Polyurethane water-based ink and preparation method thereof

Abstract

The invention relates to the technical field of ink, and discloses polyurethane water-based ink and a preparation method thereof.The polyurethane water-based ink is obtained by adding water-based polyurethane resin, quaternary phosphonium salt modified imidazole, quaternized polyurethane, water-based pigment, a thickening agent, a flatting agent, a defoaming agent and deionized water into a stirrer and stirring. A quaternary phosphonium salt group and an imidazole group in the quaternary phosphonium salt modified imidazole have a relatively good antibacterial effect. A quaternary ammonium salt group in quaternized polyurethane also has a better antibacterial effect, and di (dimethylamino) methyl vinyl silane and 2-chloroethanol are subjected to quaternization reaction, so that the substitution degree of quaternary ammonium salt is improved, and the antibacterial effect of the quaternary ammonium salt is further improved; and the polyurethane structure also has relatively good wear resistance.

Description

Technical Field

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

[0002] Water-based ink is an ink made with water as solvent. Compared with organic ink, it is less toxic and less harmful to the body, but its antibacterial effect is poor, which greatly limits its application field. For example, patent CN113354983B discloses a fire-resistant ink and its preparation method, which includes the following components: 30-45 parts of saturated polyester resin, 35-50 parts of fire-resistant grinding slurry, 10-15 parts of silicone-polyurethane copolymer, 1.4-2.6 parts of additives, and 5-10 parts of solvents; it has good flame retardant and fireproof effects, but its antibacterial and wear resistance properties are not improved. Summary of the invention

[0003] 1. Technical issues to be resolved

[0004] In view of the deficiencies of the prior art, the present invention provides a polyurethane water-based ink and a preparation method thereof, which has good antibacterial and wear resistance.

[0005] (II) Technical solution

[0006] To achieve the above-mentioned purpose, the present invention provides the following technical scheme: a polyurethane water-based ink and a preparation method thereof, a polyurethane water-based ink, comprising the following components by weight: 30-45 parts by weight of water-based polyurethane resin, 0.2-0.3 parts by weight of quaternary phosphate-modified imidazole, 0.14-0.22 parts by weight of quaternized polyurethane, 0.5-1 parts by weight of water-based pigment, 0.1-0.2 parts by weight of thickener, 0.2-0.3 parts by weight of leveling agent, 0.1-0.13 parts by weight of defoamer, and 20-25 parts by weight of deionized water.

[0007] Preferably, the preparation method of the quaternary phosphonium salt modified imidazole is:

[0008] Step 1: Add 1-(3-aminopropyl)imidazole, p-chloromethylbenzoic acid and potassium hydroxide catalyst to a reactor filled with N,N-dimethylformamide solvent, introduce nitrogen protection, react at 75-90°C for 6-8h, and then distill under reduced pressure and wash to obtain intermediate 1;

[0009] Step 2: Add intermediate 1 and triphenylphosphine to carbon tetrachloride, stir and mix, and incubate at 30-45°C for 2-4 hours. After the mixture is purified by acetone, and dried to obtain quaternary phosphonium salt-modified imidazole.

[0010] Preferably, in the step 1, the dosage ratio of N,N-dimethylformamide, 1-(3-aminopropyl)imidazole, p-chloromethylbenzoic acid and potassium hydroxide catalyst is 35-55 mL: 1.21-1.34 g: 1.16-1.28 g: 2-3 mg.

[0011] Preferably, in the step 2, the usage ratio of the intermediate 1, triphenylphosphine and carbon tetrachloride is 1 g: 0.83-0.92 g: 40-50 mL.

