CN114592378B - Temperature-variable anti-counterfeiting paperboard and production process thereof - Google Patents

Temperature-variable anti-counterfeiting paperboard and production process thereof Download PDF

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Publication number
CN114592378B
CN114592378B CN202210208506.6A CN202210208506A CN114592378B CN 114592378 B CN114592378 B CN 114592378B CN 202210208506 A CN202210208506 A CN 202210208506A CN 114592378 B CN114592378 B CN 114592378B
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temperature
pulp
counterfeiting
paper layer
paperboard
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CN114592378A (en
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吴小伟
叶景桥
卿贵庭
代伟
曾庆芳
蒋成
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Zhejiang Yishu Paper Group Co ltd
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Zhejiang Yishu Paper Group Co ltd
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
    • D21B1/00—Fibrous raw materials or their mechanical treatment
    • D21B1/04—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres
    • D21B1/12—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by wet methods, by the use of steam
    • D21B1/30—Defibrating by other means
    • D21B1/34—Kneading or mixing; Pulpers
    • D21B1/345—Pulpers
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21D—TREATMENT OF THE MATERIALS BEFORE PASSING TO THE PAPER-MAKING MACHINE
    • D21D1/00—Methods of beating or refining; Beaters of the Hollander type
    • D21D1/20—Methods of refining
    • D21D1/30—Disc mills
    • D21D1/303—Double disc mills
    • 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
    • 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
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/42—Ribbons or strips
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
    • D21H21/48—Elements suited for physical verification, e.g. by irradiation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/64—Paper recycling

Abstract

The invention relates to the technical field of card paper production, in particular to a temperature-variable anti-counterfeiting card paper and a production process thereof; wherein, the pulp used by the anti-counterfeiting bottom paper layer consists of 65 to 80 weight percent of hardwood pulp and the balance of coniferous chemical sulfate pulp; the pulp used for the core paper layer consists of 55 to 70 percent of maple chemical mechanical pulp and the balance of birch chemical mechanical pulp; the pulp used by the anti-counterfeiting surface paper layer consists of 20 to 30 percent of softwood chemical sulfate pulp and the balance of eucalyptus chemical mechanical pulp; the paperboard produced by the invention has the advantages of quick temperature-dependent color development effect, good anti-counterfeiting performance and effective widening of the application field; moreover, only a small amount of temperature-change fibers are added into the sizing agent used for the bottom paper layer and the sizing agent used for the surface paper, so that the purpose of saving the usage amount of the temperature-change fibers is achieved, and the purpose of saving the cost is also achieved; in addition, the paperboard prepared by the invention has better antibacterial performance, the service life of the paperboard is effectively prolonged, and the quality of the paperboard is also ensured.

Description

Temperature-variable anti-counterfeiting paperboard and production process thereof
Technical Field
The invention relates to the technical field of paperboard production, in particular to a temperature-variable anti-counterfeiting paperboard and a production process thereof.
Background
Paperboard is a generic term for a type of thick paper between paper and paperboard, weighing about 120 grams or more per square meter, and is used for postcards, cards, album sheets, and the like. The paper surface of the paperboard is fine, smooth, firm and wear-resistant. Depending on the application, the cardboard has different properties, such as good water resistance, and appropriate flexibility.
The existing card paper has certain mechanical property, but the existing card paper has no anti-counterfeiting property, so that the application range of the existing card paper is relatively limited. Moreover, the antibacterial performance of the antibacterial agent is relatively poor, and the service life of the antibacterial agent is shortened to a certain extent. Therefore, it is an urgent technical problem to be solved by those skilled in the art to provide a temperature-variable anti-counterfeit cardboard and a production process thereof.
Disclosure of Invention
The invention aims to provide a temperature-variable anti-counterfeiting paperboard and a production process thereof, the produced paperboard has the advantages of quick color development effect, good anti-counterfeiting performance and effective widening of the application field; meanwhile, only a small amount of temperature-change fibers are added into the sizing agent used for the bottom paper layer and the sizing agent used for the surface paper, so that the purpose of saving the usage amount of the temperature-change fibers is achieved, and the purpose of saving the cost is also achieved; in addition, the paperboard prepared by the invention has better antibacterial performance, the service life of the paperboard is effectively prolonged, and the quality of the paperboard is also ensured.
