CN113459694A - Waterproof printing process for paper printed matter - Google Patents
Waterproof printing process for paper printed matter Download PDFInfo
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- CN113459694A CN113459694A CN202110881334.4A CN202110881334A CN113459694A CN 113459694 A CN113459694 A CN 113459694A CN 202110881334 A CN202110881334 A CN 202110881334A CN 113459694 A CN113459694 A CN 113459694A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0011—Pre-treatment or treatment during printing of the recording material, e.g. heating, irradiating
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/50—Spraying or projecting
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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
- D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
- D21H25/04—Physical treatment, e.g. heating, irradiating
- D21H25/06—Physical treatment, e.g. heating, irradiating of impregnated or coated paper
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Paper (AREA)
Abstract
The invention discloses a waterproof printing process for paper printed matters. Has the advantages that: (1) the color uniformity of the multilayer core-shell dye is enhanced by using the polymeric nanospheres as media to adsorb the pigment through temperature and pH regulation. (2) The multi-layer shell-core dye is dispersed in water to obtain the low-viscosity water-based anti-counterfeiting ink, and the stability and adaptability of the water-based anti-counterfeiting ink are enhanced and the preparation of high-quality paper printed matters is enhanced without adding extra polymers. (3) Lactic acid, hydroxyl on the surface of paper and hydroxyl of N-trimethyl chitosan are crosslinked to form an enhanced network through esterification reaction, the surface is dehydrated, and the mechanical property, the waterproof property and the antibacterial property of the paper are enhanced. (4) The electron beam irradiation is adopted to break the polymethacrylate molecules on the surface of the multi-layer shell-core dye, so that the hydroxyethyl methacrylate inside is exposed, and the firmness of the pigment and paper is enhanced. In conjunction with the problem of this strength on the paper surface and low viscosity inks.
Description
Technical Field
The invention relates to the technical field of printing, in particular to a waterproof printing process for a paper printed matter.
Background
Printing is one of four ancient inventions in China, and paper printing is a long-history subject. With the development of modern science and technology, the printing technology not only serves books, but also designs the printing in multiple fields such as express packaging and the like. With the application of different fields, the printing technology and the printing ink used for printing are diversified.
At present, the printing ink which is relatively environment-friendly is generally formed by mixing a polymer serving as a binder and a water-based pigment, but the printing ink has poor stability, and the problems of uneven ink distribution, fuzzy ink pollution and the like caused by a large number of polymer particles due to humidity and temperature during printing are solved; it has also been studied to increase the stability of the ink by directly co-encapsulating the ink; however, this method is difficult to control the pigment in the polymer ink, cannot determine the uniformity of the pigment coating in the polymer ink, and is easy to generate different polymer inks, resulting in large color difference.
Meanwhile, in the printing process, the relationship between the paper strength and the ink viscosity needs to be balanced. In general, when the strength of paper is high, it is necessary to increase the viscosity of ink for increasing the coloring power. However, the increase in viscosity of the ink causes a phenomenon of paper sticking on the surface during printing, and contamination of the ink roller lowers printing efficiency. In addition, paper printed matter is very easy to be limited in application due to poor water resistance.
Therefore, the waterproof printing process for obtaining the paper printed matter has important significance in solving the problems.
Disclosure of Invention
The invention aims to provide a waterproof printing process of a paper printed matter, which aims to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a waterproof printing process of a paper printed matter comprises the following steps:
step 1: ultrasonically dispersing a multilayer shell-core pigment in water; obtaining the water-based anti-counterfeiting ink with the viscosity of 4.6-5.8 mPa & s and the surface tension of 38-42 mN/m;
step 2: paper surface pretreatment: ultrasonically dispersing N-trimethyl chitosan, lactic acid and tin chloride in deionized water to form a pretreatment solution; injecting the paper into a high-pressure spray gun, and uniformly spraying the paper on the paper; drying at high temperature under reduced pressure to obtain paper A;
and step 3: injecting the water-based anti-counterfeiting ink into a printing machine for printing; irradiating an electron beam; drying at high temperature and normal pressure to obtain the paper printed matter.
