CN109468876B - Wear-resistant paper and manufacturing method thereof - Google Patents
Wear-resistant paper and manufacturing method thereof Download PDFInfo
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- CN109468876B CN109468876B CN201811228320.7A CN201811228320A CN109468876B CN 109468876 B CN109468876 B CN 109468876B CN 201811228320 A CN201811228320 A CN 201811228320A CN 109468876 B CN109468876 B CN 109468876B
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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
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/385—Oxides, hydroxides or carbonates
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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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/64—Inorganic compounds
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Abstract
The present invention relates to a wear-resistant paper andthe manufacturing method comprises the steps that the wear-resistant paper comprises base paper, modified impregnating resin which is impregnated and coated on the inner layer and the outer layer of the base paper, and a composite wear-resistant reinforcing phase which is compatible with the modified impregnating resin layer on one side of the base paper; wherein the modified impregnating resin comprises the following raw materials: modified matrix resin glue solution, acetaldehyde solution, sodium hydroxide solution and modified enzymatic hydrolysis lignin; wherein, the modified matrix resin glue solution comprises the following raw materials: formaldehyde solution, acetaldehyde solution, sodium hydroxide solution, melamine and deionized water; the raw materials of the modified enzymatic hydrolysis lignin comprise: enzymolysis lignin, deionized water, a sodium hydroxide solution and a formaldehyde solution; wherein the composite wear-resistant enhanced phase is formed by depositing nano TiO on the surface2Nano gamma-Al2O3Powder, beta-Si3N4And (3) powder composition. Compared with the prior art, the wear-resistant paper provided by the embodiment of the invention can obviously improve the performances such as wear resistance, transparency and strength and can obviously reduce the process cost.
Description
Technical Field
The invention belongs to the technical field of impregnated paper production, and particularly relates to wear-resistant paper and a manufacturing method thereof.
Background
Along with economic development, the living standard of people is improved, the building industry is continuously developed, in recent years, the impregnated paper reinforced wood floor is deeply favored by the market due to the advantages of attractive appearance, fashion, rich product types and the like, is developed into a main product with the largest share in the floor market of China, and is widely applied to floor laying in family rooms and public places.
The impregnated paper reinforced wood floor is formed by hot-pressing and fusing an impregnated surface wear-resistant layer, decorative paper, balance paper and a base material. The impregnated paper reinforced wood floor not only eliminates the hard and cold feeling of cement, stone and ceramic floor materials, but also overcomes the defects of the solid wood floor such as abrasion resistance, burning resistance and pollution resistance, and compared with the solid wood floor, the impregnated paper reinforced wood floor has the advantages of low price, more convenient construction and installation, almost seamless assembly, smoothness and smoothness.
In practical applications, the properties of impregnated paper reinforced wood floorings depend to a large extent on the properties of the surface wear protection layer, i.e. the properties of the wear-resistant impregnated paper. The corrosion resistance, the etching resistance and the abrasion resistance of the abrasion-resistant paper, particularly the abrasion resistance, directly determine the service life of the impregnated paper reinforced wood floor. The wear-resistant paper is also required to endow the surface layer of the floor with good wear-resistant property, and simultaneously have good transparency, so that the attractiveness and the use of decorative patterns of the composite floor are not influenced. In addition, with the enhancement of environmental awareness of people, the requirement on the environmental protection property of the wear-resistant paper is higher and higher.
At present, the existing wear-resistant impregnated paper mainly has the following defects: 1) the existing wear-resistant impregnated paper adopts Al2O3As a reinforcing phase, the reinforcing phase is added into the base paper or is mixed with impregnating resin to impregnate the base paper; al (Al)2O3The dispersibility and the compatibility with the impregnating resin of (b) are main reasons for hindering the further improvement of the performance of the wear-resistant paper; 2) in order to reduce the cost, the prior wear-resistant paper adopts a large amount of low-toxicity urea-formaldehyde resin to partially replace melamine to carry out multi-pass impregnation, so that the manufactured wear-resistant paper and the reinforced wood board have the problem of releasing formaldehyde inevitably; 3) the existing process has high cost and high requirements on equipment and raw materials: for increasing Al2O3The dispersibility in the resin requires continuous recycling of the mixed resin, requires special equipment for the impregnation line, and also imposes high requirements on the resin used.
