CN109338817B - Composite coating decorative paper and preparation method thereof - Google Patents
Composite coating decorative paper and preparation method thereof Download PDFInfo
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- CN109338817B CN109338817B CN201811472318.4A CN201811472318A CN109338817B CN 109338817 B CN109338817 B CN 109338817B CN 201811472318 A CN201811472318 A CN 201811472318A CN 109338817 B CN109338817 B CN 109338817B
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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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/18—Paper- or board-based structures for surface covering
- D21H27/20—Flexible structures being applied by the user, e.g. wallpaper
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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
- 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
- D21H23/52—Addition to the formed paper by contacting paper with a device carrying the material
Abstract
The invention relates to composite coating decorative paper and a preparation method thereof, wherein the composite coating decorative paper comprises decorative printing paper and is coated on the decorative printing paperSiO outside decorative printing paper2‑ZrO2Sol coating and nano Al coated outside sol coating on one side of decorative printing paper2O3Reinforced SiO2Coating with sol; wherein the SiO2‑ZrO2The raw materials of the sol coating comprise: zirconium source mixed liquor, silicon source mixed liquor, 3-aminopropyl triethoxysilane, hydrochloric acid and promoting mixed liquor; the SiO2The raw materials of the sol coating comprise ethyl orthosilicate, gamma-methacryloxypropyl trimethoxysilane, absolute ethyl alcohol, deionized water, hydrochloric acid and 4.5 to 5.2 weight parts of ammonia water; the Al is2O3Has an average particle diameter of 15nm to 28 nm. Compared with the prior art, the composite coating decorative paper disclosed by the embodiment of the invention has excellent wet strength and tensile strength performance, does not relate to formaldehyde and phenol, and does not need to be added with wear-resistant impregnated paper in an outer layer in practical application.
Description
Technical Field
The invention belongs to the field of new materials, and particularly relates to composite coating decorative paper and a preparation method thereof.
Background
In recent years, the decorative artificial board is widely applied to the fields of public buildings, home decoration and the like due to the advantages of beauty, fashion, various types and the like. The facing artificial board is formed by hot-pressing and fusing a surface wear-resistant layer, middle-layer decorative paper, bottom balance paper and an artificial wood base material which are respectively impregnated by resin, namely the resin-impregnated paper reinforced wood floor. The surface wear-resistant layer has the function of ensuring wear resistance, corrosion resistance and moisture resistance, and the middle decorative paper has the function of providing beautiful decorative patterns.
The prior decorative paper uses amino resin such as urea-formaldehyde resin or phenolic resin and the like as impregnating adhesive to carry out impregnation coating treatment on decorative printing paper, and mainly has the following defects: 1) the formaldehyde and the phenolic aldehyde are inevitably contained, and free formaldehyde and free phenol are released in production and application, so that the environment and the human body are harmed; 2) the existing decorative paper has complex production process, low efficiency and serious waste of raw material cost due to the limitation of an impregnating resin system and an impregnating process; 3) the dipping coating layer formed by the existing resin system has low transparency and no wear resistance, and a wear-resistant layer is required to be pasted on the outer layer of the dipping coating layer, so that the integral transparency is further reduced; 4) the existing decorative paper has low wet strength, is easy to break in the production process and has high production cost. Therefore, how to adopt an environment-friendly material system and a preparation process has important significance in improving the strength and other properties of the decorative paper, particularly obviously improving the transparency and the wear resistance of the decorative paper and preparing the decorative paper with good transparency and wear resistance.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides composite coating decorative paper and a preparation method thereof, and the gist of the invention is as follows:
according to one aspect of the invention, the composite coating decorative paper comprises decorative printing paper and SiO coated on the outer side of the decorative printing paper2-ZrO2Sol coating and nano Al coated outside sol coating on one side of decorative printing paper2O3Reinforced SiO2Coating with sol; wherein the SiO2-ZrO2The raw materials of the sol coating comprise: 100 parts by weight of zirconium source mixed solution, 102 parts by weight of silicon source mixed solution, 108 parts by weight of silicon source mixed solution, 2.5 to 3.9 parts by weight of 3-aminopropyltriethoxysilane, 8.9 to 10.2 parts by weight of hydrochloric acid and 5.2 to 5.9 parts by weight of accelerating mixed solution; the SiO2The raw materials of the sol coating comprise 100 weight parts of ethyl orthosilicate, 1.5 to 7.2 weight parts of gamma-methacryloxypropyltrimethoxysilane, 12 weight parts of absolute ethyl alcohol, 39 weight parts of deionized water, 3.2 to 3.9 weight parts of hydrochloric acid and 4.5 to 5.2 weight parts of ammonia water; the Al is2O3Has an average particle diameter of 15nm to 28 nm.
