WO2015021814A1 - Cuir tpu-pu à adhésif thermofusible sans couture, et son procédé de préparation - Google Patents

Cuir tpu-pu à adhésif thermofusible sans couture, et son procédé de préparation Download PDF

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Publication number
WO2015021814A1
WO2015021814A1 PCT/CN2014/079497 CN2014079497W WO2015021814A1 WO 2015021814 A1 WO2015021814 A1 WO 2015021814A1 CN 2014079497 W CN2014079497 W CN 2014079497W WO 2015021814 A1 WO2015021814 A1 WO 2015021814A1
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weight
parts
tpu
melt adhesive
hot melt
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PCT/CN2014/079497
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English (en)
Chinese (zh)
Inventor
何建雄
王一良
Original Assignee
东莞市雄林新材料科技股份有限公司
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Publication of WO2015021814A1 publication Critical patent/WO2015021814A1/fr

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

Definitions

  • the invention relates to the technical field of leather materials, and more particularly to a seam-free hot melt adhesive TPU PU leather and a preparation method thereof.
  • the invention is based on the above technical problems, and proposes a new type of seam-free hot melt adhesive TPU-PU leather and a preparation method thereof, and the innovation of the raw materials of the leather layers is combined with the long-term production practice experience of the company.
  • the seam-free TPU-PU leather according to the present invention can be directly attached to various articles, and has the technical advantages of being firmly adhered, durable, environmentally friendly, and having no invisible damage to the human body, and fundamentally solving Sewing and docking and the various undesirable factors brought by the existing industrial glue in the application of leather products.
  • a seam-free hot melt adhesive TPU-PU leather comprising a release paper, a hot melt adhesive coated on the release paper, a TPU film adhered to the hot melt adhesive, and a pressure applied to the TPU film a dry PU film; wherein the release paper comprises a paper base layer A1, a bonding layer A2, a plastic layer A3, a transition layer A4, and a release layer A5, and the plastic layer A3 is bonded to the paper by a bonding layer A2.
  • the transition layer A4 is disposed on the plastic layer A3, the release layer A5 is disposed on the transition layer A4, and the adhesive layer A2 is an aqueous polypropylene coating layer, and the usage amount is per square. 5-8 ⁇ , a thickness of 0.
  • the plastic layer A3 is a polyethylene terephthalate film having a thickness of 18-25 microns
  • the transition layer A4 is 62-68 weight Parts of inorganic particles, 32-36 parts by weight of silicone-acrylic emulsion, 3-5 parts by weight of sodium fatty acid methyl ester sulfonate, 2-4 parts by weight of dodecyl dimethyl benzyl ammonium chloride and 45-55
  • the parts by weight of water are prepared by mixing and stirring, and the film thickness is 15-20 micrometers, and the thickness of the release layer A5 is 20-25 micrometers and 58-65 parts by weight of polypropylene, 26-34 parts by weight.
  • the polyester polyol passing through a low molecular weight aliphatic diol and an aliphatic dicarboxylic acid, aromatic
  • the dicarboxylic acid is polycondensed at 100-26 CTC to prepare a hydroxyl terminated polyester diol having a molecular weight of 2000 6000, and the aliphatic dicarboxylic acid is selected from adipic acid, fumaric acid, maleic acid or suberic acid.
  • the aromatic dicarboxylic acid is selected from the group consisting of phthalic acid, terephthalic acid or isophthalic acid
  • the aliphatic diol is selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, methyl propylene glycol, 1 , 4-butanediol, 1,6-hexanediol, 1, 3-butanediol, 1,5-pentanediol or dodecylhexylene glycol
  • the diisocyanate is 4, 4 '-diphenyl Methane diisocyanate or 1,6-hexamethylene diisocyanate
  • the polyether polyol is selected from polytetrahydrofuran ether diol or propylene oxide copolymer diol
  • the chain extender is one selected from the group consisting of 1,6-hexanediol, methylpropanediol, and 1,4-butanediol; , 6-tertiary butyl-4-methylphenol or tetra ⁇ -(3,5-tri-butyl-4-hydroxyphenyl)propionic acid ⁇ pentaerythritol ester, the tackifying resin being selected from the group consisting of polyethylene 5 ⁇ 0 ⁇ 0. 5-15. 0 ⁇ 0. 5-15. 0 ⁇ 0. 5-15. 0 ⁇ /10 minutes of polypropylene, 5% to 25% of the melt index of 0. 01-2.
  • the flame retardant halide is prepared by mixing and extruding a polyethylene elastomer, a linear polyethylene, a polypropylene and an anti-aging agent raw material; wherein the composition of the TPU raw material for preparing the TPU film is: 60- 70 parts by weight of a polymer polyol selected from one or more selected from the group consisting of polytetrahydrofuran ether glycol having a molecular weight of 1000 and polyethylene butylene glycol butylene glycol polyol having a molecular weight of 3000; 30-35 by weight Parts of 1,4-cyclohexane diisocyan
  • the composition of the PU raw material for preparing the dry PU film is: 55-70% of the main agent, 20-37% of methyl ethyl ketone, 3-10% of black sand, 0.5 -1% of a tert-butyl hydroperoxide, 0. 8-1% of a matte agent composed of a calcium filler, 0. 6-0. 9% of an anti-wear agent composed of an aromatic silicone oil, 0. 2-0. 6% of a benzotriazole ultraviolet absorber and 0. 5-1.
