CN103437195B - Sewing-free hot melt adhesive TPU-PU leather and preparation method thereof - Google Patents

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

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Publication number
CN103437195B
CN103437195B CN201310360221.5A CN201310360221A CN103437195B CN 103437195 B CN103437195 B CN 103437195B CN 201310360221 A CN201310360221 A CN 201310360221A CN 103437195 B CN103437195 B CN 103437195B
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weight portion
hot melt
melt adhesive
tpu
raw material
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CN103437195A (en
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何建雄
王一良
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Dongguan Xionglin New Materials Technology Co Ltd
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Dongguan Xionglin New Materials Technology Co Ltd
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Priority to PCT/CN2014/079497 priority patent/WO2015021814A1/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
    • C08G18/2018—Heterocyclic amines; Salts thereof containing one heterocyclic ring having one nitrogen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/001—Release paper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/12—Coating on the layer surface on paper layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/20—Compositions for hot melt adhesives

Abstract

The invention provides a piece of novel sewing-free hot melt adhesive TPU-PU leather, and a preparation method thereof. The TPU-PU leather comprises release paper, a hot melt adhesive film, a TPU film and a dry-type PU film, wherein the release paper comprises a paper bottom layer, an adhesive layer, a plastic layer, a transition layer, and a release layer; a hot melt adhesive raw material is composed of polyester polyol, diisocyanate, polyether polyol, and a plurality of additives; a TPU raw material is composed of polymer polybasic alcohol, 1,4-cyclohexane-diisocyanate, a chain extender and a plurality of functional additives; a PU raw material is composed of polyester dibasic alcohol, straight chain diol, isocyanate, TDI trimer, dimethyl formamide, butanone, black sand, and a plurality of functional addictives. Through the adoption of the preparation method, innovations are conducted on the raw material components of the release paper, the hot melt adhesive, the TPU film and the PU film; the manufactured sewing-free TPU-PU leather has the technical advantages of firmness in adhesion, durability, environment-friendly materials, no invisible harm to a human body, and the like.

Description

Hot melt adhesive TPU-PU leather of a kind of vehicle slit preventing and preparation method thereof
Technical field
The present invention relates to leather substance technical field, hot melt adhesive TPU-PU leather relating to a kind of vehicle slit preventing more specifically and preparation method thereof.
Background technology
In prior art, in the production industry such as clothing, shoemaking, case and bag, handbag, seat, military project of China and foreign countries, the fabric that all goods attach is all adopt traditional pin seam mode to refute to have connect.This mode of production, not only labour intensity is large, production cost is high, more due to product easily rupture by External Force Acting linear slit place, the problem such as tearing notch and decortication, have a strong impact on service life and the quality of product, consumer cost also obviously increases.Also because product fabrics all at present adopts mostly is PVC leather, and PVC material itself has toxogenin containing polyvinyl chloride and DEHA etc., carcinogenesis is had to human body, use is absolutely unsafe, and used in leather docile in prior art be all industrial liquid glue, solid gum mostly, these melt adhesive materials have and mostly all have toxicity, and at aspect of performances such as elasticity, acidproof, alkaline-resisting, water-fastness, resistance to dry-cleaning, tension stress, adhesions, there is certain defect, and be undesirable environmental protection jointing material.
Summary of the invention
The present invention is based on above-mentioned technical problem, hot melt adhesive TPU-PU leather of a kind of novel vehicle slit preventing and preparation method thereof is proposed, by innovating from component each layer raw material of leather, in conjunction with the production experience that our company is long-term, final formation vehicle slit preventing TPU-PU of the present invention leather, can directly be fitted on various article, and have firm pasting, durable, material environmental protection, to human body without technical advantages such as any stealthy injuries, fundamentally solve sewing and refute and connect and various undesirable elements that existing industrial glue brings in leather products is applied.
The technical scheme that the present invention solves the problems of the technologies described above is as follows:
A hot melt adhesive TPU-PU leather for vehicle slit preventing, comprises release liners, the hot melt adhesive be coated in release liners, the dry type PU film that is pasted on the TPU membrane in hot melt adhesive and pastes pressure viscosity with described TPU membrane, wherein said release liners comprises paper bottom A1, tack coat A2, plastic layer A3, transition zone A4 and release layer A5, described plastic layer A3 is adhered on described paper bottom A1 by tack coat A2, described transition zone A4 is arranged at described plastic layer A3, described release layer A5 is arranged at described transition zone A4, described tack coat A2 is aqueous polyacrylamide coating layer, use amount is every square metre of 5-8 gram, thickness is 0.8-4 micron, described plastic layer A3 is the polyethylene terephthalate film of thickness between 18-25 micron, described transition zone A4 is by the inorganic particulate of 62-68 weight portion, the Silicone acrylic emulsion of 32-36 weight portion, the methyl sodiosul foaliphatate of 3-5 weight portion, the dodecyl benzyl dimethyl ammonium chloride of 2-4 weight portion and the water mix and blend of 45-55 weight portion are prepared from, and film forming thickness is at 15-20 micron, the thickness of described release layer A5 is 20-25 micron and by the polypropylene of 58-65 weight portion, the poly(4-methyl-1-pentene) of 26-34 weight portion, the vinyl silicone oil of 6-9 weight portion, 2 of 1-2 weight portion, 2 '-methylene-bis--(4, 6 di-t-butyl phenoxy groups) tert butyl peroxy benzoate of sodium phosphate and 0.1-0.8 weight portion is prepared from, wherein said hot melt adhesive is by the polyester polyol of 60-70 weight portion, the vulcabond of 15-20 weight portion, the polyether polyol of 3-5 weight portion, the catalyst of 0.8-1.5 weight portion, the chain extender of 0.5-1.2 weight portion, 1.5-1.8 weight portion antioxidant, the tackifying resin of 4-6 weight portion, the fire retardant of 2-4 weight portion, the flexibilizer of 2-4 weight portion is prepared from, described polyester polyol is by low molecular weight aliphatic dihydroxy alcohol and aliphatic dicarboxylic acid, aromatic binary carboxylic acid polycondensation reaction and be prepared into the hydroxyl telechelic polyester glycol that molecular weight is 2000-6000 at 100-260 DEG C, described aliphatic dicarboxylic acid is selected oneself diacid, fumaric acid, maleic acid or suberic acid, described aromatic binary carboxylic acid is selected from phthalic acid, terephthalic acid (TPA) or M-phthalic acid, described aliphatic dihydroxy alcohol is selected from ethylene glycol, diethylene glycol (DEG), propylene glycol, methyl propanediol, 1, 4-butanediol, 1, 6-hexylene glycol, 1, 3-butanediol, 1, 5 pentanediols or dodecyl hexylene glycol, described vulcabond adopts 4,4 '-methyl diphenylene diisocyanate or 1,6-hexamethylene diisocyanate, described polyether polyol is selected from PTMG or propylene oxide copolymer glycols, one or more in described catalyst choice dibutyl tin laurate, triethanolamine or dual-morpholinyl diethyl ether, the one in 1,6-hexylene glycol, methyl propanediol, BDO selected by described chain extender, described antioxidant selects 2,6-tri-grades of butyl-4-methylphenols or four { β-(3,5-tri-grades of butyl-4-hydroxy phenyls) propionic acid pentaerythritol ester, described tackifying resin be selected from polyethylene vinyl acetate copolymer, terminal hydroxy group thermoplastic polyester, hydrogenated rosin resin one or more, the composition of described fire retardant is by mass percentage: the inorganic filler being selected from least one in powdered talc, kaolinite, sericite, silica and diatomite of the polypropylene of melt index 0.5-15.0 gram/10 minutes of 30%-70%, the polyethylene of melt index 0.01-2.0 gram/10 minutes of 5%-25%, 20%-40%, the organic fire-resisting halide being selected from decabrominated dipheny base ether, ten dichloro ten dihydro dimethano benzene azoles cyclo-octene or its mixture of 5%-35%, described flexibilizer is extruded by the mixing of polyethylene elastomer, Hi-fax, polypropylene and antiaging agent raw material and is formed, wherein prepare consisting of of the TPU raw material of described TPU membrane: the polymer polyatomic alcohol of 60-70 weight portion, be selected from molecular weight be 1000 PTMG, molecular weight be one or more in the poly-adipate glycol butanediol ester polyalcohol of 3000, Isosorbide-5-Nitrae-the cyclohexane diisocyanate of 30-35 weight portion, the chain extender of 4-9 weight portion, described chain extender is BDO, the Carbodiimides hydrolysis agent of 3-5 weight portion, 1-3 weight portion, decabromodiphenylethane that particle mean size is less than or equal to 4 microns mixes the organohalogen compounds fire retardant of micro-fumed silica, the antioxidant of 0.2-0.8 weight portion, described antioxidant is β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] at least one in pentaerythritol ester and two [(2,4-di-tert-butyl-phenyl) phosphorous acid] pentaerythritol ester, two (2,2,6,6-tetramethyl-4-piperidyl) SA ester hindered amine light stabilizer of 0.1-0.5 weight portion, the montanin wax of 0.4-0.8 weight portion and/or erucyl amide wax series lubricant agent, the titanium system of 0.05-0.2 weight portion or bismuth series catalysts, the PU raw material wherein preparing described dry type PU film consists of: the host of 55-70%, the butanone of 20-37%, the black sand of 3-10%, the tert-butyl hydroperoxide of 0.5-1%, the cloudy surface agent be made up of calcium class filler of 0.8-1%, the anti-wear agent be made up of aromatic series silicone oil of 0.6-0.9%, the Benzotriazole Ultraviolet Stabilizer of 0.2-0.6% and the antistatic agent be made up of metal dust or conductive black of 0.5-1.2%, consisting of of described host self: the polyester diol of 12-28%, the straight diol of 1-5%, the diphenyl methane-4 of 6-18%, 4 '-vulcabond, the TDI tripolymer of 1-3%, the dimethyl formamide of 20-70%, the butanone of 0-30%, the hydroxy-ethyl acrylate of 2-6%, each component all by mass percentage.
Further according to hot melt adhesive TPU-PU leather of the present invention, the composition of the inorganic particulate in the transition zone of wherein said release liners comprises particle diameter and is 0.5-0.8 micron and accounts for the clay of inorganic particulate total content 25%, particle diameter at 1-2 micron to account for the barium sulfate powder of 60% of inorganic particulate total content and particle diameter at 3-5 micron and account for the calcium carbonate of 15% of inorganic particulate total content; The structural formula of the vinyl silicone oil in wherein said release layer is: in formula, R1 and R3 is-CH3, R2 be-CH=CH2, m span be 2000 ~ 3000, n span is 3 ~ 6.