According to the scheme, the pigment is encapsulated by a viscous polymer, and then the pigment is directly dispersed in water to form the water-based anti-counterfeiting ink with certain viscosity and surface tension, so that the controllability of the viscosity of the ink is enhanced, the stability of the ink is enhanced, and the stability of ink jetting during printing is enhanced. High printing density is achieved and the quality of paper prints is enhanced.
Optimally, in the step 3, the irradiation temperature is 110 ℃, the energy is 2.5keV, and the time is 5-10 seconds; the drying temperature is 150-155 ℃. The irradiation process is to degrade and break the methacrylate on the surface in the multi-layer core-shell dye to form free radicals of methyl ethylene and 2-methyl propylene.
Preferably, in step 2, the high-temperature reduced-pressure drying process: setting the heating rate to be 2 ℃/min, heating to 70-80 ℃, setting the vacuum degree to be 0.06-0.08 Mpa, and drying for 20-25 minutes; setting the heating rate to be 4 ℃/min, heating to 140-150 ℃, and continuously drying for 2-3 hours. The drying mode is controlled in order that the electronegative lactic acid is stably adsorbed on the paper surface under the guidance of electropositive N-trimethyl chitosan, and is crosslinked with hydroxyl on the paper surface and hydroxyl of the N-trimethyl chitosan through an esterification reaction to form an enhanced network, the surface is dehydrated, the mechanical property of the paper is enhanced, and meanwhile, the permeation of oxygen and water is hindered by the compact crosslinking density. Thereby enhancing water resistance. However, the viscosity of the ink needs to be enhanced due to the increase of the surface strength of the paper, but the viscosity of the aqueous anti-counterfeiting ink in the scheme is low, so that powder falling and pigment falling can occur, and thus the internal hydroxyethyl methacrylate is exposed through irradiation degradation, and the firmness of the pigment and the paper is enhanced. Meanwhile, the low-viscosity ink has proper adhesive force to paper during printing, so that the phenomenon of paper sticking on the surface during printing is reduced. The printability of paper is enhanced.
Preferably, in step 2, the pretreatment solution comprises the following components: 16-28 parts of N-trimethyl chitosan, 6-8 parts of lactic acid, 0.01-0.05 part of stannic chloride and 80-86 parts of deionized water. Compared with chitosan and carboxymethyl chitosan, N-trimethyl chitosan has better antibacterial property, and cation ionization is better under alkalescent ink, so that accurate electrostatic adsorption with electronegative ink is realized.
Preferably, in step 1, the preparation method of the multilayer core-shell pigment comprises the following steps: respectively ultrasonically dispersing water-based pigment and polymeric nanospheres in deionized water to obtain a pigment solution and a nanosphere dispersion liquid; setting the temperature to be 90-95 ℃, and adjusting the pH value to be 7.3-8.1; dropwise adding the dispersed liquid into the pigment solution, and stirring for 2-3 hours; centrifuging, dispersing solid particles in deionized water, setting the temperature to be 70-72 ℃, and dropwise adding a methacrylate-potassium persulfate mixed aqueous solution; the dripping time is 30-40 minutes, and the reaction is carried out for 1-1.5 hours to obtain the multilayer shell-core pigment.
Compared with the ink formed by directly mixing the polymer serving as the adhesive with the water-based pigment, the printing stability is enhanced, and the problems of uneven ink distribution, fuzzy ink pollution and the like caused by a large number of polymer particles due to humidity and temperature during printing are reduced; compared with the second method, the printing ink is directly encapsulated by copolymerization; increasing the difficulty of controlling the color of the polymer ink, failing to determine the uniformity of pigment coverage in the polymer ink, resulting in differential polymer inks, leading to the appearance of color differences. In the scheme, the prepared uniform particle polymeric nanospheres are used as media, the water-based pigment is dyed under a certain condition, and then the thin-layer polymer is encapsulated to form the multilayer core-shell pigment, so that the uniformity and the stability are enhanced, the printing quality of paper printed matters is ensured, the density of printing colors is increased, and the color depth is enhanced.
