Nano modified water-based gravure ink and preparation method thereof

Abstract

The invention discloses nano-modified water-based gravure ink, which is prepared from the following raw materials in parts by weight: 30 to 40 parts of deionized water, 30 to 35 parts of acrylic emulsion, 10 to 20 parts of waterborne polyurethane resin, 8 to 12 parts of pigment, 6 to 10 parts of silane coupling blender, 2 to 5 parts of hydroxymethyl cellulose, 1 to 3 parts of defoaming agent and 5 to 10 parts of nano-modified filler. According to the nano-modified water-based gravure ink, the acrylic emulsion and the water-based polyurethane resin are adopted as raw materials, and the silane coupling blender and the nano-modified filler are added as functional auxiliaries, so that the blending and coordination effects of the acrylic emulsion and the water-based polyurethane resin are optimized, the interfacial property of the raw materials of a system is improved, and meanwhile, the adhesive force and the wear resistance of a product are enhanced; and meanwhile, the product is remarkable in corrosion resistance, scratch resistance and ultraviolet resistance stability.

Description

Technical Field

[0001] The invention relates to the technical field of inks, and in particular to nano-modified water-based gravure ink and a preparation method thereof. Background Art

[0002] Printing ink plays an important role in daily printing applications. It is a key material for achieving color expression and pattern communication. With the continuous improvement of environmental awareness, water-based ink has gradually replaced traditional organic deionized water ink and become the mainstream in the modern printing industry. However, although water-based ink has advantages in environmental friendliness and safety, it still has the following problems in terms of performance: Adhesion problem: Water-based inks often encounter poor adhesion problems during use, especially on non-absorbent substrates (such as plastic films, metal surfaces, etc.), which are prone to peeling; Poor wear resistance: Although water-based ink has advantages in terms of environmental protection and safety, its coating has poor wear resistance. Since the ink contains more water-based components, the coating surface is easily affected by external forces such as friction and scratching, resulting in blurring, peeling or damage of patterns and texts; Insufficient corrosion resistance and UV stability: Water-based inks have poor corrosion resistance and UV stability, especially when exposed to harsh environmental conditions (such as strong sunlight, high humidity or chemical corrosion environment). Their performance is easily degraded, resulting in a shortened service life of the printed product and affecting its applicability in high-performance applications.

[0003] At present, in order to improve the performance of water-based gravure ink, especially adhesion and wear resistance, researchers have begun to use nanofiller modification technology. Nanofillers such as nano silicon carbide and nano talc can effectively enhance the hardness, wear resistance and mechanical strength of ink due to their extremely small particle size and excellent physical and chemical properties. However, this modification method also brings some problems: Poor compatibility between organic and inorganic interfaces: The compatibility between nanofillers and the matrix resin in water-based inks is poor, resulting in a weak bond between the filler and the matrix resin, affecting the adhesion of the coating and may even cause the ink coating to peel off or crack, further affecting the performance of the ink.

[0004] Adhesion and abrasion resistance are difficult to coordinate: In traditional water-based inks, the addition of fillers can enhance the abrasion resistance and hardness of the ink, but often leads to a decrease in adhesion. This is because the presence of nanofillers may increase the rigidity of the coating, reduce the flexible bonding between the ink and the substrate, and thus reduce the adhesion, which makes it more difficult to balance adhesion and abrasion resistance, and it is difficult to meet both requirements in the same product. Summary of the invention

[0005] In view of the defects of the prior art, the object of the present invention is to provide a nano-modified water-based gravure ink and a preparation method thereof to solve the problems raised in the above background technology.

[0006] The present invention solves the technical problem by adopting the following technical solution: The present invention provides a nano-modified water-based gravure ink, comprising the following raw materials in parts by weight: 30-40 parts of deionized water, 30-35 parts of acrylic emulsion, 10-20 parts of waterborne polyurethane resin, 8-12 parts of pigment, 6-10 parts of silane coupling agent, 2-5 parts of hydroxymethyl cellulose, 1-3 parts of defoaming agent, and 5-10 parts of nano-modified filler.

