阅读说明：本技术 一种防静电抗菌型装饰纸的制备方法 (Preparation method of anti-static antibacterial decorative paper ) 是由 陈关荣 于 2019-09-28 设计创作，主要内容包括：本发明公开了一种防静电抗菌型装饰纸的制备方法,属于装饰品制备技术领域。本发明将硫化钠与乙酸锌反应生成硫化锌,将硫酸钛与氨水反应生成,再加入硫化锌高温焙烧生成二氧化钛、氧化锌纳米级颗粒,与装饰纸的接触面积大大提高,加强超细粉与原纸材料的粘结吸附程度,利用二氧化钛良好的力学强度和光催化性能提高装饰纸的耐磨性能和抗菌性能；将棉花、农作物秸秆用酸液浸泡和碱液高温高压分解,分离其中的植物纤维成分,并将植物纤维水解,使植物纤维链长变短,将植物纤维与原纸的接触程度增加,并在高温高压条件下纤维表面生成大量的羧基、羟基基团,提高纤维成分的粘结程度,在静电条件下金属离子传导,散去产生的静电使装饰纸难以产生静电。(The invention discloses a preparation method of anti-static and anti-bacterial decorative paper, and belongs to the technical field of decoration preparation. According to the invention, sodium sulfide reacts with zinc acetate to generate zinc sulfide, titanium sulfate reacts with ammonia water to generate titanium dioxide and zinc oxide nano-grade particles, and then zinc sulfide is added for high-temperature roasting to generate titanium dioxide and zinc oxide nano-grade particles, so that the contact area with decorative paper is greatly increased, the bonding adsorption degree of ultrafine powder and raw paper material is enhanced, and the wear resistance and antibacterial property of the decorative paper are improved by utilizing the good mechanical strength and photocatalytic property of titanium dioxide; the method comprises the steps of soaking cotton and crop straws in acid liquor, decomposing the cotton and crop straws with alkali liquor at high temperature and high pressure, separating plant fiber components, hydrolyzing the plant fibers to shorten the chain length of the plant fibers, increasing the contact degree of the plant fibers and base paper, generating a large amount of carboxyl and hydroxyl groups on the fiber surface under the conditions of high temperature and high pressure, improving the bonding degree of the fiber components, conducting metal ions under the condition of static electricity, and dissipating the generated static electricity to enable decorative paper to be difficult to generate static electricity.)

1. A preparation method of anti-static antibacterial decorative paper is characterized by comprising the following specific preparation steps:

putting the thermal hydrolysis reaction liquid, cellulase and self-made nano powder into an enzymolysis tank, uniformly mixing, placing the enzymolysis tank in a greenhouse at the indoor temperature of 25-28 ℃, standing for 12-14 hours to prepare an enzymolysis reaction liquid, uniformly mixing the enzymolysis reaction liquid, caprolactam, diethylene glycol and an ethanol solution with the mass fraction of 20-25% to prepare an organic mixed liquid, coating the organic mixed liquid on base paper, standing for 40-50 minutes, placing the base paper in an oven, drying for 3-4 hours at the temperature of 80-85 ℃, and discharging to obtain the anti-static antibacterial decorative paper;

the specific preparation steps of the thermal hydrolysis reaction liquid are as follows:

(1) putting cotton and crop straws into an oven, drying for 60-80 min at the temperature of 70-80 ℃, putting the dried cotton and crop straws into a crusher, crushing to obtain a dried material, putting the dried material and 8-12% hydrochloric acid solution by mass into a beaker, and stirring for 2-3 h at the rotating speed of 300-400 r/min by using a stirrer to obtain acidic slurry;

(2) adding the acidic slurry into a reaction kettle, dropwise adding 8-12% by mass of sodium hydroxide solution into the reaction kettle to adjust the pH value to 11-12, filling nitrogen into the reaction kettle to increase the pressure in the reaction kettle to 0.8-1.2 MPa, increasing the temperature in the reaction kettle to 130-150 ℃, reacting at constant temperature and constant pressure for 60-80 min, dropwise adding 6-10% by mass of acetic acid solution to adjust the pH value to be neutral, and thus obtaining a thermal hydrolysis reaction solution;

the specific preparation steps of the self-made nano powder are as follows:

(1) putting sodium sulfide and zinc acetate into a stirrer to be uniformly mixed to obtain a mixed material, putting the mixed material and deionized water into a beaker according to the mass ratio of 1:20, stirring for 30-40 min at the rotating speed of 300-400 r/min by using the stirrer, placing the beaker into an inner container of a hydrothermal kettle after stirring, raising the temperature in the inner container to 70-80 ℃, oscillating at constant temperature for 10-12 h, and performing suction filtration after oscillating to obtain a reaction solid product;

