CN103437195A - 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

Info

Publication number
CN103437195A
CN103437195A CN2013103602215A CN201310360221A CN103437195A CN 103437195 A CN103437195 A CN 103437195A CN 2013103602215 A CN2013103602215 A CN 2013103602215A CN 201310360221 A CN201310360221 A CN 201310360221A CN 103437195 A CN103437195 A CN 103437195A
Authority
CN
China
Prior art keywords
weight portion
hot melt
melt adhesive
tpu
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2013103602215A
Other languages
Chinese (zh)
Other versions
CN103437195B (en
Inventor
何建雄
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongguan Xionglin New Materials Technology Co Ltd
Original Assignee
Dongguan Xionglin New Materials Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dongguan Xionglin New Materials Technology Co Ltd filed Critical Dongguan Xionglin New Materials Technology Co Ltd
Priority to CN201310360221.5A priority Critical patent/CN103437195B/en
Publication of CN103437195A publication Critical patent/CN103437195A/en
Priority to PCT/CN2014/079497 priority patent/WO2015021814A1/en
Application granted granted Critical
Publication of CN103437195B publication Critical patent/CN103437195B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

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 the leather substance technical field, relate to more specifically hot melt adhesive TPU-PU leather of a kind of vehicle slit preventing and preparation method thereof.
Background technology
In prior art, in production industries such as clothing at home and abroad, shoemaking, case and bag, handbag, seat, military projects, the fabric that all goods attach, be all to 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, is subject to the problems such as the easily fracture of External Force Acting linear slit place, tearing notch and decortication, has a strong impact on service life and the quality of product, and consumer cost also obviously increases.What also because of at present all product fabrics, mostly adopt is the PVC leather, and the PVC material itself contains polyvinyl chloride and DEHA etc., toxogenin is arranged, human body is had to carcinogenesis, use is absolutely unsafe, and used in the leather docile in prior art be mostly all industrial liquid glue, solid gum, these melten gel materials have and mostly all have toxicity, and there is certain defect at aspect of performances such as elasticity, acidproof, alkaline-resisting, water-fastness, anti-dry-cleaning, tension stress, adhesions, 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 each layer of raw material of leather innovated from component, the long-term production experience in conjunction with our company, final formation vehicle slit preventing TPU-PU leather of the present invention, can directly be fitted on various article, and there is firm pasting, durable, material environmental protection, to human body without technical advantages such as any stealthy injuries, fundamentally solved sewing and refuted 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 kind of hot melt adhesive TPU-PU leather of vehicle slit preventing, comprise release liners, be coated on the hot melt adhesive on release liners, the dry type PU film that is pasted on the TPU film on hot melt adhesive and with described TPU film, pressure viscosity is pasted, 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 the aqueous polyacrylamide coating layer, use amount is every square metre of 5-8 gram, thickness is the 0.8-4 micron, described plastic layer A3 is the polyethylene terephthalate film of thickness between the 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 water mix and blend of the dodecyl benzyl dimethyl ammonium chloride of 2-4 weight portion and 45-55 weight portion is prepared from, and film forming thickness is at the 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, 0.8-1.5 the catalyst of weight portion, 0.5-1.2 the chain extender of 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 is prepared into 100-260 ℃ of lower polycondensation reaction the hydroxyl telechelic polyester glycol that the molecule amount is 2000-6000, the described aliphatic dicarboxylic acid diacid of selecting oneself, 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, the 4-butanediol, 1, the 6-hexylene glycol, 1, the 3-butanediol, 1, 5 pentanediols or dodecyl hexylene glycol, described vulcabond employing 4,4 '-methyl diphenylene diisocyanate or 1,6-hexamethylene diisocyanate, described polyether polyol is selected from PTMG or propylene oxide copolymerization glycol, described catalyst is selected one or more in dibutyl tin laurate, triethanolamine or dual-morpholinyl diethyl ether, described chain extender is selected a kind of in 1,6-hexylene glycol, methyl propanediol, BDO, described antioxidant selects 2, tri-grades of butyl of 6--4-methylphenol or four { β-(3, tri-grades of butyl of 5--4-hydroxy phenyl) propionic acid } pentaerythritol ester, described tackifying resin is selected from one or more of polyethylene vinyl acetate copolymer, terminal hydroxy group thermoplastic polyester, Foral resin, the composition of described fire retardant is by mass percentage: the inorganic filler that is selected from powdered talc, kaolinite, sericite, silica and diatomite at least one of the polyethylene of the melt index 0.5-15.0 gram of the 30%-70%/polypropylene of 10 minutes, the melt index 0.01-2.0 gram of 5%-25%/10 minutes, 20%-40%, the organic fire-resisting halide that is 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 and is formed by polyethylene elastomer, Hi-fax, polypropylene and the mixing of antiaging agent raw material, the consisting of of TPU raw material that wherein prepares described TPU film: the polymer polyatomic alcohol of 60-70 weight portion, one or more in the poly-adipate glycol butanediol ester polyalcohol that PTMG, the molecular weight that to be selected from molecular weight be 1000 is 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, the 1-3 weight portion, particle mean size is less than or equal to the organohalogen compounds fire retardant that the decabrominated dipheny base ethane of 4 microns mixes micro-fumed silica, 0.2-0.8 the antioxidant of weight portion, described antioxidant is β-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid, four [β-(3, the 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, 0.1-0.5 two (2,2,6,6-tetramethyl-4-piperidyl) SA ester hindered amine light stabilizer of weight portion, 0.4-0.8 the montanin wax of weight portion and/or erucyl amide wax series lubricant agent, 0.05-0.2 the titanium system of weight portion or bismuth series catalysts, the PU raw material that wherein prepares 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 formed by calcium class filler of 0.8-1%, the anti-wear agent formed by aromatic series silicone oil of 0.6-0.9%, the antistatic agent formed by metal dust or conductive black of the Benzotriazole Ultraviolet Stabilizer of 0.2-0.6% and 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 of 6-18%-4, 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 comprise particle diameter be 0.5-0.8 micron and the clay that accounts for inorganic particulate total content 25%, particle diameter the 1-2 micron and account for 60% barium sulfate powder of inorganic particulate total content and particle diameter at the 3-5 micron and account for 15% calcium carbonate of inorganic particulate total content; The structural formula of the vinyl silicone oil in wherein said release layer is:
Figure BDA0000367472330000031
in formula, R1 and R3 are-CH3, and R2 is-CH=CH2 that the m span is that 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 portions, Silicone acrylic emulsion 35 weight portions, methyl sodiosul foaliphatate 4 weight portions, 3 parts of dodecyl benzyl dimethyl ammonium chloride weight and water 50 weight portions; 2 of the vinyl silicone oil of the poly(4-methyl-1-pentene) of the polypropylene that the raw materials of described release layer is 60 weight portions, 30 weight portions, 8 weight portions, 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
Figure BDA0000367472330000041
middle R1 and R3 be-CH3, and 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 tackifying resin of the catalyst of the vulcabond of the polyester polyol of 65 weight portions, 18 weight portions, the polyether polyol of 4 weight portions, 1 weight portion, the chain extender of 1 weight portion, 1.6 weight portion antioxidants, 5 weight portions, the fire retardant of 3 weight portions, the flexibilizer of 3 weight portions; Described flexibilizer is mixed to extrude by the antiaging agent raw material of 31% polyethylene elastomer, 19% Hi-fax, 49% polypropylene and 1% by weight and forms; The organohalogen compounds that the inorganic filler that described fire retardant is mixed by melt index 5 grams of the 50 % by weight/polypropylene of 10 minutes, melt index 0.8 gram of the 20 % by weight/polyethylene of 10 minutes, the powdered talc of 20 % by weight and kaolinite, the decabrominated dipheny base ether of 10 % by weight and ten dichloro ten dihydro dimethano benzene azoles cyclo-octene mix form.
Further according to hot melt adhesive TPU-PU leather of the present invention, the poly-adipate glycol butanediol ester polyalcohol that the molecular weight that consists of 65 weight portions of wherein said TPU raw material is 3000, 0.6 the β of weight portion-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid antioxidant, 0.3 two (2 of weight portion, 2, 6, 6-tetramethyl-4-piperidyl) SA ester light stabilizer, 0.6 the erucyl amide wax series lubricant agent of weight portion, the Carbodiimides hydrolysis agent of 4 weight portions, 32 weight portions and temperature 60 ℃ 1, the 4-cyclohexane diisocyanate, 1 of 6 weight portions, the agent of 4-chain expansion of succinic acid, 0.1 the bismuth series catalysts of weight portion, the decabrominated dipheny base ethane 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: 60% host, 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 and 1% antistatic agent, the composition of wherein said host self is by mass percentage: 20% polyester diol, 10% butanone, 50% dimethyl formamide, 3% straight diol, 12% diphenyl methane-4, 4 '-vulcabond, 2% TDI tripolymer and 3% hydroxy-ethyl acrylate.
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, vertically 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 kind of preparation method of hot melt adhesive TPU-PU leather of vehicle slit preventing, is characterized in that, said method comprising the steps of:
(1) prepare release liners
(1), select paper bottom A1, and the aqueous polyacrylamide tack coat A2 that coating thickness is the 0.8-4 micron on described paper bottom A1, then paste thickness be on described tack coat A2 the 18-25 micron by the film formed plastic layer A3 of polyethylene terephthalate, 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 the inorganic particulate of pouring the 62-68 weight portion into and being mixed by clay, barium sulfate powder and calcium carbonate powder, and high-speed stirred is uniformly dispersed it, then in scattered slurry, add the Silicone acrylic emulsion of 32-36 weight portion, after with glass bar, solution being mixed, the dodecyl benzyl dimethyl ammonium chloride of 2-4 weight portion is added on wherein, continue to stir, make the transition zone coating fluid;
(3), use the evenly described transition zone coating fluid of coating of scraper on plastic layer A3, and under 80 ℃ the heating 30 seconds film-formings, control thickness at the 15-20 micron, then the transition zone A4 after film forming is carried out to the press polish processing under 120 ℃, the condition of linear pressure 150KN/m, speed of a motor vehicle 10m/min;
