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CN109530190A - A kind of automobile artificial leather texture polyurethane leather and preparation method thereof - Google Patents

A kind of automobile artificial leather texture polyurethane leather and preparation method thereof Download PDF

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Publication number
CN109530190A
CN109530190A CN201811055207.3A CN201811055207A CN109530190A CN 109530190 A CN109530190 A CN 109530190A CN 201811055207 A CN201811055207 A CN 201811055207A CN 109530190 A CN109530190 A CN 109530190A
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CN
China
Prior art keywords
layer
tpu
melt adhesive
weight
leather
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Withdrawn
Application number
CN201811055207.3A
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Chinese (zh)
Inventor
王良
王一良
何建雄
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Dongguan Xionglin New Materials Technology Co Ltd
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Dongguan Xionglin New Materials Technology Co Ltd
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Priority to CN201811055207.3A priority Critical patent/CN109530190A/en
Publication of CN109530190A publication Critical patent/CN109530190A/en
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0406—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being air
    • B05D3/0413—Heating with air
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/08—Interconnection of layers by mechanical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2503/00—Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B2037/1269—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives multi-component adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/003—Interior finishings

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Abstract

The present invention relates to a kind of automobile artificial leather texture polyurethane leathers, which is characterized in that the polyurethane leather includes the successively base cloth layer of lamination, hot melt adhesive layer and epidermis；The hot melt adhesive layer includes TPU hot melt adhesive layer or EVA hot-melt adhesive layer.Due to using new TPU hot melt adhesive film, adhesion strength greatly improves automobile artificial leather texture polyurethane leather provided by the invention, reaches as high as 8.0kg/25mm.By using specific PU film, TPU membrane and base fabric, it has excellent performance the comprehensive physical of the polyurethane leather of preparation, shaped article feel is greasy smooth, leather texture is clear, no less than the feel of corium, PVC artificial leather and corium can be substituted completely, while adding antimicrobial moiety, and there is certain antibacterial effect.

Description

A kind of automobile artificial leather texture polyurethane leather and preparation method thereof
Technical field
The invention belongs to artificial leather manufacturing fields, and in particular to a kind of low smell polyurethane leather and preparation method thereof.
Background technique
With China's rapid development of economy, the demand of leather and fur products is increasing, and class is also higher and higher.In automobile Dressing leather has been widely used in the inside gadget of riding vehicle, carrier.Leather for automobile interiors, optimal selection are corium, but It is serious that corium pollutes environment in its own production process, and content of beary metal is easy exceeded, becomes a useful person in inside gadget process Rate is lower, and it is expensive, it is difficult to be received by low and middle-grade passenger cars；And people gradually pay attention to environmental protection, are advocating Today of environmental protection and energy saving, sustainable development, people also start to develop leather fabric to replace animal's leather, to avoid to wild The injury of animal and destruction to natural environment.
Rtificial leather is also imitation leather or rubber, is the general name of the artificial materials such as PVC and PU.It is in woven fabric base or nonwoven On Bu Ji, formed by the foaming such as the PVC and PU of various different formulations or overlay film processing and fabricating, it can be according to varying strength, wear-resisting Degree, the requirements such as degree and color, gloss, floral designs of resisting cold are processed into, with designs and varieties are various, waterproof performance is good, not care about one's appearance Neatly, the feature that utilization rate is high and price is cheap with respect to corium.Vapour is currently, automobile door plate, face fabric for automobile seat, instrument board, vehicle The positions such as compartment inner wall, Roof of vehicle, steering wheel cover, mainly using materials compound with polyvinyl chloride, polyurethane etc. such as non-woven cloths Material.Common polyvinyl chloride rtificial leather is there are Boardy Feeling, comfort is poor, loss of properties on aging, smell weight, plasticizer are easy to migrate The defects of precipitation, so the common PVC artificial leather in automobile interior decoration is gradually replaced polyurethane (PU) synthetic leather at present. And existing Synthetic Leather production technology is complex at present, the Shortcomings such as wearability, flexibility, feature of environmental protection.
This field needs to develop a kind of polyurethane leather, and performance can match in excellence or beauty with PU polyurethane, but has low VOC and the feature of environmental protection.
Summary of the invention
The purpose of the present invention is to provide a kind of automobile artificial leather texture polyurethane leather, the polyurethane leather includes The successively base cloth layer of lamination, hot melt adhesive layer and epidermis；The hot melt adhesive layer includes TPU hot melt adhesive layer and EVA hot-melt adhesive layer.
The hot melt adhesive layer adhesion strength of automobile artificial leather texture polyurethane leather provided by the invention is big, and it is poly- to play raising The effect of being firmly bonded property of urethane leather, base cloth layer and PU film play the role of improve polyurethane leather mechanical performance, make its PVC artificial leather and corium can be substituted in mechanical performance.The present invention cooperates base cloth layer and epidermis by setting hot melt adhesive layer, obtains Having stable high-temperature performance property was obtained, such as qualitative change will not occur under the conditions of 150 DEG C of high temperature, while there is wear-resisting, heat-resisting, resistance to song Folding, the excellent properties such as flexibility is good, surface texture is clear.
The TPU hot melt adhesive layer to prepare raw material in parts by weight include the following raw material component:
As an example, TPU hot melt adhesive layer of the present invention is prepared in raw material, polyester polyol can be 36 parts, 37 Part, 38 parts, 39 parts, 40 parts, 41 parts, 43 parts or 44 parts etc.；Diisocyanate can be 32 parts, 35 parts, 38 parts, 40 parts, 42 Part, 45 parts, 48 parts or 50 parts etc.；Catalyst can be 0.2 part, 0.4 part, 0.6 part, 0.8 part, 1.0 parts, 1.2 parts, 1.5 parts or 1.8 parts etc.；Chain extender can be 2 parts, 3 parts, 5 parts, 8 parts, 9 parts, 10 parts, 12 parts or 14 parts etc..
Preferably, the polyester polyol includes polyester polyol of sebacic acid series, and preferred molecular weight is 1000~2000 (examples Such as 1100,1200,1300,1400,1500,1600,1700,1800,1900) polyester polyol of sebacic acid series.
Preferably, the polyester polyol of sebacic acid series the preparation method comprises the following steps: by decanedioic acid, terephthalic acid (TPA) and ethylene glycol Mixing, then be added zirconic acid isopropyl ester, be warming up to 120~200 DEG C (such as 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C etc.) carry out polycondensation reaction obtain polyester polyol of sebacic acid series.
Preferably, the molar ratio of the decanedioic acid and terephthalic acid (TPA) be 1:2~3 (such as 1:2.2,1:2.4,1:2.6, 1:2.8,1:2.9 etc.).
