Preparation method of acid and alkali resistant ink for battery film

Abstract

The present application relates to the technical field of ink preparation, and in particular to a preparation method of acid and alkali resistant ink for battery film; the acid and alkali resistant ink for battery film is prepared by using acid and alkali resistant ketone aldehyde resin, acrylic resin, epoxy resin, dispersing agent, leveling agent, thixotropic agent, solvent and pigment; the acid and alkali resistant ink for battery film prepared by the present application has a smooth and flat surface, good adhesion and gloss, and strong adhesion; the acid and alkali resistant ink for battery film prepared by the present application contains diphenyl ether aldehyde ketone resin and organic titanium aldehyde ketone resin mixture, has good acid and alkali resistance, and the ink surface has no obvious color difference and the ink layer has no cracking, falling and other phenomena.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of ink preparation, and in particular to a preparation method of acid- and alkali-resistant ink for a battery film. BACKGROUND

[0002] Batteries are one of the most widely used commodities in our daily life, such as various remote controllers, calculators, flashlights, children's toys, clocks and the like, which cannot be separated from dry batteries, and the dry batteries have the advantages of small size, convenient carrying, high energy conversion rate, stable and reliable energy supply, and bring great convenience to our life and work.

[0003] Chinese patent CN114958080A discloses a PETG heat-shrinkable film dry battery label special environmental protection ink and a preparation method thereof, which comprises the following raw materials in parts by weight: chloroether resin 13-18 parts; pigment 8-35 parts; dispersing agent 0.2-1 part; polyethylene wax 0.5-3 parts; CAB resin 1-2 parts; ethyl acetate 15-35 parts; n-propyl acetate 10-48 parts; the raw materials are simple, and all requirements can be met by using the chloroether and CAB resins; the production process is simple, the process conditions are easy to control, the preparation time is short, the production cost is low, batch production is easy, the economic effect is obvious, and the production requirements of industrialization are met, the application is suitable for high-speed printing and shallow screen printing. The application is water-resistant, acid- and alkali-resistant, heat-resistant and aging-resistant, and guarantees the service life of the battery.

[0004] Chinese patent CN105838138A provides a scratch-resistant and corrosion-resistant ink, which comprises the following components in parts by weight: polyurethane modified epoxy acrylate resin 55-68 parts, dammar resin 14-21 parts, terpene phenolic resin 7-12 parts, butyl methacrylate 3-8 parts, calcium lignosulfonate 4-9 parts, nano silicon dioxide 3-7 parts, mica iron oxide 1.8-3.4 parts, short carbon fiber 3-6 parts, benzoxazolyl 2-5 parts, coupling agent 1-3.2 parts, leveling agent 1.5-2.7 parts, and solvent 125-150 parts. The scratch-resistant and corrosion-resistant ink prepared by the application has high hardness after drying, strong adhesion, scratch resistance, excellent acid and alkali corrosion resistance, can meet the application requirements of harsh environments, and has good market prospects.

[0005] CN107652765A discloses a kind of corrosion-resistant ink and preparation method thereof, the preparation method includes: 1) in the condition of solvent, glass fiber, silane coupling agent, polypropylene resin and magnesium silicate are mixed, and mixed solution M1 is prepared;2) after mixed solution M1 is dried and grinded, powder M2 is prepared;3) graphene oxide, powder M2 and fumed silica are placed under the condition of temperature 200-300 DEG C heat treatment, and dry powder M3 is prepared;4) silicone resin, dry powder M3, solvent and processing aid are mixed, and corrosion-resistant ink is prepared.The glass fiber, silane coupling agent, polypropylene resin and magnesium silicate of the application are mixed and dried, and then the above powder is heat treated with graphene oxide and fumed silica, and the heat treated powder is mixed with silicone resin, solvent and processing aid to prepare ink, so that the ink prepared by the above materials and methods has good corrosion resistance in actual use.