According to an exemplary embodiment of the present invention, the transparency of the composite coating is not less than 91.1%.
According to an exemplary embodiment of the invention, the composite coating decorative paper has a basis weight of not more than 41g/m2The wet strength is not less than 8.21MPa, the tensile strength is not less than 19.5MPa, the abrasion-resistant revolution is not less than 8212 revolutions, and no formaldehyde or phenol is released.
According to another aspect of the invention, a method of making a composite coated decor paper, the method comprising:
SiO22-ZrO2Preparation of the Sol
At room temperature, dissolving tetrabutyl zirconate in absolute ethyl alcohol according to the weight ratio of 1:10.2-23.1, and preparing a zirconium source mixed solution; dissolving ethyl silicate in absolute ethyl alcohol according to the weight ratio of 1:2.9-11.8 to prepare silicon source mixed solution;
fully mixing 100 parts by weight of zirconium source mixed solution and 108 parts by weight of silicon source mixed solution 102-102, adding 2.5-3.9 parts by weight of 3-aminopropyltriethoxysilane, stirring uniformly, adding 8.9-10.2 parts by weight of hydrochloric acid, stirring uniformly, and adding 5.2-5.9 parts by weight of accelerating mixed solution; after being stirred evenly, the mixture is kept stand for 30 minutes to prepare SiO2-ZrO2Sol;
II, Al2O3Reinforced SiO2Preparation of the Sol
3)Al2O3Reinforcing phase modification treatment
Hydrophobic gas phase nano Al is added according to the weight ratio of 1:182O3Adding the powder into trimethylolpropane triacrylate, ultrasonic dispersing at 45 deg.C for 30min, and drying at 80 deg.C to obtain modified Al2O3A powder reinforcing phase;
adding the modified powder into absolute ethyl alcohol according to the weight ratio of 1:55, and carrying out ultrasonic treatment for 30min to obtain Al2O3Enhanced phase ethanol dispersion.
4)SiO2Preparation of the Sol
At room temperature, uniformly stirring 100 parts by weight of ethyl orthosilicate, 1.5-7.2 parts by weight of gamma-methacryloxypropyltrimethoxysilane, 12 parts by weight of absolute ethyl alcohol and 39 parts by weight of deionized water at 50 ℃ for 20 min; adding 3.2-3.9 weight parts of hydrochloric acid, stirring at 60 deg.C, adding 4.5-5.2 weight parts of ammonia water, reacting at constant temperature for 2.5 hr to obtain SiO2And (3) sol.
Preparation of composite coating decorative paper
5) Pretreatment of decorative paper
Drying the decorative paper under the conditions of vacuum negative pressure of 0.05MPa and 75 ℃, and carrying out constant-temperature pretreatment on the decorative paper, wherein the treatment time is 15-25 min;
6)SiO2-ZrO2sol coating application
SiO at a temperature of 55 DEG C2-ZrO2All sol isUniformly coating the outer side of the pretreated decorative paper, and carrying out constant temperature treatment at 80 ℃ for 30 min;
7)Al2O3reinforced SiO2Sol coating
Mixing SiO2SiO coated on one side of decorative printing paper by sol2-ZrO2The outside of the sol coating;
spraying Al by air2O3Enhanced phase ethanol dispersion to SiO2Uniformly spraying the sol, wherein the spraying amount is 2.8-6.6% of the weight of the SiO2 sol;
8) purification treatment
Placing the decorative paper coated with the sol coating in a purification dryer storing absolute ethyl alcohol, then reducing the temperature in the purification dryer to-5 ℃, and introducing liquid CO2Purifying for 30 min;
and drying the purified decorative paper at 135 ℃ and storing.
According to an exemplary embodiment of the present invention, the promoting mixture is composed of deionized water, isopropanol, and ammonia water at a volume ratio of 55:28: 17.
According to an exemplary embodiment of the present invention, the hydrochloric acid has a concentration of 0.2mol/L and the ammonia water has a concentration of 0.2 mol/L.
According to an exemplary embodiment of the invention, the SiO2-ZrO2The coating thickness of the sol is 8-28 μm.
According to an exemplary embodiment of the invention, the SiO2The coating thickness of the sol is 2-6 μm.