Therefore, how to prepare the high-performance wear-resistant paper with the environmental protection characteristic and reduce the production cost has important significance.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides wear-resistant paper and a preparation method thereof, and the main points of the wear-resistant paper are as follows:
according to one aspect of the invention, the wear-resistant paper comprises base paper, modified impregnating resin which is impregnated and coated on the inner layer and the outer layer of the base paper, and a composite wear-resistant reinforcing phase which is compatible with the modified impregnating resin layer on one side of the base paper; wherein the modified impregnating resin comprises the following raw materials: modified matrix resin glue solution, acetaldehyde solution, sodium hydroxide solution and modified enzymatic hydrolysis lignin; wherein, the modified matrix resin glue solution comprises the following raw materials: formaldehyde solution, acetaldehyde solution, sodium hydroxide solution, melamine and deionized water; the raw materials of the modified enzymatic hydrolysis lignin comprise: enzymolysis lignin, deionized water, a sodium hydroxide solution and a formaldehyde solution; wherein the composite wear-resistant enhanced phase is formed by depositing nano TiO on the surface2Nano gamma-Al2O3Powder, beta-Si3N4Powder composition; the nano gamma-Al2O3Powder and beta-Si3N4The mixing proportion of the powder is 100 parts by weight: (0.5-5), the average grain diameter is 50nm-65nm and 30nm-50nm respectively, and the average thickness of the nano TiO2 deposited on the surface is 5nm-10 nm.
According to an exemplary embodiment of the present invention, the modified impregnating resin raw material comprises: 400 parts by weight of modified matrix resin glue solution, 120 parts by weight of 40% acetaldehyde solution, 1-10 parts by weight of modified enzymatic hydrolysis lignin and 160-220 parts by weight of 28% sodium hydroxide.
According to an exemplary embodiment of the present invention, the modified base resin glue solution comprises the following raw materials: 100 parts by weight of a 38% formaldehyde solution, 35 parts by weight of a 40% acetaldehyde solution, 350 parts by weight of melamine and 260 parts by weight of deionized water and 190 parts by weight of a 33% sodium hydroxide solution.
According to an exemplary embodiment of the present invention, the raw material of the modified enzymatic hydrolyzed lignin comprises: 100 parts of enzymatic hydrolysis lignin, 310-350 parts of deionized water, 15-50 parts of 28% formaldehyde solution and 80-135 parts of 33% sodium hydroxide solution.
According to an exemplary embodiment of the invention, the wear resistant paper has a volatile content of 6.3% to 8.2% and a degree of pre-curing of 42% to 53%; the wear-resistant paper has the basis weight of 29g/m2-45 g/m2, the tightness of not more than 0.33g/cm3, the transparency of 49% -72%, the longitudinal tensile strength of not less than 5.38kN/m, the longitudinal wet strength of not less than 3.93kN/m and the wear-resistant revolution of not less than 6809.
According to another aspect of the present invention, a method of manufacturing wear resistant paper, the method comprising:
preparation of composite wear-resistant reinforcing phase
1) Compounding a reinforcing phase: nano gamma-Al2O3Powder, beta-Si3N4The powder is fully and uniformly mixed according to the weight portion of 100 (0.5-5);
2) surface treatment of the reinforcing phase: depositing nano TiO on the surface of the mixed powder2；
Specifically, absolute ethyl alcohol, 4-hydroxy-3-methoxyacetophenone, diethanolamine, tetrabutyl titanate and titanium tetrachloride are prepared according to the volume ratio of 25:1:2:4:1, 4-hydroxy-3-methoxyacetophenone and tetrabutyl titanate are sequentially added into the absolute ethyl alcohol to be uniformly mixed, and the diethanolamine and the titanium tetrachloride are sequentially added for 2-5s to obtain a sol solution;
dissolving the mixed powder in absolute ethyl alcohol according to the weight ratio of 8:100 to obtain a uniform solution; adding the obtained uniform solution into the sol solution according to the weight ratio of 100:535, electromagnetically stirring at 35 +/-2 ℃ for 25-40 min, fully cleaning with absolute ethyl alcohol, and performing heat preservation at 60 +/-1 ℃ for 15-25 min to obtain the surface deposited nano TiO2The composite reinforced powder of (1).
