CN111923540B - Wear-resistant and yellowing-resistant decorative material and preparation method thereof - Google Patents

Wear-resistant and yellowing-resistant decorative material and preparation method thereof Download PDF

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Publication number
CN111923540B
CN111923540B CN202011088196.6A CN202011088196A CN111923540B CN 111923540 B CN111923540 B CN 111923540B CN 202011088196 A CN202011088196 A CN 202011088196A CN 111923540 B CN111923540 B CN 111923540B
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coating
titanium dioxide
nano titanium
resistant
decorative paper
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CN111923540A (en
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林锦樑
杨健武
林真
崔倩文
张嘉栋
刘嘉诚
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Guangdong Tian'an Polymer Technology Co ltd
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Guangdong Tian'an Polymer Technology Co ltd
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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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1207—Heat-activated adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/52—Epoxy resins
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/57—Polyureas; Polyurethanes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1207—Heat-activated adhesive
    • B32B2037/1215—Hot-melt adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0076—Curing, vulcanising, cross-linking
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/12—Coating on the layer surface on paper layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2471/00—Floor coverings
    • 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
    • B32B2479/00—Furniture

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Thermal Sciences (AREA)
  • Laminated Bodies (AREA)
  • Paper (AREA)

Abstract

The invention discloses a wear-resistant yellowing-resistant decorative material and a preparation method thereof. The decorative material comprises decorative paper and a coating which permeates into the interior of the decorative paper and is cured, wherein the coating comprises at least one of acrylic epoxy ester, acrylic novolac epoxy ester, polyurethane acrylate oligomer, polyester acrylate and an active monomer, the coating also comprises modified nano titanium dioxide, and the surface of the modified nano titanium dioxide is coated with quaternary ammonium salt chitosan and sulfonated lignin, so that the wear resistance, the light color fastness and the yellowing resistance of the decorative material can be effectively improved.

Description

Wear-resistant and yellowing-resistant decorative material and preparation method thereof
Technical Field
The invention relates to the technical field of decorative materials, in particular to a wear-resistant and yellowing-resistant decorative material and a preparation method thereof.
Background
The decorative paper is an important raw material in building materials and is widely applied to decorative boards, laminate wood floors and veneers for offices and furnitureThe material and other fields can play the roles of providing decoration of the patterns and covering for preventing the bottom layer glue solution from seeping. The decorative paper has good impregnation performance and printing performance, and the decorative paper is pasted on products such as furniture and the like, so that a novel and attractive effect can be given to the products, and the defects of multiple gaps, monotonous design and the like of the products such as the furniture and the like are overcome. However, the paper surface of the decorative paper is easily abraded in a large area when being rubbed, and the original function of the decorative paper is lost, so that certain inorganic filler needs to be added into the impregnating resin of the decorative paper based on the special requirement of certain application fields on the wear-resisting property of the decorative material. For example, CN201910412607.3, CN202010344389.7 and the like coat the decorative paper with a coating containing titanium dioxide nanoparticles, thereby increasing the wear resistance of the decorative paper, making the decorative paper less prone to wear, and prolonging the service life of the decorative paper. However, decorative paper is deteriorated by factors such as light irradiation when used as an indoor or outdoor material, and particularly, a photoactivation point exists on the surface of titanium dioxide, so that under sunlight irradiation, oxygen ions on the crystal lattice can lose two electrons and become oxygen atoms, and the released electrons are converted into oxygen atoms by Ti4+Trapped and reduced to Ti3+In the reaction process, nascent oxygen is released, and the decorative paper can be yellowed in a short period, so that the attractiveness and durability of the decorative material are influenced. Therefore, there is a need to develop a novel facing material excellent in abrasion resistance, light fastness and yellowing resistance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a wear-resistant and yellowing-resistant decorative material which has good wear resistance, light color fastness and yellowing resistance.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the wear-resistant and yellowing-resistant decorative material comprises a plastic film, decorative paper and a coating which permeates into the decorative paper and is solidified, wherein the plastic film is attached to the upper surface of the decorative paper; the coating comprises at least one of acrylic acid epoxy ester, acrylic acid novolac epoxy ester, polyurethane acrylate oligomer, polyester acrylate and active monomer, and also comprises modified nano titanium dioxide, wherein the surface of the modified nano titanium dioxide is coated with quaternary ammonium salt chitosan and sulfonated lignin.
According to the invention, the modified nano titanium dioxide is added into the coating, and the wear resistance of the decorative paper is effectively improved by utilizing the good mechanical strength of the titanium dioxide, so that the decorative paper is less prone to wear.
In addition, because the nano titanium dioxide has small particle size, is easy to agglomerate and has crowding effect, so that the light stability of the nano titanium dioxide is influenced.
The existing decorative paper is generally impregnated with melamine resin, however, nascent oxygen released in the titanium dioxide photoreaction process is easy to oxidize melamine, so that molecules are broken and degraded, and the color of the decorative material is obviously changed; the coating comprises at least one of acrylic epoxy ester, acrylic novolac epoxy ester, polyurethane acrylate oligomer, polyester acrylate and active monomer, and the components are compounded with nano titanium dioxide, so that the prepared decorative material obviously has better light color fastness and yellowing resistance, has good flexibility, does not obviously crack after being bent, and can be subjected to flat pasting, coating and modeling pasting treatment.
