A process for printing on the surface of a gel and its applications

Abstract

The present invention provides a process for printing on the surface of a gel and its application, belonging to the technical field of printing. The printing material in the present invention comprises 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 color 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 crosslinking agent and 0.5-3 parts of photoinitiator. Applying the printing material prepared in the present invention to the printing process does not require chemical treatment of the substrate material, does not damage the surface of substrates such as gels, and the printing material itself has good adhesion and excellent environmental resistance.

Description

Technical Field

[0001] The present invention belongs to the technical field of printing, and particularly relates to a process for printing on the surface of a gel and its application. Background Art

[0002] Printing materials refer to materials used for printing patterns on various substrates (such as textiles, papers, plastics, metals, gels, etc.). These materials usually contain pigments or dyes, binders, thickeners, dispersants, surfactants, crosslinking agents, and other additives to ensure that the patterns can exhibit the expected colors, clarity, and durability on the substrates. Printing materials are applied in the fields of textile printing, packaging materials, personal care products, medical supplies, and food packaging, etc.

[0003] Printing materials are classified into dye-based printing materials, pigment-based printing materials, resin-based printing materials, functional printing materials, and environmentally friendly printing materials, etc. according to the main components. Resin-based printing materials can be used to improve the abrasion resistance and adhesion of printed patterns. However, in the actual application process, the chemical or physical bonding force between the printing material and the substrate is not strong enough, resulting in the problem of a relatively low service life of the printed pattern. To address the above problems, the currently adopted methods mostly use different types of binders for different substrates to ensure good adhesion, and improve the surface energy of the substrate through methods such as corona treatment. For some substrates, the surface roughness can also be increased by mechanical grinding to improve the bonding force between the substrate and the printing material.

[0004] The above methods for pre-treating the substrate can improve the bonding force between the substrate and the printing material to a certain extent. However, this method of pre-treating the substrate will damage the surface of the substrate, especially the surface of the gel substrate. Moreover, 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, when the printing material is used for a long time, especially when the external environment changes, due to the unreasonable material composition of the printing material itself, its environmental resistance properties such as water resistance, solvent resistance, light resistance, and heat resistance all become 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 a gel and its application to solve the problems of unreasonable composition design of the printing material, poor adhesion, and poor environmental resistance properties.

[0006] To achieve the above purpose, the present invention provides the following technical solutions:

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

[0008] (1) Clean the surface of the gel print.

[0009] (2) Dissolve the printing material in acetone, and then coat it on the outer surface of the printed product according to the pattern.

[0010] The printing material comprises the following components by weight parts: 80 - 100 parts of compound sodium alginate, 30 - 50 parts of compound fatty alcohol polyoxyethylene ether, 20 - 30 parts of color 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 crosslinking agent and 0.5 - 3 parts of photoinitiator.

[0011] The compound sodium alginate comprises sodium alginate, first modified sodium alginate and second modified sodium alginate in a mass ratio of (8 - 10):(3 - 5):1; the first modified sodium alginate is obtained by the reaction of organic amine and 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 the reaction of organic compound containing epoxy group and sodium alginate, and the organic compound containing epoxy group comprises epichlorohydrin, butyl epoxyethane and decyl epoxyethane in a mass ratio of 1:(1.5 - 2.5):(5 - 8).

[0012] The compound 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 the reaction of aldehyde acid organic matter and fatty alcohol polyoxyethylene ether, and the aldehyde acid organic matter comprises glucuronic acid, arabinonic acid and mannuronic acid in a mass ratio of (3 - 5):(0.8 - 1.2):1.

[0013] (3) Irradiate under ultraviolet light, and after curing is completed, a printed product with a printed pattern is obtained.