Preparation of modified impregnating resin
1) Activating and modifying enzymolysis lignin: fully and uniformly mixing 100 parts by weight of enzymatic hydrolysis lignin and 350 parts by weight of 310-350 parts by weight of deionized water, adjusting the pH value to 8.2-8.5 by adopting 80-135 parts by weight of 33% sodium hydroxide solution, adding 15-50 parts by weight of 28% formaldehyde solution, heating to 65-80 ℃, preserving the temperature for 30-55 min, carrying out condensation reflux, and carrying out rotary evaporation to obtain modified enzymatic hydrolysis lignin;
2) preparing modified matrix resin glue solution: fully mixing 100 parts by weight of 38% formaldehyde solution and 35 parts by weight of 40% acetaldehyde solution, adjusting the pH value to 9.0 by adopting 130-190 parts by weight of 33% sodium hydroxide solution, and preserving the temperature for 30-50min at 30 ℃; adding 350 parts by weight of melamine and 260 parts by weight of deionized water, and keeping the temperature at 65 +/-2 ℃ for 30min to obtain matrix resin glue solution;
3) preparing modified impregnating resin: putting 100 parts by weight of modified matrix resin glue solution and 120 parts by weight of 40% acetaldehyde solution into a reaction kettle, adjusting the pH value to 8.5-8.8 by adopting 160 parts by weight of 220 parts by weight of 28% sodium hydroxide, and reacting for 25min at 75 ℃; adding 100 parts by weight of modified matrix resin glue solution, adjusting the pH value to 6.2-6.8, and reacting for 30min at 80 ℃; adding 200 parts by weight of modified matrix resin glue solution and 1-10 parts by weight of modified enzymatic hydrolysis lignin, adjusting the pH value to 7.8-8.2, reacting at 95 ℃ for 30min, and cooling to 50 ℃ to obtain modified impregnating resin glue solution; immersing the glue solution into a supercritical dryer storing absolute ethyl alcoholIntroducing liquid CO2Performing solvent replacement to remove formaldehyde, acetaldehyde and ethanol in the glue solution to obtain modified impregnating resin;
preparation of wear-resistant paper
1) Dipping and gluing the base paper in modified dipping resin;
2) uniformly spraying the composite reinforced powder on the wear-resistant surface of the impregnated paper;
3) drying to obtain the wear-resistant paper.
According to an exemplary embodiment of the present invention, the base paper is made of 100% bleached sulfite softwood pulp having a freeness of 36 ° SR to 38 ° SR and a basis weight of 18g/m2-25g/m2。
According to an exemplary embodiment of the invention, the total amount of said immersion glue is 250-550%.
According to the exemplary embodiment of the present invention, the addition amount of the composite reinforcing powder is 10g/m2-20g/m2。
According to an exemplary embodiment of the present invention, the drying process is four stages, the first stage drying temperature is 115 ℃ to 120 ℃, the second stage drying temperature is 125 ℃ to 130 ℃, the third stage drying temperature is 135 ℃ to 140 ℃, and the fourth stage drying temperature is 120 ℃ to 125 ℃.
Compared with the prior art, the wear-resistant paper provided by the embodiment of the invention 1) adopts nanoscale Al2O3、Si3N4As a reinforcing phase, through the optimized selection of crystal form, grain diameter and mixing ratio, and adopts nano TiO2Carrying out surface deposition and activation treatment on the mixed reinforcing phase, so that the wear resistance of the wear-resistant paper is remarkably improved while the compatibility of the reinforcing phase and the impregnating resin is improved; 2) performing activation modification on lignin by adopting enzymolysis; adopting indexes such as formaldehyde, acetaldehyde, melamine and the like to modify resin glue solution; the modified impregnating resin is prepared by adopting activated modified enzymatic hydrolysis lignin, modified resin glue solution, acetaldehyde solution, sodium hydroxide and the like, so that the impregnating performance and the environmental protection performance of the impregnating resin are obviously improved; 3) the wear-resistant paper has the advantages that the wear-resistant performance, transparency, strength and other performances of the wear-resistant paper are obviously improved, and meanwhile, the process cost is obviously reduced.
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 wear-resistant paper
Preparation of composite wear-resistant reinforcing phase
1) Compounding a reinforcing phase: mixing nano gamma-Al with the particle size of 50nm2O3Powder, beta-Si with grain diameter of 50nm3N4The powder is fully and uniformly mixed according to the weight portion of 100: 0.5;
2) surface treatment of the reinforcing phase: depositing nano TiO on the surface of the mixed powder2The deposition thickness is 10 nm;
specifically, absolute ethyl alcohol, 4-hydroxy-3-methoxyacetophenone, diethanolamine, tetrabutyl titanate and titanium tetrachloride are prepared according to the volume ratio of 25:1:2:4:1, 4-hydroxy-3-methoxyacetophenone and tetrabutyl titanate are sequentially added into the absolute ethyl alcohol to be uniformly mixed, and the diethanolamine and the titanium tetrachloride are sequentially added for 2-5s to obtain a sol solution;
dissolving the mixed powder in absolute ethyl alcohol according to the weight part ratio of 8:100 (mixed powder: absolute ethyl alcohol) to obtain a uniform solution; adding the obtained uniform solution into the sol solution according to the weight ratio of 100:535, electromagnetically stirring at the temperature of 35 +/-2 ℃ for 25-40 min, fully cleaning by using absolute ethyl alcohol, carrying out heat preservation treatment at the temperature of 60 +/-1 ℃, and preserving heat for 15-25 min to obtain the surface deposited nano TiO2The composite reinforced powder of (1).
