WO2015021814A1

WO2015021814A1 - Sewing-free hot melt adhesive tpu-pu leather and preparation method thereof

Info

Publication number: WO2015021814A1
Application number: PCT/CN2014/079497
Authority: WO
Inventors: 何建雄; 王一良
Original assignee: 东莞市雄林新材料科技股份有限公司
Priority date: 2013-08-16
Filing date: 2014-06-09
Publication date: 2015-02-19
Also published as: CN103437195A; CN103437195B

Abstract

The present invention provides a novel sewing-free hot melt adhesive TPU-PU leather and a preparation method thereof. The hot melt adhesive TPU-PU leather comprises a release paper, a hot melt adhesive film, a TPU film, and a dry PU film. The release paper comprises a bottom paper layer, an adhesive layer, a plastic layer, a transition layer, and a release layer; a hot melt adhesive raw material comprises polyester polyol, diisocyanate, polyether polyol, and a plurality of additives; a TPU raw material comprises polymer polybasic alcohol, 1,4-cyclohexane-diisocyanate, a chain extender, and a plurality of functional additives; and a PU raw material comprises polyester glycol, straight-chain diol, isocyanate, TDI Tripolymer, dimethylformamide, butanone, black sand, and a plurality of functional additives. According to the present invention, innovations are conducted on raw material components of the release paper, the hot melt adhesive, the TPU film, and the PU film; and the prepared sewing-free TPU-PU leather has the technical advantages of firm adhesion, durability, environmentally-friendly materials, no invisible harm to human body, and the like.

Description

Seamless hot melt adhesive TPU-PU leather and preparation method thereof

Technical field

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.

Background technique

In the prior art, in the production industries of clothing, shoes, bags, handbags, seats, military and other products in China and abroad, the fabrics attached to all products are connected by conventional stitching methods. This kind of production method not only has high labor intensity and high production cost, but also has problems such as easy breakage, tearing and peeling of the product due to 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, the PVC material itself contains toxic elements such as polyvinyl chloride and ethylhexylamine, which are carcinogenic to the human body and extremely unsafe to use, and are in the prior art. Most of the leather plasters used are industrial liquid glues and solid glues. Most of these melt materials are toxic, and they are elastic, acid-resistant, alkali-resistant, wash-resistant, dry-cleaning, tensile-resistant, and durable. It has certain defects in performance and is not an ideal environmentally friendly adhesive material.

Summary of the invention

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. Finally, 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.

The technical solution of the present invention to solve the above technical problems is as follows:

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. On the bottom layer A1, 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克, a thickness of 0. 8- 4 microns, 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. Poly 4-methyl-1- 5-0, 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 Preparation of parts by weight of t-butyl peroxybenzoate; wherein the hot melt adhesive comprises 60-70 parts by weight of polyester polyol, 15-20 parts by weight of diisocyanate, 3-5 parts by weight of poly Ethylene polyol, 0. 8-1. 5 parts by weight of the catalyst, 0. 5-1. 2 parts by weight of the chain extender, 1. 5-1. 8 parts by weight of the antioxidant, 4-6 parts by weight of the thickening a 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 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, and 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; is the catalyst selected from dibutyltin dilaurate, triethanolamine or double? One or more of morphyl diethyl ether; 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{β-(3,5-tri-butyl-4-hydroxyphenyl)propionic acid} pentaerythritol ester, the tackifying resin being selected from the group consisting of polyethylene 5克。 0克。 0. 5-15. 0克。 0. 5-15. 0克。 0. 5-15. 0克/10 minutes of polypropylene, 5% to 25% of the melt index of 0. 01-2. 0 g/10 minutes of polyethylene, 20% _40% selected from powdered talc, kaolinite, sericite, dioxide An inorganic filler of at least one of silicon and diatomaceous earth, 5% to 35% of selected from decabromodiphenyl ether, dodecachlorododecyl benzoxazole, or a mixture thereof 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 diisocyanate; 4-9 parts by weight of a chain extender, the chain extender is 1,4-butanediol; 3-5 parts by weight of a carbodiimide-based hydrolysis inhibitor ; 1-3 parts by weight of an organic halide flame retardant of decabromodiphenylacetamide mixed micro-fumed silica having an average particle size of less than or equal to 4 μm; Agent, the antioxidant is

(4-hydroxy-3,5-di-tert-butylphenyl)propanoic acid n-octadecyl alcohol, tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid] pentaerythritol ester And 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-piperidinyl) aerate hindered amine light stabilizer: 0. 4-0. 8 parts by weight of a montan wax and / or erucamide wax lubricant; 0. 05-0. 2 weight 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. 2% of an antistatic agent consisting of metal powder or conductive carbon black, The 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 μm and accounting for 60% of the total inorganic particles, and calcium carbonate having a particle diameter of 3-5 μm and accounting for 15% of the total inorganic particles;

CH _₃ ΓθΗ ₃ Ί "CH _₃ ~] CH ₃

Ri - Si - 0 - Si - 0 - - Si - 0 - Si - R3

CH ₃ CH ₃ k ί3⁄4

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.

Further, the hot melt adhesive TPU-PU leather according to the present invention, wherein the thickness of the adhesive layer A2 is 2. 5 μm, the thickness of the plastic layer A3 is 20 μm, and the thickness of the transition layer A4 is 15 μm, the release layer A5 has a thickness of 25 μm, 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. 3 parts by weight of dimethylbenzylammonium chloride and 50 parts by weight of water; 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重量份的乙乙苯苯苯苯份份份份份份份份份份份份份份份Formate,

R3 is - CH3,

R2 is - CH=CH2, m=2500, n=4.

Further, 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 composition of the organic halide mixed with decabromodiphenyl ether and dodecachlorododecyl benzoxazole cyclooctene. 重量重量。 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 β-(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.