According to an exemplary embodiment of the present invention, Al is sprayed using an air spraying method2O3Enhanced phase ethanol dispersion to SiO2When the sol is uniformly sprayed, the spraying distance is 125-280mm, and the spraying angle is 60 ℃.
The invention uses SiO2-ZrO2Preparation of sol, Al2O3Reinforced SiO2The preparation of the sol realizes the preparation of the composite coating decorative paper. Compared with the prior art, the composite coating decorative paper provided by the embodiment of the invention has the following substantial advantages: 1) SiO22-ZrO2Sol and Al2O3Reinforced SiO2The composite coating formed by the sol has excellent transparency and wear resistance, and in practical application, wear-resistant impregnated paper does not need to be added on the outer layer of the decorative paper of the composite coating prepared by the invention; 2) SiO22-ZrO2Sol and Al2O3Reinforced SiO2The composite coating formed by the sol has excellent wet strength and tensile strength, and the performance of the decorative paper in the processing, application and installation processes is obviously improved; 3) SiO22-ZrO2Sol and Al2O3Reinforced SiO2The composite coating formed by the sol does not relate to formaldehyde and phenol, free aldehyde and free phenol cannot volatilize in the production and practical application processes, and the composite coating is completely environment-friendly.
Detailed Description
In order to make the technical solution and advantages of the present invention more apparent, the present invention is further described in detail by the following specific examples. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1: preparation of composite coating decorative paper
SiO22-ZrO2Preparation of the Sol
At room temperature, dissolving tetrabutyl zirconate in absolute ethyl alcohol according to the weight ratio of 1:10.2, and preparing a zirconium source mixed solution; dissolving ethyl silicate in absolute ethyl alcohol according to the weight ratio of 1:2.9 to prepare a silicon source mixed solution;
fully mixing 100 parts by weight of zirconium source mixed solution and 102 parts by weight of silicon source mixed solution, adding 2.5 parts by weight of 3-aminopropyltriethoxysilane, uniformly stirring, adding 8.9 parts by weight of 0.2mol/L hydrochloric acid, uniformly stirring, adding 5.2 parts by weight of promoting mixed solution, wherein the promoting mixed solution consists of deionized water, isopropanol and 0.2mol/L ammonia water in a volume ratio of 55:28: 17; after being stirred evenly, the mixture is kept stand for 30 minutes to prepare SiO2-ZrO2Sol gel；
II, Al2O3Reinforced SiO2Preparation of the Sol
1)Al2O3Reinforcing phase modification treatment
Hydrophobic gas phase nano Al is added according to the weight ratio of 1:182O3Adding the powder into trimethylolpropane triacrylate, ultrasonic dispersing at 45 deg.C for 30min, and drying at 80 deg.C to obtain modified Al2O3A powder reinforcing phase;
adding the modified powder into absolute ethyl alcohol according to the weight ratio of 1:55, and carrying out ultrasonic treatment for 30min to obtain Al2O3Enhanced phase ethanol dispersion.
2)SiO2Preparation of the Sol
At room temperature, 100 parts by weight of ethyl orthosilicate, 1.5 parts by weight of gamma-methacryloxypropyltrimethoxysilane, 12 parts by weight of absolute ethyl alcohol and 39 parts by weight of deionized water are uniformly stirred at 50 ℃ for 20 min; adding 3.2 parts by weight of 0.2mol/L hydrochloric acid, continuously stirring at 60 ℃, adding 4.5 parts by weight of 0.2mol/L ammonia water, reacting at constant temperature for 2.5h to obtain SiO2And (3) sol.
Preparation of composite coating decorative paper
1) Pretreatment of decorative paper
Drying the decorative paper under the conditions of vacuum negative pressure of 0.05MPa and 75 ℃, and carrying out constant-temperature pretreatment on the decorative paper, wherein the treatment time is 25 min;
2)SiO2-ZrO2sol coating application
SiO at a temperature of 55 DEG C2-ZrO2Uniformly coating the sol on the outer side of the pretreated decorative paper, wherein the coating thickness is 8 mu m, and carrying out constant temperature treatment at 80 ℃ for 30 min;
3)Al2O3reinforced SiO2Sol coating
Mixing SiO2SiO coated on one side of decorative printing paper by sol2-ZrO2The coating thickness of the outer side of the sol coating is 2 mu m;
spraying Al by air2O3Enhanced phase ethanol dispersion pairSiO2Uniformly spraying the sol, wherein the spraying distance is 125mm, the spraying angle is 60 ℃, and the spraying amount is SiO22.8 percent of the weight of the sol;
4) purification treatment
Placing the decorative paper coated with the sol coating in a purification dryer storing absolute ethyl alcohol, then reducing the temperature in the purification dryer to-5 ℃, and introducing liquid CO2Purifying for 30 min;
and drying the purified decorative paper at 135 ℃ and storing.