Preferably, the molar ratio of the ethylene glycol and decanedioic acid be 3.5~4.5:1, such as 3.6:1,3.7:1,3.8:1, 3.9:1,4.0:1,4.1:1,4.2:1,4.3:1,4.4:1 etc..
Preferably, the additional amount of the zirconic acid isopropyl ester is 3 × 10-3~4 × 10-3Mol/mol decanedioic acid.
Preferably, the diisocyanate includes '-diphenylmethane diisocyanate or toluene di-isocyanate(TDI).
Polyester polyol of sebacic acid series is esterified simultaneously by decanedioic acid and terephthalic acid (TPA), wherein containing proper ratio Short chain acids and aromatic acid, aromatic group compound with regular structure, good crystallinity can be improved mechanical performance, but excessively high crystallinity is led It causes caking property to be deteriorated, after compounding decanedioic acid, can be improved adhesive property.
Preferably, first catalyst includes p-methyl benzenesulfonic acid, dibutyl tin dilaurate, antimony glycol, four isopropyls Any a kind or at least two kinds of of combination in base titanate esters.The combination such as tin dilaurate of typical but non-limiting second catalyst Dibutyl tin and antimony glycol, antimony glycol and tetra isopropyl titanate.
Preferably, the chain extender includes 1,6- hexylene glycol, methyl propanediol, any a kind in 1,4-butanediol or extremely Few 2 kinds of combination.The combination of typical but non-limiting chain extender such as 1,6- hexylene glycol and methyl propanediol, 1,6- hexylene glycol with 1,4- butanediol.
Preferably, the raw material for preparing of the TPU hot melt adhesive layer further includes 0.1~1 parts by weight (such as 0.2 parts by weight, 0.3 Parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight etc.) it is first anti- Oxygen agent.
Preferably, first antioxidant includes antioxidant 245, antioxidant 1135, antioxidant PUR67, antioxidant PUR68 In any a kind or at least two kinds of of combination.
Preferably, the TPU hot melt adhesive layer prepares the fire retardant that raw material further includes 0.1~5 parts by weight, such as 0.5 part, 1.0 parts, 1.5 parts, 2.0 parts, 2.5 parts, 3.0 parts, 3.5 parts, 4.0 parts or 4.5 parts etc..
Preferably, the fire retardant include: by weight percentage the dimethylphosphite of 20~30wt%, 30~ The pentaerythrite of the ammonium polyphosphate of 40wt%, 30~40wt%.
In the fire retardant, the mass percentage of the dimethylphosphite can for 20%, 22%, 24%, 26%, 28% or 30% etc., the mass percentage of the ammonium polyphosphate can for 30%, 32%, 34%, 36%, 38% or 40% etc., the mass percentage of the pentaerythrite can be 30%, 32%, 34%, 36%, 38% or 40% etc..
Preferably, the TPU hot melt adhesive layer prepares the tackifying resin that raw material further includes 0.1~5 parts by weight, such as 0.5 Part, 1.0 parts, 1.5 parts, 2.0 parts, 2.5 parts, 3.0 parts, 3.5 parts, 4.0 parts or 4.5 parts etc..
Preferably, the tackifying resin includes polyethylene vinyl acetate copolymer, terminal hydroxy group thermoplastic polyester, hydrogenation pine Any a kind or at least two kinds of of combination in botany bar gum.
Preferably, the epidermis includes PU layers of dry type, any a kind or at least two kinds of of composite layer in TPU layer.
Preferably, the epidermis be TPU layer and PU layer of dry type of composite layer, preferred thickness than for 1:1 TPU layer with The composite layer that PU layers of dry type.
Preferably, the TPU layer and PU layers of dry type of composite layer are by the way that PU resin working solution to be coated in the TPU layer Drying bonding obtains.
Preferably, TPU membrane layer is set between TPU hot melt adhesive layer and epidermis.
Preferably, the TPU layer is set to PU layers between hot melt adhesive layer.
Preferably, the TPU layer to prepare raw material in parts by weight include the following raw material component:
The thermoplastic polyurethane particle to prepare raw material in parts by weight include following component:
Preferably, the weight average molecular weight of the polyhexamethylene carbonate diol is 1000~2000, such as weight average molecular weight It is 1100,1200,1300,1400,1500,1600,1700,1800,1900 or 2000 etc..
Preferably, any a kind or at least 2 in oleamide, erucyl amide or behenamide of the slipping agent The combination of kind；Typical but non-limiting combination such as oleamide and erucyl amide, oleamide and behenamide.
Preferably, second antioxidant is selected from distearyl pentaerythritol phosphite, triphenyl phosphite, two fourths Base hydroxy-methylbenzene BHT, N, any a kind in bis- [[3- (3,5)-di-tert-butyl-hydroxy phenyl] propiono] hexamethylene diamines of N '-or At least two kinds of combinations；Typical but non-limiting combination such as distearyl pentaerythritol phosphite and triphenyl phosphite, Asia Triphenyl phosphate and dibutyl hydroxy toluene etc..
Preferably, any a kind or at least two kinds of of combination of the anti ultraviolet agent in UV-P, UV-328 or UV-B83； Typical but non-limiting combination such as UV-P and UV-328, UV-P and UV-B83.
Preferably, second catalyst includes p-methyl benzenesulfonic acid, dibutyl tin dilaurate, antimony glycol, four isopropyls Any a kind or at least two kinds of of combination in base titanate esters.The combination such as tin dilaurate of typical but non-limiting second catalyst Dibutyl tin and antimony glycol, antimony glycol and tetra isopropyl titanate.
Preferably, the base cloth layer with a thickness of 0.1~3.0mm, such as can for 0.1mm, 0.3mm, 0.5mm, 0.7mm, 0.9mm, 1.2mm, 1.5mm, 1.8mm, 2.0mm, 2.3mm, 2.5mm or 3.0mm etc..
Preferably, the hot melt adhesive layer with a thickness of 0.01~0.1mm, such as can for 0.02mm, 0.03mm, 0.04mm, 0.05mm, 0.06mm, 0.07mm, 0.08mm, 0.09mm or 0.1mm etc..
Preferably, the TPU hot melt adhesive layer is with a thickness of 0.01~0.1mm.
Preferably, the EVA hot-melt adhesive layer is with a thickness of 0.01~0.1mm.
Preferably, the epidermis with a thickness of 0.01~0.2mm, such as can for 0.01mm, 0.03mm, 0.05mm, 0.07mm, 0.09mm, 0.12mm, 0.15mm, 0.18mm or 0.20mm etc..
