CN109367159B

CN109367159B - Multifunctional composite decorative material

Info

Publication number: CN109367159B
Application number: CN201811214942.4A
Authority: CN
Inventors: 郭镜哲; 陈红章; 吴强林
Original assignee: Anhui Bauhinia Wallpaper Co ltd
Current assignee: Anhui Bauhinia Wallpaper Co ltd
Priority date: 2018-10-18
Filing date: 2018-10-18
Publication date: 2021-06-29
Anticipated expiration: 2038-10-18
Also published as: CN109367159A

Abstract

The invention belongs to the field of decorative materials, and particularly relates to a multifunctional composite decorative material. The technical proposal is as follows: the composite decorative material comprises a 4-layer structure, and sequentially comprises the following components from inside to outside: non-woven fabrics layer, PVC paste resin layer, calendering material layer and ultra-thin carbon nanotube coating. The invention creatively uses the 4-layer structure, and provides the wall surface composite decorative material which has beautiful vision, convenient printing, safety, no toxicity, high strength, scraping resistance, scrubbing resistance, ageing resistance, fire resistance, water resistance, mildew resistance, crack resistance, convenient construction and good decorative effect.

Description

Multifunctional composite decorative material

Technical Field

The invention belongs to the field of decorative materials, and particularly relates to a multifunctional composite decorative material.

Background

Along with the further promotion of people's living standard, people are also constantly promoting to the fitment requirement of building, furniture, not only require relevant ornamental material to have characteristics such as the style is changeable, the color is various, the pattern is abundant, the vision is pleasing to the eye, decorative effect is good, still require to have characteristics such as fire prevention and water proofing, wear-resisting resistant scraping, safety ring protects, construction convenience, easily change, this has just proposed higher requirement to enterprises such as traditional wall paper, wall cloth, decorative board.

With the increasing maturity of industries such as wallpaper, wall cloth and veneer in China and the enhancement of safety and environmental awareness of people, people pay attention to the diversity of colors and styles of the wallpaper, the wall cloth and the veneer, and pay more attention to the practical, safe and environmental-friendly performances of products. The novel wallpaper, wall cloth and veneer with the functions of scraping resistance, easy cleaning, aging resistance, high temperature resistance, fire prevention, water prevention, formaldehyde removal, deodorization and the like and with various patterns of various colors begin to be in a pretty market. Related products achieve the corresponding functions of flame retardance, easy cleaning, heat preservation, scratch resistance, water resistance and the like mainly by coating, bonding, hot melting or compounding one or more functional coatings on the surface layers of paper, cloth or wood, and Chinese patents in the aspect of the flame retardance, the heat preservation, the scratch resistance, the water resistance and the like include CN103074815, CN206127727, CN102776805, CN103485504, CN100526554, CN107060235, CN206530006, CN107326749, CN206085878, CN107143105, CN107053382, CN108032592 and the like. The functional wallpaper, wall cloth or veneer prepared by the methods all have an important problem that the wallpaper, wall cloth or veneer has single functionality and is not full-function enough.

Therefore, the wall composite decorative material with complete functions has great high-end market demand.

Disclosure of Invention

The invention aims to provide a multifunctional composite decorative material.

In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: the composite decorative material comprises a 4-layer structure, and sequentially comprises the following components from inside to outside: non-woven fabrics layer, PVC paste resin layer, calendering material layer and ultra-thin carbon nanotube coating.

Preferably, the non-woven fabric layer is made of a mixture of glass fibers and polyimide fibers.

Preferably, the composite decorative material comprises, by weight, 25-100 parts of glass fibers, 25-200 parts of polyimide fibers, 50-600 parts of PVC paste resin, 1-200 parts of a calendering material and 0.1-1.2 parts of an ultrathin carbon nanotube coating material.

Preferably, the formula of the composite decorative material comprises, by weight, 50 parts of glass fiber, 98 parts of polyimide fiber, 100 parts of PVC paste resin, 50 parts of a calendaring material and 0.3 part of an ultrathin carbon nanotube coating material.

Preferably, the non-woven fabric layer is manufactured in a manner that: and taking 2-6 glass fibers and polyimide fibers in total as a group, mixing and weaving the glass fibers and the polyimide fibers to form a fiber bundle, and carding and reinforcing the fiber bundle to obtain the fiber-reinforced plastic composite material.

