive TPU leather's structure and constitution are the same, and the only difference is: the sewing-free hot melt adhesive TPU leather further comprises a non-TPU film, the non-TPU film is arranged between the TPU film and the TPU hot melt adhesive film, and the non-TPU film is the EVA foaming film described in embodiment 4'.
The preparation method of the sewing-free hot melt adhesive TPU leather is the same as that of the embodiment 5.
Examples 6 to 7
The only difference between the structure and the composition of the sewing-free hot melt adhesive TPU leather and the sewing-free hot melt adhesive TPU leather in the embodiment 4 is that an EVA foaming film is replaced by a PU foaming film and a PVC foaming film respectively.
The preparation method is the same as that described in example 4.
Examples 8 to 9
The only difference between the structure and the composition of the sewing-free hot melt adhesive TPU leather and the sewing-free hot melt adhesive TPU leather in the embodiment 5 is that an EVA foaming film is replaced by a PU foaming film and a PVC foaming film respectively.
The preparation method is the same as that described in example 5.
Example 10
The only difference between the structure and the composition of the sewing-free hot melt adhesive TPU leather shown in the figure 6 and the sewing-free hot melt adhesive TPU leather described in the embodiment 3 is as follows: the sewing-free hot melt adhesive TPU leather further comprises another layer of TPU hot melt adhesive membrane, and the TPU hot melt adhesive membrane is arranged between the PU membrane and the TPU membrane.
The preparation method comprises the following steps:
(1) utilizing a roller to perform opposite pressing compounding on a first TPU hot melt adhesive film obtained by casting and a TPU film obtained by casting to form a first composite film;
(2) the first composite film and the second TPU hot melt adhesive film are pressed and compounded by using a roller to form a second composite film;
(3) pressing and compounding the second composite film and the PU film by using a roller to form a third composite film; wherein the surface of the roller is provided with patterns;
(4) and optionally bonding a release paper or a release film on the second composite film to form the sewing-free hot melt adhesive TPU leather.
Example 11
The only difference between the structure and the composition of the sewing-free hot melt adhesive TPU leather shown in the figure 7 and the sewing-free hot melt adhesive TPU leather described in the embodiment 5 is as follows: the sewing-free hot melt adhesive TPU leather further comprises another layer of non-TPU film, and the non-TPU hot melt adhesive film is arranged between the TPU film and the TPU hot melt adhesive film.
The preparation method of the sewing-free hot melt adhesive TPU leather comprises the following steps:
(1) utilizing a roller to perform counter-pressure compounding on the TPU hot melt adhesive film obtained by casting, the TPU film obtained by casting and the first non-TPU film to form a first composite film;
(2) pressing and compounding the first composite film and the second non-TPU film by using a roller to form a second composite film;
(3) pressing and compounding the second composite film and the PU film by using a roller to form a third composite film; wherein the surface of the roller is provided with patterns;
(3) and optionally bonding a release paper or a release film on the third composite film to form the sewing-free hot melt adhesive TPU leather.
The main performances of the TPU leather without the sewing hot melt adhesive are detected, and the detection results are as follows:
the bonding strength of the sewing-free hot melt adhesive TPU leather obtained in the embodiment is as follows: 8.0-10 Kg/25 mm;
in addition, the performances of the no-sewing hot melt adhesive TPU leather obtained in the embodiment 2 and the embodiments after the embodiment 2 are as follows:
1. hardness: 70-75A;
2. tensile strength: transverse direction is 38.1-40.2 MPa, and longitudinal direction is 30.2-35.1 MPa;
3. tear strength: the warp direction is 68.5-72.5 kgf/cm; the weft direction is 66.0-70.0 kgf/cm;
4. abrasion strength: under the pressure of 9KPa, no abrasion phenomenon occurs after 650 turns of grinding;
5. elongation percentage: 850-1000%.
Wherein the performances of the no-sewing hot melt adhesive TPU leather in the embodiments are, from good to bad, example 5 ", example 5 ', example 5, example 10, example 11, example 4", example 4 ', example 4, example 3 ", example 3 ', example 3, example 2", example 2 ', example 2, example 1 ", example 1 ' and example 1.
Comparative example 1
The procedure of example 5 was repeated, except that the aliphatic diol was replaced with the aromatic diol.
Comparative example 2
The procedure of example 5 was repeated, except that the aliphatic dicarboxylic acid was replaced with an aromatic dicarboxylic acid.
Comparative example 3
The procedure of example 5 was repeated, except that the weight average molecular weight of the hydroxyl-terminated polyester diol was changed to 1100-1200.
