WO2015021813A1 - 一种免车缝的热熔胶tpu皮革及其制备方法 - Google Patents
一种免车缝的热熔胶tpu皮革及其制备方法 Download PDFInfo
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- WO2015021813A1 WO2015021813A1 PCT/CN2014/079496 CN2014079496W WO2015021813A1 WO 2015021813 A1 WO2015021813 A1 WO 2015021813A1 CN 2014079496 W CN2014079496 W CN 2014079496W WO 2015021813 A1 WO2015021813 A1 WO 2015021813A1
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- melt adhesive
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- tpu
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C—CHEMISTRY; METALLURGY
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- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
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- C09J2423/10—Presence of homo or copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C09J2475/006—Presence of polyurethane in the substrate
Definitions
- the invention relates to the technical field of leather materials, and more particularly to a seam-free hot melt adhesive TPU leather and a preparation method thereof. Background technique
- the invention is based on the above technical problems, and proposes a novel seam-free hot-melt adhesive TPU leather and a preparation method thereof, and the innovation of the raw material component by the hot melt adhesive and the TPU film, combined with the long-term production of the company.
- Practical experience using this innovation to develop a plasticity hot melt adhesive and TPU film extrusion molding, and finally form the seam-free TPU leather of the present invention, which can be directly attached to various articles, and has
- the technical advantages of strong adhesion, long-lasting durability, environmentally friendly materials and no invisible damage to the human body have fundamentally solved the various factors that are caused by the seaming of the sewing seam and the application of the existing industrial rubber in the leather product.
- a seam-free hot melt adhesive TPU leather comprising a release paper, a hot melt adhesive film coated on the release paper, and a TPU film adhered to the hot melt adhesive;
- the release paper comprises a paper bottom 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 bottom layer Al1 through the adhesive layer A2.
- the transition layer A4 is disposed on the plastic layer A3, the release layer A5 is disposed on the transition layer A4, and the adhesive layer A2 is an aqueous polypropylene coating layer, and the usage amount is 5-8 grams per square meter.
- the thickness of the plastic layer A3 is a polyethylene terephthalate film having a thickness of 18-25 ⁇ m, and the transition layer A4 is composed of 62-68 parts by weight of inorganic particles.
- the release layer A5 has a thickness of 20-25 microns and is composed of 58-65 parts by weight of polypropylene, 26-34 parts by weight of poly 4-methyl-1-penta Alkene, 6-9 parts by weight of vinyl silicone oil, 1_2 parts by weight of 2, 2 '-methylene group- Preparation of bis-B,6-di-tert-butylphenoxyphosphate and 0.
- 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 100-26 (TC) to prepare a terminal hydroxyl polyester diol having a molecular weight of 2000-6000.
- the aliphatic dicarboxylic acid is selected from the group consisting of adipic acid, fumaric acid, maleic acid or suberic acid, and the aromatic dicarboxylic acid is selected from the group consisting of phthalic acid, terephthalic acid or isophthalic acid.
- the aliphatic diol is selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, methyl propylene glycol, 1, 4-butanediol, 1,6-hexanediol, 1, 3-butanediol, 5 pentanediol or dodecyl hexanediol
- the diisocyanate is 4, 4 '-diphenylmethane diisocyanate or 1,6-hexamethylene diisocyanate
- the polyether polyol is selected from polytetrahydrofuran ether glycol or propylene oxide copolymer diol
- the catalyst is one or more selected from the group consisting of dibutyltin dilaurate, triethanolamine or dimorpholinyl diethyl ether
- the chain extender is selected from 1,6-hexanediol, methylpropanediol, 1, 4- One of butanediol
- the toughening agent is a mixture of polyethylene elastomer, linear polyethylene, polypropylene and anti-aging agent ;
- composition of the TPU raw material in which the TPU film is prepared is: 60-70 parts by weight of a polymer polyol selected from polytetrahydrofuran ether glycol having a molecular weight of 1000 and polyethylene butadiene glycol adipate having a molecular weight of 3000 One or more of ester polyols; 30-35 parts by weight of 1,4-cyclohexane diisocyanate; 4-9 parts by weight of a chain extender, said chain extender being 1,4-butanediol 3-5 parts by weight of a carbodiimide hydrolysis resistant agent; 1-3 parts by weight of an organic halide resistance of decabromodiphenylethane mixed micro-fumed silica having an average particle size of less than or equal to 4 microns a flammable agent; 1-2 parts by weight of an aromatic silicone oil anti-wear agent; 0.
- a polymer polyol selected from polytetrahydrofuran ether glycol having a molecular weight
- an antioxidant the antioxidant is ⁇ _ (4-hydroxy-3, 5-di-tert-butyl) Benzophenyl)propanoic acid n-octadecyl alcohol ester, tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester and bis[(2,4-di-tert-butyl) At least one of pentaerythritol esters; 0. 1-0. 5 parts by weight of bis(2,2,6,6-tetramethyl-4-piperidinyl) alginate hindered amine Light stabilizers; 0. 2-0.
- a clay, barium sulfate powder having a particle diameter of 1-2 ⁇ m and accounting for 60% of the total content of inorganic particles, and calcium carbonate having a particle diameter of 3-5 ⁇ m and accounting for 15% of the total content of inorganic particles;
- the hot melt adhesive TPU leather according to the present invention wherein the thickness of the adhesive layer A2 is 2.5 ⁇ m, the thickness of the plastic layer A3 is 20 ⁇ m, and the thickness of the transition layer A4 is 15 ⁇ m.
- the release layer A5 has a thickness of 25 ⁇ m, and the preparation material of the transition layer is 65 parts by weight of inorganic particles, 35 parts by weight of a silicone-acrylic emulsion, 4 parts by weight of sodium fatty acid methyl ester sulfonate, and dodecyldimethyl 3 parts by weight of benzyl ammonium 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 ⁇ Ester, said B
- R3 is - CH3
- R2 is
- the hot melt adhesive TPU 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 polyol.
- the toughener is prepared by mixing and extruding 31% polyethylene elastomer, 19% linear polyethylene, 49% polypropylene and 1% anti-aging agent raw material; the flame retardant is 50% by weight
- the content of the composition of the TPU raw material is 65 parts by weight of a polyethylene adipate ethylene glycol butanediol polyol having a molecular weight of 3000, 0. 6 parts by weight --(4-hydroxy-3, 5-di-tert-butylphenyl) propionic acid n-octadecyl alcohol ester antioxidant, 0.3 parts by weight of bis(2, 2, 6, 6-tetramethyl- 4-piperidinyl) aerate light stabilizer, 0.4 parts by weight of a benzotriazole ultraviolet absorber, 0.6 parts by weight of a erucamide wax lubricant, 4 parts by weight a carbodiimide hydrolysis inhibitor, 32 parts by weight of 1,4-cyclohexane diisocyanate at 60 ° C, 6 parts by weight of a 1,4-butanediol chain extender, 0.1 part by weight Lanthanide catalyst, 2 parts by weight of decabromodiphenylethane mixed with micro-
- the hot melt adhesive TPU leather according to the present invention wherein the hot melt adhesive TPU leather has a tensile strength of 28.2 Kgf, a longitudinal length of 25. 3 Kgf ; the tear strength of the hot melt adhesive TPU leather is The elongation of the hot melt adhesive TPU leather is greater than or equal to 2. 5Kg / 25; the elongation of the hot melt adhesive TPU leather is greater than or equal to 700%; Hot melt adhesive TPU leather has a Shore hardness of 95 or more.
- a method for preparing a seam-free hot melt adhesive TPU leather comprising the following steps:
- the paper base layer Al is selected, and an aqueous polypropylene bonding layer A2 having a thickness of 0.8 to 4 ⁇ m is coated on the paper substrate A1, and then a thickness of 18- is adhered to the bonding layer A2.
- a 25 micron plastic layer A3 formed of a polyethylene terephthalate film, which is then cured for a certain period of time;
- transition layer coating liquid on the plastic layer A3 using a doctor blade, and curing at 80 ° C for 30 seconds to form a film, controlling the film thickness to be 15-20 ⁇ m, and then forming the film.
- the transition layer A4 is calendered under conditions of 120 ° C, a line pressure of 150 KN/m, and a vehicle speed of 10 m/min;
- the alcohol is selected from the group consisting of polytetrahydrofuran ether diol and propylene oxide copolymer diol
- the antioxidant is selected from the group consisting of 2,6-tris-butyl-4-methylphenol or tetra ⁇ -(3,5-tri-butyl-4-hydroxyphenyl)propionic acid ⁇ pentaerythritol
- An ester the tackifying resin being selected from one or more of a polyethylene-vinyl acetate copolymer, a hydroxyl terminated thermoplastic polyester, and a hydrogenated rosin resin;
- the diisocyanate is one of 4, 4'-diphenylmethane diisocyanate or 1,6-hexamethylene diisocyanate
- the catalyst is selected from dibutyltin dilaurate, triethanolamine or bismorpholinyl One or more of ethyl ether;
- the polymer polyol is a polytetrahydrofuran ether glycol having a molecular weight of 1000 and/or a molecular weight of 3000 Polyethylene adipate ethylene glycol butylene glycol polyol, 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-piperidinyl) Aerated amine light stabilizer, 0.2-0.6 parts by weight of benzotriazole ultraviolet absorber, 0.4-0.8 parts by weight of montan wax and / or erucamide wax lubricant and 3-5 a part by weight of a carbodiimide hydrolysis-resistant agent, which is sufficiently stirred to obtain a polymer polyol mixed solution, wherein the antioxidant is ⁇ _(4-hydroxy-3, 5-di-tert-butylphenyl)propionic acid Octade
- the hot melt adhesive raw material prepared in the step (2) is processed into a rubber compound by an extruder, and the rubber material is sent into a 150 degree temperature extruder to melt into a paste, and then extruded by the extruder die. Casting onto the release paper, and then pressing and cooling the pressure roller to form a hot melt adhesive film;
- the preparation material of the transition layer is 65 parts by weight of inorganic particles, 35 parts by weight of a silicone-acrylic emulsion, and sodium fatty acid methyl ester sulfonate. 5 ⁇ 25 ⁇ The granules having a particle size of 0. 5-0.
