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

Abstract

The invention proposes a novel sewing-free hot-melt adhesive TPU-PU leather and a preparation method thereof. The hot-melt adhesive TPU-PU leather includes a release paper, a hot-melt adhesive film, a TPU film and a dry PU film. Paper includes paper bottom layer, adhesive layer, plastic layer, transition layer and release layer. The raw material of hot melt adhesive is composed of polyester polyol, diisocyanate, polyether polyol and several additives. The raw material of TPU is composed of polymer polyol, 1, Composed of 4-cyclohexane diisocyanate, chain extender and several functional additives, PU raw materials are polyester diol, linear diol, isocyanate, TDI trimer, dimethylformamide, butanone, black sand And several functional additives. The invention innovates the raw material components of release paper, hot-melt adhesive, TPU and PU film, and the prepared sewing-free TPU-PU leather has the characteristics of firm adhesion, durability, environmental protection, and no harm to the human body. Any technical advantages such as stealth damage.

Description

A kind of sewing-free hot melt adhesive TPU-PU leather and preparation method thereof

technical field

The invention relates to the technical field of leather materials, in particular to a sewing-free hot-melt adhesive TPU-PU leather and a preparation method thereof.

Background technique

In the prior art, in the production industries of garments, shoes, bags, handbags, seats, military industry, etc. at home and abroad, the fabrics attached to all products are all spliced by traditional stitching methods. This production method not only has high labor intensity and high production cost, but also has problems such as easy fracture, tearing and peeling at the seam of the product under the action of external force, which seriously affects the service life and quality of the product, and the consumption cost is also significantly increased. Also because most of the current product fabrics are made of PVC leather, and the PVC material itself contains toxic elements such as polyvinyl chloride and ethylhexylamine, which is carcinogenic to the human body and is extremely unsafe to use. Most of the glue used in the pasting is industrial liquid glue and solid glue. Most of these melt glue materials are toxic, and they have good properties such as elasticity, acid resistance, alkali resistance, washing resistance, dry cleaning resistance, tension resistance, and adhesion. Aspects have certain defects, and are not ideal environmental protection adhesive materials.

Contents of the invention

Based on the above technical problems, the present invention proposes a new type of sewing-free hot-melt adhesive TPU-PU leather and its preparation method. By innovating the raw materials of each layer of leather from the components, combined with the company's long-term production practice experience, Finally, the sewing-free TPU-PU leather of the present invention is formed, which can be directly attached to various items, and has technical advantages such as firm adhesion, durability, environmental protection, and no invisible harm to the human body, fundamentally solving the problem of It eliminates various adverse factors caused by seam splicing and the application of existing industrial glue in leather products.

The technical scheme that the present invention solves the problems of the technologies described above is as follows:

A kind of sewing-free hot-melt adhesive TPU-PU leather, comprising a release paper, a hot-melt adhesive coated on the release paper, a TPU film pasted on the hot-melt adhesive, and an adhesive bonded against the TPU film. Dry PU film; wherein the release paper includes a paper bottom layer A1, an adhesive 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 an adhesive layer A2 On the bottom layer A1, the transition layer A4 is arranged on the plastic layer A3, the release layer A5 is arranged on the transition layer A4, the adhesive layer A2 is a water-based polypropylene coating layer, and the usage amount is per square 5-8 grams per meter, with a thickness of 0.8-4 microns, the plastic layer A3 is a polyethylene terephthalate film with a thickness of 18-25 microns, and the transition layer A4 consists of 62-68 parts by weight of Inorganic particles, 32-36 parts by weight of silicon 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 parts by weight It is prepared by mixing and stirring with water, and the thickness of the film is 15-20 microns. The thickness of the release layer A5 is 20-25 microns and is composed of 58-65 parts by weight of polypropylene, 26-34 parts by weight of poly4 -Methyl-1-pentene, 6-9 parts by weight of vinyl silicone 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 tert-butyl peroxybenzoate; wherein said hot-melt adhesive consists of 60-70 parts by weight of polyester polyol, 15-20 parts by weight of diisocyanate, 3-5 Parts by weight of polyether polyol, 0.8-1.5 parts by weight of catalyst, 0.5-1.2 parts by weight of chain extender, 1.5-1.8 parts by weight of antioxidant, 4-6 parts by weight of tackifying resin, 2-4 parts by weight of Flame retardant, 2-4 parts by weight of the toughening agent, the polyester polyol is prepared by low molecular weight aliphatic dihydric alcohol and aliphatic dicarboxylic acid, aromatic dicarboxylic acid at 100-260 Polycondensation reaction at ℃ to prepare hydroxyl-terminated polyester diol with a molecular weight of 2000-6000, the aliphatic dicarboxylic acid is selected from adipic acid, fumaric acid, maleic acid or suberic acid, and the aromatic dicarboxylic acid The carboxylic acid is selected from phthalic acid, terephthalic acid or isophthalic acid, and the aliphatic dihydric alcohol is selected from ethylene glycol, diethylene glycol, propylene glycol, methyl propylene glycol, 1,4-butanediol , 1,6-hexanediol, 1,3-butanediol, 1,5-pentanediol or dodecylhexanediol; the diisocyanate uses 4,4'-diphenylmethane diisocyanate or 1 , 6-hexamethylene diisocyanate; the polyether polyol is selected from polytetrahydrofuran ether glycol or propylene oxide copolymerized glycol; the catalyst is selected from dibutyltin dilaurate, triethanolamine or bismorpholino diethyl One or several ethers; the chain extender is selected from 1,6-hexanediol, methyl propylene glycol, and 1,4-butanediol; the antioxidant is selected from 2,6-tertiary Butyl-4-methylphenol or tetrakis{β-(3,5-tertiary butyl-4-hydroxyphenyl)propionate}pentaerythritol ester, the tackifying resin Grease is selected from one or more of polyethylene-vinyl acetate copolymers, hydroxyl-terminated thermoplastic polyesters, and hydrogenated rosin resins; the composition of the flame retardant is calculated by mass percentage: 30%-70% melt index 0.5- 15.0 g/10 min of polypropylene, 5%-25% of polyethylene with a melt index of 0.01-2.0 g/10 min, 20%-40% of powdered talc, kaolinite, sericite, silica And at least one inorganic filler in diatomaceous earth, 5%-35% of organic flame retardant halides selected from decabromodiphenyl ether, dodecachlorododecahydrodimethyloxazocyclooctene or a mixture thereof ; The toughening agent is formed by mixing and extruding polyethylene elastomer, linear polyethylene, polypropylene and anti-aging agent raw materials; wherein the composition of the TPU raw material for preparing the TPU film is: 60-70 parts by weight of polymerized Polyhydric alcohol, selected from one or more of polytetrahydrofuran ether glycol with a molecular weight of 1000 and polyethylene adipate butylene glycol ester polyol with a molecular weight of 3000; 30-35 parts by weight of 1,4 - cyclohexane diisocyanate; 4-9 parts by weight of chain extender, the chain extender is 1,4-butanediol; 3-5 parts by weight of carbodiimide hydrolysis resistance agent; 1-3 parts by weight 0.2-0.8 parts by weight of decabromodiphenylethane mixed with a small amount of fumed silica as an organic halide flame retardant with an average particle size less than or equal to 4 microns; the antioxidant is β -(4-Hydroxy-3,5-di-tert-butyl-phenyl)propionate n-octadecyl, tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol At least one of bis[(2,4-di-tert-butylphenyl)phosphite]pentaerythritol ester; 0.1-0.5 parts by weight of bis(2,2,6,6-tetramethyl-4-piper Pyridyl) sebacate hindered amine light stabilizer; 0.4-0.8 parts by weight of montan wax and/or erucamide wax lubricant; 0.05-0.2 parts by weight of titanium or bismuth catalyst; wherein the prepared The PU raw material composition of 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 tert-butyl hydroperoxide, 0.8-1 % of fogging agent composed of calcium filler, 0.6-0.9% of anti-wear agent composed of aromatic silicone oil, 0.2-0.6% of benzotriazole ultraviolet absorber and 0.5-1.2% of metal powder or the antistatic agent composed of conductive carbon black, the main agent itself is composed of: 12-28% polyester diol, 1-5% straight-chain diol, 6-18% diphenylmethane- 4,4'-diisocyanate, 1-3% TDI trimer, 20-70% dimethylformamide, 0-30% methyl ethyl ketone, 2-6% hydroxyethyl acrylate, each component All are calculated by mass percentage.

Further according to the hot-melt adhesive TPU-PU leather of the present invention, wherein the composition of the inorganic particles in the transition layer of the release paper includes clay with a particle size of 0.5-0.8 micron and accounting for 25% of the total content of the inorganic particles, Barium sulfate powder with a particle size of 1-2 microns and accounting for 60% of the total content of inorganic particles and calcium carbonate with a particle size of 3-5 microns and accounting for 15% of the total content of inorganic particles; wherein the ethylene in the release layer The structural formula of base silicone oil is: In the formula, R1 and R3 are -CH3, R2 is -CH=CH2, the range of m is 2000-3000, and the range of n is 3-6.

Further according to the hot melt adhesive TPU-PU leather of the present invention, wherein the thickness of the bonding layer A2 is 2.5 microns, the thickness of the plastic layer A3 is 20 microns, and the thickness of the transition layer A4 is 15 microns , the thickness of the release layer A5 is 25 microns, and the preparation raw materials of the transition layer are 65 parts by weight of inorganic particles, 35 parts by weight of silicon-acrylic emulsion, 4 parts by weight of sodium fatty acid methyl ester sulfonate, dimethyl dodecyl 3 parts by weight of benzyl ammonium chloride and 50 parts by weight of water; the raw materials for the preparation of the release layer are 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-butylphenoxy) sodium phosphate and 0.5 parts by weight of tert-butyl peroxybenzoate, the Structural formula of vinyl silicone oil Among them, R1 and R3 are -CH3, R2 is -CH=CH2, m=2500, n=4.