(4), after being mixed, the vinyl silicone oil of the poly(4-methyl-1-pentene) of the polypropylene of 58-65 weight portion, 26-34 weight portion and 6-9 weight portion is heated to 90 ℃, be incubated and add 2 of 1-2 weight portion after 2 hours, 2 '-methylene-bis--(4,6 di-t-butyl phenoxy groups) tert butyl peroxy benzoate of sodium phosphate and 0.1-0.8 weight portion mixing, then form release layer A5 by the extruder Extrusion Coating in the surface of described transition zone A4, control thickness at the 20-25 micron;
(2), preparation hot melt adhesive raw material
(1), the tackifying resin of the antioxidant of the polyether polyol of the polyester polyol of 60-70 weight portion, 3-5 weight portion, 1.5-1.8 weight portion and 4-6 weight portion is placed in to reactor, be heated to 120～140 ℃, be uniformly mixed lower vacuum dehydration 1.5～2h, vacuum is less than 0.05MPa, then is cooled to 70～75 ℃, wherein said polyester polyol is for passing through low molecular weight aliphatic dihydroxy alcohol and aliphatic dicarboxylic acid, aromatic binary carboxylic acid is prepared into 100-260 ℃ of lower polycondensation reaction the hydroxyl telechelic polyester glycol that the molecule amount is 2000-6000, described polyether polyol is selected from PTMG, a kind of in propylene oxide copolymerization glycol, described antioxidant is selected from 2, tri-grades of butyl of 6--4-methylphenol or four { β-(3, tri-grades of butyl of 5--4-hydroxy phenyl) propionic acid } pentaerythritol ester, described tackifying resin is selected from the polyethylene vinyl acetate copolymer, the terminal hydroxy group thermoplastic polyester, one or more of Foral 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 85～95 ℃ the reaction 1-1.5h; Wherein said vulcabond adopts 4,4 '-a kind of in methyl diphenylene diisocyanate or 1,6-hexamethylene diisocyanate, described catalyst is selected one or more in dibutyl tin laurate, triethanolamine or dual-morpholinyl diethyl ether;
(3), under nitrogen protection, the flexibilizer of the fire retardant of the chain extender of 0.5-1.2 weight portion, 2-4 weight portion, 2-4 weight portion is joined in the product of step (2), and at 75～85 ℃ of stirring reaction 45min-1.0h; Wherein said chain extender is selected a kind of in 1,6-hexylene glycol, methyl propanediol, BDO, and described fire retardant is comprised of polypropylene, polyethylene, inorganic filler and organic fire-resisting halide; Described flexibilizer is selected polyolefine toughener;
(4), passing into the bottom discharge of nitrogen protection condition, form the hot melt adhesive raw material after slaking is cooling;
(3), preparation TPU raw material
(1), the polymer polyatomic alcohol of 60-70 weight portion is placed in to reactor, and be heated to 80-90 ℃, described polymer polyatomic alcohol is the poly-adipate glycol butanediol ester polyalcohol that the molecular weight PTMG that is 1000 and/or molecular weight are 3000, then the antioxidant that adds the 0.2-0.8 weight portion, 0.1-0.5 two (2 of weight portion, 2, 6, 6-tetramethyl-4-piperidyl) SA ester hindered amine light stabilizer, 0.4-0.8 the Carbodiimides hydrolysis agent of the montanin wax of weight portion and/or erucyl amide wax series lubricant agent and 3-5 weight portion, obtain the polymer polyatomic alcohol mixed solution after fully stirring, wherein said antioxidant is β-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and two [(2, the 4-di-tert-butyl-phenyl) phosphorous acid] at least one in pentaerythritol ester,
(2), to add in described polymer polyatomic alcohol mixed solution the 30-35 weight portion, temperature is at the Isosorbide-5-Nitrae-cyclohexane diisocyanate of 55-65 ℃, after being uniformly mixed, obtains initial reaction mixture;
(3), keep the temperature of above-mentioned reactant mixture and add the BDO chain extender of 4-9 weight portion and titanium system or the bismuth series catalysts of 0.05-0.2 weight portion, and control temperature 150-210 ℃, pressure 4-8MPa reaction 1h left and right;
(4), when the reaction melt temperature reaches between 180-210 ℃, add the 1-3 weight portion and particle mean size be less than or equal to 4 microns mix the organohalogen compounds fire retardant of micro-fumed silica by decabrominated dipheny base ethane, reaction was dewatered after the scheduled time, drying and slaking, obtained the Polyurethane Thermoplastic Elastomer raw material;
(4), preparation PU raw material
(1) prepare host: by the polyester diol of 12-28%, the butanone of 0-30%, the dimethyl formamide of 20-70%, the straight diol of 1-5% is put into reaction pot stirring at normal temperature 20-40 minute, after mixing, at normal temperatures by the diphenyl methane of 6-18%-4, 4 '-after vulcabond is put into reaction pot, heat temperature raising also makes it react after 1-3 hour under 70-80 ℃, the TDI tripolymer that adds again 1-3%, under 60-80 ℃, reaction is after 1-3 hour, after progressively being cooled to 40-50 ℃, the hydroxy-ethyl acrylate that adds 2-6%, stir after 0.5 hour the discharge of lowering the temperature, make 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% is mixed, disperse 10-20 minute in high speed dispersor, standing froth breaking makes the PU raw material after 4 hours;
(5), laminating prepares vehicle slit preventing hot melt adhesive TPU-PU leather
(1), prepare release liners, hot melt adhesive raw material, TPU raw material and the PU raw material prepare by above-mentioned steps, and release liners be placed in to relevant device pave;
(2) the hot melt adhesive raw material, prepared by step (two) is processed into sizing material through extruder, the extruder that sizing material is sent into 150 degree temperature is melt into pasty state, extrude rear curtain coating to described strippable paper by extruder die head again, then through to pinch roller to pressing-cooling-batch, form hot melt adhesive film;
(3), by step (three), prepared TPU raw material is extruded into the TPU film, and be placed in respectively on two cradles with above-mentioned hot melt adhesive film, the height that hot melt adhesive film and TPU film is entered simultaneously be provided with constant temperature is to carrying out in pinch roller pressing, to the temperature of pinch roller more than 160 ℃, thereby make low-melting hot melt adhesive moment with TPU film be bonded as one to pinch roller when pressing at height, cooling rear formation has the TPU film of hot melt adhesive;
(4), the PU raw material that step (four) is prepared pours on release liners, by cradle, drives the release liners operation with the PU material, through scraper and baking box, the PU raw material is fully struck off and is baked to respectively and micro-ly make dry type PU film after dry;
(5), by dry type PU film by gluing after with step (3) make with the TPU film of hot melt adhesive be sent to simultaneously decorative pattern in pinch roller to molded, then batch after fast cooling by cooling device, make the hot melt adhesive vehicle slit preventing TPU-PU leather of the sandwich construction by dry type PU film+TPU film+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 portions, Silicone acrylic emulsion 35 weight portions, methyl sodiosul foaliphatate 4 weight portions, dodecyl benzyl dimethyl ammonium chloride 3 weight portions and water 50 weight portions, specifically the consisting of of described inorganic particulate: the clay particle diameter is that 0.5-0.8 micron and content are 25%, barium sulfate powder particle diameter is 60% at 1-2 micron and content, the calcium carbonate powder particle diameter is 15% at 3-5 micron and content; 2 of the vinyl silicone oil of the poly(4-methyl-1-pentene) of the polypropylene that the raw materials of described release layer is 60 weight portions, 30 weight portions, 8 weight portions, 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 are-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, select oneself diacid, fumaric acid, maleic acid or suberic acid of the aliphatic dicarboxylic acid of preparation polyester polyol in step (two) wherein, 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 pentanediol or dodecyl hexylene glycol; Specifically consisting of of described fire retardant: the polyethylene of the melt index 0.5-15.0 gram of the 30-70 % by weight/polypropylene of 10 minutes, the melt index 0.01-2.0 gram of 5-25 % by weight/10 minutes, 20-30 % by weight be selected from the organic fire-resisting halide that at least one inorganic filler, 5-15 % by weight in powdered talc, kaolinite, sericite, silica and diatomite is selected from decabrominated dipheny base ether, ten dichloro ten dihydro dimethano benzene azoles cyclo-octene or its mixture; Described flexibilizer is extruded and is formed after being mixed by polyethylene elastomer, Hi-fax, polypropylene PP and antiaging agent raw material, and the shared mass percent of each raw material 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, the poly-adipate glycol butanediol ester polyalcohol that in wherein said step (three), the molecular weight that consists of 65 weight portions of TPU raw material is 3000, 0.6 the β of weight portion-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid antioxidant, 0.3 two (2 of weight portion, 2, 6, 6-tetramethyl-4-piperidyl) SA ester light stabilizer, 0.6 the erucyl amide wax series lubricant agent of weight portion, the Carbodiimides hydrolysis agent of 4 weight portions, 32 weight portions and temperature 60 ℃ 1, the 4-cyclohexane diisocyanate, 1 of 6 weight portions, the agent of 4-chain expansion of succinic acid, 0.1 the bismuth series catalysts of weight portion, the decabrominated dipheny base ethane 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: 60% host, 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 and 1% antistatic agent, the composition of wherein said host self is by mass percentage: 20% polyester diol, 10% butanone, 50% dimethyl formamide, 3% straight diol, 12% diphenyl methane-4, 4 '-vulcabond, 2% TDI tripolymer and 3% hydroxy-ethyl acrylate.
Technical characteristics of the present invention and technique effect are:
(1) adopted the sandwich construction release liners of innovative design, especially wherein the innovative design of Multifunctional layered and release layer, make release liners provided by the present invention be applied in leather and fur products have abnormal excellent physicochemical property, and, and the adhesion strength between hot melt adhesive is high, hardening time is fast, belong to the desirable base material in high-quality leather.
(2) adopted 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 advantages such as environmental protection, no side effects, as desirable environmental protection jointing material, the performance such as hot melt adhesive of the present invention has low melting point, high, acidproof, alkaline-resisting, water-fastness, the anti-dry-cleaning of elastic force, tension stress is strong, adhesion is strong, melting point is low
(3) the TPU film adopted and PU film improve by the innovation on raw material, many defects of existing TPU and PU have been overcome, the most of characteristic that not only has rubber and common plastics, but also have good comprehensive physical and chemical property, can be used as and replace PVC, PU artificial leather and other leather fabric fully.
(4) the hot melt adhesive TPU-PU leather of vehicle slit preventing provided by the present invention, in the situation that qualitative change can not occur in high temperature 190 degree, be very easy to and cloth, rubber (moulding) rubber material, the wooden material surface that waits is bonding, can be widely used in clothing, footwear, handbag, case and bag, seat, building decorations etc. are manufactured industry, and the product after laminating is water-fastness, dry-cleaning, product has wear-resisting, heat-resisting, the performance of anti-complications, hot melt adhesive of the present invention and the contained essence of TPU raw material, through SGS, detect, there is biocompatible property, nontoxic, tasteless, without allergic reaction, product is environmental protection extremely, pollution-free effect, to have one of desirable environmental protection laminating fabric 21st century.