If the content of the modified nano titanium dioxide in the coating is too low, the wear resistance improvement effect of the coating on the decorative material is not obvious, and if the content of the modified nano titanium dioxide is too high, the light color fastness and the yellowing resistance of the decorative paper material are obviously reduced, so that the mass percentage of the modified nano titanium dioxide in the coating is preferably 3-10%.
It is well known in the art that the reactive monomer is a small organic molecule containing a polymerizable functional group, which acts to regulate viscosity and participate in the curing reaction in the coating composition.
The active monomer comprises at least one of monofunctional monomer, bifunctional monomer and polyfunctional monomer, and the monofunctional monomer can be at least one of alkoxylated phenol acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, tetrahydrofuran acrylate and isodecyl acrylate; the bifunctional monomer may be at least one selected from the group consisting of alkoxy hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate, and triethylene glycol dimethacrylate; the polyfunctional monomer may be at least one selected from among propoxy (6) -modified trimethylolpropane triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol tetraacrylate and dipentaerythritol pentaacrylate.
Preferably, the preparation method of the modified nano titanium dioxide comprises the following steps:
1) dissolving quaternary ammonium salt chitosan in water to obtain a quaternary ammonium salt chitosan solution, adding nano titanium dioxide into the quaternary ammonium salt chitosan solution, stirring for 8-12h under the conditions that the temperature is 45-50 ℃ and the stirring speed is 100-200 r/min, centrifuging and drying;
2) dissolving the sulfonated lignin in water to obtain a sulfonated lignin solution, adding the nano titanium dioxide treated in the step (1), performing ultrasonic dispersion for 2-5h at the temperature of 60-80 ℃, and performing centrifugation, washing and drying to obtain modified nano titanium dioxide particles.
The modified nano titanium dioxide prepared by the method has good compatibility with a coating matrix, reduces the agglomeration phenomenon of the nano titanium dioxide, effectively improves the light stability of the nano titanium dioxide, and is more favorable for improving the yellowing resistance of the decorative material.
Preferably, the addition amount of the quaternary ammonium salt chitosan is 0.1-1.0% of the mass of the nano titanium dioxide, and the modified nano titanium dioxide prepared in the range of the addition amount has good light stability.
Preferably, the addition amount of the sulfonated lignin is 0.2-0.4% of the mass of the nano titanium dioxide, which is beneficial to improving the light stability of the modified nano titanium dioxide.
The plastic film is attached to the upper surface of the decorative paper, so that the flexibility of the wear-resistant and yellowing-resistant decorative material can be further improved, and the processing of the wear-resistant and yellowing-resistant decorative material is facilitated. Preferably, the plastic film is a biaxially stretched film or a cast film, and the plastic film comprises a main plastic film layer selected from a polypropylene film, a polyethylene film, a polyester film or a polyurethane film, and at least one hot melt adhesive layer. Compared with a polyvinyl chloride film, the selected plastic film has better weather resistance and more excellent yellowing resistance, wherein the polyethylene film has good flexibility, relatively low strength and insufficient scraping resistance; the polyester film has higher hardness and good scratch resistance, but has poor flexibility, cannot be embossed for the second time and only can be used as a plain weave product; the polyurethane film has higher cost, and the invention more preferably selects the polypropylene film by comprehensively considering the factors of flexibility, strength, scratch resistance, pollution resistance, weather resistance and the like, cost and the like.
The invention also provides a preparation method of the wear-resistant and yellowing-resistant decorative material, which comprises the following steps: coating the coating on the upper surface or the lower surface of the decorative paper, and curing the coating by electron beams after the coating permeates into the decorative paper;
or after a plastic film is attached to the upper surface of the decorative paper, coating the lower surface of the decorative paper with the coating, and curing the coating by electron beams after the coating permeates into the decorative paper.
Preferably, the viscosity of the coating is 5 to 200 cps; the coating amount of the coating is 20-100 g/m2. According to the invention, through optimizing the viscosity and the coating amount of the coating, the toughness of the wear-resistant and yellowing-resistant decorative material is improved after curing, the bonding strength between the decorative paper and the plastic film is improved, and the peeling between the decorative paper and the plastic film is avoided.
Preferably, the electron beam curing dosage is 5-50 kGy, the running speed of the decorating material during curing is 10-200 m/min, and the cured decorating material has good toughness.
Compared with the prior art, the invention has the beneficial effects that:
the decorative material contains modified nano titanium dioxide, and the surface of the modified nano titanium dioxide is coated with quaternary ammonium salt chitosan and sulfonated lignin, so that the wear resistance, the light color fastness and the yellowing resistance of the decorative material can be effectively improved.
Drawings
Fig. 1 is a result of a performance test of the decorating material prepared in examples and comparative examples.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
In the examples, the experimental methods used were all conventional methods unless otherwise specified, and the materials, reagents and the like used were commercially available without otherwise specified.