Further according to the hot melt adhesive TPU-PU leather of the present invention, wherein the preparation raw materials of the hot melt adhesive consist of: 65 parts by weight of polyester polyol, 18 parts by weight of diisocyanate, 4 parts by weight of polyether The catalyst of polyol, 1 weight part, the chain extender of 1 weight part, the tackifying resin of 1.6 weight parts antioxidant, the tackifying resin of 5 weight parts, the flame retardant of 3 weight parts, the toughening agent of 3 weight parts; The toughening agent is mixed and extruded by 31% polyethylene elastomer, 19% linear polyethylene, 49% polypropylene and 1% antiaging agent raw materials by weight; the flame retardant is formed by 50% by weight Polypropylene with a melt index of 5 g/10 minutes, 20% by weight of polyethylene with a melt index of 0.8 g/10 minutes, 20% by weight of powdered talc and kaolinite mixed inorganic fillers, 10% by weight of decabromodi Composed of organic halides mixed with phenyl ether and dodecachlorododecahydrodimethyloxazolidine.

Further according to the hot melt adhesive TPU-PU leather of the present invention, wherein the composition of the TPU raw material is 65 parts by weight of polyethylene adipate polybutylene adipate polyol with a molecular weight of 3000, 0.6 parts by weight of β-(4-hydroxy-3,5-di-tert-butylphenyl) n-octadecyl propionate antioxidant, 0.3 parts by weight of bis(2,2,6,6-tetramethyl-4- piperidinyl) sebacate light stabilizer, 0.6 parts by weight of erucamide wax lubricant, 4 parts by weight of carbodiimide hydrolysis resistance agent, 32 parts by weight of 1,4- Organohalogenation of cyclohexane diisocyanate, 6 parts by weight of 1,4-butanediol chain extender, 0.1 parts by weight of bismuth catalyst, and 2 parts by weight of decabromodiphenylethane mixed with trace amount of fumed silica flame retardants.

Further according to the hot melt adhesive TPU-PU leather of the present invention, wherein the composition of the PU raw material is calculated by mass percentage: 60% of the main agent, 30% of methyl ethyl ketone, 6% of black sand, 0.8% of Tertiary butyl hydroperoxide, 0.8% matting agent, 0.8% wear-resistant agent, 0.6% ultraviolet absorber and 1% antistatic agent, wherein the composition of the main agent itself is calculated by mass percentage: 20% % of polyester diol, 10% of butanone, 50% of dimethylformamide, 3% of linear diol, 12% of diphenylmethane-4,4'-diisocyanate, 2% of TDI trimer and 3% hydroxyethyl acrylate.

Further according to the hot-melt adhesive TPU-PU leather of the present invention, wherein the tensile strength of the hot-melt adhesive TPU-PU leather is 34.2kgf in the transverse direction and 29.2kgf in the longitudinal direction; the tearing strength of the hot-melt adhesive TPU-PU leather is The cracking strength is 6.1kgf in the warp direction; 5.2kgf in the weft direction; the bonding strength of the hot-melt adhesive TPU-PU leather is greater than or equal to 3.0Kg/25㎜; the elongation of the hot-melt adhesive TPU-PU leather is greater than or equal to 600 %; The Shore hardness of the hot melt adhesive TPU-PU leather is greater than or equal to 98.

A kind of preparation method of the hot-melt adhesive TPU-PU leather of exempting from sewing, it is characterized in that, described method comprises the following steps:

(1) Preparation of release paper

(1) Select the paper bottom layer A1, and coat the water-based polypropylene adhesive layer A2 with a thickness of 0.8-4 microns on the paper bottom layer A1, and then paste the adhesive layer A2 with a thickness of 18-25 microns A plastic layer A3 formed of a polyethylene terephthalate film, which is then cured for a certain period of time;

(2) Pour 3-5 parts by weight of sodium fatty acid methyl ester sulfonate into 45-55 parts by weight of water, stir well, then pour 62-68 parts by weight and mix with clay, barium sulfate powder and calcium carbonate powder The prepared inorganic particles are stirred at high speed to disperse them evenly, then add 32-36 parts by weight of silicon acrylic emulsion into the dispersed slurry, mix the solution evenly with a glass rod, and then add 2-4 parts by weight of twelve Alkyl dimethyl benzyl ammonium chloride is added therein, and the stirring is continued to make a transition layer coating solution;

(3) Use a scraper to uniformly coat the transition layer coating liquid on the plastic layer A3, and heat at 80°C for 30 seconds to solidify to form a film, control the film thickness at 15-20 microns, and then apply the transition layer after film formation Layer A4 is calendered under the conditions of 120°C, line pressure 150KN/m, and vehicle speed 10m/min;

(4) Mix 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 vinyl silicone oil, heat to 90°C and keep warm for 2 After 1 hour, add 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 tert-butyl peroxybenzoate and mix evenly, then extrude and coat the surface of the transition layer A4 through an extruder to form a release layer A5, and control the thickness at 20-25 microns;

(2) Preparation of hot melt adhesive raw materials

(1) Put 60-70 parts by weight of polyester polyol, 3-5 parts by weight of polyether polyol, 1.5-1.8 parts by weight of antioxidant and 4-6 parts by weight of tackifying resin in the reactor , heated to 120-140°C, vacuum dehydrated for 1.5-2 hours under stirring and mixing, the vacuum degree is less than 0.05MPa, and then cooled to 70-75°C; wherein the polyester polyol is obtained by low molecular weight aliphatic diol and fat The polycondensation reaction of aromatic dicarboxylic acids and aromatic dicarboxylic acids at 100-260°C prepares hydroxyl-terminated polyester diols with a molecular weight of 2000-6000, and the polyether polyols are selected from polytetrahydrofuran ether diols, A kind of in oxypropylene copolyethylene glycol, described antioxidant is selected from 2,6-tertiary butyl-4-methylphenol or tetra{β-(3,5-tertiary butyl-4-hydroxyphenyl ) pentaerythritol propionate, wherein the tackifying resin is selected from one or more of polyethylene-vinyl acetate copolymer, hydroxyl-terminated thermoplastic polyester, and hydrogenated rosin resin;

(2) Under nitrogen protection, add 15-20 parts by weight of diisocyanate and 0.8-1.5 parts by weight of catalyst to the reaction product of step (1), and react at 85-95°C for 1-1.5 hours; The diisocyanate adopts one of 4,4'-diphenylmethane diisocyanate or 1,6-hexamethylene diisocyanate, and the catalyst selects dibutyltin dilaurate, triethanolamine or bismorpholino diisocyanate. One or more of ethyl ethers;

(3) Under nitrogen protection, add 0.5-1.2 parts by weight of chain extender, 2-4 parts by weight of flame retardant, and 2-4 parts by weight of toughening agent into the reaction product of step (2), And stir and react at 75-85°C for 45min-1.0h; wherein the chain extender is selected from one of 1,6-hexanediol, methylpropanediol, and 1,4-butanediol, and the flame retardant is composed of It is composed of polypropylene, polyethylene, inorganic filler and organic flame retardant halide; the toughening agent is polyolefin toughening agent;

(4) Discharging under nitrogen protection conditions, aging and cooling to form hot melt adhesive raw materials;

(3) Preparation of TPU raw materials

(1) Put 60-70 parts by weight of polymer polyol in the reaction kettle and heat it to 80-90°C. The polymer polyol is polytetrahydrofuran ether diol with a molecular weight of 1000 and/or a molecular weight of 3000 polyethylene adipate polybutylene glycol ester polyol, then add 0.2-0.8 parts by weight of antioxidant, 0.1-0.5 parts by weight of two (2,2,6,6-tetramethyl-4-piper Pyridyl) sebacate hindered amine light stabilizer, 0.4-0.8 parts by weight of montan wax and/or erucamide wax lubricant and 3-5 parts by weight of carbodiimide hydrolysis-resistant agent, fully After stirring, a polymer polyol mixed solution is obtained, wherein the antioxidant is β-(4-hydroxy-3,5-di-tert-butylphenyl) n-octadecyl propionate, tetrakis[β-(3 , at least one of 5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol ester and bis[(2,4-di-tert-butylphenyl)phosphite]pentaerythritol ester;

(2) Add 30-35 parts by weight of 1,4-cyclohexane diisocyanate at a temperature of 55-65°C to the polymer polyol mixed solution, stir and mix to obtain a preliminary reaction mixture;

(3) Keep the temperature of the above reaction mixture and add 4-9 parts by weight of 1,4-butanediol chain extender and 0.05-0.2 parts by weight of titanium or bismuth catalyst, and control the temperature at 150-210 °C , The pressure is 4-8MPa and the reaction is about 1h;

(4) When the temperature of the reaction melt reaches 180-210°C, add 1-3 parts by weight of an organic compound made of decabromodiphenylethane mixed with a small amount of fumed silica with an average particle size of less than or equal to 4 microns. Halide flame retardant, dehydration, drying and curing after a predetermined reaction time to obtain thermoplastic polyurethane elastomer raw materials;

(4) Preparation of PU raw materials

(1) Prepare the main ingredient: put 12-28% polyester diol, 0-30% butanone, 20-70% dimethylformamide, and 1-5% linear diol into the reaction Stir in the pot at room temperature for 20-40 minutes, after mixing evenly, put 6-18% diphenylmethane-4,4'-diisocyanate into the reaction pot at room temperature, heat up and make it at 70-80 After reacting at ℃ for 1-3 hours, add 1-3% TDI trimer, react at 60-80℃ for 1-3 hours, gradually cool down to 40-50℃, add 2-6% acrylic acid Hydroxyethyl ester, cooling and discharging after stirring for 0.5 hours, to obtain the main agent;

(2) Mix 55-70% of the main agent, 20-37% of methyl ethyl ketone, 3-10% of black sand, 0.5-1% of tert-butyl hydroperoxide, 0.8-1% of fogging agent, 0.6 -0.9% anti-wear agent, 0.2-0.6% ultraviolet absorber, 0.5-1.2% antistatic agent are mixed, dispersed in a high-speed disperser for 10-20 minutes, and left to defoam for 4 hours to obtain PU raw materials;

