Process for printing on gel surface and application thereof

Abstract

The invention provides a process for printing on the surface of gel and application of the process, and belongs to the technical field of printing. The printing material is prepared from the following components in parts by weight: 80 to 100 parts of composite sodium alginate, 30 to 50 parts of composite fatty alcohol-polyoxyethylene ether, 20 to 30 parts of color fixing agent, 15 to 20 parts of humectant, 0.1 to 15 parts of dye, 10 to 20 parts of filler, 3 to 5 parts of dispersing agent, 3 to 5 parts of surfactant, 30 to 50 parts of cross-linking agent and 0.5 to 3 parts of photoinitiator. When the prepared printing material is applied to a printing process, chemical treatment does not need to be carried out on a matrix material, the surface of a matrix such as gel is not damaged, and the printing material has good adhesiveness and excellent environment resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of printing, and in particular relates to a process for printing on a gel surface and an application thereof. Background Art

[0002] Printing materials refer to materials used for printing patterns on various substrates (such as textiles, paper, plastics, metals, gels, etc.). These materials usually contain pigments or dyes, adhesives, thickeners, dispersants, surfactants, cross-linking agents and other additives to ensure that the pattern can show the expected color, clarity and durability on the substrate. Printing materials are used in textile printing, packaging materials, personal care products, medical supplies and food packaging.

[0003] Printing materials are divided into dye-based printing materials, pigment-based printing materials, resin-based printing materials, functional printing materials and environmentally friendly printing materials according to their main components. Resin-based printing materials can be used to improve the wear resistance and adhesion of printed patterns. However, in actual application, the chemical or physical bonding between the printing material and the substrate is not strong enough, resulting in a low service life of the printed pattern. In response to the above problems, the current methods are mostly to use different types of adhesives for different substrates to ensure good adhesion, and to increase the surface energy of the substrate by methods such as corona treatment. For some substrates, the surface roughness can also be increased by mechanical grinding, thereby improving the bonding between the substrate and the printing material.

[0004] The above-mentioned method of pretreating the substrate can improve the bonding force between the substrate and the printing material to a certain extent, but this method of pretreating the substrate will damage the surface of the substrate, especially the surface of the gel substrate. Although it can improve the bonding force between the substrate and the printing material in the initial stage, thereby improving the adhesion of the printing material, the printing material is used for a long time, especially when the external environment changes, the material composition of the printing material itself is unreasonable, and its environmental resistance such as water resistance, solvent resistance, light resistance and heat resistance becomes poor, and the service life of the printing material is short. Summary of the invention

[0005] The purpose of the present invention is to provide a process for printing on the surface of gel and its application, so as to solve the problems of unreasonable design of the composition of the printing material, poor adhesion and environmental resistance.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] The first aspect of the present invention provides a process for printing on a gel surface, comprising the following steps:

[0008] (1) Clean the surface of the gel printed product;

[0009] (2) dissolving the printing material in acetone and then applying it to the outer surface of the printed product according to the pattern;

[0010] The printing material includes the following components in parts by weight: 80-100 parts of composite sodium alginate, 30-50 parts of composite fatty alcohol polyoxyethylene ether, 20-30 parts of fixing agent, 15-20 parts of moisturizing agent, 0.1-15 parts of dye, 10-20 parts of filler, 3-5 parts of dispersant, 3-5 parts of surfactant, 30-50 parts of cross-linking agent and 0.5-3 parts of photoinitiator;

[0011] The composite sodium alginate comprises sodium alginate, a first modified sodium alginate and a second modified sodium alginate in a mass ratio of (8-10):(3-5):1; the first modified sodium alginate is obtained by reacting an organic amine with sodium alginate, and the organic amine comprises triethylamine, triisopropylamine and polyethyleneimine in a mass ratio of (5-8):(2-4):1; the second modified ammonium alginate is obtained by reacting an organic compound containing an epoxy group with sodium alginate, and the organic compound containing an epoxy group comprises epichlorohydrin, butyl oxirane and decyl oxirane in a mass ratio of 1:(1.5-2.5):(5-8);

[0012] The composite fatty alcohol polyoxyethylene ether comprises fatty alcohol polyoxyethylene ether and modified fatty alcohol polyoxyethylene ether in a mass ratio of (1-3): (0.5-0.8); the modified fatty alcohol polyoxyethylene ether is obtained by reacting aldehyde acid organic matter with fatty alcohol polyoxyethylene ether, and the aldehyde acid organic matter comprises glucuronic acid, arabinonic acid and mannose aldehyde in a mass ratio of (3-5): (0.8-1.2): 1;

[0013] (3) Irradiate under ultraviolet light to complete curing, and obtain a printed product with a printed pattern.