[0007] Preferably, the nano-modified water-based gravure ink comprises the following raw materials in parts by weight: 35 parts of deionized water, 32.5 parts of acrylic emulsion, 15 parts of waterborne polyurethane resin, 10 parts of pigment, 8 parts of silane coupling regulator, 3.5 parts of hydroxymethyl cellulose, 2 parts of defoaming agent, and 7.5 parts of nano-modified filler.

[0008] Preferably, the deionized water is acetone; the solid content of the acrylic emulsion is 45-50%; the pigment is one of aniline, pyrazole, and metal-free phthalocyanine blue; and the defoamer is a silicone defoamer.

[0009] Preferably, the preparation method of the silane coupling agent is: S1: adding a silane coupling agent to a dopamine hydrochloride solution at a weight ratio of 2:5, and then adding sodium dodecylbenzene sulfonate in an amount of 10-15% of the total amount of the silane coupling agent, and stirring to obtain a blend; S2: adding boron nitride powder to a 5% by mass lanthanum chloride solution in a weight ratio of 2:5, stirring sufficiently, then filtering and drying to obtain a lanthanum boron nitride agent; The lanthanum boron nitride agent and the ball milling liquid are mixed and ball milled in a weight ratio of 5:3, and after the ball milling is completed, the mixture is filtered and dried to obtain an additive; The ball milling solution comprises the following raw materials in parts by weight: 2-3 parts of silicon carbide powder, 1-2 parts of carbon nanotubes, 4-7 parts of chitosan solution with a mass fraction of 4% and 2-3 parts of yttrium oxide.

[0010] S3: The additive and the blend are uniformly stirred in a weight ratio of 4:7 to obtain a silane coupling blend.

[0011] Preferably, the mass fraction of the dopamine hydrochloride solution is 2-5%; and the silane coupling agent is silane coupling agent KH550.

[0012] Preferably, the mixing and ball milling treatment is carried out at a ball milling speed of 1000-1500 r / min and the ball milling is carried out for 1 hour.

[0013] Preferably, the preparation method of the nano-modified filler is: S11: stirring the nano-hydroxyapatite in a sufficient amount of potassium permanganate solution, then washing and drying, and preheating the dried nano-hydroxyapatite at 60-65° C. for 1 h to obtain preheated nano-hydroxyapatite; S12: adding 2-5 parts of nano silicon carbide whiskers and 1-3 parts of flaky talc to 5-8 parts of sodium lignin sulfonate solution, and then adding 2-3 parts of urea, stirring evenly to obtain a filler liquid; S13: stirring the preheated nano-hydroxyapatite and the filler liquid in a weight ratio of 3:5, filtering and drying after the stirring is completed to obtain a nano-modified filler.

[0014] Preferably, the stirring speed of the stirring treatment is 550-750 r / min, and the stirring time is 1 hour.

[0015] Preferably, the mass fraction of the potassium permanganate solution is 2-5%; the mass fraction of the sodium lignin sulfonate solution is 4-7%.

[0016] The present invention also provides a method for preparing a nano-modified water-based gravure ink, comprising adding a pigment, a silane coupling agent, a nano-modified filler, and deionized water into a dispersion container, dispersing the mixture at a speed of 1000 rpm for 1 hour, adding an acrylic emulsion and a water-based polyurethane resin, increasing the speed to 3000 rpm, dispersing and grinding the mixture for 1 hour, filtering the mixture, adding hydroxymethyl cellulose, and stirring the mixture until the viscosity is stable, thereby obtaining a nano-modified water-based gravure ink.