- the barium sulfate powder has a particle diameter of 1-2 micrometers and a content of 60%
- 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, L 5 parts by weight of 2,2 '-methylene-bis-(4,6-di-tert-butylphenoxy) Sodium phosphate and the structural formula of the vinyl silicone oil
- the preparation method 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 suberic acid, aromatic binary
- the carboxylic acid is selected from the group consisting of phthalic acid, terephthalic acid or isophthalic acid
- the aliphatic diol is selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, methyl propylene glycol, 1, 4-butanediol, 1, 6 ⁇
- the toughening agent is formed by mixing polyethylene elastomer, linear polyethylene, polypropylene PP and anti-aging agent raw materials, and extruding, Mass percentage share of raw materials: polyethylene elastomer 31%, 19% linear polyethylene, polypropylene 49% of the olefin and 1% of the anti-aging agent.
- composition of the composition of the TPU raw material is 65 parts by weight of polyethylene adipate ethylene glycol butanediol polyol, 0.6 weight Parts of ⁇ -(4-hydroxy-3, 5-di-tert-butylphenyl)propionic acid n-octadecyl alcohol antioxidant, 0.3 parts by weight of two (2, 2, 6, 6-tetra a pyridyl acrylate light stabilizer, 0.4 parts by weight of a benzotriazole ultraviolet absorber, 0.6 parts by weight of a erucamide wax lubricant, and 4 parts by weight of carbonization a diimine hydrolysis-resistant agent, 32 parts by weight of 1,4-cyclohexane diisocyanate having a temperature of 60 ° C, 6 parts by weight of a 1,4-butanediol chain extender, 0.1 part by weight of hydrazine a catalyst, 2 parts by weight of decabromodiphenylethane mixed with a
- the innovative design of multi-layer structure release paper especially the innovative design of multi-functional layer and release layer, makes the release paper provided by the invention have excellent physical and chemical properties in leather products. It has high bonding strength with hot melt adhesive and fast curing time. It is an ideal substrate for high quality leather.
- the hot melt adhesive of the invention has low melting point, high elasticity, acid resistance, alkali resistance, water washing resistance, dry cleaning resistance, strong tensile strength, strong subsequent force, low melting point and the like.
- the TPU film used overcomes many defects of the existing TPU through innovative innovations in raw materials. It not only possesses most of the characteristics of rubber and ordinary plastics, but also has excellent comprehensive physical and chemical properties, which can be completely replaced. PVC, PU artificial leather and other leather fabrics.
- the seam-free hot-melt adhesive TPU 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, wood, etc. It can be widely used in the manufacturing industry 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, and the invention
- the hot melt adhesive and the raw material contained in the TPU raw material are biomedical, non-toxic, odorless and non-allergic. It is extremely environmentally friendly and non-polluting. It is an ideal environmental protection in the 21st century. One of the fit fabrics.
- FIG. 1 is a schematic view showing the hot melt adhesive film formed by extruding the hot melt adhesive of the present invention onto a release paper;
- Figure 2 is a schematic view showing the hot-melt adhesive film shown in Figure 1 and a TPU film laminated to the seam-free hot melt adhesive TPU leather of the present invention
- Figure 3 is a schematic view showing the structure of a release paper used in the present invention
- A1 - paper bottom layer A2-bond layer, A3-plastic layer, A4-transition layer, A5-release layer.
- the composition of most of the raw material substances is measured in "parts by weight", and the “parts by weight” only indicates the relationship between the components in each substance (the same mass percentage). , does not represent the actual quality of use, that is to say, some components of different substances may have the same or similar parts by weight, but it does not mean that these components have the same or similar mass content in each substance.
- the seam-free hot melt adhesive TPU leather of the present invention comprises a release paper, a hot melt adhesive film and a TPU film, and the preparation of the seam-free hot melt adhesive TPU leather adopts a double-sided bonding method, specifically including the following Steps:
- Step 1 Prepare release paper, hot melt adhesive raw material and TPU raw material, which are unique to the company and one of the main inventions of the present invention, and the raw material formulation and preparation method thereof will be given in detail 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 seam-free hot melt adhesive film, as shown in FIG. 1;
- Step 3 extruding the prepared TPU raw material into a TPU film, and placing the coiled hot melt adhesive film and the TPU film on the two feeding racks respectively, so that the hot melt adhesive film and the TPU film simultaneously enter a constant temperature level. Press the pressure on the pressure roller. Since the temperature of the pressure roller is as high as 160 or more, the hot melt adhesive having a low melting point is instantly bonded to the TPU when the pressure roller is pressed against the pressure roller, and is cooled to form a new material of a seamless hot melt adhesive leather, such as Figure 2 shows.
- the key technologies of the present invention include: the formulation of a highly viscous hot melt adhesive, the key formulation of a TPU film, and the selection of various functional admixtures (masterbatch) therein and the preparation of release paper as a substrate.
- TPU thermoplastic polyurethane
- PU Polyurethane, also known as polyurethane
- the physical properties such as rigidity are good decorative formula materials.
- the present invention combines long-term production practices and has undergone extensive experiments to innovate a new type of polyurethane hot melt adhesive and TPU material by changing the formulation components and additives.
- the product has multiple physical properties such as better adhesion, tear resistance, abrasion resistance, and high temperature resistance.
- the release paper provided by the present invention has a multi-layer structure, specifically including a paper base layer A1, on which a plastic layer A3 is bonded via a bonding layer A2, in the plastic layer.
- a transition layer A4 is disposed on A3, and a release layer A5 is disposed on the transition layer A4.
- the plastic layer A3 is a polyethylene terephthalate film (i.e., a PET film) having a thickness of 18 to 25 ⁇ m, preferably 20 ⁇ m.
- the adhesive layer A2 bonds the paper underlayer A1 and the polyethylene terephthalate film A3, and the adhesive layer A2 is an aqueous polypropylene (PP) coating layer, and the amount used is per square. 5 ⁇ The thickness of 0. 8_4 micron, preferably 6 grams per square meter, a thickness of 1-2. 5 microns.
- the transition layer A4 consists of inorganic particles, silicone-acrylic emulsion, sodium fatty acid methyl sulfonate, dodecyldimethylbenzyl ammonium chloride and water.
- 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 sulfonate, 2_4 parts of dodecyl dimethyl benzyl ammonium chloride, 45-55 parts of water; the composition of inorganic particles includes particle size 0. 5-0. 8 micron, clay which accounts for 25% of total inorganic particles, barium sulfate powder with a particle size of 1-2 micrometers, 60% of total inorganic particles, and particle size of 3-5 micrometers, accounting for inorganic 15% of the total content of calcium carbonate.
- 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 at 80 ° C for 30 seconds to form a film having a film thickness of 15 to 20 ⁇ m, and then the film-forming transition layer A4 was formed. Calendering is carried out at 120 °C, line pressure 150KN/m, and vehicle speed lOm/min. After calendering, the micro-cavities in the transition layer are reduced, and the film layer becomes smoother, resulting in a denser and smoother surface.
- the state is more conducive to the laying of the release layer thereon, and the smooth surface of the transition layer allows the surface of the final release layer to have a mirror surface smoothness, which ensures the surface state and gloss of the final leather product.
- the arrangement of the transition layer ensures that the release paper has anti-permeability and smooth surface as a whole, wherein the silicone-acrylic emulsion is cured by heating, can form a dense film, can effectively block the penetration of the solvent on the paper base, and the silicon-acrylic
- the film formed by the 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 release layer surface and the overall release paper.
- the smoothness of the surface condition of the release paper is very beneficial to improve the smooth gloss of the entire leather product based on the release paper.
- 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 to 0.
- 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 90 ° C, and after adding for 2 hours, adding 1-2 parts by weight. 2, 2 '-methylene-bis-(4,6-di-tert-butylphenoxy) sodium phosphate and 0. 1-0.
- the release paper used in the present invention is prepared by the above method, and the release paper is tested to be very suitable for coating the hot melt adhesive and the TPU film layer of the present invention, preferably the release paper of the present invention.
- the thickness is 80-100 microns, but it is not limited to this, and can be adjusted according to actual needs.
- the components of the hot melt adhesive extruded on the release paper described above include:
- polyester polyol 5-1 ⁇ 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, 2-4 parts by weight of a flame retardant, and 2-4 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 to prepare a hydroxyl terminated 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-tributylbutyl-4-methylphenol or tetra ⁇ -(3,5-tri-butyl-4-hydroxyphenyl)propanoate ⁇ pentaerythritol ester;
- the tackifying resin is selected from one or more of a polyethylene-vinyl acetate copolymer, a hydroxyl terminated thermoplastic polyester, and a hydrogenated rosin resin; and the specific composition of the flame retardant is 30-70% by mass. 0. 5-15. 0 g/10min of polypropylene, 5-25% of the melt index of 0.01-2.
- Og/lOmin of polyethylene 20-30% of at least one inorganic filler selected from the group consisting of powdered talc, kaolinite, sericite, silica and diatomaceous earth, 5 -15% of an organic flame retardant halide selected from the group consisting of decabromodiphenyl ether, dodecachlorododecyl benzoxacyclooctene or a mixture thereof.
- the toughening agent selects a polyolefin toughening agent, wherein the PE (polyethylene) elastomer, the linear polyethylene, the polypropylene (PP) and the anti-aging agent raw materials are mixed and extruded, and the mass percentage of each raw material It is: PE (polyethylene) elastomer 31%, linear polyethylene 19%, polypropylene (PP) 49%, anti-aging agent 1%.
- the TPU raw material composition for forming a TPU film in the present invention is:
- a polymer polyol which is one of polytetrahydrofuran ether glycol having a molecular weight of 1000 and 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 resistance agent; 1-3 parts by weight of a flame retardant, and the flame retardant is an organic halide flame retardant of decabromodiphenylethane mixed micro-fumed silica
- the average particle size is less than or equal to 4 microns; 1-2 parts by weight of the anti-wear agent, the anti-wear agent is composed of an aromatic silicone oil; 0.2-0.8 parts by weight of an antioxidant, the antioxidant is ⁇ _ (4 - Hydroxy-3,
- thermoplastic polyurethane elastomer TPU for forming a film from the above raw materials is as follows: (1) First, the above parts by weight of the polymer polyol is placed in a reaction vessel, and heated to 80-90 ° C, and then added to the above parts by weight of an antioxidant, a hindered amine light stabilizer, benzotriazole A UV-like absorbent, a lubricant and a hydrolysis-resistant agent are sufficiently stirred to obtain a polymer polyol mixed solution.