Further according to hot melt adhesive TPU-PU leather of the present invention, the thickness of wherein said tack coat A2 is 2.5 microns, the thickness of described plastic layer A3 is 20 microns, described transition zone A4 thickness be 15 microns, the thickness of described release layer A5 is 25 microns, and the raw materials of described transition zone is inorganic particulate 65 weight portion, Silicone acrylic emulsion 35 weight portion, methyl sodiosul foaliphatate 4 weight portion, dodecyl benzyl dimethyl ammonium chloride weight 3 parts and water 50 weight portion; The raw materials of described release layer is the polypropylene of 60 weight portions, the poly(4-methyl-1-pentene) of 30 weight portions, the vinyl silicone oil of 8 weight portions, 2 of 1.5 weight portions, 2 '-methylene-bis--(4,6 di-t-butyl phenoxy groups) tert butyl peroxy benzoate of sodium phosphate and 0.5 weight portion, the structural formula of described vinyl silicone oil middle R1 and R3 is-CH3, R2 is-CH=CH2, m=2500, n=4.
Further according to hot melt adhesive TPU-PU leather of the present invention, the raw materials of wherein said hot melt adhesive consists of: the chain extender of the polyether polyol of the polyester polyol of 65 weight portions, the vulcabond of 18 weight portions, 4 weight portions, the catalyst of 1 weight portion, 1 weight portion, 1.6 weight portion antioxidants, the tackifying resin of 5 weight portions, the fire retardant of 3 weight portions, the flexibilizer of 3 weight portions; Described flexibilizer by weight by 31% polyethylene elastomer, the Hi-fax of 19%, the polypropylene of 49% and 1% antiaging agent raw material mix and extrude and form; Described fire retardant by 50 % by weight the melt index polypropylene of 5 grams/10 minutes, the melt index polyethylene of 0.8 gram/10 minutes of 20 % by weight, inorganic filler that the powdered talc of 20 % by weight and kaolinite mix, 10 % by weight decabrominated dipheny base ether and the organohalogen compounds that mix of ten dichloro ten dihydro dimethano benzene azoles cyclo-octene form.
Further according to hot melt adhesive TPU-PU leather of the present invention, the molecular weight consisting of 65 weight portions of wherein said TPU raw material is the poly-adipate glycol butanediol ester polyalcohol of 3000, β-(the 4-hydroxyl-3 of 0.6 weight portion, 5-di-tert-butyl-phenyl) propionic acid positive octadecanol ester antioxidant, two (2 of 0.3 weight portion, 2, 6, 6-tetramethyl-4-piperidyl) SA ester light stabilizer, the erucyl amide wax series lubricant agent of 0.6 weight portion, the Carbodiimides hydrolysis agent of 4 weight portions, 32 weight portions and temperature 60 DEG C 1, 4-cyclohexane diisocyanate, 1 of 6 weight portions, the agent of 4-chain expansion of succinic acid, the bismuth series catalysts of 0.1 weight portion, the decabromodiphenylethane of 2 weight portions mixes the organohalogen compounds fire retardant of micro-fumed silica.
Further according to hot melt adhesive TPU-PU leather of the present invention, the composition of wherein said PU raw material is by mass percentage: the host of 60%, the butanone of 30%, the black sand of 6%, the tert-butyl hydroperoxide of 0.8%, the cloudy surface agent of 0.8%, the anti-wear agent of 0.8%, the ultra-violet absorber of 0.6% and the antistatic agent of 1%, the composition of wherein said host self is by mass percentage: the polyester diol of 20%, the butanone of 10%, the dimethyl formamide of 50%, the straight diol of 3%, the diphenyl methane-4 of 12%, 4 '-vulcabond, the TDI tripolymer of 2% and the hydroxy-ethyl acrylate of 3%.
Further according to hot melt adhesive TPU-PU leather of the present invention, the TENSILE STRENGTH of wherein said hot melt adhesive TPU-PU leather is horizontal 34.2kgf, longitudinal 29.2kgf; The tearing strength of described hot melt adhesive TPU-PU leather is warp-wise 6.1kgf; Broadwise 5.2kgf; The adhesive strength of described hot melt adhesive TPU-PU leather is more than or equal to 3.0Kg/25 ㎜; The percentage elongation of described hot melt adhesive TPU-PU leather is more than or equal to 600%; The Shao Er hardness of described hot melt adhesive TPU-PU leather is more than or equal to 98.
A preparation method for the hot melt adhesive TPU-PU leather of vehicle slit preventing, is characterized in that, said method comprising the steps of:
(1) release liners is prepared
(1) paper bottom A1, is selected, and coating thickness is the aqueous polyacrylamide tack coat A2 of 0.8-4 micron on described paper bottom A1, then on described tack coat A2, paste the plastic layer A3 formed by polyethylene terephthalate film that thickness is 18-25 micron, then solidify certain hour;
(2), the methyl sodiosul foaliphatate of 3-5 weight portion is poured in the water of 45-55 weight portion, stir, then 62-68 weight portion is poured into and the inorganic particulate be mixed by clay, barium sulfate powder and calcium carbonate powder, and high-speed stirred is uniformly dispersed, then in scattered slurry, add the Silicone acrylic emulsion of 32-36 weight portion, after solution being mixed with glass bar, the dodecyl benzyl dimethyl ammonium chloride of 2-4 weight portion is added on wherein, continue to stir, make transition zone coating fluid;
(3), on plastic layer A3, transition zone coating fluid described in scraper even spread is used, and 30 seconds film-formings are heated at 80 DEG C, control thickness at 15-20 micron, then by the transition zone A4 after film forming 120 DEG C, linear pressure 150KN/m, speed of a motor vehicle 10m/min condition under carry out press polish process;
(4) 90 DEG C are heated to after, the poly(4-methyl-1-pentene) of the polypropylene of 58-65 weight portion, 26-34 weight portion and the vinyl silicone oil of 6-9 weight portion being mixed, be incubated and add 2 of 1-2 weight portion after 2 hours, 2 '-methylene-bis--(4,6 di-t-butyl phenoxy groups) sodium phosphate and 0.1-0.8 weight portion tert butyl peroxy benzoate and mix, then form release layer A5 by extruder Extrusion Coating in the surface of described transition zone A4, control thickness at 20-25 micron;
(2), hot melt adhesive raw material is prepared
(1), the tackifying resin of the polyether polyol of the polyester polyol of 60-70 weight portion, 3-5 weight portion, the antioxidant of 1.5-1.8 weight portion and 4-6 weight portion is placed in reactor, be heated to 120 ~ 140 DEG C, be uniformly mixed lower vacuum dehydration 1.5 ~ 2h, vacuum is less than 0.05MPa, is then cooled to 70 ~ 75 DEG C, wherein said polyester polyol is by low molecular weight aliphatic dihydroxy alcohol and aliphatic dicarboxylic acid, aromatic binary carboxylic acid polycondensation reaction and be prepared into the hydroxyl telechelic polyester glycol that molecular weight is 2000-6000 at 100-260 DEG C, described polyether polyol is selected from PTMG, one in propylene oxide copolymer glycols, described antioxidant is selected from 2, 6-tri-grades of butyl-4-methylphenols or four { β-(3, 5-tri-grades of butyl-4-hydroxy phenyls) propionic acid } pentaerythritol ester, described tackifying resin is selected from polyethylene vinyl acetate copolymer, terminal hydroxy group thermoplastic polyester, one or more of hydrogenated rosin resin,
(2), under nitrogen protection, the catalyst of the vulcabond of 15-20 weight portion and 0.8-1.5 weight portion is joined in the product of step (1), and at 85 ~ 95 DEG C of reaction 1-1.5h; Wherein said vulcabond adopts 4, the one in 4 '-methyl diphenylene diisocyanate or 1,6-hexamethylene diisocyanate, one or more in described catalyst choice dibutyl tin laurate, triethanolamine or dual-morpholinyl diethyl ether;
(3), under nitrogen protection, the fire retardant of the chain extender of 0.5-1.2 weight portion, 2-4 weight portion, the flexibilizer of 2-4 weight portion are joined in the product of step (2), and at 75 ~ 85 DEG C of stirring reaction 45min-1.0h; The one in 1,6-hexylene glycol, methyl propanediol, BDO selected by wherein said chain extender, and described fire retardant is made up of polypropylene, polyethylene, inorganic filler and organic fire-resisting halide; Polyolefine toughener selected by described flexibilizer;
(4), pass into the bottom discharge of nitrogen protection condition, after slaking cooling, be formed as hot melt adhesive raw material;
(3), TPU raw material is prepared
(1), the polymer polyatomic alcohol of 60-70 weight portion is placed in reactor, and be heated to 80-90 DEG C, described polymer polyatomic alcohol to be molecular weight be 1000 PTMG and/or molecular weight be 3000 poly-adipate glycol butanediol ester polyalcohol, then the antioxidant of 0.2-0.8 weight portion is added, two (2 of 0.1-0.5 weight portion, 2, 6, 6-tetramethyl-4-piperidyl) SA ester hindered amine light stabilizer, the montanin wax of 0.4-0.8 weight portion and/or the Carbodiimides hydrolysis agent of erucyl amide wax series lubricant agent and 3-5 weight portion, polymer polyol mixed alkoxide solution is obtained after abundant stirring, wherein said antioxidant is β-(4-hydroxyl-3, 5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and two [(2, 4-di-tert-butyl-phenyl) phosphorous acid] at least one in pentaerythritol ester,
(2), add in described polymer polyol mixed alkoxide solution 30-35 weight portion, temperature at the Isosorbide-5-Nitrae-cyclohexane diisocyanate of 55-65 DEG C, obtain initial reaction mixture after being uniformly mixed;
(3), keep the temperature of above-mentioned reactant mixture and add the BDO chain extender of 4-9 weight portion and the titanium system of 0.05-0.2 weight portion or bismuth series catalysts, and control temperature 150-210 DEG C, pressure 4-8MPa reacts about 1h;
(4), when reaction melt temperature reaches between 180-210 DEG C, add 1-3 weight portion and particle mean size is less than or equal to the organohalogen compounds fire retardant being mixed micro-fumed silica by decabromodiphenylethane of 4 microns, carry out dewatering after the reaction scheduled time, dry and slaking, obtain Polyurethane Thermoplastic Elastomer raw material;
(4), PU raw material is prepared
(1) host is prepared: by the polyester diol of 12-28%, the butanone of 0-30%, the dimethyl formamide of 20-70%, the straight diol of 1-5% puts into reaction pot stirring at normal temperature 20-40 minute, after mixing, at normal temperatures by the diphenyl methane-4 of 6-18%, after 4 '-vulcabond puts into reaction pot, heat temperature raising after making it react 1-3 hour at 70-80 DEG C, add the TDI tripolymer of 1-3% again, react 1-3 hour at 60-80 DEG C after, after being progressively cooled to 40-50 DEG C, add the hydroxy-ethyl acrylate of 2-6%, stir discharge of lowering the temperature after 0.5 hour, obtained described host,
(2) after the antistatic agent of the ultra-violet absorber of the anti-wear agent of the cloudy surface agent of the tert-butyl hydroperoxide of the black sand of the butanone of the host of 55-70%, 20-37%, 3-10%, 0.5-1%, 0.8-1%, 0.6-0.9%, 0.2-0.6%, 0.5-1.2% being mixed, in high speed dispersor dispersion 10-20 minute, leave standstill froth breaking and obtain PU raw material after 4 hours;
(5), vehicle slit preventing hot melt adhesive TPU-PU leather is prepared in laminating
(1), prepare release liners, hot melt adhesive raw material, TPU raw material and the PU raw material prepared by above-mentioned steps, and release liners is placed in relevant device paves;
(2), hot melt adhesive raw material prepared by step (two) is processed into sizing material through extruder, the extruder that 150 degree of temperature sent into by sizing material is melt into pasty state, extrude rear curtain coating on described strippable paper by extruder die head again, then warp is to pinch roller to press-cool-batching, and forms hot melt adhesive film;
(3), the TPU raw material prepared by step (three) is extruded into TPU membrane, and be placed on two cradles respectively with above-mentioned hot melt adhesive film, height hot melt adhesive film and TPU membrane being entered simultaneously be provided with constant temperature carries out pressure in pinch roller, to the temperature of pinch roller more than 160 DEG C, thus make low-melting hot melt adhesive be bonded as one to pinch roller to moment during pressure and TPU membrane at height, form the TPU film with hot melt adhesive after cooling;
(4), the PU raw material prepared by step (four) is poured in release liners, drives the release liners of expecting with PU to run by cradle, through scraper and baking box PU raw material fully struck off respectively and is baked to micro-dry after make dry type PU film;
(5), by dry type PU film by the TPU film with hot melt adhesive obtained with step (3) after gluing be sent to simultaneously decorative pattern in pinch roller to molded, then batch after being cooled fast by cooling device, obtain the hot melt adhesive vehicle slit preventing TPU-PU leather by the sandwich construction of dry type PU film+TPU membrane+hot melt adhesive film of the present invention.