Preferably, the non-woven fabric layer is manufactured in a manner that: the method comprises the following steps of taking 1 glass fiber and 2 polyimide fibers as a group, weaving the glass fibers and the polyimide fibers in a three-strand twist braid mode to form a fiber bundle, and carding and reinforcing the fiber bundle to obtain the fiber-reinforced composite material.

Preferably, the glass fiber and the polyimide fiber are toughened and then woven;

the toughening mode is as follows: adding 2-10 parts by weight of carbon nano tubes into 100 parts by weight of ethanol or chloroform, and uniformly dispersing by ultrasonic to obtain a fiber toughening agent; respectively immersing the glass fiber and the polyimide fiber in a fiber toughening agent, soaking overnight, then carefully taking out each fiber, slowly heating to 80-90 ℃ from room temperature in a vacuum environment, keeping the temperature and drying, and controlling the heating speed to be 0.5-0.8 ℃/min to obtain the toughened glass fiber and polyimide fiber.

Preferably, the formulation of the PVC paste resin is as follows: 30-35 wt% of dioctyl phthalate, 0.5 wt% of nano boron nitride, 1-3 wt% of nano rutile type titanium dioxide or Ti³⁺/TiO₂2-4 wt% of micron barium sulfate, 38-48 wt% of paste resin P450, 10-20 wt% of polyimide powder, 0-7 wt% of microsphere foaming agent and 2 wt% of barium-zinc heat stabilizer.

Preferably, the preparation method of the PVC paste resin comprises the following steps: adding dioctyl phthalate, nano boron nitride, nano rutile type titanium dioxide or Ti into a reaction kettle at normal temperature and normal pressure³⁺/TiO₂Dispersing the micron barium sulfate at 12000r/min for 5min, and then adding paste resin P450, polyimide powder, a microsphere foaming agent and a barium-zinc heat stabilizer;

after mixing, the dispersion is carried out for three times according to the following steps: dispersing at 2000r/min for 5min, 6000r/min for 2min, and 3000r/min for 30 min; after the dispersion is finished, dispersing for 15min at 2500r/min within 24-48 h to obtain the PVC paste resin.

Preferably, the Ti is³⁺/TiO₂The preparation method comprises the following steps: mixing TiCl₄Dissolving completely in anhydrous ethanol, performing ultrasonic treatment for 10min, and adding TiCl₄Stirring and reacting 40% of simple substance zinc for 30min, and then adding TiCl₄1-1.5 times of TiF in mass₃Carrying out ultrasonic treatment for 10min, and then carrying out heat preservation for 20-14 h at 150 ℃; cooling and drying to obtain the required Ti³⁺/TiO₂。

The invention has the following beneficial effects:

1. the invention creatively uses the 4-layer structure, and provides the wall surface composite decorative material which has beautiful vision, convenient printing, safety, no toxicity, high strength, scraping resistance, scrubbing resistance, ageing resistance, fire resistance, water resistance, mildew resistance, crack resistance, convenient construction and good decorative effect.

2. The base material of the composite decorative material is non-woven fabric, when the non-woven fabric is woven, filament fibers are easy to break, the surface is smooth, the fibers are not curled, the net forming performance is poor, and the reinforcement is not easy, so that the non-woven fabric is difficult to be directly used for manufacturing the non-woven fabric. Generally, the filaments are cut into staple fibers, carded into a web, and then needled for reinforcement. But then the characteristics of the filament fibers are lost and the fibers are easily lost. The invention creatively uses the carbon nano tube to toughen the glass fiber and the polyimide fiber, thereby avoiding the fiber from being broken in the weaving process; then weaving the toughened fibers by taking 1 glass fiber and 2 polyimide fibers as a group in a three-strand twisted braid mode; and carding the knitted fiber bundles into a net, and needling and reinforcing the net to generate the non-woven fabric.

The mode for preparing the non-woven fabric overcomes the defect that glass fiber is fragile and easy to break, retains the characteristics of filament fiber, has the advantages of glass fiber and polyamide-imide fiber, is safe and nontoxic, has excellent mechanical property, is scratch-resistant, aging-resistant, fireproof and waterproof, has excellent air permeability and toughness, is stable in size, has wide application range, and has self-cleaning capability.