In order to achieve the purpose, the invention provides the following technical scheme:
a temperature-variable anti-counterfeiting card paper comprises an anti-counterfeiting base paper layer, a core paper layer and an anti-counterfeiting surface paper layer from bottom to top in sequence;
the pulp used by the anti-counterfeiting bottom paper layer consists of 65-80 wt% of hardwood pulp and the balance of coniferous chemical sulfate pulp;
the pulp used by the core paper layer consists of 55-70% of maple chemical mechanical pulp and the balance of birch chemical mechanical pulp;
the pulp used by the anti-counterfeiting surface paper layer consists of 20 to 30 percent of softwood chemical sulfate pulp and the balance of eucalyptus chemical mechanical pulp.
Furthermore, the anti-counterfeiting surface paper layer has the basis weight of 27-32 g/m 2 The ration of the anti-counterfeiting bottom paper layer is 26 to 30g/m 2 。
A production process of temperature-variable anti-counterfeiting paperboard comprises the following steps:
firstly, respectively mixing a proper amount of hardwood pulp and coniferous chemical sulfate pulp, putting the mixture into a hydrapulper through a chain plate machine, then adding a proper amount of temperature-variable fibers into the hydrapulper, performing pulping treatment on the obtained material through a double-disc grinder after the pulping is finished, and sending the pulp after the pulping into a pulping tank to prepare anti-counterfeiting bottom paper layer pulp;
step two, respectively mixing a proper amount of maple chemical mechanical pulp and birch chemical mechanical pulp, putting the mixture into a hydrapulper through a chain plate machine for pulping, then pulping the pulp subjected to pulping through a double-disc grinder, and sending the pulp subjected to pulping to a pulping tank to prepare core paper layer pulp;
step three, respectively mixing a proper amount of needle-leaved wood chemical sulfate pulp and eucalyptus chemical mechanical pulp, putting the mixture into a hydrapulper through a chain plate machine, adding a proper amount of temperature-variable fibers into the hydrapulper, performing disintegration, then performing pulp grinding treatment on the obtained material through a double-disc grinder after the disintegration is finished, and sending the pulp after the pulp grinding into a pulp forming pool to prepare anti-counterfeiting surface paper layer pulp;
step four, diluting the obtained anti-counterfeiting bottom paper layer slurry and anti-counterfeiting surface paper layer slurry by a fan pump, and then feeding the diluted anti-counterfeiting bottom paper layer slurry and anti-counterfeiting surface paper layer slurry into a bottom paper layer pulp box and a surface paper layer pulp box; diluting the core paper layer slurry by a fan pump and then feeding the diluted core paper layer slurry into a core paper layer head box; wherein, a top net former arranged behind a bottom paper layer pulp flow box carries out reverse dehydration treatment to form paper, and simultaneously, a proper amount of sizing agent, additive and antibacterial agent are added at the feed inlet of a fan pump to be uniformly mixed;
step five, spraying starch on the formed paper, and compounding an anti-counterfeiting bottom paper layer at the bottom of the core paper layer and an anti-counterfeiting surface paper layer at the top of the core layer; and pressing, dehydrating and drying the obtained paper, then sequentially carrying out calendaring treatment on the paper by a hot roller soft calendar, and carrying out slitting treatment after rolling by a rolling machine to obtain the temperature-variable anti-counterfeiting paperboard finished product.
Furthermore, the more actual colors of the products in the first step, the second step and the third step need to add no pigment or pigment with corresponding colors.
Furthermore, the usage amount of the temperature-variable fibers is 1.8-2.5% of the total mass of the mixed pulp in the pulper in the first step and the pulper in the second step; and the mass concentration of the slurry after the disintegration treatment in the first step and the second step is 4.5-6.8%.
Furthermore, the preparation method of the temperature-variable fiber comprises the following steps:
cleaning polyvinyl alcohol slices, then putting the polyvinyl alcohol slices into a proper amount of distilled water at the temperature of 95-99 ℃, and obtaining spinning stock solution with the concentration of 35-50% after the polyvinyl alcohol is completely dissolved; the obtained spinning solution is output by a metering pump and sprayed out by a spinneret plate to enter a spinning channel; industrial nitrogen with temperature-variable powder (manufactured by Beijing Chenlei science and technology Co., ltd.) is fed into a spinning channel from an air inlet, blown out from an air outlet, and the blown-out spinning stock solution is solidified and molded, and then the obtained temperature-variable fiber crude product is treated by a godet roller, a hot press roller, a formaldehyde condensation treatment bath, an ultraviolet radiation area, a water bath and a drying roller in sequence, and then the temperature-variable fiber finished product is obtained by collection.
Furthermore, the reversible color change temperature range of the temperature change powder is 50-60 ℃, the temperature change powder is white at normal temperature, the white temperature change powder is dissolved after being heated, the paper is recovered to the original color, and the addition amount of the temperature change powder is 2.5-3.5% of that of the polyvinyl alcohol.