Further, the hot melt adhesive TPU-PU leather according to the present invention, 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:

(1) Preparation of release paper

(1), the paper substrate A1 is selected, and an aqueous polypropylene bonding layer A2 having a thickness of 0.8 to 4 μm 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;

(2), 3-5 parts by weight of sodium fatty acid methyl ester sulfonate is poured into 45-55 parts by weight of water, stirred uniformly, then poured into 62-68 parts by weight and mixed by clay, barium sulfate powder and calcium carbonate powder The prepared inorganic particles are uniformly dispersed by high-speed stirring, and then 32-36 parts by weight of a silicone-acrylic emulsion is added to the dispersed slurry, and the solution is uniformly mixed with a glass rod to prepare 2-4 parts by weight of twelve An alkyl dimethyl benzyl chloride hinge is added thereto, and the stirring is continued uniformly to prepare a transition layer coating liquid;

(3) uniformly coating the 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 μm, 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;

(4), mixing 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, heating to 90 ° C, keeping warm After the 1-2 parts by weight of 2,2'-methylene-bis-(4,6-di-tert-butylphenoxy) sodium phosphate and 0. 1-0. Oxidize the benzoate and mix it evenly, then pass through the extruder Extrusion coating on the surface of the transition layer A4 to form a release layer A5, controlling the thickness of 20-25 microns;

(2) Preparation of hot melt adhesive materials

(1) 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-(3,5-tert-butyl-4-hydroxyphenyl) Propionic acid} 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;

(2), under nitrogen protection, 15-20 parts by weight of diisocyanate and 0.8-1.5 parts by weight of the catalyst is added to the reaction product of step (1), and reacted at 85~95 ° C for l-1.5h _; Wherein the diisocyanate is one of 4,4'-diphenylformamidine diisocyanate or 1,6-hexamethylene diisocyanate, and the catalyst is selected from dibutyltin dilaurate, triethanolamine or dimorpholine. One or more of the group of diethyl ether;

(3) adding 0.5-1.2 parts by weight of a chain extender, 2-4 parts by weight of a flame retardant, and 2-4 parts by weight of a toughening agent to the reaction product of the step (2) under nitrogen protection. And stirring the reaction at 75 to 85 ° C for 45 min-l. Oh; wherein the chain extender selects one of 1,6-hexanediol, methylpropanediol, and 1, 4-butanediol, the resistance The flammable agent is composed of polypropylene, polyethylene, inorganic filler and organic flame retardant halide; the toughening agent is selected from a polyolefin toughening agent;

(4), discharging under the condition of nitrogen protection, forming a hot melt adhesive raw material after being matured and cooled;

(3) Preparation of TPU raw materials

(1), 60-70 parts by weight of the polymer polyol is placed in a reaction vessel and heated to 80-90 ° C, 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 β-(4-hydroxy-3, 5-di-tert-butylphenyl)propionate, and four [β-( At least one of pentaerythritol ester of 3, 5-di-tert-butyl 4-hydroxyphenyl) propionic acid and bis[(2,4-di-tert-butylphenyl)phosphite] pentaerythritol ester;

(2) adding 30-35 parts by weight of 1,4-cyclohexyl diisocyanate having a temperature of 55-65'C to the polymer polyol mixed solution, and stirring and mixing to obtain a preliminary reaction mixture;

(3) maintaining the temperature of the above reaction mixture and adding 4-9 parts by weight of a 1,4-butanediol chain extender and 0.05-0.2 weight Parts of titanium or lanthanide catalyst, and control the temperature at 150-210 ° C, pressure 4-8MPa reaction about 1h;

(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;

(4) Preparation of PU raw materials

(1) Preparation of 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;

(2) 55-70% of the main agent, 20-37% of methyl ethyl ketone, 3- 10% black sand, 0. 5-1% of t-butyl hydroperoxide, 0. 8-1% of fog The surface agent, 0. 6-0. 9% of the anti-wear agent, 0. 2- 0. 6% of the ultraviolet absorber, 0. 5- 1. 2% of the antistatic agent is mixed, dispersed in the high-speed disperser 10 -20 minutes, after standing and defoaming for 4 hours, the PU raw material was obtained;

(5), fitting and preparing seam-free hot melt adhesive TPU- PU leather

(1) preparing a release paper, a hot melt adhesive raw material, a TPU raw material and a PU raw material prepared by the above steps, and placing the release paper in the relevant equipment to be flattened;

(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;

(3) extruding the TPU raw material prepared in the step (3) into a TPU film, and placing the hot melt adhesive film on the two feeding racks respectively, so that the hot melt adhesive film and the TPU film simultaneously enter a constant temperature setting. The high and low pressure is applied to the pressure roller, and the temperature of the pressure roller is 16 (TC or more, so that the hot melt adhesive with low melting point is bonded to the TPU film instantaneously when the pressure roller is pressed against the pressure roller, and is formed after cooling. Hot melt adhesive TPU film;

(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;

(5), 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.

Further, in the method for preparing a hot melt adhesive TPU-PU leather according to the present invention, in the step (1) of preparing a release paper, 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微米的含量为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

Rl and R3 are -CH:,, R2 is -CH = C3⁄4, m=2500, η=4'

Further, the method for preparing a hot melt adhesive TPU-PU leather according to the present invention, 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, and 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 %的熔指数为0. 5-15. 0 g / 10 min of polypropylene, 5_25 wt% of the melt index 0. 01-2. 0 g / 10 min of polyethylene, 20-30 wt% of selected from powder At least one inorganic filler in talc, kaolinite, sericite, silica, and diatomaceous earth, 5-15% by weight selected from the group consisting of decabromodiphenyl ether, dodecachlorododecyl dibenzoxazole ring An organic flame retardant halide of octene or a mixture thereof; 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.