Specifically, the method comprises the following steps: according to the scheme, styrene, hydroxyethyl methacrylate and methyl methacrylate are used as monomers to prepare a polymeric nanosphere, the polymeric nanosphere is heated and adsorbed at the temperature of 90-95 ℃, firstly, due to the fact that the surface of the polymeric nanosphere has abundant carboxyl groups, hydrogen bonds are formed with hydroxyl groups or amino groups in a water-based dye, and the pH value of adsorption is adjusted at the temperature to achieve the optimal adsorption effect; the pH value is 7.3-8.1, when the pH value is less than 7, the macromolecular polymer is tightly crosslinked, fewer ionized carboxyl groups are on the surface of the polymerized nanospheres, more dye molecules are adsorbed on the surface of the polymer, and the dye molecules cannot migrate inwards; when the pH value is more than 7.3, the macromolecules are broken to generate more ionized carboxyl groups, and gaps are generated among macromolecular chains, so that the pigment is moved inwards along the carboxyl groups, and the multilayer shell-core pigment is more stable; when the pH value is more than 8.1, the macromolecular chains of the polymer are broken more; due to the irradiation process in the subsequent steps, the internal polymeric nanospheres are broken, more dye molecules are exposed, and due to the breakage, the surface viscosity is increased, so that the surface wear resistance of the paper printing ink is reduced.
In the scheme, the prepared polymeric nanospheres have relatively uniform particle sizes, so that the pigment adsorbed by the nanospheres is relatively uniform, and the prepared multilayer core-shell pigment has uniform quality and uniform color. Meanwhile, in order to enhance the dispersibility and stability of the ink in an aqueous solution, a layer of methacrylate polymer is coated on the surface, and the relative abundance carboxyl generates electronegativity, so that static electricity is repelled, and the ink is more stable in the aqueous solution. The prepared water-based anti-counterfeiting ink has the capability of self-curing to form a film, and the surface tension of the prepared multi-layer core-shell pigment is similar to that of water, so that the water-based ink does not need to add extra polymer, and only needs to adjust the adding amount of the multi-layer core-shell pigment and the amount of the pigment adsorbed by the polymeric nanospheres, thereby achieving the adjustment of the color depth. Meanwhile, due to the low viscosity of the polymer, the thickness of the ink film can be reduced on the basis of increasing the color density. Therefore, the printability is improved, the negative influence of high-viscosity substances on paper printed matters caused by factors such as humidity and temperature is reduced, and the printing efficiency is reduced due to the high increase of the viscosity and the cleaning times of the ink roller.
Preferably, the preparation method of the polymeric nanosphere comprises the following steps: ultrasonically dispersing a surfactant and 1/3 potassium persulfate in deionized water; setting the stirring speed to be 200-300 rmp and the temperature to be 70-78 ℃, dropwise adding 2/5 methacrylate aqueous solution and 7-hydroxycoumarin solution, and reacting for 50-60 minutes; setting the stirring speed to be 400-600 rpm, continuously adding 3/5 methacrylate solution, glycidyl methacrylate solution, hydroxyethyl methacrylate solution and styrene solution, mixing and stirring for 15-20 minutes, dropwise adding 2/3 potassium persulfate aqueous solution for 40-45 minutes, and reacting for 5-7 hours; to obtain the polymeric nanospheres.
The polymeric nanosphere is formed by copolymerizing 7-hydroxycoumarin with methacrylic acid, then epoxidizing the copolymer with glycidyl methacrylate, and then copolymerizing methacrylic acid, styrene and hydroxyethyl methacrylate. The internal 7-hydroxycoumarin has the characteristic of fluorescence and luminescence, and can realize anti-counterfeiting judgment through ultraviolet irradiation. While enhancing the photostability of the multilayer core-shell pigment. In addition, the added hydroxyethyl methacrylate is a relatively strong adhesive, and can enhance the uniformity of printing. The adhesion of the pigment to the paper material can be enhanced. Usually, the pigment is directly added, but when printing, the binder migrates with the movement of the liquid phase, resulting in uneven distribution of the pigment in the thickness direction. Therefore, the nano-composite material is encapsulated, the positioning is realized by utilizing the difference of electronegativity of methacrylate and N-trimethyl chitosan ions, and then the methacrylate on the surface is degraded and broken by irradiation to form free radicals of methyl ethylene and 2-methyl propylene; so that the internal hydroxyethyl methacrylate is exposed. The fastness of the pigment and paper is enhanced. During irradiation, the hydroxyethyl methacrylate does not break due to entanglement between styrene molecules and methacrylic acid molecules. And then in the high-temperature drying process, the printing ink forms a film, and the methyl ethylene and the 2-methyl propylene are migrated and fixed on the surface of the film layer, so that the protection of the printing ink is enhanced, and the waterproofness is increased.