Further according to hot melt adhesive TPU-PU leather preparation method of the present invention, wherein prepare in the step () of release liners: the raw materials of described transition zone is inorganic particulate 65 weight portion, Silicone acrylic emulsion 35 weight portion, methyl sodiosul foaliphatate 4 weight portion, dodecyl benzyl dimethyl ammonium chloride 3 weight portion and water 50 weight portion, specifically consisting of of described inorganic particulate: clay particle diameter be 0.5-0.8 micron and content be 25%, barium sulfate powder diameter at 1-2 micron and content be 60%, calcium carbonate powder particle diameter is at 3-5 micron and content is 15%; The raw materials of described release layer is the polypropylene of 60 weight portions, the poly(4-methyl-1-pentene) of 30 weight portions, the vinyl silicone oil of 8 weight portions, 2 of 1.5 weight portions, 2 '-methylene-bis--(4,6 di-t-butyl phenoxy groups) tert butyl peroxy benzoate of sodium phosphate and 0.5 weight portion, the structural formula of described vinyl silicone oil middle R1 and R3 is-CH 3, R2 is-CH=CH 2, m=2500, n=4.
Further according to hot melt adhesive TPU-PU leather preparation method of the present invention, wherein the aliphatic dicarboxylic acid of preparation polyester polyol is selected oneself diacid, fumaric acid, maleic acid or suberic acid in step (two), aromatic binary carboxylic acid is selected from phthalic acid, terephthalic acid (TPA) or M-phthalic acid, aliphatic dihydroxy alcohol is selected from ethylene glycol, diethylene glycol (DEG), propylene glycol, methyl propanediol, 1,4-butanediol, 1,6-hexylene glycol, 1,3-BDO, 1,5 pentanediols or dodecyl hexylene glycol; The polypropylene of melt index 0.5-15.0 gram/10 minutes of specifically consisting of of described fire retardant: 30-70 % by weight, the polyethylene of melt index 0.01-2.0 gram/10 minutes of 5-25 % by weight, 20-30 % by weight be selected from least one inorganic filler in powdered talc, kaolinite, sericite, silica and diatomite, organic fire-resisting halide that 5-15 % by weight is selected from decabrominated dipheny base ether, ten dichloro ten dihydro dimethano benzene azoles cyclo-octene or its mixture; Described flexibilizer is extruded after being mixed by polyethylene elastomer, Hi-fax, polypropylene PP and antiaging agent raw material and is formed, and shared by each raw material, mass percent is: polyethylene elastomer 31%, Hi-fax 19%, polypropylene 49%, antiaging agent 1%.
Further according to hot melt adhesive TPU-PU leather preparation method of the present invention, in wherein said step (three), the molecular weight consisting of 65 weight portions of TPU raw material is the poly-adipate glycol butanediol ester polyalcohol of 3000, β-(the 4-hydroxyl-3 of 0.6 weight portion, 5-di-tert-butyl-phenyl) propionic acid positive octadecanol ester antioxidant, two (2 of 0.3 weight portion, 2, 6, 6-tetramethyl-4-piperidyl) SA ester light stabilizer, the erucyl amide wax series lubricant agent of 0.6 weight portion, the Carbodiimides hydrolysis agent of 4 weight portions, 32 weight portions and temperature 60 DEG C 1, 4-cyclohexane diisocyanate, 1 of 6 weight portions, the agent of 4-chain expansion of succinic acid, the bismuth series catalysts of 0.1 weight portion, the decabromodiphenylethane of 2 weight portions mixes the organohalogen compounds fire retardant of micro-fumed silica.
Further according to hot melt adhesive TPU-PU leather preparation method of the present invention, in wherein said step (four), the composition of PU raw material is by mass percentage: the host of 60%, the butanone of 30%, the black sand of 6%, the tert-butyl hydroperoxide of 0.8%, the cloudy surface agent of 0.8%, the anti-wear agent of 0.8%, the ultra-violet absorber of 0.6% and the antistatic agent of 1%, the composition of wherein said host self is by mass percentage: the polyester diol of 20%, the butanone of 10%, the dimethyl formamide of 50%, the straight diol of 3%, the diphenyl methane-4 of 12%, 4 '-vulcabond, the TDI tripolymer of 2% and the hydroxy-ethyl acrylate of 3%.
Technical characteristics of the present invention and technique effect are:
(1) have employed the sandwich construction release liners of innovative design, especially the wherein innovative design of Multifunctional layered and release layer, release liners provided by the present invention is made to be applied in leather and fur products the physicochemical property with exceptional, and and adhesion strength between hot melt adhesive is high, hardening time is fast, belong to the desirable base material in high-quality leather.
(2) have employed the low melting point hot melt adhesive of original creation, it is the adhesive that a kind of plasticity is strong, the liquid glue that desirable generation is industrial and solid gum and PU glue, there is the advantage such as environmental protection, no side effects, as desirable environmental protection jointing material, the performances such as hot melt adhesive of the present invention has low melting point, high, acidproof, alkaline-resisting, water-fastness, the resistance to dry-cleaning of elastic force, tension stress is strong, adhesion is strong, melting point is low
(3) TPU film adopted and PU film are improved by the innovation on raw material, overcome many defects of existing TPU and PU, not only have most of characteristic of rubber and common plastics, but also have excellent comprehensive physical and chemical property, can be used as and replace PVC, PU artificial leather and other leather fabric completely.
(4) the hot melt adhesive TPU-PU leather of vehicle slit preventing provided by the present invention, all qualitative change can not be there is when high temperature 190 degree, be very easy to and cloth, rubber (moulding) rubber material, the wooden material surface that waits bonds, clothing can be widely used in, footwear, handbag, case and bag, seat, industry manufactured by building decorations etc., and laminating after product water-fastness, dry-cleaning, product has wear-resisting, heat-resisting, the performance of resistance to complications, essence contained by hot melt adhesive of the present invention and TPU raw material, detect through SGS, there is biocompatible property, nontoxic, tasteless, without allergic reaction, product is environmental protection extremely, pollution-free effect, have one of desirable environmental protection laminating fabric 21st century.
Accompanying drawing explanation
Accompanying drawing 1 is that hot melt adhesive of the present invention is extruded into schematic diagram release liners being formed hot melt adhesive film;
Accompanying drawing 2 is the product schematic diagram after hot melt adhesive film shown in accompanying drawing 1 and TPU membrane pressing;
Accompanying drawing 3 is the film layer structure schematic diagram of the hot melt adhesive TPU-PU leather of vehicle slit preventing of the present invention;
Accompanying drawing 4 is for being applied to the structural representation of the release liners in the present invention;
A1-paper bottom, A2-tack coat, A3-plastic layer, A4-transition zone, A5-release layer in figure;
S1-release liners, S2-hot melt adhesive film, S3-TPU film, S4-dry type PU film in figure.
Detailed description of the invention
Below technical scheme of the present invention is described in detail, to enable those skilled in the art's understanding the solution of the present invention clearly, but does not therefore limit the scope of the invention.Here need first to illustrate: in the present invention, the composition of most raw material is with " weight portion " metering proportion, this " weight portion " only represents the component proportional quantity relation of often kind of material inside, similar with mass percent, do not represent actual service property (quality), that is some component of different material may have identical or close weight portion, but and does not mean that these components have identical or close mass content in each material.
First shaped article of the hot melt adhesive TPU-PU leather of vehicle slit preventing of the present invention and preparation method thereof is described.The shaped article of hot melt adhesive TPU-PU leather of the present invention comprises release liners S1, the hot melt adhesive film S2 be coated on release liners S1, be pasted on the TPU membrane S3 on hot melt adhesive film S2 and be pressed on the dry type PU film S4 on TPU membrane S3.