(2) putting titanium sulfate and deionized water into a beaker, preparing a mixed solution by using a stirring device at the rotating speed of 500-600 r/min for 30-40 min, dropwise adding 6-10% of ammonia water into the beaker, continuously stirring for 40-50 min to obtain mixed slurry, adding a reaction solid product accounting for 8-12% of the mass of the mixed slurry into the beaker, and uniformly mixing to obtain a solid-liquid mixture;

(3) putting the solid-liquid mixture and ammonia water with the mass fraction of 10-15% into a three-neck flask, uniformly mixing to obtain a reaction emulsion, putting the three-neck flask into a water bath kettle with the water bath temperature of 70-75 ℃, heating at a constant temperature for 12-14 h, filtering after heating to obtain a filter cake, sequentially cleaning the filter cake with hydrogen peroxide and distilled water for 3-5 times, putting the filter cake into a muffle furnace, raising the temperature in the muffle furnace to 630-650 ℃, roasting at the constant temperature for 100-120 min, and grinding after roasting to obtain the self-made nano powder.

2. The method for preparing the antistatic antibacterial decorative paper according to claim 1, wherein the method comprises the following steps: preferably, the thermal hydrolysis reaction liquid is 20-24 parts by weight, the cellulase is 1.0-1.4 parts by weight, and the homemade nano powder is 7-10 parts by weight.

3. The method for preparing the antistatic antibacterial decorative paper according to claim 1, wherein the method comprises the following steps: preferably, the enzymolysis reaction solution comprises, by weight, 10-12 parts of caprolactam, 1-2 parts of caprolactam, 4-5 parts of diethylene glycol and 20-25 parts of an ethanol solution with the mass fraction of 20-25%.

4. The method for preparing the antistatic antibacterial decorative paper according to claim 1, wherein the method comprises the following steps: the mass ratio of the cotton to the crop straws in the specific preparation step (1) of the pyrohydrolysis reaction solution is 5: 1.

5. The method for preparing the antistatic antibacterial decorative paper according to claim 1, wherein the method comprises the following steps: the mass ratio of the dry material to the hydrochloric acid solution with the mass fraction of 8-12% in the specific preparation step (1) of the thermal hydrolysis reaction liquid is 1: 5.

6. The method for preparing the antistatic antibacterial decorative paper according to claim 1, wherein the method comprises the following steps: the mass ratio of the sodium sulfide to the zinc acetate in the specific preparation step (1) of the self-made nano powder is 1: 3.

7. the method for preparing the antistatic antibacterial decorative paper according to claim 1, wherein the method comprises the following steps: the mass ratio of the titanium sulfate to the deionized water in the specific preparation step (2) of the self-made nano powder is 1: 10.

8. The method for preparing the antistatic antibacterial decorative paper according to claim 1, wherein the method comprises the following steps: specifically, in the step (2), ammonia water with the mass fraction of 6-10% is added dropwise into the beaker, and the mass of the ammonia water is 12-16% of the mass of the mixed solution.

9. The method for preparing the antistatic antibacterial decorative paper according to claim 1, wherein the method comprises the following steps: the mass ratio of the solid-liquid mixture to 10-15% of ammonia water in the specific preparation step (3) of the self-made nano powder is 15: 1.

Technical Field

The invention discloses a preparation method of anti-static and anti-bacterial decorative paper, and belongs to the technical field of decoration preparation.

Background

Decorative paper is an essential raw material in many building material products, such as low-pressure plates and high-pressure plates used for furniture and cabinets, and also fire-proof plates, floors and the like. The decorative paper is placed under the surface paper in the product structure, and mainly plays the roles of providing decoration of patterns and covering for preventing the seepage of bottom glue solution. This layer requires paper with good hiding power, impregnation and printing properties. The decorative paper requires smooth surface, good absorptivity and adaptability, even hue required by ground color and bright color required by color.