  • composition of the main agent itself is: 12-28% polyester diol, 1-5% linear diol, 6-18% diphenylformam-4,4'-diisocyanate, 1 - 3% TDI trimer, 20-70% dimethylformamide, 0-30% methyl ethyl ketone, 2-6% hydroxyethyl acrylate, each component being by mass percentage.
  • the granules having a particle size of 0. 5-0. 8 microns and accounting for a total content of inorganic particles of 25, the composition of the inorganic particles in the transition layer of the release layer. % clay, barium sulfate powder having a particle size of 1-2 ⁇ m and accounting for 60% of the total inorganic particles, and calcium carbonate having a particle diameter of 3-5 ⁇ m and accounting for 15% of the total inorganic particles;
  • the structural formula of the vinyl silicone oil in the release layer is: > ⁇ J m L ”n , where
  • R1 and R3 are -CH3, R2 is -CH2, CH2, m is in the range of 2000 to 3000, and n is in the range of 3 to 6.
  • the hot melt adhesive TPU-PU leather wherein the thickness of the adhesive layer A2 is 2. 5 ⁇ m, the thickness of the plastic layer A3 is 20 ⁇ m, and the thickness of the transition layer A4 is 15 ⁇ m, the release layer A5 has a thickness of 25 ⁇ m, and the preparation material of the transition layer is 65 parts by weight of inorganic particles, 35 parts by weight of a silicone-acrylic emulsion, 4 parts by weight of sodium fatty acid methyl sulfonate, and dodecyl group.
  • the raw material for preparing the release layer is 60 parts by weight of polypropylene, 30 parts by weight of poly 4-methyl-1-pentene, and 8 parts by weight 5 ⁇ Formate,
  • R3 is - CH3
  • the hot melt adhesive TPU-PU leather according to the present invention wherein the raw material composition of the hot melt adhesive is: 65 parts by weight of a polyester polyol, 18 parts by weight of a diisocyanate, and 4 parts by weight of a polyether.
  • a polyol 1 part by weight of a catalyst, 1 part by weight of a chain extender, 1.6 parts by weight of an antioxidant, 5 parts by weight of a tackifying resin, 3 parts by weight of a flame retardant, and 3 parts by weight of a toughening agent;
  • the toughening agent is prepared by mixing and extruding 31% polyethylene elastomer, 19% linear polyethylene, 49% polypropylene and 1% anti-aging agent raw material by weight;
  • the flame retardant is 50 % by weight of melt index 5 g/10 min of polypropylene, 20 wt% of melt index of 0.8 g/10 min of polyethylene, 20 wt% of powdered talc and kaolinite mixed inorganic filler, 10% by weight
  • the weight of the composition of the TPU raw material is 65 parts by weight of polyethylene adipate ethylene glycol butanediol polyol, 0.6 weight Part of ⁇ -(4-hydroxy-3, 5-di-tert-butylphenyl) propionic acid n-octadecyl alcohol ester antioxidant, 0.3 parts by weight of two (2, 2, 6, 6-tetra a pyridyl amide light stabilizer, 0.6 parts by weight of a erucamide wax lubricant, 4 parts by weight of a carbodiimide hydrolysis resistance agent, 32 parts by weight and a temperature of 60 1,C cyclohexyl diisocyanate at ° C, 6 parts by weight of a 1,4-butanediol chain extender, 0.1 part by weight of a ruthenium catalyst, and 2 parts by weight of decabromodiphenyl acetam.
  • An organic halide flame retardant of micro-fumed silica is 65
  • the hot melt adhesive TPU-PU leather wherein the composition of the PU raw material is by mass percentage: 60% of the main agent, 30% of methyl ethyl ketone, 6% of black sand, 0.8 % of t-butyl hydroperoxide, 0.8% of matte agent, 0.8% of anti-wear agent, 0.6% of UV absorber and 1% of antistatic agent, wherein the main agent itself
  • the composition is by mass percentage: 20% polyester diol, 10% methyl ethyl ketone, 50% dimethylformamide, 3% linear diol, 12% diphenyl ketone-4, 4'-diisocyanate, 2% TDI trimer and 3% hydroxyethyl acrylate.
  • the hot melt adhesive TPU-PU leather according to the present invention, wherein the hot melt adhesive TPU-PU leather has a tensile strength of 34. 2 kgf, a longitudinal length of 29. 2 kgf ;
  • the bond strength of the PU leather is 6. lkgf; latitudinal 5. 2 kgf ; the bond strength of the hot melt adhesive TPU-PU leather is greater than or equal to 3. OKg I 25 mm ;
  • the hot melt adhesive TPU-PU The elongation of the leather is greater than or equal to 600%; the hot melt adhesive TPU-PU leather has a Shore hardness of 98 or more.