The decorative papers of the following examples and comparative examples were selected from virgin impregnated papers having a thickness of 0.08 mm; the thickness of the plastic film was 0.04 mm.
The performance test method of the decorative material comprises the following steps:
flexibility: and (3) bending the decorative material, and observing whether the surface of the decorative material has obvious cracking phenomenon after conventional flat pasting, coating and modeling pasting treatment.
Wear resistance: testing according to a method for measuring the wear resistance of the 4.42 surface in GB/T17657-2013;
color fastness to light: GB/T17657-2013 at 4.30 specifies a method for testing with a xenon arc lamp.
Example 1
The wear-resistant and yellowing-resistant decorative material comprises a plastic film, decorative paper and a coating which permeates into the decorative paper and is solidified, wherein the coating comprises a polyurethane acrylate oligomer, TMPTA and modified nano titanium dioxide, the viscosity of the coating is 20cps, the mass percentage of the modified nano titanium dioxide in the coating is 1%, and the surface of the modified nano titanium dioxide is coated with quaternary ammonium salt chitosan and sulfonated lignin; the plastic film is a biaxial stretching film and comprises a polypropylene film and at least one layer of hot melt adhesive layer, and the plastic film is attached to the upper surface of the decorative paper through the hot melt adhesive layer.
The preparation method of the wear-resistant yellowing-resistant decorative material comprises the following steps:
(1) preparing a coating with the viscosity of 20cps by adopting a polyurethane acrylate oligomer, TMPTA and modified nano titanium dioxide;
the preparation method of the modified nano titanium dioxide comprises the following steps:
1.1) dissolving quaternary ammonium salt chitosan in water to obtain a quaternary ammonium salt chitosan solution, adding nano titanium dioxide into the quaternary ammonium salt chitosan solution, stirring for 10 hours at the temperature of 45 ℃ and the stirring speed of 150r/min, centrifuging and drying;
1.2) dissolving the sulfonated lignin in water to obtain a sulfonated lignin solution, adding the nano titanium dioxide treated in the step 1.1), ultrasonically dispersing for 2h at 75 ℃, and centrifuging, washing and drying to obtain modified nano titanium dioxide particles;
the addition amount of the quaternary ammonium salt chitosan is 0.8 percent of the mass of the nano titanium dioxide, and the addition amount of the sulfonated lignin is 0.3 percent of the mass of the nano titanium dioxide;
(2) attaching a plastic film to the upper surface of the decorative paper;
(3) coating prepared in the step (1) is mixed according to the ratio of 30 g/m2The coating amount is coated on the lower surface of the decorative paper, the coating penetrates into the decorative paper and is cured by electron beams, wherein the dosage of electron beam curing is 15 kGy, the running speed of the paper during curing is 10 m/min, and the wear-resistant yellowing-resistant decorative material is obtained after the inspection is qualified.
Example 2
The wear-resistant and yellowing-resistant decorative material comprises a plastic film, decorative paper and a coating which permeates into the decorative paper and is solidified, wherein the coating comprises a polyurethane acrylate oligomer, trimethylolpropane triacrylate (TMPTA) and modified nano titanium dioxide, the viscosity of the coating is 20cps, the mass percentage of the modified nano titanium dioxide in the coating is 3%, and the surface of the modified nano titanium dioxide is coated with quaternary ammonium salt chitosan and sulfonated lignin; the plastic film is a biaxial stretching film and comprises a polypropylene film and at least one layer of hot melt adhesive layer, and the plastic film is attached to the upper surface of the decorative paper through the hot melt adhesive layer.
The preparation method of the wear-resistant yellowing-resistant decorative material comprises the following steps:
(1) preparing a coating with the viscosity of 20cps by adopting a polyurethane acrylate oligomer, TMPTA and modified nano titanium dioxide;
the preparation method of the modified nano titanium dioxide comprises the following steps:
1.1) dissolving quaternary ammonium salt chitosan in water to obtain a quaternary ammonium salt chitosan solution, adding nano titanium dioxide into the quaternary ammonium salt chitosan solution, stirring for 10 hours at the temperature of 45 ℃ and the stirring speed of 150r/min, centrifuging and drying;
1.2) dissolving the sulfonated lignin in water to obtain a sulfonated lignin solution, adding the nano titanium dioxide treated in the step 1.1), ultrasonically dispersing for 2h at 75 ℃, and centrifuging, washing and drying to obtain modified nano titanium dioxide particles;
the addition amount of the quaternary ammonium salt chitosan is 0.8 percent of the mass of the nano titanium dioxide, and the addition amount of the sulfonated lignin is 0.3 percent of the mass of the nano titanium dioxide;
(2) attaching a plastic film to the upper surface of the decorative paper;
(3) coating prepared in the step (1) is mixed according to the ratio of 30 g/m2The coating amount is coated on the lower surface of the decorative paper, the coating penetrates into the decorative paper and is cured by electron beams, wherein the dosage of electron beam curing is 15 kGy, the running speed of the paper during curing is 10 m/min, and the wear-resistant yellowing-resistant decorative material is obtained after the inspection is qualified.