Preparation of modified impregnating resin
1) Activating and modifying enzymolysis lignin: fully and uniformly mixing 100 parts by weight of enzymatic hydrolysis lignin and 310 parts by weight of deionized water, adjusting the pH value to 8.2-8.5 by adopting 80 parts by weight of 33% sodium hydroxide solution, adding 15 parts by weight of 28% formaldehyde solution, heating to 65-80 ℃, preserving the temperature for 30-55 min, condensing, refluxing and rotationally evaporating to obtain modified enzymatic hydrolysis lignin;
2) preparing modified matrix resin glue solution: fully mixing 100 parts by weight of 38% formaldehyde solution and 35 parts by weight of 40% acetaldehyde solution, adjusting the pH value to 9.0 by adopting 130 parts by weight of 33% sodium hydroxide solution, and preserving the temperature for 30-50min at 30 ℃; adding 290 parts by weight of melamine and 260 parts by weight of deionized water, and keeping the temperature at 65 +/-2 ℃ for 30min to obtain a matrix resin glue solution;
3) preparing modified impregnating resin: putting 100 parts by weight of modified matrix resin glue solution and 120 parts by weight of 40% acetaldehyde solution into a reaction kettle, adjusting the pH value to 8.5-8.8 by adopting 160 parts by weight of 28% sodium hydroxide, and reacting for 25min at 75 ℃; adding 100 parts by weight of modified matrix resin glue solution, adjusting the pH value to 6.2-6.8, and reacting for 30min at 80 ℃; adding 200 parts by weight of modified matrix resin glue solution and 1 part by weight of modified enzymatic hydrolysis lignin, adjusting the pH value to 7.8-8.2, reacting at 95 ℃ for 30min, and cooling to 50 ℃ to obtain modified impregnating resin glue solution; immersing the glue solution into a supercritical dryer storing absolute ethyl alcohol, and introducing liquid CO2Performing solvent replacement to remove formaldehyde, acetaldehyde and ethanol in the glue solution to obtain modified impregnating resin;
preparation of wear-resistant paper
1) The base paper adopts 100% bleached sulfite softwood pulp as a raw material, the beating degree is 36-38 DEG SR, and the quantitative is 18g/m2(ii) a Dipping and gluing the base paper in modified dipping resin, wherein the total amount of dipping and gluing is 250%;
2) uniformly spraying composite reinforced powder on the wear-resistant surface of the impregnated paper, wherein the addition amount of the composite reinforced powder is 10g/m2；
3) And (3) drying, wherein the drying treatment is carried out in four stages, the first stage drying temperature is 115-120 ℃, the second stage drying temperature is 125-130 ℃, the third stage drying temperature is 135-140 ℃, and the fourth stage drying temperature is 120-125 ℃, so as to obtain the wear-resistant paper.
Example 2: preparation of wear-resistant paper
Preparation of composite wear-resistant reinforcing phase
1) Compounding a reinforcing phase: mixing nano gamma-Al with the particle size of 55nm2O3Powder, beta-Si with grain diameter of 45nm3N4The powder is fully and uniformly mixed according to the weight portion of 100: 1.5;
2) surface treatment of the reinforcing phase: depositing nano TiO on the surface of the mixed powder2The deposition thickness is 8 nm;
specifically, absolute ethyl alcohol, 4-hydroxy-3-methoxyacetophenone, diethanolamine, tetrabutyl titanate and titanium tetrachloride are prepared according to the volume ratio of 25:1:2:4:1, 4-hydroxy-3-methoxyacetophenone and tetrabutyl titanate are sequentially added into the absolute ethyl alcohol to be uniformly mixed, and the diethanolamine and the titanium tetrachloride are sequentially added for 2-5s to obtain a sol solution;
dissolving the mixed powder in absolute ethyl alcohol according to the weight part ratio of 8:100 to obtain a uniform solution; adding the obtained uniform solution into the sol solution according to the weight ratio of 100:535, electromagnetically stirring at the temperature of 35 +/-2 ℃ for 25-40 min, fully cleaning by using absolute ethyl alcohol, carrying out heat preservation treatment at the temperature of 60 +/-1 ℃, and preserving heat for 15-25 min to obtain the surface deposited nano TiO2The composite reinforced powder of (1).