Comparative example 4
The procedure of example 5 was repeated, except that the tetrahydrofuran-oxypropylene copolyol having a weight average molecular weight of 600 to 900 was replaced with polyoxypropylene glycol having a weight average molecular weight of 600 to 900.
Comparative example 5
The procedure was as in example 5 except that tolylene diisocyanate was replaced with tolylene diisocyanate.
Comparative example 6
The TPU-removing hot melt adhesive film comprises the following raw material components in parts by weight: 28 parts of polyester polyol; 33 parts of polyether polyol; 18 parts of diisocyanate; 0.4 part of catalyst; the procedure of example 5 was repeated, except that 0.4 part of the chain extender was used.
Comparative example 7
The TPU-removing hot melt adhesive film comprises the following raw material components in parts by weight: 42 parts of polyester polyol; 46 parts of polyether polyol; 52 parts of diisocyanate; 2.5 parts of a catalyst; 11 parts of a chain extender; 2 parts of an antioxidant; 5 parts of a flame retardant; the procedure of example 5 was repeated, except that 5 parts of the toughening agent was used.
The bonding strength of the hot melt adhesive TPU leather without sewing obtained by the comparative example is only 60-78% of that of each product in the example;
in addition, the hardness, tensile strength, tear strength, abrasion strength and elongation of the product obtained by the comparative example are all lower than the corresponding performances of the product obtained by the example, and are only 75-85% of the performance data. Therefore, the TPU hot melt adhesive film provided by the invention has a reasonable formula, is matched with each other, and exerts excellent performance, and in addition, the specific PU film, the TPU film and the non-TPU film are matched with each other, and also shows excellent performance.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (29)

1. The sewing-free hot melt adhesive TPU leather with the bonding strength of 8.0-10 kg/25mm is characterized by comprising at least one layer of PU film, at least two layers of TPU hot melt adhesive films, at least one layer of TPU film, at least one layer of non-TPU film and release paper or release film optionally matched with the TPU hot melt adhesive films, wherein the TPU hot melt adhesive films are arranged on one side of the PU film, the TPU film and the non-TPU film are arranged between the PU film and the TPU hot melt adhesive films, and the non-TPU film comprises an EVA foaming film;
the EVA foaming film comprises the following components in parts by weight: 30-90 parts of main materials, 0.1-30 parts of filling agents, 1-20 parts of foaming agents, 0.01-5 parts of foaming promoters, 0.01-5 parts of lubricating agents, 0.01-10 parts of antistatic agents and 0.01-5 parts of flame retardants; the main material comprises 50 (1-3) to (5-10) of ethylene-vinyl acetate copolymer, thermoplastic polyurethane elastomer and polyolefin thermoplastic elastomer in mass ratio;
the TPU hot melt adhesive film comprises the following raw material components in parts by weight:
30-40 parts of polyester polyol, 35-45 parts of polyether polyol, 20-50 parts of diisocyanate, 0.5-2 parts of catalyst, 0.5-10 parts of chain extender, 0-1 part of antioxidant, 0-4 parts of flame retardant and 0-4 parts of flexibilizer; the polyester polyol is a hydroxyl-terminated polyester diol with the weight-average molecular weight of 500-1000, which is prepared by the polycondensation reaction of aliphatic diol and aliphatic dicarboxylic acid at 120-200 ℃; the polyether polyol is tetrahydrofuran-propylene oxide copolymerization diol with the weight-average molecular weight of 600-900; the diisocyanate is phenyl methylene diisocyanate;
the aliphatic diol is selected from a mixture of ethylene glycol and dodecyl hexanediol with the mass ratio of (1-5) to 1; the aliphatic dicarboxylic acid is selected from a mixture of adipic acid and suberic acid in a mass ratio of (2-6): 1;
the thickness of the TPU hot melt adhesive film is 0.01-1.0 mm; the thickness of the PU film is 0.01-3.0 mm; the thickness of the release paper or the release film is 0.01-1.0 mm; the thickness of the non-TPU film is 0.01-3.0 mm;
the PU film comprises the following raw material components in parts by weight:
32-38 parts of poly propylene glycol adipate glycol with the weight-average molecular weight of 1000-2000, 30-35 parts of tetrahydrofuran-propylene oxide copolymer glycol with the weight-average molecular weight of 1000-1500, 22-38 parts of isophorone diisocyanate, 0.5-2 parts of a catalyst and 0.5-5 parts of a chain extender.