Further, 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重量份的二(2, 2。 The polyol, 0. 6 parts by weight of β-(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-tetramethyl- 4 -piperidinyl) succinate 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-cyclohexyl diisocyanate having a temperature of 60 ° 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 ten An organic halide flame retardant of bromodiphenylacetamide mixed with micro-fumed silica.

Further, 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. 8% t-butyl hydroperoxide, 0.8% matte finish, 0.8% anti-wear agent, 0.6% UV absorber and 1% antistatic agent, Wherein the 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 main technical features and technical effects of the present invention are:

(1) 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.

(2) It adopts the original low melting point hot melt adhesive, which is a kind of plasticity strong adhesive. It can replace industrial liquid glue, solid glue and PU glue. It has the advantages of environmental protection, no toxicity and no side effects. The environmentally friendly adhesive material, 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.

(3) The 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.

(4) 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.

DRAWINGS

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;

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;

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;

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

In the figure, S 1-release paper, S2-hot melt adhesive film, S3-TPU film, and S4-dry PU film.

detailed description

The technical solutions of the present invention are described in detail below to enable those skilled in the art to understand the present invention more clearly, but do not limit the scope of the present invention. It should be noted first that: In the present invention, 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.

First, the molded product of the seam-free hot melt adhesive TPU-PU leather of the present invention and a preparation method thereof will be described. 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. TPU film S3, as shown in Figure 2;

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. Formed dry PU film S4;

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. Because TPU (thermoplastic polyurethane) and PU (Polyurethane, also known as polyurethane) are environmentally friendly materials, and because PU materials only need to be simply modified, different densities, elasticity, and The physical properties such as rigidity are good decorative formula materials. 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. In combination with mathematical models and practical verification, multiple sets of experimental data were collected to determine the influence factors between the components, and the best ratio was calculated by theory, and the final formulation was applied to the test. The product of the present invention has multiple physical properties such as better adhesion, tear resistance, abrasion resistance, and high temperature resistance.

The composition and preparation of the release paper S1 used in the present invention are as follows:

As shown in FIG. 4, 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. Specifically, the plastic layer A3 is a polyethylene terephthalate film (i.e., a PET film) having a thickness of 18 to 25 μm, preferably 20 μm. 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微米。 The thickness of 0. 8-micron, preferably 1-2. 5 microns. 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. 8 micrometers, which accounts for 25% of the total inorganic particles, a barium sulfate powder having a particle diameter of 1-2 micrometers and a total content of 60% of the total inorganic particles, and a particle diameter of 3-5 micrometers. Calcium carbonate accounting for 15% of the total inorganic particles. 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. Pour into the above stirring solution, disperse it evenly by high-speed stirring, add the above-mentioned parts by weight of the silicone-acrylic emulsion to the dispersed slurry, mix the solution uniformly with a glass rod, and then add the above-mentioned parts by weight of dodecyl group. Dimethylbenzylammonium chloride was added thereto, and stirring was continued to obtain a transition layer coating liquid. Then, 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 μm, and then the film-forming transition layer A4 was 120. °C, line pressure 150KN/m, calendering treatment under the condition of lOm/min, reducing the tiny holes in the transition layer after calendering, making the film smoother and getting a more dense and smooth surface state. It is more conducive to the laying of the release layer on the upper layer, and the smooth surface of the transition layer makes the surface of the final release layer have a mirror surface flatness, which ensures the surface state and gloss of the final leather product. 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:

CH ₂ , m value The range is 2000~3000, and the value of n ranges from 3 to 6. 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:

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{β-(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. 0 g/10 min of 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 specific preparation process of the above hot melt adhesive is as follows:

(1) 60 to 70 parts by weight of the polyester polyol, 3-5 parts by weight of the polyether polyol, 1.5 to 1.8 parts by weight of the antioxidant, and 4 to 6 parts by weight of the tackifying resin are placed in the reaction according to the above parts by weight In the kettle, heated to 120~14 (TC, vacuum dehydrated under stirring and mixing for 1.5~2h, vacuum degree less than 0.05MPa, and then cooled to 70~75 °C;

(2) under nitrogen protection, 15-20 parts by weight of diisocyanate and 0.8-1.5 parts by weight of the catalyst is added to the reaction product of step (1), and reacted at 85~95 'C for 1- 1.5h;

(3) 0.5 to 1.2 parts by weight of a chain extender, 2-4 parts by weight of a flame retardant, and 2 to 4 parts by weight of a toughening agent are added to the reaction product of the step (2) under nitrogen protection, and Stirring reaction at 75~85 ° C for 45 min - l. Oh;

(4) discharging under the condition of nitrogen protection, forming a hot-melt raw material used in the present invention after being matured for a certain period of time, and feeding it into an extruder, and extruding and extruding it from the extruder die to the attached Figure 2 shows the release paper S1.

The TPU raw material composition for forming the TPU film S3 in the present invention is:

60-70 parts by weight of the polymer polyol; 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 μm; 0.2 to 0.8 parts by weight of the antioxidant, and the antioxidant is β-(4-hydroxy-3, 5-di-tert-butylphenyl)propanoic acid. Alcohol ester, tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester and bis[(2,4-di-tert-butylphenyl)phosphite] pentaerythritol ester At least one; 0.1-0.5 parts by weight of a hindered amine light stabilizer, specifically bis(2,2,6,6-tetramethyl-4-piperidinyl)succinate; 0.4-0.8 parts by weight Montan wax and / or An erucamide wax lubricant; 0.05 to 0.2 parts by weight of a titanium or lanthanide catalyst.

The specific method for preparing the thermoplastic polyurethane elastomer TPU for forming a film from the above raw materials is as follows:

(1) First, 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.

