CN112064398B - Preparation method of high-strength hydrophobic environment-friendly wallpaper - Google Patents
Preparation method of high-strength hydrophobic environment-friendly wallpaper Download PDFInfo
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F11/00—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines
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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
- D21H23/54—Rubbing devices, e.g. brush, pad, felt
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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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- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
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Abstract
The high-strength hydrophobic environment-friendly wallpaper comprises a high-strength wallpaper base layer and high-strength hydrophobic wallpaper, wherein the high-strength hydrophobic wallpaper is located on the high-strength wallpaper base layer and is provided with a micro-nano structure hydrophobic layer. The permanent wet strength resin and the polycarboxyl cross-linked composite microfibrillated cellulose are added into the wallpaper base layer, so that the tensile strength and toughness of the paper can be improved, the stress mismatching degree between the hydrophobic layer of the subsequent micro-nano structure and the wallpaper base layer can be relieved, the wallpaper is not easy to damage and deform in the construction process, and the construction difficulty of the wallpaper is reduced. The hydrophobic layer of the micro-nano structure has a cross section shape of a waveform structure, and meanwhile, an excellent hydrophobic structure can be formed by combining the nano titanium dioxide mastoid structure in the hydrophobic layer, so that the wallpaper has excellent hydrophobicity and photocatalytic characteristics. In addition, the wave-shaped structure of the hydrophobic layer also enables the toughness of the hydrophobic layer in a two-dimensional X-Y plane of the wallpaper to be improved, and the construction difficulty of the wallpaper is reduced.
Description
Technical Field
The invention relates to a preparation method of high-strength hydrophobic environment-friendly wallpaper and the wallpaper prepared by the method.
Background
With the improvement of living standard, people have higher and higher requirements on aesthetic feeling, health, comfort and the like of interior decoration, and compared with the traditional paint printing decoration, the wallpaper decoration is more and more popular with people. The wallpaper is obtained by using raw paper made of wood pulp fibers or directly using non-woven fabrics as a base and performing post-treatment steps such as printing and the like. At present, among the commonly used environment-friendly wallpapers on the market, the wallpaper based on the base paper made of wood pulp fiber is more.
However, in the using process, the wallpaper is easily affected by pollutants and moisture in a humid environment and is attached to the surface of the wallpaper, so that the wallpaper is easy to mildew and change color, and the appearance and the service life of the wallpaper are affected. Hydrophobic wallpaper may well solve this problem.
At present, the common hydrophobic wallpaper in the market comprises two types, one type is that a UV coating is coated on the surface of a wallpaper base layer, and the hydrophobicity of the UV coating is utilized; the other type is that a plurality of structures are laminated on the surface of a base layer, and then a waterproof layer is arranged on the outer layer. The two kinds of hydrophobic wallpaper have the defects of high manufacturing process difficulty, high cost, high wallpaper construction difficulty, unstable combination of a hydrophobic UV coating or a waterproof layer and a wallpaper base layer, poor hydrophobicity and the like.
In order to improve the base layer and the hydrophobic layer of the hydrophobic wallpaper, the invention aims to provide the hydrophobic wallpaper which is relatively simple in preparation process, good in hydrophobic performance and easy to construct.
Disclosure of Invention
In order to solve the problems in the existing hydrophobic wallpaper, the invention provides a preparation method of high-strength hydrophobic environment-friendly wallpaper. The high-strength hydrophobic environment-friendly wallpaper comprises two aspects, wherein one aspect is a high-strength wallpaper base layer, and the other aspect is a hydrophobic layer with a micro-nano structure.
High-strength wallpaper base layer
The high-strength wallpaper base layer is base paper which is prepared from composite paper pulp serving as a raw material through a papermaking process, and the preparation method comprises the following steps:
taking needle-leaf pulp and broad-leaf pulp with the mass ratio of 1-3:1 as raw material pulp, pulping in a pulper for 30-50 minutes, controlling the pulping degree at 35-40 DEG SR, then adding permanent wet strength resin, polycarboxyl crosslinking composite microfibrillated cellulose and a cationic starch composition into the composite pulp, controlling the concentration of the permanent wet strength resin at 0.02-0.05%, controlling the concentration of the polycarboxyl crosslinking composite microfibrillated cellulose at 0.1-0.3%, controlling the concentration of the cationic starch composition at 0.05-0.1%, stirring for 30-60 minutes at the temperature of 60-80 ℃ and the rotation speed of 300-600 rpm; then, the net is netted, made into paper, dried and formed.