[0014] In order to further improve the adhesion of the printing material on the substrate in the prior art, the present invention adds sodium alginate and fatty alcohol polyoxyethylene ether to the printing material, wherein sodium alginate can improve the adhesion of the printing material on the substrate, and fatty alcohol polyoxyethylene ether is a commonly used nonionic surfactant with good wettability and dispersibility. Its presence can reduce the surface tension of the liquid, making it easier for the printing material to adhere to the surface of the gel substrate. However, the present invention finds that the above materials have limited improvement on the adhesion of the printing material to the substrate, and the adhesion of the printing material on the substrate is easily affected by the external environment. In view of this problem, the present invention modifies sodium alginate and fatty alcohol polyoxyethylene ether respectively, further improving the adhesion and stability of the printing material.

[0015] The composite sodium alginate used in the present invention includes sodium alginate, a first modified sodium alginate and a second modified sodium alginate. This combination can significantly improve the adhesion of the printing material on the gel and its environmental stability. The adhesion of the printing material of the present invention is improved. The reason for analysis is: the first modified sodium alginate introduces positively charged amine groups through the reaction of organic amines with sodium alginate. These amine groups can form electrostatic attraction with negatively charged groups (such as carboxyl or hydroxyl) on the surface of the substrate, thereby enhancing the adhesion. The modified sodium alginate molecules can form a more complex cross-linked network with unmodified sodium alginate molecules and other components. Such a network structure can provide additional mechanical strength, so that the printing material is more firmly attached to the surface of the substrate. The environmental stability of the printing material in the present invention is reflected in the improvement of comprehensive properties such as water resistance, solvent resistance, thermal stability, light stability, and aging resistance. Reason for analysis: The amine groups in the first modified sodium alginate can reduce water erosion to a certain extent because they can compete with water molecules for adsorption sites and reduce the interaction between water molecules and the polymer main chain. The second modified sodium alginate increases the overall hydrophobicity of the material and reduces the water absorption rate by introducing hydrophobic epoxy groups. The chemical bonds formed after modification, especially covalent bonds, can resist the dissolution effect of the solvent and prevent the material from decomposing in the solvent environment. The introduced modified groups increase the interaction between molecules. For example, the introduction of epoxy groups can enhance thermal stability through cross-linking, thereby improving the thermal stability of the material. The functional groups introduced by modification increase the material's antioxidant capacity and reduce the generation of free radicals, thereby delaying the aging process of the material.

[0016] The composite fatty alcohol polyoxyethylene ether used in the present invention includes fatty alcohol polyoxyethylene ether and modified fatty alcohol polyoxyethylene ether. The modified fatty alcohol polyoxyethylene ether makes the printing material easier to spread and fit closely on the substrate surface, thereby improving the adhesion. Analysis reason: The modified fatty alcohol polyoxyethylene ether can introduce new functional groups, such as aldehyde groups, by reacting with aldehyde acid organic matter. These groups can enhance the wettability of the material to the substrate surface, so that the printing material can better penetrate the microporous structure of the substrate surface, thereby enhancing the adhesion. The composite fatty alcohol polyoxyethylene ether of the present invention can also synergistically improve the interface bonding between the printing material and the substrate surface, and further improve the environmental stability. Analysis reason: The mixed use of fatty alcohol polyoxyethylene ether and modified fatty alcohol polyoxyethylene ether can adjust the hydrophilic-hydrophobic balance of the printing material, so that it has a certain hydrophobicity while maintaining good wettability, thereby improving the water resistance of the material. The functional groups in the modified fatty alcohol polyoxyethylene ether can improve the structural rigidity of the material, making it not easy to deform at high temperature, thereby improving the thermal stability. Some aldehyde acid organic compounds may have certain antioxidant properties. Their presence can help inhibit light-induced free radical reactions, thereby improving the light stability of the material. The antioxidant groups in the modified fatty alcohol polyoxyethylene ether can reduce the generation of free radicals and delay the aging process of the material. In addition, the enhanced intermolecular forces can also help resist degradation caused by environmental factors. The introduction of modified fatty alcohol polyoxyethylene ether can increase the intermolecular forces, making the material more stable in the solvent and not easily dissolved or destroyed by the solvent.