3. In order to make the non-woven fabric material have more excellent processing property and be more suitable for printing and the like, the non-woven fabric is coated with a layer of PVC paste resin. However, PVC paste resins are not flameproof and require the addition of flame retardants. Most of the traditional flame retardants are halogen flame retardants (represented by chlorine and bromine), have certain toxicity, and are not suitable for fields with high requirements such as home decoration. Inorganic flame retardants (such as aluminum hydroxide and magnesium hydroxide) or reactive flame retardants (MCA and TBP) are toxic or otherwise decomposed products after encountering fire; if not, the flame retardant can slowly self-decompose and gradually lose the flame retardant effect; or the flame retardant is poor in flame retardant effect due to small addition amount of the flame retardant, and the performance of the PVC paste resin is seriously influenced due to large addition amount of the flame retardant, so that the flame retardant is not ideal.

The invention creatively takes the polyimide powder as the flame retardant, has no toxicity or harm and stable performance, and can further improve the performances of wear resistance, heat resistance, aging resistance, radiation resistance and the like of the composite material. The oxygen index of the polyimide powder is up to 48, and after the polyimide powder is added into the PVC paste resin used in the invention, the oxygen index of the prepared PVC paste resin is up to more than 27, and the PVC paste resin belongs to a flame-retardant grade.

4. The invention also provides a method for preparing Ti³⁺/TiO₂And adding to the PVC paste resin. TiO 2₂The formaldehyde removing agent has the capability of removing formaldehyde; meanwhile, the negatively charged electrons excited by light have strong bactericidal action, and can endow the material with the capabilities of sterilization and self-cleaning. But ordinary TiO₂Because of its large forbidden band width, it can only produce negatively charged electrons under the excitation of ultraviolet light, and Ti³⁺Can be in TiO₂The conduction band bottom of (A) is introduced into a local state, thereby enabling TiO to be₂Negatively charged electrons can be excited by visible light or even infrared light.

TiF₃F in (1)^-Change TiO₂The morphology of (A) is such that the interior thereof is dissolved and diffuses outward to form a vacant shell TiO₂In a high temperature process, TiO₂Oxygen atoms in the crystal lattice are removed to form oxygen vacancies to attract TiF₃Of Ti³⁺And is wrapped inside the hollow structure or adsorbedIn TiO₂Surface of Ti to form³⁺/TiO₂The composite decorative material has the capabilities of removing formaldehyde, sterilizing and self-cleaning in daily use and under a common illumination environment.

5. According to the invention, a layer of PVC calendering skin or PU calendering skin is laminated on the outer layer of the PVC paste resin, and the PVC calendering skin or PU calendering skin can be subjected to processes such as embossing and embossing according to requirements, so that the naked-eye 3D visual effect of the composite decorative material is endowed.

The PVC calendering skin or the PU calendering skin is not fireproof and cannot be directly added with flame retardant materials, so the invention also creatively sprays a layer of ultrathin (the thickness is 0.5-1.5 mu m) carbon nano tube coating material on the surface of the calendering skin to improve the performances of wear resistance, fire resistance, water resistance, corrosion resistance and the like.

Detailed Description

Firstly, the formula of the invention.

1. The total formula of the invention is as follows: 25-100 parts of glass fiber, 25-200 parts of polyimide fiber, 50-600 parts of PVC paste resin, 1-200 parts of rolling material and 0.1-1.2 parts of ultrathin carbon nanotube coating material.

2. In the formula, the preferable scheme except the PVC paste resin is as follows:

(1) the glass fiber is alkali-free glass fiber or medium-alkali glass fiber, and the average length of the glass fiber is more than 50 cm.

(2) The polyimide fiber is an ether homopolymerization type polyimide fiber, the tensile strength of the polyimide fiber is more than 3cN/dtex, and the modulus of the polyimide fiber is more than 9 GPa. The more preferable scheme is as follows: the polyimide fiber is P84 type polyimide powder, and is synthesized by aromatic diamine and aromatic dianhydride.

The calendering material is a PVC calendering film or a PU calendering skin, and the thickness of the calendering material is 5-80 threads.