Furthermore, the sizing agent is any one of AKD and ASA neutral sizing agents, and the dosage of the sizing agent is 1.2-1.8% of the mass of the corresponding sizing agent.
Furthermore, the additive is aluminum sulfate, and the dosage of the aluminum sulfate is 1.0-1.6% of the mass of the corresponding slurry.
Furthermore, the dosage of the antibacterial agent is 3.6-4.5% of the mass of the corresponding slurry, and the preparation method of the antibacterial agent comprises the following steps:
i, dispersing cerium oxide with the average particle size of 6-15 nm in a proper amount of distilled water at the temperature of 70-85 ℃ according to the solid-to-liquid ratio of 0.08-0.12 g/mL, then adding 4-8% by mass of hexamethylene diamine into the obtained dispersion, and carrying out magnetic stirring reaction for 5-8 h; after the reaction is finished, filtering out solid materials in the reaction product, washing the reaction product for 2 to 3 times by using distilled water, washing the reaction product for 2 to 3 times by using acetone, and then drying the reaction product to store the obtained solid materials for later use;
II, putting the obtained solid material into a proper amount of distilled water with the temperature of 60-75 ℃ according to the solid-liquid ratio of 0.06-0.1 g/mL, then supplementing polyhexamethylene guanidine with the mass of 15-25% of the solid material into the distilled water, carrying out heat preservation stirring reaction for 3-6 hours, then carrying out filtration and drying treatment on the solid material, and storing the solid material for later use;
and III, soaking the obtained solid powder in a proper amount of 40-60 mg/mL butyl p-hydroxybenzoate acetone solution according to a solid-to-liquid ratio of 0.06-0.15 g/mL, oscillating the solution at an oscillation speed of 350-450 r/min for 10-15 h, centrifuging to remove supernatant, and drying the obtained powdery solid to obtain the finished product of the antibacterial additive.
Furthermore, the using amount of the starch is 0.8-1.2% of the mass of the paper; and the temperature of the upper roller is set to be 150-160 ℃ during calendaring treatment, and the pressure of the pressurizing line is set to be 45-60N/cm.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention takes polyvinyl alcohol as raw material and prepares the polyvinyl alcohol into spinning solution with certain concentration, then the spinning solution and the temperature-change powder enter a spinning shaft together, and finally the obtained spinning is solidified and molded to prepare a temperature-change fiber crude product. And treating the obtained crude product by a godet roller, a hot press roller and other processes in sequence to finally prepare a temperature-variable fiber finished product. The temperature-variable fiber is used as the raw material for preparing the anti-counterfeiting base paper layer and the anti-counterfeiting surface paper layer, so that the prepared anti-counterfeiting base paper layer and the anti-counterfeiting surface paper layer have good temperature-variable effect. The prepared paperboard product is white at normal temperature, and changes into the original color of paper when heated to 50-60 ℃. The prepared paperboard product has the advantages of quick temperature-changing color development effect, good anti-counterfeiting performance and effective widening of the application field. In addition, only a small amount of temperature-change fibers are added into the sizing agent used for the bottom paper layer and the sizing agent used for the surface paper, so that the purpose of saving the usage amount of the temperature-change fibers is achieved, and the purpose of saving the cost is also achieved.
2. According to the invention, the nano-scale cerium oxide and hexamethylene diamine are used as raw materials, the hexamethylene diamine and the cerium oxide are connected by chemical bonds with larger bond energy through the interaction of the hexamethylene diamine and the surface of the cerium oxide, and then the hexamethylene diamine is used as a medium to effectively graft the polyhexamethylene guanidine on the surface of the cerium oxide. The cerium oxide grafted by the polyhexamethylene guanidine is immersed in an acetone solution of butyl p-hydroxybenzoate, so that the butyl p-hydroxybenzoate in the cerium oxide can be effectively loaded on the surface of the cerium oxide, and finally, the prepared antibacterial agent has good antibacterial performance under the synergistic cooperation of the butyl p-hydroxybenzoate and the polyhexamethylene guanidine, the service life of the paperboard is effectively prolonged, and the quality of the paperboard is guaranteed.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A temperature-variable anti-counterfeiting card paper comprises an anti-counterfeiting base paper layer, a core paper layer and an anti-counterfeiting surface paper layer from bottom to top in sequence;
the pulp used by the anti-counterfeiting bottom paper layer consists of 65wt% of hardwood pulp and the balance of coniferous chemical sulfate pulp;
the pulp used for the core paper layer consists of 55 percent of maple chemical mechanical pulp and the balance of birch chemical mechanical pulp;
the pulp used for the anti-counterfeiting surface paper layer consists of 20 percent of softwood chemical sulfate pulp and the balance of eucalyptus chemimechanical pulp.
