CN112127208A - High-strength wear-resistant impregnated decorative paper and preparation method thereof - Google Patents

High-strength wear-resistant impregnated decorative paper and preparation method thereof Download PDF

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CN112127208A
CN112127208A CN202011001963.5A CN202011001963A CN112127208A CN 112127208 A CN112127208 A CN 112127208A CN 202011001963 A CN202011001963 A CN 202011001963A CN 112127208 A CN112127208 A CN 112127208A
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wear
layer
resistant
mixture
adhesive
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李英
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Guangdong Fumei New Material Technology Co ltd
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Guangdong Fumei New Material Technology Co ltd
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    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • D21H19/82—Paper comprising more than one coating superposed
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/385—Oxides, hydroxides or carbonates
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/46—Non-macromolecular organic compounds
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/62—Macromolecular organic compounds or oligomers thereof obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the 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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/70—Multistep processes; Apparatus for adding one or several substances in portions or in various ways to the paper, not covered by another single group of this main group
    • D21H23/72—Plural serial stages only
    • 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
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30—Multi-ply
    • D21H27/40—Multi-ply at least one of the sheets being non-planar, e.g. crêped

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention relates to the technical field of decorative paper, in particular to high-strength wear-resistant impregnated decorative paper and a preparation method thereof. The invention aims to provide high-strength wear-resistant impregnated decorative paper which has the advantages of excellent wear resistance, scratch resistance and moisture resistance, long service life, good environmental protection performance, capability of reducing environmental pollution, simple structure and low production cost.

Description

High-strength wear-resistant impregnated decorative paper and preparation method thereof
Technical Field
The invention relates to the technical field of decorative paper, in particular to high-strength wear-resistant impregnated decorative paper and a preparation method thereof.
Background
The impregnated decorative paper is prepared by mixing non-woven wood pulp, PE and plant fibers, and has super-strong absorption capacity and dissolution resistance. At present, with the progress of society and the improvement of living standard of people, the impregnated decorative paper is widely applied to the veneering of cupboards, wardrobes and composite floors, and the environmental protection problem and the use safety, such as moisture resistance and flame retardance, of the impregnated decorative paper are increasingly attracting attention of people. In the prior art, the wear resistance of the impregnated decorative paper is poor, so that the service life of the impregnated paper is limited, and the environmental protection and the use safety of the impregnated decorative paper need to be further improved. The surface wear resistance is a main index, and in the prior art, the impregnated decorative paper has poor grinding performance, so that the service life and the decorative effect of the impregnated decorative paper are limited.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the high-strength wear-resistant impregnated decorative paper which has the advantages of excellent wear resistance, scratch resistance and moisture resistance, long service life, good environmental protection performance, capability of reducing pollution to the environment, simple structure and low production cost.
The invention aims to provide a preparation method of high-strength wear-resistant impregnated decorative paper, which is simple and efficient, convenient to operate and control, high in quality of produced products and beneficial to industrial production.
The purpose of the invention is realized by the following technical scheme: the utility model provides a wear-resisting flooding decorative paper of high strength, includes the raw paper layer, coats in the hot melt adhesive stratum reticulare of raw paper layer upper surface, coats in the first wearing layer of hot melt adhesive stratum reticulare upper surface to and coat in the second wearing layer of first wearing layer upper surface, the upper surface of first wearing layer sets up to the corrugated type, the lower surface of second wearing layer sets up to the corrugated type, the length direction of flute in the first wearing layer is crisscross perpendicularly with the length direction of flute in the second wearing layer, the second wearing layer is formed by the coating of wear-resisting adhesive.
The wear-resistant impregnated decorative paper has the advantages of excellent wear resistance, scratch resistance and moisture resistance, long service life, good environmental protection performance, capability of reducing environmental pollution, simple structure and low production cost.
Preferably, the wear-resistant adhesive comprises the following raw materials in parts by weight:
Figure BDA0002694646790000021
the alumina particles are a mixture of alumina particles with the particle size of 25-45 mu m and alumina particles with the particle size of 1-5 mu m according to the weight ratio of 0.8-1.2: 0.6-1.0.