[0017] Preferably, the preparation method of the first modified sodium alginate is:

[0018] Add sodium alginate and organic amine to a flask containing tetrahydrofuran, place in an ice bath, dissolve olefinic acid chloride in dichloromethane A and place in a constant pressure dropping funnel, control the dropping rate, and stir for 6 to 12 hours; let stand overnight, filter, and distill under reduced pressure, inject deionized water into the concentrate, shake to dissolve, add dichloromethane B to extract, shake, stand, separate, take the water phase, add 1 mol / L hydrochloric acid solution, shake, inject ethanol to precipitate, filter, and vacuum dry the insoluble matter at 60 to 80° C. for 3 to 5 hours to obtain the first modified sodium alginate;

[0019] The mass ratio of sodium alginate and organic amine is (35-45):(0.5-1); the dosage ratio of triethylamine, tetrahydrofuran, olefinic acid chloride, dichloromethane A, deionized water, dichloromethane B, hydrochloric acid solution and ethanol is: 1 mol: 500 mL: 1 mol: 300 mL: 300 mL: 400 mL: 200 mL: 1500 mL.

[0020] Preferably, the preparation method of the second modified sodium alginate is:

[0021] Adding sodium alginate to deionized water, stirring for 2 to 4 hours at a water bath temperature of 50 to 55° C., adding an organic compound containing an epoxy group, stirring for 0.5 to 2 hours, standing for 30 minutes, filtering and drying to obtain a second modified sodium alginate;

[0022] The mass ratio of sodium alginate to the organic compound containing epoxy groups is (3-6): (4-5), and the mass ratio of sodium alginate to water is (3-6): (80-120).

[0023] Preferably, the preparation method of modified fatty alcohol polyoxyethylene ether is:

[0024] Add fatty alcohol polyoxyethylene ether to deionized water, stir and dissolve, then add aldehyde acid organic matter and alkaline catalyst, raise the temperature to 60-80°C, stir and react for 5-6 hours, extract and dry after the reaction to obtain modified fatty alcohol polyoxyethylene ether;

[0025] The dosage ratio of fatty alcohol polyoxyethylene ether, water, aldehyde acid organic matter and alkaline catalyst is 80-120g: 300-500mL: 30-50g: 0.5-2g.

[0026] Preferably, the preparation process of the printing material is:

[0027] 1) taking a composite fatty alcohol polyoxyethylene ether, a filler, a dye, a dispersant and a surfactant, mixing them, and then stirring them to obtain a mixture A for standby use;

[0028] 2) taking composite sodium alginate and a color fixing agent, mixing them, grinding and crushing them into 110 meshes to obtain a mixture B for later use;

[0029] 3) Dissolving mixture A with twice the amount of ethanol solution to obtain a mixed solution A, uniformly adding mixture B to the mixed solution A to obtain a mixed solution C, and then heating the mixed solution C, maintaining uniform stirring during the heating process, and the stirring time is 30 minutes;

[0030] 4) taking a moisturizer, a cross-linking agent and a photoinitiator, mixing them evenly to obtain a mixture D, adding the mixture D to the mixed solution C, then adding acetic acid to the mixed solution, adjusting the pH to 4, homogenizing and beating the mixed solution, steaming the mixture after beating, and then drying the mixture to obtain a printing material.

[0031] Preferably, the color fixing agent is one or a mixture of diacetone acrylamide and methyl ethyl ketone peroxide; the humectant is one or a mixture of glycerol and diethylene glycol; the dye is one or a mixture of organic dyes and inorganic dyes; and the filler is one or a mixture of calcium carbonate and talcum powder.

[0032] The dyes in the present invention can be mixed according to the desired color and are not limited to organic dyes and inorganic dyes. Inorganic dyes include but are not limited to titanium dioxide.

[0033] Preferably, the dispersant is one or more of methylpentanol, sodium pyrophosphate, and triethylhexyl phosphoric acid; the surfactant is one or more of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, and potassium oleate; the crosslinking agent is one or more of acrylic acid, methacrylic acid, and 2-acrylamide-2-methylpropane sulfonic acid; and the photoinitiator is one or more of 1173, 2959, 184, or TPO.

[0034] Preferably, the mass ratio of the printing material to acetone is 1:(5-8), and the ultraviolet irradiation time is 0.5-10h.

[0035] The second aspect of the present invention provides a printed product having a printed pattern prepared by the above preparation method.