(2) adding the above-mentioned parts by weight of the 1,4-cyclohexane diisocyanate having a temperature of 55-65 ° C to the polymer polyol mixed solution, stirring and mixing to obtain a preliminary reaction mixture; (3) maintaining the temperature of the above reaction mixture and adding the above-mentioned parts by weight of the 1,4-butanediol chain extender and the catalyst, and controlling the temperature at 150-210 ° C and a pressure of 4-8 MPa for about 1 h.

(4) When the reaction melt temperature reaches between 180 and 21 CTC, the above-mentioned parts by weight of the flame retardant is added, and after a predetermined period of time, dehydration, drying and aging are carried out to obtain a thermoplastic polyurethane elastomer raw material.

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.

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

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. 2% of an 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, 6-18% diphenylformamidine-4, 4 '-diisocyanate, 1-3% TDI trimer, 20-70 % dimethylformamide, 0-30% methyl ethyl ketone, 2-6% hydroxyethyl acrylate.

A method of preparing a dry PU film S4 by the above materials:

(1) Preparation of 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;

(2) 55-70% of the main agent, 20-37% of methyl ethyl ketone, 3-10% of black sand, 0. 5-1% of t-butyl hydroperoxide, 0. 8-1% of fog The surface agent, 0. 6-0. 9% of the anti-wear agent, 0. 2-0. 6% of the ultraviolet absorber, 0. 5- 1. 2% of the antistatic agent is mixed, dispersed in a high-speed disperser 10 -20 minutes, after standing for 4 hours, defoaming to the release paper S1, the release paper S1 with the PU material is driven by the feeding rack, and the PU raw materials are fully smoothed and baked to the micro thousand by the scraper and the oven respectively. Thereafter, a dry PU film S4 was produced. After the above-mentioned dry PU film S4 is sized and then fed into the press wheel by the TPU film S3 with the hot melt adhesive, 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.

Finally, the main properties of the sewn-free hot melt adhesive TPU-PU leather of the present invention obtained by the above method were tested, and the test results were as follows:

1, hardness: 65~70/A; 2, tensile strength: transverse 34.2 kg, longitudinal 29. 2 kgf;

3, tear strength: warp direction 6. lkgf; latitude 5. 2 kgf;

4. Wear strength: Under the pressure of 9Kpa, there is no wear after grinding 650 turns;

5. Bonding strength: 3. 0Kg / 25 mm.

6. Elongation: ^600%;

7, Shore hardness: 98.

The main performance comparison with the same type of products is as follows:

Therefore, 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. Moreover, 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.

Example 1

A preferred embodiment of the invention is given below.

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

First, the preparation of release paper S1

The paper base layer Al is selected, and an aqueous polypropylene (PP) bonding layer A2 having a thickness of 2.5 μm is coated on the paper substrate A1, and then a polyethylene pair having a thickness of 20 μm is pasted on the bonding layer A2. The ethylene phthalate film A3 is cured for a certain period of time. Then, 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. And uniformly coated on the polyethylene terephthalate film A3 using a doctor blade, and subjected to curing and calendering to form a transition layer A4 having a thickness of 15 μm, and finally extruded on the transition layer A4. The coating layer has a thickness of 25 μm, and 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. 5 parts by weight of t-butyl peroxybenzoate, 5 parts by weight of 2,2'-methylene-bis-(4,6-di-tert-butylphenoxy) sodium phosphate, and 0.5 parts by weight of t-butyl peroxybenzoate The structural formula of vinyl silicone oil is:

Rl and R3 -C¾, R2 is - CH two CH _2, m to about 2500, n = 4. Thus, a release paper S1 as a leather substrate of the present invention was prepared.

Second, the preparation of polyurethane hot melt adhesive raw materials

(1) 65 parts by weight of a polyester polyol, 4 parts by weight of a polyether polyol, 1.6 parts by weight of an antioxidant, and 5 parts by weight of a tackifying resin are placed in a reaction vessel, and heated to 120 ° C, 5小时, The temperature is less than 0. 05MPa, and then the temperature is lowered to 7CTC;

(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;

(3) 1 part by weight of a chain extender, 3 parts by weight of a flame retardant, and 3 parts by weight of a toughening agent are added to the reaction product of the step (2) under nitrogen protection, and the reaction is stirred at 85 ° C. l. Oh;

(4) Discharged under the condition of nitrogen protection, and matured for a certain period of time to form a polyurethane hot melt adhesive raw material.

Wherein 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{β-(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 dodecachlorododecyl benzoxazole cyclooctene. 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.

Third, the preparation of TPU raw materials

6重量份的β - (4), 6 parts by weight of β- (4) -hydroxy-3,5-di-tert-butylphenyl)propanoic acid, octadecyl alcohol ester antioxidant, 0.3 parts by weight of bis(2,2,6,6-tetramethyl-4-piperidine) 6) parts by weight of erucamide wax A lubricant such as a lubricant and 4 parts by weight of a carbodiimide-based hydrolysis inhibitor are sufficiently stirred to obtain a polymer polyol mixed solution.

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

(3) maintaining the temperature of the above reaction mixture and adding 6 parts by weight of 1,4-butanediol chain extender and 0.1 part by weight of the ruthenium catalyst, and controlling the temperature at 180-210 ° C, pressure 6MPa reaction lh about.

(4) When the 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.

Fourth, the preparation of dry PU film S4

(1) Preparation of main agent: 20% of polyester diol, 10% of methyl ketone, 50% of dimethylformamide, 3% of linear diol are placed in a reaction pot at a temperature of 30% by mass. After mixing for 12 minutes, put 12% diphenylmethane-4,4'-diisocyanate into the reaction pot at room temperature, heat up and react at 80 ° C for 2 hours, then add 2 % of the TDI trimer, after reacting at 80 Torr for 2 hours, gradually cooling to 40 ° C, adding 3% hydroxyethyl acrylate, stirring 0. 5 hours, cooling the discharge, to obtain the main agent;

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.