According to the invention, the modified alkyd resin is modified by adopting the acrylic resin, so that the adhesive force and the corrosion resistance of the wear-resistant adhesive film-forming substance are obviously improved, and the impact resistance, the wear resistance and the heat resistance of the prepared wear-resistant adhesive coating film-forming substance are greatly improved through the modified alkyd resin; the fumed silica can make up the defects of weak interaction force and low cohesive energy among modified alkyd resin, urea-formaldehyde resin and alumina particles, improve the mechanical property of the prepared wear-resistant adhesive, play a role in reinforcing effect and enhancing wear resistance, avoid the problem that the wear-resistant adhesive lacks adhesive due to flowing in the curing process, improve the thixotropic property of the adhesive solution to control the fluidity of the wear-resistant adhesive, adjust the curing speed, improve the wear-resistant effect of a wear-resistant layer obtained after curing, prolong the service life and facilitate operation and construction; the adopted azodiisoheptonitrile does not contain cyano, the decomposition product is nontoxic, and the high-efficiency polymerization can be initiated at low temperature and low concentration to generate high linear and high molecular weight polymers; in addition, the dosage of the azodiisoheptanonitrile is required to be controlled to be 1-3 parts, if the dosage of the initiator is small, the polymerization reaction is not sufficiently initiated, the monomer reaction is incomplete, the molecular weight of the copolymer is large, the viscosity of the composite adhesive is high, the heat dissipation is difficult, the gel is easy to generate, and the instability of the composite adhesive is caused; the aluminum oxide particles with the particle size of 25-45 mu m and the aluminum oxide particles with the particle size of 1-5 mu m are formed according to the weight ratio of 0.8-1.2:0.6-1.0, so that the wear resistance of the prepared wear-resistant adhesive after film formation can be remarkably improved, and the wear resistance of the wear-resistant impregnated decorative paper can be remarkably improved by coating the wear-resistant impregnated decorative paper; the adopted polyvinyl alcohol is a biodegradable high polymer material, the molecular chain of the material contains hydroxyl groups and has good water solubility, the polyvinyl alcohol also has good film forming property, high crystallinity and high barrier property and excellent oil-resistant ester and solvent-resistant properties, the polyvinyl alcohol is used as a water-soluble synthetic binder, the solvent is volatilized when the material is heated, molecules of the polyvinyl alcohol are closely contacted to form a film with certain mechanical strength by virtue of the adsorption effect among the molecules, the film forming property of the material can be improved, and the mechanical property of the material can also be improved; the adopted chitosan has high deacetylation degree, the antibacterial activity of the chitosan is higher, the positive charge of the chitosan is increased due to the increase of the amino amount, so that the contact with negative cell bodies of bacteria is improved, the growth of the bacteria is interfered, in addition, the cell walls of the bacteria are firstly separated from the cell membranes by the chitosan, then the cell membranes are destroyed, so that intracellular enzymes and nucleic acid are leaked, meanwhile, amino positive ions and high-molecular-weight chitosan are combined with the bacterial cells in the chitosan acid solution, and the cell membrane structure is destroyed, so that the permeation of potassium ions and ATP is caused, so that the antibacterial purpose is achieved, and the prepared wear-resistant adhesive has good antibacterial performance besides excellent wear resistance; the urea-formaldehyde resin has weak acid and weak base resistance, good insulating property and excellent wear resistance, and not only can improve the bonding property of the prepared wear-resistant adhesive, but also can assist in improving the wear resistance.
Preferably, each part of the modified alkyd resin comprises the following raw materials in parts by weight:
Figure BDA0002694646790000031
Figure BDA0002694646790000041
the catalyst was chromium acetylacetonate MSDS.
Preferably, the modified alkyd resin is prepared by the following method:
s1, mixing acrylic resin and alkyd resin according to parts by weight, adding the mixture into a reaction device, melting and stirring for 20-40min, adding pearl powder and a catalyst, and continuously stirring for 30-60min to obtain a mixture A for later use;
s2, adding abietic acid and phthalic anhydride into pentaerythritol according to parts by weight, heating to 80-120 ℃, continuously stirring at the speed of 600r/min for 60-90min, heating to 140-180 ℃, and continuously stirring at the same speed for 30-60min to obtain a mixture B for later use;
s3, adding the mixture B obtained in the step S2 into the mixture A obtained in the step S1, heating to 160 ℃, continuously stirring for 20-40min, feeding into an extruder, melting, extruding and cooling to obtain the modified alkyd resin.
The modified alkyd resin is synthesized into carboxyl-terminated alkyd resin by using phthalic anhydride, abietic acid and pentaerythritol, and the carboxyl on the alkyd resin is reacted with the allyl on the acrylic resin to introduce the acrylic resin into the alkyd resin. Acrylic resin is introduced into alkyd resin from a molecular layer to form a macromolecular structure, so that the alkyd resin has an alkyd structure and a propylene structure on a molecular chain, the advantages of corrosion resistance and high hardness of the acrylic resin are reserved, and the alkyd resin has the advantages of strong adhesive force and strong toughness, and the wear resistance, the impact resistance and the heat resistance of the prepared wear-resistant adhesive coating film-forming material can be greatly improved through the modified alkyd resin; compared with the common paint, the prepared wear-resistant adhesive has the characteristics of strong adhesive force, good flexibility, quick drying and the like. The modified alkyd resin prepared by the method has the advantages of strong adhesive force and strong toughness; the heating temperature in step S3 needs to be strictly controlled to be 120-160 ℃, which is unfavorable for mixing the components of mixture a and mixture B if the temperature is too high, and is also unfavorable for mixing the components of mixture a and mixture B if the temperature is too low.
Preferably, each portion of the plasticizer is at least one of polyimide, di-n-octyl phthalate, and glycerin. Each part of the curing agent is a mixture of aluminum ammonium sulfate, magnesium sulfate and ammonium chloride according to the weight ratio of 0.1-0.5:0.4-0.8: 0.6-1.0.
The toughening agent adopted in the invention has good compatibility with the modified alkyd resin and the urea-formaldehyde resin, so that the dispersion capacity and the absorption capacity of the matrix to impact energy are improved, and the toughness is increased; after the curing agent is added, the curing agent absorbs water and becomes magnesium sulfate with water to crystallize and accelerate the curing of the modified alkyd resin, and the crosslinking degree of the modified alkyd resin is increased, so that the adhesiveness and the water resistance of the wear-resistant adhesive are improved, and the bonding strength of the wear-resistant adhesive can be improved by cooperating with the excellent performances of aluminum ammonium sulfate, magnesium sulfate and ammonium chloride.
