CN106827751B - A kind of environment-friendly type automobile inner decoration composite material and preparation method - Google Patents
A kind of environment-friendly type automobile inner decoration composite material and preparation method Download PDFInfo
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- CN106827751B CN106827751B CN201710069769.2A CN201710069769A CN106827751B CN 106827751 B CN106827751 B CN 106827751B CN 201710069769 A CN201710069769 A CN 201710069769A CN 106827751 B CN106827751 B CN 106827751B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention provides a kind of environment-friendly type automobile inner decoration composite material and preparation method, automobile interior decoration composite material includes epidermis 1, foaming layer 2, hot melt adhesive layer 3 and skeleton structure layer 4, epidermis is TPU membrane layer, TPO film layer, PU film layer, PP film layer, PVC film layer or skin corium, foaming layer is PPF foaming layer (IXPP), PU foaming layer or PE foaming layer, hot melt adhesive layer is TPU hot melt adhesive layer, EVA hot-melt adhesive layer, PE hot melt adhesive layer, PA hot melt adhesive layer or this is several and other are modified/not modified hot melt adhesive layer, skeleton structure is MODIFIED PP material, PC/ABS modified material, ABS MODIFIED PP composite material or PP material.The present invention is bonded on the surface layer with foaming layer with skeleton structure using Environmental-friendhot hot melt adhesive, solve environmental issue, the high cost problem that traditional glue spraying water-drying-attaching process production automobile interior decoration composite material generates, the bondability of product is good, rejection rate is low, effectively guarantee forming quality of products, saves equipment, artificial and space；It is the low smell of product, low volatilization, high-low temperature resistant, weather-proof, it is not easy to peel off, production process environmental protection is pollution-free.
Description
Technical field
The invention belongs to technical field of polymer materials, are related to a kind of automobile interior decoration composite material and preparation method, especially
It is related to a kind of environment-friendly type automobile inner decoration composite material and preparation method.
Background technique
Instrument board is the important component of automobile interior decoration.In recent years, with the continuous progress of technology, more operating works
It can be integrated into instrument board.Obviously, in order to ensure the various instrument and part that are supported can run at high speed and vibrate
Worked normally under state, instrument board must have enough rigidity, and occur to reduce external force when accident to just, copilot
Impact also requires instrument board to have good energy absorption capacity.Meanwhile for comfortable and aesthetic requirement, the feel of instrument board, skin
Line, color and tone etc. are also increasingly subject to the attention of people.
In short, instrument board collects safety, functionality, comfort and dicoration in one as a kind of unique inner-decoration component
Body, the quality of these performances have become one of the major criterion for judging vehicle grade.Generally, instrument provisioned in different vehicles
Plate grade is entirely different.According to the configuration requirement of vehicle, suitable instrument board production technology may be selected, reduce life to reach
Produce the purpose of cost.
Decorative sheet in middle of vehicle door generallys use three-decker: epidermis uses PVC or PVC+ABS material；Buffer layer uses PUR
Foamed material；Skeleton is using materials such as MODIFIED PP, ABS.Traditional decorative sheet in middle of vehicle door has the following problems:
(1) decorative sheet in middle of vehicle door is difficult to recycle.Decorative sheet in middle of vehicle door has three-decker, and the material category of each layer is different
It causes, thermal characteristics is also inconsistent.Therefore, it when decorative sheet in middle of vehicle door recycles, needs first to split epidermis, buffer layer and skeleton,
The recycling of each layer is carried out again.The recycling of traditional decorative sheet in middle of vehicle door is extremely complex, and process is more, and can not recycle completely.
(2) traditional decorative sheet in middle of vehicle door epidermis uses PVC or PVC+ABS material.PVC or PVC+ABS material is in addition to packet
Basic resin is included, addition plasticizer, stabilizer etc. are also needed.PVC or PVC+ABS epidermis thermal stability is poor, will cause not after heated
With the degradation of degree, small-molecule substance is released, volatility is high, causes in-vehicle air pollution.
The trim panels material such as traditional arrangements for automotive doors, instrument board, which generally passes through, repeatedly to be formed, complex process, equipment valuableness,
High production cost.Superficial layer, foaming layer and casing play are bonded usually using organic glue or other adhesive, with spraying
Or rolling gluing or other processing methods, long-time service release noxious material are harmful to the human body, not environmentally.Product surface lines,
Color consistency is poor, and grain pattern is limited, and color is not easy to replace.During processing not environmentally, there are pollution, Fei Rengong.
Therefore, it is expected to obtain one kind in this field may be easy to process, and adhesive strength is high, and wearability is excellent, have high
Tearing strength and dimensional stability are not easy to peel off, and comfortable feel is good, environmental protection, and specious automotive interior material.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of automobile interior decoration composite material and its preparation sides
Method is especially to provide a kind of environment-friendly type automobile inner decoration composite material and preparation method.
In order to achieve that object of the invention, the invention adopts the following technical scheme:
On the one hand, the present invention provides a kind of environment-friendly type automobile inner decoration composite material, the environment-friendly type automobile inner decoration composite wood
Material successively includes epidermis, foaming layer, hot melt adhesive layer and skeleton structure from top to bottom.
Preferably, the epidermis is TPU membrane layer, TPO film (thermoplastic polyolefin film) layer, PU film layer, PP film layer or true
Any one in cortex, preferably TPO film layer.
Preferably, the epidermis is that environmentally friendly treated the epidermis in surface is carried out using aqueous or oleoresin.
Preferably, the epidermis layer surface has decorative pattern.
Preferably, the foaming layer is any one in PP foaming layer, PPF foaming layer, PU foaming layer or PE foaming layer,
It is preferred that PPF foaming layer.
Preferably, the hot melt adhesive layer is in TPU hot melt adhesive layer, EVA hot-melt adhesive layer, PE hot melt adhesive layer or PA hot melt adhesive layer
Any one, preferred TPU hot melt adhesive layer.
Preferably, the skeleton structure is glass MODIFIED PP composite material, carbon fiber MODIFIED PP composite material or ABS MODIFIED PP
Any one in composite material.
Preferably, the epidermis with a thickness of 0.01mm-5.0mm, such as 0.01mm, 0.05mm, 0.08mm, 0.1mm,
0.3mm、0.5mm、0.8mm、1mm、1.3mm、1.5mm、1.8mm、2mm、2.5mm、2.8mm、3mm、3.5mm、3.8mm、4mm、
4.5mm, 4.8mm or 5mm, preferably 1.0mm-5.0mm.
Preferably, the foaming layer with a thickness of 1.0mm-10.0mm, such as 1mm, 1.3mm, 1.5mm, 1.8mm, 2mm,
2.5mm, 3mm, 3.5mm, 4mm, 4.5mm, 5mm, 6mm, 7mm, 8mm, 9mm or 10mm, preferably 1.0mm-5.0mm.
Preferably, the hot melt adhesive layer with a thickness of 0.01mm-2.0mm, such as 0.01mm, 0.03mm, 0.05mm,
0.08mm, 0.1mm, 0.3mm, 0.5mm, 0.8mm, 1mm, 1.3mm, 1.5mm, 1.8mm or 2mm, preferably 1.0mm-2.0mm.
Preferably, the skeleton structure layer with a thickness of 0.1mm-10mm, such as 1mm, 1.3mm, 1.5mm, 1.8mm,
2mm, 2.5mm, 3mm, 3.5mm, 4mm, 4.5mm, 5mm, 6mm, 7mm, 8mm, 9mm or 10mm, preferably 5.0mm-8.0mm.
In the structure of automobile interior decoration composite material of the invention, the thickness needs between each layer are mutually coordinated, if its
In a certain layer it is blocked up or excessively thin, the performance of integral material may all be generated it is certain influence, for example, if epidermis is too thick, then
May due in use, automobile interior decoration composite material when needing to bend, each interlayer unbalance stress, and interlayer is caused to be easy to
Sliding, influences integrally-built stability；If the thickness of hot melt adhesive layer is too thin, can adhesiveness be declined, if hot melt
Glue-line it is too thick, although can be strongly adhered in skeleton structure layer, bending when can make unbalance stress, cause interlayer
Sliding, influences integrally-built stability.
Preferably, the raw material of the TPO film layer includes following ingredient:
In the present invention, using cross-linked thermoplastic elastomer as the surface layer material bed of material, wearability is good, and machine-shaping property is excellent
It is different.