Example 2: preparation of composite coating decorative paper
SiO22-ZrO2Preparation of the Sol
At room temperature, dissolving tetrabutyl zirconate in absolute ethyl alcohol according to the weight ratio of 1:11.8 to prepare a zirconium source mixed solution; dissolving ethyl silicate in absolute ethyl alcohol according to the weight ratio of 1:3.5 to prepare a silicon source mixed solution;
fully mixing 100 parts by weight of zirconium source mixed solution and 103 parts by weight of silicon source mixed solution, adding 2.8 parts by weight of 3-aminopropyltriethoxysilane, uniformly stirring, adding 9.1 parts by weight of 0.2mol/L hydrochloric acid, uniformly stirring, adding 5.3 parts by weight of promoting mixed solution, wherein the promoting mixed solution consists of deionized water, isopropanol and 0.2mol/L ammonia water in a volume ratio of 55:28: 17; after being stirred evenly, the mixture is kept stand for 30 minutes to prepare SiO2-ZrO2Sol;
II, Al2O3Reinforced SiO2Preparation of the Sol
1)Al2O3Reinforcing phase modification treatment
Hydrophobic gas phase nano Al is added according to the weight ratio of 1:182O3Adding the powder into trimethylolpropane triacrylate, ultrasonic dispersing at 45 deg.C for 30min, and drying at 80 deg.C to obtain modified Al2O3A powder reinforcing phase;
adding the modified powder into absolute ethyl alcohol according to the weight ratio of 1:55, and carrying out ultrasonic treatment for 30min to obtain Al2O3Enhanced phase ethanol dispersion.
2)SiO2Preparation of the Sol
At room temperature, uniformly stirring 100 parts by weight of ethyl orthosilicate, 2.8 parts by weight of gamma-methacryloxypropyltrimethoxysilane, 12 parts by weight of absolute ethyl alcohol and 39 parts by weight of deionized water at 50 ℃ for 20 min; adding 3.4 parts by weight of 0.2mol/L hydrochloric acid, continuously stirring at 60 ℃, adding 4.5 parts by weight of 0.2mol/L ammonia water, reacting at constant temperature for 2.5h to obtain SiO2And (3) sol.
Preparation of composite coating decorative paper
1) Pretreatment of decorative paper
Drying the decorative paper under the conditions of vacuum negative pressure of 0.05MPa and 75 ℃, and carrying out constant-temperature pretreatment on the decorative paper, wherein the treatment time is 25 min;
2)SiO2-ZrO2sol coating application
SiO at a temperature of 55 DEG C2-ZrO2Uniformly coating the sol on the outer side of the pretreated decorative paper, wherein the coating thickness is 12 mu m, and carrying out constant temperature treatment at 80 ℃ for 30 min;
3)Al2O3reinforced SiO2Sol coating
Mixing SiO2SiO coated on one side of decorative printing paper by sol2-ZrO2The coating thickness of the outer side of the sol coating is 3 mu m;
spraying Al by air2O3Enhanced phase ethanol dispersion to SiO2Uniformly spraying the sol, wherein the spraying distance is 135mm, the spraying angle is 60 ℃, and the spraying amount is SiO23.3 percent of the weight of the sol;
4) purification treatment
Placing the decorative paper coated with the sol coating in a purification dryer storing absolute ethyl alcohol, then reducing the temperature in the purification dryer to-5 ℃, and introducing liquid CO2Purifying for 30 min;
and drying the purified decorative paper at 135 ℃ and storing.