(5) Lamination and preparation of sewing-free hot melt adhesive TPU-PU leather

(1) Prepare the release paper, hot melt adhesive raw materials, TPU raw materials and PU raw materials prepared through the above steps, and place the release paper in related equipment to lay flat;

(2) Process the hot-melt adhesive raw material prepared in step (2) into a rubber material through an extruder, and the rubber material is sent to the extruder at a temperature of 150 degrees to melt into a paste, and then extruded by the extruder die Casting onto the release paper, and then press against the pressing wheel—cooling—rolling to form a hot melt adhesive film;

(3) Extrude the TPU raw material prepared in step (3) into a TPU film, and place it on two feeding racks with the above hot melt adhesive film, so that the hot melt adhesive film and TPU film enter the thermostatic chamber at the same time. The pressure is carried out in the high and low pressure rollers, and the temperature of the pressure rollers is above 160°C, so that the hot melt adhesive with a low melting point is instantly bonded to the TPU film when the high and low pressure rollers are pressed against each other, and after cooling, it forms a bond with heat. Melt TPU film;

(4) Pour the PU raw material prepared in step (4) onto the release paper, and the release paper with the PU material is driven by the feeding rack, and the PU raw material is fully scraped and baked to a slight degree by a scraper and an oven respectively. Dry to make dry PU film;

(5) After gluing the dry PU film and the TPU film with hot melt adhesive prepared in step (3), it is sent to the patterned counter-pressing wheel at the same time, and then it is quickly cooled by the cooling device and rolled up. Take, and obtain the hot-melt adhesive-free sewing TPU-PU leather of the multi-layer structure of dry PU film+TPU film+hot-melt adhesive film according to the present invention.

Further according to the method for preparing hot-melt adhesive TPU-PU leather according to the present invention, in the step (1) of preparing release paper: the raw materials for preparing the transition layer are 65 parts by weight of inorganic particles and 35 parts by weight of silicon-acrylic emulsion , 4 parts by weight of sodium fatty acid methyl ester sulfonate, 3 parts by weight of dodecyl dimethyl benzyl ammonium chloride and 50 parts by weight of water, the specific composition of the inorganic particles is: the clay particle diameter is 0.5-0.8 micron and The content is 25%, the particle size of barium sulfate powder is 1-2 microns and the content is 60%, the particle size of calcium carbonate powder is 3-5 microns and the content is 15%; the preparation raw 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 Oxygen) sodium phosphate and 0.5 parts by weight of tert-butyl peroxybenzoate, the structural formula of the vinyl silicone oil wherein R1 and R3 are -CH ₃ , R2 is -CH=CH ₂ , m=2500, n=4.

Further according to the method for preparing hot melt adhesive TPU-PU leather according to the present invention, wherein the aliphatic dicarboxylic acid for preparing polyester polyol in step (2) is selected from adipic acid, fumaric acid, maleic acid or octane Diacid, aromatic dicarboxylic acid selected from phthalic acid, terephthalic acid or isophthalic acid, aliphatic dihydric alcohol selected from 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 specific composition of the flame retardant is: 30-70 wt. % of polypropylene with a melt index of 0.5-15.0 grams/10 minutes, 5-25% by weight of polyethylene with a melt index of 0.01-2.0 grams/10 minutes, 20-30% by weight of powdery talc, kaolinite, At least one inorganic filler in sericite, silicon dioxide and diatomaceous earth, 5-15% by weight selected from decabromodiphenyl ether, dodecachlorododecahydrodimethyloxazocyclooctene or a mixture thereof Organic flame retardant halides; the toughening agent is extruded by mixing polyethylene elastomer, linear polyethylene, polypropylene PP and anti-aging agent raw materials, and the mass percentage of each raw material is: polyethylene elastomer 31 %, linear polyethylene 19%, polypropylene 49%, anti-aging agent 1%.

Further according to the hot melt adhesive TPU-PU leather preparation method of the present invention, wherein the composition of the TPU raw material in the step (3) is 65 parts by weight of polyethylene adipate with a molecular weight of 3000 Polyol, 0.6 parts by weight of β-(4-hydroxy-3,5-di-tert-butylphenyl) n-octadecyl propionate antioxidant, 0.3 parts by weight of bis(2,2,6,6 -tetramethyl-4-piperidinyl) sebacate light stabilizer, 0.6 parts by weight of erucamide wax lubricant, 4 parts by weight of carbodiimide hydrolysis-resistant agent, 32 parts by weight and temperature at 1,4-cyclohexane diisocyanate at 60°C, 6 parts by weight of 1,4-butanediol chain extender, 0.1 part by weight of bismuth catalyst, and 2 parts by weight of decabromodiphenylethane Organohalide flame retardant for making silica.

Further according to the method for preparing hot-melt adhesive TPU-PU leather according to the present invention, wherein the composition of the PU raw material in the step (4) is calculated by mass percentage: 60% of the main agent, 30% of methyl ethyl ketone, 6% of Black sand, 0.8% tert-butyl hydroperoxide, 0.8% fogging agent, 0.8% wear-resistant agent, 0.6% ultraviolet absorber and 1% antistatic agent, wherein the composition of the main agent itself Calculated by mass percentage: 20% polyester diol, 10% butanone, 50% dimethylformamide, 3% linear diol, 12% diphenylmethane-4,4' - Diisocyanate, 2% TDI Trimer and 3% Hydroxyethyl Acrylate.

The main technical characteristics and technical effects of the present invention are:

(1) The innovatively designed multi-layer structure release paper, especially the innovative design of the multi-functional layer and the release layer, makes the release paper provided by the present invention have exceptionally excellent physical and chemical properties when applied to leather products, And it has high bonding strength with hot melt adhesive and fast curing time, which is an ideal base material for high-quality leather.

(2) The original low-melting point hot-melt adhesive is adopted, which is a kind of adhesive with strong plasticity, which can replace industrial liquid glue, solid glue and PU glue. It has the advantages of environmental protection, non-toxic and no side effects, etc. Environmentally friendly adhesive materials, the hot melt adhesive of the present invention has properties such as low melting point, high elasticity, acid resistance, alkali resistance, water washing resistance, dry cleaning resistance, strong tensile strength, strong adhesion, and low melting point.

(3) The TPU film and PU film used have overcome many defects of the existing TPU and PU through the innovation and improvement of raw materials. They not only have most of the characteristics of rubber and ordinary plastics, but also have excellent comprehensive physical and chemical properties. , can be used as a complete substitute for PVC, PU artificial leather and other leather fabrics.

(4) The sewing-free hot-melt adhesive TPU-PU leather provided by the present invention will not change qualitatively at a high temperature of 190 degrees, and it is very easy to stick to the surface of materials such as cloth, rubber (plastic) leather, and wood. It can be widely used in the manufacturing industries of clothing, footwear, handbags, luggage, seats, architectural decoration, etc., and the products after lamination are resistant to washing and dry cleaning, and the products have the properties of wear resistance, heat resistance and bending resistance. The elements contained in the hot melt adhesive and TPU raw materials used in the present invention have been tested by SGS and have biomedical properties, are non-toxic, tasteless, and have no allergic reactions. The products are extremely environmentally friendly and non-polluting, and are ideal for the 21st century. One of the most environmentally friendly fit fabrics.

Description of drawings

Accompanying drawing 1 is the schematic diagram that hot-melt adhesive of the present invention is extruded to form hot-melt adhesive film on release paper;

Accompanying drawing 2 is the product schematic diagram after hot-melt adhesive film and TPU film lamination shown in accompanying drawing 1;

Accompanying drawing 3 is the film structure schematic diagram of the hot-melt adhesive TPU-PU leather of exempting from sewing according to the present invention;

Accompanying drawing 4 is the structural representation of the release paper applied in the present invention;

In the figure, A1-paper bottom layer, A2-adhesive layer, A3-plastic layer, A4-transition layer, A5-release layer;

In the figure, S1-release paper, S2-hot melt adhesive film, S3-TPU film, S4-dry PU film.

Detailed ways

The technical solution of the present invention is described in detail below, so that those skilled in the art can understand the solution of the present invention more clearly, but the protection scope of the present invention is not limited thereby. What needs to be explained first here is that the composition of most raw materials in the present invention is measured in "parts by weight", and this "parts by weight" only represents the relationship between the proportions of components inside each material, similar to mass percentages, It does not represent the actual mass used, which means that some components of different substances may have the same or similar weight parts, but it does not mean that these components have the same or similar mass content in each substance.

First, the molded product of the sewing-free hot-melt adhesive TPU-PU leather of the present invention and its preparation method are described. The molded product of the hot melt adhesive TPU-PU leather of the present invention comprises a release paper S1, a hot melt adhesive film S2 coated on the release paper S1, a TPU film S3 pasted on the hot melt adhesive film S2 and a press bonded Dry PU film S4 on TPU film S3.

The preparation of the sewing-free hot melt adhesive TPU-PU leather of the present invention adopts the method of multi-layer bonding, specifically comprises the following steps:

Step 1. Prepare release paper S1, hot melt adhesive raw materials, TPU raw materials and PU raw materials. These raw materials belong to our company's original creation and are also one of the main invention points of the present invention. The raw material formula and preparation will be given in detail later method.

Step 2. The prepared hot-melt collagen material is processed into a rubber material through an extruder, and the rubber material is sent to an extruder at a temperature of up to 150 degrees to be melted into a paste, and then extruded by the extruder die to flow Extend to the release paper which plays the role of isolation, and then press against the pressing wheel-cool-coil to form a seamless hot-melt adhesive film S2, as shown in Figure 1;

Step 3. Extrude the prepared TPU raw material into TPU film S3, and place the rolls of hot melt adhesive film S2 and TPU film S3 on two feeding racks respectively, so that the hot melt adhesive film S2 and TPU film S3 enter simultaneously The high and low pressure rollers with constant temperature are set for pressure, and the temperature of the pressure rollers is above 160°C, so that the hot melt adhesive is instantly bonded with the TPU when the high and low pressure rollers are pressed against each other, forming a hot melt adhesive TPU film S3, as shown in accompanying drawing 2;

Step 4. Pour the prepared PU raw material onto the release paper S1, and the release paper S1 with the PU material is driven by the feeding frame to run, and the PU raw material is fully scraped and baked to slightly dry by a scraper and an oven respectively. into dry PU film S4;

Step 5. After gluing, the dry PU film S4 and the TPU film S3 attached with hot melt adhesive are simultaneously sent to the pattern counter-pressing wheel for pressure forming, and then quickly cooled by the cooling device and then coiled to obtain the present invention. The sewing-free hot-melt adhesive TPU-PU leather with a multi-layer structure of dry PU film+TPU film+hot-melt adhesive film.