Decorative papers are classified into various categories, which can be classified into various categories according to their basis weights and uses. Quantitatively dividing according to decorative paper: tissue paper with a basis weight of less than or equal to 30g/m²(ii) a Decorative paper (titanium white paper) with the quantitative ratio of more than or equal to 40g/m²At a rate of 70 to 120g/m²Mainly comprises the following steps. According to the application: the Baoli paper-tissue paper has wood grains printed on the surface, is used for veneering MDF, HDF and plywood, and needs an adhesive when being veneered and needs to be coated after being veneered. The gorgeous paper-tissue paper is printed and coated on the paper surface, is used for the facing of MDF, HDF and plywood, an adhesive is used for facing, and the coating is not needed after the facing, and is used for places with low requirements on wear resistance. The pre-painted paper, namely the decorative paper, is printed with wood grains, is soaked or coated with a small amount of resin, has the resin content of 20-60 percent, is used for MDF facing with low ration, is used for edge banding with high ration, needs to apply an adhesive during facing, is not generally coated after facing, and has higher wear resistance than gorgeous paper. The low-pressure melamine impregnated paper, namely decorative paper, is printed with wood grains and impregnated with low-pressure melamine resin, wherein the resin content is 130-150 percent. The resin content is 70-100% for the reinforced wood floor, and the wear resistance depends on the surface paper. High-pressure melamine impregnated paper, namely decorative paper, is printed with wood grains, is impregnated with high-pressure melamine resin, contains 60-100 percent of resin, is used for manufacturing decorative laminated boards, and has abrasion resistance depending on surface paper. The prior packing paper has poor antibacterial and antistatic performances and poor wear resistance.

The antibacterial and mildewproof agents are mainly divided into inorganic antibacterial and mildewproof agents and organic antibacterial and mildewproof agents. The inorganic antibacterial agent is obtained by fixing metals such as silver, copper and zinc or ions thereof on the surface of a porous material such as zeolite and silica gel by physical adsorption or ion exchange, etc. by utilizing the antibacterial ability of the metals such as silver, copper and zinc, etc., and then adding the antibacterial agent to a product. The patent: CN2556247Y provides a method for preparing antibacterial impregnated bond paper, the adopted material is nano titanium oxide or nano zinc oxide, and the material has certain antibacterial property, but the strength is only 1/1000 of that of nano silver material.

In areas such as machine rooms and electronic equipment, static hazards are large, equipment damage and fire disasters are easily caused by static electricity, faults or misoperation of the electronic equipment are caused, electromagnetic interference is caused, integrated circuits and precise electronic components are punctured, and explosion and fire disasters are easily caused in production places with many flammable and explosive products or dust and oil mist. Therefore, effective antistatic is particularly important today in the ubiquitous presence of electronic products.

The surface resistance of the antistatic plate is generally 10⁷～10⁹Ohm is only a thin layer, needs to be adhered to other composite materials, is troublesome to use and high in cost, and has fire resistance and water resistance which are difficult to meet the living requirements; important facilities such as airplanes, spacecraft and the like cannot meet the safety requirement of normal operation by simple surface antistatic. On the premise of not changing the high density and other excellent performances of the existing decorative plate, the traditional process is difficult to enable the decorative plate to reach the antistatic level, although the surface resistance can reach the standard, the bulk resistance is not feasible, and the difficulty of breaking through the prior art is achieved.

Therefore, the invention of decorative paper with good antibacterial, antistatic and wear-resisting properties is necessary for the technical field of ornament preparation.

Disclosure of Invention

The technical problems to be solved by the invention are as follows: aiming at the defects of poor antibacterial and antistatic performances and poor wear resistance of the existing decorative paper, the preparation method of the antistatic antibacterial decorative paper is provided.

In order to solve the technical problems, the invention adopts the technical scheme that:

the preparation method of the anti-static antibacterial decorative paper comprises the following steps:

putting the thermal hydrolysis reaction liquid, cellulase and self-made nano powder into an enzymolysis tank, uniformly mixing, placing the enzymolysis tank in a greenhouse at the indoor temperature of 25-28 ℃, standing for 12-14 hours to prepare an enzymolysis reaction liquid, uniformly mixing the enzymolysis reaction liquid, caprolactam, diethylene glycol and an ethanol solution with the mass fraction of 20-25% to prepare an organic mixed liquid, coating the organic mixed liquid on base paper, standing for 40-50 minutes, placing the base paper in an oven, drying for 3-4 hours at the temperature of 80-85 ℃, and discharging to obtain the anti-static antibacterial decorative paper;

the specific preparation steps of the thermal hydrolysis reaction liquid are as follows:

(1) putting cotton and crop straws into an oven, drying for 60-80 min at the temperature of 70-80 ℃, putting the dried cotton and crop straws into a crusher, crushing to obtain a dried material, putting the dried material and 8-12% hydrochloric acid solution by mass into a beaker, and stirring for 2-3 h at the rotating speed of 300-400 r/min by using a stirrer to obtain acidic slurry;

