A kind of seal ink and its preparation method

Abstract

The present application discloses a seal ink and a preparation method thereof. The seal ink comprises the following components in parts by weight: 5-20 parts of thermochromic powder, 5-25 parts of alkylphenol polyoxyethylene ether, 5-25 parts of epoxy acrylate resin modified acrylate copolymer composite emulsion, 0.1-2 parts of leveling agent, 0.1-2 parts of polyether modified polysiloxane, 0.1-2 parts of antioxidant, and 12-47 parts of solvent. The seal ink provided by the present application has the characteristics of safety, environmental protection, good water resistance, quick drying, and clear patterns.

Description

Technical Field

[0001] This application relates to the technical field of seals, and particularly to a seal ink and a preparation method thereof. Background Art

[0002] Stamp ink is a special ink used for seal production and printing.

[0003] According to the type of solvent used, stamp ink can be divided into oil-based stamp ink, alcohol-based stamp ink and water-based stamp ink. Oil-based stamp ink mainly uses vegetable oil, mineral oil, esters and hydrocarbon solvents as solvents. This kind of stamp ink has good binding property of pigments and resins, is easy to produce, and has excellent weather resistance. It also has relatively high stability when used in combination with a stamp pad. However, recent usage shows that oil-based stamp ink is prone to bleeding on paper, has a slow drying speed, is prone to deformation and excessive oil output under high pressure, and the imprints are not clear enough.

[0004] Water-based stamp ink mainly uses water as a solvent. Since water has low cost, is non-toxic and pollution-free, it is particularly suitable for fields with high environmental protection and toxicity requirements. However, in actual use, due to the slow volatility and strong polarity of water, it is easy to deform the paper and generate bubbles during the processing, which affects the performance and usage effect of the stamp ink.

[0005] Although alcohol-based stamp ink has good binding property with paper, relatively high printing clarity, and fast drying speed, it is prone to being blurred in a humid environment. Summary of the Invention

[0006] In order to solve at least one of the above technical problems and develop an alcohol-based stamp ink with environmental protection, good water resistance and high pattern clarity rate, this application provides a seal ink and a preparation method thereof.

[0007] In a first aspect, this application provides a water-resistant seal ink. The seal ink comprises the following components by weight: 5-20 parts of thermochromic powder, 5-25 parts of alkylphenol polyoxyethylene ether, 5-25 parts of epoxy acrylate resin modified acrylate copolymer composite emulsion, 0.1-2 parts of leveling agent, 0.1-2 parts of polyether modified polysiloxane, 0.1-2 parts of antioxidant, and 12-47 parts of solvent.

[0008] By adopting the above technical solutions, the present application can preferably improve the water resistance of the stamp ink, and has the characteristics of quick drying, safe and environmentally friendly composition, and high pattern clarity rate. Among them, the present application can improve the water resistance of the acrylate emulsion by using the epoxy acrylate resin modified acrylate copolymer composite emulsion, thereby further improving the water resistance of the ink. By adding this composite emulsion to the ink, its polymer components can be dispersed in the ink in the form of an emulsion to form a stable emulsion system. When the ink dries, the epoxy acrylate resin modified acrylate copolymer can form a firm film with good water resistance. This film can resist the penetration of moisture in a humid environment, reduce the erosion and dissolution of moisture to the ink, thereby improving the water resistance of the stamp ink. The thermochromic powder can cause the color of the ink to change when heated or cooled. This thermochromic effect can make the stamp ink show an obvious contrast effect during use, thereby making the pattern more clearly visible. The alkylphenol polyoxyethylene ether can improve the fluidity and ductility of the ink, make the ink more evenly distributed on the stamp, can make the pattern details clearer, and reduce the occurrence of blurring and unclear situations.