The method of lamination coating is taked in the preparation of the hot melt adhesive TPU-PU leather of vehicle slit preventing of the present invention, specifically comprises the following steps:
Step one, preparation release liners S1, hot melt adhesive raw material, TPU raw material and PU raw material, these raw materials belong to our company original creation, be also one of primary object of the present invention, can be detailed below provide its composition of raw materials and preparation method.
Step 2, prepared hot melt adhesive raw material are processed into sizing material through extruder, the extruder that sizing material is sent into up to 150 degree of temperature is melt into pasty state, again by extruder die head extrude rear curtain coating to buffer action strippable paper on, then through to pinch roller to press-cool-batching, formed without sewn hot-melt adhesive film S2, as shown in Figure 1;
Step 3, prepared TPU raw material is extruded into TPU membrane S3, and the hot melt adhesive film S2 of rolling and TPU membrane S3 is placed on two cradles respectively, height hot melt adhesive film S2 and TPU membrane S3 being entered simultaneously be provided with constant temperature carries out pressure in pinch roller, to the temperature of pinch roller more than 160 DEG C, hot melt adhesive is made to be bonded as one to pinch roller to moment during pressure and TPU at height, form the TPU membrane S3 with hot melt adhesive, as shown in Figure 2;
Step 4, prepared PU raw material is poured on release liners S1, drives the release liners S1 expected with PU to run by cradle, through scraper and baking box PU raw material fully struck off respectively and is baked to micro-dry after make dry type PU film S4;
Step 5, by dry type PU film S4 by after gluing be sent to the TPU membrane S3 of hot melt adhesive simultaneously decorative pattern in pinch roller to molded, then batch after being cooled fast by cooling device, obtain the vehicle slit preventing hot melt adhesive TPU-PU leather by the sandwich construction of dry type PU film+TPU membrane+hot melt adhesive film of the present invention.
Key technology of the present invention comprises: the preparation of the formula of high viscosity hot melt adhesive, the critical formulations of TPU, PU film and the wherein various selection of function additive (master batch) and the release liners S1 as base material.Due to TPU(Polyurethane Thermoplastic Elastomer Thermoplastic polyurethane) and PU(Polyurethane, polyurethanes, also claim: polyurethane), belong to environment-friendly materials, and only need simple modification formula due to PU raw material, just different density can be obtained, elasticity, the physical properties such as rigidity, belong to and well decorate formula materials, the present invention is in conjunction with long-term production practices and through a large amount of tests, a kind of novel polyurethane hot melt of proposition of innovation and TPU/PU material, by changing formula constituent and additive, combined mathematical module and practical proof, utilize the experimental data collection of many groups thus determine the factor of influence between each component, and go out optimum proportioning by theory calculate, and last formula is applied to test, the product of the present invention obtained after checking has better cementability, tear resistance, ABRASION RESISTANCE, the multiple physical performances such as heat-resisting quantity.
Be applied to the composition of release liners S1 of the present invention and be prepared as follows:
As shown in Figure 4, release liners S1 provided by the present invention has sandwich construction, specifically comprises paper bottom A1, and described paper bottom A1 is bonded with plastic layer A3 by tack coat A2, described plastic layer A3 is provided with transition zone A4, described transition zone A4 is provided with release layer A5.Concrete described plastic layer A3 is polyethylene terephthalate film (i.e. PET film), and thickness is 18-25 micron, preferably 20 microns.The bonding described paper bottom A1 of described tack coat A2 and described polyethylene terephthalate film A3, described tack coat A2 is aqueous polyacrylamide (PP) coating layer, and use amount is every square metre of 5-8 gram, and thickness is 0.8-4 micron, preferably 6 grams every square metre, thickness is 1-2.5 micron.Described transition zone A4 composition comprises inorganic particulate, Silicone acrylic emulsion, methyl sodiosul foaliphatate, dodecyl benzyl dimethyl ammonium chloride and water, the parts by weight of each component are: inorganic particulate 62-68 part, Silicone acrylic emulsion 32-36 part, methyl sodiosul foaliphatate 3-5 part, dodecyl benzyl dimethyl ammonium chloride 2-4 part, water 45-55 part; Wherein the composition of inorganic particulate comprises that particle diameter is 0.5-0.8 micron, the clay that accounts for inorganic particulate total content 25%, particle diameter 1-2 micron, account for inorganic particulate total content 60% barium sulfate powder and particle diameter 3-5 micron, account for inorganic particulate total content 15% calcium carbonate.The preparation process of described transition zone A4 is that the methyl sodiosul foaliphatate of above-mentioned weight portion is poured in the water of above-mentioned weight portion, stir, pour in above-mentioned agitating solution according to above-mentioned weight portion after clay included by inorganic particulate, barium sulfate powder and calcium carbonate are mixed, high-speed stirred is used to be uniformly dispersed, the Silicone acrylic emulsion of above-mentioned weight portion is added in scattered slurry, with glass bar, solution is mixed, again the dodecyl benzyl dimethyl ammonium chloride of above-mentioned weight portion is added on wherein, continue to stir, make transition zone coating fluid.Then on described plastic layer A3, transition zone coating fluid described in scraper even spread is used, and 30 seconds film-formings are heated at 80 DEG C, thickness 15-20 micron, then by the transition zone A4 after film forming at 120 DEG C, linear pressure 150KN/m, press polish process is carried out under speed of a motor vehicle 10m/min condition, the small hole in transition zone is decreased after press polish process, rete is made to become more smooth, obtain more fine and close level and smooth surface state, the advantageously laying of release layer thereon, and transition zone even curface makes final release layer surface have minute surface flatness, ensure that surface state and the glossiness of final leather products.The setting of described transition zone ensure that release liners S1 entirety has the level and smooth of anti-permeability and surface, Silicone acrylic emulsion is wherein through being heating and curing, fine and close film can be formed, effectively can intercept the osmosis of solvent to paper substrate, and the film that Silicone acrylic emulsion is formed also has good solvent resistance, solvent is applied the situation that it there will not be dissolved destruction film and other base materials, and the roughened state on paper bottom A1 and plastic layer A3 surface is effectively masked through transition zone, ensure that the flatness of release layer surface and release liners S1 entirety, the level and smooth glossiness being smoothly very beneficial for the whole leather products improved based on release liners S1 of this release liners S1 surface state.The composition of the above-mentioned release layer A5 that described transition zone A4 is arranged comprises: the polypropylene of 58-65 weight portion, the poly(4-methyl-1-pentene) of 26-34 weight portion, the vinyl silicone oil of 6-9 weight portion, 2 of 1-2 weight portion, 2 '-methylene-bis--(4,6 di-t-butyl phenoxy groups) tert butyl peroxy benzoate of sodium phosphate and 0.1-0.8 weight portion, the structural formula of wherein said vinyl silicone oil is:
in formula, R1 and R3 is-CH 3, R2 is-CH=CH 2, m span is 2000 ~ 3000, n span is 3 ~ 6.The preparation process of described release layer is be heated to 90 DEG C after the polypropylene of above-mentioned weight portion, poly(4-methyl-1-pentene) and vinyl silicone oil being mixed, be incubated and add 2 of 1-2 weight portion after 2 hours, 2 '-methylene-bis--(4,6 di-t-butyl phenoxy groups) sodium phosphate and 0.1-0.8 weight portion tert butyl peroxy benzoate and mix, then pass through extruder Extrusion Coating in the surface of transition zone A4, control the thickness of release layer at 20-25 micron.By 2 in this release layer, 2 '-methylene-bis--(4,6 di-t-butyl phenoxy groups) sodium phosphate and tert butyl peroxy benzoate accelerate the cross-linking reaction of the double bond causing polyolefinic double bond and vinyl silicone oil, and comprises polyolefin is wherein added, because the compatibility of polyolefin and polyurethane etc. is better, the properties of product after the release liners S1 therefore with this release layer and the hot melt adhesive containing polyurethane bond are better.The release liners S1 be applied in the present invention is prepared by said method, this release liners S1 is very suitable for the coating of hot melt adhesive of the present invention and PU film through overtesting, the thickness of preferred release liners S1 of the present invention is at 80-100 micron, but not as limit, can regulate according to actual needs.
The material component extruding the hot melt adhesive on above-mentioned strippable paper comprises:
The chain extender of the polyether polyol of the polyester polyol of 60-70 weight portion, the vulcabond of 15-20 weight portion, 3-5 weight portion, the catalyst of .8-1.5 weight portion, 0.5-1.2 weight portion, 1.5-1.8 weight portion antioxidant, the tackifying resin of 4-6 weight portion, the fire retardant of 2-4 weight portion, the flexibilizer of 2-4 weight portion.
Described polyester polyol is by the polycondensation reaction and be prepared into the hydroxyl telechelic polyester glycol that molecular weight is 2000-6000 at 100-260 DEG C of low molecular weight aliphatic dihydroxy alcohol and aliphatic dicarboxylic acid, aromatic binary carboxylic acid.Described aliphatic dicarboxylic acid comprises adipic acid, fumaric acid, maleic acid or suberic acid; Described aromatic binary carboxylic acid comprises phthalic acid, terephthalic acid (TPA) or M-phthalic acid; Described aliphatic dihydroxy alcohol comprises ethylene glycol, diethylene glycol (DEG), propylene glycol, methyl propanediol, BDO, 1,6-hexylene glycol, 1,3-BDO, 1,5 pentanediols or dodecyl hexylene glycol.
Described vulcabond adopts 4, the one in 4 '-methyl diphenylene diisocyanate, 1,6-hexamethylene diisocyanate;
Described polyether polyol is selected from the one in PTMG, propylene oxide copolymer glycols;
One or more in described catalyst choice dibutyl tin laurate, triethanolamine or dual-morpholinyl diethyl ether;
The one in 1,6-hexylene glycol, methyl propanediol, BDO selected by described chain extender;
Described antioxidant is selected from 2,6-, tri-grades of butyl-4-methylphenols or four { β-(3,5-, tri-grades of butyl-4-hydroxy phenyls) propionic acid } pentaerythritol ester;
Described tackifying resin be selected from polyethylene vinyl acetate copolymer, terminal hydroxy group thermoplastic polyester, hydrogenated rosin resin one or more;
The polypropylene of melt index 0.5-15.0 gram/10 minutes of specifically consisting of of described fire retardant: 30-70 % by weight, the polyethylene of melt index 0.01-2.0 gram/10 minutes of 5-25 % by weight, 20-30 % by weight be selected from least one inorganic filler in powdered talc, kaolinite, sericite, silica and diatomite, organic fire-resisting halide that 5-15 % by weight is selected from decabrominated dipheny base ether, ten dichloro ten dihydro dimethano benzene azoles cyclo-octene or its mixture.