[0014] In order to further improve the adhesion of the printing material to the substrate material in the prior art, sodium alginate and fatty alcohol polyoxyethylene ether are added to the printing material in the present invention. Among them, sodium alginate can improve the adhesion of the printing material to the substrate, and fatty alcohol polyoxyethylene ether is a commonly used non - ionic surfactant with good wettability and dispersibility. Its existence 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 - mentioned materials have limited improvement in the adhesion of the printing material to the substrate, and the adhesion of the printing material to the substrate is extremely vulnerable to the external environment. To solve 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] In the present invention, the composite sodium alginate used includes sodium alginate, the first modified sodium alginate, and the second modified sodium alginate. The combined use of these can significantly improve the adhesion of the printing material to the gel and its environmental stability resistance. The adhesion of the printing material in the present invention is improved. The reasons are analyzed as follows: The first modified sodium alginate introduces positively charged amine groups through the reaction of organic amine with sodium alginate. These amine groups can form electrostatic attraction with the negatively charged groups (such as carboxyl or hydroxyl groups) on the substrate surface, thereby enhancing the adhesion force. 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, making the printing material adhere more firmly to the substrate surface. 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 anti-aging property. The reasons are analyzed as follows: The amine groups in the first modified sodium alginate can, to a certain extent, reduce the erosion of water because they can compete with water molecules for adsorption sites and reduce the interaction between water molecules and the polymer backbone. 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 of solvents and prevent the material from decomposing in a solvent environment. The introduced modified groups increase the intermolecular interaction force. For example, the introduction of epoxy groups can enhance the thermal stability through cross-linking, improving the thermal stability of the material. The functional groups introduced through modification increase the antioxidant capacity of the material, reduce the generation of free radicals, and thus delay 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 closely adhere to the surface of the substrate, thereby improving the adhesion. The reason is analyzed as follows: The modified fatty alcohol polyoxyethylene ether can introduce new functional groups, such as aldehyde groups, etc., by reacting with aldehyde acid organic compounds. These groups can enhance the wettability of the material to the substrate surface, enable the printing material to better penetrate into the microporous structure of the substrate surface, and further enhance the adhesion. The composite fatty alcohol polyoxyethylene ether of the present invention can also synergistically improve the interfacial bonding situation between the printing material and the substrate surface, and further improve the environmental stability. The reason is analyzed as follows: The mixed use of fatty alcohol polyoxyethylene ether and modified fatty alcohol polyoxyethylene ether can adjust the hydrophilic-hydrophobic balance of the printing material, making it have 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 easily deformed at high temperatures, thereby improving the thermal stability. Some aldehyde acid organic compounds may have certain antioxidant properties, and their presence can help inhibit the photoinduced free radical reaction, 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 also help to resist degradation caused by environmental factors. The introduction of the modified fatty alcohol polyoxyethylene ether can increase the intermolecular forces, making the material more stable in the solvent and not easily dissolved or damaged by the solvent.

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

[0018] Add sodium alginate and organic amine into a flask containing tetrahydrofuran, and cool it in an ice bath. Dissolve alkenyl acyl chloride in dichloromethane A and place it in a constant pressure dropping funnel. Control the dropping rate and stir for 6 - 12 h; let it stand overnight, filter, distill under reduced pressure. Inject deionized water into the concentrate, oscillate to dissolve, add dichloromethane B for extraction, oscillate, let it stand, separate the layers, take the aqueous phase, add 1 mol / L hydrochloric acid solution, oscillate, inject ethanol for precipitation, filter, and vacuum dry the insoluble matter at 60 - 80 °C for 3 - 5 h to obtain the first modified sodium alginate;

[0019] The mass ratio of sodium alginate to organic amine is (35 - 45):(0.5 - 1); the dosage ratio of triethylamine, tetrahydrofuran, alkenyl acyl 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 as follows:

[0021] Sodium alginate was added to deionized water, stirred for 2 - 4 h under the condition that the water bath temperature was 50 - 55 °C, an organic compound containing an epoxy group was added, after stirring and reacting for 0.5 - 2 h, it was left standing for 30 min, and after filtration and drying, the second modified sodium alginate was obtained;

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

[0023] Preferably, the preparation method of the modified fatty alcohol polyoxyethylene ether was as follows:

[0024] The fatty alcohol polyoxyethylene ether was added to deionized water, after stirring and dissolving, an aldehyde acid organic compound and a basic catalyst were added, the temperature was raised to 60 - 80 °C, stirred and reacted for 5 - 6 h, after the reaction ended, it was subjected to extraction and drying to obtain the modified fatty alcohol polyoxyethylene ether;

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

[0026] Preferably, the preparation process of the printing material was as follows:

[0027] 1) Take the composite fatty alcohol polyoxyethylene ether, filler, dye, dispersant and surfactant for mixing, and then stir evenly to obtain mixture A for standby;

[0028] 2) Take the composite sodium alginate and the fixing agent, after mixing, grind and crush to 110 meshes to obtain mixture B for standby;

[0029] 3) Dissolve mixture A with twice the amount of ethanol solution to obtain mixed solution A, uniformly add mixture B to mixed solution A to obtain mixed solution C, and then heat mixed solution C, keep stirring evenly during the heating process, and the stirring time is 30 min;

[0030] 4) Take the humectant, crosslinking agent and photoinitiator, mix evenly to obtain mixture D, add mixture D to mixed solution C, then add acetic acid to the mixed solution, adjust the pH to 4, perform homogenization beating treatment on the mixed solution, perform steaming treatment after the beating ends, and then dry the mixture to obtain the printing material.

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

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

[0033] Preferably, the dispersant is one or more of methyl pentanol, sodium pyrophosphate, and triethylhexyl phosphate; the surfactant is one or more of sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, and potassium oleate; the crosslinking agent is one or more of acrylic acid, methacrylic acid, and 2-acrylamido-2-methylpropanesulfonic acid; 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 light irradiation time is 0.5-10 h.

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

[0036] The third aspect of the present invention provides an application of the printing material, and the application of the printed matter with a printed pattern in the fields 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 as follows:

[0038] 1. In the present invention, the modified sodium alginate used in the printing material is modified by organic amines (such as triethylamine, triisopropylamine, and polyethyleneimine) for the first modified sodium alginate, which enhances its binding force with the substrate. The second modified sodium alginate is modified by an organic compound containing an epoxy group (such as epichlorohydrin, butyl ethylene oxide, and decyl ethylene oxide), 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 substances (such as glucuronic acid, arabinonic acid, and mannuronic acid), which improves its binding force with the substrate and further enhances the 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 comprehensively improves the stability of the printing material, making it have water resistance, solvent resistance, thermal stability, light stability, and anti-aging properties.

[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., expanding the use range of the printing material. Detailed implementation mode

[0042] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0043] Embodiment 1

[0044] This embodiment provides a printing material, which includes the following components by weight: 95 parts of compound sodium alginate, 40 parts of compound fatty alcohol polyoxyethylene ether, 25 parts of 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 crosslinking agent, and 1 part of photoinitiator;

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

[0046] The moisturizing agent is glycerol;

[0047] The dye is titanium dioxide;

[0048] The filler is calcium carbonate;

[0049] The dispersant is sodium pyrophosphate;

[0050] The surfactant is sodium dodecylbenzenesulfonate;

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

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

[0053] The compound 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 the reaction of organic amine and sodium alginate, and 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 the reaction of an organic compound containing an epoxy group and sodium alginate, and the organic compound containing an epoxy group is epichlorohydrin, butyl ethylene oxide (CAS: 1436-34-6), and decyl ethylene oxide (CAS: 18633-25-5) in a mass ratio of 1:2:6;

[0056] The compound 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 the reaction of an aldehyde acid organic substance and a fatty alcohol polyoxyethylene ether. The aldehyde acid organic substance is glucuronic acid (CAS: 6556-12-3), arabinonic acid (CAS: 6703-05-5) and mannuronic acid (CAS: 6814-36-4) in a mass ratio of 4:1:1.