  • a method for preparing a seam-free hot melt adhesive TPU-PU leather characterized in that the method comprises the following steps:
  • the paper substrate A1 is selected, and an aqueous polypropylene bonding layer A2 having a thickness of 0.8 to 4 ⁇ m is coated on the paper substrate A1, and then a thickness of 18- is adhered to the bonding layer A2.
  • a 25 micron plastic layer A3 formed of a polyethylene terephthalate film, which is then cured for a certain period of time;
  • transition layer coating liquid on the plastic layer A3 using a doctor blade, and curing at 80 ° C for 30 seconds to form a film, controlling the film thickness to be 15-20 ⁇ m, and then forming the film.
  • the transition layer A4 is calendered under conditions of 120 ° C, a line pressure of 150 KN/m, and a vehicle speed of 10 m/min;
  • polyester polyol placing 60-70 parts by weight of the polyester polyol, 3-5 parts by weight of the polyether polyol, 1.5-1.8 parts by weight of the antioxidant, and 4-6 parts by weight of the tackifying resin in the reaction vessel , heating to 120 ⁇ 140 ° C, vacuum dehydration under stirring and mixing for 1.5 to 2 h, vacuum degree less than 0.05 MPa, and then cooling to 70 to 75 ° C; wherein the polyester polyol is passed through low molecular weight aliphatic diol Preparing a hydroxyl group-terminated polyester diol having a molecular weight of 2000-6000 by polycondensation reaction with an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid at 100-260 Torr, wherein the polyether polyol is selected from polytetrahydrofuran ether diol And one of propylene oxide copolymer diols selected from the group consisting of 2,6-tertiary butyl-4-methylphenol or tetra-
  • diisocyanate is one of 4,4'-diphenylformamidine diisocyanate or 1,6-hexamethylene diisocyanate
  • the catalyst is selected from dibutyltin dilaurate, triethanolamine or dimorpholine.
  • the polymer polyol is a polytetrahydrofuran ether glycol having a molecular weight of 1000 and/or the molecular weight is 3000 polybutylene adipate glycol butanol, then 0.2-0.8 parts by weight of antioxidant, 0.1-0.5 parts by weight of bis(2, 2, 6, 6-tetramethyl-4- a piperidinyl) aerated amine light stabilizer, 0.4-0.8 parts by weight of a montan wax and/or a erucamide wax lubricant, and 3-5 parts by weight of a carbodiimide hydrolysis resistant agent, After thorough stirring, a polymer polyol mixed solution is obtained, wherein the antioxidant is n-octadecyl ⁇ -(4-hydroxy-3, 5-di-tert-butylphenyl)propionate, and four [ ⁇ -( At least one of pent
  • thermoplastic polyurethane elastomer raw material (4), when the reaction melt temperature reaches 180-210 Torr, adding 1-3 parts by weight of an organic halogenated mixture of decabromodiphenylethane mixed micro-fumed silica with an average particle size of less than or equal to 4 microns a flame retardant, dehydrating, drying and aging after a predetermined reaction time to obtain a thermoplastic polyurethane elastomer raw material;
  • a main agent 12-28% of a polyester diol, 0-30% of methyl ethyl ketone, 20-70% of dimethylformamide, and 1-5% of a linear diol are placed in a reaction Stir in the pot at room temperature for 20-40 minutes. After mixing well, put 6-18% diphenylformamidine-4,4 '-diisocyanate into the reaction pot at room temperature, heat up and let it at 70- After reacting for 1-3 hours at 80 Torr, add 1-3% TDI trimer, react at 60-80 ° C for 1-3 hours, then gradually lower the temperature to 40-50 ° C, then add 2-6% acrylic acid. Hydroxyethyl ester, stirring 0. 5 hours, cooling the discharge, to obtain the main agent;
  • step (2) the hot melt adhesive material prepared in step (2) is processed into a rubber material through an extruder, and the rubber material is fed into a temperature of 150 degrees.
  • the extruder is melted into a paste, extruded by an extruder die, and then cast onto the release paper, and then cooled and wound by a pair of press rolls to form a hot melt adhesive film;
  • step (4) the PU raw material prepared in step (4) is sprayed onto the release paper, and the release paper with the PU material is driven by the feeding rack to completely flatten the PU raw material and bake it to the micro by the scraper and the oven respectively. Dry to make a dry PU film;
  • the dry PU film is passed through the sizing and the hot-melt-coated TPU film prepared in the step (3) is simultaneously fed into the pattern to the pressure roller, and then rapidly cooled by the cooling device.
  • the hot-melt glue-free TPU-PU leather of the multi-layer structure of the dry PU film + TPU film + hot melt adhesive film of the present invention is obtained.
  • the preparation material of the transition layer is 65 parts by weight of inorganic particles and 35 parts by weight of silicone-acrylic emulsion. , fatty acid methyl ester sodium sulfonate 4 heavy 5 ⁇ 25%, The content of the clay is 0. 5-0. 8 microns and the content is 25%, the content of the clay is 0. 5-0. 8 microns and the content is 25%.