V. Preparation of seam-free hot melt adhesive TPU-PU leather

(1) preparing a release paper Sl, a hot melt adhesive raw material, a TPU raw material and a PU raw material prepared by the above method, and placing the release paper S1 in the relevant equipment to be flattened;

(2), 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;

(3), 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 At the same time, 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. Integrally, after cooling, a TPU film S3 with a hot melt adhesive film is formed, as shown in FIG. 2;

(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 operate, and the PU raw material is fully smoothed and baked to the micro-dry after being scraped and oven respectively. Forming a dry PU film S4; (5), the dry PU film S4 is passed through the sizing and the hot-melt-coated TPU film S3 prepared in the step (3) is simultaneously fed into the pattern pressing press in the press wheel, and then rapidly cooled by the cooling device. After the coiling, the hot-melt glue-free TPU-PU leather of the multilayer structure of the dry PU film S4 + TPU film S3 + hot melt film S2 of the present invention is obtained.

The above is only a description of the preferred embodiments of the present invention, and the technical solutions of the present invention are not limited thereto. Any known modifications made by those skilled in the art based on the main technical idea of the present invention belong to the present invention. The technical scope of the invention is defined by the scope of the claims.

Claims

WO 2015/021814 claims PCT/CN2014/079497, a sewing-free hot melt adhesive TPU-PU leather, characterized in that it includes a release paper and hot melt adhesive coated on the release paper (S1) Film (S2), TPU film (S3) pasted on the hot melt adhesive film (S2), and dry PU film (S4) pasted against the TPU film (S3); wherein the release paper (S1 ) includes paper bottom layer (A1), adhesive layer (A2), plastic layer (A3), transition layer (A4) and release layer (A5), the plastic layer (A3) is bonded through the adhesive layer (A2) On the paper bottom layer (A1), the transition layer (A4) is provided on the plastic layer (A3), the release layer (A5) is provided on the transition layer (A4), the adhesive layer The binding layer (A2) is a water-based polypropylene coating layer, the usage amount is 5-8 grams per square meter, and the thickness is 0.8-4 microns. The plastic layer (A3) is polyparaphenylene with a thickness of 18-25 microns. Ethylene glycol diformate film, the transition layer (A4) consists of 62-68 parts by weight 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 It is prepared by mixing and stirring 20 parts of dodecyldimethylbenzyl ammonium chloride and 45-55 parts by weight of water, and the film thickness is 15-20 microns, and the thickness of the release layer (A5) is 20 -25 micron and 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, and 1_2 parts by weight of 2, 2'-methylene Bis-bis-(4,6 di-tert-butylphenoxy) sodium phosphate and 0.1-0.8 parts by weight of tert-butyl peroxy benzoate are mixed and prepared; wherein the hot melt adhesive film is made by hot The hot melt adhesive is prepared by extruding raw materials for melt glue. The hot melt glue is composed 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 and 2-4 parts by weight of toughening agent. ; The polyester polyol is prepared into a terminal hydroxyl group with a molecular weight of 2000-6000 through a polycondensation reaction of a low molecular weight aliphatic diol, an aliphatic dicarboxylic acid, and an aromatic dicarboxylic acid at 100-260°C. Polyester diol, the aliphatic dicarboxylic acid is selected from adipic acid, fumaric acid, maleic acid or suberic acid, the aromatic dicarboxylic acid is selected from phthalic acid, terephthalic acid or Isophthalic acid, the aliphatic glycol is selected from ethylene glycol, diethylene glycol, propylene glycol, methylpropanediol, 1,4-butanediol, 1,6-hexanediol, 1,3-butanediol alcohol, 1,5-pentanediol or dodecylhexanediol; the diisocyanate is 4,4'-diphenylmethane diisocyanate or 1,6-hexamethylene diisocyanate; the polyether polyether The alcohol is selected from polytetrahydrofuran ether glycol or propylene oxide copolymer glycol; the catalyst is selected from one or more of dibutyltin dilaurate, triethanolamine or bismorpholinyl diethyl ether; the chain extender is selected One of 1, 6-hexanediol, methylpropanediol and 1, 4-butanediol; the antioxidant is selected from 2, 6-tertiary butyl-4-methylphenol or tetra{β-(3 , 5-tertiary butyl-4-hydroxyphenyl) pentaerythritol propionate; the tackifying resin is selected from one or more of polyethylene-vinyl acetate copolymer, hydroxyl-terminated thermoplastic polyester, and hydrogenated rosin resin ; The composition of the flame retardant is calculated in mass percentage: 30%-70% polypropylene with a melt index of 0.5-15.0 g/10min, 5%-25% polyethylene with a melt index of 0.01-2.0 g/10min, 20% _40% of at least one inorganic filler selected from powdered talc, kaolinite, sericite, silica and diatomaceous earth and 5% to 35% of at least one selected from the group consisting of decabromodiphenyl ether and dodecachloride Organic flame retardant compound of hydrogen dimethylbenzole cyclooctene or its mixture; The toughening agent is mixed and extruded from polyethylene elastomer, linear polyethylene, polypropylene and anti-aging agent raw materials; wherein it is prepared The composition of the TPU raw material of the TPU film (S3) is: 60-70 parts by weight of polymer polyol, selected from polytetrahydrofuran ether glycol with a molecular weight of 1000, polyethylene butylene adipate with a molecular weight of 3000 One or two types of alcohol ester polyols; 30-35 parts by weight of 1, 4-cyclohexane diisocyanate; 4-9 parts by weight of a chain extender, and the chain extender is 1, 4-butane diisocyanate Alcohol; 3-5 parts by weight of carbodiimide hydrolysis resistant agent; 1-3 parts by weight of decabromodiphenylethane with an average particle size less than or equal to 4 microns mixed with a trace amount of fumed silica organic halide Flame retardant; 0.2-0.8 parts by weight of antioxidant, the antioxidant is β_(4-hydroxy-3, 5-di-tert-butylphenyl) n-octadecyl propionate , at least one of tetra[β_(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol ester and di[(2,4-di-tert-butylphenyl)phosphite]pentaerythritol ester 0. 