Preferably, the raw materials of the multilayer shell-core pigment comprise the following components: 48-43 parts of polymeric nanospheres, 22-27 parts of water-based pigment, 12-15 parts of methacrylate and 0.5-1 part of potassium persulfate.
Preferably, the raw materials of the polymeric nanosphere comprise 5-8 parts of 7-hydroxycoumarin, 20-26 parts of methyl methacrylate, 32-38 parts of styrene, 8-10 parts of hydroxyethyl methacrylate, 11-14 parts of glycidyl methacrylate and 1.5-2.2 parts of ammonium persulfate.
Preferably, the average particle size of the polymeric nanospheres is 300-360 nm; the average particle size of the multilayer core-shell pigment is 352-410 nm.
Compared with the prior art, the invention has the following beneficial effects: (1) the color uniformity of the multilayer core-shell dye is enhanced by using the polymeric nanospheres as media to adsorb the pigment through temperature and pH regulation. (2) The multi-layer shell-core dye is dispersed in water to obtain the low-viscosity water-based anti-counterfeiting ink, and the stability and adaptability of the water-based anti-counterfeiting ink are enhanced and the preparation of high-quality paper printed matters is enhanced without adding extra polymers. (3) Lactic acid, hydroxyl on the surface of paper and hydroxyl of N-trimethyl chitosan are crosslinked to form an enhanced network through esterification reaction, the surface is dehydrated, and the mechanical property, the waterproof property and the antibacterial property of the paper are enhanced. (4) The electron beam irradiation is adopted to break the polymethacrylate molecules on the surface of the multi-layer shell-core dye, so that the hydroxyethyl methacrylate inside is exposed, and the firmness of the pigment and paper is enhanced. In conjunction with the problem of this strength on the paper surface and low viscosity inks.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
The pigment used in the examples below was malachite green.
Example 1:
step 1: (1) weighing 6g of 7-hydroxycoumarin, 22g of methyl methacrylate, 35g of styrene, 9g of hydroxyethyl methacrylate, 13g of glycidyl methacrylate and 1.86g of ammonium persulfate for later use; ultrasonically dispersing sodium dodecyl benzene sulfonate and 1/3 potassium persulfate in deionized water; setting the stirring speed at 260rmp and the temperature at 75 ℃, dropwise adding 2/5 methacrylate aqueous solution and 7-hydroxycoumarin solution, and reacting for 52 minutes; setting the stirring speed to be 580rpm, continuously adding 3/5 methacrylate solution, glycidyl methacrylate solution, hydroxyethyl methacrylate solution and styrene solution, mixing and stirring for 16 minutes, dropwise adding 2/3 potassium persulfate aqueous solution for 40-45 minutes, and reacting for 6 hours; to obtain the polymeric nanospheres. (2) Weighing 45g of polymeric nanosphere, 27g of water-based pigment, 13g of methacrylate and 0.6g of potassium persulfate for later use; respectively ultrasonically dispersing water-based pigment and polymeric nanospheres in deionized water to obtain a pigment solution and a nanosphere dispersion liquid; setting the temperature to be 90-95 ℃, and adjusting the pH value to be 7.8; dropwise adding the dispersed liquid into the pigment solution, and stirring for 2-3 hours; centrifuging, dispersing solid particles in deionized water, setting the temperature to be 71 ℃, and dropwise adding a methacrylate-potassium persulfate mixed aqueous solution; the dropping time was 35 minutes, and the reaction was carried out for 1.1 hours to obtain a multilayer core-shell pigment.