[0012] Preferably, the preparation method of the quaternized polyurethane is:

[0013] S1. Add 2.1-2.4 g of di(dimethylamino)methylvinylsilane to 25-35 mL of N,N-dimethylamide solvent, stir and disperse, then continue to add 4.3-4.7 g of 2-chloroethanol thereto, carry out quaternization reaction, react at 70-85 ° C, and then distill under reduced pressure after completion, wash and dry to obtain quaternary ammonium salt modified vinyl silane;

[0014] S2. Under a nitrogen atmosphere, add 1.32-1.44 g of olefinic polyurethane, 0.82-1.13 g of quaternary ammonium salt-modified olefinic silane, and 1-1.3 g of methyl acrylate into a reactor, stir evenly, and continue to add 0.01-0.012 g of azobisisobutyronitrile catalyst, react for 12-14 hours, cool to room temperature after reaction, wash with deionized water, and dry to obtain quaternary polyurethane.

[0015] In the above reaction process, the tertiary amine group in di(dimethylamino)methylvinylsilane (CAS: 13368-45-1) and the chlorine in 2-chloroethanol are quaternized to generate a quaternary ammonium salt group, and an olefin group is introduced, and then polymerization reaction is continued with olefinated polyurethane and methyl acrylate to obtain a quaternary polyurethane.

[0016] Preferably, the reaction time in S1 is 3-4h.

[0017] Preferably, the reaction temperature in S2 is 90-110°C.

[0018] Preferably, the preparation method of the polyurethane water-based ink is: adding water-based polyurethane resin, quaternary phosphite-modified imidazole, quaternized polyurethane, water-based pigment, thickener, leveling agent, defoamer, and deionized water into a stirrer, stirring for 4-6 minutes to obtain the polyurethane water-based ink.

[0019] (III) Beneficial technical effects

[0020] The invention prepares polyurethane water-based ink by adding water-based polyurethane resin, quaternary phosphonium salt modified imidazole, quaternary ammonium polyurethane, water-based pigment, thickener, leveling agent, defoamer and deionized water into a stirrer and stirring.

[0021] The quaternary phosphonium salt group and imidazole group in the quaternary phosphonium salt modified imidazole have good antibacterial effect. After the quaternary phosphonium salt interacts with the negative charge on the surface of the bacterial cell membrane, it will change the structure of the cell membrane, increase the permeability of the cell membrane, and leak the substances in the cell, leading to the death of bacteria; the imidazole group mainly interferes with the synthesis of the cell wall, inhibits the activity of metabolic enzymes, and destroys the integrity of the cell membrane, leading to the death of bacteria; the quaternary ammonium salt group in the quaternized polyurethane also has a good antibacterial effect, and di(dimethylamino)methylvinylsilane and 2-chloroethanol undergo a quaternization reaction, which increases the degree of substitution of the quaternary ammonium salt and further improves its antibacterial effect; the polyurethane structure itself also has good wear resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 It is the reaction formula of quaternary phosphonium salt modified imidazole. DETAILED DESCRIPTION

[0023] Preparation of olefinic polyurethane: Referring to the literature "Study on the surface of quaternary ammonium salt grafted modified materials and their antibacterial properties", methyl methacrylate isothiocyanate was poured into a round-bottom flask equipped with a magnet and an unmodified membrane, and nitrogen was introduced to expel the air in the flask. The oil bath controlled at 65°C was sealed with a membrane, and 0.75 mL of triethylamine was injected with a syringe, and the reaction was carried out under nitrogen protection for 10 hours. After the reaction, it was ultrasonically cleaned with ethanol several times, placed in a vacuum drying oven at 40°C for 1 day, and dried and stored to obtain olefinic polyurethane.

[0024] The water-based pigment is permanent orange G, model YHO-1304; the thickener model is H416E; the leveling agent model is BYK-333, and the defoamer model is B-109.

[0025] Example 1

[0026] (1) Add 1-(3-aminopropyl)imidazole, p-chloromethylbenzoic acid, and potassium hydroxide catalyst to a reactor filled with N,N-dimethylformamide solvent, wherein the amount ratio of N,N-dimethylformamide, 1-(3-aminopropyl)imidazole, p-chloromethylbenzoic acid, and potassium hydroxide catalyst is 35 mL:1.21 g:1.16 g:2 mg, and pass nitrogen gas for protection. React at 75° C. for 6 h. After the reaction, distill under reduced pressure and wash to obtain intermediate 1;