Preferably, each part of the antioxidant is a mixture of the antioxidant DNP, the antioxidant 1010 and the antioxidant 168 according to the weight ratio of 0.6-1.0:0.4-0.8: 0.8-1.2.
The antioxidant 1010 adopted by the invention has excellent oxidation resistance on urea-formaldehyde resin and modified alkyd resin, the antioxidant 1010 can effectively prevent thermal oxidation degradation of the wear-resistant adhesive in a long-term aging process, so that the service life of the wear-resistant adhesive is prolonged, and in addition, the antioxidant 1010 can be used together with the antioxidant 168 to have a synergistic effect; the antioxidant 168 and the antioxidant DNP3 are auxiliary antioxidants of the antioxidant 1010, are compounded with the main antioxidant 1010, have good synergistic effect, can effectively prevent the urea-formaldehyde resin and the modified alkyd resin from being thermally degraded in basic injection molding, and provide extra long-term protection for the wear-resistant adhesive.
Preferably, the abrasion-resistant adhesive is prepared by the following method:
e1, adding the modified alkyd resin, the urea-formaldehyde resin, the azobisisoheptonitrile, the alumina particles and the filler into a stirring device according to the parts by weight, mixing, heating to 60-80 ℃, and continuously stirring at the speed of 400-450r/min for 30-60min to obtain a mixture A for later use;
e2, mixing and stirring the polyvinyl alcohol, the chitosan and the antioxidant uniformly according to the parts by weight, heating to 60-80 ℃, and continuously stirring for 30-50min to obtain a mixture B for later use;
e3, adding the mixture B obtained in the step E2, the plasticizer and the curing agent into the mixture A obtained in the step E1, heating to 50-90 ℃, stirring at the speed of 350-450r/min for 40-60min, and cooling to obtain the wear-resistant adhesive.
The wear-resistant adhesive prepared by the method has good wear resistance, antibacterial property, strength, toughness, impact resistance and other properties and adhesive properties. In the preparation process, the stirring speed in the step E1 needs to be strictly controlled to be 400-450r/min, if the stirring speed is too fast, a large amount of foam is contained in the mixture A, the subsequent defoaming treatment is not facilitated, and if the stirring speed is low, the modified alkyd resin, the urea-formaldehyde resin, the azodiisoheptanonitrile, the alumina particles and the filler are insufficiently mixed, so that the reinforcing effect of the alumina particles and the filler on the modified alkyd resin and the urea-formaldehyde resin is reduced; in addition, the heating temperature in step E2 needs to be controlled to 60-80 ℃, and if the heating temperature is too high, the composite action between the polyvinyl alcohol and the chitosan is reduced, and if the heating temperature is too low, the reaction is not sufficiently performed, so that the grafting action of the polyvinyl alcohol and the chitosan is reduced, and the strength and the film-forming property of the prepared wear-resistant adhesive are relatively reduced.
The invention also provides a preparation method of the high-strength wear-resistant impregnated decorative paper, which comprises the following steps:
1) taking a raw paper layer, printing a layer of hot melt adhesive on the upper surface of the raw paper layer, and drying to form a hot melt adhesive net layer;
2) coating a layer of surface adhesive on the upper surface of the hot melt adhesive net layer, and drying to form a first wear-resistant layer;
3) and coating a layer of wear-resistant adhesive on the upper surface of the first wear-resistant layer, and drying to form a second wear-resistant layer so as to prepare the high-strength wear-resistant impregnated decorative paper.
More preferably, the amount of the abrasion-resistant adhesive applied in the step 3) is 10 to 40g/m2Drying at the temperature of 100-140 ℃ until the water content of the wear-resistant adhesive is not more than 7 percent; the gluing amount in the step 2) is 8-16g/m2Drying at 110-120 deg.c to 15-25 mim.
The high-strength wear-resistant impregnated decorative paper is prepared by the steps, so that the prepared high-strength wear-resistant impregnated decorative paper has excellent wear resistance, antibacterial property and mechanical property, is long in service life, has good environmental protection property due to the fact that the flame-retardant layer of the high-strength wear-resistant impregnated decorative paper uses the composite flame-retardant adhesive, reduces the formaldehyde release amount of the wear-resistant impregnated decorative paper on the whole, can reduce pollution to the environment, and is simple in structure and low in cost. By strictly controlling the using amount, the gluing amount and the drying process of the composite flame-retardant material, the material can be saved, and the toughness and the service life of the wear-resistant impregnated decorative paper can be ensured.
The invention has the beneficial effects that: according to the high-strength wear-resistant impregnated decorative paper, the hot melt adhesive net layer, the first wear-resistant layer and the second wear-resistant layer are sequentially arranged on the raw paper layer, so that the prepared decorative paper has excellent wear resistance, antibacterial property and mechanical property and long service life, and the second wear-resistant layer uses the wear-resistant adhesive, so that the second wear-resistant layer has good wear resistance, antibacterial property, mechanical property and environmental protection property, the formaldehyde release amount of the decorative paper is integrally reduced, the pollution to the environment can be reduced, in addition, the structure is simple, and the production cost is low.