Step 2: ultrasonically dispersing a multilayer shell-core pigment in water; obtaining the water-based anti-counterfeiting ink with the viscosity of 5.2mPa & s and the surface tension of 40 mN/m;
and step 3: paper surface pretreatment: ultrasonically dispersing 24g of N-trimethyl chitosan, 7.5g of lactic acid and 0.03g of tin chloride in 85g of deionized water to form a pretreatment solution; injecting the paper into a high-pressure spray gun, and uniformly spraying the paper on the paper; setting the heating rate to be 2 ℃/min, heating to 78 ℃, setting the vacuum degree to be 0.07Mpa, and drying for 22 minutes; setting the heating rate to be 4 ℃/min, heating to 145 ℃, and continuously drying for 2.5 hours to obtain the paper A;
and 4, step 4: injecting the water-based anti-counterfeiting ink into a printing machine for printing; setting the irradiation temperature at 110 ℃, the energy at 2.5keV and the electron beam irradiation for 8 seconds; and setting the drying temperature to 152 ℃ and drying at normal pressure to obtain the paper printed matter.
In the scheme, the average particle size of the polymeric nanospheres is 325 nm; the multilayer core-shell pigment has an average particle size of 384 nm.
Example 2:
step 1: (1) weighing 8g of 7-hydroxycoumarin, 26g of methyl methacrylate, 38g of styrene, 10g of hydroxyethyl methacrylate, 14g of glycidyl methacrylate and 2.2g of ammonium persulfate for later use; ultrasonically dispersing sodium dodecyl benzene sulfonate and 1/3 potassium persulfate in deionized water; setting the stirring speed to be 300rmp and the temperature to be 78 ℃, dripping 2/5 methacrylate aqueous solution and 7-hydroxycoumarin solution, and reacting for 60 minutes; setting the stirring speed to be 600rpm, continuously adding 3/5 methacrylate solution, glycidyl methacrylate solution, hydroxyethyl methacrylate solution and styrene solution, mixing and stirring for 20 minutes, dropwise adding 2/3 potassium persulfate aqueous solution for 45 minutes, and reacting for 7 hours; to obtain the polymeric nanospheres. (2) Weighing 43g of polymeric nanosphere, 27g of water-based pigment, 15g of methacrylate and 1g of potassium persulfate for later use; respectively ultrasonically dispersing water-based pigment and polymeric nanospheres in deionized water to obtain a pigment solution and a nanosphere dispersion liquid; setting the temperature to 95 ℃, and adjusting the pH value to 8.1; dripping the dispersion liquid into the pigment solution, and stirring for 3 hours; centrifuging, dispersing solid particles in deionized water, setting the temperature at 72 ℃, and dropwise adding a methacrylate-potassium persulfate mixed aqueous solution; the dropping time was 40 minutes, and the reaction was carried out for 1.5 hours to obtain a multilayer core-shell pigment.
Step 2: ultrasonically dispersing a multilayer shell-core pigment in water; obtaining the water-based anti-counterfeiting ink with the viscosity of 5.8mPa & s and the surface tension of 42 mN/m;
and step 3: paper surface pretreatment: ultrasonically dispersing 28g of N-trimethyl chitosan, 8g of lactic acid and 0.05g of tin chloride in 80-86 g of deionized water to form a pretreatment solution; injecting the paper into a high-pressure spray gun, and uniformly spraying the paper on the paper; setting the heating rate to be 2 ℃/min, heating to 80 ℃, setting the vacuum degree to be 0.08Mpa, and drying for 25 minutes; setting a heating rate of 4 ℃/min, heating to 150 ℃, and continuously drying for 2-3 hours to obtain paper A;
and 4, step 4: injecting the water-based anti-counterfeiting ink into a printing machine for printing; setting the irradiation temperature at 110 ℃, the energy at 2.5keV and the electron beam irradiation for 10 seconds; and setting the drying temperature to 155 ℃ and drying at normal pressure to obtain the paper printed matter.