[0009] Optionally, the stamp ink comprises the following components by weight: 15-20 parts of thermochromic powder, 21-25 parts of alkylphenol polyoxyethylene ether, 21-25 parts of epoxy acrylate resin modified acrylate copolymer composite emulsion, 0.8-2 parts of leveling agent, 1.1-2 parts of polyether modified polysiloxane, 1.3-2 parts of antioxidant, and 30-47 parts of solvent.

[0010] Optionally, the weight ratio of the alkylphenol polyoxyethylene ether to the epoxy acrylate resin modified acrylate copolymer composite emulsion is 1:(1-1.2).

[0011] By adopting the above technical solutions, when the weight ratio of the alkylphenol polyoxyethylene ether to the epoxy acrylate resin modified acrylate copolymer composite emulsion is 1:(1-1.2), the prepared ink has the advantages of better water resistance and faster drying speed.

[0012] Optionally, the weight ratio of the alkylphenol polyoxyethylene ether to the epoxy acrylate resin modified acrylate copolymer composite emulsion is 1:1.15.

[0013] Optionally, the leveling agent includes one of leveling agent BYK307 and leveling agent BYK380N.

[0014] Optionally, the antioxidant includes antioxidant 1010.

[0015] Optionally, the solvent includes at least one of 2-methyl-1-propanol and cyclohexanol.

[0016] Second aspect, the present application provides a preparation method of a water-resistant stamp ink, and the preparation method includes the following steps:

[0017] S1. Mix the thermochromic powder and alkylphenol polyoxyethylene ether, add a solvent, stir, and obtain a first mixture;

[0018] S2. Mix and stir the epoxy acrylate resin-modified acrylate copolymer composite emulsion and polyether-modified polysiloxane to obtain a second mixture;

[0019] S3. Mix and stir the first mixture and the second mixture, and add a leveling agent and an antioxidant for mixing to obtain the water-resistant stamp ink.

[0020] By adopting the above technical solution, the ink prepared by the present application through the above method has the characteristics of good water resistance and bonding performance, clear patterns, and environmental protection. Among them, the thermochromic powder can achieve the thermochromic effect, and the mixing of the thermochromic powder and alkylphenol polyoxyethylene ether can improve the pattern clarity; the mixing of the epoxy acrylate resin-modified acrylate copolymer composite emulsion and polyether-modified polysiloxane makes the ink have good adhesiveness and water resistance; the addition of the leveling agent helps to evenly distribute and reduce the occurrence of blurring; the addition of the antioxidant can increase the stability of the ink and extend its service life.

[0021] Optionally, the preparation method of the epoxy acrylate resin-modified acrylate copolymer composite emulsion includes the following steps:

[0022] A1. Dissolve the epoxy acrylate resin in the acrylate monomer to obtain a solution of epoxy resin and acrylate monomer;

[0023] A2. Dropwise add the solution of epoxy resin and acrylate monomer prepared in step A1 to the aqueous solution of the emulsifier and disperse at high speed to obtain a pre-emulsion;

[0024] A3. Mix 10% of the total weight of ammonium persulfate, an emulsifier, and sodium bicarbonate, heat up to 80 °C, dropwise add 10% of the total weight of the pre-emulsion prepared in step A2, keep warm for 30 min, then dropwise add the remaining pre-emulsion and the remaining ammonium persulfate, heat up to 90 °C, keep warm for 1 h, cool, and adjust the pH to weakly alkaline to obtain the epoxy acrylate resin-modified acrylate copolymer composite emulsion.

[0025] By adopting the above technical solution, through the above preparation method of the epoxy acrylate resin-modified acrylate copolymer composite emulsion, the present application can improve the adhesion and water resistance of the acrylate emulsion, so that the pattern can be kept stable for a long time and the pattern can be made clearer.

[0026] Optionally, in the preparation method of the epoxy acrylate resin-modified acrylate copolymer composite emulsion, the weight ratio of the epoxy acrylate, acrylate monomer, emulsifier, ammonium persulfate, and sodium bicarbonate is (10-12):100:6:(1-1.5):2.