- reaction melt temperature reaches between 180 and 2 KTC
- the above-mentioned parts by weight of the flame retardant, the anti-wear agent, the matte agent and the antistatic agent are added, and the reaction is dehydrated, dried and matured after a predetermined reaction time to obtain thermoplasticity.
- 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 prepared thermoplastic polyurethane elastomer raw material is again sent to an extruder to extrude the TPU film, and is bonded to the rolled hot melt adhesive film by the above method to obtain the jointless heat according to the present invention. Melt leather.
- Bonding strength 2. 5Kg / 25 mm.
- the seamless-melting hot-melt adhesive TPU leather prepared by the invention is prepared by adopting an innovative formula and preparing a release paper, a hot melt adhesive and a TPU film, in particular, a special formula of a polyurethane hot melt adhesive and a TPU film, so that The final tensile strength, tear strength, abrasion strength, bond strength, surface gloss and other properties of the leather products have been greatly improved, even at high temperatures of 190 degrees. In the case of no change in quality, it can be widely used in the manufacturing industries such as clothing, footwear, handbags, bags, seats, building decoration. Moreover, the "new type of seam-free hot-melt adhesive TPU leather" described in the present invention combined with the long-term innovation practice has not been reported in the literature at home and abroad, and is the world's first.
- the seam-free hot melt adhesive TPU leather of the present invention is prepared in the following manner.
- the paper base layer Al is selected, and an aqueous polypropylene (PP) bonding layer A2 having a thickness of 2.5 ⁇ m is coated on the paper substrate A1, and then a polyethylene pair having a thickness of 20 ⁇ m is pasted on the bonding layer A2.
- the ethylene phthalate film A3 is cured for a certain period of time.
- a transition layer coating was prepared in accordance with 65 parts by weight of the inorganic particles, 35 parts by weight of the silicone-acrylic emulsion, 4 parts by weight of the fatty acid methyl ester sulfonate, 3 parts by weight of lauryl dimethyl benzyl ammonium chloride, and 50 parts by weight of water.
- the coating layer has a thickness of 25 ⁇ m
- the composition of the release layer comprises: 60 parts by weight of polypropylene, 30 parts by weight of poly 4-methyl-1-pentene, and 8 parts by weight of vinyl silicone oil.
- R1 and R3 are -CH 3
- m about 2,500
- n 4.
- 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 180-240 ° C, wherein The aliphatic 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 and 1, 3-butanediol, 1,5 pentanediol or dodecyl hexanediol.
- the diisocyanate is 4, 4'-diphenylmethane diisocyanate;
- the polyether polyol is polytetrahydrofuran ether glycol;
- the catalyst is selected to be dimorpholinyl diethyl ether; 6-hexanediol;
- the antioxidant is selected from tetra ⁇ -(3,5-tri-butyl-4-hydroxyphenyl)propionic acid ⁇ pentaerythritol ester;
- the tackifying resin is selected to be a hydrogenated rosin resin;
- the flame retardant consists of: 50% by weight of polypropylene with a melt index of 5 g/lOmin, 20% by weight of polyethylene with a melt index of 0.8 g/10 min, 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 dodecachloro
- the toughening agent selects a polyolefin toughening agent, which is prepared by mixing PE (polyethylene) elastomer, linear polyethylene, polypropylene (PP) and anti-aging agent raw materials: PE (polyethylene) elasticity 31% of body, 19% of linear polyethylene, 49% of polypropylene (PP), and 1% of anti-aging agent.
- reaction melt temperature reaches 200, 2 parts by weight of decabromodiphenylethane mixed with micro-fumed silica organic halide flame retardant, 1.5 parts by weight of aromatic silicone oil
- An anti-static agent 2 parts by weight of a matting agent composed of a calcium filler, and 0.8 parts by weight of an antistatic agent composed of conductive carbon black, which are dehydrated, dried and matured after a predetermined reaction, thereby obtaining a thermoplastic polyurethane elastomer. raw material.