The accompanying drawing explanation
Accompanying drawing 1 is for being extruded into hot melt adhesive of the present invention in the schematic diagram that forms hot melt adhesive film on release liners;
Accompanying drawing 2 is the product schematic diagram after hot melt adhesive film shown in accompanying drawing 1 and TPU mould are closed;
The film layer structure schematic diagram of the hot melt adhesive TPU-PU leather that accompanying drawing 3 is 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.
The specific embodiment
Below technical scheme of the present invention is described in detail so that those skilled in the art can more clearly understand the solution of the present invention, but therefore do not limit the scope of the invention.Here need at first to illustrate: in the present invention, the composition of most raw materials is with " weight portion " metering proportion, this " weight portion " only means the component proportional quantity relation of every kind of material inside, similar with mass percent, do not represent actual service property (quality), some component that is to say 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.
At 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, be coated on hot melt adhesive film S2 on release liners S1, be pasted on the TPU film S3 on hot melt adhesive film S2 and be pressed on the dry type PU film S4 on TPU film 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 1, preparation release liners S1, hot melt adhesive raw material, TPU raw material and PU raw material, these raw materials belong to our company's original creation, are also one of main inventive points of the present invention, in the back can be detailed provide its composition of raw materials and preparation method.
Step 2, by prepared hot melt adhesive raw material through extruder and be processed into sizing material, the extruder that sizing material is sent into up to 150 degree temperature is melt into pasty state, extrude rear curtain coating to the strippable paper that plays buffer action by extruder die head again, then through to pinch roller to pressing-cooling-batch, formation is without sewn hot-melt adhesive film S2, as shown in Figure 1;
Step 3, prepared TPU raw material is extruded into to TPU film S3, and the hot melt adhesive film S2 of rolling and TPU film S3 are placed in respectively on two cradles, the height that hot melt adhesive film S2 and TPU film S3 is entered simultaneously be provided with constant temperature is to carrying out in pinch roller pressing, to the temperature of pinch roller more than 160 ℃, make hot melt adhesive be bonded as one at height to pinch roller moment and TPU when pressing, form the TPU film S3 with hot melt adhesive, as shown in Figure 2;
Step 4, that prepared PU raw material is poured to release liners S1 is upper, by cradle, drives the release liners S1 operation with the PU material, through scraper and baking box, the PU raw material is fully struck off and is baked to respectively and micro-ly make dry type PU film S4 after dry;
Step 5, by dry type PU film S4 by gluing after with the TPU film S3 of hot melt adhesive, be sent to simultaneously decorative pattern in pinch roller to molded, then batch after fast cooling by cooling device, make the vehicle slit preventing hot melt adhesive TPU-PU leather of the sandwich construction by dry type PU film+TPU film+hot melt adhesive film of the present invention.
Key technology of the present invention comprises: the critical formulations of the formula of high viscosity hot melt adhesive, TPU, PU film and wherein various function additives (master batch) selection and as the preparation of the release liners S1 of base material.Due to TPU(Polyurethane Thermoplastic Elastomer Thermoplastic polyurethane) and PU(Polyurethane, polyurethanes, also claim: polyurethane), belong to environment-friendly materials, and because the PU raw material only needs the simple modification formula, just can obtain different density, elasticity, the physical properties such as rigidity, belong to good decoration 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 and the TPU/PU material of innovation, by changing formula constituent and additive, combined mathematical module and practical proof, thereby utilize the collection of many group experimental datas to determine the factor of influence between each component, and calculate best proportioning by theory, and last formula is applied to test, after checking, resulting product of the present invention has better cementability, tear resistance, ABRASION RESISTANCE, the multiple physical property 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, on described paper bottom A1, by tack coat A2, is bonded with plastic layer A3, be provided with transition zone A4 on described plastic layer A3, on described transition zone A4, be provided with release layer A5.Concrete described plastic layer A3 is polyethylene terephthalate film (being the PET film), and thickness is the 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 the 0.8-4 micron, preferred every square metre of 6 grams, thickness is the 1-2.5 micron.Described transition zone A4 forms and 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 the 0.5-0.8 micron, accounts for the clay of inorganic particulate total content 25%, particle diameter at 1-2 micron, 60% the barium sulfate powder that accounts for the inorganic particulate total content and particle diameter at the 3-5 micron, account for 15% calcium carbonate of inorganic particulate total content.The methyl sodiosul foaliphatate that the preparation process of described transition zone A4 is above-mentioned weight portion is poured in the water of above-mentioned weight portion, stir, by inorganic particulate, included clay, barium sulfate powder and calcium carbonate is poured in above-mentioned agitating solution according to above-mentioned weight portion after mixing, use high-speed stirred that it is uniformly dispersed, the Silicone acrylic emulsion that adds above-mentioned weight portion 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 the transition zone coating fluid.Then use the evenly described transition zone coating fluid of coating of scraper on described plastic layer A3, and under 80 ℃ the heating 30 seconds film-formings, thickness 15-20 micron, then by the transition zone A4 after film forming at 120 ℃, linear pressure 150KN/m, carry out the press polish processing under speed of a motor vehicle 10m/min condition, press polish has reduced the small hole in the transition zone after processing, make rete become Paint Gloss, obtain more fine and close level and smooth surface state, the laying of more favourable release layer thereon, and the transition zone even curface makes final release layer surface have the minute surface flatness, surface state and the glossiness of final leather products have been guaranteed.Arranging of described transition zone guaranteed that release liners S1 integral body has the level and smooth of anti-permeability and surface, Silicone acrylic emulsion wherein is through being heating and curing, can form fine and close film, can effectively intercept the osmosis of solvent to paper substrate, and the film that Silicone acrylic emulsion forms also has good solvent resistance, solvent is applied to the situation that not there will be dissolved destruction film and other base materials on it, and effectively covered the coarse state on paper bottom A1 and plastic layer A3 surface through transition zone, guaranteed the flatness of release layer surface and release liners S1 integral body, smoothly being very beneficial for improving of this release liners S1 surface state be take the level and smooth glossiness of release liners S1 as the whole leather products on basis.The composition of the upper above-mentioned release layer A5 arranged of described transition zone A4 comprises: 2 of the poly(4-methyl-1-pentene) of the polypropylene of 58-65 weight portion, 26-34 weight portion, the vinyl silicone oil of 6-9 weight portion, 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:
Figure BDA0000367472330000121
in formula, R1 and R3 are-CH 3, R2 is-CH=CH 2, the m span is that 2000～3000, n span is 3～6.The preparation process of described release layer is heated to 90 ℃ for after the polypropylene of above-mentioned weight portion, poly(4-methyl-1-pentene) and vinyl silicone oil are mixed, be incubated and add 2 of 1-2 weight portion after 2 hours, 2 '-methylene-bis--(4,6 di-t-butyl phenoxy groups) tert butyl peroxy benzoate of sodium phosphate and 0.1-0.8 weight portion mixing, then pass through the extruder Extrusion Coating in the surface of transition zone A4, control the thickness of release layer at the 20-25 micron.Pass through 2 in this release layer, 2 '-methylene-bis--(4,6 di-t-butyl phenoxy groups) sodium phosphate and tert butyl peroxy benzoate are accelerated the cross-linking reaction of two keys of polyolefinic pair of key of initiation and vinyl silicone oil, and polyolefin content is wherein added, because the compatibility of polyolefin and polyurethane etc. is better, the properties of product after the hot melt adhesive that therefore has the release liners S1 of this release layer and contain polyurethane is bonding are better.Prepare the release liners S1 be applied in the present invention 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 the 80-100 micron, but, not as limit, can regulate according to actual needs.
The material component of extruding the hot melt adhesive on above-mentioned strippable paper comprises:
The tackifying resin 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 .8-1.5 weight portion, 0.5-1.2 weight portion, 1.5-1.8 weight portion antioxidant, 4-6 weight portion, the fire retardant of 2-4 weight portion, the flexibilizer of 2-4 weight portion.
Described polyester polyol is prepared into 100-260 ℃ of lower polycondensation reaction the hydroxyl telechelic polyester glycol that the molecule amount is 2000-6000 by 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 pentanediol or dodecyl hexylene glycol.
Described vulcabond adopts 4,4 '-methyl diphenylene diisocyanate, 1, a kind of in the 6-hexamethylene diisocyanate;
Described polyether polyol is selected from a kind of in PTMG, propylene oxide copolymerization glycol;
Described catalyst is selected one or more in dibutyl tin laurate, triethanolamine or dual-morpholinyl diethyl ether;
Described chain extender is selected a kind of in 1,6-hexylene glycol, methyl propanediol, BDO;
Described antioxidant is selected from tri-grades of butyl of 2,6--4-methylphenol or four { β-(tri-grades of butyl of 3,5--4-hydroxy phenyl) propionic acid } pentaerythritol ester;
Described tackifying resin is selected from one or more of polyethylene vinyl acetate copolymer, terminal hydroxy group thermoplastic polyester, Foral resin;
Specifically consisting of of described fire retardant: the polyethylene of the melt index 0.5-15.0 gram of the 30-70 % by weight/polypropylene of 10 minutes, the melt index 0.01-2.0 gram of 5-25 % by weight/10 minutes, 20-30 % by weight be selected from the organic fire-resisting halide that at least one inorganic filler, 5-15 % by weight in powdered talc, kaolinite, sericite, silica and diatomite is selected from decabrominated dipheny base ether, ten dichloro ten dihydro dimethano benzene azoles cyclo-octene or its mixture.
Described flexibilizer is selected polyolefine toughener, extrude and form after wherein being mixed by PE (polyethylene) elastomer, Hi-fax, polypropylene (PP) and antiaging agent raw material, the shared mass percent of each raw material 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 to reactor, be heated to 120～140 ℃, be uniformly mixed lower vacuum dehydration 1.5～2h, vacuum is less than 0.05MPa, then is cooled to 70～75 ℃;