[0027] (2) adding intermediate 1 and triphenylphosphine to carbon tetrachloride, wherein the ratio of intermediate 1, triphenylphosphine and carbon tetrachloride is 1 g:0.83 g:40 mL, stirring and mixing, at 30° C. for 2 h, after which purification by acetone and drying to obtain quaternary phosphonium salt-modified imidazole;

[0028] (3) adding 2.1 g of di(dimethylamino)methylvinylsilane to 25 mL of N,N-dimethylamide solvent, stirring and dispersing, and then adding 4.3 g of 2-chloroethanol to the solvent for quaternization reaction at 70° C. for 3 h. After the reaction, distilling under reduced pressure, washing and drying were performed to obtain quaternary ammonium salt-modified vinylsilane;

[0029] (4) Under a nitrogen atmosphere, 1.32 g of olefinic polyurethane, 0.82 g of quaternary ammonium salt-modified olefinic silane, and 1 g of methyl acrylate were added to a reactor and stirred evenly. 0.01 g of azobisisobutyronitrile catalyst was added thereto and reacted for 12 h at a reaction temperature of 90 ° C. After the reaction was completed, the mixture was cooled to room temperature, washed with deionized water, and dried to obtain a quaternary polyurethane;

[0030] (5) 30 parts by weight of an aqueous polyurethane resin, 0.2 parts by weight of a quaternary phosphate-modified imidazole, 0.14 parts by weight of a quaternized polyurethane, 0.5 parts by weight of an aqueous pigment, 0.1 parts by weight of a thickener, 0.2 parts by weight of a leveling agent, 0.1 parts by weight of a defoaming agent, and 20 parts by weight of deionized water were added to a stirrer and stirred for 4 minutes to obtain a polyurethane aqueous ink.

[0031] Example 2

[0032] (1) Add 1-(3-aminopropyl)imidazole, p-chloromethylbenzoic acid, and potassium hydroxide catalyst to a reactor filled with N,N-dimethylformamide solvent, wherein the amount ratio of N,N-dimethylformamide, 1-(3-aminopropyl)imidazole, p-chloromethylbenzoic acid, and potassium hydroxide catalyst is 55 mL:1.34 g:1.28 g:3 mg, and pass nitrogen protection, react at 90° C. for 8 h, and then distill under reduced pressure and wash to obtain intermediate 1;

[0033] (2) adding intermediate 1 and triphenylphosphine to carbon tetrachloride, wherein the ratio of intermediate 1, triphenylphosphine and carbon tetrachloride is 1 g:0.92 g:50 mL, stirring and mixing, at 45° C. for 4 h, after which purification by acetone and drying to obtain quaternary phosphonium salt-modified imidazole;

[0034] (3) adding 2.4 g of di(dimethylamino)methylvinylsilane to 35 mL of N,N-dimethylamide solvent, stirring and dispersing, and then adding 4.7 g of 2-chloroethanol thereto to carry out quaternization reaction at 85° C. for 4 h. After completion, distilling under reduced pressure, washing and drying are performed to obtain quaternary ammonium salt-modified vinylsilane;

[0035] (4) Under a nitrogen atmosphere, 1.44 g of olefinic polyurethane, 1.13 g of quaternary ammonium salt-modified olefinic silane, and 1.3 g of methyl acrylate were added to a reactor and stirred evenly. 0.012 g of azobisisobutyronitrile catalyst was added thereto and reacted for 14 h at a reaction temperature of 110 ° C. After the reaction was completed, the reaction was cooled to room temperature, washed with deionized water, and dried to obtain a quaternary polyurethane;

[0036] (5) 45 parts by weight of an aqueous polyurethane resin, 0.3 parts by weight of a quaternary phosphate-modified imidazole, 0.22 parts by weight of a quaternized polyurethane, 1 part by weight of an aqueous pigment, 0.2 parts by weight of a thickener, 0.3 parts by weight of a leveling agent, 0.13 parts by weight of a defoaming agent, and 25 parts by weight of deionized water were added to a stirrer and stirred for 6 minutes to obtain a polyurethane aqueous ink.