Wherein the permanent wet strength resin is a crosslinked resin selected from one or more of polyamidoamine-epihalohydrin resins, polydiisocyanate resins, polyamidoamine-epihalohydrin resins, polyisocyanate resins, urea-formaldehyde resins, and melamine-formaldehyde resins.
Wherein the cationic starch composition is corn or cassava cationic starch with the degree of substitution of 0.02-0.04.
The preparation method of the polycarboxyl cross-linked composite microfibrillated cellulose comprises the following steps:
adding a polycarboxyl compound into hot water to prepare an acid solution with the mass concentration of 20-40%, adding microfibrillated cellulose into the acid solution, mixing and dispersing uniformly, wherein the mass concentration of the microfibrillated cellulose is 1-3%, then performing microwave treatment at 80-100 ℃ to obtain a suspension of the polycarboxyl cross-linked composite microfibrillated cellulose, and finally washing and deacidifying the suspension to obtain the polycarboxyl cross-linked composite microfibrillated cellulose.
Wherein the frequency of the microwave treatment is 1000-2000MHz, and the microwave treatment time is 30-90 min.
Wherein the polycarboxyl compound is selected from one or more of malonic acid, adipic acid, glutaric acid, citric acid and succinic acid, and is preferably citric acid.
Second, hydrophobic layer with micro-nano structure
The hydrophobic layer of the micro-nano structure is directly formed on the surface of the high-strength wallpaper base layer, the hydrophobic layer comprises hydrophobic titanium dioxide nanoparticles and fluorine copolymer resin, the thickness of the hydrophobic layer is 500-1000 nm, the hydrophobic layer of the micro-nano structure is in the shape of the cross section of a waveform structure, the height difference between the wave crest and the wave trough of the waveform structure is about 100-300nm, and the distance between adjacent wave crests is 300-500 nm.
The preparation method comprises the following steps:
the preparation method comprises the following steps of (1) mixing hydrophobic titanium dioxide nano-particles and a fluorine-based copolymer resin in a mass ratio of (30-70): (70-30) mixing the components in the mixture, then dispersing the mixture in a mixed solution of water and isopropanol, wherein the total concentration of the hydrophobic titanium dioxide nano particles and the fluorine copolymer resin is about 60-75 percent to obtain hydrophobic layer dispersion liquid, then the mask of the shutter structure or the mask of the grid structure is attached to the high-strength wallpaper base layer, then the hydrophobic layer dispersion liquid is brushed on the surface of the mask, and the gap of the mask is filled with the hydrophobic layer dispersion liquid, then removing the mask in the direction vertical to the wallpaper substrate, standing for 30-60s to make a small amount of hydrophobic layer dispersion flow to the non-brush-coated area, and then rapidly drying at 90-120 ℃ to obtain the hydrophobic layer of the micro-nano structure with the cross section of the waveform structure.
The cross section shape of the wave-shaped structure is that in a two-dimensional X-Y plane of the wallpaper, the cross section along the X direction of the wallpaper has a wave-shaped shape and/or the cross section along the Y direction of the wallpaper has a wave-shaped shape.
The hydrophobic titanium dioxide nanoparticles have a particle size in the range of 5 to 100nm, preferably 10 to 30 nm.
Finally, the invention also provides the high-strength hydrophobic environment-friendly wallpaper which is composed of the high-strength wallpaper base layer and the hydrophobic layer of the micro-nano structure positioned on the high-strength wallpaper base layer.
In the wallpaper of the invention, in the preparation process of the wallpaper base layer, the permanent wet strength resin is added in the pulp, the permanent wet strength resin can effectively balance fiber charges in the pulp, and can also interact with the subsequently added polycarboxyl cross-linked composite microfibrillated cellulose and cationic starch composition, so that the expansion and shrinkage deformation of the fibers in the direction perpendicular to the major diameter of the cellulose fibers are restrained and limited to a certain extent, and the tensile strength of the paper is improved.