Example 3: preparation of composite coating decorative paper
SiO22-ZrO2Preparation of the Sol
At room temperature, dissolving tetrabutyl zirconate in absolute ethyl alcohol according to the weight ratio of 1:15.2, and preparing a zirconium source mixed solution; dissolving ethyl silicate in absolute ethyl alcohol according to the weight ratio of 1:5.8 to prepare a silicon source mixed solution;
fully mixing 100 parts by weight of a zirconium source mixed solution and 105 parts by weight of a silicon source mixed solution, adding 2.9 parts by weight of 3-aminopropyltriethoxysilane, uniformly stirring, adding 9.2 parts by weight of 0.2mol/L hydrochloric acid, uniformly stirring, adding 5.5 parts by weight of a promoting mixed solution, wherein the promoting mixed solution consists of deionized water, isopropanol and 0.2mol/L ammonia water in a volume ratio of 55:28: 17; after being stirred evenly, the mixture is kept stand for 30 minutes to prepare SiO2-ZrO2Sol;
II, Al2O3Reinforced SiO2Preparation of the Sol
1)Al2O3Reinforcing phase modification treatment
Hydrophobic gas phase nano Al is added according to the weight ratio of 1:182O3Adding the powder into trimethylolpropane triacrylate, ultrasonic dispersing at 45 deg.C for 30min, and drying at 80 deg.C to obtain modified Al2O3A powder reinforcing phase;
adding the modified powder into absolute ethyl alcohol according to the weight ratio of 1:55, and carrying out ultrasonic treatment for 30min to obtain Al2O3Enhanced phase ethanol dispersion.
2)SiO2Preparation of the Sol
At room temperature, uniformly stirring 100 parts by weight of ethyl orthosilicate, 3.3 parts by weight of gamma-methacryloxypropyltrimethoxysilane, 12 parts by weight of absolute ethyl alcohol and 39 parts by weight of deionized water at 50 ℃ for 20 min; adding 3.5 parts by weight of 0.2mol/L hydrochloric acid, continuously stirring at 60 ℃, adding 4.5 parts by weight of 0.2mol/L ammonia water, reacting at constant temperature for 2.5h to obtain SiO2And (3) sol.
Preparation of composite coating decorative paper
1) Pretreatment of decorative paper
Drying the decorative paper under the conditions of vacuum negative pressure of 0.05MPa and 75 ℃, and carrying out constant-temperature pretreatment on the decorative paper, wherein the treatment time is 25 min;
2)SiO2-ZrO2sol coating application
SiO at a temperature of 55 DEG C2-ZrO2Uniformly coating the sol on the outer side of the pretreated decorative paper, wherein the coating thickness is 15 mu m, and carrying out constant temperature treatment at 80 ℃ for 30 min;
3)Al2O3reinforced SiO2Sol coating
Mixing SiO2SiO coated on one side of decorative printing paper by sol2-ZrO2The coating thickness of the outer side of the sol coating is 5 mu m;
spraying Al by air2O3Enhanced phase ethanol dispersion to SiO2Uniformly spraying sol, wherein the spraying distance is 210mm, the spraying angle is 60 ℃, and the spraying amount is SiO23.5 percent of the weight of the sol;
4) purification treatment
Placing the decorative paper coated with the sol coating in a purification dryer storing absolute ethyl alcohol, then reducing the temperature in the purification dryer to-5 ℃, and introducing liquid CO2Purifying for 30 min;
and drying the purified decorative paper at 135 ℃ and storing.
Example 4: preparation of composite coating decorative paper
SiO22-ZrO2Preparation of the Sol
At room temperature, dissolving tetrabutyl zirconate in absolute ethyl alcohol according to the weight ratio of 1:18.5 to prepare a zirconium source mixed solution; dissolving ethyl silicate in absolute ethyl alcohol according to the weight ratio of 1:9.5 to prepare a silicon source mixed solution;
fully mixing 100 parts by weight of a zirconium source mixed solution and 105 parts by weight of a silicon source mixed solution, adding 3.5 parts by weight of 3-aminopropyltriethoxysilane, uniformly stirring, adding 9.5 parts by weight of 0.2mol/L hydrochloric acid, uniformly stirring, adding 5.6 parts by weight of a promoting mixed solution, wherein the promoting mixed solution consists of deionized water, isopropanol and 0.2mol/L ammonia water in a volume ratio of 55:28: 17; stirring uniformly, standing for 30 minutes to obtainSiO2-ZrO2Sol;
II, Al2O3Reinforced SiO2Preparation of the Sol
1)Al2O3Reinforcing phase modification treatment
Hydrophobic gas phase nano Al is added according to the weight ratio of 1:182O3Adding the powder into trimethylolpropane triacrylate, ultrasonic dispersing at 45 deg.C for 30min, and drying at 80 deg.C to obtain modified Al2O3A powder reinforcing phase;
adding the modified powder into absolute ethyl alcohol according to the weight ratio of 1:55, and carrying out ultrasonic treatment for 30min to obtain Al2O3Enhanced phase ethanol dispersion.