- the prepared hot melt adhesive raw material is processed into a rubber compound through an extruder, and the rubber material is fed into an extruder melted at a temperature of up to 150 degrees. Pasting into a paste, and then extruding from the extruder die, casting onto the release paper, and then pressing and cooling the pressure roller to form a hot melt adhesive film as shown in FIG. 1;
- the prepared TPU raw material is also extruded into a TPU film, and the hot melt adhesive film which is wound in the step (2) is placed on two feeding racks respectively, so that the hot melt adhesive film and the TPU film enter simultaneously.
- the temperature is set to be constant in the pressure roller, and the temperature of the pressure roller is above 160, so that the hot melt adhesive with low melting point is bonded to the TPU film instantaneously when the pressure is pressed against the pressure roller, and then cooled and formed.
- the seamless hot melt adhesive leather of the present invention is as shown in FIG.
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Abstract
本发明提出一种新型的免车缝的热熔胶TPU皮革及其制备方法,热熔胶TPU皮革包括离型纸、热熔胶膜和TPU膜,离型纸包括纸底层、粘结层、塑料层、过渡层和离型层,热熔胶原料由聚酯多元醇、二异氰酸酯、聚醚多元醇和若干添加剂组成,TPU原料由聚合物多元醇、 1,4—环己烷二异氰酸酯、扩链剂以及若干功能助剂组成;本发明通过对离型纸、热熔胶粘合剂和TPU薄膜从原料组份上进行创新,利用可塑性强的热熔胶粘合剂与TPU薄膜进行挤压成型,所制得的免车缝TPU皮革具有粘贴牢固、持久耐用、材质环保、对人体无任何隐形伤害等技术优势。
Description
说 明 书 一种免车缝的热熔胶 TPU皮革及其制备方法
技术领域
本发明涉及皮革材料技术领域, 更具体的涉及一种免车缝的热熔胶 TPU皮革及其制备方法。 背景技术
现有技术中, 在中外的制衣、 制鞋、 箱包、 手袋、 座椅、 军工等产品生产行业, 所有制品贴 附的面料, 都是采用传统的针缝方式来驳接完成。 这种生产方式, 不仅劳动强度大、 生产成 本高, 更由于产品受外力作用线缝处容易断裂、 撕口和脱皮等问题, 严重影响产品的使用寿 命和质量, 消费成本也明显增大。还因为目前所有的产品面料大多采用的是 PVC皮革, 而 PVC 材料本身含有聚氯乙烯和乙基己基胺等有毒原素, 对人体有致癌作用, 使用极不安全, 而且 现有技术中在皮革贴服中所用到的多半都是工业用的液体胶水、 固体胶以及 PU胶, 这些熔胶 材料具有多半都具有毒性, 而且在弹性、 耐酸、 耐碱、 耐水洗、 耐干洗、 抗张力、 接着力等 性能方面具有一定缺陷, 并是不理想的环保粘合材料。
发明内容
本发明基于上述技术问题, 提出一种新型的免车缝的热熔胶 TPU皮革及其制备方法, 通过对 热熔胶粘合剂和 TPU薄膜从原料组份上进行创新, 结合本公司长期的生产实践经验, 采用这 种创新研发出来可塑性强的热熔胶粘合剂与 TPU薄膜进行挤压成型, 最终形成本发明所述的 免车缝 TPU皮革, 可直接贴合在各种物品上, 并具有粘贴牢固、 持久耐用、 材质环保、 对人 体无任何隐形伤害等技术优势, 从根本上解决了车缝驳接以及现有工业胶在皮革产品应用中 带来的各种不良因素。
本发明解决上述技术问题的技术方案如下:
一种免车缝的热熔胶 TPU皮革, 包括离型纸、 涂覆于离型纸上的热熔胶膜和粘贴于热熔胶上 的 TPU膜;
其中所述离型纸包括纸底层 Al、 粘结层 A2、 塑料层 A3、 过渡层 A4和离型层 A5, 所述塑料层 A3通过粘结层 A2粘接于所述纸底层 Al l, 所述过渡层 A4设置于所述塑料层 A3, 所述离型 层 A5设置于所述过渡层 A4,所述粘结层 A2为水性聚丙烯涂布层,使用量为每平方米 5-8克, 厚度为 0. 8-4微米, 所述塑料层 A3为厚度在 18-25微米间的聚对苯二甲酸乙二醇酯膜, 所述 过渡层 A4由 62-68重量份的无机粒子、 32-36重量份的硅丙乳液、 3_5重量份的脂肪酸甲酯 磺酸钠、 2-4重量份的十二烷基二甲基苄基氯化铵和 45-55重量份的水混合搅拌制备而成, 且成膜厚度在 15-20微米, 所述离型层 A5的厚度为 20-25微米且由 58_65重量份的聚丙烯、 26-34重量份的聚 4-甲基 -1-戊烯、 6-9重量份的乙烯基硅油、 1_2重量份的 2, 2 ' -亚甲基-
双 -4, 6二叔丁基苯氧基磷酸钠和 0. 1-0. 8重量份的叔丁基过氧化苯甲酸酯制备而成; 其中所述热熔胶由 60-70重量份的聚酯多元醇、 15-20重量份的二异氰酸酯、 3-5重量份的聚 醚多元醇、 0. 8-1. 5重量份的催化剂、 0. 5-1. 2重量份的扩链剂、 1. 5-1. 8重量份抗氧化剂、 4-6重量份的增粘树脂、 2-4重量份的阻燃剂、 2-4重量份的增韧剂制备而成, 所述的聚酯多 元醇通过低分子量脂肪族二元醇与脂肪族二元羧酸、 芳香族二元羧酸在 100-26(TC下缩聚反 应而制备成分子量为 2000-6000的端羟基聚酯二醇, 所述脂肪族二元羧酸选自己二酸、 富马 酸、 马来酸或辛二酸, 所述芳香族二元羧酸选自邻苯二甲酸、 对苯二甲酸或间苯二甲酸, 所 述脂肪族二元醇选自乙二醇、 二甘醇、 丙二醇、 甲基丙二醇、 1, 4- 丁二醇、 1, 6- 己二醇、 1, 3- 丁二醇、 1, 5 戊二醇或十二烷基己二醇; 所述二异氰酸酯采用 4, 4 ' -二苯基甲烷二 异氰酸酯或 1, 6- 六亚甲基二异氰酸酯; 所述聚醚多元醇选自聚四氢呋喃醚二醇或氧化丙烯 共聚二醇; 所述催化剂选择二月桂酸二丁基锡、 三乙醇胺或双吗啉基二乙基醚中的一种或几 种; 所述扩链剂选择 1, 6-己二醇、 甲基丙二醇、 1, 4- 丁二醇中的一种; 所述抗氧化剂选 择 2, 6-三级丁基 -4-甲基苯酚或四 { β - (3, 5- 三级丁基 -4- 羟基苯基) 丙酸 }季戊四醇酯; 所述增粘树脂选自聚乙烯 -醋酸乙烯共聚物、端羟基热塑性聚酯、氢化松香树脂的一种或几种; 所述阻燃剂的具体组成为: 30-70重量%的熔融指数 0. 5-15. 0 g/10min的聚丙烯、 5_25 重量% 的熔融指数 0. 01-2. 0 g/10min的聚乙烯、 20_30 重量%的选自粉末状滑石、 高岭石、 绢云母、 二氧化硅以及硅藻土中的至少一种无机填料、 5-15 重量%选自十溴二苯基醚、 十二氯十二氢 二甲桥苯唑环辛烯及其混合物的有机阻燃卤化物; 所述增韧剂由聚乙烯弹性体、线型聚乙烯、 聚丙烯和防老化剂原料混合挤出而成;
其中制备所述 TPU膜的 TPU原料的组成为: 60-70重量份的聚合物多元醇,选自分子量为 1000 的聚四氢呋喃醚二醇、 分子量为 3000 的聚己二酸乙二醇丁二醇酯多元醇中的一种或多种; 30-35重量份的 1, 4- 环己烷二异氰酸酯; 4-9重量份的扩链剂, 所述扩链剂为 1, 4- 丁二醇; 3-5重量份的碳化二亚胺类耐水解剂; 1-3重量份的、平均粒度小于或等于 4微米的十溴二苯 基乙烷混合微量煅制二氧化硅的有机卤化物阻燃剂; 1-2重量份的芳香族硅油耐磨剂 ; 0. 2-0. 8 重量份的抗氧剂,所述抗氧剂为 β _ ( 4- 羟基 -3, 5- 二叔丁基苯基)丙酸正十八碳醇酯、四 [ β - ( 3, 5- 二叔丁基 -4- 羟基苯基)丙酸] 季戊四醇酯和二 [ ( 2, 4- 二叔丁基苯基)亚磷酸] 季 戊四醇酯中的至少一种; 0. 1-0. 5重量份的二 (2, 2, 6, 6- 四甲基 -4- 哌啶基) 葵二酸酯受阻 胺类光稳定剂; 0. 2-0. 6重量份的苯并三唑类紫外线吸收剂; 0. 4-0. 8重量份的蒙旦蜡和 / 或 芥酸酰胺蜡类润滑剂; 1-3重量份的由钙类填充剂组成的雾面剂; 0. 5-1. 2重量份的由金属粉 末或导电炭黑组成的防静电剂; 0. 05-0. 2重量份的钛系或铋系催化剂。