[0036] The third aspect of the present invention provides an application of a printing material, and an application of a printed product with a printing pattern in the field of personal care products, medical supplies, and food packaging.

[0037] Compared with the prior art, the advantages and beneficial effects of the present invention are:

[0038] 1. The modified sodium alginate used in the printing material of the present invention, the first modified sodium alginate is modified by organic amines (such as triethylamine, triisopropylamine and polyethyleneimine), which enhances its binding force with the substrate. The second modified sodium alginate is modified by organic compounds containing epoxy groups (such as epichlorohydrin, butyl oxirane and decyl oxirane), which improves the chemical crosslinking degree with other raw materials and synergistically enhances the adhesion of the printing material on the substrate.

[0039] 2. The composite fatty alcohol polyoxyethylene ether of the present invention is modified by aldehyde acid organic matter (such as glucuronic acid, arabinonic acid and mannose aldehyde), thereby improving its binding force with the substrate and further enhancing its adhesion.

[0040] 3. The use of composite sodium alginate and composite fatty alcohol polyoxyethylene ether in the present invention not only improves the adhesion of the printing material, but also can comprehensively improve the stability of the printing material, making it have water resistance, solvent resistance, thermal stability, light stability and aging resistance.

[0041] 4. The printing material of the present invention has good adhesion and stability, and can be widely used in the fields of personal care products, medical supplies, food packaging, etc., thus expanding the application scope of the printing material. DETAILED DESCRIPTION

[0042] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. 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.

[0043] Example 1

[0044] This embodiment provides a printing material, which includes the following components in parts by weight: 95 parts of composite sodium alginate, 40 parts of composite fatty alcohol polyoxyethylene ether, 25 parts of color fixing agent, 18 parts of moisturizing agent, 8 parts of dye, 15 parts of filler, 4 parts of dispersant, 4 parts of surfactant, 35 parts of cross-linking agent and 1 part of photoinitiator;

[0045] The fixing agent is diacetone acrylamide (CAS: 2873-97-4);

[0046] The humectant is glycerin;

[0047] The dye is titanium dioxide;

[0048] The filler is calcium carbonate;

[0049] The dispersant is sodium pyrophosphate;

[0050] The surfactant is sodium dodecylbenzene sulfonate;

[0051] The crosslinking agent is methacrylic acid (CAS: 79-41-4);

[0052] The photoinitiator is TPO (CAS: 75980-60-8);

[0053] The composite sodium alginate is sodium alginate (CAS: 9005-38-3), the first modified sodium alginate and the second modified sodium alginate in a mass ratio of 9:4:1;

[0054] The first modified sodium alginate is obtained by reacting an organic amine with sodium alginate, wherein the organic amine is triethylamine, triisopropylamine and polyethyleneimine (CAS: 9002-98-6) in a mass ratio of 6:3:1;

[0055] The second modified ammonium alginate is obtained by reacting an organic compound containing an epoxy group with sodium alginate, wherein the organic compound containing an epoxy group is epichlorohydrin, butyl oxirane (CAS: 1436-34-6) and decyl oxirane (CAS: 18633-25-5) in a mass ratio of 1:2:6;

[0056] The composite fatty alcohol polyoxyethylene ether is fatty alcohol polyoxyethylene ether (CAS: 37335-03-8) and modified fatty alcohol polyoxyethylene ether in a mass ratio of 2:0.7;

[0057] The modified fatty alcohol polyoxyethylene ether is obtained by reacting an aldehyde acid organic substance with a fatty alcohol polyoxyethylene ether, wherein the aldehyde acid organic substance is glucuronic acid (CAS: 6556-12-3), arabinonic acid (CAS: 6703-05-5) and mannose aldehyde (CAS: 6814-36-4) in a mass ratio of 4:1:1.

[0058] This embodiment provides a method for preparing a printing material, comprising the following steps:

[0059] (1) The preparation method of the first modified sodium alginate is:

[0060] Sodium alginate and organic amine are added to a flask containing tetrahydrofuran, and ice bath is applied. 10-undecenoyl chloride (CAS: 38460-95-6) is dissolved in dichloromethane A and placed in a constant pressure dropping funnel. The dropping rate is controlled and stirred for 10 hours. The mixture is allowed to stand overnight, filtered, and distilled under reduced pressure. Deionized water is injected into the concentrate, and the mixture is shaken to dissolve. Dichloromethane B is added for extraction, shaken, allowed to stand, and separated. The aqueous phase is taken, 1 mol / L hydrochloric acid solution is added, shaken, ethanol is injected for precipitation, and filtered. The insoluble matter is vacuum dried at 60° C. for 3 hours to obtain the first modified sodium alginate.