Preferably, the TPU layer with a thickness of 0.01~0.1mm, such as can for 0.01mm, 0.02mm, 0.03mm, 0.04mm, 0.05mm, 0.06mm, 0.07mm, 0.08mm, 0.09mm or 0.10mm etc..
Preferably, the base cloth layer includes not weaving fabric of superfine fiber, and preferred unit area weight is 50-400g/m2 (such as can be 100g/m2、120g/m2、150g/m2、180g/m2、200g/m2、220g/m2、 250g/m2、280g/m2、 300g/m2、320g/m2、350g/m2、380g/m2Or 400g/m2Deng) not weaving fabric of superfine fiber.
Preferably, the hot melt adhesive layer is by the way that hot melt adhesive to be cast to obtain.
After curtain coating prepares hot melt adhesive layer, hot melt adhesive layer and base cloth layer are pressed, on the one hand can be improved hot melt adhesive layer and base The bond strength of layer of cloth, reduces the thickness of hot melt adhesive layer, on the other hand can reduce prior art hot melt adhesive spraying preparation hot melt Air pollution caused by glue-line.
The second object of the present invention is to providing a kind of preparation method of polyurethane leather described in the first purpose, the preparation side Method includes the following steps:
(1) preparation of TPU hot melt adhesive film: it is mixed with raw material according to the composition of raw materials for preparing of TPU hot melt adhesive layer, screw rod squeezes TPU hot-melt adhesive granules are obtained out, and it is 180~220 DEG C that the TPU hot-melt adhesive granules, which are passed through single screw extrusion machine according to temperature, (such as 185 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, 205 DEG C, 210 DEG C, 215 DEG C or 220 DEG C etc.), die head temperature are 180~210 The TPU hot melt that the condition of DEG C (such as 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, 205 DEG C or 210 DEG C etc.) is cast The TPU hot melt adhesive film is carried out, formation first composite membrane compound to pressing with base fabric by glue film；
(2) the TPU layer compound stage: it is mixed with raw material according to the composition of raw materials for preparing of TPU layer, Screw Extrusion obtains TPU Membrane granule, by the TPU membrane particle by single screw extrusion machine according to temperature be 180~220 DEG C (such as 185 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, 205 DEG C, 210 DEG C, 215 DEG C or 220 DEG C etc.), die head temperature be 180~210 DEG C (such as 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, 205 DEG C or 210 DEG C etc.) condition be cast to obtain TPU layer；By the TPU layer and the first composite membrane It is compound to pressing, form the second composite membrane；
(3) the PU film process stage: PU resin is added on coating machine, and PU resin working solution is uniformly coated on second and is answered Close film TPU membrane layer surface, through 80~100 DEG C (such as 80 DEG C, 82 DEG C, 85 DEG C, 88 DEG C, 90 DEG C, 92 DEG C, 95 DEG C, 98 DEG C or 100 DEG C etc.) tunnel-type hot air drying machine is dry, batches spare, obtain polyurethane leather；
Optionally, step (4)~(6) are carried out after step (3):
(4) release paper processing stage: polyurethane leather is unreeled, and surface is handled by heating mantles, then passes through emulation dermatoglyph Reason release paper is embossed, and release paper is removed, and cooling winding obtains artificial leather texture polyurethane leather semi-finished product；
(5) crumple process: it is 70-90 DEG C that the artificial leather texture polyurethane leather semi-finished product of acquisition, which are placed in temperature, In boarding machine, line half an hour is rubbed, that is, completes rubbing program；
(6) arranging process: finally the semi-finished product for completing rubbing program taken out into final finishing out of boarding machine, be in rolls institute The automobile artificial leather texture polyurethane leather stated.
Preferably, scraper lower edge and second composite membrane 0.1~0.5cm of spacing in step (3) described coating machine platform, such as 0.2mm, 0.3mm, 0.4mm etc..
Compared with prior art, the invention has the following advantages:
(1) automobile artificial leather texture polyurethane leather provided by the invention is glued due to using new TPU hot melt adhesive film Knotting strength greatly improves, and reaches as high as 8.0kg/25mm,.
(2) by using specific PU film, TPU membrane and base fabric, keep the comprehensive physical performance of the polyurethane leather of preparation excellent Different, shaped article feel is greasy smooth, and leather texture is clear, no less than the feel of corium, can substitute PVC artificial leather and true completely Skin, while antimicrobial moiety is added, and there is certain antibacterial effect.
(3) under the conditions of 150 DEG C of high temperature matter will not occur for automobile artificial leather texture polyurethane leather provided by the invention Become, has wear-resisting (under the pressure of 9kPa, wear phenomenon is unobvious after 1000 turns of mill), heat-resisting, resistance to complications, flexibility good (soft Hardness is in 80~85A), the excellent properties such as surface texture is clear, good permeability is smooth not to be adhered, transverse tensile strength 34.8 ~40.6MPa, longitudinal tensile strength are 32.6~38.1MPa, and radial tearing strength is 69.5~74.3kgf/cm, broadwise tearing Intensity is 68.0~73.2kgf/cm, and quality is prominent.
(4) in optimal technical scheme, curtain coating prepares the technique rolled after hot melt adhesive layer, can be improved hot melt adhesive Adhesion strength, reduces the thickness of hot melt adhesive layer, on the other hand can reduce prior art hot melt adhesive spraying and prepares hot melt adhesive layer and makes At air pollution.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.
Those skilled in the art are not construed as to this hair it will be clearly understood that the described embodiments are merely helpful in understanding the present invention Bright concrete restriction.
Embodiment 1
A kind of automobile artificial leather texture polyurethane leather, the base fabric layer superfine fibre of the 1.5mm thickness including successively lamination Non-woven cloth (weight per unit area 200g/m2), the TPU hot melt adhesive layer of 0.05mm thickness, by 0.05mm thickness TPU membrane layer and The composite layer of the PU layer composition of 0.05mm thickness.
The TPU hot melt adhesive layer to prepare raw material in parts by weight include the following raw material component:
The polyester polyol the preparation method comprises the following steps: by 1mol decanedioic acid, 2.5mol terephthalic acid (TPA) and 4.0mol second two Alcohol mixing, is then added 0.003mol zirconic acid isopropyl ester, is warming up to 160 DEG C of progress polycondensation reactions and obtains decanedioic acid system polyester polyols Alcohol (weight average molecular weight 1500)；
The fire retardant by include: by weight percentage 30wt% dimethylphosphite, 35wt% ammonium polyphosphate, 35wt% pentaerythrite；
PU layers of the preparation method includes: that PU resin working solution is coated in TPU layer to dry bonding；The PU resin The formula of working solution is as follows: 85 parts by weight of polyurethane resin；22 parts by weight of dimethylformamide；40 parts by weight of ethyl acetate；Table 3 parts by weight of face coagent sulfated castor oil；1.0 parts by weight of antibacterial agent dodecyl dimethyl benzyl ammonium bromide；5 weight of toner Measure part.