[0017] Compared with the prior art, the present invention has the following beneficial effects: (1) The ink of the present invention optimizes the overall performance of the ink by mixing the acrylic emulsion, waterborne polyurethane resin, hydroxymethyl cellulose, silane coupling agent and nano-modified filler. The waterborne polyurethane resin in the matrix resin has good adhesion and wear resistance, and can improve the scratch resistance and wear resistance of the coating. The acrylic emulsion helps to provide better weather resistance and UV resistance. Through this formula design, the ink can improve the wear resistance while ensuring adhesion. (2) By introducing a silane coupling agent, the compatibility between the filler and the acrylic emulsion and the waterborne polyurethane resin is improved through chemical modification. The silane coupling agent is used to adjust the raw materials such as the dopamine hydrochloride solution with the silane coupling agent, and then the additives are coordinated and improved. The boron nitride in the additive is treated with a lanthanum solution, which helps to enhance the UV resistance of the ink, provide better UV stability, and avoid aging problems caused by ultraviolet rays. In addition, the ball milling is improved by ball milling with a ball milling liquid. Carbon nanotubes can improve the interaction between silicon carbide powder and other components and enhance the mechanical properties. At the same time, the high specific surface area of ​​carbon nanotubes can provide more surface contact sites, promote the grafting and interface enhancement of the silane coupling agent, effectively enhance the adhesion of the organic-inorganic interface, improve the adhesion performance of the ink, and avoid the decrease in adhesion caused by poor interface. (3) The chemical resistance and thermal stability of nano-hydroxyapatite and silicon carbide in the nano-modified filler improve the UV resistance and corrosion resistance of the coating. Nano-hydroxyapatite is treated with potassium permanganate solution and oxidized to remove surface impurities and impure substances, thereby improving its surface activity and facilitating its combination with other fillers. The long fibrous structure of the nano-silicon carbide whiskers in the filler solution enables it to enhance interaction in the coating, providing excellent impact resistance and wear resistance. When the nano-silicon carbide whiskers are combined with talc, silicon carbide provides hardness and enhances mechanical properties. Performance, while talc helps lubricate, reduce friction, and synergistically improve the wear resistance and scratch resistance of the coating. The addition of talc can also adjust the dispersibility of silicon carbide and prevent it from agglomerating in the ink, thereby improving the uniformity and dispersibility of the filler and ensuring the smoothness and durability of the ink coating; the combination of sodium lignin sulfonate and urea enhances the dispersibility of the filler and improves the adhesion and stability of the coating. Sodium lignin sulfonate provides dispersing effect, and urea ensures that the stability and viscosity of the filler liquid can be effectively controlled before the filler is added to the matrix resin, thereby achieving a more uniform ink coating. DETAILED DESCRIPTION

[0018] The following is a clear and complete description of the technical solutions in the embodiments of the present invention in conjunction with specific embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0019] Example 1. The nano-modified water-based gravure ink of this embodiment includes the following raw materials in parts by weight: 30 parts of deionized water, 30 parts of acrylic emulsion, 10 parts of waterborne polyurethane resin, 8 parts of pigment, 6 parts of silane coupling regulator, 2 parts of hydroxymethyl cellulose, 1 part of defoaming agent, and 5 parts of nano-modified filler.

[0020] The solid content of the acrylic emulsion is 45%; the pigment is metal-free phthalocyanine blue; and the defoaming agent is an organosilicon defoaming agent.

[0021] The preparation method of the silane coupling agent of this embodiment is: S1: adding a silane coupling agent to a dopamine hydrochloride solution at a weight ratio of 2:5, and then adding sodium dodecylbenzene sulfonate in an amount of 10% of the total amount of the silane coupling agent, and stirring to obtain a blend; S2: adding boron nitride powder to a 5% by mass lanthanum chloride solution in a weight ratio of 2:5, stirring sufficiently, then filtering and drying to obtain a lanthanum boron nitride agent; The lanthanum boron nitride agent and the ball milling liquid are mixed and ball milled in a weight ratio of 5:3, and after the ball milling is completed, the mixture is filtered and dried to obtain an additive; The ball milling solution includes the following raw materials in parts by weight: 2 parts of silicon carbide powder, 1 part of carbon nanotubes, 4 parts of chitosan solution with a mass fraction of 4%, and 2 parts of yttrium oxide.