[0061] The mass ratio of sodium alginate and organic amine is 40:0.8; the dosage ratio of triethylamine, tetrahydrofuran, 10-undecenoyl chloride, dichloromethane A, deionized water, dichloromethane B, hydrochloric acid solution, and ethanol is: 1 mol: 500 mL: 1 mol: 300 mL: 300 mL: 400 mL: 200 mL: 1500 mL.

[0062] (2) The preparation method of the second modified sodium alginate is:

[0063] Add deionized water to sodium alginate, stir for 3 hours at a water bath temperature of 50°C, add an organic compound containing an epoxy group, stir for 1 hour, let stand for 30 minutes, filter and dry to obtain a second modified sodium alginate;

[0064] The mass ratio of sodium alginate to the organic compound containing epoxy groups is 4:5, and the mass ratio of sodium alginate to deionized water is 4:100.

[0065] The preparation method of modified fatty alcohol polyoxyethylene ether is:

[0066] Fatty alcohol polyoxyethylene ether (model AEO-7, ethylene oxide addition number 7) was added to deionized water, stirred and dissolved, and then aldehyde acid organic matter and sodium hydroxide were added, the temperature was raised to 70°C, and the reaction was stirred for 5.5 hours. After the reaction was completed, the modified fatty alcohol polyoxyethylene ether was obtained by extraction and drying;

[0067] The dosage ratio of fatty alcohol polyoxyethylene ether, deionized water, aldehyde acid organic matter and sodium hydroxide is 100g:400mL:40g:1.5g.

[0068] (3) The preparation process of printing materials is:

[0069] 1) taking a composite fatty alcohol polyoxyethylene ether, a filler, a dye, a dispersant and a surfactant, mixing them, and then stirring them to obtain a mixture A for standby use;

[0070] 2) taking composite sodium alginate and a color fixing agent, mixing them, grinding and crushing them into 110 meshes to obtain a mixture B for later use;

[0071] 3) Dissolving mixture A with twice the amount of ethanol solution to obtain a mixed solution A, uniformly adding mixture B to the mixed solution A to obtain a mixed solution C, and then heating the mixed solution C, maintaining uniform stirring during the heating process, and the stirring time is 30 minutes;

[0072] 4) taking a moisturizer, a cross-linking agent and a photoinitiator, mixing them evenly to obtain a mixture D, adding the mixture D to the mixed solution C, then adding acetic acid to the mixed solution, adjusting the pH to 4, homogenizing and beating the mixed solution, steaming the mixture after beating, and then drying the mixture to obtain a printing material.

[0073] This embodiment provides a process for printing on a gel surface, comprising the following steps:

[0074] (1) Clean the surface of gel printed products;

[0075] (2) dissolving the printing material in acetone, with the mass ratio of the printing material to acetone being 1:6, and then evenly coating the outer surface of the gel-printed product according to the pattern;

[0076] (3) Irradiate under ultraviolet light for 5 hours, and curing is completed to obtain a gel print with a printed pattern.

[0077] Example 2

[0078] The difference between this embodiment and embodiment 1 is that the composition of the printing material is different.

[0079] In this embodiment, the printing material includes the following components in parts by weight: 85 parts of composite sodium alginate, 35 parts of composite fatty alcohol polyoxyethylene ether, 25 parts of fixing agent, 15 parts of humectant, 5 parts of dye, 12 parts of filler, 4 parts of dispersant, 4 parts of surfactant, 32 parts of cross-linking agent and 0.8 parts of photoinitiator.

[0080] Comparative Example 1

[0081] The difference between this comparative example and Example 1 is that the mass ratio of sodium alginate, the first modified sodium alginate and the second modified sodium alginate is 9:4:5.

[0082] Comparative Example 2

[0083] The difference between this comparative example and Example 1 is that the mass ratio of triethylamine, triisopropylamine and polyethyleneimine is 6:3:3.

[0084] Comparative Example 3

[0085] The difference between this comparative example and Example 1 is that the organic amine does not contain polyethyleneimine, and the mass ratio of triethylamine to triisopropylamine is 6:3.

[0086] Comparative Example 4

[0087] The difference between this comparative example and Example 1 is that the mass ratio of epichlorohydrin, butyl ethylene oxide and decyl ethylene oxide is 1:5:6.