(2) adding the acidic slurry into a reaction kettle, dropwise adding 8-12% by mass of sodium hydroxide solution into the reaction kettle to adjust the pH value to 11-12, filling nitrogen into the reaction kettle to increase the pressure in the reaction kettle to 0.8-1.2 MPa, increasing the temperature in the reaction kettle to 130-150 ℃, reacting at constant temperature and constant pressure for 60-80 min, dropwise adding 6-10% by mass of acetic acid solution to adjust the pH value to be neutral, and thus obtaining a thermal hydrolysis reaction solution;

the specific preparation steps of the self-made nano powder are as follows:

(1) putting sodium sulfide and zinc acetate into a stirrer to be uniformly mixed to obtain a mixed material, putting the mixed material and deionized water into a beaker according to the mass ratio of 1:20, stirring for 30-40 min at the rotating speed of 300-400 r/min by using the stirrer, placing the beaker into an inner container of a hydrothermal kettle after stirring, raising the temperature in the inner container to 70-80 ℃, oscillating at constant temperature for 10-12 h, and performing suction filtration after oscillating to obtain a reaction solid product;

(2) putting titanium sulfate and deionized water into a beaker, preparing a mixed solution by using a stirring device at the rotating speed of 500-600 r/min for 30-40 min, dropwise adding 6-10% of ammonia water into the beaker, continuously stirring for 40-50 min to obtain mixed slurry, adding a reaction solid product accounting for 8-12% of the mass of the mixed slurry into the beaker, and uniformly mixing to obtain a solid-liquid mixture;

(3) putting the solid-liquid mixture and ammonia water with the mass fraction of 10-15% into a three-neck flask, uniformly mixing to obtain a reaction emulsion, putting the three-neck flask into a water bath kettle with the water bath temperature of 70-75 ℃, heating at a constant temperature for 12-14 h, filtering after heating to obtain a filter cake, sequentially cleaning the filter cake with hydrogen peroxide and distilled water for 3-5 times, putting the filter cake into a muffle furnace, raising the temperature in the muffle furnace to 630-650 ℃, roasting at the constant temperature for 100-120 min, and grinding after roasting to obtain the self-made nano powder.

Preferably, the thermal hydrolysis reaction liquid is 20-24 parts by weight, the cellulase is 1.0-1.4 parts by weight, and the homemade nano powder is 7-10 parts by weight.

Preferably, the enzymolysis reaction solution comprises, by weight, 10-12 parts of caprolactam, 1-2 parts of caprolactam, 4-5 parts of diethylene glycol and 20-25 parts of an ethanol solution with the mass fraction of 20-25%.

The mass ratio of the cotton to the crop straws in the specific preparation step (1) of the pyrohydrolysis reaction solution is 5: 1.

The mass ratio of the dry material to the hydrochloric acid solution with the mass fraction of 8-12% in the specific preparation step (1) of the thermal hydrolysis reaction liquid is 1: 5.

The mass ratio of the sodium sulfide to the zinc acetate in the specific preparation step (1) of the self-made nano powder is 1: 3.

the mass ratio of the titanium sulfate to the deionized water in the specific preparation step (2) of the self-made nano powder is 1: 10.

Specifically, in the step (2), ammonia water with the mass fraction of 6-10% is added dropwise into the beaker, and the mass of the ammonia water is 12-16% of the mass of the mixed solution.

The mass ratio of the solid-liquid mixture to 10-15% of ammonia water in the specific preparation step (3) of the self-made nano powder is 15: 1.

The beneficial technical effects of the invention are as follows:

(1) firstly, mixing sodium sulfide and zinc acetate, adding the mixture into water, heating to prepare a reaction solid product, adding titanium sulfate into deionized water, dropwise adding ammonia water to react to prepare a mixed slurry, mixing the mixed slurry and the reaction solid product to prepare a solid-liquid mixture, mixing the solid-liquid mixture with the ammonia water, heating to react after mixing, filtering after reaction to obtain filter residue, washing, roasting at high temperature to prepare self-made nano powder, mixing and drying cotton and crops, soaking with hydrochloric acid to prepare an acidic slurry, adjusting the pH value to be alkaline, performing high-temperature and high-pressure reaction to prepare a thermal hydrolysis reaction liquid, mixing the thermal hydrolysis reaction liquid with cellulase and the self-made nano powder for enzymolysis to prepare an enzymolysis reaction liquid, mixing the enzymolysis reaction liquid with organic solutions, coating base paper on the base paper and drying to obtain the anti-static antibacterial decorative paper, and reacting the invention with the sodium sulfide and the zinc acetate to generate the zinc sulfide, titanium sulfate and ammonia water react to generate titanium dioxide and zinc oxide nano-grade particles, zinc sulfide is added to be roasted at high temperature to generate titanium dioxide and zinc oxide nano-grade particles, the generated titanium dioxide/zinc oxide composite material is in an ultrafine powder structure, the dispersibility is easy to improve, the contact area with decorative paper is greatly improved, the bonding adsorption degree of the ultrafine powder and a raw paper material is enhanced, a layer of titanium dioxide and zinc oxide film layer covers the surface of the decorative paper, and the wear resistance and the antibacterial performance of the decorative paper are improved by utilizing the good mechanical strength and the good photocatalytic performance of the titanium dioxide;