Example 3
The wear-resistant and yellowing-resistant decorative material comprises a plastic film, decorative paper and a coating which permeates into the decorative paper and is solidified, wherein the coating comprises a polyurethane acrylate oligomer, TMPTA and modified nano titanium dioxide, the viscosity of the coating is 20cps, the mass percentage of the modified nano titanium dioxide in the coating is 6%, and the surface of the modified nano titanium dioxide is coated with quaternary ammonium salt chitosan and sulfonated lignin; the plastic film is a biaxial stretching film and comprises a polypropylene film and at least one layer of hot melt adhesive layer, and the plastic film is attached to the upper surface of the decorative paper through the hot melt adhesive layer.
The preparation method of the wear-resistant yellowing-resistant decorative material comprises the following steps:
(1) preparing a coating with the viscosity of 20cps by adopting a polyurethane acrylate oligomer, TMPTA and modified nano titanium dioxide;
the preparation method of the modified nano titanium dioxide comprises the following steps:
1.1) dissolving quaternary ammonium salt chitosan in water to obtain a quaternary ammonium salt chitosan solution, adding nano titanium dioxide into the quaternary ammonium salt chitosan solution, stirring for 10 hours at the temperature of 45 ℃ and the stirring speed of 150r/min, centrifuging and drying;
1.2) dissolving the sulfonated lignin in water to obtain a sulfonated lignin solution, adding the nano titanium dioxide treated in the step 1.1), ultrasonically dispersing for 2h at 75 ℃, and centrifuging, washing and drying to obtain modified nano titanium dioxide particles;
the addition amount of the quaternary ammonium salt chitosan is 0.8 percent of the mass of the nano titanium dioxide, and the addition amount of the sulfonated lignin is 0.3 percent of the mass of the nano titanium dioxide;
(2) attaching a plastic film to the upper surface of the decorative paper;
(3) coating prepared in the step (1) is mixed according to the ratio of 30 g/m2The coating amount is coated on the lower surface of the decorative paper, the coating penetrates into the decorative paper and is cured by electron beams, wherein the dosage of electron beam curing is 15 kGy, the running speed of the paper during curing is 10 m/min, and the wear-resistant yellowing-resistant decorative material is obtained after the inspection is qualified.
Example 4
The wear-resistant and yellowing-resistant decorative material comprises a plastic film, decorative paper and a coating which permeates into the decorative paper and is solidified, wherein the coating comprises a polyurethane acrylate oligomer, TMPTA and modified nano titanium dioxide, the viscosity of the coating is 20cps, the mass percentage of the modified nano titanium dioxide in the coating is 10%, and the surface of the modified nano titanium dioxide is coated with quaternary ammonium salt chitosan and sulfonated lignin; the plastic film is a biaxial stretching film and comprises a polypropylene film and at least one layer of hot melt adhesive layer, and the plastic film is attached to the upper surface of the decorative paper through the hot melt adhesive layer.
The preparation method of the wear-resistant yellowing-resistant decorative material comprises the following steps:
(1) preparing a coating with the viscosity of 20cps by adopting a polyurethane acrylate oligomer, TMPTA and modified nano titanium dioxide;
the preparation method of the modified nano titanium dioxide comprises the following steps:
1.1) dissolving quaternary ammonium salt chitosan in water to obtain a quaternary ammonium salt chitosan solution, adding nano titanium dioxide into the quaternary ammonium salt chitosan solution, stirring for 10 hours at the temperature of 45 ℃ and the stirring speed of 150r/min, centrifuging and drying;
1.2) dissolving the sulfonated lignin in water to obtain a sulfonated lignin solution, adding the nano titanium dioxide treated in the step 1.1), ultrasonically dispersing for 2h at 75 ℃, and centrifuging, washing and drying to obtain modified nano titanium dioxide particles;
the addition amount of the quaternary ammonium salt chitosan is 0.8 percent of the mass of the nano titanium dioxide, and the addition amount of the sulfonated lignin is 0.3 percent of the mass of the nano titanium dioxide;
(2) attaching a plastic film to the upper surface of the decorative paper;
(3) coating prepared in the step (1) is mixed according to the ratio of 30 g/m2The coating amount is coated on the lower surface of the decorative paper, the coating penetrates into the decorative paper and is cured by electron beams, wherein the dosage of electron beam curing is 15 kGy, the running speed of the paper during curing is 10 m/min, and the wear-resistant yellowing-resistant decorative material is obtained after the inspection is qualified.
Example 5
The wear-resistant and yellowing-resistant decorative material comprises a plastic film, decorative paper and a coating which permeates into the decorative paper and is solidified, wherein the coating comprises a polyurethane acrylate oligomer, TMPTA and modified nano titanium dioxide, the viscosity of the coating is 20cps, the mass percentage of the modified nano titanium dioxide in the coating is 15%, and the surface of the modified nano titanium dioxide is coated with quaternary ammonium salt chitosan and sulfonated lignin; the plastic film is a biaxial stretching film and comprises a polypropylene film and at least one layer of hot melt adhesive layer, and the plastic film is attached to the upper surface of the decorative paper through the hot melt adhesive layer.