[0088] Comparative Example 5

[0089] The difference between this comparative example and Example 1 is that the organic compound containing epoxy groups does not contain epichlorohydrin, and the mass ratio of butyl oxirane to decyl oxirane is 2:6.

[0090] Comparative Example 6

[0091] The difference between this comparative example and Example 1 is that the composite sodium alginate is replaced by a mixture of sodium alginate and the first modified sodium alginate, and the mass ratio of sodium alginate to the first modified sodium alginate is 9:4.

[0092] Comparative Example 7

[0093] The difference between this comparative example and Example 1 is that the composite sodium alginate is replaced by sodium alginate.

[0094] Comparative Example 8

[0095] The difference between this comparative example and Example 1 is that the mass ratio of glucuronic acid, arabinonic acid and mannose aldehyde is 4:3:1.

[0096] Comparative Example 9

[0097] The difference between this comparative example and Example 1 is that no arabinonic acid is added to the aldehyde organic matter, and the mass ratio of glucuronic acid to mannose aldehyde is 4:1.

[0098] Comparative Example 10

[0099] The difference between this comparative example and Example 1 is that the complex fatty alcohol polyoxyethylene ether is replaced by pure fatty alcohol polyoxyethylene ether.

[0100] Performance Testing

[0101] The adhesion of the printed patterns prepared in the examples and comparative examples was tested according to GB / T 1720-1979. The test results are shown in Table 1.

[0102] The scoring criteria are as follows:

[0103] Grade 0: The paint film is not peeled off at all.

[0104] Level 1: The paint film is hardly peeled off.

[0105] Level 2: A small amount of paint film is peeled off.

[0106] Level 3: A certain area of ​​the paint film is peeled off.

[0107] Level 4: A large area of ​​the paint film is peeled off.

[0108] Level 5: The paint film is almost completely peeled off.

[0109] The gel-printed products with printed patterns prepared in the examples and comparative examples were placed in room temperature water and soaked for 2 days. They were then taken out and dried at room temperature and the above adhesion test was performed again.

[0110] The printed patterns prepared in the examples and comparative examples were immersed in a 5% hydrochloric acid aqueous solution at room temperature for 12 hours, taken out and dried at room temperature, and then the above adhesion test was performed again.

[0111] The printed patterns prepared in the examples and comparative examples were immersed in a 5% sodium hydroxide aqueous solution at room temperature for 12 hours, taken out and dried at room temperature, and then the above adhesion test was performed again.

[0112] The printed patterns prepared in the examples and comparative examples were placed at 80° C. for 2 days, cooled to room temperature, and the above adhesion test was performed again.

[0113] After the printed patterns prepared in the examples and comparative examples were placed under natural light for 7 days, the above adhesion test was performed again. The test results are shown in Table 1.

[0114] Table 1: Performance test results

[0115]

[0116]

[0117] It can be seen from the above performance test results that the printing materials of Examples 1-2 have good adhesion and environmental resistance. This is mainly because composite sodium alginate and composite fatty alcohol polyoxyethylene ether are added to the printing materials of the present invention, which not only changes the interface bonding effect between the substrate and the printing material, but also increases the adhesion of the printing material itself.