[0027] Preferably, the weight ratio of the epoxy acrylate, acrylate monomer, emulsifier, ammonium persulfate, and sodium bicarbonate is 11:100:6:(1.4):2.

[0028] By adopting the above technical solution, the ink prepared in this application has better water resistance.

[0029] Optionally, the acrylate monomer is a mixture of butyl acrylate, styrene, and methyl methacrylate, and the weight ratio of butyl acrylate, styrene, and methyl methacrylate is 1:1:1.

[0030] Optionally, the emulsifier is a mixture of ethoxylated alkylphenol ammonium sulfate (emulsifier TX-4SA) and Triton X-100, and the weight ratio of ethoxylated alkylphenol ammonium sulfate (emulsifier TX-4SA) and Triton X-100 is (1-1.5):1.

[0031] In summary, the present invention includes at least one of the following beneficial technical effects:

[0032] 1. This application can preferably improve the water resistance of the stamp ink, and has the characteristics of quick drying, safe and environmentally friendly components, and high pattern clarity rate.

[0033] 2. The ink prepared by this application through the above method has good water resistance and bonding properties, clear patterns, and is environmentally friendly. Among them, the thermochromic powder can achieve a thermochromic effect, and the mixture of the thermochromic powder and alkylphenol polyoxyethylene ether can improve the pattern clarity; the mixture of the epoxy acrylate resin-modified acrylate copolymer composite emulsion and polyether-modified polysiloxane makes the ink have good bonding and water resistance; the addition of the leveling agent helps to evenly distribute and reduce the occurrence of blurring; the addition of the antioxidant can increase the stability of the ink and extend its service life.

[0034] 3. Through the preparation method of the above epoxy acrylate resin-modified acrylate copolymer composite emulsion, this application can improve the adhesion and water resistance of the acrylate emulsion, so that the pattern can be kept stable for a long time and the pattern can be clearer. Specific Embodiments

[0035] The following further elaborates on this application with reference to examples.

[0036] Alkylphenol polyoxyethylene ether: CAS No. is 9036-19-5.

[0037] Epoxy acrylate resin: The manufacturer is Langfang Xiangteng Chemical Co., Ltd., and the model is FX-450.

[0038] Butyl acrylate: The manufacturer is Sinopharm Chemical Reagent Co., Ltd., and the CAS No. is 141-32-2.

[0039] Styrene: The manufacturer is Sinopharm Chemical Reagent Co., Ltd., and the CAS No. is 100-42-5.

[0040] Methyl methacrylate: The manufacturer is Sinopharm Chemical Reagent Co., Ltd., and the CAS No. is 80-62-6.

[0041] Emulsifier: The manufacturer of ethoxylated alkylphenol ammonium sulfate (emulsifier TX-4SA) is: Jiangsu Haian Petrochemical Factory, and the CAS No. is 9051-57-4.

[0042] Emulsifier: Triton x-100: The manufacturer is Sinopharm Chemical Reagent Co., Ltd., and the CAS No. is 9002-93-1.

[0043] Leveling agent BYK307: The manufacturer is Guangzhou Haoliangda International Trade Co., Ltd.; the model is BYK307.

[0044] Leveling agent BYK 380N: The manufacturer is Ningbo Huiwangcheng Plastic Chemical Co., Ltd.

[0045] Antioxidant 1010: The manufacturer is Hebei Dachang Chemical Technology Co., Ltd.; the CAS No. is 6683-19-8.

[0046] The solvent is 2-methyl-1-propanol: The manufacturer is MERCK, and the CAS No. is 78-83-1.

[0047] The solvent is cyclohexanol: The purity is 98%.

[0048] Ammonium persulfate: The manufacturer is Shanghai Senfei Chemical; the CAS No. is 7727-54-0.