2. The no-sewing hot melt adhesive TPU leather of claim 1, wherein the aliphatic diol is selected from any one of ethylene glycol, diethylene glycol, propylene glycol, methyl propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 3-butanediol, 1,5 pentanediol, or dodecyl hexanediol, or a combination of at least two thereof.
3. The no-sewing hot melt adhesive TPU leather of claim 1, wherein the aliphatic dicarboxylic acid is selected from any one of adipic acid, fumaric acid, maleic acid, or suberic acid, or a combination of at least two thereof.
4. The no-seam hot melt adhesive TPU leather of claim 1, wherein the catalyst is selected from any one or a combination of at least two of dibutyl tin dilaurate, triethanolamine, or bis-morpholinyl diethyl ether.
5. The no-sewing hot melt adhesive TPU leather of claim 1, wherein the chain extender is selected from any one of 1, 6-hexanediol, methyl propylene glycol, or 1, 4-butanediol or a combination of at least two thereof.
6. The no-sewing hot melt adhesive TPU leather of claim 1, wherein the antioxidant is selected from 2, 6-tertiary butyl-4-methylphenol and/or pentaerythrityl tetrakis { β - (3, 5-tertiary butyl-4-hydroxyphenyl) propanoate }.
7. The no-sewing hot melt adhesive TPU leather of claim 1, wherein the flame retardant comprises the following components by mass percent: 18 to 80 percent of polypropylene with a melt index of 0.5 to 15.0g/10min, 1 to 50 percent of polyethylene with a melt index of 0.01 to 2.0g/10min, 15 to 60 percent of inorganic filler selected from one or the combination of at least two of powdery talc, kaolinite, sericite, silicon dioxide or diatomite, and 0.5 to 60 percent of organic halide selected from decabromodiphenyl ether and/or dodecachlorododeca-dihydrobenzene cyclooctene.
8. The no-sewing hot melt adhesive TPU leather of claim 1, wherein the toughening agent is obtained by mixing and extruding polyethylene elastomer, linear polyethylene, polypropylene and an anti-aging agent.
9. The sewing-free hot melt adhesive TPU leather as claimed in claim 1, wherein the TPU hot melt adhesive film further comprises 1-10 parts of tackifying resin, wherein the tackifying resin is selected from one or a combination of at least two of polyethylene-vinyl acetate copolymer, hydroxyl-terminated thermoplastic polyester and hydrogenated rosin resin.
10. The no-sewing hot melt adhesive TPU leather of claim 1, wherein the chain extender is selected from any one of 1, 6-hexanediol, methyl propylene glycol, or 1, 4-butanediol or a combination of at least two thereof.
11. The no-sewing hot melt adhesive TPU leather of claim 1, wherein the chain extender is selected from a mixture of 1, 6-hexanediol and 1, 4-butanediol in a mass ratio of (2-5): 1.
12. The sewing-free hot melt adhesive TPU leather as claimed in claim 1, wherein the PU film further comprises 1-3 parts by weight of a colorant.
13. The no-sewing hot melt adhesive TPU leather of claim 1, wherein the release paper or release film is made of any one or a combination of at least two of PVC, EVA, PP or PE.
14. The sewing-free hot melt adhesive TPU leather as claimed in claim 1, wherein the TPU film comprises the following raw materials in parts by weight:
86-98 parts of thermoplastic polyurethane particles, 0.1-3 parts of a slipping agent, 0.1-1 part of an antioxidant, 0.1-2 parts of an anti-ultraviolet agent and 0.1-3 parts of a filler;
the thermoplastic polyurethane particle comprises the following raw material components in parts by weight:
5-10 parts of poly propylene glycol adipate glycol with the weight-average molecular weight of 2200-3200, 20-25 parts of poly hexamethylene carbonate glycol with the weight-average molecular weight of 1000-2000, 20-25 parts of poly tetramethylene ether glycol with the weight-average molecular weight of 1000-1500, 12-18 parts of 1, 5-naphthalene diisocyanate, 18-25 parts of benzylidene diisocyanate, 4-6 parts of chain extender and 0.5-1 part of catalyst.
15. The no-sewing hot melt adhesive TPU leather of claim 14, wherein the slip agent is selected from any one of silicone oil, methyl silicone oil, water soluble silicone oil or hydroxy silicone oil or a combination of at least two thereof.
16. The no-sewing hot melt adhesive TPU leather of claim 14, wherein the antioxidant is selected from any one of or a combination of at least two of tetrakis [ methylene-3, 3 ', 5- (di-t-butyl-4-hydroxy-phenyl) propionate ] pentaerythritol ester, N' -bis [ [3- (3,5) -di-t-butyl-4-hydroxyphenyl ] propionyl ] hexanediamine, tris [2, 4-di-t-butylphenyl ] phosphite, or pentaerythritol stearate diphosphite.