The polycarboxyl cross-linked composite microfibrillated cellulose can effectively improve the toughness of paper, and can relieve the stress mismatching degree between a hydrophobic layer of a subsequent micro-nano structure and a wallpaper base layer, so that the wallpaper is not easy to damage and deform in the construction process, and the construction difficulty of the wallpaper is reduced. Meanwhile, the hydrophobic layer of the micro-nano structure on the surface of the wallpaper can be guaranteed not to be damaged after the wallpaper is constructed, and the hydrophobic performance is good.
The hydrophobic layer of the micro-nano structure has the cross section shape of a waveform structure, meanwhile, hydrophobic titanium dioxide nanoparticles are used in a hydrophobic layer dispersion liquid, after drying, part of the nanoparticles on the surface are exposed on the surface of the hydrophobic layer to form a nano mastoid structure, and an excellent hydrophobic structure can be formed by combining the micro-nano waveform structure, so that the wallpaper has excellent hydrophobicity. In addition, the hydrophobic layer has a waveform structure, namely the thickness of the hydrophobic layer on a two-dimensional X-Y plane of the wallpaper has the characteristic of periodic fluctuation, so that the toughness of the hydrophobic layer in the two-dimensional X-Y plane of the wallpaper is improved. In the construction process of the wallpaper, the hydrophobic layer cannot be damaged by tensile stress in the two-dimensional X-Y plane of the wallpaper, so that the wallpaper after construction still has excellent hydrophobicity, and the construction difficulty is reduced.
Meanwhile, the hydrophobic layer on the surface layer contains nano titanium dioxide particles, has a photocatalysis effect, can effectively catalyze and degrade organic pollutants, purifies air after indoor decoration, and is environment-friendly and safe.
Detailed Description
The invention will now be further illustrated by reference to specific examples. It is to be understood that these examples are intended in part, and not in whole, to illustrate the present invention. Any modifications which can be easily made by a person skilled in the art to the present invention without departing from the technical solution and concept of the present invention will fall within the scope of the claims of the present invention.
Example 1
The high-strength hydrophobic environment-friendly wallpaper comprises a high-strength wallpaper base layer and a hydrophobic layer with a micro-nano structure positioned on the high-strength hydrophobic environment-friendly wallpaper base layer.
The high-strength wallpaper base layer is base paper obtained by taking composite paper pulp as a raw material through a papermaking process, and the preparation method comprises the following steps:
taking the paper pulp with the mass ratio of needle pulp to broad leaf pulp being 2:1 as raw material pulp, pulping in a pulper for 35 minutes, controlling the pulping degree to be about 35-40 DEG SR, then adding permanent wet strength resin, polycarboxyl crosslinking composite microfibrillated cellulose and a cationic starch composition into the composite paper pulp, controlling the mass concentration of the permanent wet strength resin to be 0.03%, the mass concentration of the polycarboxyl crosslinking composite microfibrillated cellulose to be 0.2%, the mass concentration of the cationic starch composition to be 0.6%, stirring for 60 minutes at the temperature of 65 ℃ and the rotating speed of 450 rpm; then, the net is netted, made into paper, dried and formed.
Wherein the permanent wet strength resin is a melamine formaldehyde resin.
The preparation method of the polycarboxyl cross-linked composite microfibrillated cellulose comprises the following steps:
adding citric acid into hot water to prepare an acid solution with the mass concentration of 38%, then adding microfibrillated cellulose into the acid solution, mixing and dispersing uniformly, wherein the mass concentration of the microfibrillated cellulose is 2%, then performing microwave treatment at 100 ℃ to obtain a suspension of the polycarboxyl cross-linked composite microfibrillated cellulose, and finally washing and deacidifying the suspension to obtain the polycarboxyl cross-linked composite microfibrillated cellulose.
Wherein the frequency of the microwave treatment is 2000MHz, and the microwave treatment time is 60 min.