The preparation method of the wear-resistant yellowing-resistant decorative material comprises the following steps:
(1) preparing a coating with the viscosity of 20cps by adopting a polyurethane acrylate oligomer, TMPTA and modified nano titanium dioxide;
the preparation method of the modified nano titanium dioxide comprises the following steps:
1.1) dissolving quaternary ammonium salt chitosan in water to obtain a quaternary ammonium salt chitosan solution, adding nano titanium dioxide into the quaternary ammonium salt chitosan solution, stirring for 10 hours at the temperature of 45 ℃ and the stirring speed of 150r/min, centrifuging and drying;
1.2) dissolving the sulfonated lignin in water to obtain a sulfonated lignin solution, adding the nano titanium dioxide treated in the step 1.1), ultrasonically dispersing for 2h at 75 ℃, and centrifuging, washing and drying to obtain modified nano titanium dioxide particles;
the addition amount of the quaternary ammonium salt chitosan is 0.8 percent of the mass of the nano titanium dioxide, and the addition amount of the sulfonated lignin is 0.3 percent of the mass of the nano titanium dioxide;
(2) attaching a plastic film to the upper surface of the decorative paper;
(3) coating prepared in the step (1) is mixed according to the ratio of 30 g/m2The coating amount is coated on the lower surface of the decorative paper, the coating penetrates into the decorative paper and is cured by electron beams, wherein the dosage of electron beam curing is 15 kGy, the running speed of the paper during curing is 10 m/min, and the wear-resistant yellowing-resistant decorative material is obtained after the inspection is qualified.
Example 6
The wear-resistant and yellowing-resistant decorative material comprises a plastic film, decorative paper and a coating which permeates into the decorative paper and is solidified, wherein the coating comprises a polyurethane acrylate oligomer, TMPTA and modified nano titanium dioxide, the viscosity of the coating is 20cps, the mass percentage of the modified nano titanium dioxide in the coating is 6%, and the surface of the modified nano titanium dioxide is coated with quaternary ammonium salt chitosan and sulfonated lignin; the plastic film is a biaxial stretching film and comprises a polypropylene film and at least one layer of hot melt adhesive layer, and the plastic film is attached to the upper surface of the decorative paper through the hot melt adhesive layer.
The preparation method of the wear-resistant yellowing-resistant decorative material comprises the following steps:
(1) preparing a coating with the viscosity of 20cps by adopting a polyurethane acrylate oligomer, TMPTA and modified nano titanium dioxide;
the preparation method of the modified nano titanium dioxide comprises the following steps:
1.1) dissolving quaternary ammonium salt chitosan in water to obtain a quaternary ammonium salt chitosan solution, adding nano titanium dioxide into the quaternary ammonium salt chitosan solution, stirring for 10 hours at the temperature of 45 ℃ and the stirring speed of 150r/min, centrifuging and drying;
1.2) dissolving the sulfonated lignin in water to obtain a sulfonated lignin solution, adding the nano titanium dioxide treated in the step 1.1), ultrasonically dispersing for 2h at 75 ℃, and centrifuging, washing and drying to obtain modified nano titanium dioxide particles;
the addition amount of the quaternary ammonium salt chitosan is 1% of the mass of the nano titanium dioxide, and the addition amount of the sulfonated lignin is 0.2% of the mass of the nano titanium dioxide;
(2) attaching a plastic film to the upper surface of the decorative paper;
(3) coating prepared in the step (1) is mixed according to the ratio of 30 g/m2The coating amount is coated on the lower surface of the decorative paper, the coating penetrates into the decorative paper and is cured by electron beams, wherein the dosage of electron beam curing is 15 kGy, the running speed of the paper during curing is 10 m/min, and the wear-resistant yellowing-resistant decorative material is obtained after the inspection is qualified.
Example 7
The wear-resistant and yellowing-resistant decorative material comprises a plastic film, decorative paper and a coating which permeates into the decorative paper and is solidified, wherein the coating comprises a polyurethane acrylate oligomer, TMPTA and modified nano titanium dioxide, the viscosity of the coating is 20cps, the mass percentage of the modified nano titanium dioxide in the coating is 6%, and the surface of the modified nano titanium dioxide is coated with quaternary ammonium salt chitosan and sulfonated lignin; the plastic film is a biaxial stretching film and comprises a polypropylene film and at least one layer of hot melt adhesive layer, and the plastic film is attached to the upper surface of the decorative paper through the hot melt adhesive layer.