The TPU membrane layer, which passes through to be cast after the mixing of selected raw material, to be obtained, and the raw material components include: heat in parts by weight 93 parts by weight of plastic polyurethane particle；0.05 parts by weight of slipping agent behenamide；0.5 weight of antioxidant dibutyl hydroxy toluene Measure part；0.5 parts by weight of UV resistant agent UV-B83；The thermoplastic polyurethane particle includes the following raw material group in parts by weight Point: weight average molecular weight is 35 parts of polyhexamethylene carbonate diol of 1500；1,5- how 15 parts of diisocyanate；Benzylidene two 25 parts of isocyanates；1,18 parts of 4- butanediol；0.5 part of catalyst.
Preparation method includes the following steps:
(1) the TPU hot melt adhesive film stage: TPU hot melt adhesive film and base fabric that TPU hot melt adhesive raw material is cast are carried out to pressure It is compound, form the first composite membrane；
(2) the TPU membrane layer compound stage: by thermoplastic polyurethane particle and auxiliary agent by single screw extrusion machine, according to screw rod Temperature is 200 DEG C, and die head temperature is that 190 DEG C of condition is cast into TPU membrane, compound to pressing with the first composite membrane, and it is multiple to form second Close film；
(3) the PU film process stage: prepared PU resin working solution is added on coating machine platform scraper, is arranged under scraper Edge and the second composite membrane spacing 0.3cm, are uniformly coated on TPU membrane surface on the second composite membrane for PU resin working solution, through tunnel Road formula air drier is dry, and temperature is batched spare at 90 DEG C or so, obtains polyurethane leather；
(4) release paper processing stage: above-mentioned polyurethane leather is unreeled, and surface is handled by heating mantles, then passes through emulation Dermatoglyph reason release paper is embossed, and release paper is removed, and cooling winding obtains artificial leather texture polyurethane leather semi-finished product；
(5) it crumples process: the artificial leather texture polyurethane leather semi-finished product of acquisition being placed in temperature is 80 DEG C and rub In line machine, line half an hour is rubbed, that is, completes rubbing program；
(6) arranging process: finally the semi-finished product for completing rubbing program taken out into final finishing out of boarding machine, be in rolls institute The automobile artificial leather texture polyurethane leather stated.
Embodiment 2
A kind of automobile artificial leather texture polyurethane leather, the base fabric layer superfine fibre of the 3.0mm thickness including successively lamination Non-woven cloth (weight per unit area 400g/m2), the TPU hot melt adhesive layer of 0.1mm thickness, by 0.1mm thickness TPU membrane layer and The composite layer of the PU layer composition of 0.1mm thickness.
The TPU hot melt adhesive layer to prepare raw material in parts by weight include the following raw material component:
The polyester polyol the preparation method comprises the following steps: by 1mol decanedioic acid, 2.5mol terephthalic acid (TPA) and 4.0mol second two Alcohol mixing, is then added 0.003mol zirconic acid isopropyl ester, is warming up to 200 DEG C of progress polycondensation reactions and obtains decanedioic acid system polyester polyols Alcohol (weight average molecular weight 2000)；
The fire retardant by include: by weight percentage 20wt% dimethylphosphite, 40wt% ammonium polyphosphate, 40wt% pentaerythrite；
PU layers of the preparation method includes: that PU resin working solution is coated in TPU layer to dry bonding；The PU resin The formula of working solution is as follows: 90 parts by weight of polyurethane resin；25 parts by weight of dimethylformamide；50 parts by weight of ethyl acetate；Table 5 parts by weight of face coagent sulfated castor oil；2 parts by weight of antibacterial agent dodecyl dimethyl benzyl ammonium bromide；10 weight of toner Measure part.
The TPU membrane layer, which passes through to be cast after the mixing of selected raw material, to be obtained, and the raw material components include: heat in parts by weight 95 parts by weight of plastic polyurethane particle；1.0 parts by weight of slipping agent erucyl amide；1.0 parts by weight of antioxidant triphenyl phosphite； 1.0 parts by weight of UV resistant agent UV-328；The thermoplastic polyurethane particle includes the following raw material component in parts by weight: weight Average molecular weight is 40 parts of polyhexamethylene carbonate diol of 2000；1,5- how 20 parts of diisocyanate；Two isocyanide of benzylidene 30 parts of acid esters；1,25 parts of 4- butanediol；1.0 parts of catalyst.
Preparation method includes the following steps:
(1) the TPU hot melt adhesive film stage: TPU hot melt adhesive film and base fabric that TPU hot melt adhesive raw material is cast are carried out to pressure It is compound, form the first composite membrane；
(2) the TPU membrane layer compound stage: by thermoplastic polyurethane particle and auxiliary agent by single screw extrusion machine, according to screw rod Temperature is 200 DEG C, and die head temperature is that 190 DEG C of condition is cast into TPU membrane, compound to pressing with the first composite membrane, and it is multiple to form second Close film；
(3) the PU film process stage: prepared PU resin working solution is added on coating machine platform scraper, is arranged under scraper Edge and the second composite membrane spacing 0.3cm, are uniformly coated on TPU membrane surface on the second composite membrane for PU resin working solution, through tunnel Road formula air drier is dry, and temperature is batched spare at 90 DEG C or so, obtains polyurethane leather；
(4) release paper processing stage: above-mentioned polyurethane leather is unreeled, and surface is handled by heating mantles, then passes through emulation Dermatoglyph reason release paper is embossed, and release paper is removed, and cooling winding obtains artificial leather texture polyurethane leather semi-finished product；
(5) it crumples process: the artificial leather texture polyurethane leather semi-finished product of acquisition being placed in temperature is 80 DEG C and rub In line machine, line half an hour is rubbed, that is, completes rubbing program；
(6) arranging process: finally the semi-finished product for completing rubbing program taken out into final finishing out of boarding machine, be in rolls institute The automobile artificial leather texture polyurethane leather stated.
Embodiment 3
A kind of automobile artificial leather texture polyurethane leather, the base fabric layer superfine fibre of the 0.1mm thickness including successively lamination Non-woven cloth (weight per unit area 200g/m2), the TPU hot melt adhesive layer of 0.01mm thickness, by 0.05mm thickness TPU membrane layer and The composite layer of the PU layer composition of 0.05mm thickness.