[0118] However, the comparative example is significantly worse than the embodiment in the corresponding performance test because it does not adopt the necessary technical solution. In comparative example 1, the mass ratio of sodium alginate, the first modified sodium alginate and the second modified sodium alginate is changed. It can be seen that the adhesion and stability of the printing material are both reduced, proving that the mass ratio of the three substances in the composite sodium alginate has an important influence on the adhesion and stability of the printing material. In comparative example 2, the mass ratio of the organic amine used in the synthesis process of the first modified sodium alginate is changed. From the results, it can be seen that the performance of the printing material is affected, indicating that the mass ratio of the three substances in the organic amine has a certain degree of influence on improving the comprehensive performance of the printing material. In comparative example 3, the type of organic amine used in the synthesis process of the first modified sodium alginate is changed, and polyethyleneimine is not added. From the results, it can be seen that the adhesion and stability of the printing material are further reduced, indicating that the three organic amines in the present invention modify sodium alginate with three amines at a specific ratio, which has an important influence on improving the comprehensive performance of the printing material. In Comparative Example 4, the proportion of the epoxy organic compound used in the second modified sodium alginate was changed. From the results, it can be seen that the mass ratio of epichlorohydrin, butyl oxirane and decyl oxirane has a certain degree of influence on the adhesion and stability of the printing material. In Comparative Example 5, the type of epoxy organic compound used in the second modified sodium alginate was changed, and no epichlorohydrin was added. From the results, it can be seen that the comprehensive performance of the printing material is further reduced, which shows that the epoxy organic compound in the present invention can be mixed in a specific proportion and a specific type to synergistically improve the comprehensive performance of the printing material. In Comparative Example 6, the second modified sodium alginate was not added to the composite sodium alginate. From the results, it can be seen that the performance of the printing material is significantly reduced, which shows that there is a synergistic effect between the sodium alginate, the first modified sodium alginate and the second modified sodium alginate in the present invention, and a denser cross-linked product can be formed, which increases the adhesion and stability of the printing material. In Comparative Example 7, only sodium alginate is used in the printing material, and the first modified sodium alginate and the second modified sodium alginate are not added. It can be seen from the results that the performance of the printing material is seriously reduced, which shows the necessity of performing two modifications on sodium alginate and compounding with pure sodium alginate in the present invention, which has a very important influence on improving the comprehensive performance of the printing material. In Comparative Example 8, the mass ratio of glucuronic acid, arabinonic acid and mannose aldehyde in the preparation process of modified fatty alcohol polyoxyethylene ether is changed. It can be seen from the results that the adhesion and stability of the printing material prepared therefrom are reduced, indicating that the modified fatty alcohol polyoxyethylene ether can change the properties of the overall printing material, increase its interface bonding with the base material, and comprehensively improve the adhesion and stability of the printing material.In Comparative Example 9, the type of aldehyde acid organic matter in the preparation process of modified fatty alcohol polyoxyethylene ether was changed, and arabinonic acid was not added. It can be seen from the results that the performance of the printing material was significantly reduced, indicating that the use of three aldehyde acid organic matters in the present invention mixed in a specific proportion has an important influence on the comprehensive improvement of the performance of the printing material. In Comparative Example 10, only pure fatty alcohol polyoxyethylene ether was used in the printing material, and it was not mixed with modified fatty alcohol polyoxyethylene ether. It can be seen from the results that the performance of the printing material prepared therefrom was seriously reduced, indicating that the modification of fatty alcohol polyoxyethylene ether in the present invention has a very important influence on improving the comprehensive performance of the adhesion and stability of the printing material. The above experimental results further prove the importance of the technical solution defined in the present invention for its technical effect.

[0119] The above is a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A process for printing on a gel surface, characterized in that: The following steps are involved: (1) Clean the surface of the gel printed product; (2) dissolving the printing material in acetone and then applying it to the outer surface of the printed product according to the pattern; The printing material includes the following components in parts by weight: 80-100 parts of composite sodium alginate, 30-50 parts of composite fatty alcohol polyoxyethylene ether, 20-30 parts of fixing agent, 15-20 parts of moisturizing agent, 0.1-15 parts of dye, 10-20 parts of filler, 3-5 parts of dispersant, 3-5 parts of surfactant, 30-50 parts of cross-linking agent and 0.5-3 parts of photoinitiator; The composite sodium alginate comprises sodium alginate, a first modified sodium alginate and a second modified sodium alginate in a mass ratio of (8-10):(3-5):1; The first modified sodium alginate is obtained by reacting an organic amine with sodium alginate, wherein the organic amine includes triethylamine, triisopropylamine and polyethyleneimine in a mass ratio of (5-8):(2-4):1; the second modified ammonium alginate is obtained by reacting an organic compound containing an epoxy group with sodium alginate, wherein the organic compound containing an epoxy group includes epichlorohydrin, butyl oxirane and decyl oxirane in a mass ratio of 1:(1.5-2.5):(5-8); The composite fatty alcohol polyoxyethylene ether comprises fatty alcohol polyoxyethylene ether and modified fatty alcohol polyoxyethylene ether in a mass ratio of (1-3): (0.5-0.8); the modified fatty alcohol polyoxyethylene ether is obtained by reacting aldehyde acid organic matter with fatty alcohol polyoxyethylene ether, and the aldehyde acid organic matter comprises glucuronic acid, arabinonic acid and mannose aldehyde in a mass ratio of (3-5): (0.8-1.2): 1; (3) Irradiate under ultraviolet light to complete curing, and obtain a printed product with a printed pattern.