The preparation method of the wear-resistant yellowing-resistant decorative material comprises the following steps:
(1) preparing a coating with the viscosity of 20cps by adopting a polyurethane acrylate oligomer, TMPTA and modified nano titanium dioxide;
the preparation method of the modified nano titanium dioxide comprises the following steps:
1.1) dissolving quaternary ammonium salt chitosan in water to obtain a quaternary ammonium salt chitosan solution, adding nano titanium dioxide into the quaternary ammonium salt chitosan solution, stirring for 10 hours at the temperature of 45 ℃ and the stirring speed of 150r/min, centrifuging and drying;
1.2) dissolving the sulfonated lignin in water to obtain a sulfonated lignin solution, adding the nano titanium dioxide treated in the step 1.1), ultrasonically dispersing for 2h at 75 ℃, and centrifuging, washing and drying to obtain modified nano titanium dioxide particles;
the addition amount of the quaternary ammonium salt chitosan is 0.1 percent of the mass of the nano titanium dioxide, and the addition amount of the sulfonated lignin is 0.4 percent of the mass of the nano titanium dioxide;
(2) attaching a plastic film to the upper surface of the decorative paper;
(3) coating prepared in the step (1) is mixed according to the ratio of 30 g/m2The coating amount is coated on the lower surface of the decorative paper, the coating penetrates into the decorative paper and is cured by electron beams, wherein the dosage of electron beam curing is 15 kGy, the running speed of the paper during curing is 10 m/min, and the wear-resistant yellowing-resistant decorative material is obtained after the inspection is qualified.
Example 8
The wear-resistant and yellowing-resistant decorative material comprises a plastic film, decorative paper and a coating which permeates into the decorative paper and is solidified, wherein the coating comprises a polyurethane acrylate oligomer, TMPTA and modified nano titanium dioxide, the viscosity of the coating is 20cps, the mass percentage of the modified nano titanium dioxide in the coating is 6%, and the surface of the modified nano titanium dioxide is coated with quaternary ammonium salt chitosan and sulfonated lignin; the plastic film is a biaxial stretching film and comprises a polypropylene film and at least one layer of hot melt adhesive layer, and the plastic film is attached to the upper surface of the decorative paper through the hot melt adhesive layer.
The preparation method of the wear-resistant yellowing-resistant decorative material comprises the following steps:
(1) preparing a coating with the viscosity of 20cps by adopting a polyurethane acrylate oligomer, TMPTA and modified nano titanium dioxide;
the preparation method of the modified nano titanium dioxide comprises the following steps:
1.1) dissolving quaternary ammonium salt chitosan in water to obtain a quaternary ammonium salt chitosan solution, adding nano titanium dioxide into the quaternary ammonium salt chitosan solution, stirring for 10 hours at the temperature of 45 ℃ and the stirring speed of 150r/min, centrifuging and drying;
1.2) dissolving the sulfonated lignin in water to obtain a sulfonated lignin solution, adding the nano titanium dioxide treated in the step 1.1), ultrasonically dispersing for 2h at 75 ℃, and centrifuging, washing and drying to obtain modified nano titanium dioxide particles;
the addition amount of the quaternary ammonium salt chitosan is 1.5 percent of the mass of the nano titanium dioxide, and the addition amount of the sulfonated lignin is 0.1 percent of the mass of the nano titanium dioxide;
(2) attaching a plastic film to the upper surface of the decorative paper;
(3) coating prepared in the step (1) is mixed according to the ratio of 30 g/m2The coating amount is coated on the lower surface of the decorative paper, the coating penetrates into the decorative paper and is cured by electron beams, wherein the dosage of electron beam curing is 15 kGy, the running speed of the paper during curing is 10 m/min, and the wear-resistant yellowing-resistant decorative material is obtained after the inspection is qualified.
Example 9
The wear-resistant and yellowing-resistant decorative material comprises a plastic film, decorative paper and a coating which permeates into the decorative paper and is cured, wherein the coating comprises acrylic novolac epoxy ester, DPGDA and modified nano titanium dioxide, the viscosity of the coating is 20cps, the mass percent of the modified nano titanium dioxide in the coating is 6%, and the surface of the modified nano titanium dioxide is coated with quaternary ammonium salt chitosan and sulfonated lignin; the plastic film is a biaxial stretching film and comprises a polypropylene film and at least one layer of hot melt adhesive layer, and the plastic film is attached to the upper surface of the decorative paper through the hot melt adhesive layer.
The preparation method of the wear-resistant yellowing-resistant decorative material comprises the following steps:
(1) preparing a coating with the viscosity of 20cps by adopting acrylic novolac epoxy ester, DPGDA and modified nano titanium dioxide;
the preparation method of the modified nano titanium dioxide comprises the following steps:
1.1) dissolving quaternary ammonium salt chitosan in water to obtain a quaternary ammonium salt chitosan solution, adding nano titanium dioxide into the quaternary ammonium salt chitosan solution, stirring for 10 hours at the temperature of 45 ℃ and the stirring speed of 150r/min, centrifuging and drying;
1.2) dissolving the sulfonated lignin in water to obtain a sulfonated lignin solution, adding the nano titanium dioxide treated in the step 1.1), ultrasonically dispersing for 2h at 75 ℃, and centrifuging, washing and drying to obtain modified nano titanium dioxide particles;
the addition amount of the quaternary ammonium salt chitosan is 0.8 percent of the mass of the nano titanium dioxide, and the addition amount of the sulfonated lignin is 0.2 percent of the mass of the nano titanium dioxide;
(2) attaching a plastic film to the upper surface of the decorative paper;
(3) coating prepared in the step (1) is mixed according to the ratio of 30 g/m2The coating amount of (2) is applied to the lower surface of the decorative paper, the coating penetrates into the interior of the decorative paper and is cured by electron beams, wherein the dosage of the electron beam curing is 15 kGy, the running speed of the paper during curing is 10 m/min, and the coating is checked and curedObtaining the wear-resistant yellowing-resistant decorative material after the step of screening.