  • the barium sulfate powder has a particle size of 1-2 micrometers and a content of 60%, and the calcium carbonate powder has a particle diameter of 3-5 micrometers and a content of 15%;
  • the preparation material of the release layer is 60 parts by weight of polypropylene, 30 Parts by weight of poly-4-methyl-1-pentene, 8 parts by weight of vinyl silicone oil, 1.5 parts by weight of 2,2 '-methylene-bis-(4,6-di-tert-butylbenzene) Acid ester, structural formula of the ethyl sulfonated silicone oil
  • the method for preparing a hot melt adhesive TPU-PU leather wherein the aliphatic dicarboxylic acid of the polyester polyol prepared in the step (2) is selected from the group consisting of adipic acid, fumaric acid, maleic acid or octane
  • the diacid, the aromatic dicarboxylic acid is selected from the group consisting of phthalic acid, terephthalic acid or isophthalic acid
  • the aliphatic diol is selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, methyl propylene glycol, 1, 4 - butanediol, 1,6-hexanediol, 1, 3-butanediol, 1,5-pentanediol or dodecylhexanediol;
  • the specific composition of the flame retardant is: 30-70 weight % ⁇ 0.
  • the toughening agent is composed of a polyethylene elastomer, a linear polyethylene, a polypropylene PP, and an anti-aging agent After the raw materials are mixed and extruded, the mass percentage of each raw material is: 31% of polyacetonitrile elastomer, 19% of linear polyethylene, 49% of polypropylene, and 1% of anti-aging agent.
  • the method for preparing a hot melt adhesive TPU-PU leather according to the present invention wherein the composition of the TPU raw material in the step (3) is 65 parts by weight of polyethylene butylene glycol adipate having a molecular weight of 3000 3 ⁇ (2, 2 ⁇ The polyol, 0.
  • the method for preparing a hot melt adhesive TPU-PU leather according to the present invention wherein the composition of the PU raw material in the step (4) is: by mass percentage: 60% of the main agent, 30% of methyl ethyl ketone, 6% Black sand, 0.
  • composition of the main agent itself is by mass percentage: 20% polyester diol, 10% methyl ethyl ketone, 50% dimethylformamide, 3% linear diol, 12% Diphenylformamidine-4,4'-diisocyanate, 2% TDI trimer and 3% hydroxyethyl acrylate.
  • the innovative design of multi-layer structure release paper especially the innovative design of multi-functional layer and release layer, makes the release paper provided by the invention have excellent physical and chemical properties in leather products. It has high bonding strength with hot melt adhesive and fast curing time. It is an ideal substrate for high quality leather.
  • the hot melt adhesive of the invention has low melting point, high elasticity, acid resistance, alkali resistance, water washing resistance, dry cleaning resistance, strong tensile strength, strong subsequent force, low melting point and the like.
  • TPU film and PU film used have overcome many defects of the existing TPU and PU through innovative innovations in raw materials. They not only possess most of the characteristics of rubber and ordinary plastics, but also have excellent comprehensive physical and chemical properties. , can be used as a complete replacement for PVC:, PU artificial leather and other leather fabrics.
  • the seam-free hot melt adhesive TPU-PU leather provided by the invention does not undergo qualitative change at a high temperature of 190 degrees, and is very easy to adhere to the surface of materials such as cloth, rubber (plastic) rubber and wood. It can be widely used in the manufacturing industries of garments, shoes, handbags, bags, seats, building decoration, etc., and the products after the fitting are resistant to washing and dry cleaning, and the products have wear resistance, heat resistance and tortuosity.
  • the hot melt adhesive and the raw material contained in the TPU raw material used in the invention have biomedical properties, are non-toxic, tasteless and have no allergic reaction, and are extremely environmentally friendly and non-polluting, and are ideal in the 21st century. One of the eco-friendly fabrics.
  • FIG. 1 is a schematic view showing the hot melt adhesive film formed by extruding the hot melt adhesive of the present invention onto a release paper;
  • FIG. 2 is a schematic view of the product after the hot melt adhesive film shown in FIG. 1 is pressed together with the TPU film;
  • FIG. 3 is a schematic structural view of a film layer of the seam-free hot melt adhesive TPU-PU leather according to the present invention.
  • Figure 4 is a schematic view showing the structure of a release paper used in the present invention.
  • A1-paper bottom layer A2-bonding layer, A3-plastic layer, A4-transition layer, A5-release layer;
  • the composition of most of the raw material substances is measured in “parts by weight”. This "parts by weight” only indicates the relationship between the composition ratios of each substance, similar to the mass percentage. Does not represent the actual quality of use, which means that certain components of different substances may have The same or similar parts by weight, but does not mean that these components have the same or similar mass content in each substance.
  • the molded product of the hot melt adhesive TPU-PU leather of the present invention comprises a release paper Sl, a hot melt adhesive film S2 coated on the release paper S1, a TPU film S3 adhered to the hot melt adhesive film S2, and a press fit. Dry PU film S4 on TPU film S3.