The hydrophobic layer of the micro-nano structure is directly formed on the surface of the high-strength wallpaper base layer, the hydrophobic layer comprises hydrophobic titanium dioxide nano particles and fluorine copolymer resin, and the thickness of the hydrophobic layer is about 600 nm. The hydrophobic layer of the micro-nano structure is that in a two-dimensional X-Y plane of the wallpaper, the cross section along the X direction of the wallpaper is provided with a waveform shape and/or the cross section along the Y direction of the wallpaper is provided with a waveform shape, the height difference between the wave crest and the wave trough of the waveform structure is about 150nm, and the distance between adjacent wave crests is 400 nm.
The preparation method comprises the following steps:
mixing hydrophobic titanium dioxide nano particles and fluorine copolymer resin according to a mass ratio of 40:60 in advance, dispersing the mixture in a mixed solution of water and isopropanol, wherein the total concentration of the hydrophobic titanium dioxide nano particles and the fluorine copolymer resin is about 65 percent to obtain hydrophobic layer dispersion liquid, then attaching a mask of a shutter structure or a mask of a grid structure to a high-strength wallpaper base layer, brushing the hydrophobic layer dispersion liquid on the surface of the mask, filling gaps of the mask with the hydrophobic layer dispersion liquid, removing the mask in a direction vertical to the wallpaper base layer, standing for 36s to enable a small amount of the hydrophobic layer dispersion liquid to be cast to an area which is not brushed, and then quickly drying at 110 ℃ to obtain the hydrophobic layer of the micro-nano structure with the cross section shape of the waveform structure.
The cross section shape of the wave-shaped structure is that in a two-dimensional X-Y plane of the wallpaper, the cross section along the X direction of the wallpaper has a wave-shaped shape, and the cross section along the Y direction of the wallpaper has a wave-shaped shape.
The hydrophobic titanium dioxide nanoparticles have a particle size in the range of about 10 to about 30 nm.
Example 2
The high-strength hydrophobic environment-friendly wallpaper comprises a high-strength wallpaper base layer and a hydrophobic layer with a micro-nano structure positioned on the high-strength hydrophobic environment-friendly wallpaper base layer.
The high-strength wallpaper base layer is base paper obtained by taking composite paper pulp as a raw material through a papermaking process, and the preparation method comprises the following steps:
taking paper pulp with the mass ratio of needle-leaf pulp to broad-leaf pulp being 3:1 as raw material pulp, pulping in a pulper for 40 minutes, controlling the pulping degree to be about 35-40 DEG SR, then adding permanent wet strength resin and polycarboxyl crosslinking composite microfibrillated cellulose into the composite paper pulp, controlling the concentration of the permanent wet strength resin to be 0.04 percent and the concentration of the polycarboxyl crosslinking composite microfibrillated cellulose to be 0.3 percent, stirring for 50 minutes at the temperature of 75 ℃ and the rotating speed of 500 rpm; then, the net is netted, made into paper, dried and formed.
Wherein the permanent wet strength resin is a urea formaldehyde resin.
The preparation method of the polycarboxyl cross-linked composite microfibrillated cellulose comprises the following steps:
adding adipic acid into hot water at 80 ℃ to prepare an acid solution with the mass concentration of 20%, adding microfibrillated cellulose into the acid solution, mixing and dispersing uniformly, wherein the mass concentration of the microfibrillated cellulose is 2%, then performing microwave treatment at 80 ℃ to obtain a suspension of the polycarboxy cross-linked composite microfibrillated cellulose, and finally washing and deacidifying the suspension to obtain the polycarboxy cross-linked composite microfibrillated cellulose.
Wherein the microwave treatment frequency is 1500MHz, and the microwave treatment time is 60 min.
The hydrophobic layer of the micro-nano structure is directly formed on the surface of the high-strength wallpaper base layer, the hydrophobic layer comprises hydrophobic titanium dioxide nanoparticles and fluorine copolymer resin, and the thickness of the hydrophobic layer is 600 nm. The hydrophobic layer of the micro-nano structure is that the cross section of the wallpaper along the X direction has a waveform shape in a two-dimensional X-Y plane of the wallpaper, the height difference between wave crests and wave troughs of the waveform structure is about 100nm, and the distance between adjacent wave crests is 300 nm.