1-0. 5 parts by weight of two (2, 2, 6, 6-tetramethyl-4-piperidinyl) subebrate hindered amine light stabilizer; 0. 4-0. 8 Parts by weight of montan wax and/or erucamide wax lubricants; 0.05-0.2 parts by weight of titanium-based or bismuth-based catalysts; wherein the PU raw material composition for preparing the dry PU film (S4) is: : 55-70% main agent, 20-37% MEK, 3-10% black sand, 0. 5-1% tert-butyl hydroperoxide, 0. 8-1% calcium filler 0. 6-0. 9% anti-wear agent composed of aromatic silicone oil, 0. 2-0. 6% benzotriazole ultraviolet absorber and 0. 5-1. 2% An antistatic agent composed of metal powder or conductive carbon black; the composition of the main agent itself is: 12-28% polyester diol, 1-5% linear diol, 6-18% diol Phenylmethane-4,4'-diisocyanate, 1-3% TDI trimer, 20-70% dimethylformamide, 0-30% butanone, 2-6% hydroxyethyl acrylate ; Each component is calculated by mass percentage. The hot melt adhesive TPU-PU leather according to claim 1, wherein the composition of the inorganic particles in the transition layer of the release paper (S1) includes a particle size of 0.5-0.8 microns. Clay with a particle size of 25% and accounting for 25% of the total content of 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 carbonic acid with a particle size of 3-5 microns and accounting for 15% of the total content of inorganic particles. Calcium powder; wherein the structural formula of the vinyl silicone oil in the release layer is: where R1 and R3 are -CH3, R2 is -CH=C, the value range of m is 2000~3000, and the value range of n is 3~ 6. . The hot melt adhesive TPU-PU leather according to claim 1 or 2, characterized in that the thickness of the adhesive layer (A2) is 2.5 microns, and the thickness of the plastic layer (A3) is 20 microns. , the thickness of the transition layer (A4) is 15 microns, and the thickness of the release layer (A5) is 25 microns. The raw materials for preparing the transition layer are 65 parts by weight of inorganic particles, 35 parts by weight of silicone-acrylic emulsion, and fatty acids 4 parts by weight of sodium methyl ester sulfonate, 3 parts by weight of dodecyldimethylbenzyl ammonium chloride and 50 parts by weight of water; the raw materials for preparing 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 the vinyl silicone oil is: and R3 is -CH3, R2 is -CH=C, m=2500, n=4. . The hot melt adhesive TPU-PU leather according to claim 1, wherein the raw materials for preparing the hot melt adhesive are composed of: 65 parts by weight of polyester polyol, 18 parts by weight of diisocyanate, 4 parts by weight 1 part by weight of polyether polyol, 1 part by weight of catalyst, 1 part by weight of chain extender, 1.6 parts by weight of antioxidant, 5 parts by weight of tackifying resin, 3 parts by weight of flame retardant, 3 parts by weight of extender. Toughening agent; The toughening agent is made by mixing and extruding 31% polyethylene elastomer, 19% linear polyethylene, 49% polypropylene and 1% anti-aging agent raw materials by weight; The fuel is composed of 50% polypropylene with a melt index of 5 g/10 minutes, 20% polyethylene with a melt index of 0.8 g/10 minutes, 20% powdered talc and kaolinite mixed inorganic fillers and 10% It is composed of an organic flame retardant halide mixed with decabromodiphenyl ether and dodecachlorododecahydrodimethylbenzole cyclooctene. . The hot melt adhesive TPU-PU leather according to claim 1, wherein the composition of the TPU raw material is 65 parts by weight of polyethylene butylene adipate polyol with a molecular weight of 3000, 0.6 parts by weight of 3-(4-hydroxy-3,5-di-tert-butylphenyl) n-octadecanol propionate antioxidant, 0.3 parts by weight of di(2,2,6, 6-tetramethyl-4-piperidinyl) subebate 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 the temperature is 60 ° C. 1, 4-cyclohexane diisocyanate, 6 parts by weight of 1, 4-butanediol chain extender, 0.1 parts by weight of bismuth catalyst, 2 parts by weight of decabromodiphenyl Organic halide flame retardant based on ethane mixed with trace amounts of fumed silica. . The hot melt adhesive TPU-PU leather according to claim 1, wherein the composition of the PU raw material is calculated as mass percentage: 60% main agent, 30% ethyl ketone, 6% black sand , 0.8% tert-butyl hydroperoxide, 0.8% matte agent, 0.8% wear-resistant agent, 0.6% ultraviolet absorber and 1% anti-static agent, wherein the The composition of the main agent itself is calculated in mass percentage: 20% polyester glycol, 10% methyl ethyl ketone, 50% dimethylformamide, 3% linear glycol, 12% diphenylmethane -4,4'-diisocyanate, 2% TDI trimer and 3% hydroxyethyl acrylate. The hot melt adhesive TPU-PU leather according to any one of claims 1 to 6, characterized in that the tensile strength of the hot melt adhesive TPU-PU leather is 34.2 kgf in the transverse direction and 29.2 kgf in the longitudinal direction. ; The tear strength of the hot-melt adhesive TPU-PU leather is 6.1 kgf in the warp direction; 5.2 kgf in the weft direction; the bonding strength of the hot-melt adhesive TPU-PU leather is greater than or equal to 3. OKg/25 mm; The elongation rate 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 method for preparing sewing-free hot melt adhesive TPU-PU leather, characterized in that the method includes the following steps: (1) Prepare release paper (S1) (1), select the paper bottom layer (Al), And apply a water-based polypropylene adhesive layer (A2) with a thickness of 0.8-4 microns on the paper bottom layer (A1), and then paste a water-based polypropylene adhesive layer (A2) with a thickness of 18-25 microns on the adhesive layer (A2). The plastic layer (A3) formed by the polyethylene terephthalate film is then solidified; (2), pour 3-5 parts by weight of sodium fatty acid methyl ester sulfonate into 45-55 parts by weight of water, and stir Evenly, then pour 