What it is in cross-linked thermoplastic elastomer of the present invention can be 50 parts by weight, 53 parts by weight, 55 weight with meter
Part, 58 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight or 80 parts by weight.
In the present invention, the dosage of the PE can be 0 parts by weight, 1 parts by weight, 5 parts by weight, 8 parts by weight, 10 weight
Part, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight or 50 parts by weight.
In the present invention, the dosage of the PP can be 0 parts by weight, 1 parts by weight, 5 parts by weight, 8 parts by weight, 10 weight
Part, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight or 50 parts by weight.
In the present invention, the dosage of the light stabilizer can be 0 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 0.8 weight
Measure part, 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.8 parts by weight, 2.0 parts by weight, 2.2 parts by weight, 2.4 parts by weight,
2.6 parts by weight, 2.8 parts by weight, 3.0 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight or 5 parts by weight.
In the present invention, the dosage of the lubrication prescription can for 0 parts by weight, 0.2 parts by weight, 0.4 parts by weight, 0.6 parts by weight,
0.8 parts by weight, 1.0 parts by weight, 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.8 parts by weight, 2.0 parts by weight, 2.2 weight
Part, 2.4 parts by weight, 2.6 parts by weight or 2.8 parts by weight.
In the present invention, the dosage of the fire retardant can be 0 parts by weight, 0.6 parts by weight, 0.8 parts by weight, 1.0 weight
Part, 1.2 parts by weight, 1.5 parts by weight, 2.0 parts by weight, 3.0 parts by weight, 4.0 parts by weight, 5.0 parts by weight, 6.0 parts by weight, 7.0
Parts by weight, 8.0 parts by weight, 9.0 parts by weight or 10 parts by weight.
In the present invention, the dosage of the Masterbatch can be 0 parts by weight, 0.2 parts by weight, 0.4 parts by weight, 0.6 weight
Part, 0.8 amount part, 1.0 parts by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 4 parts by weight, 4.5 parts by weight, 5
Parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight or 10 parts by weight.
Preferably, the cross-linked thermoplastic elastomer material includes following ingredient:
Preferably, the raw material of the cross-linked thermoplastic elastomer also include 0.1-20 parts by weight (such as 0.2 parts by weight,
0.8 parts by weight, 1 parts by weight, 3 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 16 weight
Part, 18 parts by weight or 20 parts by weight) other additives.
Preferably, other described additives include in antiager, light stabilizer or antioxidant any one or extremely
Few two kinds of combination.
What it is in olefin rubber of the present invention can be 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 weight with meter
Part, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70
Parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight or 90 parts by weight.
In the present invention, the dosage of the olefine kind resin can be 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 weights
Measure part, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight,
70 parts by weight, 75 parts by weight, 80 parts by weight or 85 parts by weight.
In the present invention, cross-linked thermoplastic elasticity can be enhanced in the olefin rubber and olefine kind resin mutual cooperation
The stability of body and its wear-resisting property and elastic property guarantee that epidermis has excellent abrasive resistance and processing performance.
In the present invention, the dosage of the crosslinking agent can be 1 parts by weight, 3 parts by weight, 5 parts by weight, 8 parts by weight, 10 weights
Measure part, 13 parts by weight, 16 parts by weight, 19 parts by weight, 22 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 33 parts by weight,
35 parts by weight, 38 parts by weight, 40 parts by weight, 43 parts by weight, 45 parts by weight, 48 parts by weight or 50 parts by weight.
In the present invention, the dosage of the plasticising oil can be 1 parts by weight, 3 parts by weight, 5 parts by weight, 8 parts by weight, 10 weights
Measure part, 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight, 20 parts by weight, 23 parts by weight, 25 parts by weight, 28 parts by weight
Or 30 parts by weight.
Preferably, the olefin rubber includes ethylene propylene diene rubber, butadiene-styrene rubber, neoprene, nitrile rubber or fluorine
In rubber any one or at least two combination, preferred nitrile rubber.
Preferably, the olefine kind resin includes PP and/or PE.
In the present invention, the PE is non-crosslinked PE.
Preferably, the PE includes any one in LDPE, LLDPE, MDPE, HDPE or UHMWPE or at least two
Combination, preferably LLDPE.
In the present invention, the PP is non-crosslinked PP.
Phase between using noncrosslinking PE and PP cooperation cross-linked thermoplastic elastomer that can make in the present invention
Capacitive is more preferable, and contact sufficiently, improves wearability and processing performance.
Preferably, the light stabilizer includes ultraviolet absorbing agent.
Preferably, the raw material of the hot melt adhesive layer includes following ingredient:
TPU hot-melt adhesive granules 70-100 parts by weight；
Lubrication prescription 0-5 parts by weight；
Modified Tackifier materials 0-30 parts by weight.
In the raw material of the hot melt adhesive layer of the invention, the content of the TPU hot-melt adhesive granules is 70 parts by weight, 73 weights
Measure part, 75 parts by weight, 78 parts by weight, 80 parts by weight, 82 parts by weight, 85 parts by weight, 88 parts by weight, 90 parts by weight, 93 parts by weight,
95 parts by weight, 98 parts by weight or 100 parts by weight.
The dosage of the lubrication prescription described in the raw material of the hot melt adhesive layer of the invention is 0 parts by weight, 0.5 parts by weight, 0.8 weight
Measure part, 1 parts by weight, 1.2 parts by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight,
4.5 parts by weight or 5 parts by weight.
Preferably, the raw material of the TPU hot-melt adhesive granules includes following component:
In the present invention, when the hot melt adhesive layer is using the TPU hot-melt adhesive granules preparation being formulated as described above, the hot melt adhesive
Layer is environment friendly and pollution-free, can using the tape casting, heat posted is legal and glue spraying method in any one method make via the hot melt adhesive
Layer is compound by the progress of the epidermis, foaming layer and skeleton structure layer, so that Coating combination is secured, it is not easily to fall off.
In the present invention, using the environment-friendly type hot melt glue being as above formulated as adhesive layer, have excellent adhesion can and
Flexibility there is heating then to melt, the cooling characteristic then glued, make the automotive interior product firmness of preparation, be not likely to produce interlayer
Peeling phenomenon, wear-resisting, environmental protection, comfortable feel, surface aesthetic.
Preferably, the diisocyanate is hexamethylene diisocyanate, cyclohexanedimethyleterephthalate diisocyanate, 1,6-
In hexamethylene diisocyanate or isophorone diisocyanate any one or at least two combination, preferred two isocyanide of hexamethyl
The combination of acid esters and hexamethylene diisocyanate.
Preferably, the hexamethylene diisocyanate and 1, hexamethylene diisocyanate in the combination of hexamethylene-diisocyanate
With 1, the mass ratio of hexamethylene-diisocyanate is 1:(5-10), such as 1:5,1:5.5,1:5.8,1:6,1:6.3,1:6.5,1:
6.8,1:7,1:7.3,1:7.5,1:7.8,1:8,1:8.5,1:8.8,1:9,1:9.4,1:9.8 or 1:10.
Preferably, the polyalcohol is the combination of the pure and mild polyester polyol of polyether polyols.
Preferably, the mass ratio of the pure and mild polyester polyol of polyether polyols is (7-9) in the polyalcohol: 1, such as 7:1,
7.3:1,7.5:1,7.8:1,8:1,8.3:1,8.5:1,8.8:1 or 9:1.
In the present invention preferably by two kinds of specific diisocyanate, polyalcohol is cooperated to use enhancing TPU hot melt adhesive
The flexibility and toughness of layer, enhance the bonding effect of this layer.
Preferably, the number-average molecular weight of the polyalcohol be 500-2000, such as 500,700,900,1000,1200,
1400,1600,1800 or 2000, preferably 500-1000.
Preferably, the catalyst includes triethanolamine, N, the bis- beautiful jade base Anaesthetie Ethers of N'-, tetra-n-butyl tin, protochloride
Any one in tin, stannous octoate, hydroxyl tin trimethyl or dibutyl tin dilaurate or at least two combination, the combination
Typical but non-limiting embodiment has: triethanolamine and N, combination, triethanolamine and the four positive fourths of the bis- beautiful jade base Anaesthetie Ethers of N'-
The combination of base tin, the combination of tetra-n-butyl tin and stannous chloride, stannous chloride and stannous octoate combination, stannous octoate and hydroxyl
The combination of tin trimethyl, the combination of hydroxyl tin trimethyl and dibutyl tin dilaurate or triethanolamine, stannous chloride and two fourths
The combination etc. of base tin dilaurate tin.