The preparation method comprises the following steps:
mixing hydrophobic titanium dioxide nano particles and fluorine copolymer resin according to a mass ratio of 55:45 in advance, dispersing the mixture in a mixed solution of water and isopropanol, wherein the total concentration of the hydrophobic titanium dioxide nano particles and the fluorine copolymer resin is about 60 percent to obtain hydrophobic layer dispersion liquid, then attaching a mask of the shutter structure to a high-strength wallpaper base layer, then brushing the hydrophobic layer dispersion liquid on the surface of the mask, filling the gap between the mask and the hydrophobic layer dispersion liquid, then removing the mask in a direction vertical to the wallpaper base layer, standing for 45s to cast a small amount of the hydrophobic layer dispersion liquid to an area which is not brushed, and then quickly drying at 120 ℃ to obtain the hydrophobic layer of the micro-nano structure with the cross section shape of the waveform structure.
The hydrophobic titanium dioxide nanoparticles have a particle size in the range of about 10 to about 30 nm.
Example 3
The high-strength hydrophobic environment-friendly wallpaper comprises a high-strength wallpaper base layer and a hydrophobic layer with a micro-nano structure positioned on the high-strength hydrophobic environment-friendly wallpaper base layer.
The high-strength wallpaper base layer is base paper obtained by taking composite paper pulp as a raw material through a papermaking process, and the preparation method comprises the following steps:
taking paper pulp with the mass ratio of needle-leaf pulp to broad-leaf pulp being 2:1 as raw material pulp, pulping for 50 minutes in a pulper, controlling the pulping degree to be about 35-40 DEG SR, then adding permanent wet strength resin and polycarboxyl crosslinking composite microfibrillated cellulose into the composite paper pulp, controlling the concentration of the permanent wet strength resin to be 0.05 percent and the concentration of the polycarboxyl crosslinking composite microfibrillated cellulose to be 0.3 percent, and stirring for 60 minutes at the temperature of 80 ℃ and the rotating speed of 600 rpm; then, the net is netted, made into paper, dried and formed.
Wherein the permanent wet strength resin is a crosslinked resin and is a polyisocyanate resin.
The preparation method of the polycarboxyl cross-linked composite microfibrillated cellulose comprises the following steps:
adding citric acid into hot water at 60 ℃ to prepare an acid solution with the mass concentration of 40%, then adding microfibrillated cellulose into the acid solution, mixing and dispersing uniformly, wherein the mass concentration of the microfibrillated cellulose is 3%, then carrying out microwave treatment at 90 ℃ to obtain a suspension of the polycarboxyl cross-linked composite microfibrillated cellulose, and finally washing and deacidifying the suspension to obtain the polycarboxyl cross-linked composite microfibrillated cellulose.
Wherein the microwave treatment frequency is 2000MHz, and the microwave treatment time is 70 min.
The hydrophobic layer of the micro-nano structure is directly formed on the surface of the high-strength wallpaper base layer, the hydrophobic layer comprises hydrophobic titanium dioxide nano particles and fluorine copolymer resin, and the thickness of the hydrophobic layer is about 800 nm. The hydrophobic layer of the micro-nano structure is that in a two-dimensional X-Y plane of the wallpaper, the cross section along the X direction of the wallpaper is provided with a waveform shape, the cross section along the Y direction of the wallpaper is provided with a waveform shape, the height difference between the wave crest and the wave trough of the waveform structure is about 250nm, and the distance between adjacent wave crests is 500 nm.
The preparation method comprises the following steps:
mixing hydrophobic titanium dioxide nano particles and fluorine copolymer resin according to a mass ratio of 65:35 in advance, dispersing the mixture in a mixed solution of water and isopropanol, wherein the total concentration of the hydrophobic titanium dioxide nano particles and the fluorine copolymer resin is about 70%, obtaining hydrophobic layer dispersion liquid, attaching a mask of a grid structure to a high-strength wallpaper base layer, brushing the hydrophobic layer dispersion liquid on the surface of the mask, filling gaps between the mask and the hydrophobic layer dispersion liquid, removing the mask in a direction vertical to the wallpaper base layer, standing for 50s, casting a small amount of hydrophobic layer dispersion liquid to an area which is not brushed, and quickly drying at 100 ℃ to obtain the hydrophobic layer of the micro-nano structure with the cross section shape of the waveform structure.