2)SiO2Preparation of the Sol
At room temperature, uniformly stirring 100 parts by weight of ethyl orthosilicate, 6.8 parts by weight of gamma-methacryloxypropyltrimethoxysilane, 12 parts by weight of absolute ethyl alcohol and 39 parts by weight of deionized water at 50 ℃ for 20 min; adding 3.6 parts by weight of 0.2mol/L hydrochloric acid, continuously stirring at 60 ℃, adding 4.8 parts by weight of 0.2mol/L ammonia water, reacting at constant temperature for 2.5h to obtain SiO2And (3) sol.
Preparation of composite coating decorative paper
1) Pretreatment of decorative paper
Drying the decorative paper under the conditions of vacuum negative pressure of 0.05MPa and 75 ℃, and carrying out constant-temperature pretreatment on the decorative paper, wherein the treatment time is 25 min;
2)SiO2-ZrO2sol coating application
SiO at a temperature of 55 DEG C2-ZrO2Uniformly coating the sol on the outer side of the pretreated decorative paper, wherein the coating thickness is 22 mu m, and carrying out constant temperature treatment at 80 ℃ for 30 min;
3)Al2O3reinforced SiO2Sol coating
Mixing SiO2SiO coated on one side of decorative printing paper by sol2-ZrO2The coating thickness of the outer side of the sol coating is 5 mu m;
spraying Al by air2O3Enhanced phase ethanol dispersion to SiO2Uniformly spraying the sol, wherein the spraying distance is 250mm, the spraying angle is 60 ℃, and the spraying amount is SiO25.2 percent of the weight of the sol;
4) purification treatment
Placing the decorative paper coated with the sol coating in a purification dryer storing absolute ethyl alcohol, then reducing the temperature in the purification dryer to-5 ℃, and introducing liquid CO2Purifying for 30 min;
and drying the purified decorative paper at 135 ℃ and storing.
Example 5: preparation of composite coating decorative paper
SiO22-ZrO2Preparation of the Sol
At room temperature, dissolving tetrabutyl zirconate in absolute ethyl alcohol according to the weight ratio of 1:23.1, and preparing a zirconium source mixed solution; dissolving ethyl silicate in absolute ethyl alcohol according to the weight ratio of 1:11.8 to prepare a silicon source mixed solution;
fully mixing 100 parts by weight of zirconium source mixed solution and 108 parts by weight of silicon source mixed solution, adding 3.9 parts by weight of 3-aminopropyltriethoxysilane, uniformly stirring, adding 10.2 parts by weight of 0.2mol/L hydrochloric acid, uniformly stirring, adding 5.9 parts by weight of promoting mixed solution, wherein the promoting mixed solution consists of deionized water, isopropanol and 0.2mol/L ammonia water in a volume ratio of 55:28: 17; after being stirred evenly, the mixture is kept stand for 30 minutes to prepare SiO2-ZrO2Sol;
II, Al2O3Reinforced SiO2Preparation of the Sol
1)Al2O3Reinforcing phase modification treatment
Hydrophobic gas phase nano Al is added according to the weight ratio of 1:182O3Adding the powder into trimethylolpropane triacrylate, ultrasonic dispersing at 45 deg.C for 30min, and drying at 80 deg.C to obtain modified Al2O3A powder reinforcing phase;
adding the modified powder into absolute ethyl alcohol according to the weight ratio of 1:55, and carrying out ultrasonic treatment for 30min to obtain Al2O3Enhanced phase ethanol dispersion.
2)SiO2Preparation of the Sol
At room temperature, uniformly stirring 100 parts by weight of ethyl orthosilicate, 7.2 parts by weight of gamma-methacryloxypropyltrimethoxysilane, 12 parts by weight of absolute ethyl alcohol and 39 parts by weight of deionized water at 50 ℃ for 20 min; adding 3.9 parts by weight of 0.2mol/L hydrochloric acid, continuously stirring at 60 ℃, adding 5.2 parts by weight of 0.2mol/L ammonia water, reacting at constant temperature for 2.5h to obtain SiO2And (3) sol.
