CN109367159A - A kind of multi-functional composite material for decoration - Google Patents

A kind of multi-functional composite material for decoration Download PDF

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Publication number
CN109367159A
CN109367159A CN201811214942.4A CN201811214942A CN109367159A CN 109367159 A CN109367159 A CN 109367159A CN 201811214942 A CN201811214942 A CN 201811214942A CN 109367159 A CN109367159 A CN 109367159A
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CN
China
Prior art keywords
composite material
decoration
parts
group
fiber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201811214942.4A
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Chinese (zh)
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CN109367159B (en
Inventor
郭镜哲
陈红章
吴强林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Anhui Bauhinia Wallpaper Ltd Co
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Anhui Bauhinia Wallpaper Ltd Co
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Priority to CN201811214942.4A priority Critical patent/CN109367159B/en
Publication of CN109367159A publication Critical patent/CN109367159A/en
Application granted granted Critical
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    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
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    • 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
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    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/08—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer the fibres or filaments of a layer being of different substances, e.g. conjugate fibres, mixture of different fibres
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C09D127/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
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    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
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    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention belongs to decoration material fields, and in particular to a kind of multi-functional composite material for decoration.The technical solution having are as follows: a kind of composite material for decoration, the composite material for decoration include 4 layers of structure, from inside to outside successively are as follows: nonwoven layer, PVC paste resin layer, rolled material layer and ultra-thin carbon nanotube coating.The present invention has creatively used 4 layers of structure, provides a kind of visual appearance, facilitates printing, is safe and non-toxic, is high-intensitive, scratch-resistant, washable, anti-aging, fire prevention, waterproof, mould proof, cracking resistance, easy for construction, the good metope composite material for decoration of decorative effect.

Description

A kind of multi-functional composite material for decoration
Technical field
The invention belongs to decoration material fields, and in particular to a kind of multi-functional composite material for decoration.
Background technique
With the further promotion of people's living standard, people require also constantly promoted for the finishing of building, furniture, The spies such as associated decorative material is enriched with changing style, color multiplicity, pattern, visual appearance, decorative effect are good are not required nothing more than Point, it is also desirable to have fire-proof and water-proof, wear-resisting scratch resistance, safety and environmental protection, it is easy for construction, the characteristics such as be easily changed, this is just to traditional More stringent requirements are proposed for the enterprises such as wallpaper, wall paper, decoration panel.
With the industries such as China's wallpaper, wall paper, decoration panel ripe day by day and people's safety and environmental protection realize reinforcement, While people pay close attention to wallpaper, wall paper, decoration panel color and style varied, the practical and safety and environmental protection of product is also focused more on Etc. performances.All kinds of scratch-resistants, easy to clean, ageing-resistant, high temperature resistant, fire prevention, waterproof with assorted style pattern, except formaldehyde, remove Novel wall paper, wall paper, the decoration panel of the functions such as smelly, start market of selling well.Related product is mainly by paper base, Bu Ji or wood The coating of material surface layer, bonding, hot melt or one or more layers compound functional coating, to reach corresponding fire-retardant, easy cleaning, heat preservation, resistance to The functions such as scraping, waterproof, the Chinese patent of this respect have CN103074815, CN206127727, CN102776805, CN103485504、CN100526554、CN107060235、CN206530006、CN107326749、CN206085878、 CN107143105, CN107053382, CN108032592 etc..Functional wallpaper, wall paper or the facing prepared by these methods Plate, there is a problem of one it is important, be exactly its wallpaper, wall paper or decoration panel functionality it is more single, it is not all-round enough.
Therefore it provides a kind of multiple functional metope composite material for decoration has great high-end market demand.
Summary of the invention
The object of the present invention is to provide a kind of multi-functional composite material for decoration.
For achieving the above object, the technical scheme adopted by the invention is that: a kind of composite material for decoration, it is described compound Ornament materials includes 4 layers of structure, from inside to outside successively are as follows: nonwoven layer, PVC paste resin layer, rolled material layer and ultra-thin carbon are received Mitron coating.
Preferably, the nonwoven layer is mixed by glass fibre and polyimide fiber.
Preferably, the formula of the composite material for decoration is, in parts by weight, 25~100 parts of glass fibre, polyimides 25~200 parts of fiber, 50~600 parts of PVC paste resin, 1~200 part of rolled material, ultra-thin carbon nanotube coating material 0.1~ 1.2 part.