(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 ℃ of reaction 1-1.5h;
(3) under nitrogen protection, the flexibilizer of the fire retardant of the chain extender of 0.5-1.2 weight portion, 2-4 weight portion, 2-4 weight portion is joined in the product of step (2), and at 75～85 ℃ of stirring reaction 45min-1.0h;
(4) passing into the bottom discharge of nitrogen protection condition, forming the hot melt adhesive raw material be applied in the present invention after the slaking certain hour, and be admitted in extruder, be extended down to shown in accompanying drawing 2 on release liners S1 by the extruder die head extrudate flow.
TPU raw material for moulding TPU film S3 in the present invention consists of:
The polymer polyatomic alcohol of 60-70 weight portion; Described polymer polyatomic alcohol is one or more in PTMG, molecular weight that molecular weight the is 1000 poly-adipate glycol butanediol ester polyalcohol that is 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, be specially the agent of Carbodiimides hydrolysis; The fire retardant of 1-3 weight portion, described fire retardant is the organohalogen compounds fire retardant that decabrominated dipheny base ethane mixes micro-fumed silica, particle mean size is less than or equal to 4 microns; 0.2-0.8 the antioxidant of weight portion, described antioxidant is β-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid, four [β-(3, the 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; 0.1-0.5 the hindered amine light stabilizer of weight portion, be specially two (2,2,6,6-tetramethyl-4-piperidyl) SA ester; 0.4-0.8 the montanin wax of weight portion and/or erucyl amide wax series lubricant agent; 0.05-0.2 the titanium system of 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) at first will in the polymer polyatomic alcohol of above-mentioned weight portion, be placed in reactor, and be heated to 80-90 ℃, then the antioxidant, hindered amine light stabilizer, lubricant and the hydrolysis agent that add above-mentioned weight portion, obtain the polymer polyatomic alcohol mixed solution after fully stirring.
(2) to add in described polymer polyatomic alcohol mixed solution above-mentioned weight portion, temperature obtains initial reaction mixture after the Isosorbide-5-Nitrae-cyclohexane diisocyanate of 55-65 ℃ 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 controlling temperature 150-210 ℃, pressure 4-8MPa reaction 1h left and right.
(4) when the reaction melt temperature reaches between 180-210 ℃, add the fire retardant of above-mentioned weight portion, reaction was dewatered after the scheduled time, drying and slaking, obtained the Polyurethane Thermoplastic Elastomer raw material.
Be applied to device prepared by above-mentioned Polyurethane Thermoplastic Elastomer raw material and can be single screw mixes device of knowing in prior art, parallel dual-screw successive reaction extruder, drying equipment etc.Prepared Polyurethane Thermoplastic Elastomer raw material is admitted in extruder again extrudes TPU film S3.
Raw material and the preparation of dry type PU film S4 of the present invention
The PU raw material that is used to form dry type PU film S4 forms to be counted with percentage by weight: the cloudy surface agent be comprised 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 comprised of aromatic series silicone oil of 0.6-0.9%, the Benzotriazole Ultraviolet Stabilizer of 0.2-0.6%, the antistatic agent be comprised 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%, 4 '-the TDI tripolymer of vulcabond, 1-3%, the hydroxy-ethyl acrylate of the dimethyl formamide of 20-70%, the butanone of 0-30%, 2-6%.
The method for preparing dry type PU film S4 by above-mentioned substance:
(1) prepare host: by the polyester diol of 12-28%, the butanone of 0-30%, the dimethyl formamide of 20-70%, the straight diol of 1-5% is put into reaction pot stirring at normal temperature 20-40 minute, after mixing, at normal temperatures by the diphenyl methane of 6-18%-4, 4 '-after vulcabond is put into reaction pot, heat temperature raising also makes it react after 1-3 hour under 70-80 ℃, the TDI tripolymer that adds again 1-3%, under 60-80 ℃, reaction is after 1-3 hour, after progressively being cooled to 40-50 ℃, the hydroxy-ethyl acrylate that adds 2-6%, stir after 0.5 hour the discharge of lowering the temperature, make 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% is mixed, disperse 10-20 minute in high speed dispersor, standing froth breaking pours on release liners S1 after 4 hours, drive the release liners S1 operation with the PU material by cradle, through scraper and baking box, the PU raw material is fully struck off and is baked to respectively and micro-ly make dry type PU film S4 after dry.
By above-mentioned dry type PU film S4 by gluing after with the TPU film S3 of aforementioned hot melten gel, be sent to simultaneously decorative pattern in pinch roller to molded, make the vehicle slit preventing hot melt adhesive TPU-PU leather of the sandwich construction by dry type PU film S4+TPU film S3+ hot melt adhesive film S2 of the present invention after cooling.
Finally the main performance without sewing hot melt adhesive TPU-PU leather of the present invention made by said method is detected, testing result is as follows:
1, soft durometer: 65～70/A;
2, TENSILE STRENGTH: horizontal 34.2kgf, vertically 29.2kgf;
3, tearing strength: warp-wise 6.1kgf; Broadwise 5.2kgf;
4, abrasion intensity: under the pressure of 9Kpa, grind 650 and turn rear without wear phenomenon;
5, adhesive strength: >=3.0Kg/25 ㎜.
6, percentage elongation: >=600%;
7, Shao Er hardness: >=98.
As follows with the main performance contrast of product of the same type:
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 the present invention is prepared without sewing hot melt adhesive TPU-PU leather, formula making release liners S1, hot melt adhesive, TPU film S3 and dry type PU by innovation, especially adopt polyurethane hot melt and the TPU film S3 laminating of special formula, make the performance such as TENSILE STRENGTH, tearing strength, abrasion intensity, adhesive strength, surface gloss of final leather products all be increased dramatically, even, in the situation that high temperature 190 degree qualitative change can not occur, can be widely used in clothing, footwear, handbag, case and bag, seat, building decoration etc. 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 have no relevant bibliographical information at home and abroad, belong to the world initiation.
Embodiment 1
Below provide a preferred embodiment of the present invention.
The hot melt adhesive TPU-PU leather for preparing in the following manner vehicle slit preventing of the present invention.
One, preparation release liners S1
Select paper bottom A1, and aqueous polyacrylamide (PP) the tack coat A2 that coating thickness is 2.5 microns on described paper bottom A1, then on described tack coat A2, paste the polyethylene terephthalate film A3 that thickness is 20 microns and solidify certain hour.Then according to inorganic particulate 65 weight portions, Silicone acrylic emulsion 35 weight portions, methyl sodiosul foaliphatate 4 weight portions, 3 parts of dodecyl benzyl dimethyl ammonium chloride weight and water 50 weight portions prepare the transition zone coating fluid, and use scraper to be uniformly coated on described polyethylene terephthalate film A3, and be cured with press polish and be processed into the transition zone A4 that thickness is 15 microns, finally on described transition zone A4, Extrusion Coating thickness is 25 microns 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, 1.5 2 of weight portion, 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:
Figure BDA0000367472330000171
Wherein R1 and R3 are-CH 3, R2 is-CH=CH 2, m approximately 2500, n=4.Thereby prepare the release liners S1 as leather substrate of the present invention.
Two, prepare the polyurethane hot melt raw material
(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 to reactor, be heated to 120 ℃, be uniformly mixed lower vacuum dehydration 1.5h, vacuum is less than 0.05MPa, then is cooled to 70 ℃;
(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 ℃ of reaction 1.5h;
(3) under nitrogen protection, the flexibilizer of the fire retardant of the chain extender of 1 weight portion, 3 weight portions, 3 weight portions is joined in the product of step (2), and at 85 ℃ of stirring reaction 1.0h;
(4) pass into the bottom discharge of nitrogen protection condition, forming the polyurethane hot melt raw material after the slaking certain hour.
Hydroxyl telechelic polyester glycol prepared 180-240 ℃ of lower polycondensation reaction by low molecular weight aliphatic dihydroxy alcohol and aliphatic dicarboxylic acid, aromatic binary carboxylic acid by wherein said polyester polyol, aliphatic dicarboxylic acid wherein select oneself diacid, fumaric acid; Aromatic binary carboxylic acid wherein is selected from phthalic acid, terephthalic acid (TPA), and aliphatic dihydroxy alcohol wherein is selected from ethylene glycol, 1,3-BDO, 1,5 pentanediol or dodecyl hexylene glycol.Described vulcabond employing 4,4 '-methyl diphenylene diisocyanate; Described polyether polyol adopts PTMG; Described catalyst is selected dual-morpholinyl diethyl ether; Described chain extender is selected 1,6-hexylene glycol; Described antioxidant is selected four { β-(tri-grades of butyl of 3,5--4-hydroxy phenyl) propionic acid } pentaerythritol ester; Described tackifying resin selective hydrogenation abietic resin; Inorganic filler, 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 that described fire retardant is mixed by: the polyethylene of the melt index 0.8g/10min of the polypropylene of the melt index 5g/10min of 50 % by weight, 20 % by weight, the powdered talc of 20 % by weight and kaolinite form.Described flexibilizer is selected polyolefine toughener, extrudes and forms after wherein being mixed by PE (polyethylene) elastomer, Hi-fax, polypropylene (PP) and antiaging agent raw material: PE (polyethylene) elastomer 31%, Hi-fax 19%, polypropylene (PP) 49%, antiaging agent 1%.
Three, preparation TPU raw material
(1) the poly-adipate glycol butanediol ester polyalcohol that is 3000 by the molecular weight of 65 weight portions is placed in reactor, and be heated to 90 ℃, then add the β of 0.6 weight portion-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) two (2 of the positive octadecanol ester of propionic acid antioxidant, 0.3 weight portion, 2,6,6-tetramethyl-4-piperidyl) the Carbodiimides hydrolysis agent of the erucyl amide wax series lubricant agent of SA ester light stabilizer, 0.6 weight portion, 4 weight portions, obtain the polymer polyatomic alcohol mixed solution after fully stirring.
(2) to add in described polymer polyatomic alcohol mixed solution 32 weight portions, temperature obtains initial reaction mixture after the Isosorbide-5-Nitrae-cyclohexane diisocyanate of 60 ℃ 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 controlling temperature 180-210 ℃, pressure 6MPa reaction 1h left and right.
(4) when the reaction melt temperature reaches between 200 ℃, add the decabrominated dipheny base ethane of 2 weight portions to mix the organohalogen compounds fire retardant of micro-fumed silica, reaction was dewatered after the scheduled time, drying and slaking, obtained the Polyurethane Thermoplastic Elastomer raw material.
Four, preparation dry type PU film S4
(1) prepare host: by mass percentage 20% polyester diol, 10% butanone, 50% dimethyl formamide, 3% straight diol are put into to the reaction pot stirring at normal temperature 30 minutes, after mixing, at normal temperatures by 12% diphenyl methane-4,4 '-after vulcabond is put into reaction pot, heat temperature raising also makes it react after 2 hours under 80 ℃, add again 2% TDI tripolymer, under 80 ℃, reaction is after 2 hours, after progressively being cooled to 40 ℃, add 3% hydroxy-ethyl acrylate, stir after 0.5 hour the discharge of lowering the temperature, make described host;