  • the preparation of the seam-free hot melt adhesive TPU-PU leather of the invention adopts a multi-layer bonding method, and specifically comprises the following steps: Step 1: preparing a release paper Sl, a hot melt adhesive raw material, a TPU raw material and a PU raw material, These raw materials are unique to the company and are also one of the main inventions of the present invention, and the raw material formulations and preparation methods thereof will be detailed later.
  • Step 2 The prepared hot-melt collagen material is passed through an extruder and processed into a rubber compound, and the rubber compound is fed into an extruder having a temperature of up to 150 degrees to be melted into a paste, and then extruded and extruded by an extruder die. Extending to the release paper for isolation, and then pressing and cooling the pressure roller to form a seamless hot melt adhesive film S2, as shown in FIG. 1;
  • Step 3 extruding the prepared TPU raw material into a TPU film S3, and placing the rolled hot melt adhesive film S2 and the TPU film S3 on two feeding racks respectively, so that the hot melt adhesive film S2 and the TPU film S3 enter simultaneously.
  • Set the temperature of the constant pressure to the pressure roller, and the temperature of the pressure roller is above 160 °C, so that the hot melt adhesive is bonded to the TPU in an instant when the pressure is pressed against the pressure roller, forming a hot melt adhesive.
  • Step 4 The prepared PU raw material is sprayed onto the release paper S1, and the release paper S1 with the PU material is driven by the feeding rack to completely flatten and bake the PU raw material to the micro dryness through the scraper and the oven respectively.
  • Step 5 the dry PU film S4 is passed through the sizing and the TPU film S3 with the hot melt adhesive is simultaneously fed into the pattern to press-fit in the press wheel, and then rapidly cooled by the cooling device and then wound up, thereby obtaining the present invention.
  • the seam-free hot melt adhesive TPU-PU leather of the multilayer structure consisting of dry PU film + TPU film + hot melt adhesive film.
  • the key technologies of the present invention include: the formulation of a highly viscous hot melt adhesive, the key formulation of the TPU, PU film, and the selection of various functional admixtures (masterbatch) therein and the preparation of the release paper S1 as a substrate.
  • TPU thermoplastic polyurethane
  • PU Polyurethane, also known as polyurethane
  • the present invention combines long-term production practice and has undergone extensive experiments to innovate a new type of polyurethane hot melt adhesive and TPU/PU material by changing the formulation components and additives.
  • the product of the present invention has multiple physical properties such as better adhesion, tear resistance, abrasion resistance, and high temperature resistance.
  • composition and preparation of the release paper S1 used in the present invention are as follows:
  • the release paper S1 provided by the present invention has a multi-layer structure, specifically including a paper bottom layer A1, at the bottom of the paper.
  • a plastic layer A3 is adhered to the layer A1 via the adhesive layer A2, a transition layer A4 is provided on the plastic layer A3, and a release layer A5 is provided on the transition layer M.
  • the plastic layer A3 is a polyethylene terephthalate film (i.e., a PET film) having a thickness of 18 to 25 ⁇ m, preferably 20 ⁇ m.
  • the adhesive layer A2 bonds the paper underlayer A1 and the polyethylene terephthalate film A3, and the adhesive layer A2 is an aqueous polypropylene (PP) coating layer, and the amount used is per square 5 ⁇ The thickness of 0. 8-micron, preferably 1-2. 5 microns.
  • PP polypropylene
  • the composition of the transition layer A4 comprises inorganic particles, a silicone-acrylic emulsion, sodium fatty acid methyl ester sulfonate, dodecyldimethylbenzyl ammonium chloride and water, and the parts by weight of each component are: inorganic particles 62- 68 parts, 32-36 parts of silicone-acrylic emulsion, 3-5 parts of sodium fatty acid methyl ester sulfonate, 2_4 parts of decyl dimethyl benzyl chloride, 45-55 parts of water; the composition of inorganic particles includes particles a clay having a diameter of 0. 5-0.
  • the preparation process of the transition layer A4 is that the above-mentioned parts by weight of sodium fatty acid methyl ester sulfonate is poured into the above-mentioned parts by weight of water, stirred uniformly, and the clay, barium sulfate powder and calcium carbonate included in the inorganic particles are uniformly mixed according to the above weight.
  • the transition layer coating liquid was uniformly coated on the plastic layer A3 using a doctor blade, and cured by heating at 80 Torr for 30 seconds to form a film having a film thickness of 15 to 20 ⁇ m, and then the film-forming transition layer A4 was 120.
  • the arrangement of the transition layer ensures that the release paper S1 has impermeability and surface smoothness as a whole, wherein the silicone-acrylic emulsion is cured by heating to form a dense film, which can effectively block the penetration of the solvent on the paper base, and the silicon
  • the film formed by the acrylic emulsion also has good solvent resistance, and the solvent is applied thereto without dissolving and destroying the film and other substrates, and the transition layer effectively masks the roughness of the surface of the paper bottom layer A1 and the plastic layer A3.
  • the state ensures the smoothness of the surface of the release layer and the overall release paper S1, and the smoothness of the surface state of the release paper S1 is very advantageous for improving the smooth gloss of the entire leather product based on the release paper S1.