(2) the invention soaks cotton and crop straw with acid liquor and decomposes with alkali liquor under high temperature and high pressure, separates plant fiber component therein, and hydrolyzes plant fiber, makes the plant fiber chain length shorten, increases the contact degree of plant fiber and base paper, and generates a large amount of carboxyl and hydroxyl groups on the fiber surface under the condition of high temperature and high pressure, improves the bonding degree of fiber component, and utilizes plant fiber to strengthen the bonding degree of each component on the surface of decorative paper and base paper, thereby enhancing the wear resistance in decorative paper, simultaneously metal ions are complexed in the fiber surface, the metal ions conduct under the condition of static electricity, and the static electricity generated is dispersed, so that the decorative paper is difficult to generate static electricity, and the invention has wide application prospect.

Detailed Description

Sodium sulfide and zinc acetate are mixed according to the mass ratio of 1: 3, putting the mixture and deionized water into a beaker according to the mass ratio of 1:20, stirring the mixture for 30-40 min at the rotating speed of 300-400 r/min by using a stirrer, putting the beaker into an inner container of a hydrothermal kettle after stirring, raising the temperature in the inner container to 70-80 ℃, oscillating the mixture at a constant temperature for 10-12 h, and performing suction filtration after oscillation to obtain a reaction solid product; putting titanium sulfate and deionized water into a beaker according to the mass ratio of 1:10, stirring for 30-40 min at the rotating speed of 500-600 r/min by using a stirring device to prepare a mixed solution, dropwise adding ammonia water with the mass fraction of 6-10% and the mass fraction of 12-16% of the mixed solution into the beaker, continuously stirring for 40-50 min to prepare mixed slurry, adding a reaction solid product with the mass fraction of 8-12% of the mixed slurry into the beaker, and uniformly mixing to prepare a solid-liquid mixture; putting the solid-liquid mixture and 10-15% ammonia water in a mass ratio of 15:1 into a three-neck flask, uniformly mixing to obtain a reaction emulsion, putting the three-neck flask into a water bath kettle with a water bath temperature of 70-75 ℃, heating at a constant temperature for 12-14 h, filtering after heating to obtain a filter cake, sequentially cleaning the filter cake with hydrogen peroxide and distilled water for 3-5 times, putting the filter cake into a muffle furnace, raising the temperature in the muffle furnace to 630-650 ℃, roasting at the constant temperature for 100-120 min, and grinding after roasting to obtain self-made nano powder for later use; putting cotton and crop straws into an oven according to a mass ratio of 5:1, drying for 60-80 min at the temperature of 70-80 ℃, putting the dried materials into a crusher to crush the materials to obtain dried materials, putting the dried materials and 8-12% hydrochloric acid solution into a beaker according to a mass ratio of 1:5, and stirring for 2-3 h at a rotating speed of 300-400 r/min by using a stirrer to obtain acid slurry; adding the acidic slurry into a reaction kettle, dropwise adding 8-12% by mass of sodium hydroxide solution into the reaction kettle to adjust the pH value to 11-12, filling nitrogen into the reaction kettle to increase the pressure in the reaction kettle to 0.8-1.2 MPa, increasing the temperature in the reaction kettle to 130-150 ℃, reacting at constant temperature and constant pressure for 60-80 min, dropwise adding 6-10% by mass of acetic acid solution to adjust the pH value to be neutral, and thus obtaining a thermal hydrolysis reaction solution; 20-24 parts of the thermal hydrolysis reaction liquid, 1.0-1.4 parts of cellulase and 7-10 parts of self-made nano powder are put into an enzymolysis tank to be uniformly mixed, the enzymolysis tank is placed in a greenhouse with the indoor temperature of 25-28 ℃ to be kept stand for 12-14 hours to prepare enzymolysis reaction liquid, 10-12 parts of enzymolysis reaction liquid, 1-2 parts of caprolactam, 4-5 parts of diethylene glycol and 20-25 parts of ethanol solution with the mass fraction of 20-25% are uniformly mixed to prepare organic mixed liquid, the organic mixed liquid is coated on base paper and kept stand for 40-50 minutes, the base paper is placed in a drying oven, drying is carried out at the temperature of 80-85 ℃ for 3-4 hours, and then the anti-static antibacterial decorative paper is obtained.