Preferably, the chain extender includes 1,4-butanediol, 1,6- hexylene glycol, diethylene glycol (DEG), diethylaminoethanol, N, N- bis-
Any one in hydroxyl (diisopropyl) aniline, ethylenediamine or the chloro- 4,4' diamino-diphenyl methane of 3,3'- bis- or at least two
The combination of kind, the combination is typical but non-limiting example has: 1,4-butanediol and 1, the combination of 6- hexylene glycol, 1,6- hexylene glycol
The combination of combination, diethylene glycol (DEG) and diethylaminoethanol with diethylene glycol (DEG), N, N- dihydroxy (diisopropyl) aniline and ethylenediamine
It combines, combination or the 1,4- butanediol, lignocaine second of 1,4- butanediol and the chloro- 4,4' diamino-diphenyl methane of 3,3'- bis-
The combination etc. of pure and mild N, N- dihydroxy (diisopropyl) aniline.
Preferably, the antioxidant includes antioxidant 1010, antioxidant 1076, irgasfos 168 or 2,6- di-t-butyl -4-
Any one in methylphenol or at least two combination, the combination is typical but non-limiting example has: antioxidant 1010 and
The combination of antioxidant 1076, the combination of antioxidant 1076 and irgasfos 168, irgasfos 168 and 2,6- di-t-butyl -4- methylbenzene
The combination or antioxidant 1010 of phenol, the combination of antioxidant 1076 and irgasfos 168 etc..
Preferably, the modified Tackifier materials are tackifying resin, Tackified emulsion, thickening powder or viscosify appointing in rosin resin
It anticipates a kind of or at least two combinations, preferably tackifying resin.
In the raw material of TPU hot-melt adhesive granules of the invention, the dosage of the diisocyanate can be 50 parts by weight, 52
Parts by weight, 55 parts by weight, 58 parts by weight, 60 parts by weight, 63 parts by weight, 65 parts by weight, 68 parts by weight, 70 parts by weight, 73 weight
Part, 75 parts by weight, 78 parts by weight or 80 parts by weight.
In the raw material of TPU hot-melt adhesive granules of the invention, the dosage of the polyalcohol can be 35 parts by weight, 36 weight
Part, 37 parts by weight, 38 parts by weight, 39 parts by weight, 40 parts by weight, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight or
50 parts by weight.
In the raw material of TPU hot-melt adhesive granules of the invention, the dosage of the catalyst can be 0.1 parts by weight, 0.5 weight
Measure part, 0.8 parts by weight, 1 parts by weight, 1.3 parts by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 weight
Part, 4 parts by weight, 4.5 parts by weight or 5 parts by weight.
In the raw material of TPU hot-melt adhesive granules of the invention, the dosage of the chain extender can be 3 parts by weight, 3.5 weight
Part, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 weight
Part, 12 parts by weight, 13 parts by weight, 14 parts by weight or 15 parts by weight.
In the raw material of TPU hot-melt adhesive granules of the invention, the dosage of the antioxidant can be 0.1 parts by weight, 0.3 weight
Measure part, 0.5 parts by weight, 0.8 parts by weight, 1 parts by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight or 5 parts by weight.
Preferably, the raw material of the skeleton structure layer includes following ingredient:
PP 80-100 parts by weight
ABS 5-30 parts by weight
Filler 0.1-10 parts by weight.
In the raw material of skeleton structure layer of the present invention, the dosage of the PP (polypropylene) can be 80 parts by weight, 82
Parts by weight, 85 parts by weight, 88 parts by weight, 90 parts by weight, 93 parts by weight, 95 parts by weight, 98 parts by weight or 100 parts by weight, it is described
The dosage of ABS (terpolymer of acrylonitrile, butadiene and styrene) can be 6 parts by weight, 8 parts by weight, 10 parts by weight, 12
Parts by weight, 14 parts by weight, 16 parts by weight, 20 parts by weight, 22 parts by weight, 24 parts by weight, 26 parts by weight or 28 parts by weight.It is described to fill out
The dosage of material can be 0.2 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1.0 parts by weight, 2.0 parts by weight, 3.0
Parts by weight, 4.0 parts by weight, 5.0 parts by weight, 6.0 parts by weight, 7.0 parts by weight, 8.0 parts by weight or 9.0 parts by weight.
On the other hand, the present invention provides the preparation method of automobile interior decoration composite material as described above, the methods are as follows:
By epidermis, foaming layer thermal-adhering synchronous with hot melt adhesive layer, 3-layer composite material is obtained, then by 3-layer composite material and skeleton
Structural material is placed in a mold, by vacuum forming, obtains the automobile interior decoration composite material.
As optimal technical scheme, the automobile interior decoration composite material the preparation method comprises the following steps: by TPO film layer, PPF foaming layer
Thermal-adhering synchronous with TPU hot melt adhesive layer obtains 3-layer composite material, then places 3-layer composite material and frame structure material
In a mold, by vacuum forming, the automobile interior decoration composite material is obtained.
As further preferred technical solution, the preparation method of the automobile interior decoration composite material the following steps are included:
(1) by olefin rubber, olefine kind resin, crosslinking agent, plasticising oil and optionally other additives according to metering ratio
It is added in reaction vessels and reacts, obtain cross-linked thermoplastic elastomer；
(2) cross-linked thermoplastic elastomer, the PE, PP, light stabilizer, lubrication prescription, fire retardant, color masterbatch obtained step (1)
Grain, than being added to melting extrusion in screw extruder, being granulated, obtains TPO particle according to metering；
(3) the TPO particle that step (2) obtain is added in screw extruder, melting extrusion, T-type curtain coating obtains TPO
Film；
(4) diisocyanate, polyalcohol, catalyst, chain extender, antioxidant are added to screw extruder according to metering ratio
Middle melting extrusion, granulation obtain TPU hot-melt adhesive granules；
(5) TPU hot-melt adhesive granules and optional lubrication prescription and Tackifier materials are added in screw extruder, melting is squeezed
Out, T-type is cast, and obtains TPU hot melt adhesive film；
(6) the TPU hot melt adhesive film heat posted synchronous with PPF foaming layer that the TPO film and step (5) obtained step (3) obtains
It closes, obtains 3-layer composite material, the 3-layer composite material and the frame structure material of injection molding are placed in a mold, led to
Vacuum forming is crossed, a kind of environment-friendly type automobile inner decoration composite material is obtained.
Preferably, the temperature of step (1) described reaction be 60-250 DEG C, such as 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C,
110℃、120℃、130℃、140℃、150℃、160℃、170℃、180℃、190℃、200℃、210℃、220℃、230
℃、240℃、250℃。
Preferably, the time of step (1) described reaction is 1-30 hours, such as 1 hour, 3 hours, 5 hours, 8 hours, 10
Hour, 12 hours, 15 hours, 18 hours, 20 hours, 24 hours, 26 hours, 28 hours or 30 hours.
Preferably, the feeding section temperature of step (2) described screw extruder is 120-230 DEG C of (120 DEG C, 140 DEG C, 170
DEG C, 180 DEG C, 200 DEG C or 230 DEG C), mixing section temperature is 120-240 DEG C of (such as 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C, 200
DEG C, 220 DEG C or 240 DEG C), extruding zone temperature is 130-260 DEG C of (such as 130 DEG C, 150 DEG C, 180 DEG C, 200 DEG C, 210 DEG C, 220
DEG C, 230 DEG C, 240 DEG C, 250 DEG C or 260 DEG C), head temperature be 120-250 DEG C (such as 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C,
200 DEG C, 230 DEG C or 250 DEG C).
The feeding section temperature of step (3) described screw extruder be 150-230 DEG C (such as 150 DEG C, 170 DEG C, 190 DEG C,
210 DEG C or 230 DEG C), mixing section temperature is 160-240 DEG C (such as 160 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 220 DEG C or 240
DEG C), extruding zone temperature is 180-280 DEG C (such as 180 DEG C, 200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C, 240 DEG C, 250 DEG C, 260 DEG C
Or 280 DEG C), head temperature is 180-270 DEG C (such as 180 DEG C, 190 DEG C, 200 DEG C, 220 DEG C, 240 DEG C or 270 DEG C).