[0022] S3: The additive and the blend are uniformly stirred in a weight ratio of 4:7 to obtain a silane coupling blend.

[0023] The mass fraction of the dopamine hydrochloride solution in this embodiment is 2%; the silane coupling agent is silane coupling agent KH550.

[0024] The mixing ball milling process in this embodiment has a ball milling speed of 1000 r / min and a ball milling time of 1 h.

[0025] The preparation method of the nano-modified filler of this embodiment is: S11: stirring the nano-hydroxyapatite in a sufficient amount of potassium permanganate solution, then washing and drying, and preheating the dried nano-hydroxyapatite at 60° C. for 1 h to obtain preheated nano-hydroxyapatite; S12: stirring the preheated nano-hydroxyapatite and the filler liquid in a weight ratio of 3:5, filtering and drying after the stirring is completed to obtain a nano-modified filler; 2 parts of nano silicon carbide whiskers and 1 part of flaky talc are added to 5 parts of sodium lignin sulfonate solution, and then 2 parts of urea are added and stirred evenly to obtain a filler liquid.

[0026] The stirring speed of the stirring process in this embodiment is 550 r / min, and the stirring is performed for 1 hour.

[0027] The mass fraction of the potassium permanganate solution in this embodiment is 2%; the mass fraction of the sodium lignin sulfonate solution is 4%.

[0028] A method for preparing a nano-modified water-based gravure ink in this embodiment comprises adding a pigment, a silane coupling agent, a nano-modified filler, and deionized water into a dispersion container, dispersing the mixture at a speed of 1000 rpm for 1 h, adding an acrylic emulsion and a water-based polyurethane resin, increasing the speed to 3000 rpm, dispersing and grinding the mixture for 1 h, filtering the mixture, adding hydroxymethyl cellulose, and stirring the mixture until the viscosity is stable, thereby obtaining a nano-modified water-based gravure ink.

[0029] Example 2. The nano-modified water-based gravure ink of this embodiment includes the following raw materials in parts by weight: 40 parts of deionized water, 35 parts of acrylic emulsion, 20 parts of waterborne polyurethane resin, 12 parts of pigment, 10 parts of silane coupling regulator, 5 parts of hydroxymethyl cellulose, 3 parts of defoaming agent, and 10 parts of nano-modified filler.

[0030] The solid content of the acrylic emulsion is 50%; the pigment is metal-free phthalocyanine blue; and the defoamer is an organosilicon defoamer.

[0031] The preparation method of the silane coupling agent of this embodiment is: S1: adding a silane coupling agent to a dopamine hydrochloride solution at a weight ratio of 2:5, and then adding sodium dodecylbenzene sulfonate in an amount of 15% of the total amount of the silane coupling agent, and stirring to obtain a blend; S2: adding boron nitride powder to a 5% by mass lanthanum chloride solution in a weight ratio of 2:5, stirring sufficiently, then filtering and drying to obtain a lanthanum boron nitride agent; The lanthanum boron nitride agent and the ball milling liquid are mixed and ball milled in a weight ratio of 5:3, and after the ball milling is completed, the mixture is filtered and dried to obtain an additive; The ball milling solution includes the following raw materials in parts by weight: 3 parts of silicon carbide powder, 2 parts of carbon nanotubes, 7 parts of chitosan solution with a mass fraction of 4% and 3 parts of yttrium oxide.

[0032] S3: The additive and the blend are uniformly stirred in a weight ratio of 4:7 to obtain a silane coupling blend.

[0033] The mass fraction of the dopamine hydrochloride solution in this embodiment is 5%; the silane coupling agent is silane coupling agent KH550.