进一步的根据本发明所述的热熔胶 TPU皮革, 其中所述离型纸的过渡层中的无机粒子的组成 包括粒径为 0. 5-0. 8微米且占无机粒子总含量 25%的粘土、 粒径在 1-2微米且占无机粒子总 含量的 60%的硫酸钡粉末和粒径在 3-5微米且占无机粒子总含量的 15%的碳酸钙;其中所述离
进一步的根据本发明所述的热熔胶 TPU皮革, 其中所述粘结层 A2的厚度为 2. 5微米, 所述塑 料层 A3的厚度为 20微米, 所述过渡层 A4厚度的为 15微米, 所述离型层 A5的厚度为 25微 米, 所述过渡层的制备原料为无机粒子 65重量份、 硅丙乳液 35重量份、 脂肪酸甲酯磺酸钠 4重量份、十二烷基二甲基苄基氯化铵重量 3份和水 50重量份; 所述离型层的制备原料为 60 重量份的聚丙烯、 30重量份的聚 4-甲基 -1-戊烯、 8重量份的乙烯基硅油、 1. 5重量份的 2, 2 ' -亚甲基 -双- (4, 6二叔丁基苯氧基) 磷酸钠和 0. 5重量份的叔丁基过氧化苯甲酸酯, 所述乙
-CH = CH2, m=2500, n=4。
进一步的根据本发明所述的热熔胶 TPU皮革, 其中所述热熔胶的制备原料组成为: 65重量份 的聚酯多元醇、 18重量份的二异氰酸酯、 4重量份的聚醚多元醇、 1重量份的催化剂、 1重量 份的扩链剂、 1. 6重量份抗氧化剂、 5重量份的增粘树脂、 3重量份的阻燃剂、 3重量份的增 韧剂;所述增韧剂按重量计由 31 %的聚乙烯弹性体、 19 %的线型聚乙烯、 49 %的聚丙烯和 1 % 的防老化剂原料混合挤出而成; 所述阻燃剂由 50重量%的熔融指数 5克 /10 分钟的聚丙烯、 20 重量%的熔融指数 0. 8克 /10分钟的聚乙烯、 20重量%的粉末状滑石和高岭石混合的无机填 料、 10重量%的十溴二苯基醚和十二氯十二氢二甲桥苯唑环辛烯混合的有机阻燃卤化物组成。 进一步的根据本发明所述的热熔胶 TPU皮革,其中所述 TPU原料的组成为 65重量份的分子量 为 3000 的聚己二酸乙二醇丁二醇酯多元醇、0. 6重量份的 β - ( 4- 羟基 -3, 5- 二叔丁基苯基) 丙酸正十八碳醇酯抗氧剂、 0. 3重量份的二 (2, 2, 6, 6- 四甲基 -4- 哌啶基) 葵二酸酯光稳定 剂、 0. 4重量份的苯并三唑类紫外线吸收剂、 0. 6重量份的芥酸酰胺蜡类润滑剂、 4重量份的
碳化二亚胺类耐水解剂、 32重量份的、 温度在 60°C的 1, 4- 环己烷二异氰酸酯、 6重量份的 1, 4- 丁二醇扩链剂、 0. 1重量份的铋系催化剂、 2重量份的十溴二苯基乙烷混合微量煅制二 氧化硅的有机卤化物阻燃剂、 1. 5重量份的由芳香族硅油组成的耐磨剂、 2重量份的由钙类填 充剂组成的雾面剂和 0. 8重量份的由导电炭黑组成的防静电剂。
进一步的根据本发明所述的热熔胶 TPU 皮革, 其中所述热熔胶 TPU 皮革的拉伸强度为横向 28. 2Kgf、 纵向 25. 3 Kgf ; 所述热熔胶 TPU皮革的撕裂强度为经向 5. OKgf、 纬向 4. 7Kgf ; 所 述热熔胶 TPU皮革的粘接强度大于等于 2. 5Kg / 25皿; 所述热熔胶 TPU皮革的伸长率大于等 于 700%; 所述热熔胶 TPU皮革的邵尔硬度大于等于 95。
一种免车缝的热熔胶 TPU皮革的制备方法, 所述方法包括以下步骤:
(一) 制备离型纸
( 1 )、选择纸底层 Al, 并在所述纸底层 A1上涂布厚度为 0. 8-4微米的水性聚丙烯粘结层 A2, 然后在所述粘结层 A2上粘贴厚度为 18-25微米的由聚对苯二甲酸乙二醇酯膜形成的塑料层 A3, 然后固化一定时间;
( 2 )、将 3-5重量份的脂肪酸甲酯磺酸钠倒入 45-55重量份的水中,搅拌均匀,然后倒入 62_68 重量份且由粘土、硫酸钡粉末和碳酸钙粉末混合制成的无机粒子, 并高速搅拌将其分散均匀, 接着在分散好的浆料里加入 32-36重量份的硅丙乳液, 用玻璃棒将溶液混合均匀后将 2-4重 量份的十二烷基二甲基苄基氯化铵添加在其中, 继续搅拌均匀, 制成过渡层涂布液;
( 3 )、在塑料层 A3上使用刮刀均匀涂布所述过渡层涂布液,并于 80°C下加热 30秒固化成膜, 控制膜厚在 15-20微米,然后将成膜后的过渡层 A4在 120°C、线压力 150KN/m、车速 10m/min 的条件下进行压光处理;
( 4)、将 58-65重量份的聚丙烯、 26-34重量份的聚 4-甲基 -1-戊烯和 6_9重量份的乙烯基硅 油混合均匀后加热至 90°C, 保温 2小时后加入 1-2重量份的 2, 2 ' -亚甲基 -双- ( 4, 6二叔丁 基苯氧基) 磷酸钠和 0. 1-0. 8重量份的叔丁基过氧化苯甲酸酯并混合均匀, 然后通过挤出机 挤出涂覆于所述过渡层 A4的表面形成离型层 A5, 控制厚度在 20-25微米;
(二)、 制备热熔胶原料
( 1 )、 将 60-70重量份的聚酯多元醇、 3-5重量份的聚醚多元醇、 L 5-1. 8重量份的抗氧化剂 和 4-6重量份的增粘树脂置于反应釜中, 加热至 120〜140°C, 在搅拌混合下真空脱水 1. 5〜 2h, 真空度小于 0. 05MPa, 然后降温至 70〜75°C ; 其中所述聚酯多元醇为通过低分子量脂肪 族二元醇与脂肪族二元羧酸、 芳香族二元羧酸在 100-260 °C下缩聚反应而制备成分子量为 2000-6000 的端羟基聚酯二醇, 所述聚醚多元醇选自聚四氢呋喃醚二醇、 氧化丙烯共聚二醇
中的一种, 所述抗氧化剂选自 2, 6-三级丁基 -4-甲基苯酚或四 {β -(3, 5- 三级丁基 -4- 羟 基苯基) 丙酸 }季戊四醇酯, 所述增粘树脂选自聚乙烯 -醋酸乙烯共聚物、端羟基热塑性聚酯、 氢化松香树脂的一种或几种;
(2)、 在氮气保护下, 将 15-20重量份的二异氰酸酯和 0.8-1.5重量份的催化剂加入到步骤 (1) 的反应产物中, 并在 85〜95°C反应 1-L5h; 其中所述二异氰酸酯采用 4, 4' -二苯基甲 烷二异氰酸酯或 1,6- 六亚甲基二异氰酸酯中的一种, 所述催化剂选择二月桂酸二丁基锡、 三乙醇胺或双吗啉基二乙基醚中的一种或几种;
(3)、 在氮气保护下, 将 0.5-1.2重量份的扩链剂、 2-4重量份的阻燃剂、 2-4重量份的增韧 剂加入到步骤 (2) 的反应产物中, 并在 75〜85°C搅拌反应 45min-L Oh; 其中所述扩链剂选 择 1, 6- 己二醇、 甲基丙二醇、 1, 4- 丁二醇中的一种, 所述阻燃剂由聚丙烯、 聚乙烯、 无 机填料和有机阻燃卤化物组成; 所述增韧剂选择聚烯烃增韧剂;
(4)、 在通入氮气保护条件下出料, 熟化冷却后形成为热熔胶原料;
(三)、 制备 TPU原料
(1)、 将 60-70重量份的聚合物多元醇置于反应釜中, 并加热至 80_90°C, 所述聚合物多元 醇为分子量为 1000 的聚四氢呋喃醚二醇和 /或分子量为 3000 的聚己二酸乙二醇丁二醇酯多 元醇, 然后加入 0.2-0.8重量份的抗氧剂、 0.1- 0.5重量份的二 (2,2,6,6- 四甲基 _4_ 哌 啶基)葵二酸酯受阻胺类光稳定剂、 0.2-0.6重量份的苯并三唑类紫外线吸收剂、 0.4-0.8重 量份的蒙旦蜡和 / 或芥酸酰胺蜡类润滑剂和 3-5重量份的碳化二亚胺类耐水解剂, 充分搅拌 后得到聚合物多元醇混合溶液, 其中所述抗氧剂为 β_ (4- 羟基 -3, 5- 二叔丁基苯基) 丙酸 正十八碳醇酯、 四 [β_ (3,5- 二叔丁基 -4-羟基苯基)丙酸] 季戊四醇酯和二[ (2,4- 二叔 丁基苯基) 亚磷酸] 季戊四醇酯中的至少一种;
(2) 向所述聚合物多元醇混合溶液中加入 30-35重量份的、 温度在 55-65 的 1,4- 环己烷二 异氰酸酯, 搅拌混合后得到初步反应混合物;
(3) 保持上述反应混合物的温度并加入 4-9重量份的 1, 4- 丁二醇扩链剂和 0.05-0.2重量 份的钛系或铋系催化剂, 并控制温度在 150-210°C、 压力 4-8MPa反应 lh左右;
(4) 当反应熔体温度达到 180-210°C间时, 加入 1-3重量份的且平均粒度小于或等于 4微米 的由十溴二苯基乙烷混合微量煅制二氧化硅的有机卤化物阻燃剂、 1-2 重量份的由芳香族硅 油组成的耐磨剂、 1-3重量份的由钙类填充剂组成的雾面剂和 0.5-1.2重量份的由金属粉末 或导电炭黑组成的防静电剂, 反应预定时间后进行脱水、 干燥和熟化, 得到热塑性聚氨酯弹 性体原料;
(四)、 贴合制备免车缝热熔胶 TPU皮革
( 1 )、 准备通过上述步骤制备的离型纸、 热熔胶原料和 TPU原料, 并将离型纸置于相关设备 中铺平;
( 2 )、 将步骤 (二) 制备的热熔胶原料经挤出机处理成胶料, 胶料送入 150度温度的挤出机 熔融成糊状, 再由挤出机模头挤出后流延到所述离形纸上, 然后经对压轮对压一冷却一卷取, 形成热熔胶膜;
( 3 )、 将步骤 (三) 所制备的 TPU原料挤出成 TPU膜, 并与上述热熔胶膜分别置于两个送料 架上, 使热熔胶膜和 TPU膜同时进入设置有恒温的高低对压轮中进行对压, 对压轮的温度在 160 以上, 从而使熔点低的热熔胶在高低对压轮对压时瞬间与 TPU膜粘合为一体, 然后冷却 成型为所述无车缝的热熔胶 TPU皮革。
进一步的根据本发明所述的制备方法, 其中制备离型纸的步骤 (一) 中: 所述过渡层的制备 原料为无机粒子 65重量份、 硅丙乳液 35重量份、 脂肪酸甲酯磺酸钠 4重量份、 十二烷基二 甲基苄基氯化铵重量 3份和水 50重量份, 所述无机粒子的具体组成为: 粘土粒径为 0. 5-0. 8 微米且含量为 25%、硫酸钡粉末粒径在 1-2微米且含量为 60%、碳酸钙粉末粒径在 3-5微米且 含量为 15%; 所述离型层的制备原料为 60重量份的聚丙烯、 30重量份的聚 4-甲基 -1-戊烯、 8重量份的乙烯基硅油、 L 5重量份的 2, 2 ' -亚甲基 -双- ( 4, 6二叔丁基苯氧基) 磷酸钠和 , 所述 乙 烯基硅 油 的 结 构 式