In the scheme, the average particle size of the polymeric nanospheres is 360 nm; the multilayer core-shell pigment has an average particle size of 410 nm.
Example 3:
step 1: (1) weighing 5g of 7-hydroxycoumarin, 20g of methyl methacrylate, 32g of styrene, 8g of hydroxyethyl methacrylate, 11g of glycidyl methacrylate and 1.5g of ammonium persulfate for later use; ultrasonically dispersing sodium dodecyl benzene sulfonate and 1/3 potassium persulfate in deionized water; setting the stirring speed to be 200-300 rmp and the temperature to be 70 ℃, dropwise adding 2/5 methacrylate aqueous solution and 7-hydroxycoumarin solution, and reacting for 50 minutes; setting the stirring speed to be 400rpm, continuously adding 3/5 methacrylate solution, glycidyl methacrylate solution, hydroxyethyl methacrylate solution and styrene solution, mixing and stirring for 15 minutes, dropwise adding 2/3 potassium persulfate aqueous solution for 40 minutes, and reacting for 5 hours; to obtain the polymeric nanospheres. (2) Weighing 48g of polymeric nanosphere, 22g of water-based pigment, 12g of methacrylate and 0.5g of potassium persulfate for later use; respectively ultrasonically dispersing water-based pigment and polymeric nanospheres in deionized water to obtain a pigment solution and a nanosphere dispersion liquid; setting the temperature to 90 ℃, and adjusting the pH value to 7.3; dripping the dispersion liquid into the pigment solution, and stirring for 2 hours; centrifuging, dispersing solid particles in deionized water, setting the temperature to be 70 ℃, and dropwise adding a methacrylate-potassium persulfate mixed aqueous solution; the dropping time is 30 minutes, and the reaction is carried out for 1 hour, thus obtaining the multilayer core-shell pigment.
Step 2: ultrasonically dispersing a multilayer shell-core pigment in water; obtaining the water-based anti-counterfeiting ink with the viscosity of 4.6mPa & s and the surface tension of 38-42 mN/m;
and step 3: paper surface pretreatment: ultrasonically dispersing 16g of N-trimethyl chitosan, 6g of lactic acid and 0.01g of stannic chloride in 80g of deionized water to form a pretreatment solution; injecting the paper into a high-pressure spray gun, and uniformly spraying the paper on the paper; setting the heating rate to be 2 ℃/min, heating to 70 ℃, setting the vacuum degree to be 0.06Mpa, and drying for 20 minutes; setting a heating rate of 4 ℃/min, heating to 140 ℃, and continuously drying for 2 hours to obtain paper A;
and 4, step 4: injecting the water-based anti-counterfeiting ink into a printing machine for printing; setting the irradiation temperature at 110 ℃, the energy at 2.5keV and the electron beam irradiation for 5 seconds; and setting the drying temperature to be 150 ℃ and drying at normal pressure to obtain the paper printed matter.
In the scheme, the average particle size of the polymeric nanospheres is 300 nm; the average particle size of the multilayer core-shell pigment is 352 nm.
Comparative example 1: the same procedure as in example 1 was repeated except that N-trimethyl chitosan was replaced with carboxymethyl chitosan;
comparative example 2: no lactic acid was added; otherwise, the same as example 1;
comparative example 3: drying at normal temperature directly without reduced pressure; otherwise, the same as example 1;
comparative example 4: the same as example 1 except that electron beam irradiation was not used;
comparative example 5: setting the pH value of the dye during adsorption to be 5; otherwise, the same as example 1;
comparative example 6: setting the pH value of the dye during adsorption to be 9; otherwise, the same as example 1;
comparative example 7: the polymeric nanospheres are not adsorbed with pigments, and are printed according to the formula of the water-based ink disclosed in patent CN544078A instead of the water-soluble acrylic resin spherical particles.