Preparation of modified impregnating resin
1) Activating and modifying enzymolysis lignin: fully and uniformly mixing 100 parts by weight of enzymatic hydrolysis lignin and 322 parts by weight of deionized water, adjusting the pH value to 8.2-8.5 by adopting 90 parts by weight of 33% sodium hydroxide solution, adding 28 parts by weight of 28% formaldehyde solution, heating to 65-80 ℃, preserving the temperature for 30-55 min, condensing, refluxing, and performing rotary evaporation to obtain modified enzymatic hydrolysis lignin;
2) preparing modified matrix resin glue solution: fully mixing 100 parts by weight of 38% formaldehyde solution and 35 parts by weight of 40% acetaldehyde solution, adjusting the pH value to 9.0 by adopting 135 parts by weight of 33% sodium hydroxide solution, and preserving the temperature for 30-50min at 30 ℃; adding 301 parts by weight of melamine and 260 parts by weight of deionized water, and keeping the temperature at 65 +/-2 ℃ for 30min to obtain matrix resin glue solution;
3) preparing modified impregnating resin: putting 100 parts by weight of modified matrix resin glue solution and 120 parts by weight of 40% acetaldehyde solution into a reaction kettle, adjusting the pH value to 8.5-8.8 by adopting 168 parts by weight of 28% sodium hydroxide, and reacting for 25min at 75 ℃; adding 100 weight parts of modified matrix resin glue solution, and adjustingThe pH value is 6.2-6.8, and the reaction is carried out for 30min at 80 ℃; adding 200 parts by weight of modified matrix resin glue solution and 2 parts by weight of modified enzymatic hydrolysis lignin, adjusting the pH value to 7.8-8.2, reacting at 95 ℃ for 30min, and cooling to 50 ℃ to obtain modified impregnating resin glue solution; immersing the glue solution into a supercritical dryer storing absolute ethyl alcohol, and introducing liquid CO2Performing solvent replacement to remove formaldehyde, acetaldehyde and ethanol in the glue solution to obtain modified impregnating resin;
preparation of wear-resistant paper
1) The base paper adopts 100% bleached sulfite softwood pulp as a raw material, the beating degree is 36-38 DEG SR, and the quantitative is 20g/m2(ii) a Dipping and gluing the base paper in modified dipping resin, wherein the total amount of dipping and gluing is 300%;
2) uniformly spraying composite reinforced powder on the wear-resistant surface of the impregnated paper, wherein the addition amount of the composite reinforced powder is 12g/m2；
3) And (3) drying, wherein the drying treatment is carried out in four stages, the first stage drying temperature is 115-120 ℃, the second stage drying temperature is 125-130 ℃, the third stage drying temperature is 135-140 ℃, and the fourth stage drying temperature is 120-125 ℃, so as to obtain the wear-resistant paper.
Example 3: preparation of wear-resistant paper
Preparation of composite wear-resistant reinforcing phase
1) Compounding a reinforcing phase: mixing nano gamma-Al with the particle size of 55nm2O3Powder, beta-Si with grain diameter of 45nm3N4The powder is fully and uniformly mixed according to the weight ratio of 100: 2;
2) surface treatment of the reinforcing phase: depositing nano TiO on the surface of the mixed powder2The deposition thickness is 7 nm;
specifically, absolute ethyl alcohol, 4-hydroxy-3-methoxyacetophenone, diethanolamine, tetrabutyl titanate and titanium tetrachloride are prepared according to the volume ratio of 25:1:2:4:1, 4-hydroxy-3-methoxyacetophenone and tetrabutyl titanate are sequentially added into the absolute ethyl alcohol to be uniformly mixed, and the diethanolamine and the titanium tetrachloride are sequentially added for 2-5s to obtain a sol solution;
dissolving the mixed powder in absolute ethyl alcohol according to the weight part ratio of 8:100 to obtain a uniform solution; according to the weight portion ratio of 100:535,adding the obtained uniform solution into sol solution, electromagnetically stirring at 35 + -2 deg.C for 25-40 min, cleaning with anhydrous ethanol, and maintaining at 60 + -1 deg.C for 15-25 min to obtain surface deposited nanometer TiO2The composite reinforced powder of (1).
Preparation of modified impregnating resin
1) Activating and modifying enzymolysis lignin: fully and uniformly mixing 100 parts by weight of enzymatic hydrolysis lignin and 334 parts by weight of deionized water, adjusting the pH value to 8.2-8.5 by adopting 105 parts by weight of 33% sodium hydroxide solution, adding 37 parts by weight of 28% formaldehyde solution, heating to 65-80 ℃, preserving the temperature for 30-55 min, condensing, refluxing, and performing rotary evaporation to obtain modified enzymatic hydrolysis lignin;
2) preparing modified matrix resin glue solution: fully mixing 100 parts by weight of 38% formaldehyde solution and 35 parts by weight of 40% acetaldehyde solution, adjusting the pH value to 9.0 by adopting 143 parts by weight of 33% sodium hydroxide solution, and preserving the temperature for 30-50min at 30 ℃; adding 321 parts by weight of melamine and 260 parts by weight of deionized water, and keeping the temperature at 65 +/-2 ℃ for 30min to obtain matrix resin glue solution;
3) preparing modified impregnating resin: putting 100 parts by weight of modified matrix resin glue solution and 120 parts of 40% acetaldehyde solution into a reaction kettle, adjusting the pH value to 8.5-8.8 by adopting 176 parts by weight of 28% sodium hydroxide, and reacting for 25min at 75 ℃; adding 100 parts by weight of modified matrix resin glue solution, adjusting the pH value to 6.2-6.8, and reacting for 30min at 80 ℃; adding 200 parts by weight of modified matrix resin glue solution and 5 parts by weight of modified enzymatic hydrolysis lignin, adjusting the pH value to 7.8-8.2, reacting at 95 ℃ for 30min, and cooling to 50 ℃ to obtain modified impregnating resin glue solution; immersing the glue solution into a supercritical dryer storing absolute ethyl alcohol, and introducing liquid CO2Performing solvent replacement to remove formaldehyde, acetaldehyde and ethanol in the glue solution to obtain modified impregnating resin;
preparation of wear-resistant paper
1) The base paper adopts 100% bleached sulfite softwood pulp as a raw material, the beating degree is 36-38 DEG SR, and the quantitative is 22g/m2(ii) a Dipping and gluing the base paper in modified dipping resin, wherein the total amount of dipping and gluing is 350%;
2) will be provided withThe composite reinforced powder is uniformly sprayed on the wear-resistant surface of the impregnated paper, and the addition amount of the composite reinforced powder is 15g/m2；
3) And (3) drying, wherein the drying treatment is carried out in four stages, the first stage drying temperature is 115-120 ℃, the second stage drying temperature is 125-130 ℃, the third stage drying temperature is 135-140 ℃, and the fourth stage drying temperature is 120-125 ℃, so as to obtain the wear-resistant paper.