62-68 parts by weight of inorganic particles made of clay, barium sulfate powder and calcium carbonate powder, and stir at high speed to disperse them evenly, then add 32-36 parts by weight into the dispersed slurry Silicone acrylic emulsion, use a glass rod to mix the solution evenly, then add 2-4 parts by weight of dodecyldimethylbenzyl ammonium chloride into it, continue to stir evenly, and prepare a transition layer coating liquid; (3 ), use a scraper to evenly apply the transition layer coating liquid on the plastic layer (A3), and heat it at 80°C for 30 seconds to solidify it into a film. Control the film thickness to 15-20 microns, and then put the film-formed The transition layer (A4) is calendered at 120°C, linear pressure 150KN/m, and vehicle speed 10m/min; (4), 58-65 parts by weight of polypropylene and 26-34 parts by weight of poly4 -Methyl-1-pentene and 6-9 parts by weight of vinyl silicone oil are mixed evenly and heated to 90°C. After 2 hours of heat preservation, 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 through an extruder and coat on the transition Form a release layer (A5) on the surface of the layer (A4), and control the thickness to 20-25 microns; (2) Prepare the hot melt adhesive raw material (1), mix 60-70 parts by weight of polyester polyol, 3-5 Parts by weight of polyether polyol, 1.5-1.8 parts by weight of antioxidants and 4-6 parts by weight of tackifying resin are placed in a reaction kettle, heated to 120~140°C, and vacuum dehydrated under stirring and mixing 1.5~2h, the vacuum degree is less than 0.05MPa, and then cooled to 70~75°C; wherein the polyester polyol is made by low molecular weight aliphatic diol and aliphatic dicarboxylic acid, aromatic dicarboxylic acid The carboxylic acid is polycondensed at 100-260°C to prepare a hydroxyl-terminated polyester diol with a molecular weight of 2000-6000; the polyether polyol is selected from one of polytetrahydrofuran ether diol and oxypropylene copolydiol. ; The antioxidant is selected from 2, 6-tertiary butyl-4-methylphenol or tetra{β_(3, 5-tertiary butyl-4-hydroxyphenyl) pentaerythritol propionate; the antioxidant The adhesive resin is selected from one or more of polyethylene-vinyl acetate copolymer, hydroxyl-terminated thermoplastic polyester, and hydrogenated rosin resin; (2), under nitrogen protection, combine 15-20 parts by weight of diisocyanate and 0.8-1.5 The catalyst in parts by weight is added to the reaction product of step (1), and reacted at 85~95°C for 1-1.5h; wherein the diisocyanate is 4,4'-diphenylmethane diisocyanate or 1,6- One of hexamethylene diisocyanate; the catalyst selects one or more of dibutyltin dilaurate, triethanolamine or bismorpholinyl diethyl ether; (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 the reaction is stirred at 75~85°C for 45 minutes -1.0h; wherein the chain extender selects one of 1,6-hexanediol, methylpropanediol, and 1,4-butanediol; the composition of the flame retardant is calculated as mass percentage: 30% _70% polypropylene with a melt index of 0.5-15.0 g/10min, 5%_25% polyethylene with a melt index of 0.01-2.0 g/10min, 20%_40% selected from powdered talc, kaolinite, sericite, At least one inorganic filler of silica and diatomite and 5% to 35% of an organic flame retardant selected from decabromodiphenyl ether, dodecachlorododecylhydrobenzole cyclooctene or a mixture thereof Halide; The toughening agent is a polyolefin toughening agent; (4), discharge the material under nitrogen protection conditions, mature and cool to form a hot melt adhesive raw material; (3), prepare the TPU raw material (1), Place 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 glycol with a molecular weight of 1000 and/or polyhexane with a molecular weight of 3000. Ethylene glycol butylene glycol diacid polyol; then add 0.2-0.8 parts by weight of antioxidant and 0.1-0.5 parts by weight of bis(2, 2, 6, 6-tetramethyl-4-piperidinyl) Subarate 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 are fully stirred to obtain Polymer polyol mixed solution, wherein the antioxidant is β_(4-hydroxy-3,5-di-tert-butylphenyl) n-octadecyl propionate, tetra[β_(3,5-di-tert-butylphenyl) At least one of (butyl-4-hydroxyphenyl) propionate] pentaerythritol ester and bis[(2,4-di-tert-butylphenyl)phosphite] pentaerythritol ester; (2), adding polyvalent elements to the polymer Add 30-35 parts by weight of 1,4-cyclohexane diisocyanate at a temperature of 55-65°C into the alcohol mixed solution, stir and mix to obtain a preliminary reaction mixture; (3), maintain 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 and the pressure of 4-8MPa for about 1 hour; (4), When the reaction melt temperature reaches between 180-210°C, add 1-3 parts by weight of an organic halide resist of decabromodiphenylethane mixed with a trace amount of fumed silica with an average particle size less than or equal to 4 microns. The fuel agent is dehydrated, dried and aged after the reaction to obtain the thermoplastic polyurethane elastomer raw material; (4) Preparation of PU raw material (1) Preparation of the main agent: 12-28% polyester diol, 0- Put 30% butanone, 20-70% dimethylformamide, and 1-5% linear diol into the reaction pot and stir at room temperature for 20-40 minutes. After mixing evenly, add 6-18% at room temperature. After the diphenylmethane-4, 4'-diisocyanate is put into the reaction pot, the temperature is raised and allowed to react at 70-80°C for 1-3 hours, and then 1-3% of TDI trimer is added , after reacting at 60-80°C for 1-3 hours, gradually cooling to 40-50°C, adding 2-6% hydroxyethyl acrylate, stirring for 0.5 hours, then cooling and discharging, to obtain the main agent ; (2) Combine 55-70% of the main agent, 20-37% of methyl ethyl ketone, 3-10% of black sand, 0.5-1% of tert-butyl hydroperoxide, and 0.8-1% of mist according to mass percentage. After mixing the surface agent, 0. 6-0. 9% wear-resistant agent, 0. 2-0. 6% ultraviolet absorber and 0. 5-1. 2% anti-static agent, disperse it in a high-speed disperser 10-20 minutes, and then left to defoam for 4 hours to obtain PU raw materials; (5) Laminating and preparing sewing-free hot melt adhesive TPU-PU leather