Experiment: the dispersibility of the ink prepared in the examples 1 to 3 and the ink prepared in the comparative examples 1 to 7 are observed, the paper printed matter is subjected to series detection, and the water resistance of the paper printed matter is measured by using an ISO2836 method as a standard. The surface strength of the paper prints was determined using the method of GB/T2679.15-1997 as standard. The tinting strength of the inks was determined using the method of GB/T14624.2-1998 as a standard. Cutting into 4cm2The paper of (4) was subjected to an antibacterial property test of Escherichia coli. Taking the method of GB/T27705-2008 as a standard, carrying out color data detection on a surface color block of a paper printed matter by a spectral density analyzer, calculating the color difference of a sample by RGB values, and taking the average color difference as a judgment basis; the saturation of the color was measured by a color density meter.
| Examples | Water resistance/grade | Surface strength/m.s-1 | Coloring power/%) | Antibacterial property/%) | Color difference/Delta E | Color saturation/level | Stability of |
| Example 1 | 5 | 2.93 | 109 | 96 | 8.5 | 18 | Superior food |
| Example 2 | 5 | 2.82 | 106 | 95 | 9.1 | 19 | Superior food |
| Example 3 | 5 | 2.86 | 105 | 96 | 8.9 | 17 | Superior food |
| Comparative example 1 | 5 | 2.53 | 96 | 90 | 8.7 | 17 | Superior food |
| Comparative example 2 | 4 | 2.32 | 110 | 97 | 8.8 | 18 | Superior food |
| Comparative example 3 | 4 | 2.67 | 106 | 95 | 8.9 | 16 | Superior food |
| Comparative example 4 | 4 | 2.71 | 92 | 95 | 8.8 | 17 | Superior food |
| Comparative example 5 | 5 | 2.92 | 107 | 97 | 8.6 | 13 | Superior food |
| Comparative example 6 | 5 | 2.88 | 106 | 96 | 9.9 | 15 | Superior food |
| Comparative example 7 | 4 | 2.85 | 95 | 95 | 11.2 | 11 | Good wine |
And (4) conclusion: the water-based anti-counterfeiting ink prepared in the embodiment 1-3 has good stability and printability; the method is used for printing to prepare paper printed matters. The printing ink has good mechanical property, tinting strength, antibacterial property and color saturation, and has no pollution and low printing chromatic aberration in the printing process.
Comparing comparative examples 1 to 8 with example 1, it can be found that: (1) comparative example 1 since N-trimethyl chitosan was replaced with carboxymethyl chitosan; the cation concentration is reduced, and the surface strength, the tinting strength and the antibacterial performance are all reduced. (2) In comparative example 2, since lactic acid was not added, the esterification reactivity was reduced, so that the strength was decreased and the water-proofing property was decreased. (3) In comparative example 3, since drying under reduced pressure was not performed, the esterification reaction was slowed, and the dehydration process was reacted with cellulose in paper, the degree of crosslinking was decreased, and the surface strength and water resistance were decreased. (4) The water resistance, tinting strength, saturation are reduced without using electron beam irradiation because: during the irradiation process, internal hydroxyethyl methacrylate is exposed. The fastness of the pigment and paper is enhanced, and meanwhile, the methyl ethylene and the 2-methyl propylene generated by degradation are migrated and fixed on the surface of the film layer, so that the protection of the ink is enhanced, and the water resistance and the surface strength are increased. (5) When the pH value of the dye during adsorption is set to be 5, the amount of the adsorbed pigment is reduced due to the reduction of the amount of free carboxyl, so that the color saturation is reduced, most of the pigment is on the surface of the ball, and after subsequent cracking, more pigment is exposed, so that the wear resistance is reduced; and when the pH value at the time of dye adsorption was set to 9, the color saturation was increased due to the increase in the dye adsorption amount, but the difference in color difference was large due to the breakage of the inner sphere. (6) When the polymeric nanoparticles are used as a binder without adsorption coating, it is found that the color difference is significantly increased, the tinting strength is decreased, and the water resistance and other data are decreased. Because the aqueous anti-counterfeiting ink is unstable, the quality of the printed paper product is reduced.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The waterproof printing process of the paper printed matter is characterized in that: the method comprises the following steps:
step 1: ultrasonically dispersing a multilayer shell-core pigment in water; obtaining the water-based anti-counterfeiting ink with the viscosity of 4.6-5.8 mPa & s and the surface tension of 38-42 mN/m;
step 2: paper surface pretreatment: ultrasonically dispersing N-trimethyl chitosan, lactic acid and tin chloride in deionized water to form a pretreatment solution; injecting the paper into a high-pressure spray gun, and uniformly spraying the paper on the paper; drying at high temperature under reduced pressure to obtain paper A;
and step 3: injecting the water-based anti-counterfeiting ink into a printing machine for printing; irradiating an electron beam; drying at high temperature and normal pressure to obtain the paper printed matter.