Example 4: preparation of wear-resistant paper
Preparation of composite wear-resistant reinforcing phase
1) Compounding a reinforcing phase: mixing nano gamma-Al with the particle size of 60nm2O3Powder, beta-Si with grain diameter of 38nm3N4The powder is fully and uniformly mixed according to the weight ratio of 100: 3.8;
2) surface treatment of the reinforcing phase: depositing nano TiO on the surface of the mixed powder2The deposition thickness is 6 nm;
specifically, absolute ethyl alcohol, 4-hydroxy-3-methoxyacetophenone, diethanolamine, tetrabutyl titanate and titanium tetrachloride are prepared according to the volume ratio of 25:1:2:4:1, 4-hydroxy-3-methoxyacetophenone and tetrabutyl titanate are sequentially added into the absolute ethyl alcohol to be uniformly mixed, and the diethanolamine and the titanium tetrachloride are sequentially added for 2-5s to obtain a sol solution;
dissolving the mixed powder in absolute ethyl alcohol according to the weight part ratio of 8:100 to obtain a uniform solution; adding the obtained uniform solution into the sol solution according to the weight ratio of 100:535, electromagnetically stirring at the temperature of 35 +/-2 ℃ for 25-40 min, fully cleaning by using absolute ethyl alcohol, carrying out heat preservation treatment at the temperature of 60 +/-1 ℃, and preserving heat for 15-25 min to obtain the surface deposited nano TiO2The composite reinforced powder of (1).
Preparation of modified impregnating resin
1) Activating and modifying enzymolysis lignin: fully and uniformly mixing 100 parts by weight of enzymatic hydrolysis lignin and 343 parts by weight of deionized water, adjusting the pH value to 8.2-8.5 by adopting 118 parts by weight of 33% sodium hydroxide solution, adding 48 parts by weight of 28% formaldehyde solution, heating to 65-80 ℃, preserving the temperature for 30-55 min, condensing, refluxing, and performing rotary evaporation to obtain modified enzymatic hydrolysis lignin;
2) preparing modified matrix resin glue solution: fully mixing 100 parts by weight of 38% formaldehyde solution and 35 parts by weight of 40% acetaldehyde solution, adjusting the pH value to 9.0 by adopting 169 parts by weight of 33% sodium hydroxide solution, and preserving the temperature for 30-50min at 30 ℃; adding 332 parts by weight of melamine and 260 parts by weight of deionized water, and keeping the temperature at 65 +/-2 ℃ for 30min to obtain a matrix resin glue solution;
3) preparing modified impregnating resin: putting 100 parts by weight of modified matrix resin glue solution and 120 parts of 40% acetaldehyde solution into a reaction kettle, adjusting the pH value to 8.5-8.8 by adopting 182 parts by weight of 28% sodium hydroxide, and reacting for 25min at 75 ℃; adding 100 parts by weight of modified matrix resin glue solution, adjusting the pH value to 6.2-6.8, and reacting for 30min at 80 ℃; adding 200 parts by weight of modified matrix resin glue solution and 8 parts by weight of modified enzymatic hydrolysis lignin, adjusting the pH value to 7.8-8.2, reacting at 95 ℃ for 30min, and cooling to 50 ℃ to obtain modified impregnating resin glue solution; immersing the glue solution into a supercritical dryer storing absolute ethyl alcohol, and introducing liquid CO2Performing solvent replacement to remove formaldehyde, acetaldehyde and ethanol in the glue solution to obtain modified impregnating resin;
preparation of wear-resistant paper
1) The base paper adopts 100% bleached sulfite softwood pulp as a raw material, the beating degree is 36-38 DEG SR, and the quantitative is 23g/m2(ii) a Dipping and gluing base paper in modified dipping resin, wherein the total amount of dipping and gluing is 480%;
2) uniformly spraying composite reinforced powder on the wear-resistant surface of the impregnated paper, wherein the addition amount of the composite reinforced powder is 18g/m2；
3) And (3) drying, wherein the drying treatment is carried out in four stages, the first stage drying temperature is 115-120 ℃, the second stage drying temperature is 125-130 ℃, the third stage drying temperature is 135-140 ℃, and the fourth stage drying temperature is 120-125 ℃, so as to obtain the wear-resistant paper.