The key technology of the present invention includes: the formulation of high-viscosity hot melt adhesive, the key formulation of TPU and PU film, the selection of various functional additives (masterbatch) and the preparation of release paper S1 as the base material. Because TPU (thermoplastic polyurethane) and PU (polyurethane, polyurethane, also known as: polyurethane) are environmentally friendly materials, and because the PU raw material only needs to modify the formula simply, it can obtain different density, elasticity, Rigidity and other physical properties are very good decorative formula materials. This invention combines long-term production practice and a large number of tests to innovatively propose a new type of polyurethane hot melt adhesive and TPU/PU material. By changing the formula components and additives , combined with mathematical models and practical verification, using multiple sets of experimental data collection to determine the impact factors between components, and calculate the optimal ratio through theory, and apply the final formula to the test, the obtained product after verification The invented product has multiple physical properties such as better adhesion, tear resistance, abrasion resistance and high temperature resistance.

The composition and preparation of release paper S1 applied to the present invention are as follows:

As shown in accompanying drawing 4, the release paper S1 provided by the present invention has a multi-layer structure, specifically includes a paper bottom layer A1, and a plastic layer A3 is bonded on the paper bottom layer A1 through an adhesive layer A2, and the plastic layer A3 is bonded on the paper bottom layer A1. A transition layer A4 is disposed on the layer A3, and a release layer A5 is disposed on the transition layer A4. Specifically, the plastic layer A3 is a polyethylene terephthalate film (ie PET film) with a thickness of 18-25 microns, preferably 20 microns. The bonding layer A2 bonds the paper bottom layer A1 and the polyethylene terephthalate film A3, and the bonding layer A2 is a water-based polypropylene (PP) coating layer, and the usage amount is per square 5-8 grams per meter, with a thickness of 0.8-4 microns, preferably 6 grams per square meter, with a thickness of 1-2.5 microns. The composition of the transition layer A4 includes inorganic particles, silicon acrylic emulsion, sodium fatty acid methyl ester sulfonate, dodecyl dimethyl benzyl ammonium chloride and water, and the parts by weight of each component are: inorganic particles 62- 68 parts, 32-36 parts of silicon acrylic emulsion, 3-5 parts of sodium fatty acid methyl ester sulfonate, 2-4 parts of dodecyl dimethyl benzyl ammonium chloride, 45-55 parts of water; the composition of inorganic particles Including clay with a particle size of 0.5-0.8 microns, accounting for 25% of the total inorganic particle content, barium sulfate powder with a particle size of 1-2 microns, accounting for 60% of the total inorganic particle content, and barium sulfate powder with a particle size of 3-5 microns, accounting for inorganic particles 15% of the total particle content of calcium carbonate. The preparation process of the transition layer A4 is that the sodium fatty acid methyl ester sulfonate of the above weight part is poured into the water of the above weight part, stirred evenly, and the clay, barium sulfate powder and calcium carbonate included in the inorganic particles are mixed uniformly according to the above weight Pour one part into the above stirring solution, use high-speed stirring to disperse it evenly, add the above-mentioned part by weight of silicone acrylic emulsion into the dispersed slurry, mix the solution evenly with a glass rod, and then add the above-mentioned part by weight of dodecyl Add dimethyl benzyl ammonium chloride therein, continue to stir evenly, and make a transition layer coating liquid. Then use a scraper to evenly coat the transition layer coating solution on the plastic layer A3, and heat at 80° C. for 30 seconds to solidify into a film with a film thickness of 15-20 microns, and then the film-formed transition layer A4 on the Calendering treatment is carried out at 120°C, linear pressure 150KN/m, and vehicle speed 10m/min. After calendering treatment, the tiny holes in the transition layer are reduced, the film layer becomes smoother, and a denser and smoother surface state is obtained. It is more conducive to the laying of the release layer on it, and the smooth surface of the transition layer makes the surface of the final release layer have mirror flatness, ensuring the surface state and gloss of the final leather product. The setting of the transition layer ensures that the release paper S1 as a whole has anti-permeability and smooth surface, and the silicon-acrylic emulsion can form a dense film after heating and curing, which can effectively block the penetration of the solvent on the paper base, and the silicone The film formed by the acrylic emulsion also has good solvent resistance, and the solvent will not dissolve and damage the film and other substrates when applied to it, and the transition layer can effectively cover the surface roughness 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 release paper S1 as a whole. The smoothness of the surface state of the release paper S1 is very conducive to improving the smoothness and glossiness of the entire leather product based on the release paper S1. The composition of the release layer A5 set on the transition layer A4 includes: 58-65 parts by weight of polypropylene, 26-34 parts by weight of poly-4-methyl-1-pentene, 6-9 parts by weight of ethylene base silicone 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 tert-butyl peroxybenzoate , wherein the structural formula of the vinyl silicone oil is:

In the formula, R1 and R3 are -CH ₃ , R2 is -CH=CH ₂ , the range of m is 2000-3000, and the range of n is 3-6. The preparation process of the release layer is to mix the above weight parts of polypropylene, poly 4-methyl-1-pentene and vinyl silicone oil evenly, heat to 90°C, and add 1-2 parts by weight of Sodium 2,2′-methylene-bis-(4,6-di-tert-butylphenoxy)phosphate and 0.1-0.8 parts by weight of tert-butyl peroxybenzoate and mixed well, then passed through the extruder Extrusion coating on the surface of the transition layer A4, control the thickness of the release layer at 20-25 microns. In this release layer, 2,2′-methylene-bis-(4,6 di-tert-butylphenoxy)sodium phosphate and tert-butyl peroxybenzoate are used to accelerate the initiation of the double bond and bond of polyolefin The cross-linking reaction of the double bond of vinyl silicone oil, and the content of polyolefin in it increases, because the affinity between polyolefin and polyurethane is better, so the release paper S1 with this release layer and the heat containing polyurethane The product performance after melt adhesive bonding is better. The release paper S1 applied in the present invention is prepared by the above-mentioned method. This release paper S1 is very suitable for the coating of the hot melt adhesive and PU film of the present invention through testing, and the preferred release paper of the present invention The thickness of S1 is 80-100 microns, but not limited thereto, and can be adjusted according to actual needs.

The raw material components of the hot melt adhesive extruded on the above-mentioned release paper include:

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 parts by weight of chain extender, 1.5-1.8 parts by weight of antioxidant, 4-6 parts by weight of tackifying resin, 2-4 parts by weight of flame retardant, and 2-4 parts by weight of toughening agent.

The polyester polyol is prepared into a hydroxyl-terminated polyester diol with a molecular weight of 2000-6000 through the polycondensation reaction of low-molecular-weight aliphatic diols, aliphatic dicarboxylic acids, and aromatic dicarboxylic acids at 100-260°C. alcohol. The aliphatic dicarboxylic acid includes adipic acid, fumaric acid, maleic acid or suberic acid; the aromatic dicarboxylic acid includes phthalic acid, terephthalic acid or isophthalic acid ; The aliphatic dihydric alcohols include 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 adopts one of 4,4'-diphenylmethane diisocyanate and 1,6-hexamethylene diisocyanate;

The polyether polyol is selected from one of polytetrahydrofuran ether glycol and oxypropylene copolymerized glycol;

The catalyst is selected from one or more of dibutyltin dilaurate, triethanolamine or bismorpholino diethyl ether;

The chain extender is selected from one of 1,6-hexanediol, methylpropanediol, and 1,4-butanediol;

The antioxidant is selected from 2,6-tertiary butyl-4-methylphenol or tetrakis {β-(3,5-tertiary butyl-4-hydroxyphenyl) propionate} pentaerythritol ester;

The tackifying resin is selected from one or more of polyethylene-vinyl acetate copolymer, hydroxyl-terminated thermoplastic polyester, and hydrogenated rosin resin;

The specific composition of the flame retardant is: 30-70% by weight of polypropylene with a melt index of 0.5-15.0 g/10 minutes, 5-25% by weight of polyethylene with a melt index of 0.01-2.0 g/10 minutes, 20- 30% by weight of at least one inorganic filler selected from powdered talc, kaolinite, sericite, silicon dioxide and diatomaceous earth, 5-15% by weight selected from decabromodiphenyl ether, dodecachlorodeca Organic flame retardant halides of dihydrodimethyloxazocyclooctene or mixtures thereof.

The toughening agent is a polyolefin toughening agent, which is extruded after mixing PE (polyethylene) elastomer, linear polyethylene, polypropylene (PP) and anti-aging agent raw materials, and the mass percentage of each raw material is It is: PE (polyethylene) elastomer 31%, linear polyethylene 19%, polypropylene (PP) 49%, anti-aging agent 1%.

The concrete preparation process of above-mentioned hot melt adhesive is:

(1) Put 60-70 parts by weight of polyester polyol, 3-5 parts by weight of polyether polyol, 1.5-1.8 parts by weight of antioxidant and 4-6 parts by weight of tackifying resin in the reaction according to the above weight parts In the kettle, heat to 120-140°C, vacuum dehydrate for 1.5-2 hours under stirring and mixing, the vacuum degree is less than 0.05MPa, and then cool down to 70-75°C;

(2) Under nitrogen protection, add 15-20 parts by weight of diisocyanate and 0.8-1.5 parts by weight of catalyst to the reaction product of step (1), and react at 85-95°C for 1-1.5 hours;

(3) Under nitrogen protection, 0.5-1.2 parts by weight of chain extender, 2-4 parts by weight of flame retardant, and 2-4 parts by weight of toughening agent are added to the reaction product of step (2), and Stir the reaction at 75-85°C for 45min-1.0h;

(4) The material is discharged under the protection condition of nitrogen gas, and after being matured for a certain period of time, it is formed into the hot-melt adhesive raw material used in the present invention, and is sent into the extruder, and is extruded by the die head of the extruder to the attached As shown in Figure 2, on the release paper S1.