进一步的根据本发明所述的制备方法, 其中步骤 (二) 中制备聚酯多元醇的脂肪族二元羧酸 选自己二酸、 富马酸、 马来酸或辛二酸, 芳香族二元羧酸选自邻苯二甲酸、 对苯二甲酸或间 苯二甲酸, 脂肪族二元醇选自乙二醇、 二甘醇、 丙二醇、 甲基丙二醇、 1, 4- 丁二醇、 1, 6- 己二醇、 1, 3- 丁二醇、 1, 5 戊二醇或十二烷基己二醇; 所述阻燃剂的具体组成为: 30-70 重量%的熔融指数 0. 5-15. 0 克 /10 分钟的聚丙烯、 5-25 重量%的熔融指数 0. 01-2. 0 克 /10 分钟的聚乙烯、 20-30 重量%的选自粉末状滑石、 高岭石、 绢云母、 二氧化硅以及硅藻土中的 至少一种无机填料、 5-15 重量 %选自十溴二苯基醚、 十二氯十二氢二甲桥苯唑环辛烯及其混 合物的有机阻燃卤化物; 所述增韧剂由聚乙烯弹性体、 线型聚乙烯、 聚丙烯 PP和防老化剂原 料混合后挤出而成, 各原料所占质量百分数为: 聚乙烯弹性体 31 %、 线型聚乙烯 19 %、 聚丙
烯 49 %、 防老化剂 1 %。
进一步的根据本发明所述的制备方法, 其中所述步骤(三) 中 TPU原料的组成为 65重量份的 分子量为 3000 的聚己二酸乙二醇丁二醇酯多元醇、 0. 6重量份的 β - ( 4- 羟基 -3, 5- 二叔丁 基苯基) 丙酸正十八碳醇酯抗氧剂、 0. 3重量份的二 (2, 2, 6, 6- 四甲基 -4- 哌啶基) 葵二酸 酯光稳定剂、 0. 4重量份的苯并三唑类紫外线吸收剂、 0. 6重量份的芥酸酰胺蜡类润滑剂、 4 重量份的碳化二亚胺类耐水解剂、 32重量份且温度在 60°C的 1, 4- 环己烷二异氰酸酯、 6重 量份的 1, 4- 丁二醇扩链剂、 0. 1重量份的铋系催化剂、 2重量份的十溴二苯基乙烷混合微量 煅制二氧化硅的有机卤化物阻燃剂、 1. 5重量份的由芳香族硅油组成的耐磨剂、 2重量份的由 钙类填充剂组成的雾面剂和 0. 8重量份的由导电炭黑组成的防静电剂。
本发明的主要技术特点和技术效果在于:
( 1 )采用了创新设计的多层结构离型纸, 尤其是其中多功能层和离型层的创新设计, 使得本 发明所提供的离型纸应用于皮革制品中具有异常优异的理化性能, 且与热熔胶之间的粘结强 度高、 固化时间快, 属于高品质皮革中的理想基材。
( 2 )采用了独创的低熔点热熔胶, 它是一种可塑性强的粘合剂, 可取代工业用的液体胶水和 固体胶及 PU胶, 具有环保、 无毒无副作用等优点, 作为理想的环保粘合材料, 本发明的热熔 胶具有低熔点、 弹力高、 耐酸、 耐碱、 耐水洗、 耐干洗、 抗张力强、 接着力强、 融点低等性 能。
( 3 )所采用的 TPU薄膜通过原料上的创新改进, 克服了现有 TPU的诸多缺陷, 不但拥有橡胶 及普通塑料的大部分特性, 而且还拥有优良的综合物理及化学性能, 可作为完全代替 PVC、 PU人造革及其它皮革面料。
( 4)本发明所提供的免车缝的热熔胶 TPU皮革, 在高温 190度的情况下都不会发生质变, 非 常容易与布料、 橡 (塑) 胶皮料、 木质等材料表面粘合, 可广泛应用在制衣、 鞋类、 手袋、 箱包、 座椅、 建筑装饰等生产制造行业, 而且贴合后的产品耐水洗、 干洗, 产品具有耐磨、 耐热、 耐曲折的性能, 本发明所采用的热熔胶及 TPU原料所含原素, 经 SGS检测, 具有生物 医学性能, 无毒、 无味、 无过敏反应, 产品极其环保、 无污染作用, 是二十一世纪极具理想 的环保贴合面料之一。
附图说明
附图 1为将本发明所述热熔胶挤出至离型纸上形成热熔胶膜的示意图;
附图 2为将附图 1所示热熔胶膜与 TPU膜压合成本发明所述免车缝的热熔胶 TPU皮革的示意 图;
附图 3为应用于本发明中的离型纸的结构示意图;
图中 A1-纸底层、 A2-粘结层、 A3-塑料层、 A4-过渡层、 A5-离型层。
具体实肺式
以下对本发明的技术方案进行详细的描述, 以使本领域技术人员能够更加清楚的理解本发明 的方案, 但并不因此限制本发明的保护范围。 这里需要首先说明的是: 本发明中多数原料物 质的组成成份以 "重量份"计量配比, 这种 "重量份"仅表示每种物质自身内的组份配比量 关系(同质量百分比), 并不代表实际的使用质量, 也就是说不同物质的某些组份可能具有相 同或相近的重量份, 但并不意味着这些组份在各物质中具有相同或相近的质量含量。
首先对本发明所述免车缝的热熔胶 TPU皮革的成型产品及其制备方法进行描述。 本发明所述 免车缝的热熔胶 TPU皮革包括离型纸、 热熔胶膜和 TPU膜, 所述免车缝的热熔胶 TPU皮革的 制备采取双面贴合的方法, 具体包括以下步骤:
步骤一、 制备离型纸、 热熔胶原料和 TPU原料, 这些原料属于本公司独创的, 也是本发明的 主要发明点之一, 在后面会详细的给出其原料配方和制备方法。
步骤二、 将所制备的热熔胶原材料经挤出机并被处理成胶料, 胶料送入高达 150度温度的挤 出机熔融成糊状, 再由挤出机模头挤出后流延到起隔离作用的离形纸上, 然后经对压轮对压 一冷却一卷取, 形成无车缝热熔胶膜, 如附图 1所示;
步骤三、 将所制备的 TPU原料挤出成 TPU膜, 并将成卷的热熔胶膜和 TPU膜分别置于两个送 料架上, 使热熔胶膜和 TPU膜同时进入设置有恒温的高低对压轮中进行对压。 由于对压轮的 温度高达 160 以上, 使熔点低的热熔胶在高低对压轮对压时瞬间与 TPU粘合为一体, 经冷 却后成型为一种无车缝热熔胶皮革新材料, 如附图 2所示。
本发明的的关健技术包括: 高粘性热熔胶的配方、 TPU 薄膜的关键配方以及其中各种功能外 加剂 (母粒) 的选择和作为基材的离型纸的制备。 由于 TPU (热塑性聚氨酯弹性体 Thermoplastic polyurethane ) 禾口 PU ( Polyurethane , 聚氨基甲酸酉旨, 也称: 聚氨酯), 属 于环保材料, 而且由于 PU原料只需要简单修改配方, 便可获得不同的密度、 弹性、 刚性等物 理性能, 属于很好的装饰配方材料, 本发明结合长期的生产实践并经过大量的试验, 创新的 提出一种新型的聚氨酯热熔胶和 TPU材料, 通过改变配方组份和添加剂, 结合数学模型和实 践验证, 利用多组实验数据采集从而确定各组分之间的影响因子, 并通过理论计算出最佳配 比, 并将最后的配方应用于试验, 验证后所得到的本发明的产品具有更好的粘接性、 抗撕裂 性、 耐磨性、 耐高温性等多重物理性能。
应用于本发明的离型纸的组成及制备如下:
如附图 3所示, 本发明所提供的离型纸具有多层结构, 具体包括纸底层 Al, 在所述纸底层 A1 上通过粘结层 A2粘接有塑料层 A3, 在所述塑料层 A3上设置有过渡层 A4, 在所述过渡层 A4 上设置有离型层 A5。 具体所述的塑料层 A3为聚对苯二甲酸乙二醇酯膜(即 PET膜), 厚度为 18-25微米, 优选 20微米。 所述粘结层 A2粘接所述纸底层 A1和所述聚对苯二甲酸乙二醇酯 膜 A3, 所述粘结层 A2为水性聚丙烯 (PP)涂布层, 使用量为每平方米 5-8克, 厚度为 0. 8_4 微米, 优选每平方米 6克, 厚度为 1-2. 5微米。 所述的过渡层 A4组成包括无机粒子、 硅丙乳 液、 脂肪酸甲酯磺酸钠、 十二烷基二甲基苄基氯化铵和水, 各组分的重量份数为: 无机粒子 62-68份, 硅丙乳液 32-36份, 脂肪酸甲酯磺酸钠 3_5份, 十二烷基二甲基苄基氯化铵 2_4 份, 水 45-55份; 其中无机粒子的组成包括粒径为 0. 5-0. 8微米、 占无机粒子总含量 25%的 粘土, 粒径在 1-2微米、 占无机粒子总含量的 60%的硫酸钡粉末和粒径在 3-5微米、 占无机 粒子总含量的 15%的碳酸钙。 所述过渡层 A4的制备过程为上述重量份的脂肪酸甲酯磺酸钠倒 入上述重量份的水中, 搅拌均匀, 将无机粒子所包括的粘土、 硫酸钡粉末和碳酸钙混合均匀 后按照上述重量份倒入上述搅拌溶液中, 使用高速搅拌将其分散均匀, 在分散好的浆料里加 入上述重量份的硅丙乳液, 用玻璃棒将溶液混合均匀, 再将上述重量份的十二烷基二甲基苄 基氯化铵添加在其中, 继续搅拌均匀, 制成过渡层涂布液。然后在所述塑料层 A3上使用刮刀 均匀涂布所述过渡层涂布液, 并于 80°C下加热 30秒固化成膜, 膜厚 15-20微米, 然后将成 膜后的过渡层 A4在 120°C, 线压力 150KN/m, 车速 lOm/min条件下进行压光处理, 压光处理 后减少了过渡层中的微小空穴, 使膜层变得更加光滑, 得到更加致密平滑的表面状态, 更加 有利于其上离型层的铺设, 而且过渡层平整的表面使得最终离型层表面具有镜面平整度, 保 证了最终皮革产品的表面状态和光泽度。 所述过渡层的设置保证了离型纸整体具有防渗透性 能和表面的平滑, 其中的硅丙乳液经过加热固化, 能形成致密的薄膜, 能够有效阻隔溶剂对 纸基的渗透作用, 而且硅丙乳液形成的薄膜还具有很好的耐溶剂性, 将溶剂施加其上不会出 现溶解破坏薄膜以及其他基材的情况, 而且经过过渡层的有效的掩盖了纸底层 A1 和塑料层 A3表面的粗糙状态, 保证了离型层表面以及离型纸整体的平滑性, 这种离型纸表面状态的平 滑非常有利于提高以离型纸为基础的整个皮革产品的平滑光泽度。所述在过渡层 A4上设子的 上述离型层 A5的组成包括: 58-65重量份的聚丙烯、 26-34重量份的聚 4-甲基 -1-戊烯、 6_9 重量份的乙烯基硅油、 1-2 重量份的 2, 2 ' -亚甲基 -双- ( 4, 6 二叔丁基苯氧基) 磷酸钠和 0. 1-0. 8重量份的叔丁基过氧化苯甲酸酯, 其中所述乙烯基硅油的结构式为:
Rl和 R3为- CH3, R2为- CH = C , m取值 范围为 2000〜3000, n 取值范围为 3〜6。 所述离型层的制备过程为将上述重量份的聚丙烯、 聚 4-甲基 -1-戊烯和乙烯基硅油混合均匀后加热至 90°C, 保温 2 小时后加入 1-2重量份的 2, 2 ' -亚甲基 -双- ( 4, 6二叔丁基苯氧基) 磷酸钠和 0. 1-0. 8重量份的叔丁基过氧化苯甲酸 酯并混合均匀, 然后通过挤出机挤出涂覆于过渡层 A4的表面, 控制离型层的厚度在 20-25微 米。 这种离型层中通过 2, 2 ' -亚甲基 -双- ( 4, 6二叔丁基苯氧基) 磷酸钠和叔丁基过氧化苯 甲酸酯加快引发聚烯烃的双键与乙烯基硅油的双键的交联反应, 且其中的聚烯烃含量加多, 由于聚烯烃与聚氨酯等的亲和性较好, 因此具有这种离型层的离型纸与含有聚氨酯的热熔胶 粘合固化后形成的皮革产品不易剥离, 提高了产品性能。 通过上述方法制备得到应用于本发 明中的离型纸, 这种离型纸经过试验非常适合于本发明所述热熔胶以及 TPU膜层的涂覆, 优 选的本发明所述离型纸的厚度在 80-100微米, 但并不以此为限, 可根据实际需要调节。 挤出在上述离形纸上的热熔胶的组份包括:
60-70重量份的聚酯多元醇、 15-20重量份的二异氰酸酯、 3-5重量份的聚醚多元醇、 . 8-1. 5 重量份的催化剂、 0. 5-1. 2重量份的扩链剂、 1. 5-1. 8重量份抗氧化剂、 4-6重量份的增粘树 脂、 2-4重量份的阻燃剂、 2-4重量份的增韧剂。
所述聚酯多元醇通过低分子量脂肪族二元醇与脂肪族二元羧酸、芳香族二元羧酸在 100-260 下缩聚反应而制备成分子量为 2000-6000的端羟基聚酯二醇。 所述的脂肪族二元羧酸包括己 二酸、 富马酸、 马来酸或辛二酸; 所述的芳香族二元羧酸包括邻苯二甲酸、 对苯二甲酸或间 苯二甲酸; 所述的脂肪族二元醇包括乙二醇、 二甘醇、 丙二醇、 甲基丙二醇、 1, 4- 丁二醇、 1, 6- 己二醇、 1, 3- 丁二醇、 1, 5 戊二醇或十二烷基己二醇。
所述二异氰酸酯采用 4, 4 ' -二苯基甲烷二异氰酸酯、 1, 6- 六亚甲基二异氰酸酯中的一种; 所述聚醚多元醇选自聚四氢呋喃醚二醇、 氧化丙烯共聚二醇中的一种;
所述催化剂选择二月桂酸二丁基锡、 三乙醇胺或双吗啉基二乙基醚中的一种或几种; 所述扩链剂选择 1, 6- 己二醇、 甲基丙二醇、 1, 4- 丁二醇中的一种;
所述抗氧化剂选自 2, 6-三级丁基 -4-甲基苯酚或四 { β - (3, 5- 三级丁基 -4- 羟基苯基) 丙 酸}季戊四醇酯;
所述增粘树脂选自聚乙烯 -醋酸乙烯共聚物、端羟基热塑性聚酯、氢化松香树脂的一种或几种; 所述阻燃剂的具体组成按质量百分比为: 30-70%的熔融指数 0. 5-15. 0 g/10min 的聚丙烯、
5-25%的熔融指数 0.01-2. Og/lOmin的聚乙烯、 20_30%的选自粉末状滑石、 高岭石、 绢云母、 二氧化硅以及硅藻土中的至少一种无机填料、 5-15%选自十溴二苯基醚、十二氯十二氢二甲桥 苯唑环辛烯或其混合物的有机阻燃卤化物。
所述增韧剂选择聚烯烃增韧剂, 其中由 PE (聚乙烯)弹性体、 线型聚乙烯、 聚丙烯 (PP)和防老 化剂原料混合后挤出而成, 各原料所占质量百分数为: PE( 聚乙烯) 弹性体 31%、 线型聚乙 烯 19%、 聚丙烯 (PP)49%、 防老化剂 1%。
上述热熔胶的具体制备过程为:
(1) 按上述重量份将 60-70重量份的聚酯多元醇、 3-5重量份的聚醚多元醇、 1.5-1.8重量 份抗氧化剂和 4-6重量份的增粘树脂置于反应釜中, 加热至 120〜140°C, 在搅拌混合下真空 脱水 L5〜2h, 真空度小于 0.05MPa, 然后降温至 70〜75°C;
(2)在氮气保护下,将 15-20重量份的二异氰酸酯和 0.8-1.5重量份的催化剂加入到步骤( 1 ) 的反应产物中, 并在 85〜95°C反应 1-1.5h;
(3) 在氮气保护下, 将 0.5-1.2重量份的扩链剂、 2-4重量份的阻燃剂、 2-4重量份的增韧 剂加入到步骤 (2) 的反应产物中, 并在 75〜85°C搅拌反应 45min-L0h;
(4)在通入氮气保护条件下出料, 熟化一定时间后形成为应用于本发明中的热熔胶原料, 并 被送入挤出机中, 由挤出机模头挤出流延至附图 2所示离型纸上。 本发明中用于成型 TPU膜的 TPU原料组成为:
60-70重量份的聚合物多元醇, 所述聚合物多元醇为分子量为 1000 的聚四氢呋喃醚二醇、 分 子量为 3000 的聚己二酸乙二醇丁二醇酯多元醇中的一种或多种; 30-35重量份的 1,4- 环己烷 二异氰酸酯; 4-9重量份的扩链剂, 所述扩链剂为 1,4- 丁二醇; 3-5重量份的耐水解剂, 具体 为碳化二亚胺类耐水解剂; 1-3重量份的阻燃剂, 所述阻燃剂为十溴二苯基乙烷混合微量煅制 二氧化硅的有机卤化物阻燃剂, 平均粒度小于或等于 4微米; 1-2重量份的耐磨剂, 所述耐磨 剂由芳香族硅油组成; 0.2-0.8重量份的抗氧剂, 所述抗氧剂为 β_ (4- 羟基 -3, 5- 二叔丁基 苯基) 丙酸正十八碳醇酯、 四 [β_ (3,5- 二叔丁基 -4- 羟基苯基) 丙酸] 季戊四醇酯和二 [ (2,4- 二叔丁基苯基) 亚磷酸] 季戊四醇酯中的至少一种; 0.1- 0.5重量份的受阻胺类光 稳定剂, 具体为二 (2,2,6,6- 四甲基 -4- 哌啶基) 葵二酸酯; 0.2-0.6重量份的苯并三唑类 紫外线吸收剂; 0.4-0.8重量份的蒙旦蜡和 / 或芥酸酰胺蜡类润滑剂; 1-3重量份的由钙类填 充剂组成的雾面剂; 0.5-1.2重量份的由金属粉末或导电炭黑组成的防静电剂; 0.05-0.2重量 份的钛系或铋系催化剂。
通过上述原料制备用于成型薄膜的热塑性聚氨酯弹性体 TPU的具体方法如下:
( 1 ) 首先将上述重量份的聚合物多元醇中置于反应釜中, 并加热至 80-90°C, 然后加入上述 重量份的抗氧剂、 受阻胺类光稳定剂、 苯并三唑类紫外线吸收剂、 润滑剂和耐水解剂, 充分 搅拌后得到聚合物多元醇混合溶液。
( 2 ) 向所述聚合物多元醇混合溶液中加入上述重量份的、温度在 55-65 的 1, 4- 环己烷二异 氰酸酯搅拌混合后得到初步反应混合物;
( 3 ) 保持上述反应混合物的温度并加入上述重量份的扩链剂: 1, 4- 丁二醇和催化剂, 并控 制温度在 150-210°C、 压力 4-8MPa反应 lh左右。
( 4) 当反应熔体温度达到 180-2KTC间时, 加入上述重量份的阻燃剂、 耐磨剂、 雾面剂和防 静电剂, 反应预定时间后进行脱水、 干燥和熟化, 即得到热塑性聚氨酯弹性体原料。
应用于上述热塑性聚氨酯弹性体原料制备的装置可为现有技术中熟知的单螺杆混合装置、 同 向双螺杆连续反应挤出机、 干燥设备等。 所制得的热塑性聚氨酯弹性体原料再次被送入挤出 机中挤出 TPU薄膜, 并通过上述方法与成卷的热熔胶膜粘合成一体, 从而得到本发明所述的 无车缝热熔胶皮革。
最后对通过上述方法制得的本发明的无车缝热熔胶 TPU皮革的主要性能进行了检测, 检测结 果如下:
1、 软硬度: 75〜80/A;
2、 拉伸强度: 横向 28. 2 kgf , 纵向 25. 3 kgf ;
3、 撕裂强度: 经向 5. 0kgf ; 纬向 4. 7 kgf ;
4、 磨耗强度: 在 9Kpa的压力下, 磨 500转后无磨损现象;
5、 粘接强度: 2. 5Kg / 25 mm。
6、 伸长率: 700%;
7、 邵尔硬度: 95。
与同类型产品的主要性能对比如下:
因此本发明所制得的无车缝热熔胶 TPU皮革, 通过创新的配方并制作离型纸、 热熔胶和 TPU 薄膜, 尤其是采用特制配方的聚氨酯热熔胶与 TPU薄膜贴合, 使得最终皮革产品的拉伸强度、 撕裂强度、 磨耗强度、 粘接强度、 表面光泽度等性能均得到大幅提升, 即使在高温 190度的
情况下都不会发生质变, 能够广泛应用在制衣、 鞋类、 手袋、 箱包、 座椅、 建筑装饰等生产 制造行业。而且本公司结合长期创新实践提出的本发明所述 "新型免车缝的热熔胶 TPU皮革" 在国内外未见相关的文献报道, 属世界首创。
实施例 1
以下给出本发明的一个优选实施方式。
通过以下方式制备本发明所述免车缝的热熔胶 TPU皮革。
一、 制备离型纸
选择纸底层 Al, 并在所述纸底层 A1上涂布厚度为 2. 5微米的水性聚丙烯 (PP)粘结层 A2, 然 后在所述粘结层 A2上粘贴厚度为 20微米的聚对苯二甲酸乙二醇酯膜 A3并固化一定时间。然 后按照无机粒子 65重量份、 硅丙乳液 35重量份、 脂肪酸甲酯磺酸钠 4重量份、 十二烷基二 甲基苄基氯化铵重量 3份和水 50重量份制备过渡层涂布液,并使用刮刀均匀涂布在所述聚对 苯二甲酸乙二醇酯膜 A3上, 并进行固化和压光处理成厚度为 15微米的过渡层 A4, 最后在所 述过渡层 A4上挤出涂覆厚度为 25微米离型层 A5, 所述离型层的组成包括: 60重量份的聚丙 烯、 30重量份的聚 4-甲基 -1-戊烯、 8重量份的乙烯基硅油、 1. 5重量份的 2, 2 ' -亚甲基-双 - ( 4, 6二叔丁基苯氧基) 磷酸钠和 0. 5重量份的叔丁基过氧化苯甲酸酯, 所述乙烯基硅油的