Example 5: preparation of wear-resistant paper
Preparation of composite wear-resistant reinforcing phase
1) Compounding a reinforcing phase: mixing the nano gamma-Al with the grain diameter of 65nm2O3Powder and beta-Si with grain diameter of 30nm3N4The powder is fully and uniformly mixed according to the weight portion of 100: 5;
2) surface treatment of the reinforcing phase: depositing nano TiO on the surface of the mixed powder2The deposition thickness is 5 nm;
specifically, absolute ethyl alcohol, 4-hydroxy-3-methoxyacetophenone, diethanolamine, tetrabutyl titanate and titanium tetrachloride are prepared according to the volume ratio of 25:1:2:4:1, 4-hydroxy-3-methoxyacetophenone and tetrabutyl titanate are sequentially added into the absolute ethyl alcohol to be uniformly mixed, and the diethanolamine and the titanium tetrachloride are sequentially added for 2-5s to obtain a sol solution;
dissolving the mixed powder in absolute ethyl alcohol according to the weight part ratio of 8:100 to obtain a uniform solution; adding the obtained uniform solution into the sol solution according to the weight ratio of 100:535, electromagnetically stirring at the temperature of 35 +/-2 ℃ for 25-40 min, fully cleaning by using absolute ethyl alcohol, carrying out heat preservation treatment at the temperature of 60 +/-1 ℃, and preserving heat for 15-25 min to obtain the surface deposited nano TiO2The composite reinforced powder of (1).
Preparation of modified impregnating resin
1) Activating and modifying enzymolysis lignin: fully and uniformly mixing 100 parts by weight of enzymatic hydrolysis lignin and 350 parts by weight of deionized water, adjusting the pH value to 8.2-8.5 by adopting 135 parts by weight of 33% sodium hydroxide solution, adding 50 parts by weight of 28% formaldehyde solution, heating to 65-80 ℃, preserving the temperature for 30-55 min, condensing, refluxing, and performing rotary evaporation to obtain modified enzymatic hydrolysis lignin;
2) preparing modified matrix resin glue solution: fully mixing 100 parts by weight of 38% formaldehyde solution and 35 parts by weight of 40% acetaldehyde solution, adjusting the pH value to 9.0 by adopting 190 parts by weight of 33% sodium hydroxide solution, and preserving the temperature for 30-50min at 30 ℃; adding 350 parts by weight of melamine and 260 parts by weight of deionized water, and keeping the temperature at 65 +/-2 ℃ for 30min to obtain matrix resin glue solution;
3) preparing modified impregnating resin: putting 100 parts by weight of modified matrix resin glue solution and 120 parts of 40% acetaldehyde solution into a reaction kettle, adjusting the pH value to 8.5-8.8 by adopting 220 parts by weight of 28% sodium hydroxide, and reacting for 25min at 75 ℃; adding 100 parts by weight of modified matrix resin glue solution, adjusting the pH value to 6.2-6.8, and reacting for 30min at 80 ℃; adding 200 parts by weight of modified matrix resin glue solution and 10 parts by weight of modified enzymatic hydrolysis lignin,adjusting the pH value to 7.8-8.2, reacting at 95 ℃ for 30min, and cooling to 50 ℃ to obtain a modified impregnating resin glue solution; immersing the glue solution into a supercritical dryer storing absolute ethyl alcohol, and introducing liquid CO2Performing solvent replacement to remove formaldehyde, acetaldehyde and ethanol in the glue solution to obtain modified impregnating resin;
preparation of wear-resistant paper
1) The base paper adopts 100% bleached sulfite softwood pulp as a raw material, the beating degree is 36-38 DEG SR, and the quantitative is 25g/m2(ii) a Dipping and gluing the base paper in modified dipping resin, wherein the total amount of dipping and gluing is 550%;
2) uniformly spraying composite reinforced powder on the wear-resistant surface of the impregnated paper, wherein the addition amount of the composite reinforced powder is 20g/m2；
3) And (3) drying, wherein the drying treatment is carried out in four stages, the first stage drying temperature is 115-120 ℃, the second stage drying temperature is 125-130 ℃, the third stage drying temperature is 135-140 ℃, and the fourth stage drying temperature is 120-125 ℃, so as to obtain the wear-resistant paper.