The TPU raw material that is used for molding TPU film S3 among the present invention consists of:

60-70 parts by weight of polymer polyol; the polymer polyol is one of polytetrahydrofuran ether glycol with a molecular weight of 1000, polyethylene adipate butylene glycol adipate polyol with a molecular weight of 3000 or Various; 30-35 parts by weight of 1,4-cyclohexane diisocyanate; 4-9 parts by weight of chain extender, the chain extender is 1,4-butanediol; 3-5 parts by weight of water-resistant decomposing agent, specifically carbodiimide hydrolysis-resistant agent; 1-3 parts by weight of the flame retardant, the flame retardant is decabromodiphenylethane mixed with a trace amount of fumed silica organic halide flame retardant agent, the average particle size is less than or equal to 4 microns; 0.2-0.8 parts by weight of antioxidant, the antioxidant is β-(4-hydroxy-3,5-di-tert-butylphenyl) propionic acid n-octadecyl Alcohol esters, tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol ester and bis[(2,4-di-tert-butylphenyl)phosphite]pentaerythritol ester At least one; 0.1-0.5 parts by weight of hindered amine light stabilizers, specifically bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate; 0.4-0.8 parts by weight of Montan wax and/or erucamide wax lubricant; 0.05-0.2 parts by weight of titanium or bismuth catalyst.

The specific method for preparing thermoplastic polyurethane elastomer TPU for forming film by above-mentioned raw materials is as follows:

(1) First, put the above weight of polymer polyol in the reaction kettle, and heat it to 80-90°C, then add the above weight of antioxidant, hindered amine light stabilizer, lubricant and hydrolysis resistance agent, after fully stirring to obtain a polymer polyol mixed solution.

(2) adding the above-mentioned parts by weight of 1,4-cyclohexane diisocyanate at a temperature of 55-65° C. to the polymer polyol mixed solution, stirring and mixing to obtain a preliminary reaction mixture;

(3) Keep the temperature of the above reaction mixture and add the above weight parts of 1,4-butanediol chain extender and catalyst, and control the temperature at 150-210°C and the pressure of 4-8MPa to react for about 1h.

(4) When the temperature of the reaction melt reaches 180-210°C, add the flame retardant in the above parts by weight, dehydrate, dry and mature after a predetermined reaction time to obtain thermoplastic polyurethane elastomer raw materials.

The devices used in the preparation of the above-mentioned thermoplastic polyurethane elastomer raw materials may be single-screw mixing devices, co-rotating twin-screw continuous reaction extruders, drying equipment, etc. well known in the prior art. The obtained thermoplastic polyurethane elastomer raw material is fed into the extruder again to extrude the TPU film S3.

Raw material and preparation of dry PU film S4 of the present invention

The PU raw material composition used to form the dry PU film S4 is calculated by weight percentage: 55-70% of the main agent, 20-37% of methyl ethyl ketone, 3-10% of black sand, 0.5-1% of tert-butyl Hydrogen peroxide, 0.8-1% fogging agent composed of calcium filler, 0.6-0.9% anti-wear agent composed of aromatic silicone oil, 0.2-0.6% benzotriazole ultraviolet absorber, 0.5 -1.2% antistatic agent composed of metal powder or conductive carbon black; the composition (weight percentage) of the main agent itself is: 12-28% polyester diol, 1-5% linear diol Alcohol, 6-18% diphenylmethane-4,4'-diisocyanate, 1-3% TDI trimer, 20-70% dimethylformamide, 0-30% methyl ethyl ketone, 2 -6% hydroxyethyl acrylate.

The method for preparing dry PU film S4 by the above-mentioned substances:

(1) Prepare the main ingredient: put 12-28% polyester diol, 0-30% butanone, 20-70% dimethylformamide, and 1-5% linear diol into the reaction Stir in the pot at room temperature for 20-40 minutes, after mixing evenly, put 6-18% diphenylmethane-4,4'-diisocyanate into the reaction pot at room temperature, heat up and make it at 70-80 After reacting at ℃ for 1-3 hours, add 1-3% TDI trimer, react at 60-80℃ for 1-3 hours, gradually cool down to 40-50℃, add 2-6% acrylic acid Hydroxyethyl ester, cooling and discharging after stirring for 0.5 hours, to obtain the main agent;

(2) Mix 55-70% of the main agent, 20-37% of methyl ethyl ketone, 3-10% of black sand, 0.5-1% of tert-butyl hydroperoxide, 0.8-1% of fogging agent, 0.6 -0.9% anti-wear agent, 0.2-0.6% UV absorber, 0.5-1.2% antistatic agent, after mixing, disperse in high-speed disperser for 10-20 minutes, let stand for 4 hours for defoaming, then pour onto release paper On S1, the release paper S1 with PU material is driven by the feeding rack, and the PU material is fully scraped and baked to slightly dry by a scraper and an oven respectively to make a dry PU film S4.

After the above-mentioned dry PU film S4 is glued and the TPU film S3 attached with the aforementioned hot-melt adhesive is simultaneously sent to the pattern counter-pressing wheel for pressure molding, after cooling, the dry-type PU film S4+TPU film of the present invention is obtained. S3 + hot-melt adhesive film S2 multi-layer structure of sewing-free hot-melt adhesive TPU-PU leather.

Finally, the main performance of the seamless hot-melt adhesive TPU-PU leather of the present invention obtained by the above method is detected, and the detection results are as follows:

1. Hardness: 65～70/A;

2. Tensile strength: transverse 34.2kgf, longitudinal 29.2kgf;

3. Tear strength: warp direction 6.1kgf; weft direction 5.2kgf;

4. Abrasion strength: under the pressure of 9Kpa, there is no abrasion phenomenon after grinding for 650 revolutions;

5. Adhesive strength: ≥3.0Kg/25㎜.

6. Elongation: ≥600%;

7. Shore hardness: ≥98.

The main performance comparison with similar products is as follows:

performance TPU pvc Nitrile rubber Neoprene natural rubber Hardness (Shore) 98 87 78 70 77 Tensile Strength 34.2, 29.2 16, 14.3 11.6 10.3 16.3 Elongation/% 600 309 400 400 574

Therefore, the non-sewing hot-melt adhesive TPU-PU leather obtained by the present invention is made of release paper S1, hot-melt adhesive, TPU film S3 and dry PU through an innovative formula, especially polyurethane hot-melt with a special formula. The glue is bonded with the TPU film S3, so that the tensile strength, tear strength, abrasion strength, adhesive strength, surface gloss and other properties of the final leather product are greatly improved, even at a high temperature of 190 degrees. Qualitative change, can be widely used in manufacturing industries such as clothing, footwear, handbags, bags, seats, architectural decoration, etc. Moreover, the "new type of sewing-free hot-melt adhesive TPU-PU leather" proposed by the company in combination with long-term innovation practice has not been reported in relevant literature at home and abroad, and it is the first in the world.

Example 1

A preferred embodiment of the present invention is given below.

The sewing-free hot-melt adhesive TPU-PU leather of the present invention is prepared in the following manner.

1. Preparation of release paper S1

Select the paper bottom layer A1, and on the paper bottom layer A1, coat a water-based polypropylene (PP) adhesive layer A2 with a thickness of 2.5 microns, and then stick a polyterephthalene with a thickness of 20 microns on the adhesive layer A2 Ethylene glycol formate film A3 and cured for a certain time. Then prepare the transition layer coating according to 65 parts by weight of inorganic particles, 35 parts by weight of silicon-acrylic emulsion, 4 parts by weight of sodium fatty acid methyl ester sulfonate, 3 parts by weight of dodecyl dimethyl benzyl ammonium chloride and 50 parts by weight of water Liquid, and uniformly coated on the polyethylene terephthalate film A3 with a doctor blade, and cured and calendered to form a transition layer A4 with a thickness of 15 microns, and finally extruded on the transition layer A4 Coating thickness is 25 micron release layer A5, and the composition of described release layer comprises: the polypropylene of 60 parts by weight, the poly-4-methyl-1-pentene of 30 parts by weight, the vinyl silicone oil of 8 parts by weight , 1.5 parts by weight of 2,2'-methylene-bis-(4,6 di-tert-butylphenoxy) sodium phosphate and 0.5 parts by weight of tert-butyl peroxybenzoate, the vinyl silicone oil The structural formula is:

Wherein R1 and R3 are -CH ₃ , R2 is -CH=CH ₂ , m is about 2500, n=4. Thus, the release paper S1 as the leather substrate of the present invention was prepared.

Second, the preparation of polyurethane hot melt adhesive raw materials

(1) Put 65 parts by weight of polyester polyol, 4 parts by weight of polyether polyol, 1.6 parts by weight of antioxidant and 5 parts by weight of tackifying resin in a reaction kettle, heat to 120°C, and mix under stirring Vacuum dehydration for 1.5h, the vacuum degree is less than 0.05MPa, then lower the temperature to 70°C;

(2) Under nitrogen protection, add 18 parts by weight of diisocyanate and 1 part by weight of catalyst to the reaction product of step (1), and react at 85°C for 1.5h;

(3) Under the protection of nitrogen, add 1 weight part of chain extender, 3 weight parts of flame retardant, and 3 weight parts of toughening agent to the reaction product of step (2), and stir the reaction at 85 °C for 1.0 h;

(4) Discharge under nitrogen protection conditions, and form polyurethane hot melt adhesive raw materials after aging for a certain period of time.