[0049] Thermochromic pigment: The manufacturer is Guangzhou Jingcai Pigment Technology Co., Ltd.; the CAS No. is 421-50-9. Specific embodiments

[0051] Example 1

[0052] This example provides a water-resistant stamp ink. The stamp ink includes the following components by weight: 5 parts of thermochromic pigment, 3 parts of alkylphenol polyoxyethylene ether, 5 parts of epoxy acrylate resin modified acrylate copolymer composite emulsion, 0.1 part of leveling agent, 0.1 part of polyether modified polysiloxane, 0.1 part of antioxidant, and 12 parts of solvent.

[0053] The preparation method of the water-resistant stamp ink comprises the following steps:

[0054] First step, first prepare an epoxy acrylate resin-modified acrylate copolymer composite emulsion, and the preparation method comprises the following steps: A1. Dissolve the epoxy acrylate resin in the acrylate monomer to obtain an epoxy resin and acrylate monomer solution;

[0055] A2. Dropwise add the epoxy resin and acrylate monomer solution obtained in step A1 into the aqueous solution of the emulsifier, and disperse at high speed to obtain a pre-emulsion; the weight ratio of the emulsifier to water is 1:1.

[0056] A3. Mix 10% of the total weight of ammonium persulfate, the emulsifier, and sodium bicarbonate, heat up to 80 °C, dropwise add 10% of the total weight of the pre-emulsion obtained in step A2, keep warm for 30 min, then dropwise add the remaining pre-emulsion and the remaining ammonium persulfate, heat up to 90 °C, keep warm for 1 h, cool down, and adjust the pH to 8.0 to obtain the epoxy acrylate resin-modified acrylate copolymer composite emulsion.

[0057] When preparing the epoxy acrylate resin-modified acrylate copolymer composite emulsion, the weight ratio of epoxy acrylate, acrylate monomer, emulsifier, ammonium persulfate, and sodium bicarbonate is 10:100:6:1:2.

[0058] Second step, then prepare the stamp ink, which comprises the following steps:

[0059] S1. Mix the thermochromic powder and alkylphenol polyoxyethylene ether, add a solvent, and stir to obtain a first mixture;

[0060] S2. Mix and stir the epoxy acrylate resin-modified acrylate copolymer composite emulsion and polyether-modified polysiloxane to obtain a second mixture;

[0061] S3. Mix and stir the first mixture and the second mixture, and add a leveling agent and an antioxidant for mixing to obtain the water-resistant stamp ink.

[0062] The leveling agent in this embodiment is leveling agent BYK307.

[0063] The antioxidant in this embodiment is antioxidant 1010.

[0064] The solvent in this embodiment is 2-methyl-1-propanol.

[0065] The emulsifier in this embodiment is a mixture of ethoxylated alkylphenol ammonium sulfate (emulsifier TX-4SA) and Triton X-100, and the weight ratio of ethoxylated alkylphenol ammonium sulfate (emulsifier TX-4SA) to Triton X-100 is 1:1.

[0066] Examples 2 - 5

[0067] The differences between Examples 2 - 5 and Example 1 lie in different parts by weight. For the different parts, refer to Table 1.

[0068] Table 1 - The differences between Examples 2 - 5 and Example 1 are shown in Table

[0069]

[0070] Comparative Examples 1 - 2

[0071] Comparative Example 1

[0072] The difference between this comparative example and Example 1 is that in this comparative example, an equal amount of acrylate emulsion is used to replace the epoxy acrylate resin - modified acrylate copolymer composite emulsion.

[0073] Comparative Example 2

[0074] The difference between this comparative example and Example 1 is that in this comparative example, the epoxy acrylate resin - modified acrylate copolymer composite emulsion is prepared by a blending method, and the preparation method includes the following steps:

[0075] Dissolve the epoxy acrylate resin in a propanol solution, then add the acrylate emulsion, and perform ultrasonic blending to obtain the epoxy acrylate resin - modified acrylate copolymer composite emulsion.

[0076] Performance test experiment:

[0077] The stamp inks prepared from Examples 1 - 5 and Comparative Examples 1 - 2 are tested for pattern clarity, water resistance, ink dispersibility, drying speed, color change ability, and adhesion. The test results are shown in Table 2.