2. The waterproof printing process of paper printed matter of claim 1, characterized in that: in the step 3, the irradiation temperature is 110 ℃, the energy is 2.5keV, and the time is 5-10 seconds; the drying temperature is 150-155 ℃.
3. The waterproof printing process of paper printed matter of claim 1, characterized in that: in step 2, the high-temperature reduced-pressure drying process: setting the heating rate to be 2 ℃/min, heating to 70-80 ℃, setting the vacuum degree to be 0.06-0.08 Mpa, and drying for 20-25 minutes; setting the heating rate to be 4 ℃/min, heating to 140-150 ℃, and continuously drying for 2-3 hours.
4. The waterproof printing process of paper printed matter of claim 1, characterized in that: in step 2, the pretreatment solution comprises the following components: 16-28 parts of N-trimethyl chitosan, 6-8 parts of lactic acid, 0.01-0.05 part of stannic chloride and 80-86 parts of deionized water.
5. The waterproof printing process of paper printed matter of claim 1, characterized in that: in step 1, the preparation method of the multilayer core-shell pigment comprises the following steps: respectively ultrasonically dispersing water-based pigment and polymeric nanospheres in deionized water to obtain a pigment solution and a nanosphere dispersion liquid; setting the temperature to be 90-95 ℃, and adjusting the pH value to be 7.3-8.1; dropwise adding the dispersed liquid into the pigment solution, and stirring for 2-3 hours; centrifuging, dispersing solid particles in deionized water, setting the temperature to be 70-72 ℃, and dropwise adding a methacrylate-potassium persulfate mixed aqueous solution; the dripping time is 30-40 minutes, and the reaction is carried out for 1-1.5 hours to obtain the multilayer shell-core pigment.
6. The waterproof printing process of paper printed matter according to claim 5, characterized in that: the preparation method of the polymeric nanosphere comprises the following steps: ultrasonically dispersing a surfactant and 1/3 potassium persulfate in deionized water; setting the stirring speed to be 200-300 rmp and the temperature to be 70-78 ℃, dropwise adding 2/5 methacrylate aqueous solution and 7-hydroxycoumarin solution, and reacting for 50-60 minutes; setting the stirring speed to be 400-600 rpm, continuously adding 3/5 methacrylate solution, glycidyl methacrylate solution, hydroxyethyl methacrylate solution and styrene solution, mixing and stirring for 15-20 minutes, dropwise adding 2/3 potassium persulfate aqueous solution for 40-45 minutes, and reacting for 5-7 hours; to obtain the polymeric nanospheres.
7. The waterproof printing process of paper printed matter of claim 1, characterized in that: the raw materials of the multilayer core-shell pigment comprise the following components: 48-43 parts of polymeric nanospheres, 22-27 parts of water-based pigment, 12-15 parts of methacrylate and 0.5-1 part of potassium persulfate.
8. The waterproof printing process of paper printed matter of claim 7, characterized in that: the raw materials of the polymeric nanosphere comprise 5-8 parts of 7-hydroxycoumarin, 20-26 parts of methyl methacrylate, 32-38 parts of styrene, 8-10 parts of hydroxyethyl methacrylate, 11-14 parts of glycidyl methacrylate and 1.5-2.2 parts of ammonium persulfate.
9. The waterproof printing process of paper printed matter of claim 7, characterized in that: the average particle size of the polymeric nanospheres is 300-360 nm; the average particle size of the multilayer core-shell pigment is 352-410 nm.
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