Wherein the polyester polyol is a hydroxyl-terminated polyester diol prepared by polycondensation of low molecular weight aliphatic diols, aliphatic dicarboxylic acids, and aromatic dicarboxylic acids at 180-240°C. The aromatic dicarboxylic acid is selected from adipic acid and fumaric acid; the aromatic dicarboxylic acid is selected from phthalic acid and terephthalic acid, and the aliphatic dihydric alcohol is selected from ethylene glycol, 1,3 - butanediol, 1,5 pentanediol or dodecylhexanediol. The diisocyanate adopts 4,4'-diphenylmethane diisocyanate; the polyether polyol adopts polytetrahydrofuran ether diol; the catalyst selects bismorpholino diethyl ether; the chain extender selects 1 , 6-hexanediol; the antioxidant selects four {β-(3,5-tertiary butyl-4-hydroxyphenyl) propionate} pentaerythritol ester; the tackifying resin selects hydrogenated rosin resin; the Flame retardant consists of: 50% by weight of polypropylene with a melt index of 5g/10min, 20% by weight of polyethylene with a melt index of 0.8g/10min, 20% by weight of powdered talc and kaolinite mixed inorganic filler, 10% by weight % organic halide flame retardant composed of decabromodiphenyl ether and dodecachlorododecahydrodimethyloxazolidine mixture. The toughening agent is polyolefin toughening agent, which is extruded after mixing PE (polyethylene) elastomer, linear polyethylene, polypropylene (PP) and anti-aging agent raw materials: PE (polyethylene) elastic Body 31%, linear polyethylene 19%, polypropylene (PP) 49%, anti-aging agent 1%.

3. Preparation of TPU raw materials

(1) Put 65 parts by weight of polyethylene adipate polybutylene adipate polyol with a molecular weight of 3000 in a reaction kettle and heat it to 90°C, then add 0.6 parts by weight of β-(4-hydroxy- 3,5-di-tert-butylphenyl) propionate n-octadecyl alcohol ester antioxidant, 0.3 parts by weight of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacic acid The ester light stabilizer, 0.6 parts by weight of erucamide wax lubricant, and 4 parts by weight of carbodiimide hydrolysis-resistant agent are fully stirred to obtain a polymer polyol mixed solution.

(2) adding 32 parts by weight of 1,4-cyclohexane diisocyanate at a temperature of 60° C. to the polymer polyol mixed solution, stirring and mixing to obtain a preliminary reaction mixture;

(3) Keep the temperature of the above reaction mixture and add 6 parts by weight of 1,4-butanediol chain extender and 0.1 part by weight of bismuth-based catalyst, and control the temperature at 180-210 °C and the pressure of 6 MPa for about 1 hour.

(4) When the temperature of the reaction melt reaches 200°C, add 2 parts by weight of decabromodiphenylethane mixed with a small amount of organic halide flame retardant of fumed silica, and perform dehydration, drying and After aging, the thermoplastic polyurethane elastomer raw material is obtained.

4. Preparation of dry PU film S4

(1) Prepare the main ingredient: put 20% polyester diol, 10% butanone, 50% dimethylformamide, and 3% linear diol into the reaction pot by mass percentage and stir at room temperature for 30 Minutes, after mixing evenly, put 12% diphenylmethane-4,4'-diisocyanate into the reaction pot at room temperature, heat up and let it react at 80°C for 2 hours, then add 2% The TDI trimer was reacted at 80°C for 2 hours, then gradually cooled to 40°C, 3% hydroxyethyl acrylate was added, stirred for 0.5 hours, then cooled and discharged to obtain the main agent;

(2) Mix 60% of the main agent, 30% of methyl ethyl ketone, 6% of black sand, 0.8% of tert-butyl hydroperoxide, 0.8% of fogging agent, 0.8% of anti-wear agent, 0.6% After mixing the ultraviolet absorber and 1% antistatic agent, disperse in a high-speed disperser for 20 minutes, let it stand for 4 hours to defoam, and pour it on the release paper S1, and the release paper S1 with PU material is driven by the feeding rack After running, the PU raw material is fully scraped and baked by scraper and oven respectively until it is slightly dry to make a dry PU film S4.

5. Lamination and preparation of sewing-free hot melt adhesive TPU-PU leather

(1) Prepare the release paper S1, hot melt adhesive raw materials, TPU raw materials and PU raw materials prepared by the above method, and place the release paper S1 in related equipment to lay flat;

(2) Process the prepared hot-melt adhesive raw material into a rubber material through an extruder, and the rubber material is sent to the extruder at a temperature of up to 150 degrees to melt into a paste, and then extruded by the extruder die and then cast onto the release paper, and then pressed against the pressure roller—cooled—coiled to form the hot melt adhesive film S2 shown in Figure 1;

(3) Extrude the prepared TPU raw material into TPU film S3, and place the rolled hot melt adhesive film S2 on two feeding racks respectively, so that the hot melt adhesive film S2 and TPU The film S3 enters the high and low pressure rollers with a constant temperature for pressure at the same time. The temperature of the pressure rollers is above 160°C, so that the hot melt adhesive with a low melting point is instantly bonded to the TPU film S3 when the high and low pressure rollers are pressed against each other. As a whole, after cooling, a TPU film S3 with a hot melt adhesive film is formed, as shown in Figure 2;

(4) Pour the prepared PU raw material onto the release paper S1, and the release paper S1 with the PU material is driven by the feeding frame to run, and the PU raw material is fully scraped and baked until slightly dry by a scraper and an oven respectively Made into dry PU film S4;

(5) After gluing the dry PU film S4 and the TPU film S3 with hot melt adhesive prepared in step (3), it is sent to the pattern counter-pressing wheel for compression molding, and then quickly cooled by the cooling device After winding, the hot-melt adhesive-free sewing TPU-PU leather with a multi-layer structure of dry PU film S4+TPU film S3+hot-melt adhesive film S2 according to the present invention is obtained.

The above is only a description of the preferred implementation of the present invention, and does not limit the technical solution of the present invention to this. Any known deformation made by those skilled in the art on the basis of the main technical concept of the present invention belongs to the protection of the present invention. The technical category of the present invention, the specific protection scope of the present invention shall be determined by the description of the claims.

Claims (12)

1. the hot melt adhesive TPU-PU leather of a vehicle slit preventing, the hot melt adhesive film (S2) it is characterized in that, comprise release liners, being coated on release liners on (S1), the dry type PU film (S4) being pasted on the TPU membrane (S3) on hot melt adhesive film (S2) and with described TPU membrane (S3), pressure viscosity being pasted;

Wherein said release liners (S1) comprises paper bottom (A1), tack coat (A2), plastic layer (A3), transition zone (A4) and release layer (A5), described plastic layer (A3) is adhered on described paper bottom (A1) by tack coat (A2), described transition zone (A4) is arranged on described plastic layer (A3), described release layer (A5) is arranged on described transition zone (A4), described tack coat (A2) is aqueous polyacrylamide coating layer, use amount is every square metre of 5-8 gram, thickness is 0.8-4 micron, described plastic layer (A3) is the polyethylene terephthalate film of thickness between 18-25 micron, described transition zone (A4) is by the inorganic particulate of 62-68 weight portion, the Silicone acrylic emulsion of 32-36 weight portion, the methyl sodiosul foaliphatate of 3-5 weight portion, the dodecyl benzyl dimethyl ammonium chloride of 2-4 weight portion and the water mix and blend of 45-55 weight portion are prepared from, and film forming thickness is at 15-20 micron, the thickness of described release layer (A5) is 20-25 micron and by the polypropylene of 58-65 weight portion, the poly(4-methyl-1-pentene) of 26-34 weight portion, the vinyl silicone oil of 6-9 weight portion, 2 of 1-2 weight portion, 2 '-methylene-bis--(4, 6 di-t-butyl phenoxy groups) tert butyl peroxy benzoate of sodium phosphate and 0.1-0.8 weight portion is mixed with and forms,

Wherein said hot melt adhesive film extrudes preparation by hot melt adhesive raw material, and described hot melt adhesive is prepared from by the flexibilizer of the chain extender of the catalyst of the polyether polyol of the vulcabond of the polyester polyol of 60-70 weight portion, 15-20 weight portion, 3-5 weight portion, 0.8-1.5 weight portion, 0.5-1.2 weight portion, 1.5-1.8 weight portion antioxidant, the tackifying resin of 4-6 weight portion, the fire retardant of 2-4 weight portion and 2-4 weight portion, described polyester polyol is by low molecular weight aliphatic dihydroxy alcohol and aliphatic dicarboxylic acid, aromatic binary carboxylic acid polycondensation reaction and be prepared into the hydroxyl telechelic polyester glycol that molecular weight is 2000-6000 at 100-260 DEG C, described aliphatic dicarboxylic acid is selected oneself diacid, fumaric acid, maleic acid or suberic acid, described aromatic binary carboxylic acid is selected from phthalic acid, terephthalic acid (TPA) or M-phthalic acid, described aliphatic dihydroxy alcohol is selected from ethylene glycol, diethylene glycol (DEG), propylene glycol, methyl propanediol, 1, 4-butanediol, 1, 6-hexylene glycol, 1, 3-butanediol, 1, 5 pentanediols or dodecyl hexylene glycol, described vulcabond adopts 4,4 '-methyl diphenylene diisocyanate or 1,6-hexamethylene diisocyanate, described polyether polyol is selected from PTMG or propylene oxide copolymer glycols, one or more in described catalyst choice dibutyl tin laurate, triethanolamine or dual-morpholinyl diethyl ether, the one in 1,6-hexylene glycol, methyl propanediol, BDO selected by described chain extender, described antioxidant selects 2,6-, tri-grades of butyl-4-methylphenols or four { β-(3,5-, tri-grades of butyl-4-hydroxy phenyls) propionic acid } pentaerythritol ester, described tackifying resin be selected from polyethylene vinyl acetate copolymer, terminal hydroxy group thermoplastic polyester, hydrogenated rosin resin one or more, the composition of described fire retardant is by mass percentage: the organic fire-resisting halide being selected from decabrominated dipheny base ether, ten dichloro ten dihydro dimethano benzene azoles cyclo-octene or its mixture of the polyethylene of the polypropylene of the melt index 0.5-15.0g/10min of 30%-70%, the melt index 0.01-2.0g/10min of 5%-25%, the inorganic filler being selected from least one in powdered talc, kaolinite, sericite, silica and diatomite of 20%-40% and 5%-35%, described flexibilizer is extruded by the mixing of polyethylene elastomer, Hi-fax, polypropylene and antiaging agent raw material and is formed,