The anti-counterfeiting surface paper layer has a fixed weight of 27g/m 2 The anti-counterfeiting bottom paper layer has the fixed weight of 26g/m 2 。
A production process of temperature-variable anti-counterfeiting paperboard comprises the following steps:
firstly, respectively mixing a proper amount of hardwood pulp and coniferous chemical sulfate pulp, putting the mixture into a hydrapulper through a chain plate machine, then adding a proper amount of temperature-variable fibers into the hydrapulper, performing pulping treatment on the obtained material through a double-disc grinder after the pulping is finished, and sending the pulp after the pulping into a pulping tank to prepare anti-counterfeiting bottom paper layer pulp;
step two, respectively mixing a proper amount of maple chemi-mechanical pulp and birch chemi-mechanical pulp, putting the mixture into a hydrapulper through a chain plate machine for pulping, then carrying out pulp grinding treatment on the pulp obtained after pulping through a double-disc grinder, and sending the pulp obtained after pulping to a pulp forming pool to obtain core paper layer pulp;
step three, respectively mixing a proper amount of needle-leaved wood chemical sulfate pulp and eucalyptus chemical mechanical pulp, putting the mixture into a hydrapulper through a chain plate machine, adding a proper amount of temperature-variable fibers into the hydrapulper, performing pulping treatment on the obtained material through a double-disc grinder after the pulping is finished, and sending the pulp after the pulping into a pulping pool to prepare anti-counterfeiting face paper layer pulp;
step four, respectively diluting the anti-counterfeiting bottom paper layer slurry and the anti-counterfeiting surface paper layer slurry by a fan pump, and then feeding the diluted anti-counterfeiting bottom paper layer slurry and anti-counterfeiting surface paper layer slurry into a bottom paper layer pulp box and a surface paper layer pulp box; diluting the core paper layer slurry by a fan pump and then feeding the diluted core paper layer slurry into a core paper layer slurry box; wherein, a top net former arranged behind a bottom paper layer pulp flow box carries out reverse dehydration treatment to form paper, and simultaneously, a proper amount of sizing agent, additive and antibacterial agent are added at the feed inlet of a fan pump to be uniformly mixed;
step five, spraying starch on the formed paper, and compounding an anti-counterfeiting bottom paper layer at the bottom of the core paper layer and an anti-counterfeiting surface paper layer at the top of the core layer; and pressing, dehydrating and drying the obtained paper, then sequentially performing calendaring treatment by a hot-roll soft calendar, and performing slitting treatment after winding by a winding machine to obtain the temperature-variable anti-counterfeiting paperboard finished product.
The usage amount of the temperature-change fibers is 1.8 percent of the total mass of the mixed pulp in the pulper in the first step and the pulper in the second step; and the mass concentration of the slurry after the disintegration treatment in the first step and the second step is 4.5 percent.
The preparation method of the temperature-variable fiber comprises the following steps:
cleaning polyvinyl alcohol slices, then putting the polyvinyl alcohol slices into a proper amount of distilled water at the temperature of 95 ℃, and obtaining spinning stock solution with the concentration of 35% after the polyvinyl alcohol is completely dissolved; the obtained spinning solution is output by a metering pump and sprayed out by a spinneret plate to enter a spinning channel; and (3) allowing the industrial nitrogen gas with the temperature change powder to enter a spinning channel from an air inlet, blowing out from an air outlet, solidifying and forming the blown-out spinning solution, sequentially treating the obtained temperature change fiber crude product by a godet roller, a hot press roller, a formal treatment bath, an ultraviolet radiation area, a water bath and a drying roller, and collecting to obtain a temperature change fiber finished product.
The reversible color change temperature range of the temperature change powder is 50 ℃, the temperature change powder is white at normal temperature, the white temperature change powder is dissolved after being heated, the paper is recovered to the original color, and the addition amount of the temperature change powder is 2.5 percent of that of the polyvinyl alcohol.
The sizing agent is AKD neutral sizing agent, and the dosage of the AKD neutral sizing agent is 1.2 percent of the mass of the corresponding sizing agent.
The additive is aluminum sulfate, and the dosage of the aluminum sulfate is 1.0 percent of the mass of the corresponding slurry.