[0034] The mixing and ball milling process in this embodiment was carried out at a ball milling speed of 1500 r / min and the ball milling was carried out for 1 h.

[0035] The preparation method of the nano-modified filler of this embodiment is: S11: stirring the nano-hydroxyapatite in a sufficient amount of potassium permanganate solution, then washing and drying, and preheating the dried nano-hydroxyapatite at 65° C. for 1 h to obtain preheated nano-hydroxyapatite; S12: stirring the preheated nano-hydroxyapatite and the filler liquid in a weight ratio of 3:5, filtering and drying after the stirring is completed to obtain a nano-modified filler; 5 parts of nano silicon carbide whiskers and 3 parts of flaky talc were added to 8 parts of sodium lignin sulfonate solution, and then 3 parts of urea were added and stirred evenly to obtain a filler liquid.

[0036] The stirring speed of the stirring process in this embodiment is 750 r / min, and the stirring is performed for 1 hour.

[0037] The mass fraction of the potassium permanganate solution in this embodiment is 5%; the mass fraction of the sodium lignin sulfonate solution is 7%.

[0038] A method for preparing a nano-modified water-based gravure ink in this embodiment is as follows: pigment, silane coupling agent, nano-modified filler, and deionized water are added to a dispersion container, dispersed at a speed of 1000 rpm for 1 hour, acrylic emulsion and water-based polyurethane resin are added, the speed is increased to 3000 rpm, dispersed and ground for 1 hour, filtered, and hydroxymethyl cellulose is added and stirred until the viscosity is stable to obtain a nano-modified water-based gravure ink.

[0039] Example 3. The nano-modified water-based gravure ink of this embodiment includes the following raw materials in parts by weight: 35 parts of deionized water, 32.5 parts of acrylic emulsion, 15 parts of waterborne polyurethane resin, 10 parts of pigment, 8 parts of silane coupling regulator, 3.5 parts of hydroxymethyl cellulose, 2 parts of defoaming agent, and 7.5 parts of nano-modified filler.

[0040] The solid content of the acrylic emulsion is 47.5%; the pigment is metal phthalocyanine blue; and the defoaming agent is an organosilicon defoaming agent.

[0041] The preparation method of the silane coupling agent of this embodiment is: S1: adding a silane coupling agent to a dopamine hydrochloride solution at a weight ratio of 2:5, and then adding sodium dodecylbenzene sulfonate in an amount of 12.5% ​​of the total amount of the silane coupling agent, and stirring to obtain a blend; S2: adding boron nitride powder to a 5% by mass lanthanum chloride solution in a weight ratio of 2:5, stirring sufficiently, then filtering and drying to obtain a lanthanum boron nitride agent; The lanthanum boron nitride agent and the ball milling liquid are mixed and ball milled in a weight ratio of 5:3, and after the ball milling is completed, the mixture is filtered and dried to obtain an additive; The ball milling solution includes the following raw materials in parts by weight: 2.5 parts of silicon carbide powder, 1.5 parts of carbon nanotubes, 5.5 parts of chitosan solution with a mass fraction of 4%, and 2.5 parts of yttrium oxide.

[0042] S3: The additive and the blend are uniformly stirred in a weight ratio of 4:7 to obtain a silane coupling blend.

[0043] The mass fraction of the dopamine hydrochloride solution in this embodiment is 3.5%; the silane coupling agent is silane coupling agent KH550.

[0044] The mixing ball milling process in this embodiment was carried out at a ball milling speed of 1250 r / min and the ball milling was carried out for 1 hour.