Preferably, the formula of the composite material for decoration is, in parts by weight, 50 parts of glass fibre, polyimide fiber 98 parts, 100 parts of PVC paste resin, 50 parts of rolled material, 0.3 part of ultra-thin carbon nanotube coating material.
Preferably, the production method of the nonwoven layer are as follows: fine with the glass fibre and the polyimides that add up to 2~6 Dimension is one group, mixed weaving forms fibre bundle, and the fibre bundle is combed networking, is reinforced to obtain the final product.
Preferably, the production method of the nonwoven layer are as follows: with 1 glass fibre and 2 polyimide fibers for one group, It carries out being knitted to form fibre bundle by three bursts of fried dough twist pigtail formulas, the fibre bundle is combed into networking, is reinforced to obtain the final product.
Preferably, it after the glass fibre and polyimide fiber carry out plus are tough, then is woven；
Described plus tough mode are as follows: in parts by weight, 2~10 parts of carbon nanotubes are added in 100 parts of ethyl alcohol or chloroform, are surpassed Sound is uniformly dispersed to get fiber reinforced dose；Glass fibre, polyimide fiber are submerged respectively in fiber reinforced dose, impregnated Night then carefully takes out each fiber, under vacuum environment, 80~90 DEG C is slowly warming up to from room temperature, heat preservation drying, heat up speed Degree control 0.5~0.8 DEG C/min to get add it is tough after glass fibre and polyimide fiber.
Preferably, the formula of the PVC paste resin are as follows: 30~35wt% dioctyl phthalate, 0.5wt% nanometer nitrogen Change boron, 1~3wt% nano rutile-type titanium dioxide or Ti3+/TiO2, 2~4wt% micron barium sulfate, 38~48wt% paste resin P450,10~20wt% polyimide powder, 0~7wt% microballoon foaming agent, 2wt% barium zinc type thermal stabilizing agent.
Preferably, the PVC paste resin the preparation method comprises the following steps: under normal temperature and pressure, phthalic acid is added in reaction kettle Dioctyl ester, nm-class boron nitride, nano rutile-type titanium dioxide or Ti3+/TiO2, micron barium sulfate, in 12000r/min disperse 5min adds paste resin P450, polyimide powder, microballoon foaming agent, barium zinc type thermal stabilizing agent；
After mixing, follow these steps successively to be dispersed three times: 2000r/min disperses 5min, 6000r/min dispersion 2min, 3000r/min disperse 30min；After dispersion, then in 24~48h, in 2500r/min dispersion 15min to get PVC Paste resin.
Preferably, the Ti3+/TiO2The preparation method comprises the following steps: by TiCl4It is completely dissolved in dehydrated alcohol, ultrasonic 10min, Adding quality is TiCl4The simple substance zinc of quality 40%, is stirred to react 30min, and adding quality is TiCl41~1.5 times of quality TiF3, ultrasonic 10min, then at 150 DEG C keep the temperature 20~14h；Cooling, drying is to get required Ti3+/TiO2。
The invention has the following advantages:
1, the present invention has creatively used 4 layers of structure, provides a kind of visual appearance, facilitates printing, is safe and non-toxic, is high Intensity, scratch-resistant, washable, anti-aging, fire prevention, waterproof, mould proof, cracking resistance, easy for construction, the good metope of decorative effect is compound Ornament materials.
2, the base material of composite material for decoration is non-woven fabrics, and when weaving non-woven fabrics, filament fiber is easily broken, surface light Sliding, fiber is without curling, and networking performance is poor, is not easy to reinforce, so being difficult to be directly used in production non-woven fabrics.Typically first by long filament It is cut into staple fiber, then combs networking, then pinprick reinforcement.But the characteristic of filament fiber is thus lost, and is easy loss Fiber.The present invention creatively first carries out plus tough glass fibre and polyimide fiber with carbon nanotube, and fiber is avoided to compile It is broken during knitting；The fiber after toughening is reused then with 1 glass fibre and 2 polyimide fibers for one group, by three The mode of stock fried dough twist pigtail is woven；The fibre bundle after braiding is combed into networking again, generates non-woven fabrics after pinprick reinforcement.