Preferably, step (2) granulation step is omitted, step (2) and step (3) is merged into following steps: will
Cross-linked thermoplastic elastomer, PE, PP, light stabilizer, lubrication prescription, fire retardant, the Masterbatch of step (1) acquisition add according to metering ratio
Enter into screw extruder, melting extrusion, T-type curtain coating obtains TPO film；
Preferably, surface environmental protection treatment is carried out to the TPO film that step (3) obtains using aqueous or oleoresin；Certainly
It can be without surface environmental protection treatment.
Preferably, the feeding section temperature of step (4) described screw extruder be 100-150 DEG C (such as 100 DEG C, 105 DEG C,
110 DEG C, 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C, 140 DEG C or 150 DEG C), mixing section temperature be 120-180 DEG C (such as 120 DEG C,
130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C or 180 DEG C), extruding zone temperature is 170-210 DEG C of (such as such as 170 DEG C, 175
DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 200 DEG C or 210 DEG C), head temperature is 150-180 DEG C (such as 150 DEG C, 160 DEG C, 170 DEG C
Or 180 DEG C).
Preferably, the feeding section temperature of step (5) described screw extruder is 60-220 DEG C of (such as 60 DEG C, 80 DEG C, 100
DEG C, 130 DEG C, 150 DEG C, 180 DEG C, 200 DEG C or 220 DEG C), mixing section temperature be 70-230 DEG C (such as 70 DEG C, 90 DEG C, 120 DEG C,
150 DEG C, 180 DEG C, 200 DEG C, 220 DEG C or 230 DEG C), extruding zone temperature is 80-230 DEG C of (such as 80 DEG C, 100 DEG C, 130 DEG C, 150
DEG C, 180 DEG C, 200 DEG C, 220 DEG C or 230 DEG C), head temperature is 70-230 DEG C of (such as 70 DEG C, 90 DEG C, 120 DEG C, 150 DEG C, 180
DEG C, 200 DEG C or 230 DEG C).
Preferably, in the present invention, it is described state thermal-adhering temperature be 50-250 DEG C, such as 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C,
90 DEG C, 100 DEG C, 120 DEG C, 150 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 240 DEG C or 250 DEG C；Preferably, the thermal-adhering temperature is
180℃。
Preferably, the pressure of the vacuum forming be -0.1~-1MPa, such as -0.1MPa, -0.2MPa, -0.3MPa, -
0.4MPa, -0.5MPa, -0.6MPa, -0.7MPa, -0.8MPa, -0.9MPa or -1MPa, preferably -0.9MPa.
Preferably, the heating temperature when vacuum forming is 50-250 DEG C, such as 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90
DEG C, 100 DEG C, 120 DEG C, 150 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 240 DEG C or 250 DEG C；It is preferred that 180 DEG C.
Preferably, if not carrying out surface environmental protection treatment to the TPO film that step (3) obtains, three layers are obtained in step (6)
After composite material, environmental protection treatment and surface detail processing (even if material surface has decorative pattern) are carried out to its surface.
Compared with the existing technology, the invention has the following advantages:
(1) present invention is bonded epidermis, foaming layer and skeleton structure using environment-friendly hot-melt glue-line, bonds journey
It spends, rejection rate is low, is effective to ensure that the Forming Quality of product；High production efficiency saves manually, efficiently solves automobile
Composite material has been easy to purse up bulging phenomenon.
(2) present invention passes through to the raw material composition of epidermis and foaming layer and skeleton structure layer and the specific choosing of thickness
It selects, compatibility between layers can be further enhanced, enhance interlayer adhesion, so that each interlayer is easy to thermal-adhering one
It rises, improves structural stability.
(3) interlayer adhesion for the automobile interior decoration composite material that the present invention is prepared is in 2.0N/mm or more, Coating combination
Securely；Tensile strength is in 35MPa or more, and for elongation at break 413% or more, Wear Resistance is excellent, strong with high tearing
Degree and dimensional stability, are not easy to peel off, and specious, and process environmental protection in the process, pollution-free.After product abandonment,
Recoverable.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of automobile interior decoration composite material of the invention, wherein 1 is epidermis, 2 be foaming layer, and 3 are
Hot melt adhesive layer, 4 be skeleton structure layer.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
In the present embodiment, a kind of environment-friendly type automobile inner decoration composite material is provided, as shown in Figure 1 comprising epidermis
(1), foaming layer (2) and the skeleton structure (4) of foaming layer lower surface is bonded in by the hot melt adhesive layer (3), the epidermis
Layer is TPO film layer, and the foaming layer is PPF foaming layer, and the hot melt adhesive layer is TPU hot melt adhesive layer, and the skeleton structure is ABS
MODIFIED PP composite material.
The raw material of the TPO film layer includes following ingredient:
It include 2 parts by weight ultraviolet absorbing agents in the light stabilizer.
The raw material of the cross-linked thermoplastic elastomer includes following ingredient:
Other described additives include antiager, light stabilizer and antioxidant.
The TPU hot melt adhesive layer is prepared by TPU hot-melt adhesive granules.
The raw material of the TPU hot-melt adhesive granules includes following component:
Wherein, the diisocyanate is hexamethylene diisocyanate and 1, the combination of hexamethylene-diisocyanate, hexamethyl
The mass ratio of diisocyanate and hexamethylene diisocyanate is 1:7；The polyalcohol is the pure and mild polyester polyol of polyether polyols
Combination, the mass ratio of the pure and mild polyester polyol of polyether polyols is 8:1；The number-average molecular weight of polyalcohol is 1000, the catalysis
Agent is tetra-n-butyl tin, and the chain extender is 1,4-butanediol, and the antioxidant is antioxidant 1010.
The raw material of the skeleton structure layer includes following ingredient:
100 parts by weight of PP
15 parts by weight of ABS
5 parts by weight of filler
In the present invention, the automobile interior decoration composite material preparation method the following steps are included:
(1) by nitrile rubber, PP, crosslinking agent, plasticising oil and optionally other additives according to metering ratio be added to reaction
It in vessel, is reacted 10 hours at 100 DEG C, obtains cross-linked thermoplastic elastomer；
(2) cross-linked thermoplastic elastomer, the PE, PP, light stabilizer, lubrication prescription, fire retardant, color masterbatch obtained step (1)
Grain, than being added to melting extrusion in screw extruder, being granulated, obtains TPO particle according to metering；The feeding of the screw extruder
Duan Wendu is 180 DEG C, and mixing section temperature is 200 DEG C, and extruding zone temperature is 210 DEG C, and head temperature is 220 DEG C；
(3) the TPO particle that step (2) obtain is added in bar extruder, melting extrusion, T-type curtain coating, the TPO of acquisition
Film can be used aqueous or oleoresin and carry out surface environmental protection treatment, can also be without surface environmental protection treatment；The screw extruder
Feeding section temperature be 175 DEG C, mixing section temperature be 180 DEG C, extruding zone temperature be 210 DEG C, head temperature be 220 DEG C.
(4) diisocyanate, polyalcohol, catalyst, chain extender, antioxidant are added to screw extruder according to metering ratio
Middle melting extrusion, granulation obtain TPU hot-melt adhesive granules；The feeding section temperature of the screw extruder is 100 DEG C, mixing section temperature
Degree is 120 DEG C, and extruding zone temperature is 170 DEG C, and head temperature is 150 DEG C.
(5) TPU hot-melt adhesive granules are added in screw extruder, melting extrusion, T-type curtain coating obtains TPU hot melt adhesive
Film；The feeding section temperature of the screw extruder is 100 DEG C, and mixing section temperature is 120 DEG C, and extruding zone temperature is 150 DEG C, head
Temperature is 180 DEG C；
(6) the TPU hot melt adhesive film heat posted synchronous with PPF foaming layer that the TPO film and step (5) obtained step (3) obtains
It closes, obtains 3-layer composite material, the 3-layer composite material and the frame structure material of injection molding are placed in a mold, led to
Vacuum forming is crossed, a kind of environment-friendly type automobile inner decoration composite material is obtained.The thermal-adhering temperature is 180 DEG C；It is described true
The pressure of suction modeling is -0.9MPa, and heating temperature when vacuum forming is 180 DEG C.TPO in obtained automobile interior decoration composite material
Film layer with a thickness of 2.0mm, PPF foaming layer with a thickness of 4.0mm, TPU hot melt adhesive film layer with a thickness of 1.0mm, skeleton structure
Layer with a thickness of 6mm.