The TPU hot melt adhesive layer to prepare raw material in parts by weight include the following raw material component:
The polyester polyol the preparation method comprises the following steps: by 1mol decanedioic acid, 2.5mol terephthalic acid (TPA) and 4.0mol second two Alcohol mixing, is then added 0.003mol zirconic acid isopropyl ester, is warming up to 160 DEG C of progress polycondensation reactions and obtains decanedioic acid system polyester polyols Alcohol (weight average molecular weight 1500)；
The fire retardant by include: by weight percentage 25wt% dimethylphosphite, 35wt% ammonium polyphosphate, 35wt% pentaerythrite；
PU layers of the preparation method includes: that PU resin working solution is coated in TPU layer to dry bonding；The PU resin The formula of working solution is as follows: 85 parts by weight of polyurethane resin；22 parts by weight of dimethylformamide；40 parts by weight of ethyl acetate；Table 3 parts by weight of face coagent sulfated castor oil；1 parts by weight of antibacterial agent dodecyl dimethyl benzyl ammonium bromide；5 weight of toner Part.
The TPU membrane layer, which passes through to be cast after the mixing of selected raw material, to be obtained, and the raw material components include: heat in parts by weight 93 parts by weight of plastic polyurethane particle；0.05 parts by weight of slipping agent behenamide；0.5 weight of antioxidant dibutyl hydroxy toluene Measure part；0.5 parts by weight of UV resistant agent UV-B83；The thermoplastic polyurethane particle includes the following raw material group in parts by weight Point: weight average molecular weight is 35 parts of polyhexamethylene carbonate diol of 1500；1,5- how 15 parts of diisocyanate；Benzylidene two 25 parts of isocyanates；1,18 parts of 4- butanediol；0.5 part of catalyst.
Preparation method includes the following steps:
(1) the TPU hot melt adhesive film stage: TPU hot melt adhesive film and base fabric that TPU hot melt adhesive raw material is cast are carried out to pressure It is compound, form the first composite membrane；
(2) the TPU membrane layer compound stage: by thermoplastic polyurethane particle and auxiliary agent by single screw extrusion machine, according to screw rod Temperature is 200 DEG C, and die head temperature is that 190 DEG C of condition is cast into TPU membrane, compound to pressing with the first composite membrane, and it is multiple to form second Close film；
(3) the PU film process stage: prepared PU resin working solution is added on coating machine platform scraper, is arranged under scraper Edge and the second composite membrane spacing 0.3cm, are uniformly coated on TPU membrane surface on the second composite membrane for PU resin working solution, through tunnel Road formula air drier is dry, and temperature is batched spare at 90 DEG C or so, obtains polyurethane leather；
(4) release paper processing stage: above-mentioned polyurethane leather is unreeled, and surface is handled by heating mantles, then passes through emulation Dermatoglyph reason release paper is embossed, and release paper is removed, and cooling winding obtains artificial leather texture polyurethane leather semi-finished product；
(5) it crumples process: the artificial leather texture polyurethane leather semi-finished product of acquisition being placed in temperature is 80 DEG C and rub In line machine, line half an hour is rubbed, that is, completes rubbing program；
(6) arranging process: finally the semi-finished product for completing rubbing program taken out into final finishing out of boarding machine, be in rolls institute The automobile artificial leather texture polyurethane leather stated.
Embodiment 4
The difference from embodiment 1 is that the automobile artificial leather texture polyurethane leather, including successively lamination Base cloth layer not weaving fabric of superfine fiber (the weight per unit area 200g/m of 1.5mm thickness2), the TPU hot melt adhesive of 0.05mm thickness The PU layer of layer, 0.01mm thickness.
Embodiment 5
The difference from example 2 is that the automobile artificial leather texture polyurethane leather, including successively lamination Base cloth layer not weaving fabric of superfine fiber (the weight per unit area 200g/m of 0.01mm thickness2), the TPU hot melt adhesive of 0.1mm thickness The PU layer of layer, 0.2mm thickness.
Embodiment 6
Difference with embodiment 3 is, the automobile artificial leather texture polyurethane leather, including successively lamination Base cloth layer not weaving fabric of superfine fiber (the weight per unit area 200g/m of 0.1mm thickness2), the TPU hot melt adhesive of 0.01mm thickness The PU layer of layer, 0.1mm thickness.
Embodiment 7
The difference from embodiment 1 is that the automobile artificial leather texture polyurethane leather, including successively lamination Base cloth layer not weaving fabric of superfine fiber (the weight per unit area 200g/m of 1.5mm thickness2), the TPU hot melt adhesive of 0.05mm thickness The PU layer of layer, 0.01mm thickness.
Embodiment 8
The difference from example 2 is that the automobile artificial leather texture polyurethane leather, including successively lamination Base cloth layer not weaving fabric of superfine fiber (the weight per unit area 200g/m of 0.01mm thickness2), the TPU hot melt adhesive of 0.1mm thickness The PU layer of layer, 0.2mm thickness.
Embodiment 9
Difference with embodiment 3 is, the automobile artificial leather texture polyurethane leather, including successively lamination Base cloth layer not weaving fabric of superfine fiber (the weight per unit area 200g/m of 0.1mm thickness2), the TPU hot melt adhesive of 0.01mm thickness The PU layer of layer, 0.1mm thickness.
Embodiment 10
The difference from embodiment 1 is that the automobile artificial leather texture polyurethane leather, including successively lamination Base cloth layer not weaving fabric of superfine fiber (the weight per unit area 200g/m of 1.5mm thickness2), the EVA hot-melt adhesive of 0.05mm thickness The PU layer of layer, 0.01mm thickness.
The step of preparation method (1) are as follows:
(1) EVA hot-melt adhesive mem stage: the EVA hot-melt adhesive film and base fabric that the EVA hot-melt adhesive for being available commercially from Bayer is cast Carry out, formation first composite membrane compound to pressing.
Embodiment 11
The difference from embodiment 1 is that the automobile artificial leather texture polyurethane leather, including successively lamination Base cloth layer not weaving fabric of superfine fiber (the weight per unit area 200g/m of 1.5mm thickness2), the TPU hot melt adhesive of 0.05mm thickness The PU layer of layer, 0.01mm thickness.
The step of preparation method (1) are as follows:
(1) the TPU hot melt adhesive film stage: the TPU hot melt adhesive that the TPU hot melt adhesive UT7-70AU for being available commercially from Bayer is cast Film carries out, formation first composite membrane compound to pressing with base fabric.
Embodiment 12
Difference with embodiment 3 is that the TPU hot melt adhesive layer is prepared in raw material, and the first catalyst is tin dilaurate Dibutyl tin.
Embodiment 13
Difference with embodiment 3 is that the TPU hot melt adhesive layer is prepared in raw material, the replacement of chain extender 1,4-butanediol For methyl propanediol.