The preparation method of the high-strength wear-resistant impregnated decorative paper is convenient to operate and control, and the produced product has high quality, and is beneficial to industrial production.
Drawings
Fig. 1 is a perspective view of the present invention.
The reference signs are: 1-raw paper layer, 2-hot melt adhesive net layer, 3-first wear-resistant layer and 4-second wear-resistant layer.
Detailed Description
For the understanding of those skilled in the art, the present invention will be further described with reference to the following examples and the accompanying fig. 1, and the description of the embodiments is not intended to limit the present invention.
Example 1
The utility model provides a wear-resisting flooding decorative paper of high strength, includes raw paper layer 1, coats in the hot melt adhesive stratum reticulare 2 of 1 upper surface of raw paper layer, coats in the first wearing layer 3 of hot melt adhesive stratum reticulare 2 upper surface to and coat in the second wearing layer 4 of first wearing layer 3 upper surface, the upper surface of first wearing layer 3 sets up to the flute type, the lower surface of second wearing layer 4 sets up to the flute type, the length direction of flute in the first wearing layer 3 and the length direction of flute in the second wearing layer 4 are crisscross perpendicularly, and second wearing layer 4 is formed by the coating of wear-resisting adhesive.
The wear-resistant adhesive comprises the following raw materials in parts by weight:
Figure BDA0002694646790000081
the alumina particles are a mixture of alumina particles with the particle size of 25 mu m and alumina particles with the particle size of 1 mu m according to the weight ratio of 0.8: 0.6.
Each part of the modified alkyd resin comprises the following raw materials in parts by weight:
Figure BDA0002694646790000082
the catalyst is chromium acetylacetonate MSDS; the acrylic resin is Mitsubishi BR-85; the alkyd resin is produced by Changzhou Guangshu chemical technology Co.
The modified alkyd resin is prepared by the following method:
s1, mixing acrylic resin and alkyd resin according to parts by weight, adding the mixture into a reaction device, melting and stirring for 20min, adding pearl powder and a catalyst, and continuously stirring for 30min to obtain a mixture A for later use;
s2, adding abietic acid and phthalic anhydride into pentaerythritol according to parts by weight, heating to 80 ℃, continuously stirring at the speed of 400r/min for 60min, heating to 140 ℃, and continuously stirring at the same speed for 30-60min to obtain a mixture B for later use;
s3, adding the mixture B obtained in the step S2 into the mixture A obtained in the step S1, heating to 120 ℃, continuously stirring for 20min, feeding into an extruder, carrying out melt extrusion, and cooling to obtain the modified alkyd resin.
Each of the plasticizers is polyimide.
Each part of the curing agent is a mixture of aluminum ammonium sulfate, magnesium sulfate and ammonium chloride according to the weight ratio of 0.1:0.4: 0.6.
Each part of the antioxidant is a mixture of an antioxidant DNP, an antioxidant 1010 and an antioxidant 168 according to the weight ratio of 0.6: 0: 0.8.
The wear-resistant adhesive is prepared by the following method:
e1, adding the modified alkyd resin, the urea-formaldehyde resin, the azobisisoheptonitrile, the alumina particles and the filler into a stirring device according to the parts by weight, mixing, heating to 60 ℃, and continuously stirring at the speed of 400r/min for 30min to obtain a mixture A for later use;
e2, mixing and stirring the polyvinyl alcohol, the chitosan and the antioxidant uniformly according to the parts by weight, heating to 60 ℃, and continuously stirring for 30min to obtain a mixture B for later use;
e3, adding the mixture B obtained in the step E2, a plasticizer and a curing agent into the mixture A obtained in the step E1, heating to 50 ℃, stirring at the speed of 350r/min for 40min, and cooling to obtain the wear-resistant adhesive.
The preparation method of the high-strength wear-resistant impregnated decorative paper comprises the following steps:
1) taking the raw paper layer 1, printing a layer of hot melt adhesive on the upper surface of the raw paper layer 1, and drying to form a hot melt adhesive net layer 2;
2) coating a layer of surface adhesive on the upper surface of the hot melt adhesive net layer 2, and drying to form a first wear-resistant layer 3;
3) and (3) coating a layer of wear-resistant adhesive on the upper surface of the first wear-resistant layer 3, drying to form a second wear-resistant layer 4, and thus obtaining the high-strength wear-resistant impregnated decorative paper.
The amount of the wear-resistant adhesive coated in the step 3) is 10g/m2Drying at 100 ℃ until the water content of the wear-resistant adhesive is not more than 7%; the gluing amount in the step 2) is 8g/m2And dried at 110 ℃ for 15 mim.
Example 2
The utility model provides a wear-resisting flooding decorative paper of high strength, includes raw paper layer 1, coats in the hot melt adhesive stratum reticulare 2 of 1 upper surface of raw paper layer, coats in the first wearing layer 3 of hot melt adhesive stratum reticulare 2 upper surface to and coat in the second wearing layer 4 of first wearing layer 3 upper surface, the upper surface of first wearing layer 3 sets up to the flute type, the lower surface of second wearing layer 4 sets up to the flute type, the length direction of flute in the first wearing layer 3 and the length direction of flute in the second wearing layer 4 are crisscross perpendicularly, second wearing layer 4 is formed by the coating of wear-resisting adhesive.