Embodiment 2
In the present embodiment, a kind of environment-friendly type automobile inner decoration composite material is provided, as shown in Figure 1 comprising epidermis
(1), foaming layer (2) and the skeleton structure (4) of foaming layer lower surface is bonded in by the hot melt adhesive layer (3), the epidermis
Layer is TPO film layer, and the foaming layer is PPF foaming layer, and the hot melt adhesive layer is TPU hot melt adhesive layer, and the skeleton structure is ABS
MODIFIED PP composite material.
The raw material of the TPO film layer includes following ingredient:
It include 0.1 parts by weight ultraviolet absorbing agent in the light stabilizer.
The raw material of the cross-linked thermoplastic elastomer includes following ingredient:
Other described additives include antiager and antioxidant.
The raw material of the TPU hot melt adhesive layer includes following ingredient:
100 parts by weight of TPU hot-melt adhesive granules
5 parts by weight of lubrication prescription
Modified 30 parts by weight of Tackifier materials.
The raw material of the TPU hot-melt adhesive granules includes following component:
Wherein, the diisocyanate is hexamethylene diisocyanate and 1, the combination of hexamethylene-diisocyanate, hexamethyl
The mass ratio of diisocyanate and hexamethylene diisocyanate is 1:8；The polyalcohol is the pure and mild polyester polyol of polyether polyols
Combination, the mass ratio of the pure and mild polyester polyol of polyether polyols is 9:1；The number-average molecular weight of polyalcohol is 800, the catalyst
For N, the bis- beautiful jade base Anaesthetie Ethers of N'-, the chain extender is diethylene glycol (DEG), and the antioxidant is irgasfos 168.
The raw material of the skeleton structure layer includes following ingredient:
100 parts by weight of PP
30 parts by weight of ABS
10 parts by weight of filler
In the present invention, the automobile interior decoration composite material preparation method the following steps are included:
(1) by nitrile rubber, PE, crosslinking agent, plasticising oil and optionally other additives according to metering ratio addition reactor
In ware, reacted 1 hour at 250 DEG C；
(2) cross-linked thermoplastic elastomer, the PE, PP, light stabilizer, lubrication prescription, fire retardant, color masterbatch obtained step (1)
Grain, than being added to melting extrusion in screw extruder, being granulated, obtains TPO particle according to metering；The feeding of the screw extruder
Duan Wendu is 170 DEG C, and mixing section temperature is 120 DEG C, and extruding zone temperature is 130 DEG C, and head temperature is 120 DEG C；
(3) the TPO particle that step (2) obtain is added in bar extruder, melting extrusion, T-type curtain coating, the TPO of acquisition
Film can be used aqueous or oleoresin and carry out surface environmental protection treatment, can also be without surface environmental protection treatment；The screw extruder
Feeding section temperature be 230 DEG C, mixing section temperature be 200 DEG C, extruding zone temperature be 240 DEG C, head temperature be 180 DEG C.
(4) diisocyanate, polyalcohol, catalyst, chain extender, antioxidant are added to screw extruder according to metering ratio
Middle melting extrusion, granulation obtain TPU hot-melt adhesive granules；The feeding section temperature of the screw extruder is 130 DEG C, mixing section temperature
Degree is 160 DEG C, and extruding zone temperature is 170 DEG C, and head temperature is 160 DEG C；
(5) TPU hot-melt adhesive granules and lubrication prescription and Tackifier materials are added in screw extruder, melting extrusion, T-type stream
Prolong, obtains TPU hot melt adhesive film；The feeding section temperature of the screw extruder is 60 DEG C, and mixing section temperature is 100 DEG C, extruding zone
Temperature is 200 DEG C, and head temperature is 230 DEG C；
(6) the TPU hot melt adhesive film heat posted synchronous with PPF foaming layer that the TPO film and step (5) obtained step (3) obtains
It closes, obtains 3-layer composite material, the 3-layer composite material and the frame structure material of injection molding are placed in a mold, led to
Vacuum forming is crossed, a kind of environment-friendly type automobile inner decoration composite material is obtained.The thermal-adhering temperature is 200 DEG C；It is described true
The pressure of suction modeling is -1MPa, and heating temperature when vacuum forming is 220 DEG C.TPO film in obtained automobile interior decoration composite material
Layer with a thickness of 5.0mm, PPF foaming layer with a thickness of 10.0mm, TPU hot melt adhesive film layer with a thickness of 2.0mm, skeleton structure layer
With a thickness of 10mm.
Embodiment 3
In the present embodiment, a kind of environment-friendly type automobile inner decoration composite material is provided, as shown in Figure 1 comprising epidermis
(1), foaming layer (2) and the skeleton structure (4) of foaming layer lower surface is bonded in by the hot melt adhesive layer (3), the epidermis
Layer is TPO film layer, and the foaming layer is PPF foaming layer, and the hot melt adhesive layer is TPU hot melt adhesive layer, and the skeleton structure is ABS
MODIFIED PP composite material.
The raw material of the TPO film layer includes following ingredient:
It include 2 parts by weight ultraviolet absorbing agents in the light stabilizer.
The raw material of the cross-linked thermoplastic elastomer includes following ingredient:
Other described additives include antiager, light stabilizer and antioxidant.
The raw material of the TPU hot melt adhesive layer includes following ingredient:
70 parts by weight of TPU hot-melt adhesive granules
2 parts by weight of lubrication prescription
Modified 10 parts by weight of Tackifier materials.
The raw material of the TPU hot-melt adhesive granules includes following component:
Wherein, the diisocyanate is hexamethylene diisocyanate and 1, the combination of hexamethylene-diisocyanate, hexamethyl
The mass ratio of diisocyanate and hexamethylene diisocyanate is 1:5；The polyalcohol is the pure and mild polyester polyol of polyether polyols
Combination, the mass ratio of the pure and mild polyester polyol of polyether polyols is 7:1；The number-average molecular weight of polyalcohol is 2000, the catalysis
Agent is dibutyl tin dilaurate, and the chain extender is 1,6- hexylene glycol, and the antioxidant is antioxidant 1076.
The raw material of the skeleton structure layer includes following ingredient:
100 parts by weight of PP
5 parts by weight of ABS
0.5 parts by weight of filler
In the present invention, the automobile interior decoration composite material preparation method the following steps are included:
(1) by butadiene-styrene rubber, PP, crosslinking agent, plasticising oil and optionally other additives according to metering ratio addition reactor
In ware, reacted 30 hours at 60 DEG C,
(2) cross-linked thermoplastic elastomer, the PE, PP, light stabilizer, lubrication prescription, fire retardant, color masterbatch obtained step (1)
Grain, than being added to melting extrusion in screw extruder, being granulated, obtains TPO particle according to metering；The feeding of the screw extruder
Duan Wendu is 120 DEG C, and mixing section temperature is 210 DEG C, and extruding zone temperature is 260 DEG C, and head temperature is 200 DEG C；
(3) the TPO particle that step (2) obtain is added in bar extruder, melting extrusion, T-type curtain coating, the TPO of acquisition
Film can be used aqueous or oleoresin and carry out surface environmental protection treatment, can also be without surface environmental protection treatment；The screw extruder
Feeding section temperature be 190 DEG C, mixing section temperature be 160 DEG C, extruding zone temperature be 180 DEG C, head temperature be 190 DEG C；
(4) by hexamethylene diisocyanate, polyoxypropyleneglycol, polybutylene glyool adipate, polyamide wax, increasing
Viscosity resin, catalyst, chain extender, antioxidant, than being added to melting extrusion in screw extruder, being granulated, obtain TPU according to metering
Hot-melt adhesive granules；The feeding section temperature of the screw extruder is 150 DEG C, and mixing section temperature is 140 DEG C, and extruding zone temperature is
210 DEG C, head temperature is 180 DEG C；
(5) TPU hot-melt adhesive granules and lubrication prescription and modified Tackifier materials are added in screw extruder, melting extrusion, T
Type curtain coating, obtains TPU hot melt adhesive film；The feeding section temperature of the screw extruder is 220 DEG C, and mixing section temperature is 140 DEG C, is squeezed
Section temperature is 190 DEG C out, and head temperature is 130 DEG C；
(6) the TPU hot melt adhesive film heat posted synchronous with PPF foaming layer that the TPO film and step (5) obtained step (3) obtains
It closes, obtains 3-layer composite material, the 3-layer composite material and the frame structure material of injection molding are placed in a mold, led to
Vacuum forming is crossed, a kind of environment-friendly type automobile inner decoration composite material is obtained.The thermal-adhering temperature is 150 DEG C；It is described true
The pressure of suction modeling is -1MPa, and heating temperature when vacuum forming is 250 DEG C.TPO film in obtained automobile interior decoration composite material
Layer with a thickness of 3mm, PPF foaming layer with a thickness of 1mm, TPU hot melt adhesive film layer with a thickness of 0.5mm, the thickness of skeleton structure layer
Degree is 5mm.