[0037] Example 3

[0038] (1) Add 1-(3-aminopropyl)imidazole, p-chloromethylbenzoic acid, and potassium hydroxide catalyst to a reactor filled with N,N-dimethylformamide solvent, wherein the amount ratio of N,N-dimethylformamide, 1-(3-aminopropyl)imidazole, p-chloromethylbenzoic acid, and potassium hydroxide catalyst is 45 mL:1.27 g:1.22 g:2.5 mg, pass nitrogen protection, react at 82° C. for 7 h, and then distill under reduced pressure and wash to obtain intermediate 1;

[0039] (2) adding intermediate 1 and triphenylphosphine to carbon tetrachloride, wherein the ratio of intermediate 1, triphenylphosphine and carbon tetrachloride is 1 g:0.87 g:45 mL, stirring and mixing, and incubating at 37° C. for 3 h. After the mixture is purified by acetone, and dried, a quaternary phosphine-modified imidazole is obtained;

[0040] (3) adding 2.2 g of di(dimethylamino)methylvinylsilane to 30 mL of N,N-dimethylamide solvent, stirring and dispersing, and then adding 4.5 g of 2-chloroethanol to the solvent for quaternization reaction at 77° C. for 3.5 h. After the reaction, distilling under reduced pressure, washing and drying were performed to obtain quaternary ammonium salt-modified vinylsilane;

[0041] (4) Under a nitrogen atmosphere, 1.38 g of olefinic polyurethane, 1.0 g of quaternary ammonium salt-modified olefinic silane, and 1.2 g of methyl acrylate were added to a reactor and stirred evenly. 0.011 g of azobisisobutyronitrile catalyst was added thereto and the reaction was carried out for 13 h at a reaction temperature of 100 ° C. After the reaction was completed, the mixture was cooled to room temperature, washed with deionized water, and dried to obtain a quaternary polyurethane;

[0042] (5) 37 parts by weight of an aqueous polyurethane resin, 0.25 parts by weight of a quaternary phosphate-modified imidazole, 0.18 parts by weight of a quaternized polyurethane, 0.7 parts by weight of an aqueous pigment, 0.15 parts by weight of a thickener, 0.25 parts by weight of a leveling agent, 0.11 parts by weight of a defoaming agent, and 22 parts by weight of deionized water were added to a stirrer and stirred for 5 minutes to obtain a polyurethane aqueous ink.

[0043] Example 4

[0044] (1) Add 1-(3-aminopropyl)imidazole, p-chloromethylbenzoic acid, and potassium hydroxide catalyst to a reactor filled with N,N-dimethylformamide solvent, wherein the amount ratio of N,N-dimethylformamide, 1-(3-aminopropyl)imidazole, p-chloromethylbenzoic acid, and potassium hydroxide catalyst is 35 mL:1.21 g:1.16 g:2 mg, and pass nitrogen gas for protection. React at 75° C. for 6 h. After the reaction, distill under reduced pressure and wash to obtain intermediate 1;

[0045] (2) adding intermediate 1 and triphenylphosphine to carbon tetrachloride, wherein the ratio of intermediate 1, triphenylphosphine and carbon tetrachloride is 1 g:0.83 g:40 mL, stirring and mixing, at 30° C. for 2 h, after which purification by acetone and drying to obtain quaternary phosphonium salt-modified imidazole;

[0046] (3) adding 2.4 g of di(dimethylamino)methylvinylsilane to 35 mL of N,N-dimethylamide solvent, stirring and dispersing, and then adding 4.7 g of 2-chloroethanol thereto to carry out quaternization reaction at 85° C. for 4 h. After completion, distilling under reduced pressure, washing and drying are performed to obtain quaternary ammonium salt-modified vinylsilane;

[0047] (4) Under a nitrogen atmosphere, 1.44 g of olefinic polyurethane, 1.13 g of quaternary ammonium salt-modified olefinic silane, and 1.3 g of methyl acrylate were added to a reactor and stirred evenly. 0.012 g of azobisisobutyronitrile catalyst was added thereto and reacted for 14 h at a reaction temperature of 110 ° C. After the reaction was completed, the reaction was cooled to room temperature, washed with deionized water, and dried to obtain a quaternary polyurethane;