This mode for preparing non-woven fabrics overcomes the crisp defect easy to break of glass fibre property itself, remains filament fiber sheet The characteristic of body, has both glass fibre and the common advantage of polyamide-imide fibre, safe and non-toxic, excellent in mechanical performance, scratch-resistant, Ageing-resistant, fire-proof and water-proof, gas permeability and excellent tenacity, dimensionally stable, it is applied widely, and there is self-cleaning ability.
3, in order to make nonwoven cloth material that there is more superior processing performance, it is more suitable for printing etc., the present invention is also in nonwoven One layer of PVC paste resin is coated on cloth.But PVC paste resin is not prevented fires, and needs additionally to add fire retardant.Traditional fire retardant is mostly Halogenated flame retardant (using chlorine system, bromine system as representative) has certain toxicity, is unsuitable for the demanding field such as house ornamentation.And inorganic resistance Agent (such as aluminium hydroxide, magnesium hydroxide) or reactive flame retardant (MCA, TBP etc.) etc. are fired, otherwise is exactly the decomposition production after meeting fire Object is toxic；Otherwise it is exactly that fire retardant will be slow selfdecomposition, gradually loses flame retardant effect；Or the small resistance of fire retardant additive amount Fuel efficiency fruit is poor, additive amount is big can seriously affect the performance of PVC paste resin, undesirable.
The invention using polyimide powder as fire retardant, nontoxic, performance is stablized, and also can further improve The performances such as wear-resisting, heat-resisting, ageing-resistant, anti-radiation of composite material.The oxygen index (OI) of polyimide powder itself is up to 48, is added to After in PVC paste resin used in the present invention, prepared PVC paste resin oxygen index (OI) is up to 27 or more, belongs to fire retardant rank.
4, Ti is prepared the present invention also provides a kind of3+/TiO2And it is added to the method in PVC paste resin.TiO2Itself has There is the ability of removal formaldehyde；Meanwhile the electronegative electronics being optically excited out has stronger bactericidal effect, can assign material Material sterilization, self-cleaning ability.But common TiO2Because its forbidden bandwidth is larger, it is negative that band could be only generated under ultraviolet excitation The electronics of electricity, and Ti3+It can be in TiO2Conduction band bottom introduce localized modes, to make TiO2It can be even infrared ray excited by visible light Electronegative electronics out.
TiF3In F-Change TiO2Pattern, make its internal dissolution and to external diffusion, form ghost TiO2, in high temperature In the process, TiO2Oxygen atom in lattice is detached from, and forms Lacking oxygen, attracts TiF3In Ti3+And wrap up to inside hollow structure, Or it is adsorbed on TiO2Surface forms Ti3+/TiO2, make composite material for decoration in routine use, under common light environment With except formaldehyde, sterilization, self-cleaning ability.
5, the present invention has pressed one layer of PVC calendering skin or PU calendering skin in the outer layer of PVC paste resin, can according to need pair It carries out hitting the techniques such as convex, embossing, to assign the visual effect of composite material for decoration naked eye 3D.
PVC calendering skin or PU calendering skin itself are not prevented fires, and can not directly add fire proofing, so the present invention also creates Property coat the carbon nanotube coating material of one layer ultra-thin (0.5~1.5 μm of thickness) in calendering epidermis face, with increase it is wear-resisting, The performances such as fire-proof and water-proof, corrosion-resistant.
Specific embodiment
One, formula of the invention.
1, total formula of the invention are as follows: in parts by weight, 25~100 parts of glass fibre, polyimide fiber 25~200 Part, 50~600 parts of PVC paste resin, 1~200 part of rolled material, 0.1~1.2 part of ultra-thin carbon nanotube coating material.
2, in the formula, the preferred embodiment in addition to PVC paste resin is as follows:
(1) glass fibre is alkali-free glass fibre or medium-alkali glass fibre, average length > 50cm.
(2) polyimide fiber be ethers homopolymerization type polyimide fiber, tensile strength > 3cN/dtex, modulus > 9GPa.Preferred scheme are as follows: the polyimide fiber is P84 type polyimide powder, by aromatic diamine and aromatic series Dianhydride synthesis.
The rolled material is that PVC calendered film or PU roll skin, with a thickness of 5~80.
The carbon nanotube coating material, preferably hydroxylated multi-walled carbon nanotubes/fluorine carbon emulsion；The hydroxylating multi wall The caliber of carbon nanotube is 10~20nm, and 0.1~1.0 μm of length, purity > 98%, hydroxy radical content is 2.8~3.2%.