Embodiment 14
Difference with embodiment 3 is that the TPU hot melt adhesive layer is prepared in raw material, and tackifying resin replaces with polyethylene- Acetate ethylene copolymer.
Embodiment 15
A kind of automobile artificial leather texture polyurethane leather, the base fabric layer superfine fibre of the 0.1mm thickness including successively lamination Non-woven cloth (weight per unit area 200g/m2), the TPU hot melt adhesive layer of 0.01mm thickness, by 0.05mm thickness TPU membrane layer and The composite layer of the PU layer composition of 0.05mm thickness.
The TPU hot melt adhesive layer to prepare raw material in parts by weight include the following raw material component:
The polyester polyol the preparation method comprises the following steps: by 1mol decanedioic acid, 2.5mol terephthalic acid (TPA) and 4.0mol second two Alcohol mixing, is then added 0.003mol zirconic acid isopropyl ester, is warming up to 160 DEG C of progress polycondensation reactions and obtains decanedioic acid system polyester polyols Alcohol (weight average molecular weight 1500)；
The fire retardant by include: by weight percentage 25wt% dimethylphosphite, 35wt% ammonium polyphosphate, 35wt% pentaerythrite；
PU layers of the preparation method includes: that PU resin working solution is sprayed in TPU layer to dry bonding；The PU resin The formula of working solution is as follows: 65 parts by weight of polyurethane resin；22 parts by weight of dimethylformamide；60 parts by weight of ethyl acetate；Table 3 parts by weight of face coagent sulfated castor oil；1 parts by weight of antibacterial agent dodecyl dimethyl benzyl ammonium bromide；5 weight of toner Part.
The TPU membrane layer, which passes through to be cast after the mixing of selected raw material, to be obtained, and the raw material components include: heat in parts by weight 93 parts by weight of plastic polyurethane particle；0.05 parts by weight of slipping agent behenamide；0.5 weight of antioxidant dibutyl hydroxy toluene Measure part；0.5 parts by weight of UV resistant agent UV-B83；The thermoplastic polyurethane particle includes the following raw material group in parts by weight Point: weight average molecular weight is 35 parts of polyhexamethylene carbonate diol of 1500；1,5- how 15 parts of diisocyanate；Benzylidene two 25 parts of isocyanates；1,18 parts of 4- butanediol；0.5 part of catalyst.
Preparation method includes the following steps:
(1) the TPU hot melt adhesive film stage: TPU hot melt adhesive is sprayed in base fabric, carry out after drying with base fabric it is compound to pressing, Form the first composite membrane；
(2) the TPU membrane layer compound stage: by thermoplastic polyurethane particle and auxiliary agent by single screw extrusion machine, according to screw rod Temperature is 200 DEG C, and die head temperature is that 190 DEG C of condition is cast into TPU membrane, compound to pressing with the first composite membrane, and it is multiple to form second Close film；
(3) the PU film process stage: prepared PU resin working solution is added on coating machine platform scraper, is arranged under scraper Edge and the second composite membrane spacing 0.3cm, are uniformly coated on TPU membrane surface on the second composite membrane for PU resin working solution, through tunnel Road formula air drier is dry, and temperature is batched spare at 90 DEG C or so, obtains polyurethane leather；
(4) release paper processing stage: above-mentioned polyurethane leather is unreeled, and surface is handled by heating mantles, then passes through emulation Dermatoglyph reason release paper is embossed, and release paper is removed, and cooling winding obtains artificial leather texture polyurethane leather semi-finished product；
(5) it crumples process: the artificial leather texture polyurethane leather semi-finished product of acquisition being placed in temperature is 80 DEG C and rub In line machine, line half an hour is rubbed, that is, completes rubbing program；
(6) arranging process: finally the semi-finished product for completing rubbing program taken out into final finishing out of boarding machine, be in rolls institute The automobile artificial leather texture polyurethane leather stated.
Performance test:
The automobile artificial leather texture polyurethane leather that embodiment obtains is performed the following performance tests:
(1) adhesion strength；The epidermis of the automobile artificial leather texture polyurethane leather of preparation and base cloth layer are shelled From strength test:
(2) hardness: hardness is tested in 23 ± 2 DEG C, the environment of humidity 65 ± 5% with Shore durometer；
(3) it tensile strength: is tested by GB/T 8949-2008；
(4) it tearing strength: is tested by GB/T 8949-2008；
(5) abrasion resistance: under the pressure of 9KPa, wear phenomenon is observed after 1000 turns of mill, Examples 1 to 9 is without abrasion Phenomenon, embodiment 10~11 have a small amount of wear phenomenon, and embodiment 12~14 is less compared with 10~11 wear phenomenon of embodiment；
(6) it elongation at break: is tested by GB/T 8949-2008；
Test result is shown in Table 1:
Table 1
As can be seen from Table 1, the epidermis and base of automobile artificial leather texture polyurethane leather provided by the invention Caking property >=8.0kg/25mm of layer of cloth, for hardness in 80~85A (shore), transverse tensile strength is 34.8~40.6MPa, is indulged It is 32.6~38.1MPa to tensile strength, radial tearing strength is 69.5~74.3kgf/cm, filling-tear resistance 68.0 ~73.2kgf/cm, under the pressure of 9kPa, wear phenomenon is unobvious after 1000 turns of mill, and elongation is 800~1000%.
In addition, when can be seen that the hot melt adhesive commercially available from selecting from the test result of embodiment 10 and 11, adhesive property Resistance to be declined slightly, tensile strength, tearing strength, elongation and abrasion are declined；And when using TPU heat provided by the invention When melten gel composition of raw materials, when preparing hot melt adhesive layer (embodiment 12) using spraying, caking property ability is declined slightly, and is stretched strong Degree, tearing strength, elongation and abrasion are declined；Supposition is because TPU hot melt adhesive provided by the invention is more suitable for logical It crosses casting method and epidermis and base bonds, reduce its influence to mechanical performance.
The Applicant declares that the present invention illustrates the process method of the present invention through the above embodiments, but the present invention not office It is limited to above-mentioned processing step, that is, does not mean that the present invention must rely on the above process steps to be carried out.Technical field Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to raw material selected by the present invention Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.