Example 6:
the performance parameters of the wear resistant papers prepared according to examples 1-5 are shown in table 1.
TABLE 1
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 (5)
1. A method of making wear-resistant paper, the method comprising:
preparation of composite wear-resistant reinforcing phase
1) IncreaseStrong phase compounding: nano gamma-Al2O3Powder, beta-Si3N4The powder is fully and uniformly mixed according to the weight part of 100 (0.5-5) to obtain mixed powder;
2) surface treatment of the reinforcing phase: depositing nano TiO on the surface of the mixed powder2；
Preparing absolute ethyl alcohol, 4-hydroxy-3-methoxyacetophenone, diethanolamine, tetrabutyl titanate and titanium tetrachloride according to a volume ratio of 25:1:2:4:1, sequentially adding the 4-hydroxy-3-methoxyacetophenone and the tetrabutyl titanate into the absolute ethyl alcohol for uniform mixing, and sequentially adding the diethanolamine and the titanium tetrachloride after 2-5s to obtain a sol solution;
dissolving the mixed powder in absolute ethyl alcohol according to the weight part ratio of 8:100 to obtain a uniform solution; adding the uniform solution into the sol solution according to the weight ratio of 100:535, electromagnetically stirring at the temperature of 35 +/-2 ℃ for 25-40 min, fully cleaning by using absolute ethyl alcohol, carrying out heat preservation treatment at the temperature of 60 +/-1 ℃ for 15-25 min to obtain the surface deposited nano TiO2The composite reinforcing powder of (1);
preparation of modified impregnating resin
1) Activating and modifying enzymolysis lignin: fully and uniformly mixing 100 parts by weight of enzymatic hydrolysis lignin and 350 parts by weight of 310-350 parts by weight of deionized water, adjusting the p H value to 8.2-8.5 by adopting 80-135 parts by weight of 33% sodium hydroxide solution, adding 15-50 parts by weight of 28% formaldehyde solution, heating to 65-80 ℃, preserving heat for 30-55 min, carrying out condensation reflux, and carrying out rotary evaporation to obtain modified enzymatic hydrolysis lignin;
2) preparing modified matrix resin glue solution: fully mixing 100 parts by weight of 38% formaldehyde solution and 35 parts by weight of 40% acetaldehyde solution, adjusting the pH value to 9.0 by adopting 130-190 parts by weight of 33% sodium hydroxide solution, and preserving the temperature for 30-50min at 30 ℃; adding 290 plus 350 parts by weight of melamine and 260 parts by weight of deionized water, and keeping the temperature at 65 +/-2 ℃ for 30min to obtain matrix resin glue solution;
3) preparing modified impregnating resin: putting 100 parts by weight of modified matrix resin glue solution and 120 parts by weight of 40% acetaldehyde solution into a reaction kettle, adjusting the p H value to 8.5-8.8 by adopting 160 parts by weight of 220 parts by weight of 28% sodium hydroxide, and reacting for 25min at 75 ℃; adding 100 parts by weight of modifying groupAdjusting the pH value of the resin liquid to 6.2-6.8, and reacting for 30min at 80 ℃; adding 200 parts by weight of modified matrix resin glue solution and 1-10 parts by weight of modified enzymatic hydrolysis lignin, adjusting the pH value to 7.8-8.2, reacting at 95 ℃ for 30min, and cooling to 50 ℃ to obtain modified impregnating resin glue solution; immersing the glue solution into a supercritical dryer storing absolute ethyl alcohol, and introducing liquid CO2Performing solvent replacement to remove formaldehyde, acetaldehyde and ethanol in the glue solution to obtain modified impregnating resin;
preparation of wear-resistant paper
1) Dipping and gluing the base paper in modified dipping resin;
2) uniformly spraying the composite reinforced powder on the wear-resistant surface of the impregnated paper;
3) drying to obtain the wear-resistant paper.
2. The method of claim 1, wherein the base paper is made from 100% bleached sulfite softwood pulp having a freeness of 36 ° SR to 38 ° SR and a basis weight of 18g/m2-25g/m2。
3. A method of manufacturing according to claim 1, wherein the total amount of said dip coating is 250-550%.
4. The production method according to claim 1, wherein the amount of the composite reinforcing powder added is 10g/m2-20g/m2。
5. The method of claim 1, wherein the drying process is performed in four stages, wherein the first stage drying temperature is 115 ℃ to 120 ℃, the second stage drying temperature is 125 ℃ to 130 ℃, the third stage drying temperature is 135 ℃ to 140 ℃, and the fourth stage drying temperature is 120 ℃ to 125 ℃.
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