Embodiment 4
In the present embodiment, a kind of environment-friendly type automobile inner decoration composite material is provided, as shown in Figure 1 comprising epidermis
(1), foaming layer (2) and the skeleton structure (4) of foaming layer lower surface is bonded in by the hot melt adhesive layer (3), the epidermis
Layer is TPO film layer, and the foaming layer is PPF foaming layer, and the hot melt adhesive layer is TPU hot melt adhesive layer, and the skeleton structure is ABS
MODIFIED PP composite material.
The raw material of the TPO film layer includes following ingredient:
It include 1 parts by weight ultraviolet absorbing agent in the light stabilizer.
The raw material of the cross-linked thermoplastic elastomer includes following ingredient:
Other described additives include antiager, light stabilizer and antioxidant.
The raw material of the TPU hot melt adhesive layer includes following ingredient:
100 parts by weight of TPU hot-melt adhesive granules
1 parts by weight of lubrication prescription.
The raw material of the TPU hot-melt adhesive granules includes following component:
Wherein, the diisocyanate is hexamethylene diisocyanate and 1, the combination of hexamethylene-diisocyanate, hexamethyl
The mass ratio of diisocyanate and hexamethylene diisocyanate is 1:10；The polyalcohol is the pure and mild polyester polyol of polyether polyols
Combination, the mass ratio of the pure and mild polyester polyol of polyether polyols is 8:1；The number-average molecular weight of polyalcohol is 500, the catalyst
For tetra-n-butyl tin, the chain extender is 1,4-butanediol, and the antioxidant is antioxidant 1010.
The raw material of the skeleton structure layer includes following ingredient:
100 parts by weight of PP
15 parts by weight of ABS
5 parts by weight of filler
In the present invention, the automobile interior decoration composite material preparation method the following steps are included:
(1) by ethylene propylene diene rubber, PE, crosslinking agent, plasticising oil and optionally other additives according to metering than addition it is anti-
It answers in vessel, is reacted 15 hours at 120 DEG C,；
(2) cross-linked thermoplastic elastomer, the PE, PP, light stabilizer, lubrication prescription, fire retardant, color masterbatch obtained step (1)
Grain, than being added to melting extrusion in screw extruder, being granulated, obtains TPO particle according to metering；The feeding of the screw extruder
Duan Wendu is 230 DEG C, and mixing section temperature is 240 DEG C, and extruding zone temperature is 240 DEG C, and head temperature is 250 DEG C；
(3) the TPO particle that step (2) obtain is added in bar extruder, melting extrusion, T-type curtain coating, the TPO of acquisition
Film can be used aqueous or oleoresin and carry out surface environmental protection treatment, can also be without surface environmental protection treatment；The screw extruder
Feeding section temperature be 150 DEG C, mixing section temperature be 230 DEG C, extruding zone temperature be 280 DEG C, head temperature be 270 DEG C；
(4) by hexamethylene diisocyanate, polyoxypropyleneglycol, polybutylene glyool adipate, polyamide wax, increasing
Viscosity resin, catalyst, chain extender, antioxidant, than being added to melting extrusion in screw extruder, being granulated, obtain TPU according to metering
Hot-melt adhesive granules；The feeding section temperature of the screw extruder is 100 DEG C, and mixing section temperature is 180 DEG C, and extruding zone temperature is
170 DEG C, head temperature is 150 DEG C；
(5) TPU hot-melt adhesive granules and lubrication prescription are added in screw extruder, melting extrusion, T-type curtain coating obtains TPU
Hot melt adhesive film；The feeding section temperature of the screw extruder is 120 DEG C, and mixing section temperature is 70 DEG C, and extruding zone temperature is 80 DEG C,
Head temperature is 90 DEG C.
(6) the TPU hot melt adhesive film heat posted synchronous with PPF foaming layer that the TPO film and step (5) obtained step (3) obtains
It closes, obtains 3-layer composite material, the 3-layer composite material and the frame structure material of injection molding are placed in a mold, led to
Vacuum forming is crossed, a kind of environment-friendly type automobile inner decoration composite material is obtained.The thermal-adhering temperature is 50 DEG C；The vacuum
The pressure of plastic uptake is -0.1MPa, and heating temperature when vacuum forming is 80 DEG C.TPO film in obtained automobile interior decoration composite material
Layer with a thickness of 1mm, PPF foaming layer with a thickness of 5mm, TPU hot melt adhesive film layer with a thickness of 1.5mm, the thickness of skeleton structure layer
Degree is 8mm.
Embodiment 5
The embodiment the difference is that only that the raw material of the TPO film layer is only cross-linked thermoplastic bullet with embodiment 1
Property body, without include PE, PP, light stabilizer, lubrication prescription, fire retardant and Masterbatch.Remaining preparation method and condition with embodiment 1
It is identical.
Embodiment 6
The embodiment the difference is that only that the raw material of the TPO film layer includes following component with embodiment 1:
Remaining preparation method and condition are same as Example 1.
Embodiment 7
The embodiment the difference is that only that the raw material of the TPO film layer includes following component with embodiment 1:
Remaining preparation method and condition are same as Example 1.
Embodiment 8
The embodiment the difference is that only that the raw material of the hot melt adhesive layer includes following ingredient with embodiment 1:
80 parts by weight of TPU hot-melt adhesive granules；
Modified 20 parts by weight of Tackifier materials.
Remaining preparation method and condition are same as Example 1.
Embodiment 9
The embodiment the difference is that only that diisocyanate is single in the raw material of TPU hot-melt adhesive granules with embodiment 1
Only hexamethylene diisocyanate.
Embodiment 10
The embodiment the difference is that only that diisocyanate is single in the raw material of TPU hot-melt adhesive granules with embodiment 1
Only hexamethylene diisocyanate.
Embodiment 11
The embodiment the difference is that only that diisocyanate is six in the raw material of TPU hot-melt adhesive granules with embodiment 1
The combination of methyl diisocyanate and cyclohexanedimethyleterephthalate diisocyanate.
Embodiment 12
The embodiment the difference is that only that diisocyanate is 1 in the raw material of TPU hot-melt adhesive granules with embodiment 1,
The combination of hexamethylene-diisocyanate and isophorone diisocyanate.
Embodiment 13
The difference of the embodiment and embodiment 1 is only that the thickness of TPO film layer in automobile interior decoration composite material that control obtains
Degree is 0.01mm, PPF foaming layer with a thickness of 5.0mm, TPU hot melt adhesive film layer with a thickness of 0.01mm, the thickness of skeleton structure layer
Degree is 6mm.
Embodiment 14
The difference of the embodiment and embodiment 1 is only that the thickness of TPO film layer in automobile interior decoration composite material that control obtains
Degree is 0.5mm, PPF foaming layer with a thickness of 4.0mm, TPU hot melt adhesive film layer with a thickness of 1.0mm, the thickness of skeleton structure layer
For 10mm.
Embodiment 15
The difference of the embodiment and embodiment 1 is only that the quality of hexamethylene diisocyanate and hexamethylene diisocyanate
Than for 1:3.
Embodiment 16
The difference of the embodiment and embodiment 1 is only that the quality of hexamethylene diisocyanate and hexamethylene diisocyanate
Than for 1:12.
Embodiment 17
The difference of the embodiment and embodiment 1 is only that the mass ratio of the pure and mild polyester polyol of polyether polyols is 5:1.
Embodiment 18
The difference of the embodiment and embodiment 1 is only that the mass ratio of the pure and mild polyester polyol of polyether polyols is 10:1.
Comparative example 1
Wherein TPU hot melt adhesive layer is changed to common glue layer by the comparative example and being different only in that for embodiment 1.