The carbon nano tube coating material is preferably hydroxylated multi-wall carbon nano tube/fluorocarbon emulsion; the tube diameter of the hydroxylated multi-wall carbon nano tube is 10-20 nm, the length of the hydroxylated multi-wall carbon nano tube is 0.1-1.0 mu m, the purity of the hydroxylated multi-wall carbon nano tube is more than 98%, and the hydroxyl content of the hydroxylated multi-wall carbon nano tube is 2.8-3.2%.

3. The formula of the PVC paste resin is as follows:

30 to 35 wt% of phthalic acid bisOctyl ester (plasticizer, DOP for short), 0.5 wt% of nano boron nitride, 1-3 wt% of nano rutile type titanium dioxide or Ti³⁺/TiO₂2-4 wt% of micron barium sulfate, 38-48 wt% of paste resin P450, 10-20 wt% of polyimide powder, 0-7 wt% of microsphere foaming agent and 2 wt% of barium-zinc heat stabilizer.

Secondly, the method comprises the specific operation steps.

1. And (4) preparing the non-woven fabric.

(1) Preparing a fiber toughening agent: adding 2-10 parts by weight of carbon nano tubes into 100 parts by weight of ethanol or chloroform, and uniformly dispersing by ultrasonic to obtain the fiber toughening agent.

(2) Respectively adding the glass fiber and the polyimide fiber into a fiber toughening agent, soaking overnight, then carefully taking out each fiber, slowly heating to 80-90 ℃ from room temperature in a vacuum environment, preserving heat and drying, wherein the heating speed is controlled at 0.5-0.8 ℃/min.

(3) The toughened fibers are mixed and woven into a bundle, and the bundle is preferably woven by taking 1 glass fiber and 2 polyimide fibers as a group in a three-strand twist braid mode.

(4) And (3) carding the fiber bundles into a net by adopting a non-woven fabric forming process, and reinforcing by needling to obtain the required non-woven fabric.

Or the step of toughening the fibers is not needed, and the non-woven fabric is prepared after the fibers are directly woven, but the comprehensive performance of the non-woven fabric is reduced.

2. Preparing PVC paste resin.

(1) Preparation of Ti³⁺/TiO₂: mixing TiCl₄Dissolving completely in anhydrous ethanol, performing ultrasonic treatment for 10min, and adding TiCl₄Stirring and reacting 40% of simple substance zinc for 30min, and then adding TiCl₄1-1.5 times of TiF in mass₃Performing ultrasonic treatment for 10min, and then performing heat preservation for 20-14 h at 150 ℃ in a sealed environment. After natural cooling, washing the precipitate with absolute ethyl alcohol for 1-2 times, washing the precipitate with deionized water for 1-2 times, and drying to obtain the required Ti³⁺/TiO₂. The product is observed by a transmission electron microscope and a scanning transmission electron microscope, and the produced TiO is discovered₂Inner partA hollow structure appears.

(2) Preparing PVC paste resin: adding DOP, nano boron nitride, nano rutile type titanium dioxide or Ti into a stainless steel stirring kettle at normal temperature and normal pressure³⁺/TiO₂Dispersing the micron barium sulfate at 12000r/min for 5min, adding paste resin P450, polyimide powder, a microsphere foaming agent (the invention uses a microsphere foaming agent F-50 which is purchased from Nippon Songban grease pharmacy Co., Ltd., and can also use other medium-low temperature expansion type microsphere foaming agents), and a barium-zinc heat stabilizer.

The three dispersions were carried out in the following order: dispersing at 2000r/min for 5min, 6000r/min for 2min, and 3000r/min for 30 min. After the dispersion is finished, dispersing for 15min at 2500r/min within 24-48 h to obtain the PVC paste resin.

If Ti is not used³⁺/TiO₂The titanium dioxide is directly used, the aim of the invention can be achieved, and the sterilization and self-cleaning capability of the prepared PVC paste resin is correspondingly reduced.