[0078] Pattern clarity: Use the ink to print a pattern and observe whether the pattern is clear and uniform.

[0079] Water resistance: Use the inks prepared from Examples 1 - 5 and Comparative Examples 1 - 2 to print pictures respectively, and place them in an environment with a humidity of 85% for 500 h. After that, detect the water absorption rate of the pattern. Water resistance = 100% - water absorption rate.

[0080] Dispersibility: Observe whether the ink dispersibility is uniform.

[0081] Drying speed: Use the ink to print a picture and observe the drying speed.

[0082] Color change: Observe whether color change occurs in an environment of 20 - 40 degrees Celsius.

[0083] Adhesion: The adhesion fastness of the ink was tested according to the method disclosed in GB / T 13217.7-2009 "Test Method for Adhesion Fastness of Liquid Ink". The printing substrate was a PET film, and 3M tape was selected as the tape.

[0084] Table 2 - The experimental test results of Examples 1 - 5 and Comparative Examples 1 - 2 are shown in the table

[0085] Test Items Pattern Clarity Water Resistance Dispersibility Drying Speed (s) Color Change Adhesion Fastness (%) Example 1 Clear 85.1 Uniform 5 Can Change Color 100 Example 2 Clear 86.2 Uniform 5 Can Change Color 100 Example 3 Clear 87.0 Uniform 5 Can Change Color 100 Example 4 Clear 88.5 Uniform 4 Can Change Color 100 Example 5 Clear 88.0 Uniform 4 Can Change Color 100 Comparative Example 1 Clear 60.1 Uniform 9 Can Change Color 82 Comparative Example 2 Unclear 77.2 Non-uniform 7 Can Change Color 84

[0086] Result analysis:

[0087] The differences between Examples 2 - 5 and Example 1 lie in the different weight parts of each component. Combining the test results in Table 2, it can be seen that the ink prepared from Example 4 has better water resistance, stronger adhesion fastness, and the clarity rate of the pattern can still reach 88% in an environment with a humidity of 85% for 500 h.

[0088] The difference between Comparative Example 1 and Example 1 is that in this comparative example, an equal amount of acrylate emulsion is used to replace the epoxy acrylate resin - modified acrylate copolymer composite emulsion. Combining the test results in Table 2, it can be seen that when using acrylate emulsion to replace the epoxy acrylate resin - modified acrylate copolymer composite emulsion, the water resistance of the ink is poor. The reason may be that copolymerizing epoxy acrylate resin and acrylate can better improve the water resistance of the ink.

[0089] The difference between Comparative Example 2 and Example 1 is that in this comparative example, the epoxy acrylate resin - modified acrylate copolymer composite emulsion is prepared by a blending method. The preparation method includes the following steps:

[0090] Dissolve the epoxy acrylate resin in a propanol solution, then add the acrylate emulsion and blend ultrasonically to obtain the epoxy acrylate resin - modified acrylate copolymer composite emulsion. Combining the test results in Table 2, it can be seen that copolymerizing epoxy acrylate resin and acrylate by physical blending leads to poor uniformity, resulting in unclear pictures and uneven dispersion.

[0091] It can be seen from this that the inks prepared in Examples 1 - 5 of this application have the characteristics of good water resistance, high pattern clarity, fast drying speed, and good dispersion.

[0092] Examples 6 - 8

[0093] Example 6

[0094] The difference between this example and Example 4 is that the total weight of alkylphenol polyoxyethylene ether and epoxy acrylate resin - modified acrylate copolymer composite emulsion is 46 parts. Among them, the weight ratio of alkylphenol polyoxyethylene ether to epoxy acrylate resin - modified acrylate copolymer composite emulsion is 1:1.1.