[0045] The preparation method of the nano-modified filler of this embodiment is: S11: stirring the nano-hydroxyapatite in a sufficient amount of potassium permanganate solution, then washing and drying, and preheating the dried nano-hydroxyapatite at 62.5° C. for 1 h to obtain preheated nano-hydroxyapatite; S12: stirring the preheated nano-hydroxyapatite and the filler liquid in a weight ratio of 3:5, filtering and drying after the stirring is completed to obtain a nano-modified filler; 3.5 parts of nano silicon carbide whiskers and 2 parts of flaky talc were added to 6.5 parts of sodium lignin sulfonate solution, and then 2.5 parts of urea were added and stirred evenly to obtain a filler liquid.

[0046] The stirring speed of the stirring process in this embodiment is 600 r / min, and the stirring is performed for 1 hour.

[0047] The mass fraction of the potassium permanganate solution in this embodiment is 3.5%; the mass fraction of the sodium lignin sulfonate solution is 5.5%.

[0048] A method for preparing a nano-modified water-based gravure ink in this embodiment comprises adding a pigment, a silane coupling agent, a nano-modified filler, and deionized water into a dispersion container, dispersing the mixture at a speed of 1000 rpm for 1 h, adding an acrylic emulsion and a water-based polyurethane resin, increasing the speed to 3000 rpm, dispersing and grinding the mixture for 1 h, filtering the mixture, adding hydroxymethyl cellulose, and stirring the mixture until the viscosity is stable, thereby obtaining a nano-modified water-based gravure ink.

[0049] Comparative Example 1. The difference from Example 3 is that no silane coupling agent is added.

[0050] Comparative Example 2. The difference from Example 3 is that no additive is added to the silane coupling agent.

[0051] Comparative Example 3. The difference from Example 3 is that no lanthanum boron nitride agent is added in the preparation of the additive.

[0052] Comparative Example 4. The difference from Example 3 is that no ball milling liquid is added during the preparation of the additive.

[0053] Comparative Example 5. The difference from Example 3 is that silicon carbide powder and carbon nanotubes are not added to the ball milling liquid. Comparative Example 6. The difference from Example 3 is that no nano-modified filler is added.

[0054] Comparative Example 7. The difference from Example 3 is that no filler liquid treatment is used in the preparation of the nano-modified filler.

[0055] Comparative Example 8. The difference from Example 3 is that no nano silicon carbide whiskers or flaky talc powder is added to the filler liquid.

[0056] Test items and results Ink adhesion test Preparation of ink layer: The ink prepared in each embodiment and comparative example was subjected to gravure printing, wherein the plastic gravure electroplate had 90 lines and a depth of 25-30 μm; the bellows length was 2.5 m, the wind speed of the bellows was 30-35 m / s, and the printing speed was 600 m / min on BOPP and PEF films.

[0057] According to GB / t13217.7-2023, the disc peeling method is used for testing. The tape is pasted on the ink printed surface, and rolled back and forth on the tape roller for 3 times, and then the sample is immediately clamped on the A disc. The exposed tape is fixed on the B disc, and then the machine is turned on, and the A disc rotates at a speed of 0.6m / s to peel off the tape.

[0058] Use a 20mm wide translucent millimeter grid paper to cover the uncovered part, count the number of grids occupied by the ink layer and the number of grids occupied by the peeled ink layer, and calculate according to the following formula: ; A is the ink adhesion, A1 is the number of ink layers remaining on the substrate after the tape is peeled off, and A2 is the number of ink layers removed.

[0059] The adhesion test results of the inks prepared in Examples 1-3 and Comparative Examples 1-8 are shown in Table 1.

[0060] Table 1 Ink abrasion resistance test The ink prepared in each embodiment and comparative example was put on the machine for gravure printing. Among them, the plastic gravure electric engraving plate has 90 lines and a depth of 25-30μm; the bellows length is 2.5m, the bellows wind speed is 30-35m / s, and it is printed on kraft paper and A4 at speeds of 100m / min and 150m / min respectively. The kraft paper and A4 paper are cut into 6cm×29.7cm and 5cm×29.7cm strips for standby use, and then the strips are fixed on the lower friction table of the printing friction tester, and the dust-free A4 white paper is wrapped on the upper friction table and fixed on the transmission arm, and a 2kg weight is placed on it, and 100 reciprocating friction experiments are carried out at a speed of 85±3r / min. The density decay rate is used to evaluate the abrasion resistance of the ink. The smaller the density decay rate, the better the abrasion resistance. The density of the printed pattern is tested by an X-Rite 310 densitometer. The calculation formula of the density decay rate R is as follows: ; D0 is the density of the printed pattern before friction, D g is the density of the printed pattern after friction. The density decay rate is represented by the average value of the test results of 5 specimens.