Preparation of composite coating decorative paper
1) Pretreatment of decorative paper
Drying the decorative paper under the conditions of vacuum negative pressure of 0.05MPa and 75 ℃, and carrying out constant-temperature pretreatment on the decorative paper, wherein the treatment time is 25 min;
2)SiO2-ZrO2sol coating application
SiO at a temperature of 55 DEG C2-ZrO2Uniformly coating the sol on the outer side of the pretreated decorative paper, wherein the coating thickness is 28 mu m, and carrying out constant temperature treatment at 80 ℃ for 30 min;
3)Al2O3reinforced SiO2Sol coating
Mixing SiO2SiO coated on one side of decorative printing paper by sol2-ZrO2The coating thickness of the outer side of the sol coating is 6 mu m;
spraying Al by air2O3Enhanced phase ethanol dispersion to SiO2Uniformly spraying sol, wherein the spraying distance is 280mm, the spraying angle is 60 ℃, and the spraying amount is SiO26.6 percent of the weight of the sol;
4) purification treatment
Placing the decorative paper coated with the sol coating in a purification dryer storing absolute ethyl alcohol, then reducing the temperature in the purification dryer to-5 ℃, and introducing liquid CO2Purifying for 30 min;
and drying the purified decorative paper at 135 ℃ and storing.
Example 6:
composite overlay decorative papers prepared according to examples 1-5, sample numbers a1, a2, A3, a4, and a5, respectively; typical urea-formaldehyde resin impregnated decor paper and phenolic resin impregnated decor paper of the prior art were used as comparative examples with sample numbers D1 and D2, respectively.
The quantitative determination is carried out according to GB/T451.2-2002 'determination of paper and paperboard quantitative'; detecting the transparency according to GB/T2679.1-2013 diffuse reflection method for determining paper transparency; detecting the wet strength according to GB/T465.2-2008 'determination of tensile strength of paper and paperboard after soaking'; the tensile strength is detected according to GB/T12914 + 2008 'determination of tensile strength of paper and paperboard'; detecting the wear resistance according to GB/T17657 and 2013 physicochemical property test method for artificial boards and decorative artificial boards; detecting the formaldehyde release amount after 180 days according to GB 18580-2017 Formaldehyde release limit in artificial boards and products thereof for interior decoration and finishing materials; detecting the phenol release amount according to GB/T31762 and 2015 Small Release cabin method for measuring the phenol release amount in the wood material and the products thereof; the results are shown in Table 1.
TABLE 1
As can be seen from table 1, compared with the prior art, the composite coating decorative paper prepared in the embodiment of the present invention has improved transparency and quantification on the premise of significantly improving wet strength and tensile strength, and meanwhile, has long-term free aldehyde groups and free phenol groups, and does not cause harm to human bodies and environment in the long-term application process.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. The composite coating decorative paper is characterized by comprising decorative printing paper and SiO coated on the outer side of the decorative printing paper2-ZrO2Sol coating and SiO coated on one side of decorative printing paper2-ZrO2Nano Al outside sol coating2O3Reinforced SiO2Coating with sol; wherein the SiO2-ZrO2The raw materials of the sol coating comprise: 100 parts by weight of zirconium source mixed solution, 102 parts by weight of silicon source mixed solution, 108 parts by weight of silicon source mixed solution, 2.5 to 3.9 parts by weight of 3-aminopropyltriethoxysilane, 8.9 to 10.2 parts by weight of hydrochloric acid and 5.2 to 5.9 parts by weight of accelerating mixed solution; nano Al2O3Reinforced SiO2SiO in sol coating2The raw materials of the sol comprise: 100 parts by weight of ethyl orthosilicate, 1.5-7.2 parts by weight of gamma-methacryloxypropyltrimethoxysilane, 12 parts by weight of absolute ethyl alcohol, 39 parts by weight of deionized water, 3.2-3.9 parts by weight of hydrochloric acid and 4.5-5.2 parts by weight of ammonia water; nano Al2O3Reinforced SiO2Nano Al in sol coating2O3Has an average particle diameter of 15nm to 28 nm.
2. The composite coated decor paper of claim 1 wherein the composite coating has a transparency of not less than 91.1%.
3. Composite coated decor paper according to any of claims 1-2, characterized in that the composite coated decor paper has a basis weight of not more than 41g/m2The wet strength is not less than 8.21MPa, the tensile strength is not less than 19.5MPa, and the abrasion-resistant revolution is not less than 8212.