The dosage of the antibacterial agent is 3.6 percent of the mass of the corresponding slurry, and the preparation method of the antibacterial agent comprises the following steps:
i, dispersing cerium oxide with the average particle size of 6nm in a proper amount of distilled water at the temperature of 70 ℃ according to the solid-to-liquid ratio of 0.08g/mL, adding hexamethylene diamine with the mass of 4% into the obtained dispersion, and carrying out magnetic stirring reaction for 5 hours; after the reaction is finished, filtering out the solid material, washing the solid material for 2 times by using distilled water, washing the solid material for 2 times by using acetone, and then drying the solid material to store the solid material for later use;
II, putting the obtained solid material into a proper amount of distilled water with the temperature of 60 ℃ according to the solid-liquid ratio of 0.06g/mL, then adding polyhexamethylene guanidine with the mass of 15% of the solid material into the distilled water, carrying out heat preservation and stirring reaction for 3 hours, filtering and drying the product, and storing the product for later use;
and III, soaking the obtained solid powder in a proper amount of 40mg/mL acetone solution of butyl p-hydroxybenzoate according to a solid-to-liquid ratio of 0.06g/mL, oscillating the powder at an oscillation speed of 350r/min for 10 hours, centrifuging the solution to remove supernatant, and drying the obtained powdery solid to obtain the finished product of the antibacterial additive.
The using amount of the starch is 0.8 percent of the mass of the paper; and the temperature of the upper roller is set to 150 ℃ during the calendaring treatment, and the pressure of the pressurizing line is set to 45N/cm.
Example 2
The production process of the temperature-variable anti-counterfeiting card paper is approximately similar to the technical scheme provided by the embodiment 1, and the main differences between the production process and the technical scheme are as follows:
the pulp used by the anti-counterfeiting bottom paper layer consists of 75wt% of hardwood pulp and the balance of coniferous chemical sulfate pulp;
the pulp used for the core paper layer consists of 65 percent of maple chemical mechanical pulp and the balance of birch chemical mechanical pulp;
the pulp used for the anti-counterfeiting surface paper layer consists of 25 percent of softwood chemical sulfate pulp and the balance of eucalyptus chemimechanical pulp.
The anti-counterfeiting surface paper layer has the fixed weight of 30g/m 2 The anti-counterfeiting bottom paper layer has the fixed weight of 28g/m 2 。
The usage amount of the temperature-change fiber is 2.0 percent of the total mass of the mixed pulp in the pulper in the first step and the pulper in the second step; and the mass concentration of the slurry after the disintegration treatment in the first step and the second step is 5.5 percent.
The preparation method of the temperature-variable fiber comprises the following steps:
cleaning polyvinyl alcohol slices, then putting the polyvinyl alcohol slices into a proper amount of distilled water at the temperature of 98 ℃, and obtaining spinning stock solution with the concentration of 45% after the polyvinyl alcohol is completely dissolved; the obtained spinning solution is output by a metering pump and sprayed out by a spinneret plate to enter a spinning channel; and (3) allowing the industrial nitrogen gas carrying temperature-change powder to enter a spinning channel from an air inlet, blowing out from an air outlet, solidifying and solidifying the blown-out spinning stock solution to form, sequentially passing the obtained temperature-change fiber crude product through a godet roller, a hot press roller, a formaldehyde condensation treatment bath, an ultraviolet radiation area, a water bath and a drying roller, and collecting to obtain a temperature-change fiber finished product.
The reversible color change temperature range of the temperature change powder is 55 ℃, the temperature change powder is white at normal temperature, the white temperature change powder is dissolved after being heated, the paper is recovered to the original color, and the addition amount of the white temperature change powder is 3.0 percent of that of polyvinyl alcohol.
The sizing agent is ASA neutral sizing agent, and the dosage of the ASA neutral sizing agent is 1.5 percent of the mass of the corresponding sizing agent.
The additive is aluminum sulfate, and the dosage of the aluminum sulfate is 1.3 percent of the mass of the corresponding slurry.
The dosage of the antibacterial agent is 4.0 percent of the mass of the corresponding slurry, and the preparation method of the antibacterial agent comprises the following steps:
i, dispersing cerium oxide with the average particle size of 10nm in a proper amount of distilled water at the temperature of 80 ℃ according to a solid-to-liquid ratio of 0.1g/mL, adding 6% by mass of hexamethylenediamine into the obtained dispersion, and carrying out magnetic stirring reaction for 7 hours; after the reaction is finished, filtering out the solid material, washing the solid material for 2 times by using distilled water, washing the solid material for 2 times by using acetone, and then drying the solid material to store the solid material for later use;
II, putting the obtained solid material into a proper amount of distilled water with the temperature of 70 ℃ according to the solid-to-liquid ratio of 0.08g/mL, then adding polyhexamethylene guanidine with the mass of 20% of the solid material into the distilled water, carrying out heat preservation and stirring reaction for 4 hours, filtering and drying the mixture, and storing the mixture for later use;
and III, soaking the obtained solid powder in a proper amount of 50mg/mL acetone solution of butyl p-hydroxybenzoate according to a solid-to-liquid ratio of 0.1g/mL, oscillating the solid powder at an oscillation speed of 400r/min for 12 hours, centrifuging the solution to remove supernatant, and drying the obtained powdery solid to obtain the finished product of the antibacterial additive.