Wherein prepare consisting of of the TPU raw material of described TPU membrane (S3): the polymer polyatomic alcohol of 60-70 weight portion, be selected from molecular weight be 1000 PTMG, molecular weight be one or both in the poly-adipate glycol butanediol ester polyalcohol of 3000; Isosorbide-5-Nitrae-the cyclohexane diisocyanate of 30-35 weight portion; The chain extender of 4-9 weight portion, described chain extender is BDO; The Carbodiimides hydrolysis agent of 3-5 weight portion; 1-3 weight portion, decabromodiphenylethane that particle mean size is less than or equal to 4 microns mixes the organohalogen compounds fire retardant of micro-fumed silica; The antioxidant of 0.2-0.8 weight portion, described antioxidant is β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] at least one in pentaerythritol ester and two [(2,4-di-tert-butyl-phenyl) phosphorous acid] pentaerythritol ester; Two (2,2,6,6-tetramethyl-4-piperidyl) SA ester hindered amine light stabilizer of 0.1-0.5 weight portion; The montanin wax of 0.4-0.8 weight portion and/or erucyl amide wax series lubricant agent; The titanium system of 0.05-0.2 weight portion or bismuth series catalysts;

The PU raw material wherein preparing described dry type PU film (S4) consists of: the antistatic agent be made up of metal dust or conductive black of the cloudy surface agent be made up of calcium class filler of the black sand of the host of 55-70%, the butanone of 20-37%, 3-10%, the tert-butyl hydroperoxide of 0.5-1%, 0.8-1%, the anti-wear agent be made up of aromatic series silicone oil of 0.6-0.9%, the Benzotriazole Ultraviolet Stabilizer of 0.2-0.6% and 0.5-1.2%; Consisting of of described host self: the diphenyl methane-4 of the polyester diol of 12-28%, the straight diol of 1-5%, 6-18%, the TDI tripolymer of 4 '-vulcabond, 1-3%, the hydroxy-ethyl acrylate of the dimethyl formamide of 20-70%, the butanone of 0-30%, 2-6%; Each component all by mass percentage.

2. hot melt adhesive TPU-PU leather according to claim 1, it is characterized in that, the composition of the inorganic particulate in the transition zone of wherein said release liners (S1) comprises particle diameter and is 0.5-0.8 micron and accounts for the clay of inorganic particulate total content 25%, particle diameter at 1-2 micron to account for the barium sulfate powder of 60% of inorganic particulate total content and particle diameter at 3-5 micron and account for the calcium carbonate powder of 15% of inorganic particulate total content; The structural formula of the vinyl silicone oil in wherein said release layer is: in formula, R1 and R3 is-CH ₃, R2 is-CH=CH ₂, m span is 2000 ~ 3000, n span is 3 ~ 6.

3. hot melt adhesive TPU-PU leather according to claim 1, it is characterized in that, the thickness of described tack coat (A2) is 2.5 microns, the thickness of described plastic layer (A3) is 20 microns, described transition zone (A4) thickness be 15 microns, the thickness of described release layer (A5) is 25 microns, and the raw materials of described transition zone is inorganic particulate 65 weight portion, Silicone acrylic emulsion 35 weight portion, methyl sodiosul foaliphatate 4 weight portion, dodecyl benzyl dimethyl ammonium chloride weight 3 parts and water 50 weight portion; The raw materials of described release layer is the polypropylene of 60 weight portions, the poly(4-methyl-1-pentene) of 30 weight portions, the vinyl silicone oil of 8 weight portions, 2 of 1.5 weight portions, 2 '-methylene-bis--(4,6 di-t-butyl phenoxy groups) tert butyl peroxy benzoate of sodium phosphate and 0.5 weight portion, the structural formula of described vinyl silicone oil is: wherein R1 and R3 is-CH ₃, R2 is-CH=CH ₂, m=2500, n=4.

4. hot melt adhesive TPU-PU leather according to claim 1, it is characterized in that, the raw materials of wherein said hot melt adhesive consists of: the chain extender of the polyether polyol of the polyester polyol of 65 weight portions, the vulcabond of 18 weight portions, 4 weight portions, the catalyst of 1 weight portion, 1 weight portion, 1.6 weight portion antioxidants, the tackifying resin of 5 weight portions, the fire retardant of 3 weight portions, the flexibilizer of 3 weight portions; Described flexibilizer by weight by 31% polyethylene elastomer, the Hi-fax of 19%, the polypropylene of 49% and 1% antiaging agent raw material mix and extrude and form; Described fire retardant by 50% the melt index polypropylene of 5 grams/10 minutes, the melt index 0.8 gram/polyethylene of 10 minutes of 20%, inorganic filler that the powdered talc of 20% and kaolinite mix and 10% the organic fire-resisting halide that mixes with ten dichloro ten dihydro dimethano benzene azoles cyclo-octene of decabrominated dipheny base ether form.

5. hot melt adhesive TPU-PU leather according to claim 1, it is characterized in that, the molecular weight consisting of 65 weight portions of wherein said TPU raw material is the poly-adipate glycol butanediol ester polyalcohol of 3000, β-(the 4-hydroxyl-3 of 0.6 weight portion, 5-di-tert-butyl-phenyl) propionic acid positive octadecanol ester antioxidant, two (2 of 0.3 weight portion, 2, 6, 6-tetramethyl-4-piperidyl) SA ester light stabilizer, the erucyl amide wax series lubricant agent of 0.6 weight portion, the Carbodiimides hydrolysis agent of 4 weight portions, 32 weight portions and temperature 60 DEG C 1, 4-cyclohexane diisocyanate, 1 of 6 weight portions, the agent of 4-chain expansion of succinic acid, the bismuth series catalysts of 0.1 weight portion, the decabromodiphenylethane of 2 weight portions mixes the organohalogen compounds fire retardant of micro-fumed silica.

6. hot melt adhesive TPU-PU leather according to claim 1, it is characterized in that, the composition of wherein said PU raw material is by mass percentage: the host of 60%, the butanone of 30%, the black sand of 6%, the tert-butyl hydroperoxide of 0.8%, the cloudy surface agent of 0.8%, the anti-wear agent of 0.8%, the ultra-violet absorber of 0.6% and the antistatic agent of 1%, the composition of wherein said host self is by mass percentage: the polyester diol of 20%, the butanone of 10%, the dimethyl formamide of 50%, the straight diol of 3%, the diphenyl methane-4 of 12%, 4 '-vulcabond, the TDI tripolymer of 2% and the hydroxy-ethyl acrylate of 3%.

7. the hot melt adhesive TPU-PU leather according to any one of claim 1-6, is characterized in that, the TENSILE STRENGTH of described hot melt adhesive TPU-PU leather is horizontal 34.2kgf, longitudinal 29.2kgf; The tearing strength of described hot melt adhesive TPU-PU leather is warp-wise 6.1kgf; Broadwise 5.2kgf; The adhesive strength of described hot melt adhesive TPU-PU leather is more than or equal to 3.0Kg/25 ㎜; The percentage elongation of described hot melt adhesive TPU-PU leather is more than or equal to 600%; The Shao Er hardness of described hot melt adhesive TPU-PU leather is more than or equal to 98.

8. a preparation method for the hot melt adhesive TPU-PU leather of vehicle slit preventing, is characterized in that, said method comprising the steps of:

(1) release liners (S1) is prepared

(1), paper bottom (A1) is selected, and coating thickness is the aqueous polyacrylamide tack coat (A2) of 0.8-4 micron on described paper bottom (A1), then be the plastic layer (A3) formed by polyethylene terephthalate film of 18-25 micron at described tack coat (A2) upper stickup thickness, then solidify certain hour;

(2), the methyl sodiosul foaliphatate of 3-5 weight portion is poured in the water of 45-55 weight portion, stir, then 62-68 weight portion is poured into and the inorganic particulate be mixed by clay, barium sulfate powder and calcium carbonate powder, and high-speed stirred is uniformly dispersed, then in scattered slurry, add the Silicone acrylic emulsion of 32-36 weight portion, after solution being mixed with glass bar, the dodecyl benzyl dimethyl ammonium chloride of 2-4 weight portion is added on wherein, continue to stir, make transition zone coating fluid;

(3), transition zone coating fluid described in plastic layer (A3) upper use scraper even spread, and 30 seconds film-formings are heated at 80 DEG C, control thickness at 15-20 micron, then by the transition zone (A4) after film forming 120 DEG C, linear pressure 150KN/m, speed of a motor vehicle 10m/min condition under carry out press polish process;

(4) 90 DEG C are heated to after, the poly(4-methyl-1-pentene) of the polypropylene of 58-65 weight portion, 26-34 weight portion and the vinyl silicone oil of 6-9 weight portion being mixed, be incubated and add 2 of 1-2 weight portion after 2 hours, 2 '-methylene-bis--(4,6 di-t-butyl phenoxy groups) sodium phosphate and 0.1-0.8 weight portion tert butyl peroxy benzoate and mix, then form release layer (A5) by extruder Extrusion Coating in the surface of described transition zone (A4), control thickness at 20-25 micron;

(2), hot melt adhesive raw material is prepared

(1), the tackifying resin of the polyether polyol of the polyester polyol of 60-70 weight portion, 3-5 weight portion, the antioxidant of 1.5-1.8 weight portion and 4-6 weight portion is placed in reactor, be heated to 120 ~ 140 DEG C, be uniformly mixed lower vacuum dehydration 1.5 ~ 2h, vacuum is less than 0.05MPa, is then cooled to 70 ~ 75 DEG C; Wherein said polyester polyol is be prepared into by low molecular weight aliphatic dihydroxy alcohol and aliphatic dicarboxylic acid, aromatic binary carboxylic acid polycondensation reaction at 100-260 DEG C the hydroxyl telechelic polyester glycol that molecular weight is 2000-6000; Described polyether polyol is selected from the one in PTMG, propylene oxide copolymer glycols; Described antioxidant is selected from 2,6-, tri-grades of butyl-4-methylphenols or four { β-(3,5-, tri-grades of butyl-4-hydroxy phenyls) propionic acid } pentaerythritol ester; Described tackifying resin be selected from polyethylene vinyl acetate copolymer, terminal hydroxy group thermoplastic polyester, hydrogenated rosin resin one or more;