(2) after 60% described host, 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 are mixed, in high speed dispersor, disperse 20 minutes, standing froth breaking pours on release liners S1 after 4 hours, drive the release liners S1 operation with the PU material by cradle, through scraper and baking box, the PU raw material is fully struck off and is baked to respectively and micro-ly make dry type PU film S4 after dry.
Five, laminating prepares vehicle slit preventing hot melt adhesive TPU-PU leather
(1), prepare release liners S1, hot melt adhesive raw material, TPU raw material and the PU raw material prepare by said method, and release liners S1 be placed in to relevant device pave;
(2), prepared hot melt adhesive raw material is processed into to sizing material through extruder, the extruder that sizing material is sent into up to 150 degree temperature is melt into pasty state, extrude rear curtain coating to described strippable paper by extruder die head again, then through to pinch roller to pressing-cooling-batch, form hot melt adhesive film S2 shown in accompanying drawing 1;
(3), prepared TPU raw material is extruded into to TPU film S3 equally, and be placed in respectively on two cradles with the hot melt adhesive film S2 of the middle rolling of step (2), the height that hot melt adhesive film S2 and TPU film S3 is entered simultaneously be provided with constant temperature is to carrying out in pinch roller pressing, to the temperature of pinch roller more than 160 ℃, thereby make low-melting hot melt adhesive be bonded as one at height to pinch roller moment and TPU film S3 when pressing, cooling rear formation is with the TPU film S3 of hot melt adhesive film, as shown in Figure 2;
(4), that prepared PU raw material is poured to release liners S1 is upper, by cradle, drives the release liners S1 operation with the PU material, through scraper and baking box, the PU raw material is fully struck off and is baked to respectively and micro-ly make dry type PU film S4 after dry;
(5), by dry type PU film S4 by gluing after with step (3) make with the TPU film S3 of hot melt adhesive be sent to simultaneously decorative pattern in pinch roller to molded, then batch after fast cooling by cooling device, make the hot melt adhesive vehicle slit preventing TPU-PU leather of the sandwich construction by dry type PU film S4+TPU film S3+ hot melt adhesive film S2 of the present invention.
Only below 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 of major technique of the present invention design 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, it is characterized in that, comprise release liners, the be coated on release liners hot melt adhesive film (S2) on (S1), the dry type PU film (S4) that is pasted on the TPU film (S3) on hot melt adhesive film (S2) and with described TPU film (S3), pressure viscosity is 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 the aqueous polyacrylamide coating layer, use amount is every square metre of 5-8 gram, thickness is the 0.8-4 micron, described plastic layer (A3) is the polyethylene terephthalate film of thickness between the 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 water mix and blend of the dodecyl benzyl dimethyl ammonium chloride of 2-4 weight portion and 45-55 weight portion is prepared from, and film forming thickness is at the 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 is extruded preparation by the hot melt adhesive raw material, and described hot melt adhesive is prepared from 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, chain extender, 1.5-1.8 weight portion antioxidant, the tackifying resin of 4-6 weight portion, the fire retardant of 2-4 weight portion and the flexibilizer of 2-4 weight portion of 0.5-1.2 weight portion, described polyester polyol is by low molecular weight aliphatic dihydroxy alcohol and aliphatic dicarboxylic acid, aromatic binary carboxylic acid is prepared into 100-260 ℃ of lower polycondensation reaction the hydroxyl telechelic polyester glycol that the molecule amount is 2000-6000, the described aliphatic dicarboxylic acid diacid of selecting oneself, 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, the 4-butanediol, 1, the 6-hexylene glycol, 1, the 3-butanediol, 1, 5 pentanediols or dodecyl hexylene glycol, described vulcabond employing 4,4 '-methyl diphenylene diisocyanate or 1,6-hexamethylene diisocyanate, described polyether polyol is selected from PTMG or propylene oxide copolymerization glycol, described catalyst is selected one or more in dibutyl tin laurate, triethanolamine or dual-morpholinyl diethyl ether, described chain extender is selected a kind of in 1,6-hexylene glycol, methyl propanediol, Isosorbide-5-Nitrae-butanediol, described antioxidant is selected tri-grades of butyl of 2,6--4-methylphenol or four { β-(tri-grades of butyl of 3,5--4-hydroxy phenyl) propionic acid } pentaerythritol ester, described tackifying resin is selected from one or more of polyethylene vinyl acetate copolymer, terminal hydroxy group thermoplastic polyester, Foral resin, the composition of described fire retardant is by mass percentage: the polyethylene of the polypropylene of the melt index 0.5-15.0 g/10min of 30%-70%, the melt index 0.01-2.0 g/10min of 5%-25%, 20%-40% are selected from the inorganic filler of at least one and the organic fire-resisting halide that is selected from decabrominated dipheny base ether, ten dichloro ten dihydro dimethano benzene azoles cyclo-octene or its mixture of 5%-35% in powdered talc, kaolinite, sericite, silica and diatomite, described flexibilizer is extruded and is formed by polyethylene elastomer, Hi-fax, polypropylene and the mixing of antiaging agent raw material,
The consisting of of TPU raw material that wherein prepares described TPU film (S3): the polymer polyatomic alcohol of 60-70 weight portion, one or both in the poly-adipate glycol butanediol ester polyalcohol that PTMG, the molecular weight that to be selected from molecular weight be 1000 is 3000; Isosorbide-5-Nitrae-the cyclohexane diisocyanate of 30-35 weight portion; The chain extender of 4-9 weight portion, described chain extender is Isosorbide-5-Nitrae-butanediol; The Carbodiimides hydrolysis agent of 3-5 weight portion; The 1-3 weight portion, particle mean size is less than or equal to the organohalogen compounds fire retardant that the decabrominated dipheny base ethane of 4 microns mixes micro-fumed silica; 0.2-0.8 the antioxidant of weight portion, described antioxidant is β-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid, four [β-(3,5-di-t-butyl-4-hydroxy phenyl) propionic acid] at least one in pentaerythritol ester and two [(2,4-di-tert-butyl-phenyl) phosphorous acid] pentaerythritol ester; 0.1-0.5 two (2,2,6,6-tetramethyl-4-piperidyl) SA ester hindered amine light stabilizer of weight portion; 0.4-0.8 the montanin wax of weight portion and/or erucyl amide wax series lubricant agent; 0.05-0.2 the titanium system of weight portion or bismuth series catalysts;
The PU raw material that wherein prepares described dry type PU film (S4) consists of: the cloudy surface agent be comprised 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 comprised of aromatic series silicone oil of 0.6-0.9%, the Benzotriazole Ultraviolet Stabilizer of 0.2-0.6% and the antistatic agent be comprised of metal dust or conductive black of 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%, 4 '-the TDI tripolymer of 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) comprise particle diameter be 0.5-0.8 micron and the clay that accounts for inorganic particulate total content 25%, particle diameter the 1-2 micron and account for 60% barium sulfate powder of inorganic particulate total content and particle diameter at the 3-5 micron and account for 15% calcium carbonate powder of inorganic particulate total content; The structural formula of the vinyl silicone oil in wherein said release layer is:, in formula, R1 and R3 are-CH3, R2 is-CH=CH2 that the m span is that 2000～3000, n span is 3～6.
3. hot melt adhesive TPU-PU leather according to claim 1 and 2, 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 portions, Silicone acrylic emulsion 35 weight portions, methyl sodiosul foaliphatate 4 weight portions, 3 parts of dodecyl benzyl dimethyl ammonium chloride weight and water 50 weight portions; 2 of the vinyl silicone oil of the poly(4-methyl-1-pentene) of the polypropylene that the raw materials of described release layer is 60 weight portions, 30 weight portions, 8 weight portions, 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: middle R1 and R3 are-CH3, R2 is-CH=CH2, 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 tackifying resin of the catalyst of the vulcabond of the polyester polyol of 65 weight portions, 18 weight portions, the polyether polyol of 4 weight portions, 1 weight portion, the chain extender of 1 weight portion, 1.6 weight portion antioxidants, 5 weight portions, the fire retardant of 3 weight portions, the flexibilizer of 3 weight portions; Described flexibilizer is mixed to extrude by the antiaging agent raw material of 31% polyethylene elastomer, 19% Hi-fax, 49% polypropylene and 1% by weight and forms; The inorganic filler that described fire retardant is mixed by 50% the melt index 5 grams/polypropylene of 10 minutes, 20% melt index, the 0.8 gram/polyethylene of 10 minutes, 20% powdered talc and kaolinite and 10% decabrominated dipheny base ether form with the organic fire-resisting halide that ten dichloro ten dihydro dimethano benzene azoles cyclo-octene mix.
5. hot melt adhesive TPU-PU leather according to claim 1, it is characterized in that, the poly-adipate glycol butanediol ester polyalcohol that the molecular weight that consists of 65 weight portions of wherein said TPU raw material is 3000, 0.6 the β of weight portion-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid antioxidant, 0.3 two (2 of weight portion, 2, 6, 6-tetramethyl-4-piperidyl) SA ester light stabilizer, 0.6 the erucyl amide wax series lubricant agent of weight portion, the Carbodiimides hydrolysis agent of 4 weight portions, 32 weight portions and temperature 60 ℃ 1, the 4-cyclohexane diisocyanate, 1 of 6 weight portions, the agent of 4-chain expansion of succinic acid, 0.1 the bismuth series catalysts of weight portion, the decabrominated dipheny base ethane 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: 60% host, 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 and 1% antistatic agent, the composition of wherein said host self is by mass percentage: 20% polyester diol, 10% butanone, 50% dimethyl formamide, 3% straight diol, 12% diphenyl methane-4, 4 '-vulcabond, 2% TDI tripolymer and 3% hydroxy-ethyl acrylate.
7. according to the described hot melt adhesive TPU-PU leather of claim 1-6 any one, it is characterized in that, the TENSILE STRENGTH of described hot melt adhesive TPU-PU leather is horizontal 34.2 kgf, vertical 29.2 kgf; The tearing strength of described hot melt adhesive TPU-PU leather is warp-wise 6.1kgf; Broadwise 5.2 kgf; 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. the preparation method of the hot melt adhesive TPU-PU leather of a vehicle slit preventing, is characterized in that, said method comprising the steps of:
(1) prepare release liners (S1)
(1), select paper bottom (A1), and the aqueous polyacrylamide tack coat (A2) that is the 0.8-4 micron at the upper coating thickness of described paper bottom (A1), then described tack coat (A2) upper paste thickness be the 18-25 micron by the film formed plastic layer of polyethylene terephthalate (A3), 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 the inorganic particulate of pouring the 62-68 weight portion into and being mixed by clay, barium sulfate powder and calcium carbonate powder, and high-speed stirred is uniformly dispersed it, then in scattered slurry, add the Silicone acrylic emulsion of 32-36 weight portion, after with glass bar, solution being mixed, the dodecyl benzyl dimethyl ammonium chloride of 2-4 weight portion is added on wherein, continue to stir, make the transition zone coating fluid;