3, the formula of the PVC paste resin are as follows:
30~35wt% dioctyl phthalate (plasticizer, hereinafter referred to as DOP), 0.5wt% nm-class boron nitride, 1~ 3wt% nano rutile-type titanium dioxide or Ti3+/TiO2, 2~4wt% micron barium sulfate, 38~48wt% paste resin P450,10 ~20wt% polyimide powder, 0~7wt% microballoon foaming agent, 2wt% barium zinc type thermal stabilizing agent.
Two, concrete operation step of the invention.
1, non-woven fabrics is prepared.
(1) it prepares fiber reinforced dose: in parts by weight, 2~10 parts of carbon nanotubes being added in 100 parts of ethyl alcohol or chloroform, Ultrasonic disperse is uniformly to get fiber reinforced dose.
(2) glass fibre, polyimide fiber are separately added into fiber reinforced dose, soaked overnight, then by each fiber Carefully take out, under vacuum environment, be slowly warming up to 80~90 DEG C from room temperature, heat preservation drying, heating rate control 0.5~ 0.8℃/min。
(3) by each fiber mixed weaving bunchy after toughening, preferably it is with 1 glass fibre, 2 polyimide fibers One group, bunchy is woven in the way of three strands of fried dough twist pigtails.
(4) non-woven fabrics moulding process is used, fibre bundle is combed into networking, pinprick reinforcement to get required non-woven fabrics.
Tough step can also be added without fiber, directly will prepare again non-woven fabrics after each fibrage, only non-woven fabrics Comprehensive performance can be declined.
2, PVC paste resin is prepared.
(1) Ti is prepared3+/TiO2: by TiCl4It is completely dissolved in dehydrated alcohol, ultrasonic 10min, adding quality is TiCl4 The simple substance zinc of quality 40%, is stirred to react 30min, and adding quality is TiCl4The TiF that 1~1.5 times of quality3, ultrasonic 10min, Then in a sealed meter environment, 150 DEG C of 20~14h of heat preservation.After natural cooling, first rinsed sediment 1~2 time with dehydrated alcohol, then It is rinsed sediment 1~2 time, is subsequently dried to get required Ti with deionized water3+/TiO2.Transmission electron microscope is carried out to product and is swept Transmission electron microscope observing is retouched, finds the TiO of production2There is hollow structure in inside.
(2) it prepares PVC paste resin: at normal temperatures and pressures, DOP, nm-class boron nitride, nanometer being added in stainless steel stirred tank Rutile type titanium white or Ti3+/TiO2, micron barium sulfate, disperse 5min in 12000r/min, add paste resin P450, poly- (it is to be purchased from Japanese Matsumoto Yushi-Seiyaku Co., Ltd. that the present invention, which uses, model microballoon hair for acid imide powder, microballoon foaming agent Infusion F-50, using other middle low-temperature expansion type microballoon foaming agents can also), barium zinc type thermal stabilizing agent.
Follow these steps successively to be dispersed three times: 2000r/min disperses 5min, and 6000r/min disperses 2min, 3000r/ Min disperses 30min.After dispersion, then in 24~48h, in 2500r/min dispersion 15min to get PVC paste resin.
If not using Ti3+/TiO2, titanium dioxide is directly used, also can achieve goal of the invention, the PVC paste only prepared The sterilization of resin, self-cleaning ability accordingly decline.
3, composite material for decoration is prepared.
PVC paste resin is uniformly coated onto the nonwoven surface and rolled material is pressed together on PVC paste as needed after dry Resin surface, specific process for pressing are the prior art, the realization such as pressing machine can be used, details are not described herein.Pressing terminates, does After dry curing molding, then in surface spraying carbon nanotube, pass through one layer formed in body surface spraying and fast-curing process Overlay film coating, coating layer thickness are 0.5~1.5 μm.Stamp is carried out after drying as needed, hits the techniques such as convex, embossing to get required Composite material for decoration.
The present invention is further expalined combined with specific embodiments below.
Embodiment one: the effect of different fiber treatment modes is shown
1,11 groups of composite material for decoration are prepared by above-mentioned formula and operating procedure.Remaining condition is identical, at toughening Reason and braiding processing, as a control group.