Claims (9)

1.一种汽车用仿真皮纹理聚氨酯皮革，其特征在于，所述聚氨酯皮革包括依次叠层的基布层、热熔胶层和表皮层；1. A simulated leather texture polyurethane leather for automobiles, characterized in that, the polyurethane leather comprises a base fabric layer, a hot-melt adhesive layer and an epidermis layer stacked in sequence; 所述热熔胶层包括TPU热熔胶层或EVA热熔胶层。The hot-melt adhesive layer includes a TPU hot-melt adhesive layer or an EVA hot-melt adhesive layer. 2.如权利要求1所述的聚氨酯皮革，其特征在于，所述TPU热熔胶层的制备原料按重量份数包括如下原料组分：2. polyurethane leather as claimed in claim 1 is characterized in that, the preparation raw material of described TPU hot-melt adhesive layer comprises following raw material components by weight: 所述聚酯多元醇包括癸二酸系聚酯多元醇，优选分子量为1000～2000的癸二酸系聚酯多元醇；The polyester polyol includes a sebacic acid-based polyester polyol, preferably a sebacic acid-based polyester polyol with a molecular weight of 1000-2000; 优选地，所述癸二酸系聚酯多元醇的制备方法为：将癸二酸、对苯二甲酸与乙二醇混合，然后加入锆酸异丙酯，升温至120～200℃进行缩聚反应得到癸二酸系聚酯多元醇；Preferably, the preparation method of the sebacic acid-based polyester polyol is as follows: mixing sebacic acid, terephthalic acid and ethylene glycol, then adding isopropyl zirconate, heating up to 120-200° C. for polycondensation reaction Obtain sebacic acid polyester polyol; 优选地，所述癸二酸和对苯二甲酸的摩尔比为1:2～3；Preferably, the molar ratio of the sebacic acid and terephthalic acid is 1:2-3; 优选地，所述乙二醇与癸二酸的摩尔比为3.5～4.5:1；Preferably, the molar ratio of ethylene glycol to sebacic acid is 3.5-4.5:1; 优选地，所述锆酸异丙酯的加入量为3×10-3～4×10-3mol/mol癸二酸。Preferably, the added amount of the isopropyl zirconate is 3×10 -3 to 4×10 -3 mol/mol sebacic acid. 3.如权利要求1或2所述的聚氨酯皮革，其特征在于，所述二异氰酸酯包括二苯甲烷二异氰酸酯或甲苯二异氰酸酯；3. The polyurethane leather according to claim 1 or 2, wherein the diisocyanate comprises diphenylmethane diisocyanate or toluene diisocyanate; 优选地，所述第一催化剂包括对甲苯磺酸、二月桂酸二丁基锡、乙二醇锑、四异丙基钛酸酯中的任意1种或至少2种的组合；Preferably, the first catalyst comprises any one or a combination of at least two of p-toluenesulfonic acid, dibutyltin dilaurate, ethylene glycol antimony, and tetraisopropyl titanate; 优选地，所述扩链剂包括1,6-己二醇、甲基丙二醇、1,4-丁二醇中的任意1种或至少2种的组合。Preferably, the chain extender includes any one or a combination of at least two of 1,6-hexanediol, methylpropanediol, and 1,4-butanediol. 4.如权利要求1～3之一所述的聚氨酯皮革，其特征在于，所述TPU热熔胶层的制备原料还包括0.1～1重量份的第一抗氧剂；4. The polyurethane leather according to one of claims 1 to 3, wherein the preparation raw material of the TPU hot-melt adhesive layer further comprises 0.1 to 1 part by weight of a first antioxidant; 优选地，所述第一抗氧剂包括抗氧剂245、抗氧剂1135、抗氧剂PUR67、抗氧剂PUR68中的任意1种或至少2种的组合；Preferably, the first antioxidant comprises any one or a combination of at least two of Antioxidant 245, Antioxidant 1135, Antioxidant PUR67, and Antioxidant PUR68; 优选地，所述TPU热熔胶层的制备原料还包括0.1～5重量份的阻燃剂；Preferably, the preparation raw materials of the TPU hot-melt adhesive layer further include 0.1 to 5 parts by weight of a flame retardant; 优选地，所述阻燃剂按重量百分比包括：20～30wt％的亚磷酸二甲酯、30～40wt％的聚磷酸铵、30～40wt％的季戊四醇；Preferably, the flame retardant comprises by weight percentage: 20-30wt% of dimethyl phosphite, 30-40wt% of ammonium polyphosphate, and 30-40wt% of pentaerythritol; 优选地，所述TPU热熔胶层的制备原料还包括0.1～5重量份的增粘树脂；Preferably, the preparation raw materials of the TPU hot-melt adhesive layer further include 0.1-5 parts by weight of tackifying resin; 优选地，所述增粘树脂包括聚乙烯-醋酸乙烯共聚物、端羟基热塑性聚酯、氢化松香树脂中的任意1种或至少2种的组合。Preferably, the tackifying resin comprises any one or a combination of at least two of polyethylene-vinyl acetate copolymer, hydroxyl-terminated thermoplastic polyester, and hydrogenated rosin resin. 5.如权利要求1～4之一所述的聚氨酯皮革，其特征在于，所述表皮层包括干式PU层、TPU层中的任意1种或至少2种的复合层；5. The polyurethane leather according to any one of claims 1 to 4, wherein the skin layer comprises any one or at least two composite layers of a dry PU layer and a TPU layer; 优选地，所述表皮层为TPU层和干式PU层的复合层，优选厚度比为1:1的TPU层和干式PU层的复合层；Preferably, the skin layer is a composite layer of a TPU layer and a dry PU layer, preferably a composite layer of a TPU layer and a dry PU layer with a thickness ratio of 1:1; 优选地，所述TPU层和干式PU层的复合层通过将PU树脂工作液涂布在所述TPU层上烘干粘合得到；Preferably, the composite layer of the TPU layer and the dry PU layer is obtained by coating the PU resin working solution on the TPU layer, drying and bonding; 优选地，所述TPU层设置于PU层和热熔胶层之间。Preferably, the TPU layer is arranged between the PU layer and the hot melt adhesive layer. 6.如权利要求1～5之一所述的聚氨酯皮革，其特征在于，所述TPU层的制备原料按重量份数包括如下原料组分：6. The polyurethane leather according to one of claims 1 to 5, wherein the preparation raw materials of the TPU layer comprise the following raw material components in parts by weight: 所述热塑性聚氨酯颗粒的制备原料按重量份数包括如下组分：The preparation raw materials of the thermoplastic polyurethane particles include the following components in parts by weight: 优选地，所述聚六亚甲基碳酸酯二醇的重均分子量为1000～2000；Preferably, the weight average molecular weight of the polyhexamethylene carbonate diol is 1000-2000; 优选地，所述爽滑剂选自油酸酰胺、芥酸酰胺或山嵛酸酰胺中的任意1种或至少2种的组合；Preferably, the slip agent is selected from any one or a combination of at least two of oleic acid amide, erucic acid amide or behenic acid amide; 优选地，所述第二抗氧化剂选自二硬脂基季戊四醇亚磷酸酯、亚磷酸三苯酯、二丁基羟基甲苯BHT、N,N’-双[[3-(3,5)-二叔丁基-4-羟基苯基]丙酰基]己二胺中的任意1种或至少2种的组合；Preferably, the second antioxidant is selected from distearyl pentaerythritol phosphite, triphenyl phosphite, dibutylhydroxytoluene BHT, N,N'-bis[[3-(3,5)-bis Any one or a combination of at least two of tert-butyl-4-hydroxyphenyl]propionyl]hexanediamine; 优选地，所述抗紫外剂选自UV-P、UV-328或UV-B83中的任意1种或至少2种的组合。