The using amount of the starch is 1.0 percent of the mass of the paper; and the temperature of the upper roller during the calendering treatment is set to 155 ℃, and the pressure of the pressurizing line is set to 55N/cm.
Example 3
The production process of the temperature-change anti-counterfeiting paperboard is approximately similar to the technical scheme provided by the embodiment 1, and the main differences between the two are as follows:
the pulp used by the anti-counterfeiting bottom paper layer consists of 80wt% of hardwood pulp and the balance of coniferous chemical sulfate pulp;
the pulp used for the core paper layer consists of 70 percent of maple chemical mechanical pulp and the balance of birch chemical mechanical pulp;
the pulp used for the anti-counterfeiting surface paper layer consists of 30 percent of softwood chemical sulfate pulp and the balance of eucalyptus chemimechanical pulp.
The anti-counterfeiting surface paper layer has the fixed weight of 32g/m 2 The anti-counterfeiting bottom paper layer has the fixed weight of 30g/m 2 。
The usage amount of the temperature-change fiber is 2.5 percent of the total mass of the mixed pulp in the pulper in the first step and the pulper in the second step; and the mass concentration of the slurry after the disintegration treatment in the first step and the second step is 6.8 percent.
The preparation method of the temperature-variable fiber comprises the following steps:
cleaning polyvinyl alcohol slices, putting the polyvinyl alcohol slices into a proper amount of distilled water at the temperature of 99 ℃, and obtaining a spinning stock solution with the concentration of 50% after the polyvinyl alcohol is completely dissolved; the obtained spinning solution is output by a metering pump and sprayed out by a spinneret plate to enter a spinning channel; and (3) allowing the industrial nitrogen gas with the temperature change powder to enter a spinning channel from an air inlet, blowing out from an air outlet, solidifying and forming the blown-out spinning solution, sequentially treating the obtained temperature change fiber crude product by a godet roller, a hot press roller, a formal treatment bath, an ultraviolet radiation area, a water bath and a drying roller, and collecting to obtain a temperature change fiber finished product.
The reversible color change temperature range of the temperature change powder is 60 ℃, the temperature change powder is white at normal temperature, the white temperature change powder is dissolved after being heated, the paper is recovered to the original color, and the addition amount of the white temperature change powder is 3.5 percent of that of the polyvinyl alcohol.
The sizing agent is AKD neutral sizing agent, and the dosage of the AKD neutral sizing agent is 1.8 percent of the mass of the corresponding sizing agent.
The additive is aluminum sulfate, and the dosage of the aluminum sulfate is 1.6 percent of the mass of the corresponding slurry.
The dosage of the antibacterial agent is 4.5 percent of the mass of the corresponding slurry, and the preparation method of the antibacterial agent comprises the following steps:
i, dispersing cerium oxide with the average particle size of 15nm in a proper amount of distilled water with the temperature of 85 ℃ according to the solid-to-liquid ratio of 0.12g/mL, adding 8% by mass of hexamethylene diamine into the obtained dispersion, and carrying out magnetic stirring reaction for 8 hours; after the reaction is finished, filtering out the solid material, washing the solid material for 3 times by using distilled water, then washing the solid material for 3 times by using acetone, and then drying the solid material to store the solid material for later use;
II, putting the obtained solid material into a proper amount of distilled water with the temperature of 75 ℃ according to the solid-to-liquid ratio of 0.1g/mL, then adding poly hexamethylene guanidine with the mass of 25% of the solid material into the distilled water, carrying out heat preservation and stirring reaction for 6 hours, filtering and drying the mixture, and storing the mixture for later use;
and III, soaking the obtained solid powder in a proper amount of 60mg/mL acetone solution of butyl p-hydroxybenzoate according to a solid-to-liquid ratio of 0.15g/mL, oscillating the powder at an oscillation speed of 450r/min for 15 hours, centrifuging the solution to remove supernatant, and drying the obtained powdery solid to obtain the finished product of the antibacterial additive.
The using amount of the starch is 1.2 percent of the mass of the paper; and the temperature of the upper roller during the calendering treatment is set to be 160 ℃, and the pressure of the pressurizing line is set to be 60N/cm.