[0048] (5) 37 parts by weight of an aqueous polyurethane resin, 0.25 parts by weight of a quaternary phosphate-modified imidazole, 0.18 parts by weight of a quaternized polyurethane, 0.7 parts by weight of an aqueous pigment, 0.15 parts by weight of a thickener, 0.25 parts by weight of a leveling agent, 0.11 parts by weight of a defoaming agent, and 20 parts by weight of deionized water were added to a stirrer and stirred for 5 minutes to obtain a polyurethane aqueous ink.

[0049] Example 5

[0050] (1) Add 1-(3-aminopropyl)imidazole, p-chloromethylbenzoic acid, and potassium hydroxide catalyst to a reactor filled with N,N-dimethylformamide solvent, wherein the amount ratio of N,N-dimethylformamide, 1-(3-aminopropyl)imidazole, p-chloromethylbenzoic acid, and potassium hydroxide catalyst is 55 mL:1.34 g:1.28 g:3 mg, and pass nitrogen protection, react at 90° C. for 8 h, and then distill under reduced pressure and wash to obtain intermediate 1;

[0051] (2) adding intermediate 1 and triphenylphosphine to carbon tetrachloride, wherein the ratio of intermediate 1, triphenylphosphine and carbon tetrachloride is 1 g:0.92 g:50 mL, stirring and mixing, at 45° C. for 4 h, after which purification by acetone and drying to obtain quaternary phosphonium salt-modified imidazole;

[0052] (3) adding 2.2 g of di(dimethylamino)methylvinylsilane to 30 mL of N,N-dimethylamide solvent, stirring and dispersing, and then adding 4.5 g of 2-chloroethanol to the solvent for quaternization reaction at 77° C. for 3.5 h. After the reaction, distilling under reduced pressure, washing and drying were performed to obtain quaternary ammonium salt-modified vinylsilane;

[0053] (4) Under a nitrogen atmosphere, 1.38 g of olefinic polyurethane, 1.0 g of quaternary ammonium salt-modified olefinic silane, and 1.2 g of methyl acrylate were added to a reactor and stirred evenly. 0.011 g of azobisisobutyronitrile catalyst was added thereto and the reaction was carried out for 13 h at a reaction temperature of 100 ° C. After the reaction was completed, the mixture was cooled to room temperature, washed with deionized water, and dried to obtain a quaternary polyurethane;

[0054] (5) 30 parts by weight of an aqueous polyurethane resin, 0.2 parts by weight of a quaternary phosphate-modified imidazole, 0.14 parts by weight of a quaternized polyurethane, 0.5 parts by weight of an aqueous pigment, 0.1 parts by weight of a thickener, 0.2 parts by weight of a leveling agent, 0.1 parts by weight of a defoaming agent, and 25 parts by weight of deionized water were added to a stirrer and stirred for 4 minutes to obtain a polyurethane aqueous ink.

[0055] Comparative Example 1

[0056] Compared with Example 5, this comparative example differs in that 1-(3-aminopropyl)imidazole is used instead of quaternary phosphonium salt-modified imidazole.

[0057] Comparative Example 2

[0058] Compared with Example 5, this comparative example is different in that polyurethane is used instead of quaternary ammonium polyurethane.

[0059] Antibacterial grade: Referring to GB / T21866-2008 Antibacterial coating (paint film) antibacterial property determination method and antibacterial effect, the sample printed with antibacterial water-based ink is used to make bacteria evenly contact the sample by film sticking. After a period of cultivation, the number of live bacteria on the sample is detected and the antibacterial rate is calculated. The test bacteria are Staphylococcus aureus and Escherichia coli. The test results are shown in Table 1.

[0060] Table 1: Antimicrobial testing.

[0061]

[0062] It can be seen from Table 1 that the polyurethane water-based ink Examples 1-5 prepared by the present invention have better antibacterial effects than Comparative Examples 1-2.