[0095] Example 7

[0096] The difference between this example and Example 4 is that the total weight of the composite emulsion of alkylphenol polyoxyethylene ether and acrylate copolymer modified by oxyacrylate resin is 46 parts. Among them, the weight ratio of the composite emulsion of alkylphenol polyoxyethylene ether and acrylate copolymer modified by oxyacrylate resin is 1:1.15.

[0097] Example 8

[0098] The difference between this example and Example 4 is that the total weight of the composite emulsion of alkylphenol polyoxyethylene ether and acrylate copolymer modified by oxyacrylate resin is 46 parts. Among them, the weight ratio of the composite emulsion of alkylphenol polyoxyethylene ether and acrylate copolymer modified by oxyacrylate resin is 1:1.2.

[0099] The test results of Examples 6 - 8 are shown in Table 3.

[0100] Table 3 - The test results of Examples 6 - 8 are shown in the table

[0101] Test Items Pattern Clarity Water Resistance Dispersibility Drying Speed (s) Color Change Adhesion Fastness (%) Example 4 Clear 88.5 Uniform 4 Can Change Color 100 Example 6 Clear 90.1 Uniform 3 Can Change Color 100 Example 7 Clear 91.3 Uniform 3 Can Change Color 100 Example 8 Clear 91.0 Uniform 3 Can Change Color 100

[0102] Result analysis:

[0103] The difference between Examples 6 - 8 and Example 4 is that the weight ratio of the composite emulsion of alkylphenol polyoxyethylene ether and acrylate copolymer modified by oxyacrylate resin is different. Combining the test results in Table 3, it can be seen that the water resistance of the ink prepared in Example 7 is better.

[0104] Examples 9 - 11

[0105] Example 9

[0106] The difference between this example and Example 7 is that the leveling agent in this example is BYK 380N.

[0107] Example 10

[0108] The difference between this example and Example 7 is that the solvent in this example is cyclohexanol.

[0109] Example 11

[0110] The difference between this example and Example 7 is that the solvent in this example is a mixture of cyclohexanol and 2 - methyl - 1 - propanol, and the weight ratio of cyclohexanol to 2 - methyl - 1 - propanol is 1:1.

[0111] The experimental test results of Examples 9 - 11 are shown in Table 4.

[0112] Table 4 - The experimental results of Examples 9 - 11 are shown in the table

[0113] Test Items Pattern Clarity Water Resistance Dispersibility Drying Speed (s) Color Change Adhesion Fastness (%) Example 7 Clear 91.3 Uniform 3 Can Change Color 100 Example 9 Clear 92.0 Uniform 3 Can Change Color 100 Example 10 Clear 92.1 Uniform 3 Can Change Color 100 Example 11 Clear 92.5 Uniform 2 Can Change Color 100

[0114] Result analysis:

[0115] Example 9 is different from Example 7 in that a different leveling agent is selected.

[0116] Examples 10-11 are different from Example 7 in that a different solvent is selected. From the results in Table 4, it can be seen that when the solvent is a mixture of cyclohexanol and 2-methyl-1-propanol, it helps to improve the drying rate.

[0117] Examples 12-14

[0118] Example 12

[0119] This example is different from Example 11 in that when preparing the epoxy acrylate resin-modified acrylate copolymer composite emulsion, the weight ratio of epoxy acrylate, acrylate monomer, emulsifier, ammonium persulfate, and sodium bicarbonate is 11:100:6:1.3:2.

[0120] Example 13

[0121] This example is different from Example 11 in that when preparing the epoxy acrylate resin-modified acrylate copolymer composite emulsion, the weight ratio of epoxy acrylate, acrylate monomer, emulsifier, ammonium persulfate, and sodium bicarbonate is 11:100:6:1.4:2.

[0122] Example 14

[0123] This example is different from Example 11 in that when preparing the epoxy acrylate resin-modified acrylate copolymer composite emulsion, the weight ratio of epoxy acrylate, acrylate monomer, emulsifier, ammonium persulfate, and sodium bicarbonate is 11:100:6:1.5:2.

[0124] For the experimental test results of Examples 12-14, see Table 5.