The parts by weight of glass fibre and polyimide fiber, processing mode, non-woven fabrics preparation method in each group, such as table 1 It is shown.Wherein, fibre bundle is not woven, refers to combing networking preparation nothing after directly mixing glass fibre and polyimide fiber Woven fabric.In bundle weave mode, glass fibre is replaced with " glass "/" glass ", replaces polyimides fine with " poly- "/" poly- fibre " Dimension, the number before " glass " and " poly- " respectively refer in mass of fibers beam, the quantity of glass fibre, polyimide fiber respectively；Such as 1 Glass 2 is poly- to refer to that 1 glass fibre and 2 polyimide fibers are one group.1 glass poly, which refers to, weighs fiber by each fibre weight number Afterwards, by glass fibre and polyimide fiber, respectively actual quantity carries out ratio cut partition, is woven again according to dividing condition； For example, having 10 containing glass fibre in the parts by weight, polyimide fiber after weighing two kinds of fibers of specified weight number There are 30, is then that one group of carry out fried dough twist pigtail formula weaves with 1 glass fibre and 3 polyimide fibers.By specific weaving manner After being woven, last extra filament fiber is voluntarily woven by the specific weaving manner；For example, in such a way that 1 glass 1 is poly- After braiding, 10 polyimide fibers of last residue, not extra glass fibre is matched, then this 10 polyimides fibres Dimension is mutually wound fibre bundle with 2 for one group.
1 each group fiber treatment mode list of table
2, each group non-woven fabrics is tested for the property.Wherein, shear strength test method by JC/T 773-2010 into Row；Gas permeability is according to GB/T 24218.15-2018 " textile non-woven cloth test method " the 15th part: the measurement of gas permeability In test method carry out；The results are shown in Table 2.
2 each group fiber treatment mode list of table
Group Shear strength (MPa) Tensile strength (MPa) Gas permeability (ml/cm2·s)
Group 1 89 659 4
Group 2 112 933 6
Group 3 107 917 3
Group 4 63 549 6
Group 5 85 860 6
Group 6 92 901 6
Group 7 109 931 5
Group 8 101 852 2
Group 9 103 899 2
Group 10 89 865 5
Group 11 109 921 4
Control group 52 421 2
Embodiment two: the effect of different PVC paste resin treatment modes is shown
1, use the non-woven fabrics of 2 preparation of group in embodiment one as base, prepare 19 groups of composite material for decoration.Wherein, always Formula are as follows: in parts by weight, 50 parts of rolled material, 0.3 part of ultra-thin carbon nanotube coating material；The rolled material selects PU pressure Prolong skin.
The formula of PVC paste resin, processing mode, parts by weight in each group, as shown in table 3.PVC paste resin in table refers to Parts by weight shared by PVC paste resin in total formula, each component refers to each component in PVC paste resin formula in PVC paste resin formula In shared mass percent.Wherein, all PVC products and equal with the good barium zinc type thermal stabilizing agent of resin intermiscibility of capable of being used for It can be used, for convenience, barium zinc type thermal stabilizing agent used in full text of the present invention is purchased from the city Dong Wan Han Zhi rubber and plastic Co., Ltd, type Number be BZ-2321.Directly to use paste resin P450 as PVC paste resin, as a control group.
The processing mode list of each PVC paste resin of table 3
2, measure of merit is carried out to the composite material for decoration of each group preparation.
(1) presentation quality and basic physics performance
It is carried out by the experimental method and standard of JG/T 509-2016 " architectural decoration nonwoven wallpaper ", inspection item includes: Colour fastness to rubbing, wet tensile load, adhesive erasible and washability.Wherein, in colour fastness to rubbing test, each group material Material effect under the friction on dry friction, wet friction and different directions is suitable, at least top grade, so directly with rub resistance color This index of fastness is shown, the different-effect not being listed in individually in the case of differentiated friction.Three weights of every group of test Multiple, the results are shown in Table 4.
4 each group composite material for decoration effect of table shows one of table
(2) composite material antibacterial, mould proof, flame retardant property test
1) antibacterial ability is tested: being that Escherichia coli and 20 μ L staphylococcus aureuses are separately added into 100m meat by 20 μ L concentration In soup culture medium, after culture by Mixed Microbes concentration dilution be 1 × 106CFU/ml obtains mixed bacteria liquid.With 5mL mixed bacteria liquid for one Group is divided into 20 groups, and every group is separately added into each group composite material for decoration 1g, and 37 DEG C, culture is for 24 hours.