[0061] The abrasion resistance test results of the inks prepared in Examples 1-3 and Comparative Examples 1-8 are shown in Table 2.

[0062] Table 2 Ink UV resistance test The ink prepared in each embodiment and comparative example was put into gravure printing machine. Among them, the plastic gravure electric engraving plate had 90 lines and a depth of 25-30μm; the bellows length was 2.5m, the bellows wind speed was 30-35m / s, and it was printed on A4 at a speed of 150m / min. The A4 paper was cut into 2cm×2cm strips, and the strips were placed under a 120V, 2×15W, 60HZD ultraviolet lamp, with the lamp tube at a distance of 3cm from the strips, and irradiated continuously for 8h. Then, the density value of the irradiated strips was measured using an X-Rite 310 densitometer, and the fading property S of the strips was calculated using the following formula: ; C0 is the spline density before irradiation, C g is the density of the specimen after irradiation, and the fading property is represented by the average value of the test results of 5 specimens.

[0063] The UV resistance test results of the inks prepared in Examples 1-3 and Comparative Examples 1-8 are shown in Table 3.

[0064] Table 3 Ink corrosion resistance test The ink prepared in each embodiment and comparative example was put into gravure printing machine. Among them, the plastic gravure electric engraving plate had 90 lines and a depth of 25-30 μm; the bellows length was 2.5 m, the bellows wind speed was 30-35 m / s, and it was printed on A4 at a speed of 150 m / min, and then the A4 paper was pressed between two filter papers with 5% sulfuric acid or 5% sodium hydroxide, and the A4 paper and the filter paper were sandwiched between glass plates, and pressed with a weight of 1 kg for 10 minutes and 60 minutes, and the degree of impregnation of the filter paper was observed. The results are shown in Table 4.

[0065] Table 4 The nano-modified water-based gravure ink products prepared in Examples 1-3 of the present invention have excellent wear resistance and adhesion properties, and the corrosion resistance, scratch resistance and UV resistance stability of the products are remarkable; It can be seen from Comparative Examples 1-8 and Example 3 that when the product does not add a silane coupling agent or a nano-modified filler, the performance of the product deteriorates significantly. The synergistic effect of the two is achieved, and the product performance effect is obvious. No additives are added to the silane coupling agent, no lanthanum boron nitride agent is added in the preparation of the additives, no ball milling liquid is added in the preparation of the additives, no silicon carbide powder and carbon nanotubes are added to the ball milling liquid, no filler liquid treatment is used in the preparation of the nano-modified filler, and no nano-silicon carbide whiskers and flaky talcum powder are added to the filler liquid. The performance of the product tends to deteriorate, and the modification method of the nano-modified filler adopts other modifications, which are not as significant as the improvement effect of the present invention. In addition, the addition of the silane coupling agent and the nano-modified filler can enhance the wear resistance and adhesion stability of the product under corrosion resistance, scratch resistance and UV resistance conditions.

[0066] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

[0067] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. Nano-modified water-based gravure ink, characterized in that: It includes the following raw materials in parts by weight: 30-40 parts of deionized water, 30-35 parts of acrylic emulsion, 10-20 parts of waterborne polyurethane resin, 8-12 parts of pigment, 6-10 parts of silane coupling agent, 2-5 parts of hydroxymethyl cellulose, 1-3 parts of defoaming agent, and 5-10 parts of nano-modified filler.