  • the composition of the release layer A5 disposed on the transition layer A4 comprises: 58-65 parts by weight of polypropylene, 26-34 parts by weight of poly 4-methyl-1-pentene, and 6-9 parts by weight of ethylene.
  • the base oil 1-2 parts by weight of 2, 2 '-methylene-bis-(4,6-di-tert-butylphenoxy) sodium phosphate and 0. 1-0. 8 parts by weight of t-butyl peroxidation a benzoate, wherein the structural formula of the vinyl silicone oil is:
  • the release layer is prepared by uniformly mixing the above-mentioned parts by weight of polypropylene, poly-4-methyl-1-pentene and vinyl silicone oil to 9 CTC, and after adding for 2 hours, adding 1-2 parts by weight of 2 , 2 '-methylene-bis-(4,6-di-tert-butylphenoxy) sodium phosphate and 0. 1-0. 8 parts by weight of t-butyl peroxybenzoate and mixed uniformly, and then passed
  • the extruder is extrusion coated on the surface of the transition layer A4, and the thickness of the release layer is controlled to be 20-25 microns.
  • This release layer accelerates the double bond of the polyolefin by 2, 2 '-methylene-bis-(4,6-di-tert-butylphenoxy)phosphate and t-butylperoxybenzoate.
  • the cross-linking reaction of the double bond of the vinyl silicone oil, and the polyolefin content thereof is increased. Since the affinity between the polyolefin and the polyurethane is good, the release paper S1 having the release layer and the heat containing the polyurethane The product after the bonding of the melt adhesive has better performance.
  • the release paper S1 used in the present invention is prepared by the above method, and the release paper S1 is tested to be very suitable for the coating of the hot melt adhesive and the PU film of the present invention, preferably the release type of the present invention.
  • the thickness of the paper S1 is 80-100 micrometers, but it is not limited thereto, and can be adjusted according to actual needs.
  • the raw material components of the hot melt adhesive extruded on the above release paper include:
  • polyester polyol 60-70 parts by weight of polyester polyol, 15-20 parts by weight of diisocyanate, 3-5 parts by weight of polyether polyol, .8-1. 5 parts by weight of catalyst, 0. 5-1.2 weight Parts of the chain extender, 1. 5-1.8 parts by weight of an antioxidant, 4-6 parts by weight of a tackifying resin, 2 to 4 parts by weight of a flame retardant, and 2 to 4 parts by weight of a toughening agent.
  • the polyester polyol is prepared by polycondensation of a low molecular weight aliphatic diol with an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid at 100-260 Torr to prepare a terminal hydroxyl polyester diol having a molecular weight of 2000-6000. .
  • the aliphatic dicarboxylic acid comprises adipic acid, fumaric acid, maleic acid or suberic acid; the aromatic dicarboxylic acid comprises phthalic acid, terephthalic acid or isophthalic acid
  • the aliphatic diol includes ethylene glycol, diethylene glycol, propylene glycol, methyl propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1, 3-butanediol, 1 5 pentanediol or dodecyl hexanediol.
  • the diisocyanate is one of 4, 4 '-diphenylmethane diisocyanate and 1,6-hexamethylene diisocyanate;
  • the polyether polyol is selected from the group consisting of polytetrahydrofuran ether diol and propylene oxide copolymer One of the alcohols;
  • the catalyst selects one or more of dibutyltin dilaurate, triethanolamine or dimorpholinyl diethyl ether;
  • the chain extender selects 1,6-hexanediol, methylpropanediol, 1, 4 - one of butylene glycol;
  • the antioxidant is selected from the group consisting of 2,6-tris-butyl-4-methylphenol or tetra ⁇ -(3,5-tri-butyl-4-hydroxyphenyl)propanoate ⁇ pentaerythritol ester;
  • the tackifying resin is selected from one or more of a polyethylene-vinyl acetate copolymer, a hydroxyl terminated thermoplastic polyester, and a hydrogenated rosin resin; the specific composition of the flame retardant is: 30-70% by weight of a melt index 0 5-15. 0 g/10 min of polypropylene, 5-25 wt% of melt index 0. 01-2.
  • polyethylene 20-30 wt% of selected from powdered talc, high At least one inorganic filler in sillimanite, sericite, silica, and diatomaceous earth, 5-15% by weight selected from decabromodiphenyl ether, dodecachlorododecyl benzoxazole cyclooctene or An organic flame retardant halide of its mixture.
  • the toughening agent selects a polyolefin toughening agent, wherein the PE (polyethylene) elastomer, the linear polyethylene, the polypropylene (PP) and the anti-aging agent raw materials are mixed and extruded, and the mass percentage of each raw material It is: PE (polyethylene) elastomer 31%, linear polyethylene 19%, polypropylene (PP) 49%, anti-aging agent 1%.