Comparative example 2
Polyalcohol is individual polyethers in the raw material for being different only in that TPU hot-melt adhesive granules of the comparative example and embodiment 1
Polyalcohol.
Comparative example 3
Polyalcohol is individual polyester in the raw material for being different only in that TPU hot-melt adhesive granules of the comparative example and embodiment 1
Polyalcohol.
Comparative example 4
The comparative example and the molecular weight of polyalcohol in the raw material for being different only in that TPU hot-melt adhesive granules of embodiment 1 are
300。
Comparative example 5
The comparative example and the molecular weight of polyalcohol in the raw material for being different only in that TPU hot-melt adhesive granules of embodiment 1 are
3000。
Comparative example 6
The comparative example and the content of diisocyanate in the raw material for being different only in that TPU hot-melt adhesive granules of embodiment 1 are
40 parts by weight.
Comparative example 7
The comparative example and the content of diisocyanate in the raw material for being different only in that TPU hot-melt adhesive granules of embodiment 1 are
90 parts by weight.
Comparative example 8
The content of polyalcohol is 25 weights in the raw material for being different only in that TPU hot-melt adhesive granules of the comparative example and embodiment 1
Measure part.
Comparative example 9
The content of polyalcohol is 50 weights in the raw material for being different only in that TPU hot-melt adhesive granules of the comparative example and embodiment 1
Measure part.
To the automobile interior decoration composite material that embodiment 1-14 and degree are prepared with ratio 1-9 carry out interlayer adhesion with
And the test of wearability, tensile strength and elongation at break, the results are shown in Table 1.
Table 1
As can be seen from Table 1, the interlayer adhesion for the automobile interior decoration composite material that the present invention is prepared 2.0N/mm with
On, Coating combination is secured, and bondability is good, and rejection rate is low, is effective to ensure that the Forming Quality of product；Wearability is good, draws
Intensity is stretched in 35MPa or more, and elongation at break has good mechanical strength and elastic property, and raw 413% or more
It produces high-efficient, saves artificial, efficiently solve composite material for cars and be easy to purse up bulging phenomenon, with high tearing strength
And dimensional stability, it is not easy to peel off, and specious.Environmental protection, pollution-free during processing.
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 (37)
1. a kind of preparation method of automobile interior decoration composite material, which is characterized in that the automobile interior decoration composite material is from top to bottom
It successively include epidermis, foaming layer, hot melt adhesive layer and skeleton structure layer；The epidermis is TPO film layer, and the foaming layer is
PPF foaming layer, the hot melt adhesive layer are TPU hot melt adhesive layer；
The automobile interior decoration composite material the preparation method comprises the following steps:
Step 1: by olefin rubber, olefine kind resin, crosslinking agent, plasticising oil and optionally other additives according to metering ratio
It is added in reaction vessels and reacts, obtain cross-linked thermoplastic elastomer；
Step 2: cross-linked thermoplastic elastomer, the PE, PP, light stabilizer, lubrication prescription, fire retardant, Masterbatch that step 1 is obtained
According to metering than being added to melting extrusion in screw extruder, being granulated, TPO particle is obtained；
Step 3: the TPO particle that step 2 obtains being added in screw extruder, melting extrusion, and T-type curtain coating obtains TPO
Film；
Step 4: diisocyanate, polyalcohol, catalyst, chain extender, antioxidant are added to screw extruder according to metering ratio
Middle melting extrusion, granulation obtain TPU hot-melt adhesive granules；
Step 5: TPU hot-melt adhesive granules and optional lubrication prescription and Tackifier materials are added in screw extruder, and melting is squeezed
Out, T-type is cast, and obtains TPU hot melt adhesive film；
Step 6: the TPU hot melt adhesive film thermal-adhering synchronous with PPF foaming layer that the TPO film and step 5 that step 3 is obtained obtain,
3-layer composite material is obtained, the 3-layer composite material and the frame structure material of injection molding are placed in a mold, passed through
Vacuum forming obtains a kind of automobile interior decoration composite material；
Wherein, the TPO film layer with a thickness of 0.1mm-5.0mm, the PPF foaming layer with a thickness of 1.0mm-5.0mm, it is described
TPU hot melt adhesive layer with a thickness of 0.01mm-1.0mm；
The thermal-adhering temperature is 50-250 DEG C.
2. preparation method according to claim 1, which is characterized in that the epidermis be using aqueous or oleoresin into
Row surface environmental protection treated epidermis.
3. preparation method according to claim 2, which is characterized in that the epidermis layer surface has decorative pattern.
4. preparation method according to claim 1, which is characterized in that the raw material of the skeleton structure layer includes that glass is modified
In PP composite material, carbon fiber MODIFIED PP composite material or ABS MODIFIED PP composite material any one or at least two combination.
5. the preparation method according to claim 4, which is characterized in that the raw material of the skeleton structure layer is ABS MODIFIED PP
Composite material.
6. preparation method according to claim 1, which is characterized in that the skeleton structure layer with a thickness of 0.1mm-
10mm。
7. preparation method according to claim 6, which is characterized in that the skeleton structure layer with a thickness of 5.0mm-
8.0mm。
8. preparation method according to claim 1, which is characterized in that the raw material of the TPO film layer includes following ingredient:
Cross-linked thermoplastic elastomer 50-80 parts by weight；
PE 0-50 parts by weight；
PP 0-50 parts by weight；
Light stabilizer 0-5 parts by weight；
Lubrication prescription 0-3 parts by weight；
Fire retardant 0-10 parts by weight；
Masterbatch 0-10 parts by weight.
9. preparation method according to claim 8, which is characterized in that the raw material of the cross-linked thermoplastic elastomer includes
Following ingredient:
Olefin rubber 10-90 parts by weight；
Olefine kind resin 10-85 parts by weight；
Crosslinking agent 1-50 parts by weight；
Plasticising oil 1-30 parts by weight.
10. preparation method according to claim 9, which is characterized in that the raw material of the cross-linked thermoplastic elastomer is also
Other additives comprising 0.1-20 parts by weight.
11. preparation method according to claim 10, which is characterized in that other described additives include antiager, light
In stabilizer or antioxidant any one or at least two combination.
12. preparation method according to claim 9, which is characterized in that the olefin rubber include ethylene propylene diene rubber,
In butadiene-styrene rubber, neoprene, nitrile rubber or fluorubber any one or at least two combination.
13. preparation method according to claim 12, which is characterized in that the olefin rubber is nitrile rubber.
14. preparation method according to claim 9, which is characterized in that the olefine kind resin includes PP and/or PE.
15. preparation method according to claim 14, which is characterized in that the PE is non-crosslinked PE.
16. preparation method according to claim 15, which is characterized in that the PE includes LDPE, LLDPE, MDPE, HDPE
In UHMWPE any one or at least two combination.
17. preparation method according to claim 16, which is characterized in that the PE is LLDPE.
18. preparation method according to claim 14, which is characterized in that the PP is non-crosslinked PP.
19. preparation method according to claim 8, which is characterized in that the light stabilizer includes ultraviolet absorbing agent.
20. preparation method according to claim 1, which is characterized in that the raw material of the hot melt adhesive layer includes following ingredient:
TPU hot-melt adhesive granules 70-100 parts by weight；
Lubrication prescription 0-5 parts by weight；
Modified Tackifier materials 0-30 parts by weight.
21. preparation method according to claim 20, which is characterized in that the raw material of the TPU hot-melt adhesive granules includes such as
Lower component:
22. preparation method according to claim 21, which is characterized in that the diisocyanate is hexamethyl diisocyanate
Any one in ester, cyclohexanedimethyleterephthalate diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate
Or at least two combination.
23. preparation method according to claim 22, which is characterized in that the diisocyanate is hexamethyl diisocyanate
The combination of ester and hexamethylene diisocyanate.
24. preparation method according to claim 23, which is characterized in that the hexamethylene diisocyanate and 1,6- oneself two
The mass ratio of hexamethylene diisocyanate and hexamethylene diisocyanate is 1:(5-10 in the combination of isocyanates).
25. preparation method according to claim 21, which is characterized in that the polyalcohol is that the pure and mild polyester of polyether polyols is more
The combination of first alcohol.
26. preparation method according to claim 25, which is characterized in that the pure and mild polyester of polyether polyols is more in the polyalcohol
The mass ratio of first alcohol is (7-9): 1.