Comparative example 1: the main differences between this embodiment and embodiment 1 are: the prepared paperboard does not contain temperature-variable fibers.
Comparative example 2: the main differences between this embodiment and embodiment 1 are: the prepared temperature-variable anti-counterfeiting cardboard adopts cerium oxide with the same quantity and the same specification to replace the antibacterial agent prepared in the invention.
Performance test
The cardboard products produced in examples 1 to 3 and comparative examples 1 to 2 were subjected to the following performance tests, respectively:
1. detecting the bursting indexes of all groups of paperboard products according to GB/T6545 detection standards;
2. detecting the longitudinal folding strength of each group of paperboard products according to GB/T2679 detection standards;
3. detecting the antibacterial performance of each group of paperboard products according to a GBT 21866-2008 detection standard;
the resulting test data are reported in the following table:
Figure BDA0003532148220000131
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Figure BDA0003532148220000141
by comparing and analyzing the relevant data in the table, the paperboard produced by the invention has the advantages of faster color development effect, better anti-counterfeiting performance and effectively widened application field. Meanwhile, only a small amount of temperature-change fibers are added into the sizing agent used for the bottom paper layer and the sizing agent used for the surface paper, so that the purpose of saving the using amount of the temperature-change fibers is achieved, and the purpose of saving the cost is also achieved. In addition, the paperboard prepared by the invention has better antibacterial performance, the service life of the paperboard is effectively prolonged, and the quality of the paperboard is also ensured. Therefore, the temperature-variable anti-counterfeiting paperboard product processed by the method has wider market prospect and is more suitable for popularization.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand the invention for and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims (9)

1. The production process of the temperature-variable anti-counterfeiting paperboard is characterized in that the temperature-variable anti-counterfeiting paperboard sequentially comprises an anti-counterfeiting base paper layer, a core paper layer and an anti-counterfeiting surface paper layer from bottom to top;
the pulp used by the anti-counterfeiting bottom paper layer consists of 65-80 wt% of hardwood pulp and the balance of coniferous chemical sulfate pulp;
the pulp used by the core paper layer consists of 55-70% of maple chemical mechanical pulp and the balance of birch chemical mechanical pulp;
the pulp used by the anti-counterfeiting surface paper layer consists of 20 to 30 percent of softwood chemical sulfate pulp and the balance of eucalyptus chemical mechanical pulp;
the method comprises the following steps:
firstly, respectively mixing a proper amount of hardwood pulp and coniferous chemical sulfate pulp, putting the mixture into a hydrapulper through a chain plate machine, then adding a proper amount of temperature-variable fibers into the hydrapulper, performing pulping treatment on the obtained material through a double-disc grinder after the pulping is finished, and sending the pulp after the pulping into a pulping tank to prepare anti-counterfeiting bottom paper layer pulp;
step two, respectively mixing a proper amount of maple chemical mechanical pulp and birch chemical mechanical pulp, putting the mixture into a hydrapulper through a chain plate machine for pulping, then pulping the pulp subjected to pulping through a double-disc grinder, and sending the pulp subjected to pulping to a pulping tank to prepare core paper layer pulp;
step three, respectively mixing a proper amount of needle-leaved wood chemical sulfate pulp and eucalyptus chemical mechanical pulp, putting the mixture into a hydrapulper through a chain plate machine, adding a proper amount of temperature-variable fibers into the hydrapulper, performing pulping treatment on the obtained material through a double-disc grinder after the pulping is finished, and sending the pulp after the pulping into a pulping pool to prepare anti-counterfeiting face paper layer pulp;
step four, diluting the obtained anti-counterfeiting bottom paper layer slurry and anti-counterfeiting surface paper layer slurry by a fan pump, and then feeding the diluted anti-counterfeiting bottom paper layer slurry and anti-counterfeiting surface paper layer slurry into a bottom paper layer pulp box and a surface paper layer pulp box; diluting the core paper layer slurry by a fan pump and then feeding the diluted core paper layer slurry into a core paper layer head box; wherein, a top net former arranged behind a bottom paper layer pulp flow box carries out reverse dehydration treatment to form paper, and simultaneously, a proper amount of sizing agent, additive and antibacterial agent are added at the feed inlet of a fan pump to be uniformly mixed;
step five, spraying starch on the formed paper, and compounding an anti-counterfeiting bottom paper layer at the bottom of the core paper layer and an anti-counterfeiting surface paper layer at the top of the core layer; pressing, dehydrating and drying the obtained paper, then sequentially carrying out calendaring treatment on the paper by a hot roller soft calendar, and carrying out slitting treatment after rolling by a rolling machine to obtain a temperature-variable anti-counterfeiting paperboard finished product;