After culture, each group material is taken out, is gently cleaned each group material surface 3 times with sterilizing PBS solution, removes material The bacterium that surface suspends or adheres to by tension of water etc. then carries out (the dye bacterium examination anyway of life or death Bacterial stain to each group material Agent box, l-7012, hero Life Technologies, Inc.；2mL PBS solution containing 3 μ L SYTO and 3 μ L propidium iodide； Red represents dead bacterium, and green represents bacterium living), it is placed under laser scanning microscope and observes, count red green fluorescence number and shared Ratio.
Wherein, red (dead bacterium)+green (bacterium living)+black (background, no bacterium presence)=100%.
2) fungicidal properties is tested: being carried out according to " mildew " test method in GB/T2423.16-2008.
3) it tests and is classified according to the flame retardant property that the method for 5.1.1 in GB8624-2012 carries out composite material.
The results are shown in Table 5.
5 each group composite material for decoration effect of table shows the two of table
Group Red (%) Green (%) Mould proof grade Flame retardant rating
Group 1 2.9 8.8 0 grade B1(B)
Group 2 4.0 7.1 0 grade B1(B)
Group 3 2.8 8.9 0 grade B1(B)
Group 4 2.9 8.7 0 grade B1(B)
Group 5 2.9 9.0 0 grade B1(B)
Group 6 2.8 9.1 0 grade B1(B)
Group 7 3.0 9.0 0 grade B1(B)
Group 8 1.2 23.1 1 grade B1(B)
Group 9 1.8 13.2 1 grade B1(B)
Group 10 3.0 8.6 0 grade B1(B)
Group 11 2.8 9.1 0 grade B1(B)
Group 12 2.9 8.9 0 grade B1(B)
Group 13 3.0 9.0 0 grade B1(C)
Group 14 3.2 9.1 0 grade B1(B)
Group 15 3.5 9.1 0 grade B1(B)
Group 16 3.5 9.3 0 grade B1(B)
Group 17 3.3 9.5 0 grade B1(B)
Group 18 3.1 9.0 0 grade B1(B)
Group 19 3.3 9.1 0 grade B1(B)
Control group 0.9 33.5 1 grade B2(E)
(3) composite material anti-pollution is tested
Each group composite material is sheared into two pieces of 5cm respectively2Sample, the common dirt of life is dripped on every piece of sample respectively Stain after retaining for 24 hours at room temperature, carries out wiping processing with neutral detergent and alcohol respectively.Observe the spot of each group composite material Residual condition.Wherein, it 5 represents without spot residual, 4, which represent slightly spot, remains, and 3 represent part spot residual, and 2 represent many dirts Stain residual, 1 represents spot does not remove completely.The results are shown in Table 6.
6 each group composite material for decoration effect of table shows the three of table
Embodiment three: the effect that difference is always formulated is shown
1,7 groups of composite material for decoration are prepared by two group 2 of embodiment of method, wherein the recipe ingredient of each group such as 7 institute of table Show.Rolled material number indicates its shared parts by weight in total formula, rolled material and carbon nanotube coating material in table Ratio, the weight ratio both referred to (corresponding carbon nanotube coating material weight number is 0.1 part~1.2 parts).Not spray carbon Nanotube coatings material is as a control group.
The recipe ingredient list of 7 each group of table
Group Rolled material Rolled material: carbon nanotube coating material
Group 1 50 parts 1000:6
Group 2 100 parts 1000:6
Group 3 150 parts 1000:6
Group 4 200 parts 1000:6
Group 5 50 parts 1000:2
Group 6 50 parts 1000:4
Group 7 50 parts 1000:8
Control group 50 parts 1:0
2, by the test method of embodiment two, the comprehensive performance of each group composite material is tested, effect is respectively such as 8~table of table 10 It is shown.