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

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

[0060] Add sodium alginate and organic amine into a flask containing tetrahydrofuran, and place it in an ice bath. Dissolve 10-undecenoyl chloride (CAS: 38460-95-6) in dichloromethane A and place it in a constant pressure dropping funnel. Control the dropping rate and stir for 10 h; let it stand overnight, filter, distill under reduced pressure, inject deionized water into the concentrate, oscillate to dissolve, add dichloromethane B for extraction, oscillate, let it stand, separate the liquid, take the aqueous phase, add 1 mol / L hydrochloric acid solution, oscillate, inject ethanol for precipitation, filter, and vacuum dry the insoluble matter at 60 °C for 3 h to obtain the first modified sodium alginate;

[0061] The mass ratio of sodium alginate to 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 as follows:

[0063] Add sodium alginate into deionized water, stir at a water bath temperature of 50 °C for 3 h, add an organic compound containing an epoxy group, stir and react for 1 h, then let it stand for 30 min, filter and dry to obtain the second modified sodium alginate;

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

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

[0066] Add fatty alcohol polyoxyethylene ether (model AEO-7, the addition number of ethylene oxide is 7) into deionized water, stir to dissolve, then add the aldehyde acid organic substance and sodium hydroxide, raise the temperature to 70 °C, stir and react for 5.5 h, and after the reaction, obtain the modified fatty alcohol polyoxyethylene ether through extraction and drying;

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

[0068] (3) The preparation process of the printing material is as follows:

[0069] 1) Take compound fatty alcohol polyoxyethylene ether, filler, dye, dispersant and surfactant, mix them, and then stir evenly to obtain mixture A for standby;

[0070] 2) Take compound sodium alginate and color fixing agent, mix them, and grind and crush them to 110 mesh to obtain mixture B for standby;

[0071] 3) Dissolve mixture A with twice the amount of ethanol solution to obtain mixed solution A. Uniformly add mixture B to mixed solution A to obtain mixed solution C, and then heat mixed solution C, and keep stirring evenly during the heating process, and the stirring time is 30 min;

[0072] 4) Take a moisturizing agent, crosslinking agent and photoinitiator, mix them evenly to obtain mixture D. Add mixture D to mixed solution C, and then add acetic acid to the mixed solution to adjust the pH to 4. Perform homogenization beating treatment on the mixed solution. After the beating is completed, perform steaming treatment, and then dry the mixture to obtain the printing material.

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

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

[0075] (2) Dissolve the printing material in acetone, and the mass ratio of the printing material to acetone is 1 : 6, and then uniformly coat it on the outer surface of the gel printed product according to the pattern;

[0076] (3) Irradiate under ultraviolet light, and the ultraviolet light irradiation time is 5 h. After curing is completed, a gel printed product with a printed pattern is obtained.

[0077] Example 2

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

[0079] The printing material in this embodiment includes the following components by weight: 85 parts of compound sodium alginate, 35 parts of compound fatty alcohol polyoxyethylene ether, 25 parts of color fixing agent, 15 parts of moisturizing agent, 5 parts of dye, 12 parts of filler, 4 parts of dispersant, 4 parts of surfactant, 32 parts of crosslinking 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 and 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 epoxyethane, and decyl epoxyethane 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 include epichlorohydrin, and the mass ratio of butyl epoxyethane and decyl epoxyethane 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 with a mixture of sodium alginate and the first modified sodium alginate, and the mass ratio of sodium alginate and 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 with 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 mannuronic acid is 4:3:1.

[0096] Comparative Example 9

[0097] The difference between this comparative example and Example 1 is that arabinonic acid is not added to the aldehyde acid organic matter, and the mass ratio of glucuronic acid and mannuronic acid is 4:1.

[0098] Comparative Example 10

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

[0100] Performance Test

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

[0102] The scoring criteria are as follows:

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

[0104] Grade 1: The paint film was hardly peeled off.

[0105] Grade 2: A small amount of the paint film was peeled off.

[0106] Grade 3: A certain area of the paint film was peeled off.

[0107] Grade 4: A large area of the paint film was peeled off.

[0108] Grade 5: Almost all of the paint film was peeled off.