Polyolefine toughener selected by described flexibilizer, extrude after wherein being mixed by PE (polyethylene) elastomer, Hi-fax, polypropylene (PP) and antiaging agent raw material and form, shared by each raw material, mass percent is: PE (polyethylene) elastomer 31%, Hi-fax 19%, polypropylene (PP) 49%, antiaging agent 1%.
The concrete preparation process of above-mentioned hot melt adhesive is:
(1) by above-mentioned weight portion, the tackifying resin of the polyether polyol of the polyester polyol of 60-70 weight portion, 3-5 weight portion, 1.5-1.8 weight portion antioxidant and 4-6 weight portion is placed in reactor, be heated to 120 ~ 140 DEG C, be uniformly mixed lower vacuum dehydration 1.5 ~ 2h, vacuum is less than 0.05MPa, is then cooled to 70 ~ 75 DEG C;
(2) under nitrogen protection, the catalyst of the vulcabond of 15-20 weight portion and 0.8-1.5 weight portion is joined in the product of step (1), and at 85 ~ 95 DEG C of reaction 1-1.5h;
(3) under nitrogen protection, the fire retardant of the chain extender of 0.5-1.2 weight portion, 2-4 weight portion, the flexibilizer of 2-4 weight portion are joined in the product of step (2), and at 75 ~ 85 DEG C of stirring reaction 45min-1.0h;
(4) passing into the bottom discharge of nitrogen protection condition, be formed as the hot melt adhesive raw material be applied in the present invention after slaking certain hour, and be admitted in extruder, be extended down on release liners S1 shown in accompanying drawing 2 by extruder die head extrudate flow.
TPU raw material for shaping TPU membrane S3 in the present invention consists of:
The polymer polyatomic alcohol of 60-70 weight portion; Described polymer polyatomic alcohol to be molecular weight be 1000 PTMG, molecular weight be one or more in the poly-adipate glycol butanediol ester polyalcohol of 3000; Isosorbide-5-Nitrae-the cyclohexane diisocyanate of 30-35 weight portion; The chain extender of 4-9 weight portion, described chain extender is BDO; The hydrolysis agent of 3-5 weight portion, is specially the agent of Carbodiimides hydrolysis; The fire retardant of 1-3 weight portion, described fire retardant is the organohalogen compounds fire retardant that decabromodiphenylethane mixes micro-fumed silica, and particle mean size is less than or equal to 4 microns; The antioxidant of 0.2-0.8 weight portion, described antioxidant is β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] at least one in pentaerythritol ester and two [(2,4-di-tert-butyl-phenyl) phosphorous acid] pentaerythritol ester; The hindered amine light stabilizer of 0.1-0.5 weight portion, is specially two (2,2,6,6-tetramethyl-4-piperidyl) SA ester; The montanin wax of 0.4-0.8 weight portion and/or erucyl amide wax series lubricant agent; The titanium system of 0.05-0.2 weight portion or bismuth series catalysts.
As follows for the preparation of the concrete grammar of the thermoplastic polyurethane elastomer of form film by above-mentioned raw materials:
(1) first reactor is placed in by the polymer polyatomic alcohol of above-mentioned weight portion, and be heated to 80-90 DEG C, then add the antioxidant of above-mentioned weight portion, hindered amine light stabilizer, lubricant and hydrolysis agent, after fully stirring, obtain polymer polyol mixed alkoxide solution.
(2) add in described polymer polyol mixed alkoxide solution above-mentioned weight portion, temperature obtains initial reaction mixture after the Isosorbide-5-Nitrae-cyclohexane diisocyanate of 55-65 DEG C is uniformly mixed;
(3) keep the temperature of above-mentioned reactant mixture and add BDO chain extender and the catalyst of above-mentioned weight portion, and control temperature 150-210 DEG C, pressure 4-8MPa reacts about 1h.
(4) when reaction melt temperature reaches between 180-210 DEG C, add the fire retardant of above-mentioned weight portion, carry out dewatering after the reaction scheduled time, dry and slaking, namely obtain Polyurethane Thermoplastic Elastomer raw material.
Be applied to device prepared by above-mentioned Polyurethane Thermoplastic Elastomer raw material and can be the singe screw mixing arrangement, parallel dual-screw successive reaction extruder, drying equipment etc. known in prior art.Obtained Polyurethane Thermoplastic Elastomer raw material is admitted in extruder again extrudes TPU membrane S3.
The raw material of dry type PU film S4 of the present invention and preparation
PU raw material composition percentage by weight for the formation of dry type PU film S4 is counted: the cloudy surface agent be made up of calcium class filler of the black sand of the host of 55-70%, the butanone of 20-37%, 3-10%, the tert-butyl hydroperoxide of 0.5-1%, 0.8-1%, the anti-wear agent be made up of aromatic series silicone oil of 0.6-0.9%, the Benzotriazole Ultraviolet Stabilizer of 0.2-0.6%, the antistatic agent be made up of metal dust or conductive black of 0.5-1.2%; The composition (percentage by weight) of described host self is again: the diphenyl methane-4 of the polyester diol of 12-28%, the straight diol of 1-5%, 6-18%, the TDI tripolymer of 4 '-vulcabond, 1-3%, the hydroxy-ethyl acrylate of the dimethyl formamide of 20-70%, the butanone of 0-30%, 2-6%.
The method of dry type PU film S4 is prepared by above-mentioned substance:
(1) host is prepared: by the polyester diol of 12-28%, the butanone of 0-30%, the dimethyl formamide of 20-70%, the straight diol of 1-5% puts into reaction pot stirring at normal temperature 20-40 minute, after mixing, at normal temperatures by the diphenyl methane-4 of 6-18%, after 4 '-vulcabond puts into reaction pot, heat temperature raising after making it react 1-3 hour at 70-80 DEG C, add the TDI tripolymer of 1-3% again, react 1-3 hour at 60-80 DEG C after, after being progressively cooled to 40-50 DEG C, add the hydroxy-ethyl acrylate of 2-6%, stir discharge of lowering the temperature after 0.5 hour, obtained described host,
(2) after the antistatic agent of the ultra-violet absorber of the anti-wear agent of the cloudy surface agent of the tert-butyl hydroperoxide of the black sand of the butanone of the host of 55-70%, 20-37%, 3-10%, 0.5-1%, 0.8-1%, 0.6-0.9%, 0.2-0.6%, 0.5-1.2% being mixed, in high speed dispersor dispersion 10-20 minute, leaving standstill froth breaking poured on release liners S1 after 4 hours, drive the release liners S1 expected with PU to run by cradle, through scraper and baking box PU raw material fully struck off respectively and is baked to micro-dry after make dry type PU film S4.
By above-mentioned dry type PU film S4 by after gluing be sent to the TPU membrane S3 of aforementioned hot melten gel simultaneously decorative pattern in pinch roller to molded, the vehicle slit preventing hot melt adhesive TPU-PU leather by the sandwich construction of dry type PU film S4+TPU film S3+ hot melt adhesive film S2 obtained of the present invention after cooling.
Finally detect the main performance without sewing hot melt adhesive TPU-PU leather of the present invention obtained by said method, testing result is as follows:
1, soft durometer: 65 ~ 70/A;
2, TENSILE STRENGTH: horizontal 34.2kgf, longitudinal 29.2kgf;
3, tearing strength: warp-wise 6.1kgf; Broadwise 5.2kgf;
4, abrasion resistance: under the pressure of 9Kpa, without wear phenomenon after grinding 650 turns;
5, adhesive strength: >=3.0Kg/25 ㎜.
6, percentage elongation: >=600%;
7, Shao Er hardness: >=98.
Contrast as follows with the main performance of similar-type products:
Performance TPU PVC Acrylonitrile-butadiene rubber Neoprene Natural rubber
Hardness (Shao Er) 98 87 78 70 77
TENSILE STRENGTH 34.2、29.2 16、14.3 11.6 10.3 16.3
Percentage elongation/% 600 309 400 400 574
Therefore obtained by the present invention without sewing hot melt adhesive TPU-PU leather, by innovation formula and make release liners S1, hot melt adhesive, TPU membrane S3 and dry type PU, especially the polyurethane hot melt of special formula and TPU membrane S3 is adopted to fit, the performances such as the TENSILE STRENGTH of final leather products, tearing strength, abrasion resistance, adhesive strength, surface gloss are all increased dramatically, even if all can not qualitative change be there is when high temperature 190 degree, clothing, footwear, handbag, case and bag, seat, building decoration etc. can be widely used in and manufacture industry.And " the hot melt adhesive TPU-PU leather of Novel free sewing " of the present invention that our company proposes in conjunction with long-term practice of innovation has no relevant bibliographical information at home and abroad, belongs to the world initiation.
Embodiment 1
Below provide a preferred embodiment of the present invention.
Prepare the hot melt adhesive TPU-PU leather of vehicle slit preventing of the present invention in the following manner.
One, release liners S1 is prepared
Select paper bottom A1, and coating thickness is aqueous polyacrylamide (PP) the tack coat A2 of 2.5 microns on described paper bottom A1, on described tack coat A2, then pastes thickness be the polyethylene terephthalate film A3 of 20 microns and solidify certain hour.Then according to inorganic particulate 65 weight portion, Silicone acrylic emulsion 35 weight portion, methyl sodiosul foaliphatate 4 weight portion, dodecyl benzyl dimethyl ammonium chloride weight 3 parts and water 50 weight portion prepare transition zone coating fluid, and use scraper to be uniformly coated on described polyethylene terephthalate film A3, and be cured and be processed into press polish the transition zone A4 that thickness is 15 microns, finally on described transition zone A4, Extrusion Coating thickness is 25 microns of release layer A5, the composition of described release layer comprises: the polypropylene of 60 weight portions, the poly(4-methyl-1-pentene) of 30 weight portions, the vinyl silicone oil of 8 weight portions, 2 of 1.5 weight portions, 2 '-methylene-bis--(4, 6 di-t-butyl phenoxy groups) tert butyl peroxy benzoate of sodium phosphate and 0.5 weight portion, the structural formula of described vinyl silicone oil is:
Wherein R1 and R3 is-CH 3, R2 is-CH=CH 2, m about 2500, n=4.Thus the release liners S1 prepared as leather substrate of the present invention.