The cross section shape of the wave-shaped structure is that in a two-dimensional X-Y plane of the wallpaper, the cross section along the X direction of the wallpaper has a wave-shaped shape and/or the cross section along the Y direction of the wallpaper has a wave-shaped shape.
The hydrophobic titanium dioxide nano-particles are hydrophobic silicon dioxide, and the particle size range of the hydrophobic silicon dioxide nano-particles is 10-30 nm.
Comparative example 1
Compared with the embodiment 3, the mask in the embodiment 3 is omitted, and the hydrophobic layer dispersion liquid is directly coated on the surface of the high-strength wallpaper base layer in a brush mode to obtain the hydrophobic layer with the thickness of about 1000 nm.
Comparative example 2
Compared with example 3, the permanent wet strength resin and the polycarboxyl cross-linked composite microfibrillated cellulose in example 3 are omitted, and the pulp with the mass ratio of needle blade pulp to broad blade pulp of 2:1 is directly used as raw pulp to be pulped, screened, made into paper and dried to be formed. And then, directly brushing the hydrophobic layer dispersion liquid on the surface of the high-strength wallpaper base layer to obtain the hydrophobic layer with the thickness of about 1000 nm.
Comparative example 3
Compared with example 3, the permanent wet strength resin and the polycarboxyl cross-linked composite microfibrillated cellulose in example 3 are omitted, and the pulp with the mass ratio of needle blade pulp to broad blade pulp of 2:1 is directly used as raw pulp to be pulped, screened, made into paper and dried to be formed. And then brushing the hydrophobic layer by using a mask to obtain the hydrophobic layer of the micro-nano structure with the cross section of the waveform structure.
The wallpaper of examples 1-3 and comparative examples 1-3 was tested for the evaluation of the hydrophobic property, and the specific results are shown in the following table.
| Water contact Angle (°) | Water roll angle (°) | Water contact Angle after construction (°) | |
| Example 1 | 155 | 5 | 155 |
| Example 2 | 155 | 5 | 155 |
| Example 3 | 156 | 5 | 156 |
| Comparative example 1 | 150 | 16 | 138 |
| Comparative example 2 | 150 | 18 | 129 |
| Comparative example 3 | 155 | 5 | 145 |
From the test results in the table above, it can be found that the high-strength hydrophobic environment-friendly wallpaper, which comprises the high-strength wallpaper base layer and the hydrophobic layer with the micro-nano structure positioned on the high-strength hydrophobic environment-friendly wallpaper base layer, has excellent hydrophobic property, and can still maintain the original excellent hydrophobic property after construction, namely the wallpaper has the characteristics of high strength and easiness in construction.