27. preparation method according to claim 21, which is characterized in that the number-average molecular weight of the polyalcohol is 500-
2000。
28. preparation method according to claim 27, which is characterized in that the number-average molecular weight of the polyalcohol is 500-
1000。
29. preparation method according to claim 21, which is characterized in that the catalyst includes triethanolamine, N, and N'- is bis-
In beautiful jade base Anaesthetie Ether, tetra-n-butyl tin, stannous chloride, stannous octoate, hydroxyl tin trimethyl or dibutyl tin dilaurate
Any one or at least two combination.
30. preparation method according to claim 21, which is characterized in that the chain extender includes 1,4-butanediol, 1,6-
Hexylene glycol, diethylene glycol (DEG), diethylaminoethanol, N, N- dihydroxy (diisopropyl) aniline, ethylenediamine or the chloro- 4,4' bis- of 3,3'- bis-
Any one in amino-diphenyl methane or at least two combination.
31. preparation method according to claim 21, which is characterized in that the antioxidant includes antioxidant 1010, antioxygen
Any one in agent 1076, irgasfos 168 or 2,6 di tert butyl 4 methyl phenol or at least two combination.
32. preparation method according to claim 20, which is characterized in that the modified Tackifier materials are tackifying resin, increase
Slimy milk liquid, thickening powder or viscosify rosin resin in any one or at least two combination.
33. preparation method according to claim 32, which is characterized in that the modified Tackifier materials are tackifying resin.
34. preparation method according to claim 1, which is characterized in that the raw material of the skeleton structure layer include as follows at
Point:
PP 80-100 parts by weight
ABS 5-30 parts by weight
Filler 0.1-10 parts by weight.
35. preparation method according to claim 1, which is characterized in that the temperature of reaction described in step 1 is 60-250 DEG C；
The time of reaction described in step 1 is 1-30 hours；
The feeding section temperature of screw extruder described in step 2 is 120-230 DEG C, and mixing section temperature is 120-240 DEG C, extruding zone
Temperature is 130-260 DEG C, and head temperature is 120-250 DEG C；
The feeding section temperature of screw extruder described in step 3 is 150-230 DEG C, and mixing section temperature is 160-240 DEG C, extruding zone
Temperature is 180-280 DEG C, and head temperature is 180-270 DEG C；
Granulation step described in step 2 is omitted, step 2 and step 3 are merged into following steps: the friendship that step 1 is obtained
Connection type thermoplastic elastomer (TPE), PE, PP, light stabilizer, lubrication prescription, fire retardant, Masterbatch are added to screw extruder according to metering ratio
In, melting extrusion, T-type curtain coating obtains TPO film；
Surface environmental protection treatment is carried out to the TPO film that step 3 obtains using aqueous or oleoresin；
The feeding section temperature of screw extruder described in step 4 is 100-150 DEG C, and mixing section temperature is 120-180 DEG C, extruding zone
Temperature is 170-210 DEG C, and head temperature is 150-180 DEG C；
The feeding section temperature of screw extruder described in step 5 is 60-220 DEG C, and mixing section temperature is 70-230 DEG C, extruding zone temperature
Degree is 80-230 DEG C, and head temperature is 70-230 DEG C.
36. preparation method according to claim 35, which is characterized in that the pressure of vacuum forming described in step 6 is -0.1
~-1MPa；
Heating temperature described in step 6 when vacuum forming is 50-250 DEG C；
It is right after step 6 obtains 3-layer composite material if not carrying out surface environmental protection treatment to the TPO film that step 3 obtains
Its surface carries out environmental protection treatment and surface detail processing.
37. the automobile interior decoration composite material that -36 described in any item methods are prepared according to claim 1.
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Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109929167B (en) * | 2017-12-18 | 2021-04-20 | 比亚迪股份有限公司 | Polyurethane olefin composition, polyurethane olefin master batch, polyurethane olefin film, surface decoration composite material and preparation method thereof |
| CN108410385A (en) * | 2018-03-16 | 2018-08-17 | 佛山市利丰日用品有限公司 | A kind of environment-friendly type decoration surface lining and preparation method thereof |
| CN108485549A (en) * | 2018-03-16 | 2018-09-04 | 佛山市利丰日用品有限公司 | A kind of vellum finish material of PVC base and preparation method thereof |
| CN108610996A (en) * | 2018-03-29 | 2018-10-02 | 重庆渝茁科技有限公司 | Light sound-proof plastic cellular board material |
| CN108749230B (en) * | 2018-05-03 | 2020-08-21 | 东莞市雄林新材料科技股份有限公司 | Novel automobile interior material and modification method thereof |
| CN109050431B (en) * | 2018-10-29 | 2022-02-01 | 何山 | Preparation method of environment-friendly automotive interior and automotive interior |
| CN111172773B (en) * | 2019-12-26 | 2022-12-23 | 华伦皮塑（苏州）有限公司 | Synthetic leather for children products and preparation method thereof |
| CN113121858B (en) * | 2019-12-31 | 2023-01-31 | 苏州瑞高新材料有限公司 | Novel transparent superconducting automotive interior material and preparation method thereof |
| CN111394038B (en) * | 2020-04-30 | 2022-03-01 | 广州鹿山新材料股份有限公司 | Spraying-free glue for plastic uptake PVC decorative film and preparation method thereof, plastic uptake plate and preparation method thereof |
| CN111849189A (en) * | 2020-06-22 | 2020-10-30 | 安徽滁州德威新材料有限公司 | Waterproof coiled material particle and preparation method and application thereof |
| WO2022134056A1 (en) * | 2020-12-25 | 2022-06-30 | 加通汽车内饰(常熟)有限公司 | Light-transmittable skin material, manufacturing process therefor, and light-transmittable composite structure |
| CN112586530A (en) * | 2020-12-29 | 2021-04-02 | 东莞市雄林新材料科技股份有限公司 | Dough sheet making equipment |
| CN113696593A (en) * | 2021-09-06 | 2021-11-26 | 苏州禾润昌新材料有限公司 | Polypropylene composite material for automobile decoration and odor removing method thereof |
| CN113978081A (en) * | 2021-11-08 | 2022-01-28 | 广东富强科技股份有限公司 | Polyurethane composite board and preparation method and application thereof |
| CN114654839A (en) * | 2022-03-17 | 2022-06-24 | 白健洪 | Convertible soft top composite material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201856424U (en) * | 2010-10-22 | 2011-06-08 | 浙江吉利汽车研究院有限公司 | Environment-friendly decorative sheet in middle of vehicle door |
| CN102336883A (en) * | 2011-07-14 | 2012-02-01 | 无锡市万力粘合材料有限公司 | Preparation method of reactive polyurethane hot melt adhesive for fabric lamination |
| CN102514337A (en) * | 2011-11-16 | 2012-06-27 | 佛山市天安塑料有限公司 | Automobile interior decoration material and production method thereof |
| CN203093937U (en) * | 2012-12-27 | 2013-07-31 | 天津博信汽车零部件有限公司 | Heat insulation pad of automobile |
| CN103965800A (en) * | 2014-05-09 | 2014-08-06 | 天津市大林新材料科技有限公司 | Environment-friendly thermoplastic polyolefin (TPO) auto interior material and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4953420B2 (en) * | 2005-12-28 | 2012-06-13 | 日本プラスト株式会社 | Molded product and insert molding method |
| CN102700114A (en) * | 2012-05-26 | 2012-10-03 | 无锡吉兴汽车声学部件科技有限公司 | Production technology of rear shelf of car |
-
2017
- 2017-02-08 CN CN201710069769.2A patent/CN106827751B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201856424U (en) * | 2010-10-22 | 2011-06-08 | 浙江吉利汽车研究院有限公司 | Environment-friendly decorative sheet in middle of vehicle door |
| CN102336883A (en) * | 2011-07-14 | 2012-02-01 | 无锡市万力粘合材料有限公司 | Preparation method of reactive polyurethane hot melt adhesive for fabric lamination |
| CN102514337A (en) * | 2011-11-16 | 2012-06-27 | 佛山市天安塑料有限公司 | Automobile interior decoration material and production method thereof |
| CN203093937U (en) * | 2012-12-27 | 2013-07-31 | 天津博信汽车零部件有限公司 | Heat insulation pad of automobile |
| CN103965800A (en) * | 2014-05-09 | 2014-08-06 | 天津市大林新材料科技有限公司 | Environment-friendly thermoplastic polyolefin (TPO) auto interior material and preparation method thereof |
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