17. The no-sewing hot melt adhesive TPU leather of claim 14, wherein the anti-UV agent is selected from any one of benzoic acid type anti-UV agent, xylene ketone type anti-UV agent or benzotriazole type anti-UV agent or a combination of at least two thereof.
18. The no-sewing hot melt adhesive TPU leather of claim 14, wherein the filler is selected from any one or a combination of at least two of talc, diatomaceous earth, calcium carbonate, or titanium dioxide.
19. The sewing-free hot melt adhesive TPU leather as claimed in claim 14, wherein the TPU film further comprises 0.01 to 50 parts by weight of a color modifier, wherein the color modifier is selected from any one or a combination of at least two of color masterbatch, carbon black or toner.
20. The sewing-free hot melt adhesive TPU leather as claimed in claim 1, wherein the TPU film has a thickness of 0.01 to 5.0 mm.
21. The sewing-free hot melt adhesive TPU leather as claimed in claim 1, wherein the filler is selected from calcium carbonate and/or talc having a particle size of 50-1000 mesh.
22. The no-sewing hot melt adhesive TPU leather of claim 1, wherein the blowing agent is AC-3000H.
23. The no-sewing hot melt adhesive TPU leather of claim 1, wherein the foaming promoter is zinc oxide powder.
24. The no-sewing hot melt adhesive TPU leather of claim 1, wherein the lubricant is stearic acid.
25. The no-sewing hot melt adhesive TPU leather of claim 1, wherein the flame retardant is an organic flame retardant and/or an inorganic flame retardant.
26. The sewing-free hot melt adhesive TPU leather as claimed in claim 1, wherein the EVA foaming film further comprises 0.1-10 parts by weight of a color modifier selected from any one of color master batches, color glues or color powders or a combination of at least two of the color modifiers.
27. The preparation method of the no-sewing hot melt adhesive TPU leather as claimed in one of claims 1 to 26, characterized in that the preparation method comprises the following steps:
(1) carrying out opposite pressing compounding on the TPU hot melt adhesive film obtained by casting and the TPU film or the non-TPU film obtained by casting to form a first composite film;
(2) the first composite film and the PU film are oppositely pressed and compounded to form a second composite film;
(3) and optionally bonding release paper or release film on the second composite film to form the sewing-free hot melt adhesive TPU leather.
28. The method according to claim 27, wherein the press-laminating of the steps (1) and (2) is performed by using at least two rollers.
29. A method as claimed in claim 28, wherein the surface of the roller is provided with a pattern.
CN201710094594.0A 2017-02-21 2017-02-21 Sewing-free hot melt adhesive TPU leather and preparation method thereof Active CN106835732B (en)

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CN107955365A (en) * 2017-11-24 2018-04-24 广东聚航新材料研究院有限公司 The TPU materials and rainbow illusion-colour thin-film sheet being bonded online for rainbow illusion-colour thin-film sheet
CN109337029A (en) * 2018-09-11 2019-02-15 东莞市雄林新材料科技股份有限公司 A kind of high abrasion TPU/ material silica gel composite and preparation method thereof

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CN103437195A (en) * 2013-08-16 2013-12-11 东莞市雄林新材料科技有限公司 Sewing-free hot melt adhesive TPU-PU leather and preparation method thereof
CN103437194A (en) * 2013-08-16 2013-12-11 东莞市雄林新材料科技有限公司 Sewing-free hot melt adhesive TPU leather and preparation method thereof
CN103627362A (en) * 2013-11-29 2014-03-12 烟台德邦科技有限公司 Reactive polyurethane hot melt adhesive and preparation method thereof
CN104313894A (en) * 2014-09-18 2015-01-28 王建岳 Preparation method of sea-island microfiber PU synthetic leather

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CN102336883A (en) * 2011-07-14 2012-02-01 无锡市万力粘合材料有限公司 Preparation method of reactive polyurethane hot melt adhesive for fabric lamination
CN103437195A (en) * 2013-08-16 2013-12-11 东莞市雄林新材料科技有限公司 Sewing-free hot melt adhesive TPU-PU leather and preparation method thereof
CN103437194A (en) * 2013-08-16 2013-12-11 东莞市雄林新材料科技有限公司 Sewing-free hot melt adhesive TPU leather and preparation method thereof
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