2. The nano-modified water-based gravure ink according to claim 1, characterized in that: The nano-modified water-based gravure ink comprises the following raw materials in parts by weight: 35 parts of deionized water, 32.5 parts of acrylic emulsion, 15 parts of waterborne polyurethane resin, 10 parts of pigment, 8 parts of silane coupling regulator, 3.5 parts of hydroxymethyl cellulose, 2 parts of defoaming agent, and 7.5 parts of nano-modified filler.

3. The nano-modified water-based gravure ink according to claim 2, characterized in that: The solid content of the acrylic emulsion is 45-50%; the pigment is one of aniline, pyrazole and metal-free phthalocyanine blue; and the defoamer is an organosilicon defoamer.

4. The nano-modified water-based gravure ink according to claim 1, characterized in that: The preparation method of the silane coupling agent is: S1: adding a silane coupling agent to a dopamine hydrochloride solution at a weight ratio of 2:5, and then adding sodium dodecylbenzene sulfonate in an amount of 10-15% of the total amount of the silane coupling agent, and stirring to obtain a blend; S2: adding boron nitride powder to a 5% by mass lanthanum chloride solution in a weight ratio of 2:5, stirring sufficiently, then filtering and drying to obtain a lanthanum boron nitride agent; The lanthanum boron nitride agent and the ball milling liquid are mixed and ball milled in a weight ratio of 5:3, and after the ball milling is completed, the mixture is filtered and dried to obtain an additive; The ball milling solution includes the following raw materials in parts by weight: 2-3 parts of silicon carbide powder, 1-2 parts of carbon nanotubes, 4-7 parts of 4% chitosan solution by weight, and 2-3 parts of yttrium oxide; S3: The additive and the blend are uniformly stirred in a weight ratio of 4:7 to obtain a silane coupling blend.

5. The nano-modified water-based gravure ink according to claim 4, characterized in that: The mass fraction of the dopamine hydrochloride solution is 2-5%; the silane coupling agent is silane coupling agent KH550.

6. The nano-modified water-based gravure ink according to claim 4, characterized in that: The mixing and ball milling process is performed at a ball milling speed of 1000-1500 r / min and the ball milling is performed for 1 hour.

7. The nano-modified water-based gravure ink according to claim 1, characterized in that: The preparation method of the nano-modified filler is: S11: stirring the nano-hydroxyapatite in a sufficient amount of potassium permanganate solution, then washing and drying, and preheating the dried nano-hydroxyapatite at 60-65° C. for 1 h to obtain preheated nano-hydroxyapatite; S12: adding 2-5 parts of nano silicon carbide whiskers and 1-3 parts of flaky talc to 5-8 parts of sodium lignin sulfonate solution, and then adding 2-3 parts of urea, stirring evenly to obtain a filler liquid; S13: stirring the preheated nano-hydroxyapatite and the filler liquid in a weight ratio of 3:5, filtering and drying after the stirring is completed to obtain a nano-modified filler.

8. The nano-modified water-based gravure ink according to claim 7, characterized in that: The stirring speed of the stirring treatment is 550-750 r / min, and the stirring is performed for 1 hour.

9. The nano-modified water-based gravure ink according to claim 7, characterized in that: The mass fraction of the potassium permanganate solution is 2-5%; the mass fraction of the sodium lignin sulfonate solution is 4-7%.

10. A method for preparing the nano-modified water-based gravure ink according to any one of claims 1 to 9, characterized in that: Pigment, silane coupling agent, nano-modified filler and deionized water were added into a dispersion container. After dispersion at 1000 rpm for 1 h, acrylic emulsion and waterborne polyurethane resin were added. The speed was increased to 3000 rpm and dispersed and ground for 1 h. After filtering, hydroxymethyl cellulose was added and stirred until the viscosity was stable to obtain a rice-modified water-based gravure ink.

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