Two, polyurethane hot melt raw material is prepared
(1) tackifying resin of the polyether polyol of the polyester polyol of 65 weight portions, 4 weight portions, 1.6 weight portion antioxidants and 5 weight portions is placed in reactor, be heated to 120 DEG C, be uniformly mixed lower vacuum dehydration 1.5h, vacuum is less than 0.05MPa, is then cooled to 70 DEG C;
(2) under nitrogen protection, the catalyst of the vulcabond of 18 weight portions and 1 weight portion is joined in the product of step (1), and at 85 DEG C of reaction 1.5h;
(3) under nitrogen protection, the fire retardant of the chain extender of 1 weight portion, 3 weight portions, the flexibilizer of 3 weight portions are joined in the product of step (2), and at 85 DEG C of stirring reaction 1.0h;
(4) passing into the bottom discharge of nitrogen protection condition, polyurethane hot melt raw material after slaking certain hour, is formed.
Wherein said polyester polyol is by low molecular weight aliphatic dihydroxy alcohol and aliphatic dicarboxylic acid, aromatic binary carboxylic acid polycondensation reaction and the hydroxyl telechelic polyester glycol prepared at 180-240 DEG C, and aliphatic dicarboxylic acid is wherein selected oneself diacid, fumaric acid; Aromatic binary carboxylic acid is wherein selected from phthalic acid, terephthalic acid (TPA), and aliphatic dihydroxy alcohol is wherein selected from ethylene glycol, 1,3-BDO, 1,5 pentanediols or dodecyl hexylene glycol.Described vulcabond adopts 4,4 '-methyl diphenylene diisocyanate; Described polyether polyol adopts PTMG; Described catalyst choice dual-morpholinyl diethyl ether; 1,6-hexylene glycol selected by described chain extender; Four { β-(3,5-, tri-grades of butyl-4-hydroxy phenyls) propionic acid } pentaerythritol ester selected by described antioxidant; Described tackifying resin selective hydrogenation abietic resin; Described fire retardant by: the inorganic filler that the polypropylene of melt index 5g/10min of 50 % by weight, the polyethylene of the melt index 0.8g/10min of 20 % by weight, the powdered talc of 20 % by weight and kaolinite mix, the decabrominated dipheny base ether of 10 % by weight and the organohalogen compounds fire retardant of ten dichloro ten dihydro dimethano benzene azoles cyclo-octene mixtures form.Polyolefine toughener selected by described flexibilizer, extrudes and forms: PE (polyethylene) elastomer 31%, Hi-fax 19%, polypropylene (PP) 49%, antiaging agent 1% after wherein being mixed by PE (polyethylene) elastomer, Hi-fax, polypropylene (PP) and antiaging agent raw material.
Three, TPU raw material is prepared
(1) by the molecular weight of 65 weight portions be 3000 poly-adipate glycol butanediol ester polyalcohol be placed in reactor, and be heated to 90 DEG C, then β-(the 4-hydroxyl-3 of 0.6 weight portion is added, 5-di-tert-butyl-phenyl) propionic acid positive octadecanol ester antioxidant, 0.3 weight portion two (2,2,6,6-tetramethyl-4-piperidyl) SA ester light stabilizer, the erucyl amide wax series lubricant agent of 0.6 weight portion, the Carbodiimides hydrolysis agent of 4 weight portions, obtain polymer polyol mixed alkoxide solution after fully stirring.
(2) add in described polymer polyol mixed alkoxide solution 32 weight portions, temperature obtains initial reaction mixture after the Isosorbide-5-Nitrae-cyclohexane diisocyanate of 60 DEG C is uniformly mixed;
(3) keep the temperature of above-mentioned reactant mixture and add the BDO chain extender of 6 weight portions and the bismuth series catalysts of 0.1 weight portion, and control temperature 180-210 DEG C, pressure 6MPa reacts about 1h.
(4) when reaction melt temperature reaches between 200 DEG C, the decabromodiphenylethane adding 2 weight portions mixes the organohalogen compounds fire retardant of micro-fumed silica, carry out dewatering after the reaction scheduled time, dry and slaking, namely obtain Polyurethane Thermoplastic Elastomer raw material.
Four, dry type PU film S4 is prepared
(1) prepare host: by mass percentage by the polyester diol of 20%, 10% butanone, the dimethyl formamide of 50%, the straight diol of 3% put into reaction pot stirring at normal temperature 30 minutes, after mixing, at normal temperatures by the diphenyl methane-4 of 12%, after 4 '-vulcabond puts into reaction pot, heat temperature raising also makes it react at 80 DEG C after 2 hours, add the TDI tripolymer of 2% again, react at 80 DEG C after 2 hours, after being progressively cooled to 40 DEG C, add the hydroxy-ethyl acrylate of 3%, stir discharge of lowering the temperature after 0.5 hour, obtained described host;
(2) by the described host of 60%, 30% butanone, 6% black sand, 0.8% tert-butyl hydroperoxide, 0.8% cloudy surface agent, 0.8% anti-wear agent, 0.6% ultra-violet absorber, 1% antistatic agent mixing after, 20 minutes are disperseed in high speed dispersor, leaving standstill froth breaking poured on release liners S1 after 4 hours, drive the release liners S1 expected with PU to run by cradle, through scraper and baking box PU raw material fully struck off respectively and is baked to micro-dry after make dry type PU film S4.
Five, vehicle slit preventing hot melt adhesive TPU-PU leather is prepared in laminating
(1), prepare release liners S1, hot melt adhesive raw material, TPU raw material and the PU raw material prepared by said method, and release liners S1 is placed in relevant device paves;
(2), prepared hot melt adhesive raw material is processed into sizing material through extruder, the extruder that sizing material is sent into up to 150 degree of temperature is melt into pasty state, extrude rear curtain coating on described strippable paper by extruder die head again, then warp is to pinch roller to press-cool-batching, and forms hot melt adhesive film S2 shown in accompanying drawing 1;
(3), prepared TPU raw material is extruded into TPU membrane S3 equally, and be placed on two cradles respectively with the hot melt adhesive film S2 of rolling in step (2), height hot melt adhesive film S2 and TPU membrane S3 being entered simultaneously be provided with constant temperature carries out pressure in pinch roller, to the temperature of pinch roller more than 160 DEG C, thus make low-melting hot melt adhesive be bonded as one to pinch roller to moment during pressure and TPU membrane S3 at height, the TPU membrane S3 with hot melt adhesive film is formed, as shown in Figure 2 after cooling;
(4), prepared PU raw material is poured on release liners S1, drives the release liners S1 expected with PU to run by cradle, through scraper and baking box PU raw material fully struck off respectively and is baked to micro-dry after make dry type PU film S4;
(5), by dry type PU film S4 by the TPU membrane S3 with hot melt adhesive obtained with step (3) after gluing be sent to simultaneously decorative pattern in pinch roller to molded, then batch after being cooled fast by cooling device, obtain the hot melt adhesive vehicle slit preventing TPU-PU leather by the sandwich construction of dry type PU film S4+TPU film S3+ hot melt adhesive film S2 of the present invention.
Below be only that the preferred embodiment of the present invention is described; technical scheme of the present invention is not limited to this; the any known distortion that those skilled in the art do on the basis that major technique of the present invention is conceived all belongs to the claimed technology category of the present invention, and the concrete protection domain of the present invention is as the criterion with the record of claims.

Claims (12)

1. the hot melt adhesive TPU-PU leather of a vehicle slit preventing, the hot melt adhesive film (S2) it is characterized in that, comprise release liners, being coated on release liners on (S1), the dry type PU film (S4) being pasted on the TPU membrane (S3) on hot melt adhesive film (S2) and with described TPU membrane (S3), pressure viscosity being pasted;
Wherein said release liners (S1) comprises paper bottom (A1), tack coat (A2), plastic layer (A3), transition zone (A4) and release layer (A5), described plastic layer (A3) is adhered on described paper bottom (A1) by tack coat (A2), described transition zone (A4) is arranged on described plastic layer (A3), described release layer (A5) is arranged on described transition zone (A4), described tack coat (A2) is aqueous polyacrylamide coating layer, use amount is every square metre of 5-8 gram, thickness is 0.8-4 micron, described plastic layer (A3) is the polyethylene terephthalate film of thickness between 18-25 micron, described transition zone (A4) is by the inorganic particulate of 62-68 weight portion, the Silicone acrylic emulsion of 32-36 weight portion, the methyl sodiosul foaliphatate of 3-5 weight portion, the dodecyl benzyl dimethyl ammonium chloride of 2-4 weight portion and the water mix and blend of 45-55 weight portion are prepared from, and film forming thickness is at 15-20 micron, the thickness of described release layer (A5) is 20-25 micron and by the polypropylene of 58-65 weight portion, the poly(4-methyl-1-pentene) of 26-34 weight portion, the vinyl silicone oil of 6-9 weight portion, 2 of 1-2 weight portion, 2 '-methylene-bis--(4, 6 di-t-butyl phenoxy groups) tert butyl peroxy benzoate of sodium phosphate and 0.1-0.8 weight portion is mixed with and forms,
Wherein said hot melt adhesive film extrudes preparation by hot melt adhesive raw material, and described hot melt adhesive is prepared from by the flexibilizer of the chain extender of the catalyst of the polyether polyol of the vulcabond of the polyester polyol of 60-70 weight portion, 15-20 weight portion, 3-5 weight portion, 0.8-1.5 weight portion, 0.5-1.2 weight portion, 1.5-1.8 weight portion antioxidant, the tackifying resin of 4-6 weight portion, the fire retardant of 2-4 weight portion and 2-4 weight portion, described polyester polyol is by low molecular weight aliphatic dihydroxy alcohol and aliphatic dicarboxylic acid, aromatic binary carboxylic acid polycondensation reaction and be prepared into the hydroxyl telechelic polyester glycol that molecular weight is 2000-6000 at 100-260 DEG C, described aliphatic dicarboxylic acid is selected oneself diacid, fumaric acid, maleic acid or suberic acid, described aromatic binary carboxylic acid is selected from phthalic acid, terephthalic acid (TPA) or M-phthalic acid, described aliphatic dihydroxy alcohol is selected from ethylene glycol, diethylene glycol (DEG), propylene glycol, methyl propanediol, 1, 4-butanediol, 1, 6-hexylene glycol, 1, 3-butanediol, 1, 5 pentanediols or dodecyl hexylene glycol, described vulcabond adopts 4,4 '-methyl diphenylene diisocyanate or 1,6-hexamethylene diisocyanate, described polyether polyol is selected from PTMG or propylene oxide copolymer glycols, one or more in described catalyst choice dibutyl tin laurate, triethanolamine or dual-morpholinyl diethyl ether, the one in 1,6-hexylene glycol, methyl propanediol, BDO selected by described chain extender, described antioxidant selects 2,6-, tri-grades of butyl-4-methylphenols or four { β-(3,5-, tri-grades of butyl-4-hydroxy phenyls) propionic acid } pentaerythritol ester, described tackifying resin be selected from polyethylene vinyl acetate copolymer, terminal hydroxy group thermoplastic polyester, hydrogenated rosin resin one or more, the composition of described fire retardant is by mass percentage: the organic fire-resisting halide being selected from decabrominated dipheny base ether, ten dichloro ten dihydro dimethano benzene azoles cyclo-octene or its mixture of the polyethylene of the polypropylene of the melt index 0.5-15.0g/10min of 30%-70%, the melt index 0.01-2.0g/10min of 5%-25%, the inorganic filler being selected from least one in powdered talc, kaolinite, sericite, silica and diatomite of 20%-40% and 5%-35%, described flexibilizer is extruded by the mixing of polyethylene elastomer, Hi-fax, polypropylene and antiaging agent raw material and is formed,
Wherein prepare consisting of of the TPU raw material of described TPU membrane (S3): the polymer polyatomic alcohol of 60-70 weight portion, be selected from molecular weight be 1000 PTMG, molecular weight be one or both in the poly-adipate glycol butanediol ester polyalcohol of 3000; Isosorbide-5-Nitrae-the cyclohexane diisocyanate of 30-35 weight portion; The chain extender of 4-9 weight portion, described chain extender is BDO; The Carbodiimides hydrolysis agent of 3-5 weight portion; 1-3 weight portion, decabromodiphenylethane that particle mean size is less than or equal to 4 microns mixes the organohalogen compounds fire retardant of micro-fumed silica; The antioxidant of 0.2-0.8 weight portion, described antioxidant is β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] at least one in pentaerythritol ester and two [(2,4-di-tert-butyl-phenyl) phosphorous acid] pentaerythritol ester; Two (2,2,6,6-tetramethyl-4-piperidyl) SA ester hindered amine light stabilizer of 0.1-0.5 weight portion; The montanin wax of 0.4-0.8 weight portion and/or erucyl amide wax series lubricant agent; The titanium system of 0.05-0.2 weight portion or bismuth series catalysts;
The PU raw material wherein preparing described dry type PU film (S4) consists of: the antistatic agent be made up of metal dust or conductive black of the cloudy surface agent be made up of calcium class filler of the black sand of the host of 55-70%, the butanone of 20-37%, 3-10%, the tert-butyl hydroperoxide of 0.5-1%, 0.8-1%, the anti-wear agent be made up of aromatic series silicone oil of 0.6-0.9%, the Benzotriazole Ultraviolet Stabilizer of 0.2-0.6% and 0.5-1.2%; Consisting of of described host self: the diphenyl methane-4 of the polyester diol of 12-28%, the straight diol of 1-5%, 6-18%, the TDI tripolymer of 4 '-vulcabond, 1-3%, the hydroxy-ethyl acrylate of the dimethyl formamide of 20-70%, the butanone of 0-30%, 2-6%; Each component all by mass percentage.