[0109] The gel prints with printed patterns prepared in the examples and comparative examples were placed in normal-temperature water and soaked for 2 days, then taken out and dried at normal temperature, and the above-mentioned adhesion test was carried out again.

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

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

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

[0113] The printed patterns prepared in the examples and comparative examples were placed under natural light and irradiated for 7 days, and then the above-mentioned adhesion test was carried out again. The test results are shown in the content of Table 1.

[0114] Table 1: Performance test results

[0115]

[0116]

[0117] From the above performance test results, it can be seen that the adhesion and environmental resistance of the printing materials in Examples 1-2 are better. This is mainly because the composite sodium alginate and composite fatty alcohol polyoxyethylene ether are added to the printing materials in the present invention, which not only changes the interfacial bonding effect between the matrix and the printing materials, but also increases the adhesiveness of the printing materials themselves.

[0118] In the comparative examples, since the necessary technical solutions were not adopted, their performance in the corresponding performance tests was significantly worse than that of the examples. In Comparative Example 1, the mass ratio of sodium alginate, the first modified sodium alginate, and the second modified sodium alginate was changed, and it can be seen that both the adhesion and stability of the printing material decreased, proving that the mass ratio of the three substances in the composite sodium alginate has an important impact 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 was changed, and it can be seen from the results that the performance of the printing material was affected, indicating that the mass ratio of the three substances in the organic amine has a certain impact 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 was changed, and polyethyleneimine was not added. It can be seen from the results that the adhesion and stability of the printing material further decreased, indicating that the three organic amines in the present invention modify sodium alginate in a specific ratio with three amines, which has an important impact on improving the comprehensive performance of the printing material. In Comparative Example 4, the ratio of the epoxy organic compound used in the second modified sodium alginate was changed, and it can be seen from the results that the mass ratio of epichlorohydrin, butyl ethylene oxide, and decyl ethylene oxide has a certain impact 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 epichlorohydrin was not added. It can be seen from the results that the comprehensive performance of the printing material further decreased, indicating that the epoxy organic compounds in the present invention can synergistically improve the comprehensive performance of the printing material when mixed in a specific ratio and specific type. In Comparative Example 6, the second modified sodium alginate was not added to the composite sodium alginate, and it can be seen from the results that the performance of the printing material decreased significantly, indicating that there is a synergistic effect between sodium alginate, the first modified sodium alginate, and the second modified sodium alginate in the present invention, which can form a denser cross-linked product and increase the adhesion and stability of the printing material. In Comparative Example 7, only sodium alginate was used in the printing material, and the first modified sodium alginate and the second modified sodium alginate were not added. It can be seen from the results that the performance of the printing material decreased severely, indicating the necessity of modifying sodium alginate twice and compounding it with pure sodium alginate in the present invention, which has a very important impact on improving the comprehensive performance of the printing material. In Comparative Example 8, the mass ratio of glucuronic acid, arabinonic acid, and mannuronic acid in the preparation process of the modified fatty alcohol polyoxyethylene ether was changed, and it can be seen from the results that the adhesion and stability of the printing material prepared decreased, indicating that the modified fatty alcohol polyoxyethylene ether can change the properties of the overall printing material, increase its interfacial bonding with the substrate material, and comprehensively improve the adhesion and stability of the printing material.In Comparative Example 9, the types of aldehyde acid organic substances in the preparation process of the modified fatty alcohol polyoxyethylene ether were changed, and arabinonic acid was not added. It can be seen from the results that the performance of the printing material decreased significantly, indicating that the use of three aldehyde acid organic substances mixed in a specific ratio in the present invention has an important impact on comprehensively improving the performance of the printing material. In Comparative Example 10, only pure fatty alcohol polyoxyethylene ether was used in the printing material and not mixed with the modified fatty alcohol polyoxyethylene ether. It can be seen from the results that the performance of the printing material prepared decreased severely, indicating that the modification of fatty alcohol polyoxyethylene ether in the present invention has a very important impact 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 effects.

[0119] The above are the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope 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 a gel surface 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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