[0063] Abrasion resistance: Use QD-3031 ink abrasion tester, with a pressure of 4 pounds and 100 friction times. Cut the sample into 25cm*6cm and fix it on the abrasion tester. Cut A4 paper into 20cm*5cm and fix it on the friction slider. Add weights to increase the pressure. Set the friction times to 100 times. After the test, observe the floating color on the A4 paper surface and the discoloration on the sample surface. The less the discoloration, the better the abrasion resistance of the ink.

[0064] Table 2: Abrasion resistance test.

[0065]

[0066]

[0067] As can be seen from Table 2, the polyurethane water-based ink prepared by the present invention does not fade, indicating that the abrasion resistance is good.

[0068] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A polyurethane water-based ink, characterized in that: The invention comprises the following components by weight: 30-45 parts by weight of waterborne polyurethane resin, 0.2-0.3 parts by weight of quaternary phosphate modified imidazole, 0.14-0.22 parts by weight of quaternized polyurethane, 0.5-1 parts by weight of waterborne pigment, 0.1-0.2 parts by weight of thickener, 0.2-0.3 parts by weight of leveling agent, 0.1-0.13 parts by weight of defoamer and 20-25 parts by weight of deionized water.

2. The polyurethane water-based ink according to claim 1, characterized in that: The preparation method of the quaternary phosphonium salt modified imidazole is: Step 1: Add 1-(3-aminopropyl)imidazole, p-chloromethylbenzoic acid and potassium hydroxide catalyst to a reactor filled with N,N-dimethylformamide solvent, introduce nitrogen protection, react at 75-90°C for 6-8h, and then distill under reduced pressure and wash to obtain intermediate 1; Step 2: Add intermediate 1 and triphenylphosphine to carbon tetrachloride, stir and mix, and incubate at 30-45°C for 2-4 hours. After the mixture is purified by acetone and dried to obtain quaternary phosphonium salt-modified imidazole.

3. The polyurethane water-based ink according to claim 2, characterized in that: In the step 1, the dosage ratio of N,N-dimethylformamide, 1-(3-aminopropyl)imidazole, p-chloromethylbenzoic acid and potassium hydroxide catalyst is 35-55 mL: 1.21-1.34 g: 1.16-1.28 g: 2-3 mg.

4. The polyurethane water-based ink according to claim 2, characterized in that: In the step 2, the usage ratio of the intermediate 1, triphenylphosphine and carbon tetrachloride is 1 g: 0.83-0.92 g: 40-50 mL.

5. The polyurethane water-based ink according to claim 1, characterized in that: The preparation method of the quaternized polyurethane is: S1. Add 2.1-2.4 g of di(dimethylamino)methylvinylsilane to 25-35 mL of N,N-dimethylamide solvent, stir and disperse, then continue to add 4.3-4.7 g of 2-chloroethanol thereto, carry out quaternization reaction, react at 70-85 ° C, and then distill under reduced pressure after completion, wash and dry to obtain quaternary ammonium salt modified vinyl silane; S2. Under a nitrogen atmosphere, add 1.32-1.44 g of olefinic polyurethane, 0.82-1.13 g of quaternary ammonium salt-modified olefinic silane, and 1-1.3 g of methyl acrylate into a reactor, stir evenly, and continue to add 0.01-0.012 g of azobisisobutyronitrile catalyst, react for 12-14 hours, cool to room temperature after reaction, wash with deionized water, and dry to obtain quaternary polyurethane.

6. The polyurethane water-based ink according to claim 5, characterized in that: The reaction time in S1 is 3-4h.

7. The polyurethane water-based ink according to claim 5, characterized in that: The reaction temperature in S2 is 90-110°C.

8. A method for preparing a polyurethane water-based ink according to any one of claims 1 to 7, characterized in that: The preparation method of the polyurethane water-based ink is as follows: adding water-based polyurethane resin, quaternary phosphonium salt modified imidazole, quaternary ammonium polyurethane, water-based pigment, thickener, leveling agent, defoamer and deionized water into a stirrer, stirring for 4-6 minutes to obtain the polyurethane water-based ink.

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