3. Preparing the composite decorative material.

PVC paste resin evenly scribbles the non-woven fabrics surface, after the drying, will roll the material pressfitting on PVC paste resin surface as required, specific pressfitting technology is prior art, can use pressfitting machine etc. to realize, no longer gives details here. And after the pressing, drying, curing and forming, spraying the carbon nano tube on the surface, and spraying and rapidly curing the carbon nano tube on the surface of the object to form a layer of coated coating with the thickness of 0.5-1.5 mu m. And after drying, carrying out processes such as printing, embossing and the like according to needs to obtain the required composite decorative material.

The invention is further explained below with reference to specific examples.

The first embodiment is as follows: effect display of different fiber treatment modes

1. 11 groups of composite decorative materials are prepared according to the formula and the operation steps. The other conditions are the same, and toughening treatment and weaving treatment are not carried out, and the obtained product is used as a control group.

The weight parts, treatment modes and non-woven fabric preparation modes of the glass fibers and the polyimide fibers in each group are shown in table 1. Wherein, the fiber bundle is not woven, which means that the non-woven fabric is prepared by directly combing and laying glass fiber and polyimide fiber. In the weaving mode of the fiber bundle, glass fiber is replaced by glass fiber, polyimide fiber is replaced by poly fiber, and the numbers in front of the glass fiber and the poly fiber respectively refer to the number of the glass fiber and the polyimide fiber in the fiber bundle; for example, 1 glass 2 poly means that 1 glass fiber and 2 polyimide fibers form a group. 1, glass poly-fiber means that after fibers are weighed according to the weight parts of the fibers, the fibers are divided according to the respective actual quantity of the glass fibers and the polyimide fibers, and then the fibers are woven according to the dividing condition; for example, after weighing two kinds of fibers in a specific weight part, the fiber contains 10 glass fibers and 30 polyimide fibers, and then weaving the fiber in a twist braid manner by using 1 glass fiber and 3 polyimide fibers as a group. After weaving according to a specific weaving mode, automatically weaving the residual filament fibers according to the specific weaving mode; for example, after weaving in a 1-glass 1-poly manner, 10 polyimide fibers are finally left, and no excess glass fibers are matched with the polyimide fibers, so that the 10 polyimide fibers are mutually wound to form a fiber bundle with 2 polyimide fibers as a group.

TABLE 1 fiber treatment protocol for each group

2. And carrying out performance test on each group of non-woven fabrics. Wherein the method for testing the shear strength is carried out according to JC/T773-2010; air permeability is as per GB/T24218.15-2018 "test methods for textile nonwovens" part 15: test methods in the determination of air permeability; the results are shown in Table 2.

TABLE 2 fiber treatment List for each group

Group of	Shear strength (MPa)	Tensile strength (MPa)	Air permeability (ml/cm)²·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

Example two: effect display of different PVC paste resin treatment modes

1. Using the nonwoven fabric prepared in group 2 of example one as a base layer, 19 sets of composite decorative materials were prepared. Wherein, the total formula is as follows: 50 parts of rolling material and 0.3 part of ultrathin carbon nanotube coating material in parts by weight; the calendering material is PU calendering skin.

The formulation, treatment and parts by weight of the PVC paste resin in each group are shown in Table 3. The PVC paste resin in the table refers to the weight portion of the PVC paste resin in the total formula, and each component in the PVC paste resin formula refers to the mass percentage of each component in the PVC paste resin formula. Wherein, all barium-zinc heat stabilizers which can be used for PVC products and have good resin solubility can be used, and for the sake of convenience, the barium-zinc heat stabilizers used in the invention are all purchased from Vast rubber and plastic Limited company of Aster Dongyi, and the type is BZ-2321. The paste resin P450 was used as PVC paste resin as it is, and used as a control.

TABLE 3 list of treatment methods for PVC paste resins

2. And carrying out effect test on the composite decorative material prepared by each group.

(1) Appearance quality and basic physical Properties

The method is carried out according to the experimental method and the standard of JG/T509-: crockfastness, wet tensile load, adhesive erasability, and washability. In the rubbing color fastness test, the effect of each group of materials under dry rubbing, wet rubbing and rubbing in different directions is equivalent and is at least excellent, so that the effect is directly shown by using the index of the rubbing color fastness, and different effects under different rubbing conditions are not separately shown. Each set was tested in triplicate and the results are shown in table 4.