The wear-resistant adhesive comprises the following raw materials in parts by weight:
Figure BDA0002694646790000101
the alumina particles are a mixture of alumina particles with the particle size of 30 mu m and alumina particles with the particle size of 2 mu m according to the weight ratio of 0.9: 0.7.
Each part of the modified alkyd resin comprises the following raw materials in parts by weight:
Figure BDA0002694646790000111
the catalyst is chromium acetylacetonate MSDS; the acrylic resin is Mitsubishi BR-85; the alkyd resin is produced by Changzhou Guangshu chemical technology Co.
The modified alkyd resin is prepared by the following method:
s1, mixing acrylic resin and alkyd resin according to parts by weight, adding the mixture into a reaction device, melting and stirring for 25min, adding pearl powder and a catalyst, and continuously stirring for 38min to obtain a mixture A for later use;
s2, adding abietic acid and phthalic anhydride into pentaerythritol according to parts by weight, heating to 90 ℃, continuously stirring at the speed of 450r/min for 68min, heating to 150 ℃, and continuously stirring at the same speed for 38min to obtain a mixture B for later use;
s3, adding the mixture B obtained in the step S2 into the mixture A obtained in the step S1, heating to 130 ℃, continuously stirring for 25min, feeding into an extruder, carrying out melt extrusion, and cooling to obtain the modified alkyd resin.
Each part of the plasticizer is di-n-octyl phthalate.
Each part of the curing agent is a mixture of aluminum ammonium sulfate, magnesium sulfate and ammonium chloride according to the weight ratio of 0.2:0.5: 0.7.
Each part of the antioxidant is a mixture of an antioxidant DNP, an antioxidant 1010 and an antioxidant 168 according to the weight ratio of 0.7:0.5: 0.9.
The wear-resistant adhesive is prepared by the following method:
e1, adding the modified alkyd resin, the urea-formaldehyde resin, the azobisisoheptonitrile, the alumina particles and the filler into a stirring device according to the parts by weight, mixing, heating to 65 ℃, and continuously stirring at the speed of 415r/min for 38min to obtain a mixture A for later use;
e2, mixing and stirring the polyvinyl alcohol, the chitosan and the antioxidant uniformly according to the parts by weight, heating to 65 ℃, and continuously stirring for 35min to obtain a mixture B for later use;
e3, adding the mixture B obtained in the step E2, a plasticizer and a curing agent into the mixture A obtained in the step E1, heating to 60 ℃, stirring at the speed of 375r/min for 45min, and cooling to obtain the wear-resistant adhesive.
The preparation method of the high-strength wear-resistant impregnated decorative paper comprises the following steps:
1) taking the raw paper layer 1, printing a layer of hot melt adhesive on the upper surface of the raw paper layer 1, and drying to form a hot melt adhesive net layer 2;
2) coating a layer of surface adhesive on the upper surface of the hot melt adhesive net layer 2, and drying to form a first wear-resistant layer 3;
3) and (3) coating a layer of wear-resistant adhesive on the upper surface of the first wear-resistant layer 3, drying to form a second wear-resistant layer 4, and thus obtaining the high-strength wear-resistant impregnated decorative paper.
The amount of the wear-resistant adhesive coated in the step 3) is 17g/m2Drying at 110 ℃ until the water content of the wear-resistant adhesive is not more than 7%; the gluing amount in the step 2) is 10g/m2And drying at 113 ℃ for 18 mim.
Example 3
The utility model provides a wear-resisting flooding decorative paper of high strength, includes raw paper layer 1, coats in the hot melt adhesive stratum reticulare 2 of 1 upper surface of raw paper layer, coats in the first wearing layer 3 of hot melt adhesive stratum reticulare 2 upper surface to and coat in the second wearing layer 4 of first wearing layer 3 upper surface, the upper surface of first wearing layer 3 sets up to the flute type, the lower surface of second wearing layer 4 sets up to the flute type, the length direction of flute in the first wearing layer 3 and the length direction of flute in the second wearing layer 4 are crisscross perpendicularly, second wearing layer 4 is formed by the coating of wear-resisting adhesive.
The wear-resistant adhesive comprises the following raw materials in parts by weight:
Figure BDA0002694646790000131
the alumina particles are a mixture of alumina particles with the particle size of 35 mu m and alumina particles with the particle size of 3 mu m according to the weight ratio of 1.0: 0.6-1.08.
Each part of the modified alkyd resin comprises the following raw materials in parts by weight:
Figure BDA0002694646790000132
the catalyst is chromium acetylacetonate MSDS; the acrylic resin is Mitsubishi BR-85; the alkyd resin is produced by Changzhou Guangshu chemical technology Co.
The modified alkyd resin is prepared by the following method:
s1, mixing acrylic resin and alkyd resin according to parts by weight, adding the mixture into a reaction device, melting and stirring for 30min, adding pearl powder and a catalyst, and continuously stirring for 40min to obtain a mixture A for later use;
s2, adding abietic acid and phthalic anhydride into pentaerythritol according to parts by weight, heating to 8100 ℃, continuously stirring at the speed of 500r/min for 75min, heating to 160 ℃, and continuously stirring at the same speed for 45min to obtain a mixture B for later use;
s3, adding the mixture B obtained in the step S2 into the mixture A obtained in the step S1, heating to 140 ℃, continuously stirring for 30min, feeding into an extruder, carrying out melt extrusion, and cooling to obtain the modified alkyd resin.