(3), at the upper evenly described transition zone coating fluid of coating of scraper that uses of plastic layer (A3), and under 80 ℃ the heating 30 seconds film-formings, control thickness at the 15-20 micron, then the transition zone after film forming (A4) is carried out to the press polish processing under 120 ℃, the condition of linear pressure 150KN/m, speed of a motor vehicle 10m/min;
(4), after being mixed, the vinyl silicone oil of the poly(4-methyl-1-pentene) of the polypropylene of 58-65 weight portion, 26-34 weight portion and 6-9 weight portion is heated to 90 ℃, be incubated and add 2 of 1-2 weight portion after 2 hours, 2 '-methylene-bis--(4,6 di-t-butyl phenoxy groups) tert butyl peroxy benzoate of sodium phosphate and 0.1-0.8 weight portion mixing, then form release layer (A5) by the extruder Extrusion Coating in the surface of described transition zone (A4), control thickness at the 20-25 micron;
(2), preparation hot melt adhesive raw material
(1), the tackifying resin of the antioxidant of the polyether polyol of the polyester polyol of 60-70 weight portion, 3-5 weight portion, 1.5-1.8 weight portion and 4-6 weight portion is placed in to reactor, be heated to 120～140 ℃, be uniformly mixed lower vacuum dehydration 1.5～2h, vacuum is less than 0.05MPa, then is cooled to 70～75 ℃; Wherein said polyester polyol is for being prepared into 100-260 ℃ of lower polycondensation reaction the hydroxyl telechelic polyester glycol that the molecule amount is 2000-6000 by low molecular weight aliphatic dihydroxy alcohol and aliphatic dicarboxylic acid, aromatic binary carboxylic acid; Described polyether polyol is selected from a kind of in PTMG, propylene oxide copolymerization glycol; Described antioxidant is selected from tri-grades of butyl of 2,6--4-methylphenol or four { β-(tri-grades of butyl of 3,5--4-hydroxy phenyl) propionic acid } pentaerythritol ester; Described tackifying resin is selected from one or more of polyethylene vinyl acetate copolymer, terminal hydroxy group thermoplastic polyester, Foral 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 85～95 ℃ the reaction 1-1.5h; Wherein said vulcabond adopts 4,4 '-a kind of in methyl diphenylene diisocyanate or 1,6-hexamethylene diisocyanate; Described catalyst is selected one or more in dibutyl tin laurate, triethanolamine or dual-morpholinyl diethyl ether;
(3), under nitrogen protection, the flexibilizer of the fire retardant of the chain extender of 0.5-1.2 weight portion, 2-4 weight portion, 2-4 weight portion is joined in the product of step (2), and at 75～85 ℃ of stirring reaction 45min-1.0h; Wherein said chain extender is selected a kind of in 1,6-hexylene glycol, methyl propanediol, Isosorbide-5-Nitrae-butanediol; The composition of described fire retardant is by mass percentage: the polyethylene of the polypropylene of the melt index 0.5-15.0 g/10min of 30%-70%, the melt index 0.01-2.0 g/10min of 5%-25%, 20%-40% are selected from the inorganic filler of at least one and the organic fire-resisting halide that is selected from decabrominated dipheny base ether, ten dichloro ten dihydro dimethano benzene azoles cyclo-octene or its mixture of 5%-35% in powdered talc, kaolinite, sericite, silica and diatomite; Described flexibilizer is selected polyolefine toughener;
(4), passing into the bottom discharge of nitrogen protection condition, form the hot melt adhesive raw material after slaking is cooling;
(3), preparation TPU raw material
(1), the polymer polyatomic alcohol of 60-70 weight portion is placed in to reactor, and being heated to 80-90 ℃, described polymer polyatomic alcohol is the poly-adipate glycol butanediol ester polyalcohol that the molecular weight PTMG that is 1000 and/or molecular weight are 3000, then the antioxidant that adds the 0.2-0.8 weight portion, 0.1-two (2 of 0.5 weight portion, 2, 6, 6-tetramethyl-4-piperidyl) SA ester hindered amine light stabilizer, 0.4-0.8 the Carbodiimides hydrolysis agent of the montanin wax of weight portion and/or erucyl amide wax series lubricant agent and 3-5 weight portion, obtain the polymer polyatomic alcohol mixed solution after fully stirring, wherein said antioxidant is β-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid, four [β-(3, 5-di-t-butyl-4-hydroxy phenyl) propionic acid] pentaerythritol ester and two [(2, the 4-di-tert-butyl-phenyl) phosphorous acid] at least one in pentaerythritol ester,
(2), to add in described polymer polyatomic alcohol mixed solution the 30-35 weight portion, temperature is at the Isosorbide-5-Nitrae-cyclohexane diisocyanate of 55-65 ℃, after being uniformly mixed, obtains initial reaction mixture;
(3), keep the temperature of above-mentioned reactant mixture and add titanium system or the bismuth series catalysts of the Isosorbide-5-Nitrae of 4-9 weight portion-chain expansion of succinic acid agent and 0.05-0.2 weight portion, and control temperature 150-210 ℃, pressure 4-8MPa reaction 1h left and right;
(4), when the reaction melt temperature reaches between 180-210 ℃, add the 1-3 weight portion and particle mean size be less than or equal to 4 microns mix the organohalogen compounds fire retardant of micro-fumed silica by decabrominated dipheny base ethane, reaction was dewatered after the scheduled time, drying and slaking, obtained the Polyurethane Thermoplastic Elastomer raw material;
(4), preparation PU raw material
(1) prepare host: 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% is put into reaction pot stirring at normal temperature 20-40 minute, after mixing, at normal temperatures by the diphenyl methane of 6-18%-4, 4 '-after vulcabond is put into reaction pot, heat temperature raising also makes it react after 1-3 hour under 70-80 ℃, the TDI tripolymer that adds again 1-3%, under 60-80 ℃, reaction is after 1-3 hour, after progressively being cooled to 40-50 ℃, the hydroxy-ethyl acrylate that adds 2-6%, stir after 0.5 hour the discharge of lowering the temperature, make described host,
(2) after by mass percentage 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% and 0.5-1.2% being mixed, disperse 10-20 minute in high speed dispersor, standing froth breaking makes the PU raw material after 4 hours;
(5), laminating prepares vehicle slit preventing hot melt adhesive TPU-PU leather
(1), prepare release liners (S1), hot melt adhesive raw material, TPU raw material and the PU raw material prepare by above-mentioned steps, and release liners (S1) be placed in to relevant device pave;
(2), hot melt adhesive raw material prepared by step (two) is processed into sizing material through extruder, sizing material is sent into 150 degree temperature
The extruder of degree is melt into pasty state, then extrudes rear curtain coating to described strippable paper by extruder die head, then through to pinch roller to pressing-cooling-batch, form hot melt adhesive film (S2);
(3), by step (three), prepared TPU raw material is extruded into TPU film (S3), and be placed in respectively on two cradles with above-mentioned hot melt adhesive film (S2), the height that hot melt adhesive film (S2) and TPU film (S3) is entered simultaneously be provided with constant temperature is to carrying out in pinch roller pressing, to the temperature of pinch roller more than 160 ℃, thereby make low-melting hot melt adhesive moment with TPU film (S3) be bonded as one to pinch roller when pressing at height, cooling rear formation has the TPU film of hot melt adhesive film;
(4), by step (four), prepared PU raw material pours on release liners (S1), drive release liners (S1) operation with the PU material by cradle, through scraper and baking box, the PU raw material is fully struck off and is baked to respectively and micro-ly make dry type PU film (S4) after dry;
(5), by dry type PU film (S4) by after gluing with step (3) make with the TPU film of hot melt adhesive film be sent to simultaneously decorative pattern in pinch roller to molded, then fast cooling rear curling by cooling device, make dry type PU film (S4) and add the hot melt adhesive TPU-PU leather of vehicle slit preventing that TPU film (S3) adds 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 portions, Silicone acrylic emulsion 35 weight portions, methyl sodiosul foaliphatate 4 weight portions, dodecyl benzyl dimethyl ammonium chloride 3 weight portions and water 50 weight portions, specifically the consisting of of described inorganic particulate: the clay particle diameter is that 0.5-0.8 micron and content are 25%, barium sulfate powder particle diameter is 60% at 1-2 micron and content, the calcium carbonate powder particle diameter is 15% at 3-5 micron and content; 2 of the vinyl silicone oil of the poly(4-methyl-1-pentene) of the polypropylene that the raw materials of described release layer is 60 weight portions, 30 weight portions, 8 weight portions, 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, in the structural formula of described vinyl silicone oil, R1 and R3 are-CH3, R2 is-CH=CH2, m=2500, n=4.
10. preparation method according to claim 8, it is characterized in that, select oneself diacid, fumaric acid, maleic acid or suberic acid of the aliphatic dicarboxylic acid of preparation polyester polyol in step (two) wherein, 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, Isosorbide-5-Nitrae-butanediol, 1,6-hexylene glycol, 1,3-butanediol, 1,5 pentanediol or dodecyl hexylene glycol; Described flexibilizer is extruded and is formed after being mixed by polyethylene elastomer, Hi-fax, polypropylene PP and antiaging agent raw material, and the shared mass percent of each raw material is: polyethylene elastomer 31%, Hi-fax 19%, polypropylene 49%, antiaging agent 1%.
11. preparation method according to claim 8, it is characterized in that, the poly-adipate glycol butanediol ester polyalcohol that in wherein said step (three), the molecular weight that consists of 65 weight portions of TPU raw material is 3000, 0.6 the β of weight portion-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid antioxidant, 0.3 two (2 of weight portion, 2, 6, 6-tetramethyl-4-piperidyl) SA ester light stabilizer, 0.6 the erucyl amide wax series lubricant agent of weight portion, the Carbodiimides hydrolysis agent of 4 weight portions, 32 weight portions and temperature 60 ℃ 1, the 4-cyclohexane diisocyanate, 1 of 6 weight portions, the agent of 4-chain expansion of succinic acid, 0.1 the bismuth series catalysts of weight portion, the decabrominated dipheny base ethane of 2 weight portions mixes the organohalogen compounds fire retardant of micro-fumed silica.
12. preparation method according to claim 8, it is characterized in that, in wherein said step (four), the composition of PU raw material is by mass percentage: 60% host, 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 and 1% antistatic agent, the composition of wherein said host self is by mass percentage: 20% polyester diol, 10% butanone, 50% dimethyl formamide, 3% straight diol, 12% diphenyl methane-4, 4 '-vulcabond, 2% TDI tripolymer and 3% hydroxy-ethyl acrylate.
CN201310360221.5A 2013-08-16 2013-08-16 Sewing-free hot melt adhesive TPU-PU leather and preparation method thereof Active CN103437195B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201310360221.5A CN103437195B (en) 2013-08-16 2013-08-16 Sewing-free hot melt adhesive TPU-PU leather and preparation method thereof
PCT/CN2014/079497 WO2015021814A1 (en) 2013-08-16 2014-06-09 Sewing-free hot melt adhesive tpu-pu leather and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310360221.5A CN103437195B (en) 2013-08-16 2013-08-16 Sewing-free hot melt adhesive TPU-PU leather and preparation method thereof