  • the TPU raw material composition for forming the TPU film S3 in the present invention is:
  • the polymer polyol is one of polytetrahydrofuran ether glycol having a molecular weight of 1000, polyethylene butylene glycol polybutylene adipate having a molecular weight of 3000 or a variety; 30-35 parts by weight of 1,4-cyclohexane diisocyanate; 4-9 parts by weight of a chain extender, the chain extender is 1,4-butanediol; 3-5 parts by weight of water resistance
  • the decomposing agent is specifically a carbodiimide hydrolysis-resistant agent; 1-3 parts by weight of a flame retardant, and the flame retardant is an organic halide flame retardant of decabromodiphenylacetamene mixed micro-fumed silica
  • the agent has an average particle size of less than or equal to 4 ⁇ m; 0.2 to 0.8 parts by weight of the antioxidant, and the antioxidant is ⁇ -(4-hydroxy-3, 5-di-tert-butylphenyl
  • Alcohol ester tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester and bis[(2,4-di-tert-butylphenyl)phosphite] pentaerythritol ester
  • thermoplastic polyurethane elastomer TPU for forming a film from the above raw materials
  • the above-mentioned parts by weight of the polymer polyol is placed in a reaction vessel, and heated to 80-9 (?), and then the above-mentioned parts by weight of an antioxidant, a hindered amine light stabilizer, a lubricant, and the like are added.
  • the hydrolysis resistant agent is stirred sufficiently to obtain a polymer polyol mixed solution.
  • the apparatus for the preparation of the above thermoplastic polyurethane elastomer raw material may be a single screw mixing apparatus, a co-rotating twin-screw continuous reaction extruder, a drying apparatus, and the like which are well known in the art.
  • the obtained thermoplastic polyurethane elastomer raw material was again fed into an extruder to extrude the TPU film S3.
  • the PU raw material composition for forming the dry PU film S4 is expressed by weight percentage: 55-70% of the main agent, 20-37% of methyl ethyl ketone, 3-10% of black sand, 0. 5-1% of the uncle 5-6. 6 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ % benzotriazole ultraviolet absorber, 0. 5-1.
  • composition (weight percentage) of the main agent itself is: 12-28 % polyester diol, 1-5% linear diol, 6-18% diphenylformamidine-4, 4 '-diisocyanate, 1-3% TDI trimer, 20-70 % dimethylformamide, 0-30% methyl ethyl ketone, 2-6% hydroxyethyl acrylate.
  • a main agent 12-28% of a polyester diol, 0-30% of methyl ethyl ketone, 20-70% of dimethylformamide, and 1-5% of a linear diol are placed in a reaction Stir in the pot at room temperature for 20-40 minutes. After mixing well, put 6-18% diphenylformamidine-4,4'-diisocyanate into the reaction pot at room temperature, heat and heat up and make it at 70- After reacting at 80 ° C for 1-3 hours, add 1-3% TDI trimer, react at 60-80 Torr for 1-3 hours, then gradually lower the temperature to 40-50 ,, then add 2-6% acrylic acid. Hydroxyethyl ester, stirring 0. 5 hours, cooling the discharge, to obtain the main agent;
  • the dry PU film S4+ is obtained by cooling.
  • TPU film S3 + hot melt adhesive film S2 multi-layer structure of seam-free hot melt adhesive TPU-PU leather.
  • Bonding strength 3. 0Kg / 25 mm.
  • the seamless-melting hot melt adhesive TPU-PU leather prepared by the invention adopts an innovative formula and prepares a release paper Sl, a hot melt adhesive, a TPU film S3 and a dry PU, in particular, a specially formulated polyurethane hot melt.
  • the glue is bonded to the TPU film S3, so that the tensile strength, tear strength, abrasion strength, bond strength and surface gloss of the final leather product are greatly improved, even at a high temperature of 190 degrees. It can be widely used in the manufacturing industry of garments, shoes, handbags, bags, seats, building decoration, etc.
  • the "new type of car-free hot-melt adhesive TPU-PU leather" described in the present invention combined with the long-term innovation practice has not been reported in the literature at home and abroad, and is the world's first.
  • the seam-free hot melt adhesive TPU-PU leather of the present invention is prepared in the following manner.
  • the paper base layer Al is selected, and an aqueous polypropylene (PP) bonding layer A2 having a thickness of 2.5 ⁇ m is coated on the paper substrate A1, and then a polyethylene pair having a thickness of 20 ⁇ m is pasted on the bonding layer A2.
  • the ethylene phthalate film A3 is cured for a certain period of time.
  • a transition layer coating was prepared in accordance with 65 parts by weight of the inorganic particles, 35 parts by weight of the silicone-acrylic emulsion, 4 parts by weight of the fatty acid methyl ester sulfonate, 3 parts by weight of lauryl dimethyl benzyl ammonium chloride, and 50 parts by weight of water.
  • the coating layer has a thickness of 25 ⁇ m
  • the composition of the release layer comprises: 60 parts by weight of polypropylene, 30 parts by weight of poly 4-methyl-1-pentene, and 8 parts by weight of vinyl silicone oil.