2. A process for printing on the surface of gel according to claim 1, characterized in that: The preparation method of the first modified sodium alginate is: Add sodium alginate and organic amine to a flask containing tetrahydrofuran, place in an ice bath, dissolve olefinic acid chloride in dichloromethane A and place in a constant pressure dropping funnel, control the dropping rate, and stir for 6 to 12 hours; let stand overnight, filter, and distill under reduced pressure, inject deionized water into the concentrate, shake to dissolve, add dichloromethane B to extract, shake, stand, separate, take the water phase, add 1 mol / L hydrochloric acid solution, shake, inject ethanol to precipitate, filter, and vacuum dry the insoluble matter at 60 to 80° C. for 3 to 5 hours to obtain the first modified sodium alginate; The mass ratio of sodium alginate and organic amine is (35-45):(0.5-1); the dosage ratio of triethylamine, tetrahydrofuran, olefinic acid chloride, dichloromethane A, deionized water, dichloromethane B, hydrochloric acid solution and ethanol is: 1 mol: 500 mL: 1 mol: 300 mL: 300 mL: 400 mL: 200 mL: 1500 mL.

3. A process for printing on the surface of gel according to claim 1, characterized in that: The preparation method of the second modified sodium alginate is: Adding sodium alginate to deionized water, stirring for 2 to 4 hours at a water bath temperature of 50 to 55° C., adding an organic compound containing an epoxy group, stirring for 0.5 to 2 hours, standing for 30 minutes, filtering and drying to obtain a second modified sodium alginate; The mass ratio of sodium alginate to the organic compound containing epoxy groups is (3-6): (4-5), and the mass ratio of sodium alginate to water is (3-6): (80-120).

4. A process for printing on the surface of gel according to claim 1, characterized in that: The preparation method of modified fatty alcohol polyoxyethylene ether is: Add fatty alcohol polyoxyethylene ether to deionized water, stir and dissolve, then add aldehyde acid organic matter and alkaline catalyst, raise the temperature to 60-80°C, stir and react for 5-6 hours, extract and dry after the reaction to obtain modified fatty alcohol polyoxyethylene ether; The dosage ratio of fatty alcohol polyoxyethylene ether, water, aldehyde acid organic matter and alkaline catalyst is 80-120g: 300-500mL: 30-50g: 0.5-2g.

5. A process for printing on the surface of gel according to claim 1, characterized in that: The preparation process of printing materials is: 1) taking a composite fatty alcohol polyoxyethylene ether, a filler, a dye, a dispersant and a surfactant, mixing them, and then stirring them to obtain a mixture A for standby use; 2) taking composite sodium alginate and a color fixing agent, mixing them, grinding and crushing them into 110 meshes to obtain a mixture B for later use; 3) Dissolving mixture A with twice the amount of ethanol solution to obtain a mixed solution A, uniformly adding mixture B to the mixed solution A to obtain a mixed solution C, and then heating the mixed solution C, maintaining uniform stirring during the heating process, and the stirring time is 30 minutes; 4) taking a moisturizer, a cross-linking agent and a photoinitiator, mixing them evenly to obtain a mixture D, adding the mixture D to the mixed solution C, then adding acetic acid to the mixed solution, adjusting the pH to 4, homogenizing and beating the mixed solution, steaming the mixture after beating, and then drying the mixture to obtain a printing material.

6. A process for printing on the surface of gel according to claim 1, characterized in that: The color fixing agent is one or a mixture of diacetone acrylamide and methyl ethyl ketone peroxide; the moisturizing agent is one or a mixture of glycerol and diethylene glycol; the dye is one or a mixture of organic dyes and inorganic dyes; and the filler is one or a mixture of calcium carbonate and talcum powder.

7. A process for printing on the surface of gel according to claim 1, characterized in that: The dispersant is one or more of methylpentanol, sodium pyrophosphate, and triethylhexyl phosphoric acid; the surfactant is one or more of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, and potassium oleate; the crosslinking agent is one or more of acrylic acid, methacrylic acid, and 2-acrylamide-2-methylpropane sulfonic acid; and the photoinitiator is one or more of 1173, 2959, 184, or TPO.

8. A process for printing on the surface of gel according to claim 1, characterized in that: The mass ratio of the printing material to acetone is 1:(5-8), and the ultraviolet irradiation time is 0.5-10h.

9. A printed product having a printed pattern prepared according to the process according to any one of claims 1 to 8.

10. Use of the printed product with a printed pattern according to claim 9 in the field of personal care products, medical supplies, and food packaging.

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