Comparative example 1
The decorative material comprises a plastic film, decorative paper and a coating which permeates into the decorative paper and is cured, wherein the coating comprises a polyurethane acrylate oligomer, TMPTA and nano titanium dioxide, the viscosity of the coating is 20cps, and the mass percentage of the nano titanium dioxide in the coating is 6%; the plastic film is a biaxial stretching film and comprises a polypropylene film and at least one layer of hot melt adhesive layer, and the plastic film is attached to the upper surface of the decorative paper through the hot melt adhesive layer.
The preparation method of the decorative material of the embodiment comprises the following steps:
(1) preparing a coating with the viscosity of 20cps by adopting polyurethane acrylate oligomer, TMPTA and nano titanium dioxide;
(2) attaching a plastic film to the upper surface of the decorative paper;
(3) coating prepared in the step (1) is mixed according to the ratio of 30 g/m2The coating amount of the coating is coated on the lower surface of the decorative paper, the coating penetrates into the interior of the decorative paper and is cured by electron beams, wherein the dose of electron beam curing is 15 kGy, the running speed of the paper during curing is 10 m/min, and the decorative material is obtained after the inspection is qualified.
Comparative example 2
The decorative material comprises a plastic film, decorative paper and a coating which permeates into the decorative paper and is cured, wherein the coating comprises a polyurethane acrylate oligomer, TMPTA and modified nano titanium dioxide, the viscosity of the coating is 20cps, the mass percentage of the modified nano titanium dioxide in the coating is 6%, and the surface of the modified nano titanium dioxide is coated with quaternary ammonium salt chitosan; the plastic film is a biaxial stretching film and comprises a polypropylene film and at least one layer of hot melt adhesive layer, and the plastic film is attached to the upper surface of the decorative paper through the hot melt adhesive layer.
The preparation method of the decorative material of the embodiment comprises the following steps:
(1) preparing a coating with the viscosity of 20cps by adopting a polyurethane acrylate oligomer, TMPTA and modified nano titanium dioxide;
the preparation method of the modified nano titanium dioxide comprises the following steps:
dissolving quaternary ammonium salt chitosan in water to obtain a quaternary ammonium salt chitosan solution, adding nano titanium dioxide into the quaternary ammonium salt chitosan solution, stirring for 10 hours at the temperature of 45 ℃ and the stirring speed of 150r/min, centrifuging and drying to obtain modified nano titanium dioxide particles; the addition amount of the quaternary ammonium salt chitosan is 1.1 percent of the mass of the nano titanium dioxide;
(2) attaching a plastic film to the upper surface of the decorative paper;
(3) coating prepared in the step (1) is mixed according to the ratio of 30 g/m2The coating amount of the coating is coated on the lower surface of the decorative paper, the coating penetrates into the interior of the decorative paper and is cured by electron beams, wherein the dose of electron beam curing is 15 kGy, the running speed of the paper during curing is 10 m/min, and the decorative material is obtained after the inspection is qualified.
Comparative example 3
The decorative material comprises a plastic film, decorative paper and a coating which permeates into the decorative paper and is cured, wherein the coating comprises a polyurethane acrylate oligomer, TMPTA and modified nano titanium dioxide, the viscosity of the coating is 20cps, the mass percent of the modified nano titanium dioxide in the coating is 6%, and the surface of the modified nano titanium dioxide is coated with sulfonated lignin; the plastic film is a biaxial stretching film and comprises a polypropylene film and at least one layer of hot melt adhesive layer, and the plastic film is attached to the upper surface of the decorative paper through the hot melt adhesive layer.
The preparation method of the decorative material of the embodiment comprises the following steps:
(1) preparing a coating with the viscosity of 20cps by adopting a polyurethane acrylate oligomer, TMPTA and modified nano titanium dioxide;
the preparation method of the modified nano titanium dioxide comprises the following steps:
dissolving sulfonated lignin in water to obtain a sulfonated lignin solution, adding nano titanium dioxide, performing ultrasonic dispersion for 2 hours at 75 ℃, centrifuging, washing and drying to obtain modified nano titanium dioxide particles, wherein the addition amount of the sulfonated lignin is 1.1% of the mass of the nano titanium dioxide;
(2) attaching a plastic film to the upper surface of the decorative paper;
(3) coating prepared in the step (1) is mixed according to the ratio of 30 g/m2The coating amount of the coating is coated on the lower surface of the decorative paper, the coating penetrates into the interior of the decorative paper and is cured by electron beams, wherein the dose of electron beam curing is 15 kGy, the running speed of the paper during curing is 10 m/min, and the decorative material is obtained after the inspection is qualified.