  • step (2) under nitrogen protection, 18 parts by weight of diisocyanate and 1 part by weight of the catalyst is added to the reaction product of step (1), and reacted at 85 ° C for 1.5 h;
  • the polyester polyol is prepared by polycondensation of a low molecular weight aliphatic diol with an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid at 180-24 CTC, wherein the aliphatic diol is aliphatic
  • the dicarboxylic acid is selected from the group consisting of adipic acid and fumaric acid; wherein the aromatic dicarboxylic acid is selected from the group consisting of phthalic acid and terephthalic acid, wherein the aliphatic diol is selected from the group consisting of ethylene glycol, 1, 3- Butylene glycol, 1,5 pentanediol or dodecyl hexanediol.
  • the diisocyanate is 4, 4 'diphenylmethane diisocyanate;
  • the polyether polyol is polytetrahydrofuran ether glycol;
  • the catalyst is selected to be dimorpholinyl diethyl ether; 6-hexanediol;
  • the antioxidant is selected from tetra ⁇ -(3,5-tris-butyl-4-hydroxyphenyl)propionic acid ⁇ pentaerythritol ester;
  • the tackifying resin is selected to be a hydrogenated rosin resin;
  • the fuel is composed of: 50% by weight of a melt index of 5 g/lOmin of polypropylene, 20% by weight of a melt index of O.Sg/lOmin of polyethylene, 20% by weight of powdered talc and kaolinite mixed inorganic filler, 10
  • the composition is composed of an organic halide flame retardant of a mixture of decabromodiphenyl ether and dodecachlor
  • the toughening agent selects a polyolefin toughening agent, which is prepared by mixing PE (polyethylene) elastomer, linear polyethylene, polypropylene (PP) and anti-aging agent raw materials: PE (polyethylene) elasticity 31% of body, 19% of linear polyethylene, 49% of polypropylene (PP), and 1% of anti-aging agent.
  • reaction melt temperature reaches 200 ° C
  • 2 parts by weight of decabromodiphenylacetamide is mixed with the micro-fumed silica organic halide flame retardant, and dehydrated and dried after a predetermined time of reaction. And aging, that is, a thermoplastic polyurethane elastomer raw material is obtained.
  • the 8% of the main agent, 30% of the butanone, 6% of the black sand, 0.8% of the t-butyl hydroperoxide, 0.8% of the matte agent, 0.8% After mixing with anti-wear agent, 0.6% UV absorber and 1% antistatic agent, it is dispersed in a high-speed disperser for 20 minutes, and then allowed to defoam for 4 hours, then dripped onto the release paper S1, which is driven by the feeding rack.
  • the release paper S1 having the PU material was run, and the PU raw material was sufficiently smoothed and baked to a fine dryness through a doctor blade and an oven to form a dry PU film S4.
  • the prepared hot melt adhesive raw material is processed into a rubber compound by an extruder, and the rubber material is fed into an extruder having a temperature of up to 150 degrees to be melted into a paste, which is then extruded by an extruder die and then cast. Put on the release paper, and then pressurize and press the pressure roller to form a hot melt adhesive film S2 shown in Figure 1;
  • the prepared TPU raw material is also extruded into the TPU film S3, and is placed on the two feeding racks together with the hot melt adhesive film S2 rolled in the step (2), so that the hot melt adhesive film S2 and TPU
  • the membrane S3 is pressed into the pressure roller with the constant temperature, and the pressure of the pressure roller is above 16 CTC, so that the hot melt adhesive with low melting point is bonded to the TPU film S3 instantaneously when the pressure roller is pressed against the pressure roller.
  • a TPU film S3 with a hot melt adhesive film is formed, as shown in FIG. 2;
  • the prepared PU raw material is sprayed onto the release paper S1, and the release paper S1 with the PU material is driven by the feeding rack to operate, and the PU raw material is fully smoothed and baked to the micro-dry after being scraped and oven respectively.

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Abstract

La présente invention concerne un nouveau cuir TPU-PU à adhésif thermofusible sans couture et un procédé de préparation de celui-ci. Le cuir TPU-PU à adhésif thermofusible comprend un papier anti-adhésif, un film d'adhésif thermofusible, un film de TPU et un film de PU sec. Le papier anti-adhésif comprend une couche de papier inférieure, une couche d'adhésif, une couche plastique, une couche de transition et une couche anti-adhésive ; une matière première d'adhésif thermofusible comprend un polyester polyol, un diisocyanate, un polyéther polyol et une pluralité d'additifs ; une matière première TPU comprend un alcool polyvalent polymère, du 1,4-cyclohexane-diisocyanate, un allongeur de chaîne et une pluralité d'additifs fonctionnels ; et une matière première PU comprend un polyester glycol, un diol à chaîne droite, un isocyanate, un tripolymère TDI, du diméthylformamide, de la butanone, du sable noir et une pluralité d'additifs fonctionnels. Selon la présente invention, les innovations sont réalisées sur des constituants de matière première du papier anti-adhésif, de l'adhésif thermofusible, du film de TPU et du film de PU ; et le cuir TPU-PU sans couture préparé possède les avantages techniques de matériaux à ferme adhérence, durables et écologiques, sans danger pour le corps humain, et similaires.
PCT/CN2014/079497 2013-08-16 2014-06-09 Cuir tpu-pu à adhésif thermofusible sans couture, et son procédé de préparation WO2015021814A1 (fr)

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