Claims (8)
1. A preparation method of high-strength hydrophobic environment-friendly wallpaper comprises the following steps:
(1) preparation of high-strength wallpaper base layer
Taking needle-leaf pulp and broad-leaf pulp with the mass ratio of 1-3:1 as raw material pulp, pulping in a pulper for 30-50 minutes, controlling the pulping degree at 35-40 DEG SR, then adding permanent wet strength resin, polycarboxyl crosslinking composite microfibrillated cellulose and a cationic starch composition into the composite pulp, controlling the concentration of the permanent wet strength resin at 0.02-0.05%, controlling the concentration of the polycarboxyl crosslinking composite microfibrillated cellulose at 0.1-0.3%, controlling the concentration of the cationic starch composition at 0.05-0.1%, stirring for 30-60 minutes at the temperature of 60-80 ℃ and the rotation speed of 300-600 rpm; then, carrying out net surfing, papermaking, drying and forming;
(2) preparation of hydrophobic layer of micro-nano structure
The preparation method comprises the following steps of (30-70) mixing hydrophobic titanium dioxide nano particles and fluorine copolymer resin in advance according to a mass ratio of: (70-30) mixing the components in the mixture, then dispersing the mixture in a mixed solution of water and isopropanol, wherein the total concentration of the hydrophobic titanium dioxide nano particles and the fluorine copolymer resin is 60-75 percent to obtain hydrophobic layer dispersion liquid, then the mask of the shutter structure or the mask of the grid structure is attached to the high-strength wallpaper base layer, then the hydrophobic layer dispersion liquid is brushed on the surface of the mask, and the gap of the mask is filled with the hydrophobic layer dispersion liquid, then removing the mask in a direction vertical to the wallpaper base layer, standing for 30-60s to make a small amount of hydrophobic layer dispersion flow to the non-brushing area, then quickly drying at 90-120 ℃ to obtain a hydrophobic layer of the micro-nano structure with the cross section of the waveform structure;
characterized in that in step (1), the permanent wet strength resin is a crosslinked resin selected from one or more of polyamidoamine-epihalohydrin resin, polyisocyanate resin, urea-formaldehyde resin, and melamine-formaldehyde resin; in the step (1), the preparation method of the polycarboxyl cross-linked composite microfibrillated cellulose comprises the following steps: adding a polycarboxyl compound into hot water to prepare an acid solution with the mass concentration of 20-40%, adding microfibrillated cellulose into the acid solution, mixing and dispersing uniformly, wherein the mass concentration of the microfibrillated cellulose is 1-3%, then performing microwave treatment at 80-100 ℃ to obtain a suspension of the polycarboxyl cross-linked composite microfibrillated cellulose, and finally washing and deacidifying the suspension to obtain the polycarboxyl cross-linked composite microfibrillated cellulose.
2. The method as claimed in claim 1, wherein in the step (1), the microwave treatment frequency is 1000-2000MHz, and the microwave treatment time is 30-90 min.
3. The method for preparing high-strength hydrophobic environment-friendly wallpaper according to claim 2, wherein in the step (1), the polycarboxyl compound is selected from one or more of malonic acid, adipic acid, glutaric acid, citric acid and succinic acid.
4. The method for preparing high-strength hydrophobic environment-friendly wallpaper as claimed in claim 3, wherein in the step (1), the cationic starch composition is corn or tapioca cationic starch with a degree of substitution of 0.02-0.04.
5. The method as claimed in claim 1, wherein in the step (2), the thickness of the hydrophobic layer is 500nm-1000nm, the hydrophobic layer of the micro-nano structure has a cross-sectional shape of a waveform structure, the height difference between the peaks and the valleys of the waveform structure is 100-300nm, and the distance between adjacent peaks is 300-500 nm.
6. The method for preparing high-strength hydrophobic environment-friendly wallpaper as claimed in claim 5, wherein in step (2), the cross-sectional shape of the wave-shaped structure is a wave-shaped structure in a cross section along an X direction of the wallpaper and/or a wave-shaped structure in a cross section along a Y direction of the wallpaper in a two-dimensional X-Y plane of the wallpaper.
7. The method for preparing high-strength hydrophobic environment-friendly wallpaper as claimed in claim 6, wherein in the step (2), the particle size of the hydrophobic titanium dioxide nanoparticles is in a range of 5-100 nm.
8. An environment-friendly wallpaper with high strength and hydrophobicity, which is prepared by the preparation method of any one of claims 1-7.
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| CN104822870A (en) * | 2013-01-31 | 2015-08-05 | 格拉特菲尔特盖恩斯巴赫股份有限公司 | Crosslinking/functionalization system for paper or non-woven web |
| CN108026698A (en) * | 2015-09-17 | 2018-05-11 | 斯道拉恩索公司 | Method for producing the film with good barrier property |
| CN107881849A (en) * | 2016-09-30 | 2018-04-06 | 凯米罗总公司 | For the method for the dimensional stability for improving paper or board product |
| CN107653740A (en) * | 2017-09-29 | 2018-02-02 | 浙江爱漫时壁纸有限公司 | A kind of waterproof wallpaper |
| CN108457130A (en) * | 2018-03-08 | 2018-08-28 | 海宁鑫墨香印刷有限公司 | A kind of production method of waterproof wallpaper |
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