the dosage of the antibacterial agent is 3.6-4.5% of the mass of the corresponding slurry, and the preparation method of the antibacterial agent comprises the following steps:
i, dispersing cerium oxide with the average particle size of 6-15 nm in a proper amount of distilled water at the temperature of 70-85 ℃ according to a solid-to-liquid ratio of 0.08-0.12 g/mL, adding 4-8% by mass of hexamethylenediamine into the obtained dispersion, and carrying out magnetic stirring reaction for 5-8 h; after the reaction is finished, filtering out solid materials in the reaction product, washing the reaction product for 2 to 3 times by using distilled water, washing the reaction product for 2 to 3 times by using acetone, and then drying the reaction product to store the obtained solid materials for later use;
II, putting the obtained solid material into a proper amount of distilled water with the temperature of 60-75 ℃ according to the solid-liquid ratio of 0.06-0.1 g/mL, then adding 15-25% by mass of polyhexamethylene guanidine into the distilled water, carrying out heat preservation stirring reaction for 3-6 h, then carrying out filtration and drying treatment on the solid material, and storing the solid material for later use;
and III, soaking the obtained solid powder into a proper amount of 40-60 mg/mL butyl p-hydroxybenzoate acetone solution according to a solid-to-liquid ratio of 0.06-0.15 g/mL, oscillating the solution at an oscillation speed of 350-450 r/min for 10-15 h, centrifuging to remove supernatant, and drying the obtained powdery solid to obtain the finished product of the antibacterial additive.
2. The production process of the temperature-variable anti-counterfeiting paperboard according to claim 1, characterized by comprising the following steps: the anti-counterfeiting surface paper layer has the ration of 27-32 g/m 2 The ration of the anti-counterfeiting bottom paper layer is 26 to 30g/m 2 。
3. The production process of the temperature-variable anti-counterfeiting paperboard according to claim 1, characterized by comprising the following steps: the usage amount of the temperature-change fiber is 1.8-2.5% of the total mass of the mixed slurry in the pulper in the first step and the pulper in the second step; and the mass concentration of the slurry after the disintegration treatment in the first step and the second step is 4.5-6.8%.
4. The production process of the temperature-variable anti-counterfeit paperboard according to claim 1 or 3, wherein the preparation method of the temperature-variable fiber comprises the following steps:
cleaning polyvinyl alcohol slices, then putting the polyvinyl alcohol slices into a proper amount of distilled water at the temperature of 95-99 ℃, and obtaining spinning stock solution with the concentration of 35-50% after the polyvinyl alcohol is completely dissolved; the obtained spinning solution is output by a metering pump and sprayed out by a spinneret plate to enter a spinning channel; and (3) allowing the industrial nitrogen gas carrying temperature-change powder to enter a spinning channel from an air inlet, blowing out from an air outlet, solidifying and solidifying the blown-out spinning stock solution to form, sequentially passing the obtained temperature-change fiber crude product through a godet roller, a hot press roller, a formaldehyde condensation treatment bath, an ultraviolet radiation area, a water bath and a drying roller, and collecting to obtain a temperature-change fiber finished product.
5. The production process of the temperature-variable anti-counterfeit paperboard according to claim 4, characterized in that: the reversible color change temperature range of the temperature change powder is 50-60 ℃, the temperature change powder is red at normal temperature, the red disappears after being heated, and the addition amount of the temperature change powder is 2.5-3.5 percent of that of the polyvinyl alcohol.
6. The production process of the temperature-variable anti-counterfeit paperboard according to claim 1, characterized in that: the sizing agent is any one of AKD and ASA neutral sizing agents, and the dosage of the sizing agent is 1.2-1.8% of the mass of the corresponding sizing agent.
7. The production process of the temperature-variable anti-counterfeiting paperboard according to claim 1, characterized by comprising the following steps: the additive is aluminum sulfate, and the dosage of the aluminum sulfate is 1.0-1.6% of the mass of the corresponding slurry.
8. The production process of the temperature-variable anti-counterfeiting paperboard according to claim 1, characterized by comprising the following steps: the using amount of the starch is 0.8-1.2% of the mass of the paper; and the temperature of the upper roller is set to be 150-160 ℃ during the calendaring treatment, and the pressure of the pressurizing line is set to be 45-60N/cm.
9. A temperature-variable anti-counterfeiting card paper is characterized in that: the temperature-variable anti-counterfeiting paperboard is produced by the production process of the temperature-variable anti-counterfeiting paperboard according to any one of claims 1 to 8.
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