4. A method of making a composite coated decor paper, the method comprising:
SiO22-ZrO2Preparation of the Sol
At room temperature, dissolving tetrabutyl zirconate in absolute ethyl alcohol according to the weight ratio of 1:10.2-23.1, and preparing a zirconium source mixed solution; dissolving ethyl silicate in absolute ethyl alcohol according to the weight ratio of 1:2.9-11.8 to prepare silicon source mixed solution;
fully mixing 100 parts by weight of zirconium source mixed solution and 108 parts by weight of silicon source mixed solution 102-102, adding 2.5-3.9 parts by weight of 3-aminopropyltriethoxysilane, stirring uniformly, adding 8.9-10.2 parts by weight of hydrochloric acid, stirring uniformly, and adding 5.2-5.9 parts by weight of accelerating mixed solution; after being stirred evenly, the mixture is kept stand for 30 minutes to prepare SiO2-ZrO2Sol;
two, nanometer Al2O3Reinforced SiO2Preparation of the Sol
1)Al2O3Reinforcing phase modification treatment
Hydrophobic gas phase nano Al is added according to the weight ratio of 1:182O3Adding the powder into trimethylolpropane triacrylate, ultrasonic dispersing at 45 deg.C for 30min, and drying at 80 deg.C to obtain modified Al2O3A powder reinforcing phase;
adding the modified powder into absolute ethyl alcohol according to the weight ratio of 1:55, and carrying out ultrasonic treatment for 30min to obtain Al2O3An enhanced phase ethanol dispersion;
2)SiO2preparation of the Sol
At room temperature, uniformly stirring 100 parts by weight of ethyl orthosilicate, 1.5-7.2 parts by weight of gamma-methacryloxypropyltrimethoxysilane, 12 parts by weight of absolute ethyl alcohol and 39 parts by weight of deionized water at 50 ℃ for 20 min; adding 3.2-3.9 weight parts of hydrochloric acid, stirring at 60 deg.C, adding 4.5-5.2 weight parts of ammonia water, reacting at constant temperature for 2.5 hr to obtain SiO2Sol;
preparation of composite coating decorative paper
1) Pretreatment of decorative paper
Drying the decorative paper under the conditions of vacuum negative pressure of 0.05MPa and 75 ℃, and carrying out constant-temperature pretreatment on the decorative paper, wherein the treatment time is 15-25 min;
2)SiO2-ZrO2sol coating application
SiO at a temperature of 55 DEG C2-ZrO2The sol is evenly coated on the outer side of the pretreated decorative paper and is positioned at the constant temperature of 80 DEG CProcessing for 30 min;
3) nano Al2O3Reinforced SiO2Sol coating
Mixing SiO2SiO coated on one side of decorative printing paper by sol2-ZrO2The outside of the sol coating;
spraying Al by air2O3Enhanced phase ethanol dispersion to SiO2Uniformly spraying the sol, wherein the spraying amount is SiO22.8-6.6% of the sol by weight;
4) purification treatment
Placing the decorative paper coated with the sol coating in a purification dryer storing absolute ethyl alcohol, then reducing the temperature in the purification dryer to-5 ℃, and introducing liquid CO2Purifying for 30 min;
and drying the purified decorative paper at 135 ℃ and storing.
5. The preparation method according to claim 4, wherein the accelerating mixed solution is composed of deionized water, isopropanol and ammonia water in a volume ratio of 55:28: 17.
6. The production method according to claim 4, wherein the concentration of the hydrochloric acid is 0.2mol/L and the concentration of the aqueous ammonia is 0.2 mol/L.
7. The method of claim 4, wherein the SiO is2-ZrO2The coating thickness of the sol is 8-28 μm.
8. The method of claim 4, wherein the SiO is2The coating thickness of the sol is 2-6 μm.
9. The method according to claim 4, wherein the Al is sprayed by air2O3Enhanced phase ethanol dispersion to SiO2When the sol is uniformly sprayed, the spraying distance is 125-280mm, and the spraying angle is 60 ℃.
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| US5069816A (en) * | 1988-01-11 | 1991-12-03 | Mmii Incorporated | Zirconium silica hydrogel compositions and methods of preparation |
| FR2758826B1 (en) * | 1997-01-27 | 1999-04-16 | Rhodia Chimie Sa | NOVEL TITANIUM DIOXIDE PIGMENT, PROCESS FOR PREPARING IT, AND USE THEREOF IN PAINT COMPOSITIONS |
| ES2452572T5 (en) * | 2001-02-20 | 2018-02-05 | Kronoplus Technical Ag | Decorative paper and procedure to impregnate a decorative paper |
| DE102004037045A1 (en) * | 2004-07-29 | 2006-04-27 | Degussa Ag | Aqueous silane nanocomposites |
| US20100167063A1 (en) * | 2006-08-14 | 2010-07-01 | Basf Se | Paper coating compounds containing silicasols |
| KR20150035612A (en) * | 2013-09-26 | 2015-04-07 | (주)엘지하우시스 | Coating sol composition for ceramic wallpaper, ceramic wallpaper and method for preparing ceramic wallpaper |
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