Publications (2)

Publication Number Publication Date
CN103437195A true CN103437195A (en) 2013-12-11
CN103437195B CN103437195B (en) 2015-01-14

Family

ID=49690905

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310360221.5A Active CN103437195B (en) 2013-08-16 2013-08-16 Sewing-free hot melt adhesive TPU-PU leather and preparation method thereof

Country Status (2)

Country Link
CN (1) CN103437195B (en)
WO (1) WO2015021814A1 (en)

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104179033A (en) * 2014-08-01 2014-12-03 陕西科技大学 Production method of functional synthetic leather for mobile phone case
CN104448787A (en) * 2014-12-10 2015-03-25 东莞市雄林新材料科技股份有限公司 Production process of novel high-performance TPU composite material
CN105050799A (en) * 2013-03-12 2015-11-11 斯特林模制复合物有限公司 A method of manufacturing a padded part primarily for an item of wear
CN105386330A (en) * 2015-12-10 2016-03-09 泉州万华世旺超纤有限责任公司 Manufacturing method of colorful light reflecting leather
CN105751665A (en) * 2014-12-16 2016-07-13 王胜鏞 Manufacturing method of four-side elastic rubber
CN106751733A (en) * 2016-12-27 2017-05-31 上海汇得科技股份有限公司 A kind of polyurethane synthetic leather resin of the scattered high abrasion of color and preparation method thereof
CN106835732A (en) * 2017-02-21 2017-06-13 东莞市雄林新材料科技股份有限公司 A kind of vehicle slit preventing PUR TPU leathers and preparation method thereof
CN106832889A (en) * 2017-02-21 2017-06-13 东莞市雄林新材料科技股份有限公司 A kind of preparation technology of Novel foaming composite membrane
CN106854291A (en) * 2016-12-28 2017-06-16 深圳泰得思科技有限公司 A kind of mould release membrance
CN107804053A (en) * 2017-11-09 2018-03-16 广州钰鑫新材料有限公司 A kind of EVA shoe bottom of surface covering PU composite membranes and preparation method thereof
CN108504083A (en) * 2018-03-10 2018-09-07 上海剑桥塑料有限公司 A kind of thermoplastic polyurethane elastomer and preparation method thereof
CN109530190A (en) * 2018-09-11 2019-03-29 东莞市雄林新材料科技股份有限公司 A kind of automobile artificial leather texture polyurethane leather and preparation method thereof
CN109762508A (en) * 2018-12-26 2019-05-17 襄阳精信汇明科技股份有限公司 Water-based hot melt adhesive with adjustable melting point and preparation method thereof
CN109971378A (en) * 2019-04-08 2019-07-05 东莞奥得时精密电子有限公司 High/low temperature laminating film and its material and technique
CN110835512A (en) * 2018-08-16 2020-02-25 重庆韩拓科技有限公司 Special PUR (polyurethane) coating adhesive for plastic steel plate and preparation method thereof
CN111019586A (en) * 2020-01-16 2020-04-17 广东安利华新材料科技有限公司 Hot melt adhesive, TPU adhesive film and preparation method
CN111423829A (en) * 2020-03-05 2020-07-17 中山爵邦时装科技有限公司 Application of semitransparent hot melt adhesive film to clothes splicing
CN111423716A (en) * 2020-05-07 2020-07-17 广州越神医疗设备有限公司 Medical plastic film and preparation method thereof
CN111619257A (en) * 2020-04-21 2020-09-04 东莞市雄林新材料科技股份有限公司 Pyrograph film and production process thereof
CN112210204A (en) * 2020-10-20 2021-01-12 广东和丰创美新型材料有限公司 Paint-free and spraying-free environment-friendly coating material and preparation method thereof
CN112227081A (en) * 2020-09-27 2021-01-15 广东卡西奥新材料有限公司 Environment-friendly scratch-resistant hydrolysis-resistant PC fabric and preparation method thereof
CN112586530A (en) * 2020-12-29 2021-04-02 东莞市雄林新材料科技股份有限公司 Dough sheet making equipment
CN114013006A (en) * 2021-10-20 2022-02-08 安徽森泰木塑科技地板有限公司 Production method of composite floor
CN114103362A (en) * 2021-12-03 2022-03-01 京良(广州)科技股份有限公司 PU material for wrapping pillow memory cotton core and preparation method thereof
CN114335667A (en) * 2021-12-29 2022-04-12 远东电池江苏有限公司 Method for improving poor edge resistance of soft package battery
CN114350280A (en) * 2022-01-18 2022-04-15 鑫序高分子材料(苏州)有限公司 High-temperature-resistant hot-melt adhesive film and preparation method thereof
CN117624692A (en) * 2024-01-25 2024-03-01 广东工业大学 Low-carbon biodegradable composite membrane and preparation method and application thereof

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109927432A (en) * 2019-04-24 2019-06-25 赵志强 A kind of silica gel 3D pattern turns to scald to the method for soft shell fabric and silica gel 3D pattern
CN110384358B (en) * 2019-07-22 2022-05-13 浙江农林大学暨阳学院 Four-in-one seat
CN111172775A (en) * 2020-01-13 2020-05-19 华懋（厦门）特种材料有限公司 Manufacturing method of tooling fabric
CN112226024A (en) * 2020-10-13 2021-01-15 浙江力邦制革有限公司 Formula and process of environment-friendly corrosion-resistant PU leather
CN113372829A (en) * 2021-07-30 2021-09-10 湖南汇齐新材料有限公司 Draw-upper insole cloth adhesive film and production process thereof
CN114369442A (en) * 2022-01-07 2022-04-19 无锡莱恩科技有限公司 Single-component hot melt adhesive for lithium battery aluminum-plastic composite film and preparation method thereof
CN114849522A (en) * 2022-04-14 2022-08-05 湖南优冠体育材料有限公司 Preparation method and device of environment-friendly high-adhesion artificial lawn glue
CN114874673B (en) * 2022-05-17 2022-12-27 安徽强邦新材料股份有限公司 Scratch-resistant treatment-free CTP plate and preparation method thereof
CN115537139B (en) * 2022-10-18 2023-07-14 广东中鼎科技发展有限公司 Waterproof breathable TPU high-low temperature film and preparation method thereof
CN115651596B (en) * 2022-12-21 2023-03-31 山东一诺威聚氨酯股份有限公司 Low-density high-thermal-conductivity polyurethane pouring sealant and preparation method thereof
CN116439489B (en) * 2023-04-21 2024-01-26 广州市艾美塑胶软管有限公司 Special-shaped flat high-elasticity easily-extruded cosmetic hose and preparation method thereof
CN116285849B (en) * 2023-05-23 2023-09-05 山东一诺威聚氨酯股份有限公司 Anti-static TPU hot melt adhesive for water-repellent nylon fabric and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010038330A (en) * 1999-10-25 2001-05-15 장병주 A manufacturing process and a product of a polyurethane artificial-leather
CN1746421A (en) * 2005-07-07 2006-03-15 靳爱晨 Production of thermoplastic polyurethane leather with figure on surface
KR100757409B1 (en) * 2007-03-07 2007-09-11 주식회사 아이시피 Manufacturing method of synthetic leather had ventilation function and its synthetic leather
WO2007139247A1 (en) * 2006-05-25 2007-12-06 Hee-Dae Park Method for manufacturing multi -layer sheet, and multi -layer sheet using the same
CN101324032A (en) * 2007-06-12 2008-12-17 何建雄 Thermoplastic polyurethane thin film color or leather changing and postprocessing methods
CN101440578A (en) * 2008-12-19 2009-05-27 安徽安利合成革股份有限公司 Novel waterproof air previous polyurethane artificial leather and preparation thereof
CN102535187A (en) * 2012-01-06 2012-07-04 福建兰峰制革有限公司 Production method of crease-free microfiber mirror-surface synthetic leather

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4447310B2 (en) * 2003-12-26 2010-04-07 三菱化学株式会社 Release paper with emboss and method for manufacturing the same
CN101914353A (en) * 2010-09-17 2010-12-15 厦门佰源塑胶制品有限公司 Aluminum foil tape with lining film and manufacturing method thereof
CN102029764A (en) * 2010-09-21 2011-04-27 东莞市雄林新材料科技有限公司 Novel TPU (Thermoplastic Polyurethanes) film
JP5196088B1 (en) * 2011-08-22 2013-05-15 Ｄｉｃ株式会社 Leather-like sheet and manufacturing method thereof
CN102493216A (en) * 2011-12-26 2012-06-13 李其树 TPU leather and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010038330A (en) * 1999-10-25 2001-05-15 장병주 A manufacturing process and a product of a polyurethane artificial-leather
CN1746421A (en) * 2005-07-07 2006-03-15 靳爱晨 Production of thermoplastic polyurethane leather with figure on surface
WO2007139247A1 (en) * 2006-05-25 2007-12-06 Hee-Dae Park Method for manufacturing multi -layer sheet, and multi -layer sheet using the same
KR100757409B1 (en) * 2007-03-07 2007-09-11 주식회사 아이시피 Manufacturing method of synthetic leather had ventilation function and its synthetic leather
CN101324032A (en) * 2007-06-12 2008-12-17 何建雄 Thermoplastic polyurethane thin film color or leather changing and postprocessing methods
CN101440578A (en) * 2008-12-19 2009-05-27 安徽安利合成革股份有限公司 Novel waterproof air previous polyurethane artificial leather and preparation thereof
CN102535187A (en) * 2012-01-06 2012-07-04 福建兰峰制革有限公司 Production method of crease-free microfiber mirror-surface synthetic leather