8 each group composite material for decoration effect of table shows one of table
9 each group composite material for decoration effect of table shows the two of table
Group Red (%) Green (%) Mould proof grade Flame retardant rating
Group 1 4.1 6.9 0 grade B1(B)
Group 2 2.7 8.8 0 grade B1(B)
Group 3 2.9 8.9 0 grade B1(B)
Group 4 2.9 8.7 0 grade B1(B)
Group 5 3.0 9.3 0 grade B1(C)
Group 6 2.8 9.1 0 grade B1(B)
Group 7 3.0 9.0 0 grade B1(B)
Control group 1.5 16.3 1 grade B2(E)
10 each group composite material for decoration effect of table shows the three of table

Claims (10)

1. a kind of composite material for decoration, it is characterised in that: the composite material for decoration includes 4 layers of structure, from inside to outside successively are as follows: Nonwoven layer, PVC paste resin layer, rolled material layer and ultra-thin carbon nanotube coating.
2. composite material for decoration according to claim 1, it is characterised in that: the nonwoven layer is by glass fibre and polyamides Imine fiber is mixed.
3. composite material for decoration according to claim 2, it is characterised in that: the formula of the composite material for decoration is to press Parts by weight, 25~100 parts of glass fibre, 25~200 parts of polyimide fiber, 50~600 parts of PVC paste resin, rolled material 1 ~200 parts, 0.1~1.2 part of ultra-thin carbon nanotube coating material.
4. composite material for decoration according to claim 3, it is characterised in that: the formula of the composite material for decoration is to press Parts by weight, 50 parts of glass fibre, 98 parts of polyimide fiber, 100 parts of PVC paste resin, 50 parts of rolled material, ultra-thin carbon nanometer 0.3 part of pipe coating material.
5. composite material for decoration according to claim 2, it is characterised in that: the production method of the nonwoven layer are as follows: with It adds up to 2~6 glass fibres and polyimide fiber is one group, mixed weaving forms fibre bundle, and the fibre bundle is combed Reason networking is reinforced to obtain the final product.
6. composite material for decoration according to claim 5, it is characterised in that: the production method of the nonwoven layer are as follows: with 1 Root glass fibre and 2 polyimide fibers are one group, carry out being knitted to form fibre bundle by three bursts of fried dough twist pigtail formulas, by the fiber Beam combing networking is reinforced to obtain the final product.
7. composite material for decoration according to claim 5, it is characterised in that: the glass fibre and polyimide fiber into After going plus being tough, then woven；
Described plus tough mode are as follows: in parts by weight, 2~10 parts of carbon nanotubes are added in 100 parts of ethyl alcohol or chloroform, ultrasound point It dissipates uniformly to get fiber reinforced dose；Glass fibre, polyimide fiber are submerged respectively in fiber reinforced dose, soaked overnight, with Each fiber is carefully taken out afterwards, under vacuum environment, 80~90 DEG C are slowly warming up to from room temperature, heat preservation is dried, heating rate control Make 0.5~0.8 DEG C/min to get add it is tough after glass fibre and polyimide fiber.
8. composite material for decoration according to claim 3, it is characterised in that: the formula of the PVC paste resin are as follows: 30~ 35wt% dioctyl phthalate, 0.5wt% nm-class boron nitride, 1~3wt% nano rutile-type titanium dioxide or Ti3+/ TiO2, 2~4wt% micron barium sulfate, 38~48wt% paste resin P450,10~20wt% polyimide powder, 0~7wt% Microballoon foaming agent, 2wt% barium zinc type thermal stabilizing agent.
9. composite material for decoration according to claim 8, it is characterised in that: the PVC paste resin the preparation method comprises the following steps: normal Under normal temperature and pressure, dioctyl phthalate, nm-class boron nitride, nano rutile-type titanium dioxide or Ti are added in reaction kettle3+/ TiO2, micron barium sulfate, in 12000r/min disperse 5min, add paste resin P450, polyimide powder, microballoon foaming Agent, barium zinc type thermal stabilizing agent；
After mixing, follow these steps successively to be dispersed three times: 2000r/min disperses 5min, and 6000r/min disperses 2min, 3000r/min disperses 30min；After dispersion, then in 24~48h, in 2500r/min dispersion 15min to get PVC paste tree Rouge.
10. composite material for decoration according to claim 8, it is characterised in that: the Ti3+/TiO2The preparation method comprises the following steps: will TiCl4It is completely dissolved in dehydrated alcohol, ultrasonic 10min, adding quality is TiCl4The simple substance zinc of quality 40%, is stirred to react 30min, adding quality is TiCl4The TiF that 1~1.5 times of quality3, ultrasonic 10min, then at 150 DEG C keep the temperature 20~14h； Cooling, drying is to get required Ti3+/TiO2。
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