[0125] Table 5 - For the experimental results of Examples 12-14, see the table

[0126] Test Items Pattern Clarity Water Resistance Dispersibility Drying Speed (s) Color Change Adhesion Fastness (%) Example 11 Clear 92.5 Uniform 2 Can Change Color 100 Example 12 Clear 93.2 Uniform 2 Can Change Color 100 Example 13 Clear 95.0 Uniform 2 Can Change Color 100 Example 14 Clear 94.4 Uniform 2 Can Change Color 100

[0127] Result analysis: The differences between Examples 12 to 14 and Example 11 are that when preparing the epoxy acrylate resin-modified acrylate copolymer composite emulsion, the amount of ammonium persulfate changes. According to the results in Table 5, it can be seen that when preparing the epoxy acrylate resin-modified acrylate copolymer composite emulsion, the amount of ammonium persulfate will affect the water resistance of the prepared ink. Combining the results in Table 5, it can be known that when the weight ratio of epoxy acrylate, acrylate monomer, emulsifier, ammonium persulfate, and sodium bicarbonate is 11:100:6:1.4:2, the water resistance of the prepared ink is better. The reason may be that when the amount of ammonium persulfate is too much, the reaction rate will be too fast, resulting in a decrease in reaction stability. Therefore, controlling the amount of ammonium sulfate is important for improving the water resistance of the ink.

[0128] Example 15

[0129] The difference between this example and Example 13 is that when preparing the epoxy acrylate resin-modified acrylate copolymer composite emulsion, the weight ratio of epoxy acrylate, acrylate monomer, emulsifier, ammonium persulfate, and sodium bicarbonate is 12:100:6:1.4:2.

[0130] The experimental test results of Example 15 are shown in Table 6.

[0131] Table 6 - The experimental results of Example 15 are shown in the following table

[0132] Test Items Pattern Clarity Water Resistance Dispersibility Drying Speed (s) Color Change Adhesion Fastness (%) Example 13 Clear 95.0 Uniform 2 Can Change Color 100 Example 15 Clear 94.8 Uniform 2 Can Change Color 100

[0133] Result analysis: The difference between Example 15 and Example 13 is that when preparing the epoxy acrylate resin-modified acrylate copolymer composite emulsion, the amount of epoxy acrylate is different. Combining the results in Table 6, it can be seen that the change in the amount of epoxy acrylate will affect the water resistance of the ink. The reason may be that when the amount of epoxy acrylate is too much, the stability of the prepared emulsion is poor, resulting in poor water resistance of the prepared ink.

[0134] Examples 16 to 18

[0135] Example 16

[0136] The difference between this example and Example 13 is that the weight ratio of ethoxylated alkylphenol ammonium sulfate (emulsifier TX-4SA) and Triton X-100 is 1.2:1.

[0137] Example 17

[0138] The difference between this example and Example 13 is that the weight ratio of ethoxylated alkylphenol ammonium sulfate (emulsifier TX-4SA) and Triton X-100 is 1.3:1.

[0139] Example 18

[0140] The difference between this example and Example 13 is that the weight ratio of ammonium ethoxylated alkylphenol sulfate (emulsifier TX-4SA) to Triton X-100 is 1.5:1.

[0141] For the experimental test results of Examples 16 to 18, see Table 7.

[0142] Table 7 - Experimental results of Examples 16 to 18 are shown in the table

[0143] Test Items Pattern Clarity Water Resistance Dispersibility Drying Speed (s) Color Change Adhesion Fastness (%) Example 13 Clear 95.0 Uniform 2 Can Change Color 100 Example 16 Clear 95.5 Uniform 2 Can Change Color 100 Example 17 Clear 96.1 Uniform 2 Can Change Color 100 Example 18 Clear 95.8 Uniform 2 Can Change Color 100

[0144] Result analysis:

[0145] The differences between Examples 16 to 18 and Example 13 are that the weight ratios of ammonium ethoxylated alkylphenol sulfate (emulsifier TX-4SA) to Triton X-100 are different. Combining the results in Table 7, it can be seen that when the weight ratio of ammonium ethoxylated alkylphenol sulfate (emulsifier TX-4SA) to Triton X-100 is 1.3:1, it has a better effect on improving the water resistance of the ink.