The decorative materials prepared in the above examples and comparative examples were subjected to performance tests, and the results are shown in fig. 1.
From the results of examples 1 to 5, it can be seen that the wear resistance improvement effect of the paint on the wear-resistant and yellowing-resistant decorative material is not obvious when the addition amount of the modified nano titanium dioxide in the paint is too small, and the light fastness of the decorative paper material is reduced when the content of the modified nano titanium dioxide is too high, so that the mass percentage of the modified nano titanium dioxide in the paint is preferably 3% to 10%.
From the results of examples 3, 6-8 and comparative examples 1-3, it can be known that by adjusting the ratio of the quaternary ammonium salt chitosan, the sulfonated lignin and the nano titanium dioxide, the modified nano titanium dioxide particles with good light stability can be prepared, and the light color fastness of the wear-resistant and yellowing-resistant decorative material can be effectively improved by adding the modified nano titanium dioxide particles into the coating.
From example 9, it can be seen that the wear-resistant and yellowing-resistant decorative material prepared by replacing the main components of the coating with the acrylic novolac epoxy ester and the DPGDA also has higher wear-resistant revolution number and light color fastness.
The wear-resistant and yellowing-resistant decorative materials prepared in examples 1 to 9 and comparative examples 1 to 3 have good flexibility, and the surfaces of the materials are not cracked after the materials are bent and subjected to conventional flat pasting, coating and modeling pasting treatment.
In addition, the above embodiment can adjust the oligomer type, monomer type, plastic film type and related process parameters in the related coating according to the actual performance requirements, for example, the inventor finds that the viscosity of the coating is 5-200 cps, and the coating amount is 20-100 g/m2After curing, is favorable forThe toughness of the wear-resistant and yellowing-resistant decorative material is improved, the bonding strength of the decorative paper and the plastic film is improved, and the decorative paper and the plastic film are prevented from being peeled off; the electron beam curing dosage is 5-50 kGy, the running speed of the wear-resistant and yellowing-resistant decorative material during curing is 10-200 m/min, and the cured wear-resistant and yellowing-resistant decorative material has good toughness.
According to actual needs, a required pattern can be printed on the wear-resistant and yellowing-resistant decorative material prepared in the embodiment, so that the wear-resistant and yellowing-resistant decorative material has various wood grains or patterns.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (6)

1. The wear-resistant and yellowing-resistant decorative material is characterized by comprising a plastic film, decorative paper and a coating which permeates into the decorative paper and is solidified, wherein the plastic film is attached to the upper surface of the decorative paper; the coating comprises at least one of acrylic epoxy ester, polyurethane acrylate oligomer and polyester acrylate, and also comprises modified nano titanium dioxide, wherein the surface of the modified nano titanium dioxide is coated with quaternary ammonium salt chitosan and sulfonated lignin; the mass percentage of the modified nano titanium dioxide in the coating is 3-10%; the addition amount of the quaternary ammonium salt chitosan is 0.1-1.0% of the mass of the nano titanium dioxide; the addition amount of the sulfonated lignin is 0.2-0.4% of the mass of the nano titanium dioxide;
the preparation method of the modified nano titanium dioxide comprises the following steps:
1) dissolving quaternary ammonium salt chitosan in water to obtain a quaternary ammonium salt chitosan solution, adding nano titanium dioxide into the quaternary ammonium salt chitosan solution, stirring for 8-12h under the conditions that the temperature is 45-50 ℃ and the stirring speed is 100-200 r/min, centrifuging and drying;
2) dissolving the sulfonated lignin in water to obtain a sulfonated lignin solution, adding the nano titanium dioxide treated in the step (1), performing ultrasonic dispersion for 2-5h at the temperature of 60-80 ℃, and performing centrifugation, washing and drying to obtain modified nano titanium dioxide particles.
2. The wear-resistant yellowing-resistant decorative material of claim 1, wherein the plastic film is a biaxially stretched film or a cast film, and the plastic film comprises a main plastic film layer and at least one hot melt adhesive layer, and the main plastic film layer is selected from a polypropylene film, a polyethylene film, a polyester film or a polyurethane film.
3. The wear and yellowing resistant decorative material of claim 2, wherein the main plastic film layer is selected from polypropylene films.
4. A method for preparing the wear-resistant yellowing-resistant decorative material as claimed in any one of claims 1 to 3, comprising the following steps: coating the coating on the upper surface or the lower surface of the decorative paper, and curing the coating by electron beams after the coating permeates into the decorative paper;
or after a plastic film is attached to the upper surface of the decorative paper, coating the lower surface of the decorative paper with the coating, and curing the coating by electron beams after the coating permeates into the decorative paper.
5. The method for preparing wear-resistant yellowing-resistant decorative material according to claim 4, wherein the viscosity of the coating is 5 to 200 cps; the coating amount of the coating is 20-100 g/m2。
6. The preparation method of the wear-resistant and yellowing-resistant decorative material according to claim 5, wherein the electron beam curing dosage is 5-50 kGy, and the running speed of the decorative material during curing is 10-200 m/min.
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