2. hot melt adhesive TPU-PU leather according to claim 1, it is characterized in that, the composition of the inorganic particulate in the transition zone of wherein said release liners (S1) comprises particle diameter and is 0.5-0.8 micron and accounts for the clay of inorganic particulate total content 25%, particle diameter at 1-2 micron to account for the barium sulfate powder of 60% of inorganic particulate total content and particle diameter at 3-5 micron and account for the calcium carbonate powder of 15% of inorganic particulate total content; The structural formula of the vinyl silicone oil in wherein said release layer is: in formula, R1 and R3 is-CH 3, R2 is-CH=CH 2, m span is 2000 ~ 3000, n span is 3 ~ 6.
3. hot melt adhesive TPU-PU leather according to claim 1, it is characterized in that, the thickness of described tack coat (A2) is 2.5 microns, the thickness of described plastic layer (A3) is 20 microns, described transition zone (A4) thickness be 15 microns, the thickness of described release layer (A5) is 25 microns, and the raw materials of described transition zone is inorganic particulate 65 weight portion, Silicone acrylic emulsion 35 weight portion, methyl sodiosul foaliphatate 4 weight portion, dodecyl benzyl dimethyl ammonium chloride weight 3 parts and water 50 weight portion; The raw materials of described release layer is the polypropylene of 60 weight portions, the poly(4-methyl-1-pentene) of 30 weight portions, the vinyl silicone oil of 8 weight portions, 2 of 1.5 weight portions, 2 '-methylene-bis--(4,6 di-t-butyl phenoxy groups) tert butyl peroxy benzoate of sodium phosphate and 0.5 weight portion, the structural formula of described vinyl silicone oil is: wherein R1 and R3 is-CH 3, R2 is-CH=CH 2, m=2500, n=4.
4. hot melt adhesive TPU-PU leather according to claim 1, it is characterized in that, the raw materials of wherein said hot melt adhesive consists of: the chain extender of the polyether polyol of the polyester polyol of 65 weight portions, the vulcabond of 18 weight portions, 4 weight portions, the catalyst of 1 weight portion, 1 weight portion, 1.6 weight portion antioxidants, the tackifying resin of 5 weight portions, the fire retardant of 3 weight portions, the flexibilizer of 3 weight portions; Described flexibilizer by weight by 31% polyethylene elastomer, the Hi-fax of 19%, the polypropylene of 49% and 1% antiaging agent raw material mix and extrude and form; Described fire retardant by 50% the melt index polypropylene of 5 grams/10 minutes, the melt index 0.8 gram/polyethylene of 10 minutes of 20%, inorganic filler that the powdered talc of 20% and kaolinite mix and 10% the organic fire-resisting halide that mixes with ten dichloro ten dihydro dimethano benzene azoles cyclo-octene of decabrominated dipheny base ether form.
5. hot melt adhesive TPU-PU leather according to claim 1, it is characterized in that, the molecular weight consisting of 65 weight portions of wherein said TPU raw material is the poly-adipate glycol butanediol ester polyalcohol of 3000, β-(the 4-hydroxyl-3 of 0.6 weight portion, 5-di-tert-butyl-phenyl) propionic acid positive octadecanol ester antioxidant, two (2 of 0.3 weight portion, 2, 6, 6-tetramethyl-4-piperidyl) SA ester light stabilizer, the erucyl amide wax series lubricant agent of 0.6 weight portion, the Carbodiimides hydrolysis agent of 4 weight portions, 32 weight portions and temperature 60 DEG C 1, 4-cyclohexane diisocyanate, 1 of 6 weight portions, the agent of 4-chain expansion of succinic acid, the bismuth series catalysts of 0.1 weight portion, the decabromodiphenylethane of 2 weight portions mixes the organohalogen compounds fire retardant of micro-fumed silica.
6. hot melt adhesive TPU-PU leather according to claim 1, it is characterized in that, the composition of wherein said PU raw material is by mass percentage: the host of 60%, the butanone of 30%, the black sand of 6%, the tert-butyl hydroperoxide of 0.8%, the cloudy surface agent of 0.8%, the anti-wear agent of 0.8%, the ultra-violet absorber of 0.6% and the antistatic agent of 1%, the composition of wherein said host self is by mass percentage: the polyester diol of 20%, the butanone of 10%, the dimethyl formamide of 50%, the straight diol of 3%, the diphenyl methane-4 of 12%, 4 '-vulcabond, the TDI tripolymer of 2% and the hydroxy-ethyl acrylate of 3%.
7. the hot melt adhesive TPU-PU leather according to any one of claim 1-6, is characterized in that, the TENSILE STRENGTH of described hot melt adhesive TPU-PU leather is horizontal 34.2kgf, longitudinal 29.2kgf; The tearing strength of described hot melt adhesive TPU-PU leather is warp-wise 6.1kgf; Broadwise 5.2kgf; The adhesive strength of described hot melt adhesive TPU-PU leather is more than or equal to 3.0Kg/25 ㎜; The percentage elongation of described hot melt adhesive TPU-PU leather is more than or equal to 600%; The Shao Er hardness of described hot melt adhesive TPU-PU leather is more than or equal to 98.