[0146] The above are all the preferred embodiments of this application. The protection scope of this application is not limited thereby. Therefore, all equivalent changes made according to the structure, shape, and principle of this application should be covered within the protection scope of this application.

Claims

1. A water-resistant stamp ink, characterized in that, The seal ink comprises the following components by weight parts: 5-20 parts of thermochromic powder, 5-25 parts of alkylphenol polyoxyethylene ether, 5-25 parts of epoxy acrylate resin modified acrylate copolymer composite emulsion, 0.1-2 parts of leveling agent, 0.1-2 parts of polyether modified polysiloxane, 0.1-2 parts of antioxidant and 12-47 parts of solvent; The weight ratio of the alkylphenol polyoxyethylene ether to the epoxy acrylate resin modified acrylate copolymer composite emulsion is 1:(1-1.2); The preparation method of the epoxy acrylate resin modified acrylate copolymer composite emulsion comprises the following steps: A1. Dissolve the epoxy acrylate resin in the acrylate monomer to obtain an epoxy resin and acrylate monomer solution; A2. Dropwise add the epoxy resin and acrylate monomer solution prepared in step A1 into the aqueous solution of the emulsifier and disperse at high speed to obtain a pre-emulsion; A3. Mix 10% of the total weight of ammonium persulfate, the emulsifier and sodium bicarbonate, heat up to 80°C, dropwise add 10% of the total weight of the pre-emulsion prepared in step A2, keep warm for 30 min, then dropwise add the remaining pre-emulsion and the remaining ammonium persulfate, heat up to 90°C, keep warm for 1 h, cool, and adjust the pH to weakly alkaline to obtain the epoxy acrylate resin modified acrylate copolymer composite emulsion; In the preparation method of the epoxy acrylate resin modified acrylate copolymer composite emulsion, the weight ratio of the epoxy acrylate, acrylate monomer, emulsifier, ammonium persulfate and sodium bicarbonate is (10-12):100:6:(1-1.5):

2.

2. The water-resistant stamp ink according to claim 1, wherein The seal ink comprises the following components by weight parts: 15-20 parts of thermochromic powder, 21-25 parts of alkylphenol polyoxyethylene ether, 21-25 parts of epoxy acrylate resin modified acrylate copolymer composite emulsion, 0.8-2 parts of leveling agent, 1.1-2 parts of polyether modified polysiloxane, 1.3-2 parts of antioxidant and 30-47 parts of solvent.

3. The water-resistant stamp ink according to claim 1, characterized in that, The weight ratio of the alkylphenol polyoxyethylene ether to the epoxy acrylate resin modified acrylate copolymer composite emulsion is 1:1.

15.

4. A water-resistant stamp ink according to claim 1, wherein The leveling agent comprises one of leveling agent BYK307 and leveling agent BYK380N.

5. A water-resistant stamp ink according to claim 1, wherein, The antioxidant comprises antioxidant 1010.

6. The water-resistant stamp ink according to claim 1, characterized in that, The solvent comprises at least one of 2-methyl-1-propanol and cyclohexanol.

7. A preparation method of the water-resistant stamp ink according to any one of claims 1 to 6, characterized in that, The preparation method comprises the following steps: S1. Mix the thermochromic powder and the alkylphenol polyoxyethylene ether, add the solvent, stir to obtain a first mixture; S2. Mix and stir the epoxy acrylate resin modified acrylate copolymer composite emulsion and the polyether modified polysiloxane to obtain a second mixture; S3. Mix and stir the first mixture and the second mixture, and add the leveling agent and the antioxidant to mix to obtain the water-resistant seal ink.

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