Preferably, the anti-ultraviolet agent is selected from any one or a combination of at least two of UV-P, UV-328 or UV-B83. 优选地，所述第二催化剂包括对甲苯磺酸、二月桂酸二丁基锡、乙二醇锑、四异丙基钛酸酯中的任意1种或至少2种的组合。Preferably, the second catalyst comprises any one or a combination of at least two of p-toluenesulfonic acid, dibutyltin dilaurate, ethylene glycol antimony, and tetraisopropyl titanate. 7.如权利要求1～6之一所述的聚氨酯皮革，其特征在于，所述基布层的厚度为0.1～3.0mm；7. The polyurethane leather according to any one of claims 1 to 6, wherein the base fabric layer has a thickness of 0.1 to 3.0 mm; 优选地，所述热熔胶层的厚度为0.01～0.1mm；Preferably, the thickness of the hot melt adhesive layer is 0.01-0.1 mm; 优选地，所述TPU热熔胶层厚度为0.01～0.1mm；Preferably, the thickness of the TPU hot melt adhesive layer is 0.01-0.1 mm; 优选地，所述EVA热熔胶层厚度为0.01～0.1mm；Preferably, the thickness of the EVA hot-melt adhesive layer is 0.01-0.1 mm; 优选地，所述表皮层的厚度为0.01～0.2mm；Preferably, the thickness of the skin layer is 0.01-0.2 mm; 优选地，所述TPU层的厚度为0.01～0.1mm；Preferably, the thickness of the TPU layer is 0.01-0.1 mm; 优选地，所述基布层包括超细纤维非织造布，优选单位面积重量为50-400g/m2的超细纤维非织造布；Preferably, the base fabric layer comprises a superfine fiber non-woven fabric, preferably a superfine fiber non-woven fabric with a weight per unit area of 50-400 g/m 2 ; 优选地，所述热熔胶层通过将热熔胶流延得到。Preferably, the hot melt adhesive layer is obtained by casting the hot melt adhesive. 8.根据权利要求1～7之一所述的聚氨酯皮革的制备方法，其特征在于，所述制备方法包括如下步骤：8. The preparation method of polyurethane leather according to one of claims 1 to 7, wherein the preparation method comprises the following steps: (1)TPU热熔胶膜的制备：按照TPU热熔胶层的制备原料配方混合制备原料，螺杆挤出得到TPU热熔胶颗粒，将所述TPU热熔胶颗粒通过单螺杆挤出机按照温度为180～220℃，模头温度为180～210℃的条件流延得到的TPU热熔胶膜，将所述TPU热熔胶膜与基布进行对压复合，形成第一复合膜；(1) Preparation of TPU hot-melt adhesive film: according to the preparation raw material formula of the TPU hot-melt adhesive layer, the raw materials are mixed and prepared, and the TPU hot-melt adhesive particles are obtained by screw extrusion, and the TPU hot-melt adhesive particles are passed through a single-screw extruder according to Casting the obtained TPU hot-melt adhesive film under the condition that the temperature is 180-220°C and the die temperature is 180-210°C, the TPU hot-melt adhesive film and the base fabric are pressed and compounded to form a first compound film; (2)TPU层复合阶段：按照TPU层的制备原料配方混合制备原料，螺杆挤出得到TPU膜颗粒，将所述TPU膜颗粒通过单螺杆挤出机按照温度为180～220℃，模头温度为180～210℃的条件流延得到TPU层；将所述TPU层与第一复合膜对压复合，形成第二复合膜；(2) TPU layer compounding stage: mixing and preparing raw materials according to the preparation raw material formula of the TPU layer, screw extrusion to obtain TPU film particles, and passing the TPU film particles through a single-screw extruder according to the temperature of 180-220 ° C, the temperature of the die head Casting at 180-210° C. to obtain a TPU layer; pressing and compounding the TPU layer and the first composite film to form a second composite film; (3)PU膜处理阶段：将PU树脂加入到涂布机上，将PU树脂工作液均匀涂布在第二复合膜的TPU层表面，经80～100℃隧道式热风干燥机干燥，卷取备用，得到聚氨酯皮革；(3) PU film treatment stage: add PU resin to the coating machine, evenly coat the PU resin working solution on the surface of the TPU layer of the second composite film, dry it in a tunnel-type hot air dryer at 80-100°C, and roll it for later use , to obtain polyurethane leather; 可选地，步骤(3)之后进行步骤(4)～(6)：Optionally, steps (4) to (6) are performed after step (3): (4)离型纸处理阶段：将聚氨酯皮革放卷，表面经过加热罩处理，再通过仿真皮纹理离型纸进行压纹，剥离离型纸，冷却收卷，得到仿真皮纹理聚氨酯皮革半成品；(4) Release paper processing stage: unwind the polyurethane leather, and the surface is treated with a heating cover, then embossed through the imitation leather texture release paper, peeled off the release paper, cooled and wound to obtain the imitation leather texture polyurethane leather semi-finished product; (5)搓揉工艺程序：将获得的仿真皮纹理聚氨酯皮革半成品置于温度为70-90℃的揉纹机内，揉纹半小时，即完成搓揉程序；(5) Kneading process procedure: place the obtained semi-finished product of simulated leather texture polyurethane leather in a kneading machine with a temperature of 70-90° C., and knead the grains for half an hour to complete the kneading procedure; (6)整理工序：最后将完成搓揉程序的半成品从揉纹机内取出后整理、成卷即为所述的汽车用仿真皮纹理聚氨酯皮革。(6) Finishing process: finally, the semi-finished product that has completed the rubbing procedure is taken out of the rubbing machine, and then the finished product is finished and rolled into a roll to obtain the simulated leather texture polyurethane leather for automobiles. 9.根据权利要求8所述的聚氨酯皮革的制备方法，其特征在于，步骤(3)所述涂布机台中刮刀下边缘与第二复合膜间距0.1～0.5cm。9 . The method for preparing polyurethane leather according to claim 8 , wherein the distance between the lower edge of the scraper and the second composite film in the step (3) of the coating machine table is 0.1-0.5 cm. 10 .
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