Table 4 one of the effect display tables of each group of composite decoration materials

(2) Composite material antibacterial, mildew-proof and flame-retardant property test

1) And (3) testing antibacterial ability: adding 20 μ L of Escherichia coli and 20 μ L of Staphylococcus aureus into 100m broth, respectively, and diluting the mixed bacteria concentration to 1 × 10⁶CFU/ml to obtain mixed bacterial liquid. And taking 5mL of mixed bacteria liquid as one group, dividing the bacteria liquid into 20 groups, adding 1g of the composite decorative materials into each group, and culturing at 37 ℃ for 24 hours.

After the culture is finished, taking out each group of materials, slightly cleaning the surface of each group of materials by using a sterilized PBS solution for 3 times, removing bacteria suspended or adhered on the surface of the materials due to the tension of water and the like, and then dyeing the materials with dead and live bacteria (a dead and live bacteria dyeing kit, L-7012, Invitrogen Life technologies, 2mL of PBS solution containing 3 muL of SYTO and 3 muL of propidium iodide; red represents dead bacteria and green represents live bacteria) in a laser scanning microscope for observation, and counting the red and green fluorescence number and the occupied ratio.

Among them, red (dead bacteria) + green (live bacteria) + black (background, no bacteria present) ═ 100%.

2) And (3) testing the mildew resistance: the test was carried out according to the test method of "Long mold" in GB/T2423.16-2008.

3) The flame retardant performance of the composite material is tested and graded according to the method of 5.1.1 in GB 8624-2012.

The results are shown in Table 5.

Table 5 second display of each group of composite decoration material effect

Group of	Red (%)	Green (%)	Mildew resistance rating	Flame retardant rating
					Group 1	2.9	8.8	Level 0	B1(B)
Group 2	4.0	7.1	Level 0	B1(B)
					Group 3	2.8	8.9	Level 0	B1(B)
Group 4	2.9	8.7	Level 0	B1(B)
					Group 5	2.9	9.0	Level 0	B1(B)
Group 6	2.8	9.1	Level 0	B1(B)
					Group 7	3.0	9.0	Level 0	B1(B)
Group 8	1.2	23.1	Level 1	B1(B)
					Group 9	1.8	13.2	Level 1	B1(B)
Group 10	3.0	8.6	Level 0	B1(B)
					Group 11	2.8	9.1	Level 0	B1(B)
Group 12	2.9	8.9	Level 0	B1(B)
					Group 13	3.0	9.0	Level 0	B1(C)
Group 14	3.2	9.1	Level 0	B1(B)
					Group 15	3.5	9.1	Level 0	B1(B)
Group 16	3.5	9.3	Level 0	B1(B)
					Group 17	3.3	9.5	Level 0	B1(B)
Group 18	3.1	9.0	Level 0	B1(B)
					Group 19	3.3	9.1	Level 0	B1(B)
Control group	0.9	33.5	Level 1	B2(E)

(3) Antifouling Property test of composite Material

Each group of composite materials is respectively cut into two pieces of 5cm²The samples are respectively dripped with a drop of common living stain, and after the samples are kept for 24 hours at room temperature, the samples are respectively wiped by neutral detergent and alcohol. The composite materials of each group were observed for stain residue. Where 5 represents no stain remaining, 4 represents a little stain remaining, 3 represents a partial stain remaining, 2 represents a lot of stain remaining, and 1 represents no stain removal at all. The results are shown in Table 6.

Third table 6 showing effect of each group of composite decorative materials

Example three: effect display of different general formulas

1. 7 sets of composite decking materials were prepared as in example set 2, with the formulation components for each set shown in Table 7. In the table, the parts of the rolled material represent the parts by weight of the total formula, and the ratio of the rolled material to the carbon nanotube coating material refers to the weight ratio of the rolled material to the carbon nanotube coating material (the parts by weight of the carbon nanotube coating material is 0.1-1.2 parts). The control group was prepared without spraying carbon nanotube coating material.

Table 7 list of formulation components for each group

Group of	Rolled material	Rolling the material: carbon nanotube coating material
			Group 1	50 portions of	1000:6
Group 2	100 portions of	1000:6
			Group 3	150 portions of	1000:6
Group 4	200 portions of	1000:6
			Group 5	50 portions of	1000:2
Group 6	50 portions of	1000:4
			Group 7	50 portions of	1000:8
Control group	50 portions of	1:0

2. The comprehensive properties of the composite materials of each group were measured according to the test method of example two, and the effects are shown in tables 8 to 10, respectively.