Each of the plasticizers is glycerol.
Each part of the curing agent is a mixture of aluminum ammonium sulfate, magnesium sulfate and ammonium chloride according to the weight ratio of 0.3:0.6: 0.8.
Each part of the antioxidant is a mixture of an antioxidant DNP, an antioxidant 1010 and an antioxidant 168 according to the weight ratio of 0.8:0.6: 1.0.
The wear-resistant adhesive is prepared by the following method:
e1, adding the modified alkyd resin, the urea-formaldehyde resin, the azobisisoheptonitrile, the alumina particles and the filler into a stirring device according to the parts by weight, mixing, heating to 70 ℃, and continuously stirring at the speed of 425r/min for 45min to obtain a mixture A for later use;
e2, mixing and stirring the polyvinyl alcohol, the chitosan and the antioxidant uniformly according to the parts by weight, heating to 70 ℃, and continuously stirring for 40min to obtain a mixture B for later use;
e3, adding the mixture B obtained in the step E2, a plasticizer and a curing agent into the mixture A obtained in the step E1, heating to 70 ℃, stirring for 50min at the speed of 420r/min, and cooling to obtain the wear-resistant adhesive.
The preparation method of the high-strength wear-resistant impregnated decorative paper comprises the following steps:
1) taking the raw paper layer 1, printing a layer of hot melt adhesive on the upper surface of the raw paper layer 1, and drying to form a hot melt adhesive net layer 2;
2) coating a layer of surface adhesive on the upper surface of the hot melt adhesive net layer 2, and drying to form a first wear-resistant layer 3;
3) and (3) coating a layer of wear-resistant adhesive on the upper surface of the first wear-resistant layer 3, drying to form a second wear-resistant layer 4, and thus obtaining the high-strength wear-resistant impregnated decorative paper.
The amount of the wear-resistant adhesive coated in the step 3) is 25g/m2Drying at 120 ℃ until the water content of the wear-resistant adhesive is not more than 7%; the gluing amount in the step 2) is 12g/m223mim were dried at 115 ℃.
Example 4
The utility model provides a wear-resisting flooding decorative paper of high strength, includes raw paper layer 1, coats in the hot melt adhesive stratum reticulare 2 of 1 upper surface of raw paper layer, coats in the first wearing layer 3 of hot melt adhesive stratum reticulare 2 upper surface to and coat in the second wearing layer 4 of first wearing layer 3 upper surface, the upper surface of first wearing layer 3 sets up to the flute type, the lower surface of second wearing layer 4 sets up to the flute type, the length direction of flute in the first wearing layer 3 and the length direction of flute in the second wearing layer 4 are crisscross perpendicularly, second wearing layer 4 is formed by the coating of wear-resisting adhesive.
The wear-resistant adhesive comprises the following raw materials in parts by weight:
Figure BDA0002694646790000151
the alumina particles are a mixture of alumina particles with the particle size of 40 mu m and alumina particles with the particle size of 4 mu m according to the weight ratio of 1.1: 0.9.
Each part of the modified alkyd resin comprises the following raw materials in parts by weight:
Figure BDA0002694646790000161
the catalyst is chromium acetylacetonate MSDS; the acrylic resin is Mitsubishi BR-85; the alkyd resin is produced by Changzhou Guangshu chemical technology Co.
The modified alkyd resin is prepared by the following method:
s1, mixing acrylic resin and alkyd resin according to parts by weight, adding the mixture into a reaction device, melting and stirring for 35min, adding pearl powder and a catalyst, and continuously stirring for 52min to obtain a mixture A for later use;
s2, adding abietic acid and phthalic anhydride into pentaerythritol according to parts by weight, heating to 110 ℃, continuously stirring at the speed of 550r/min for 82min, heating to 170 ℃, and continuously stirring at the same speed for 52min to obtain a mixture B for later use;
s3, adding the mixture B obtained in the step S2 into the mixture A obtained in the step S1, heating to 150 ℃, continuously stirring for 35min, feeding into an extruder, carrying out melt extrusion, and cooling to obtain the modified alkyd resin.
Each of the plasticizers is polyimide.
Each part of the curing agent is a mixture of aluminum ammonium sulfate, magnesium sulfate and ammonium chloride according to the weight ratio of 0.4:0.7: 0.9.
Each part of the antioxidant is a mixture of an antioxidant DNP, an antioxidant 1010 and an antioxidant 168 according to the weight ratio of 0.9:0.7: 1.1.
The wear-resistant adhesive is prepared by the following method:
e1, adding the modified alkyd resin, the urea-formaldehyde resin, the azobisisoheptonitrile, the alumina particles and the filler into a stirring device according to the parts by weight, mixing, heating to 75 ℃, and continuously stirring at the speed of 435r/min for 52min to obtain a mixture A for later use;
e2, mixing and stirring the polyvinyl alcohol, the chitosan and the antioxidant uniformly according to the parts by weight, heating to 75 ℃, and continuously stirring for 45min to obtain a mixture B for later use;
e3, adding the mixture B obtained in the step E2, a plasticizer and a curing agent into the mixture A obtained in the step E1, heating to 80 ℃, stirring at the speed of 425r/min for 55min, and cooling to obtain the wear-resistant adhesive.