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
AUšRA BANUŠKEVIČIŪTĖ等: "Formation of Thermoplastic Polyurethane (TPU) Nano/Micro Fibers by", 《MATERIALS SCIENCE》, vol. 17, no. 3, 31 December 2011 (2011-12-31) *
JUN YANG等: "Preparation and Surface Properties of Silicone-", 《JCT RESEARCH》, vol. 3, no. 4, 31 October 2006 (2006-10-31) *
余永生等: "警服用PU 热熔胶衬布的研发", 《产业用纺织品》, no. 235, 25 April 2010 (2010-04-25) *
王熙等: "织物胶粘剂的研究进展", 《中国胶粘剂》, vol. 18, no. 8, 30 August 2009 (2009-08-30) *
赵磊等: "防水透湿PU膜层压复合机织物的性能研究", 《产业用纺织品》, no. 2, 25 February 2013 (2013-02-25) *

Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105050799B (en) * 2013-03-12 2017-08-25 斯特林模制复合物有限公司 The method that manufacture is mainly used in the liner part of wearing article
CN105050799A (en) * 2013-03-12 2015-11-11 斯特林模制复合物有限公司 A method of manufacturing a padded part primarily for an item of wear
CN104179033B (en) * 2014-08-01 2016-07-20 陕西科技大学 A kind of cell-phone cover production method of functional synthetic leather
CN104179033A (en) * 2014-08-01 2014-12-03 陕西科技大学 Production method of functional synthetic leather for mobile phone case
CN104448787A (en) * 2014-12-10 2015-03-25 东莞市雄林新材料科技股份有限公司 Production process of novel high-performance TPU composite material
CN105751665A (en) * 2014-12-16 2016-07-13 王胜鏞 Manufacturing method of four-side elastic rubber
CN105386330A (en) * 2015-12-10 2016-03-09 泉州万华世旺超纤有限责任公司 Manufacturing method of colorful light reflecting leather
CN106751733A (en) * 2016-12-27 2017-05-31 上海汇得科技股份有限公司 A kind of polyurethane synthetic leather resin of the scattered high abrasion of color and preparation method thereof
CN106751733B (en) * 2016-12-27 2019-12-17 上海汇得科技股份有限公司 Polyurethane synthetic leather resin with good color dispersion and high wear resistance and preparation method thereof
CN106854291A (en) * 2016-12-28 2017-06-16 深圳泰得思科技有限公司 A kind of mould release membrance
CN106832889A (en) * 2017-02-21 2017-06-13 东莞市雄林新材料科技股份有限公司 A kind of preparation technology of Novel foaming composite membrane
CN106835732A (en) * 2017-02-21 2017-06-13 东莞市雄林新材料科技股份有限公司 A kind of vehicle slit preventing PUR TPU leathers and preparation method thereof
CN106835732B (en) * 2017-02-21 2020-02-14 东莞市雄林新材料科技股份有限公司 Sewing-free hot melt adhesive TPU leather and preparation method thereof
CN107804053A (en) * 2017-11-09 2018-03-16 广州钰鑫新材料有限公司 A kind of EVA shoe bottom of surface covering PU composite membranes and preparation method thereof
CN108504083A (en) * 2018-03-10 2018-09-07 上海剑桥塑料有限公司 A kind of thermoplastic polyurethane elastomer and preparation method thereof
CN110835512A (en) * 2018-08-16 2020-02-25 重庆韩拓科技有限公司 Special PUR (polyurethane) coating adhesive for plastic steel plate and preparation method thereof
CN110835512B (en) * 2018-08-16 2022-05-13 重庆韩拓科技有限公司 Special PUR (polyurethane) coating adhesive for plastic steel plate and preparation method thereof
CN109530190A (en) * 2018-09-11 2019-03-29 东莞市雄林新材料科技股份有限公司 A kind of automobile artificial leather texture polyurethane leather and preparation method thereof
CN109762508A (en) * 2018-12-26 2019-05-17 襄阳精信汇明科技股份有限公司 Water-based hot melt adhesive with adjustable melting point and preparation method thereof
CN109762508B (en) * 2018-12-26 2021-12-14 襄阳精信汇明科技股份有限公司 Water-based hot melt adhesive with adjustable melting point and preparation method thereof
CN109971378B (en) * 2019-04-08 2021-08-10 东莞奥得时精密电子有限公司 High-low temperature adhesive film and material and process thereof
CN109971378A (en) * 2019-04-08 2019-07-05 东莞奥得时精密电子有限公司 High/low temperature laminating film and its material and technique
CN111019586A (en) * 2020-01-16 2020-04-17 广东安利华新材料科技有限公司 Hot melt adhesive, TPU adhesive film and preparation method
CN111019586B (en) * 2020-01-16 2022-05-17 广东安利华新材料科技有限公司 Hot melt adhesive, TPU adhesive film and preparation method
CN111423829A (en) * 2020-03-05 2020-07-17 中山爵邦时装科技有限公司 Application of semitransparent hot melt adhesive film to clothes splicing
CN111619257A (en) * 2020-04-21 2020-09-04 东莞市雄林新材料科技股份有限公司 Pyrograph film and production process thereof
CN111423716A (en) * 2020-05-07 2020-07-17 广州越神医疗设备有限公司 Medical plastic film and preparation method thereof
CN112227081A (en) * 2020-09-27 2021-01-15 广东卡西奥新材料有限公司 Environment-friendly scratch-resistant hydrolysis-resistant PC fabric and preparation method thereof
CN112210204A (en) * 2020-10-20 2021-01-12 广东和丰创美新型材料有限公司 Paint-free and spraying-free environment-friendly coating material and preparation method thereof
CN112586530A (en) * 2020-12-29 2021-04-02 东莞市雄林新材料科技股份有限公司 Dough sheet making equipment
CN114013006A (en) * 2021-10-20 2022-02-08 安徽森泰木塑科技地板有限公司 Production method of composite floor
CN114013006B (en) * 2021-10-20 2023-11-07 安徽森泰木塑科技地板有限公司 Production method of composite floor
CN114103362A (en) * 2021-12-03 2022-03-01 京良(广州)科技股份有限公司 PU material for wrapping pillow memory cotton core and preparation method thereof
CN114335667A (en) * 2021-12-29 2022-04-12 远东电池江苏有限公司 Method for improving poor edge resistance of soft package battery
CN114350280A (en) * 2022-01-18 2022-04-15 鑫序高分子材料(苏州)有限公司 High-temperature-resistant hot-melt adhesive film and preparation method thereof
CN117624692A (en) * 2024-01-25 2024-03-01 广东工业大学 Low-carbon biodegradable composite membrane and preparation method and application thereof

Also Published As

Publication number Publication date
WO2015021814A1 (en) 2015-02-19
CN103437195B (en) 2015-01-14

Similar Documents

Publication Publication Date Title
CN103437195B (en) Sewing-free hot melt adhesive TPU-PU leather and preparation method thereof
CN103437194B (en) Sewing-free hot melt adhesive TPU leather and preparation method thereof
CN102414240B (en) Polyurethane and manufacturing method therefor, master batch, ink binder, ink composition, thermoplastic polymer composition for molding, molded body, and compound molded body and manufacturing method therefor
CN103450649B (en) High-toughness polylactic acid/cross-linked polyurethane mixture and preparation method thereof
CN105694430B (en) TPU foamed material and preparation method thereof
CN102181031A (en) Durable polyurethane resin for sofa leather and preparation method of the durable polyurethane resin
CN107384289A (en) A kind of high thermal polyurethane PUR and three layers of heat sealing adhesive tape
CN103571364A (en) Hot-melt-adhesive laminated TPU (thermoplastic polyurethane) foamed film
CN104479181A (en) Novel adhesion promoting system tire belt ply and preparation method thereof
EP2342250A1 (en) Tpu compositions for melt coating processes
CN106432973A (en) Production method of PVC/TPU/BOVC blended plastic decoration film
CN101503861A (en) Two-liquid type rapid stripping synthetic leather composite overlay
CN113307928B (en) Polyurethane resin and preparation method and application thereof
CN114846107A (en) Polyurethane hot melt adhesive composition and method for preparing same
CN107778827A (en) TPU expanded materials and its production technology
CN101817976A (en) Polyurethane elastic floor board and preparation method thereof
JP2005126595A (en) Polyurethane resin composition and hot melt adhesive using the same
JP4810854B2 (en) Polyurethane film with excellent blocking resistance
CN109880048B (en) Solvent-resistant polyurethane primer and preparation method thereof
CN107177242A (en) TPO automotive interior material of resistance to alcohol and preparation method thereof
CN115232591B (en) Reactive polyurethane hot melt adhesive and preparation method thereof
CN112297551B (en) Evacuation slide/life raft capsule material and manufacturing method thereof
CN108610467A (en) One-way type solvent-free polyurethane resin, the dermatine containing the resin and its manufacturing method
JPH09221640A (en) Hot melt film adhesive and its production
CN111155328B (en) Modified TPU artificial leather and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C53 Correction of patent of invention or patent application
CB02 Change of applicant information

Address after: 523000 Guangdong city in Dongguan Province town of Kau Ya Industrial Zone

Applicant after: Dongguan Xionglin New Material Technology Co., Ltd.

Address before: 523000 Guangdong city in Dongguan Province town of Kau Ya Village Industrial Zone

Applicant before: Dongguan Xionglin New Material Technology Co., Ltd.

CB03 Change of inventor or designer information

Inventor after: He Jianxiong

Inventor after: Wang Yiliang

Inventor before: He Jianxiong

COR Change of bibliographic data

Free format text: CORRECT: INVENTOR; FROM: HE JIANXIONG TO: HE JIANXIONG WANG YILIANG

C14 Grant of patent or utility model
GR01 Patent grant