(1), prepare the release paper (S1), hot melt adhesive raw material, TPU raw material and PU raw material prepared through the above steps, and place the release paper (S1) in the relevant equipment and lay it flat;

(2). The hot melt adhesive raw material prepared in step (2) is processed into rubber material through an extruder. The rubber material is sent to the extruder at a temperature of 150 degrees to melt into a paste, and then extruded from the die head of the extruder. Casting onto the release paper, then pressing with a pressing wheel, cooling and rolling up to form a hot melt adhesive film (S2);

(3). Extrude the TPU raw material prepared in step (3) into a TPU film (S3), and place it with the above-mentioned hot melt adhesive film (S2) on two feeding racks respectively, so that the hot melt adhesive film (S2) At the same time, the TPU film (S3) enters the high and low pressure wheels equipped with constant temperature for pressure. The temperature of the pressure wheel is above 160°C, so that the hot melt adhesive with a low melting point can instantly contact the high and low pressure wheels when the pressure is applied. The TPU film (S3) is bonded into one body, and after cooling, a TPU film with a hot melt adhesive film is formed;

(4). Pour the PU raw material prepared in step (4) onto the release paper (S1). The release paper (S1) with PU material is driven by the feeding rack to run. The PU raw material is fully dried through the scraper and oven respectively. Smooth and bake until slightly dry to make dry PU film (S4);

(5). After the dry PU film (S4) is glued, the TPU film with the hot melt adhesive film prepared in step (3) is simultaneously sent to the pattern pressing wheel for pressure forming, and then passes through the cooling device. After rapid cooling and curling, the dry PU film (S4) is obtained.

TPU film (S3) Heated melt adhesive film (S2) is a multi-layer structure of hot melt adhesive TPU-PU leather that does not require sewing.

, The preparation method according to claim 8, characterized in that, in the step (1) of preparing the release paper (S1): the raw materials for preparing the transition layer are 65 parts by weight of inorganic particles and 35 parts by weight of silicone-acrylic emulsion , sodium fatty acid methyl ester sulfonate 4 parts by weight, 3 parts by weight of dodecyldimethylbenzyl ammonium chloride and 50 parts by weight of water. The specific composition of the inorganic particles is: clay particle size is 0.5-0.8 microns and content is 25%, barium sulfate powder The particle size of calcium carbonate 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 raw materials for preparing the release layer are 60 parts by weight of polypropylene and 30 parts by weight of polypropylene. 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 parts of tert-butyl peroxybenzoate, the vinyl silicone oil

Rl and R3 are -CH ₃ and R2 is _CH:

C, m=2500, n=4.

. The preparation method according to claim 8, wherein the aliphatic dicarboxylic acid used to prepare the polyester polyol in step (2) is selected from adipic acid, fumaric acid, maleic acid or suberic acid, The aromatic dicarboxylic acid is selected from phthalic acid, terephthalic acid or isophthalic acid, and the aliphatic diol is selected from ethylene glycol, diethylene glycol, propylene glycol, methylpropylene glycol, and 1,4-butanediol. alcohol, 1, 6-hexanediol, 1, 3-butanediol, 1, 5-pentanediol or dodecylhexanediol; the toughening agent is composed of polyethylene elastomer, linear polyethylene, polyethylene Propylene PP and anti-aging agent raw materials are mixed and extruded. The mass percentages of each raw material are: polyethylene elastomer 31%, linear polyethylene 19%, polypropylene 49%, and anti-aging agent 1%.

, The preparation method according to claim 8, wherein the composition of the TPU raw material in step (3) is 65 parts by weight of polyethylene butylene adipate polyol with a molecular weight of 3000, 0.6 parts by weight of β-(4-hydroxy-3, 5-di-tert-butylphenyl) n-octadecanol propionate antioxidant, 0.3 parts by weight of di(2, 2, 6, 6-tetramethyl) Base-4-piperidinyl) subebrate 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 the temperature is at 60°C 1, 4-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 were mixed and calcined in a trace amount Organic compound flame retardant for making silica.

, The preparation method according to claim 8, characterized in that, the composition of the PU raw material in step (4) is calculated in mass percentage: 60% main agent, 30% butanone, 6% black sand , 0.8% tert-butyl hydroperoxide, 0.8% matte agent, 0.8% wear-resistant agent, 0.6% ultraviolet absorber and 1% anti-static agent, where the composition of the main agent itself is in mass percentage Calculated as: 20% Polyester Diol, 10% Methyl Ketone, 50% Dimethylformamide, 3% Linear Diol, 12% Diphenylmethane-4,4'-Diisocyanate , 2% TDI trimer and 3% hydroxyethyl acrylate.