The preparation method of the high-strength wear-resistant impregnated decorative paper comprises the following steps:
1) taking the raw paper layer 1, printing a layer of hot melt adhesive on the upper surface of the raw paper layer 1, and drying to form a hot melt adhesive net layer 2;
2) coating a layer of surface adhesive on the upper surface of the hot melt adhesive net layer 2, and drying to form a first wear-resistant layer 3;
3) and (3) coating a layer of wear-resistant adhesive on the upper surface of the first wear-resistant layer 3, drying to form a second wear-resistant layer 4, and thus obtaining the high-strength wear-resistant impregnated decorative paper.
The amount of the wear-resistant adhesive coated in the step 3) is 33g/m2Drying at 130 ℃ until the water content of the wear-resistant adhesive is not more than 7%; the gluing amount in the step 2) is 14g/m2And dried at 118 ℃ for 23 mim.
Example 5
The utility model provides a wear-resisting flooding decorative paper of high strength, includes raw paper layer 1, coats in the hot melt adhesive stratum reticulare 2 of 1 upper surface of raw paper layer, coats in the first wearing layer 3 of hot melt adhesive stratum reticulare 2 upper surface to and coat in the second wearing layer 4 of first wearing layer 3 upper surface, the upper surface of first wearing layer 3 sets up to the flute type, the lower surface of second wearing layer 4 sets up to the flute type, the length direction of flute in the first wearing layer 3 and the length direction of flute in the second wearing layer 4 are crisscross perpendicularly, second wearing layer 4 is formed by the coating of wear-resisting adhesive.
The wear-resistant adhesive comprises the following raw materials in parts by weight:
Figure BDA0002694646790000181
the alumina particles are a mixture of alumina particles with the particle size of 45 mu m and alumina particles with the particle size of 5 mu m according to the weight ratio of 1.2: 1.0.
Each part of the modified alkyd resin comprises the following raw materials in parts by weight:
Figure BDA0002694646790000182
the catalyst is chromium acetylacetonate MSDS; the acrylic resin is Mitsubishi BR-85; the alkyd resin is produced by Changzhou Guangshu chemical technology Co.
The modified alkyd resin is prepared by the following method:
s1, mixing acrylic resin and alkyd resin according to parts by weight, adding the mixture into a reaction device, melting and stirring for 40min, adding pearl powder and a catalyst, and continuously stirring for 60min to obtain a mixture A for later use;
s2, adding abietic acid and phthalic anhydride into pentaerythritol according to parts by weight, heating to 120 ℃, continuously stirring at the speed of 600r/min for 90min, heating to 180 ℃, and continuously stirring at the same speed for 60min to obtain a mixture B for later use;
s3, adding the mixture B obtained in the step S2 into the mixture A obtained in the step S1, heating to 160 ℃, continuously stirring for 40min, feeding into an extruder, carrying out melt extrusion, and cooling to obtain the modified alkyd resin.
Each part of the plasticizer is di-n-octyl phthalate.
Each part of the curing agent is a mixture of aluminum ammonium sulfate, magnesium sulfate and ammonium chloride according to the weight ratio of 0.5:0.8: 1.0.
Each part of the antioxidant is a mixture of antioxidant DNP, antioxidant 1010 and antioxidant 168 according to the weight ratio of 1.0:0.8: 1.2.
The wear-resistant adhesive is prepared by the following method:
e1, adding the modified alkyd resin, the urea-formaldehyde resin, the azobisisoheptonitrile, the alumina particles and the filler into a stirring device according to the parts by weight, mixing, heating to 80 ℃, and continuously stirring at the speed of 450r/min for 60min to obtain a mixture A for later use;
e2, mixing and stirring the polyvinyl alcohol, the chitosan and the antioxidant uniformly according to the parts by weight, heating to 80 ℃, and continuously stirring for 50min to obtain a mixture B for later use;
e3, adding the mixture B obtained in the step E2, a plasticizer and a curing agent into the mixture A obtained in the step E1, heating to 90 ℃, stirring at the speed of 450r/min for 60min, and cooling to obtain the wear-resistant adhesive.
The preparation method of the high-strength wear-resistant impregnated decorative paper comprises the following steps:
1) taking the raw paper layer 1, printing a layer of hot melt adhesive on the upper surface of the raw paper layer 1, and drying to form a hot melt adhesive net layer 2;
2) coating a layer of surface adhesive on the upper surface of the hot melt adhesive net layer 2, and drying to form a first wear-resistant layer 3;
3) and (3) coating a layer of wear-resistant adhesive on the upper surface of the first wear-resistant layer 3, drying to form a second wear-resistant layer 4, and thus obtaining the high-strength wear-resistant impregnated decorative paper.
The amount of the wear-resistant adhesive coated in the step 3) is 40g/m2Drying at 140 ℃ until the water content of the wear-resistant adhesive is not more than 7%; the gluing amount in the step 2) is 16g/m2And drying at-120 ℃ for 25 mim.
Comparative example 1
This comparative example differs from example 1 above in that: the alkyd resin was not modified in this comparative example. The remainder of this comparative example is the same as example 1 and will not be described again here.