8. a preparation method for the hot melt adhesive TPU-PU leather of vehicle slit preventing, is characterized in that, said method comprising the steps of:
(1) release liners (S1) is prepared
(1), paper bottom (A1) is selected, and coating thickness is the aqueous polyacrylamide tack coat (A2) of 0.8-4 micron on described paper bottom (A1), then be the plastic layer (A3) formed by polyethylene terephthalate film of 18-25 micron at described tack coat (A2) upper stickup thickness, then solidify certain hour;
(2), the methyl sodiosul foaliphatate of 3-5 weight portion is poured in the water of 45-55 weight portion, stir, then 62-68 weight portion is poured into and the inorganic particulate be mixed by clay, barium sulfate powder and calcium carbonate powder, and high-speed stirred is uniformly dispersed, then in scattered slurry, add the Silicone acrylic emulsion of 32-36 weight portion, after solution being mixed with glass bar, the dodecyl benzyl dimethyl ammonium chloride of 2-4 weight portion is added on wherein, continue to stir, make transition zone coating fluid;
(3), transition zone coating fluid described in plastic layer (A3) upper use scraper even spread, and 30 seconds film-formings are heated at 80 DEG C, control thickness at 15-20 micron, then by the transition zone (A4) after film forming 120 DEG C, linear pressure 150KN/m, speed of a motor vehicle 10m/min condition under carry out press polish process;
(4) 90 DEG C are heated to after, the poly(4-methyl-1-pentene) of the polypropylene of 58-65 weight portion, 26-34 weight portion and the vinyl silicone oil of 6-9 weight portion being mixed, be incubated and add 2 of 1-2 weight portion after 2 hours, 2 '-methylene-bis--(4,6 di-t-butyl phenoxy groups) sodium phosphate and 0.1-0.8 weight portion tert butyl peroxy benzoate and mix, then form release layer (A5) by extruder Extrusion Coating in the surface of described transition zone (A4), control thickness at 20-25 micron;
(2), hot melt adhesive raw material is prepared
(1), the tackifying resin of the polyether polyol of the polyester polyol of 60-70 weight portion, 3-5 weight portion, the antioxidant of 1.5-1.8 weight portion and 4-6 weight portion is placed in reactor, be heated to 120 ~ 140 DEG C, be uniformly mixed lower vacuum dehydration 1.5 ~ 2h, vacuum is less than 0.05MPa, is then cooled to 70 ~ 75 DEG C; Wherein said polyester polyol is be prepared into by low molecular weight aliphatic dihydroxy alcohol and aliphatic dicarboxylic acid, aromatic binary carboxylic acid polycondensation reaction at 100-260 DEG C the hydroxyl telechelic polyester glycol that molecular weight is 2000-6000; Described polyether polyol is selected from the one in PTMG, propylene oxide copolymer glycols; Described antioxidant is selected from 2,6-, tri-grades of butyl-4-methylphenols or four { β-(3,5-, tri-grades of butyl-4-hydroxy phenyls) propionic acid } pentaerythritol ester; Described tackifying resin be selected from polyethylene vinyl acetate copolymer, terminal hydroxy group thermoplastic polyester, hydrogenated rosin resin one or more;
(2), under nitrogen protection, the catalyst of the vulcabond of 15-20 weight portion and 0.8-1.5 weight portion is joined in the product of step (1), and at 85 ~ 95 DEG C of reaction 1-1.5h; Wherein said vulcabond adopts 4, the one in 4 '-methyl diphenylene diisocyanate or 1,6-hexamethylene diisocyanate; One or more in described catalyst choice dibutyl tin laurate, triethanolamine or dual-morpholinyl diethyl ether;
(3), under nitrogen protection, the fire retardant of the chain extender of 0.5-1.2 weight portion, 2-4 weight portion, the flexibilizer of 2-4 weight portion are joined in the product of step (2), and at 75 ~ 85 DEG C of stirring reaction 45min-1.0h; The one in 1,6-hexylene glycol, methyl propanediol, BDO selected by wherein said chain extender; The composition of described fire retardant is by mass percentage: the organic fire-resisting halide being selected from decabrominated dipheny base ether, ten dichloro ten dihydro dimethano benzene azoles cyclo-octene or its mixture of the polyethylene of the polypropylene of the melt index 0.5-15.0g/10min of 30%-70%, the melt index 0.01-2.0g/10min of 5%-25%, the inorganic filler being selected from least one in powdered talc, kaolinite, sericite, silica and diatomite of 20%-40% and 5%-35%; Polyolefine toughener selected by described flexibilizer;
(4), pass into the bottom discharge of nitrogen protection condition, after slaking cooling, be formed as hot melt adhesive raw material;
(3), TPU raw material is prepared
(1), the polymer polyatomic alcohol of 60-70 weight portion is placed in reactor, and be heated to 80-90 DEG C, described polymer polyatomic alcohol to be molecular weight be 1000 PTMG and/or molecular weight be 3000 poly-adipate glycol butanediol ester polyalcohol, then the antioxidant of 0.2-0.8 weight portion is added, two (2 of 0.1-0.5 weight portion, 2, 6, 6-tetramethyl-4-piperidyl) SA ester hindered amine light stabilizer, the montanin wax of 0.4-0.8 weight portion and/or the Carbodiimides hydrolysis agent of erucyl amide wax series lubricant agent and 3-5 weight portion, polymer polyol mixed alkoxide solution is obtained after abundant stirring, wherein said antioxidant is β-(4-hydroxyl-3, 5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and two [(2, 4-di-tert-butyl-phenyl) phosphorous acid] at least one in pentaerythritol ester,
(2), add in described polymer polyol mixed alkoxide solution 30-35 weight portion, temperature at the Isosorbide-5-Nitrae-cyclohexane diisocyanate of 55-65 DEG C, obtain initial reaction mixture after being uniformly mixed;
(3), keep the temperature of above-mentioned reactant mixture and add the BDO chain extender of 4-9 weight portion and the titanium system of 0.05-0.2 weight portion or bismuth series catalysts, and control temperature 150-210 DEG C, pressure 4-8MPa reacts about 1h;
(4), when reaction melt temperature reaches between 180-210 DEG C, add 1-3 weight portion and particle mean size is less than or equal to the organohalogen compounds fire retardant being mixed micro-fumed silica by decabromodiphenylethane of 4 microns, carry out dewatering after the reaction scheduled time, dry and slaking, obtain Polyurethane Thermoplastic Elastomer raw material;
(4), PU raw material is prepared
(1) host is prepared: by mass percentage by the polyester diol of 12-28%, the butanone of 0-30%, the dimethyl formamide of 20-70%, the straight diol of 1-5% puts into reaction pot stirring at normal temperature 20-40 minute, after mixing, at normal temperatures by the diphenyl methane-4 of 6-18%, after 4 '-vulcabond puts into reaction pot, heat temperature raising after making it react 1-3 hour at 70-80 DEG C, add the TDI tripolymer of 1-3% again, react 1-3 hour at 60-80 DEG C after, after being progressively cooled to 40-50 DEG C, add the hydroxy-ethyl acrylate of 2-6%, stir discharge of lowering the temperature after 0.5 hour, obtained described host,
(2) by mass percentage by after the mixing of the antistatic agent of the cloudy surface agent of the tert-butyl hydroperoxide of the black sand of the butanone of the host of 55-70%, 20-37%, 3-10%, 0.5-1%, 0.8-1%, the anti-wear agent of 0.6-0.9%, the ultra-violet absorber of 0.2-0.6% and 0.5-1.2%, in high speed dispersor, disperse 10-20 minute, leave standstill froth breaking and obtain PU raw material after 4 hours;
(5), vehicle slit preventing hot melt adhesive TPU-PU leather is prepared in laminating
(1), prepare release liners (S1), hot melt adhesive raw material, TPU raw material and the PU raw material prepared by above-mentioned steps, and release liners (S1) is placed in relevant device paves;
(2), hot melt adhesive raw material prepared by step (two) is processed into sizing material through extruder, the extruder that 150 degree of temperature sent into by sizing material is melt into pasty state, rear curtain coating is extruded in described release liners again by extruder die head, then warp is to pinch roller to press-cool-batching, and forms hot melt adhesive film (S2);
(3), the TPU raw material prepared by step (three) is extruded into TPU membrane (S3), and be placed on two cradles respectively with above-mentioned hot melt adhesive film (S2), make hot melt adhesive film (S2) and TPU membrane (S3) enter the height being provided with constant temperature to carry out pressure in pinch roller simultaneously, to the temperature of pinch roller more than 160 DEG C, thus make low-melting hot melt adhesive be bonded as one to pinch roller to moment during pressure and TPU membrane (S3) at height, form the TPU membrane with hot melt adhesive film after cooling;
(4), the PU raw material prepared by step (four) is poured in release liners (S1), drive the release liners (S1) of expecting with PU to run by cradle, through scraper and baking box PU raw material fully struck off respectively and is baked to micro-dry after make dry type PU film (S4);
(5), by dry type PU film (S4) by the TPU membrane with hot melt adhesive film obtained with step (3) after gluing be sent to simultaneously decorative pattern in pinch roller to molded, then cooled rear curling fast by cooling device, obtained dry type PU film (S4) adds the hot melt adhesive TPU-PU leather that TPU membrane (S3) adds the vehicle slit preventing of the sandwich construction of hot melt adhesive film (S2).
9. preparation method according to claim 8, it is characterized in that, wherein prepare in the step () of release liners (S1): the raw materials of described transition zone is inorganic particulate 65 weight portion, Silicone acrylic emulsion 35 weight portion, methyl sodiosul foaliphatate 4 weight portion, dodecyl benzyl dimethyl ammonium chloride 3 weight portion and water 50 weight portion, specifically consisting of of described inorganic particulate: clay particle diameter be 0.5-0.8 micron and content be 25%, barium sulfate powder diameter at 1-2 micron and content be 60%, calcium carbonate powder particle diameter is at 3-5 micron and content is 15%; The raw materials of described release layer is the polypropylene of 60 weight portions, the poly(4-methyl-1-pentene) of 30 weight portions, the vinyl silicone oil of 8 weight portions, 2 of 1.5 weight portions, 2 '-methylene-bis--(4,6 di-t-butyl phenoxy groups) tert butyl peroxy benzoate of sodium phosphate and 0.5 weight portion, the structural formula of described vinyl silicone oil is: wherein R1 and R3 is-CH 3, R2 is-CH=CH 2, m=2500, n=4.
10. preparation method according to claim 8, it is characterized in that, wherein the aliphatic dicarboxylic acid of preparation polyester polyol is selected oneself diacid, fumaric acid, maleic acid or suberic acid in step (two), aromatic binary carboxylic acid is selected from phthalic acid, terephthalic acid (TPA) or M-phthalic acid, aliphatic dihydroxy alcohol is selected from ethylene glycol, diethylene glycol (DEG), propylene glycol, methyl propanediol, BDO, 1,6-hexylene glycol, 1,3-butanediol, 1,5 pentanediols or dodecyl hexylene glycol; Described flexibilizer is extruded after being mixed by polyethylene elastomer, Hi-fax, polypropylene PP and antiaging agent raw material and is formed, and shared by each raw material, mass percent is: polyethylene elastomer 31%, Hi-fax 19%, polypropylene 49%, antiaging agent 1%.
11. preparation methods according to claim 8, it is characterized in that, in wherein said step (three), the molecular weight consisting of 65 weight portions of TPU raw material is the poly-adipate glycol butanediol ester polyalcohol of 3000, β-(the 4-hydroxyl-3 of 0.6 weight portion, 5-di-tert-butyl-phenyl) propionic acid positive octadecanol ester antioxidant, two (2 of 0.3 weight portion, 2, 6, 6-tetramethyl-4-piperidyl) SA ester light stabilizer, the erucyl amide wax series lubricant agent of 0.6 weight portion, the Carbodiimides hydrolysis agent of 4 weight portions, 32 weight portions and temperature 60 DEG C 1, 4-cyclohexane diisocyanate, 1 of 6 weight portions, the agent of 4-chain expansion of succinic acid, the bismuth series catalysts of 0.1 weight portion, the decabromodiphenylethane of 2 weight portions mixes the organohalogen compounds fire retardant of micro-fumed silica.
12. preparation methods according to claim 8, it is characterized in that, in wherein said step (four), the composition of PU raw material is by mass percentage: the host of 60%, the butanone of 30%, the black sand of 6%, the tert-butyl hydroperoxide of 0.8%, the cloudy surface agent of 0.8%, the anti-wear agent of 0.8%, the ultra-violet absorber of 0.6% and the antistatic agent of 1%, the composition of wherein said host self is by mass percentage: the polyester diol of 20%, the butanone of 10%, the dimethyl formamide of 50%, the straight diol of 3%, the diphenyl methane-4 of 12%, 4 '-vulcabond, the TDI tripolymer of 2% and the hydroxy-ethyl acrylate of 3%.
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