其中 R1和 R3为 -CH3, R2为 -CH = CH2, m=2500左右, n=4。 从而制备得到作为本发明所述皮革 基材的离型纸。
二、 制备聚氨酯热熔胶原料
( 1 )将 65重量份的聚酯多元醇、 4重量份的聚醚多元醇、 1. 6重量份抗氧化剂和 5重量份的 增粘树脂置于反应釜中, 加热至 120 °C, 在搅拌混合下真空脱水 1. 5h, 真空度小于 0. 05MPa, 然后降温至 70 °C ;
( 2 )在氮气保护下, 将 18重量份的二异氰酸酯和 1重量份的催化剂加入到步骤(1 ) 的反应 产物中, 并在 85 °C反应 1. 5h;
( 3 ) 在氮气保护下, 将 1重量份的扩链剂、 3重量份的阻燃剂、 3重量份的增韧剂加入到步 骤 (2 ) 的反应产物中, 并在 85 °C搅拌反应 L Oh;
( 4 ) 在通入氮气保护条件下出料, 熟化一定时间后形成聚氨酯热熔胶原料。
其中所述聚酯多元醇通过低分子量脂肪族二元醇与脂肪族二元羧酸、 芳香族二元羧酸在 180-240°C下缩聚反应而制备的端羟基聚酯二醇,其中的脂肪族二元羧酸选自己二酸、富马酸; 其中的芳香族二元羧酸选自邻苯二甲酸、 对苯二甲酸, 其中的脂肪族二元醇选自乙二醇、 1, 3- 丁二醇、 1, 5 戊二醇或十二烷基己二醇。 所述二异氰酸酯采用 4, 4' -二苯基甲烷二异氰 酸酯; 所述聚醚多元醇采用聚四氢呋喃醚二醇; 所述催化剂选择双吗啉基二乙基醚; 所述扩 链剂选择 1, 6- 己二醇; 所述抗氧化剂选择四 {β _(3, 5- 三级丁基 -4- 羟基苯基) 丙酸 }季 戊四醇酯; 所述增粘树脂选择氢化松香树脂; 所述阻燃剂由: 50重量%的熔融指数 5 g/lOmin 的聚丙烯、 20 重量%的熔融指数 0.8 g/10min的聚乙烯、 20重量%的粉末状滑石和高岭石混 合的无机填料、 10 重量%的十溴二苯基醚和十二氯十二氢二甲桥苯唑环辛烯混合物的有机卤 化物阻燃剂组成。 所述增韧剂选择聚烯烃增韧剂, 其中由 PE (聚乙烯)弹性体、 线型聚乙烯、 聚丙烯 (PP)和防老化剂原料混合后挤出而成: PE ( 聚乙烯) 弹性体 31%、 线型聚乙烯 19%、 聚丙烯 (PP)49%、 防老化剂 1%。
三、 制备 TPU原料
(1) 将 65重量份的分子量为 3000 的聚己二酸乙二醇丁二醇酯多元醇置于反应釜中, 并加热 至 90°C,然后加入 0.6重量份的 β_(4- 羟基 -3, 5- 二叔丁基苯基)丙酸正十八碳醇酯抗氧剂、 0.3重量份的二(2,2,6,6- 四甲基 -4- 哌啶基)葵二酸酯光稳定剂、 0.4重量份的苯并三唑类 紫外线吸收剂、 0.6重量份的芥酸酰胺蜡类润滑剂、 4重量份的碳化二亚胺类耐水解剂, 充分 搅拌后得到聚合物多元醇混合溶液。
(2) 向所述聚合物多元醇混合溶液中加入 32重量份的、 温度在 60°C的 1,4- 环己烷二异氰酸 酯搅拌混合后得到初步反应混合物;
(3)保持上述反应混合物的温度并加入 6重量份的 1, 4- 丁二醇扩链剂和 0.1重量份的铋系 催化剂, 并控制温度在 180-210°C、 压力 6MPa反应 lh左右。
(4) 当反应熔体温度达到 200 间时, 加入 2重量份的十溴二苯基乙烷混合微量煅制二氧化 硅的有机卤化物阻燃剂、 1.5重量份的由芳香族硅油组成的耐磨剂、 2重量份的由钙类填充剂 组成的雾面剂和 0.8重量份的由导电炭黑组成的防静电剂, 反应预定时间后进行脱水、 干燥 和熟化, 即得到热塑性聚氨酯弹性体原料。
四、 贴合制备免车缝热熔胶 TPU皮革
(1)、 准备通过上述方法制备的离型纸、 热熔胶原料和 TPU原料, 并将离型纸置于相关设备 中铺平;
(2)、 将所制备的热熔胶原料经挤出机处理成胶料, 胶料送入高达 150度温度的挤出机熔融
成糊状, 再由挤出机模头挤出后流延到所述离形纸上, 然后经对压轮对压一冷却一卷取, 形 成附图 1所示热熔胶膜;
( 3)、 将所制备的 TPU原料同样挤出成 TPU膜, 并与步骤(2 ) 中成卷的热熔胶膜分别置于两 个送料架上, 使热熔胶膜和 TPU膜同时进入设置有恒温的高低对压轮中进行对压, 对压轮的 温度在 160 以上, 从而使熔点低的热熔胶在高低对压轮对压时瞬间与 TPU膜粘合为一体, 然后冷却成型为本发明所述的无车缝热熔胶皮革, 如附图 2所示。
以上仅是对本发明的优选实施方式进行了描述, 并不将本发明的技术方案限制于此, 本领域 技术人员在本发明的主要技术构思的基础上所作的任何公知变形都属于本发明所要保护的技 术范畴, 本发明具体的保护范围以权利要求书的记载为准。
Claims
(1)、 将 60-70重量份的聚合物多元醇置于反应釜中, 并加热至 80_90°C, 所述聚合物 多元醇为分子量为 1000 的聚四氢呋喃醚二醇和 /或分子量为 3000 的聚己二酸乙二醇 丁二醇酯多元醇,然后加入 0.2-0.8重量份的抗氧剂、 0.1- 0.5重量份的二(2, 2, 6, 6_ 四甲基 -4- 哌啶基) 葵二酸酯受阻胺类光稳定剂、 0.2-0.6重量份的苯并三唑类紫外 线吸收剂、 0.4-0.8重量份的蒙旦蜡和 / 或芥酸酰胺蜡类润滑剂和 3-5重量份的碳化 二亚胺类耐水解剂, 充分搅拌后得到聚合物多元醇混合溶液, 其中所述抗氧剂为 β _ (4- 羟基 -3, 5- 二叔丁基苯基) 丙酸正十八碳醇酯、 四 [β_ (3,5- 二叔丁基 -4- 羟 基苯基) 丙酸] 季戊四醇酯和二[ (2,4- 二叔丁基苯基) 亚磷酸] 季戊四醇酯中的至 少一种;
(2)、 向所述聚合物多元醇混合溶液中加入 30-35重量份的、 温度在 55-65 的 1,4- 环己 烷二异氰酸酯, 搅拌混合后得到初步反应混合物;
(3)、 保持上述反应混合物的温度并加入 4-9重量份的 1,4- 丁二醇扩链剂和 0.05-0.2 重量份的钛系或铋系催化剂, 并控制温度在 150-210°C、 压力 4-8MPa反应 lh左右;
(4)、 当反应熔体温度达到 180_210°C间时, 加入 1-3重量份的且平均粒度小于或等于 4 微米的由十溴二苯基乙烷混合微量煅制二氧化硅的有机卤化物阻燃剂、 1-2重量份的由 芳香族硅油组成的耐磨剂、 1-3重量份的由钙类填充剂组成的雾面剂和 0.5-1.2重量份 的由金属粉末或导电炭黑组成的防静电剂, 反应后进行脱水、干燥和熟化, 得到热塑性 聚氨酯弹性体原料;
(四)、 贴合制备免车缝热熔胶 TPU皮革
(1)、 准备通过上述步骤制备的离型纸、 热熔胶原料和 TPU原料, 并将离型纸置 于相关设备中铺平;
(2)、 将步骤 (二) 制备的热熔胶原料经挤出机处理成胶料, 胶料送入 150度温
度的挤出机熔融成糊状, 再由挤出机模头挤出后流延到所述离形纸上, 然后经对压轮 对压一冷却一卷取, 形成热熔胶膜;
( 3)、 将步骤 (三) 所制备的 TPU原料挤出成 TPU膜, 并与上述热熔胶膜分别置于两个 送料架上, 使热熔胶膜和 TPU膜同时进入设置有恒温的高低对压轮中进行对压, 对压 轮的温度在 160 以上,从而使熔点低的热熔胶在高低对压轮对压时瞬间与 TPU膜粘合 为一体, 然后冷却成型为无车缝的热熔胶 TPU皮革。
、 根据权利要求 7所述的制备方法, 其特征在于, 其中制备离型纸的步骤 (一) 中: 所述 过渡层的制备原料为无机粒子 65重量份、 硅丙乳液 35重量份、 脂肪酸甲酯磺酸钠 4重 量份、十二烷基二甲基苄基氯化铵 3重量份和水 50重量份,所述无机粒子的具体组成为: 粘土粒径为 0. 5-0. 8微米且含量为 25%、 硫酸钡粉末粒径在 1-2微米且含量为 60%、 碳酸 钙粉末粒径在 3-5微米且含量为 15%; 所述离型层的制备原料为 60重量份的聚丙烯、 30 重量份的聚 4-甲基 -1-戊烯、 8重量份的乙烯基硅油、1. 5重量份的 2, 2 ' -亚甲基-双 -( 4, 6 苯甲酸酯, 所述乙烯基硅油的结
、 根据权利要求 7所述的制备方法, 其特征在于, 其中步骤 (二) 中制备聚酯多元醇的脂 肪族二元羧酸选自己二酸、 富马酸、 马来酸或辛二酸, 芳香族二元羧酸选自邻苯二甲酸、 对苯二甲酸或间苯二甲酸, 脂肪族二元醇选自乙二醇、 二甘醇、 丙二醇、 甲基丙二醇、 1, 4- 丁二醇、 1, 6- 己二醇、 1, 3- 丁二醇、 1, 5 戊二醇或十二烷基己二醇; 所述增韧 剂由聚乙烯弹性体、 线型聚乙烯、 聚丙烯 PP和防老化剂原料混合后挤出而成, 各原料所 占质量百分数为: 聚乙烯弹性体 31 %、 线型聚乙烯 19 %、 聚丙烯 49 %、 防老化剂 1 %。0、 根据权利要求 7所述的制备方法, 其特征在于, 其中所述步骤 (三) 中 TPU原料的 组成为 65重量份的分子量为 3000 的聚己二酸乙二醇丁二醇酯多元醇、 0. 6重量份的 β -
( 4- 羟基 -3, 5- 二叔丁基苯基)丙酸正十八碳醇酯抗氧剂、 0. 3重量份的二(2, 2, 6, 6- 四 甲基 -4- 哌啶基) 葵二酸酯光稳定剂、 0. 4重量份的苯并三唑类紫外线吸收剂、 0. 6重量 份的芥酸酰胺蜡类润滑剂、 4重量份的碳化二亚胺类耐水解剂、 32重量份且温度在 60 的 1, 4- 环己烷二异氰酸酯、 6重量份的 1, 4- 丁二醇扩链剂、 0. 1重量份的铋系催化剂、
2重量份的十溴二苯基乙烷混合微量煅制二氧化硅的有机卤化物阻燃剂、 1. 5重量份的由
芳香族硅油组成的耐磨剂、 2重量份的由钙类填充剂组成的雾面剂和 0. 8重量份的由导电 炭黑组成的防静电剂。
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