Comparative example 2
This comparative example differs from example 3 above in that: in this comparative example no phthalic anhydride and pentaerythritol were added in the preparation of the modified alkyd resin and the remaining raw materials were mixed in the proportions of example 3. The remainder of this comparative example is the same as example 3 and will not be described again here.
Comparative example 3
This comparative example differs from example 5 above in that: no alumina particles were added in this comparative example. The remainder of this comparative example is the same as example 5 and will not be described again here.
The abrasion resistance, the edge crush strength (GB/T6544-:
TABLE 1
Figure BDA0002694646790000201
Figure BDA0002694646790000211
From the above, the high-strength wear-resistant impregnated decorative paper of the invention has excellent wear resistance, edge pressure strength, antibacterial rate and moisture regain. According to the invention, the wear-resistant adhesive is added with the modified alkyd resin, the phthalic anhydride and the pentaerythritol are added when the alkyd resin is modified, and the aluminum oxide particles are added in the wear-resistant adhesive, so that the wear resistance, the edge pressure strength, the antibacterial rate and the moisture regain of the strength wear-resistant impregnated decorative paper can be improved, and the wear-resistant impregnated decorative paper has the characteristics of good wear resistance effect, good buffering performance and long service life.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.

Claims (9)

1. The high-strength wear-resistant impregnated decorative paper is characterized in that: including raw paper layer, the hot melt adhesive stratum reticulare of scribbling the raw paper layer upper surface, scribble the first wearing layer of hot melt adhesive stratum reticulare upper surface to and scribble the second wearing layer of first wearing layer upper surface, the upper surface of first wearing layer sets up to the corrugated type, the lower surface of second wearing layer sets up to the corrugated type, the length direction of flute is crisscross perpendicularly in the length direction of flute in the first wearing layer and the second wearing layer, the second wearing layer is formed by wear-resistant adhesive coating.
2. A high strength wear resistant impregnated decor paper according to claim 1 wherein: the wear-resistant adhesive comprises the following raw materials in parts by weight:
Figure FDA0002694646780000011
3. a high strength wear resistant impregnated decor paper according to claim 2 wherein: each part of the modified alkyd resin comprises the following raw materials in parts by weight:
Figure FDA0002694646780000012
Figure FDA0002694646780000021
4. a high strength abrasion resistant impregnated decor paper according to claim 3 wherein: the modified alkyd resin is prepared by the following method:
s1, mixing acrylic resin and alkyd resin according to parts by weight, adding the mixture into a reaction device, melting and stirring for 20-40min, adding pearl powder and a catalyst, and continuously stirring for 30-60min to obtain a mixture A for later use;
s2, adding abietic acid and phthalic anhydride into pentaerythritol according to parts by weight, heating to 80-120 ℃, continuously stirring at the speed of 600r/min for 60-90min, heating to 140-180 ℃, and continuously stirring at the same speed for 30-60min to obtain a mixture B for later use;
s3, adding the mixture B obtained in the step S2 into the mixture A obtained in the step S1, heating to 160 ℃, continuously stirring for 20-40min, feeding into an extruder, melting, extruding and cooling to obtain the modified alkyd resin.
5. A high strength wear resistant impregnated decor paper according to claim 2 wherein: each part of the plasticizer is at least one of polyimide, di-n-octyl phthalate and glycerol.
6. A high strength wear resistant impregnated decor paper according to claim 2 wherein: each part of the curing agent is a mixture of aluminum ammonium sulfate, magnesium sulfate and ammonium chloride according to the weight ratio of 0.1-0.5:0.4-0.8: 0.6-1.0.
7. A high strength wear resistant impregnated decor paper according to claim 2 wherein: each part of the antioxidant is a mixture of an antioxidant DNP, an antioxidant 1010 and an antioxidant 168 according to the weight ratio of 0.6-1.0:0.4-0.8: 0.8-1.2.
8. A high strength wear resistant impregnated decor paper according to any of claims 2-7 wherein: the wear-resistant adhesive is prepared by the following method:
e1, adding the modified alkyd resin, the urea-formaldehyde resin, the azobisisoheptonitrile, the alumina particles and the filler into a stirring device according to the parts by weight, mixing, heating to 60-80 ℃, and continuously stirring at the speed of 400-450r/min for 30-60min to obtain a mixture A for later use;
e2, mixing and stirring the polyvinyl alcohol, the chitosan and the antioxidant uniformly according to the parts by weight, heating to 60-80 ℃, and continuously stirring for 30-50min to obtain a mixture B for later use;
e3, adding the mixture B obtained in the step E2, the plasticizer and the curing agent into the mixture A obtained in the step E1, heating to 50-90 ℃, stirring at the speed of 350-450r/min for 40-60min, and cooling to obtain the wear-resistant adhesive.
9. A method for preparing a high strength wear resistant impregnated decor paper according to any of claims 2-7, characterized in that: the method comprises the following steps:
1) taking a raw paper layer, printing a layer of hot melt adhesive on the upper surface of the raw paper layer, and drying to form a hot melt adhesive net layer;
2) coating a layer of surface adhesive on the upper surface of the hot melt adhesive net layer, and drying to form a first wear-resistant layer;
3) and coating a layer of wear-resistant adhesive on the upper surface of the first wear-resistant layer, and drying to form a second wear-resistant layer so as to prepare the high-strength wear-resistant impregnated decorative paper.
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