(2), under nitrogen protection, the catalyst of the vulcabond of 15-20 weight portion and 0.8-1.5 weight portion is joined in the product of step (1), and at 85 ~ 95 DEG C of reaction 1-1.5h; Wherein said vulcabond adopts 4, the one in 4 '-methyl diphenylene diisocyanate or 1,6-hexamethylene diisocyanate; One or more in described catalyst choice dibutyl tin laurate, triethanolamine or dual-morpholinyl diethyl ether;

(3), under nitrogen protection, the fire retardant of the chain extender of 0.5-1.2 weight portion, 2-4 weight portion, the flexibilizer of 2-4 weight portion are joined in the product of step (2), and at 75 ~ 85 DEG C of stirring reaction 45min-1.0h; The one in 1,6-hexylene glycol, methyl propanediol, BDO selected by wherein said chain extender; The composition of described fire retardant is by mass percentage: the organic fire-resisting halide being selected from decabrominated dipheny base ether, ten dichloro ten dihydro dimethano benzene azoles cyclo-octene or its mixture of the polyethylene of the polypropylene of the melt index 0.5-15.0g/10min of 30%-70%, the melt index 0.01-2.0g/10min of 5%-25%, the inorganic filler being selected from least one in powdered talc, kaolinite, sericite, silica and diatomite of 20%-40% and 5%-35%; Polyolefine toughener selected by described flexibilizer;

(4), pass into the bottom discharge of nitrogen protection condition, after slaking cooling, be formed as hot melt adhesive raw material;

(3), TPU raw material is prepared

(1), the polymer polyatomic alcohol of 60-70 weight portion is placed in reactor, and be heated to 80-90 DEG C, described polymer polyatomic alcohol to be molecular weight be 1000 PTMG and/or molecular weight be 3000 poly-adipate glycol butanediol ester polyalcohol, then the antioxidant of 0.2-0.8 weight portion is added, two (2 of 0.1-0.5 weight portion, 2, 6, 6-tetramethyl-4-piperidyl) SA ester hindered amine light stabilizer, the montanin wax of 0.4-0.8 weight portion and/or the Carbodiimides hydrolysis agent of erucyl amide wax series lubricant agent and 3-5 weight portion, polymer polyol mixed alkoxide solution is obtained after abundant stirring, wherein said antioxidant is β-(4-hydroxyl-3, 5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and two [(2, 4-di-tert-butyl-phenyl) phosphorous acid] at least one in pentaerythritol ester,

(2), add in described polymer polyol mixed alkoxide solution 30-35 weight portion, temperature at the Isosorbide-5-Nitrae-cyclohexane diisocyanate of 55-65 DEG C, obtain initial reaction mixture after being uniformly mixed;

(3), keep the temperature of above-mentioned reactant mixture and add the BDO chain extender of 4-9 weight portion and the titanium system of 0.05-0.2 weight portion or bismuth series catalysts, and control temperature 150-210 DEG C, pressure 4-8MPa reacts about 1h;

(4), when reaction melt temperature reaches between 180-210 DEG C, add 1-3 weight portion and particle mean size is less than or equal to the organohalogen compounds fire retardant being mixed micro-fumed silica by decabromodiphenylethane of 4 microns, carry out dewatering after the reaction scheduled time, dry and slaking, obtain Polyurethane Thermoplastic Elastomer raw material;

(4), PU raw material is prepared

(1) host is prepared: by mass percentage by the polyester diol of 12-28%, the butanone of 0-30%, the dimethyl formamide of 20-70%, the straight diol of 1-5% puts into reaction pot stirring at normal temperature 20-40 minute, after mixing, at normal temperatures by the diphenyl methane-4 of 6-18%, after 4 '-vulcabond puts into reaction pot, heat temperature raising after making it react 1-3 hour at 70-80 DEG C, add the TDI tripolymer of 1-3% again, react 1-3 hour at 60-80 DEG C after, after being progressively cooled to 40-50 DEG C, add the hydroxy-ethyl acrylate of 2-6%, stir discharge of lowering the temperature after 0.5 hour, obtained described host,

(2) by mass percentage by after the mixing of the antistatic agent of the cloudy surface agent of the tert-butyl hydroperoxide of the black sand of the butanone of the host of 55-70%, 20-37%, 3-10%, 0.5-1%, 0.8-1%, the anti-wear agent of 0.6-0.9%, the ultra-violet absorber of 0.2-0.6% and 0.5-1.2%, in high speed dispersor, disperse 10-20 minute, leave standstill froth breaking and obtain PU raw material after 4 hours;

(5), vehicle slit preventing hot melt adhesive TPU-PU leather is prepared in laminating

(1), prepare release liners (S1), hot melt adhesive raw material, TPU raw material and the PU raw material prepared by above-mentioned steps, and release liners (S1) is placed in relevant device paves;

(2), hot melt adhesive raw material prepared by step (two) is processed into sizing material through extruder, the extruder that 150 degree of temperature sent into by sizing material is melt into pasty state, rear curtain coating is extruded in described release liners again by extruder die head, then warp is to pinch roller to press-cool-batching, and forms hot melt adhesive film (S2);

(3), the TPU raw material prepared by step (three) is extruded into TPU membrane (S3), and be placed on two cradles respectively with above-mentioned hot melt adhesive film (S2), make hot melt adhesive film (S2) and TPU membrane (S3) enter the height being provided with constant temperature to carry out pressure in pinch roller simultaneously, to the temperature of pinch roller more than 160 DEG C, thus make low-melting hot melt adhesive be bonded as one to pinch roller to moment during pressure and TPU membrane (S3) at height, form the TPU membrane with hot melt adhesive film after cooling;

(4), the PU raw material prepared by step (four) is poured in release liners (S1), drive the release liners (S1) of expecting with PU to run by cradle, through scraper and baking box PU raw material fully struck off respectively and is baked to micro-dry after make dry type PU film (S4);

(5), by dry type PU film (S4) by the TPU membrane with hot melt adhesive film obtained with step (3) after gluing be sent to simultaneously decorative pattern in pinch roller to molded, then cooled rear curling fast by cooling device, obtained dry type PU film (S4) adds the hot melt adhesive TPU-PU leather that TPU membrane (S3) adds the vehicle slit preventing of the sandwich construction of hot melt adhesive film (S2).

9. preparation method according to claim 8, it is characterized in that, wherein prepare in the step () of release liners (S1): the raw materials of described transition zone is inorganic particulate 65 weight portion, Silicone acrylic emulsion 35 weight portion, methyl sodiosul foaliphatate 4 weight portion, dodecyl benzyl dimethyl ammonium chloride 3 weight portion and water 50 weight portion, specifically consisting of of described inorganic particulate: clay particle diameter be 0.5-0.8 micron and content be 25%, barium sulfate powder diameter at 1-2 micron and content be 60%, calcium carbonate powder particle diameter is at 3-5 micron and content is 15%; The raw materials of described release layer is the polypropylene of 60 weight portions, the poly(4-methyl-1-pentene) of 30 weight portions, the vinyl silicone oil of 8 weight portions, 2 of 1.5 weight portions, 2 '-methylene-bis--(4,6 di-t-butyl phenoxy groups) tert butyl peroxy benzoate of sodium phosphate and 0.5 weight portion, the structural formula of described vinyl silicone oil is: wherein R1 and R3 is-CH ₃, R2 is-CH=CH ₂, m=2500, n=4.

10. preparation method according to claim 8, it is characterized in that, wherein the aliphatic dicarboxylic acid of preparation polyester polyol is selected oneself diacid, fumaric acid, maleic acid or suberic acid in step (two), aromatic binary carboxylic acid is selected from phthalic acid, terephthalic acid (TPA) or M-phthalic acid, aliphatic dihydroxy alcohol is selected from ethylene glycol, diethylene glycol (DEG), propylene glycol, methyl propanediol, BDO, 1,6-hexylene glycol, 1,3-butanediol, 1,5 pentanediols or dodecyl hexylene glycol; Described flexibilizer is extruded after being mixed by polyethylene elastomer, Hi-fax, polypropylene PP and antiaging agent raw material and is formed, and shared by each raw material, mass percent is: polyethylene elastomer 31%, Hi-fax 19%, polypropylene 49%, antiaging agent 1%.

11. preparation methods according to claim 8, it is characterized in that, in wherein said step (three), the molecular weight consisting of 65 weight portions of TPU raw material is the poly-adipate glycol butanediol ester polyalcohol of 3000, β-(the 4-hydroxyl-3 of 0.6 weight portion, 5-di-tert-butyl-phenyl) propionic acid positive octadecanol ester antioxidant, two (2 of 0.3 weight portion, 2, 6, 6-tetramethyl-4-piperidyl) SA ester light stabilizer, the erucyl amide wax series lubricant agent of 0.6 weight portion, the Carbodiimides hydrolysis agent of 4 weight portions, 32 weight portions and temperature 60 DEG C 1, 4-cyclohexane diisocyanate, 1 of 6 weight portions, the agent of 4-chain expansion of succinic acid, the bismuth series catalysts of 0.1 weight portion, the decabromodiphenylethane of 2 weight portions mixes the organohalogen compounds fire retardant of micro-fumed silica.

12. preparation methods according to claim 8, it is characterized in that, in wherein said step (four), the composition of PU raw material is by mass percentage: the host of 60%, the butanone of 30%, the black sand of 6%, the tert-butyl hydroperoxide of 0.8%, the cloudy surface agent of 0.8%, the anti-wear agent of 0.8%, the ultra-violet absorber of 0.6% and the antistatic agent of 1%, the composition of wherein said host self is by mass percentage: the polyester diol of 20%, the butanone of 10%, the dimethyl formamide of 50%, the straight diol of 3%, the diphenyl methane-4 of 12%, 4 '-vulcabond, the TDI tripolymer of 2% and the hydroxy-ethyl acrylate of 3%.