Table 8 one of the effect display tables of each group of composite decorative materials

Table 9 second display of each group of composite decoration material effect

Group of	Red (%)	Green (%)	Mildew resistance rating	Flame retardant rating
					Group 1	4.1	6.9	Level 0	B1(B)
Group 2	2.7	8.8	Level 0	B1(B)
					Group 3	2.9	8.9	Level 0	B1(B)
Group 4	2.9	8.7	Level 0	B1(B)
					Group 5	3.0	9.3	Level 0	B1(C)
Group 6	2.8	9.1	Level 0	B1(B)
					Group 7	3.0	9.0	Level 0	B1(B)
Control group	1.5	16.3	Level 1	B2(E)

Third table 10 showing effect of each group of composite decorative materials

Claims

1. A composite decorative material is characterized in that: the composite decorative material comprises a 4-layer structure, and sequentially comprises the following components from inside to outside: the composite material comprises a non-woven fabric layer, a PVC paste resin layer, a calendaring material layer and an ultrathin carbon nanotube coating;

the non-woven fabric layer is prepared by mixing glass fibers and polyimide fibers;

the manufacturing method of the non-woven fabric layer comprises the following steps: the fiber bundle is prepared by taking 2-6 glass fibers and polyimide fibers in total as a group, mixing and weaving the glass fibers and the polyimide fibers to form a fiber bundle, and carding and reinforcing the fiber bundle to form a net.

2. The composite decorative material of claim 1, wherein: the formula of the composite decorative material comprises, by weight, 25-100 parts of glass fiber, 25-200 parts of polyimide fiber, 50-600 parts of PVC paste resin, 1-200 parts of a calendering material and 0.1-1.2 parts of an ultrathin carbon nanotube coating material.

3. The composite decorative material of claim 2, wherein: the formula of the composite decorative material comprises, by weight, 50 parts of glass fiber, 98 parts of polyimide fiber, 100 parts of PVC paste resin, 50 parts of rolling material and 0.3 part of ultrathin carbon nanotube coating material.

4. The composite decorative material of claim 1, wherein: the manufacturing method of the non-woven fabric layer comprises the following steps: the method comprises the following steps of taking 1 glass fiber and 2 polyimide fibers as a group, weaving the glass fibers and the polyimide fibers in a three-strand twist braid mode to form a fiber bundle, and carding and reinforcing the fiber bundle to obtain the fiber-reinforced composite material.

5. The composite decorative material of claim 1, wherein: the glass fiber and the polyimide fiber are toughened and then woven;

6. The composite decorative material of claim 2, wherein: the formula of the PVC paste resin is as follows: 30-35 wt% of dioctyl phthalate, 0.5 wt% of nano boron nitride, 1-3 wt% of nano rutile type titanium dioxide or Ti³⁺/TiO₂2-4 wt% of micron barium sulfate, 38-48 wt% of paste resin P450, 10-20 wt% of polyimide powder, 0-7 wt% of microsphere foaming agent and 2 wt% of barium-zinc heat stabilizer.

7. The composite decorative material of claim 6, wherein: the preparation method of the PVC paste resin comprises the following steps: adding dioctyl phthalate, nano boron nitride, nano rutile type titanium dioxide or Ti into a reaction kettle at normal temperature and normal pressure³⁺/TiO₂Dispersing the micron barium sulfate at 12000r/min for 5min, and then adding paste resin P450, polyimide powder, a microsphere foaming agent and a barium-zinc heat stabilizer;

8. The composite decorative material of claim 7, wherein: the Ti³⁺/TiO₂The preparation method comprises the following steps: mixing TiCl₄Dissolving completely in anhydrous ethanol, performing ultrasonic treatment for 10min, and adding TiCl₄Stirring and reacting 40% of simple substance zinc for 30min, and then adding TiCl₄1-1.5 times of TiF in mass₃Carrying out ultrasonic treatment for 10min, and then carrying out heat preservation for 20-14 h at 150 ℃; cooling and drying to obtain the required Ti³⁺/TiO₂。