[0006] The ink prepared by the above patent and prior art has problems such as insufficient acid and alkali resistance, poor adhesion and the like. SUMMARY

[0007] The present application aims to overcome the shortcomings of the prior art and provide a preparation method of acid and alkali resistant ink for battery film. The method uses acid and alkali resistant ketone aldehyde resin, acrylic resin, epoxy resin, dispersant, leveling agent, thixotropic agent, solvent and pigment to prepare acid and alkali resistant ink for battery film, which has smooth and flat surface, good adhesion and gloss, and strong adhesion.

[0008] In one aspect of the present application, a preparation method of acid and alkali resistant ink for battery film is provided, and the operation steps are as follows:

[0009] A1: 15-20 parts of acid and alkali resistant ketone aldehyde resin, 1-3 parts of acrylic resin, 1-3 parts of epoxy resin, 0.1-1 parts of dispersant, 0.5-2 parts of leveling agent, 0.1-1 parts of thixotropic agent, 40-60 parts of solvent are weighed by weight parts, and stirred for 30-80 min;

[0010] A2: continue to add 3-7 parts of pigment and 15-25 parts of solvent, stir for 20-40 min, and obtain acid and alkali resistant ink for battery film.

[0011] Preferably, the dispersant is TEGODispers 610, TEGODispers 610S, TEGODispers 630, TEGODispers 655, TEGODispers 710, TEGODispers 740W, TEGODispers 750W, TEGODispers 755W and TEGODispers 760W.

[0012] Preferably, the leveling agent is isophorone, diacetone alcohol, polydimethylsiloxane.

[0013] Preferably, the thixotropic agent is organic bentonite, hydrogenated castor oil, polyamide wax.

[0014] Preferably, the pigment is titanium dioxide, carbon black, organic red, azo yellow, phthalocyanine green, phthalocyanine blue.

[0015] Preferably, the solvent is terpineol, turpentine, silicone oil, diethylene glycol, polyethylene glycol.

[0016] In another aspect of the present application, the present application provides a preparation method of the acid and alkali resistant ketone aldehyde resin, and the operation steps are as follows:

[0017] H1: 20-40 parts of finely ground aldehyde ketone resin, 200-300 parts of dichloromethane, 6-10 parts of allyl isocyanate, 0.4-2 parts of dibutyl tin oxide are added in a reaction kettle, and the reaction is carried out at 80-90℃ for 30-70 minutes;

[0018] H2: 0.05-0.5 parts of 4,4'-dithioxyphenyl ether, 0.4-2 parts of tetramethyl guanidine are further added, the stirrer is started, the reaction is carried out at 70-80℃ for 20-40 minutes, 0.07-0.6 parts of mercapto organic titanium complex is further added, the reaction is carried out at 70-80℃ for 30-70 minutes, and the reaction is completed; dichloromethane is distilled out under reduced pressure to obtain the acid and alkali resistant ketone aldehyde resin.

[0019] Preferably, the preparation method of the mercapto organic titanium complex is as follows:

[0020] According to mass parts, 11-22 parts of 2-mercapto pyridine, 14-26 parts of titanium chloride, 200-220 parts of dichloromethane are added in a stirring kettle, and the stirring is carried out at 30-40℃ for 30-50 minutes; dichloromethane is distilled out to obtain the mercapto organic titanium complex.

[0021] The preparation mechanism of the above-mentioned acid and alkali resistant ketone aldehyde resin in the present application is as follows:

[0022] (1) The hydroxyl group of the aldehyde ketone resin is subjected to condensation reaction with allyl isocyanate to obtain an aldehyde ketone resin containing allyl group;

[0023] (2) 4,4'-dithioxyphenyl ether is subjected to mercapto addition reaction with the aldehyde ketone resin containing allyl group to obtain an aldehyde ketone resin containing dithioxyphenyl ether group; mercapto organic titanium complex is subjected to mercapto addition reaction with the aldehyde ketone resin containing allyl group to obtain the acid and alkali resistant ketone aldehyde resin.

[0024] Compared with the prior art, the present application has the following technical advantages:

[0025] (1) The acid and alkali resistant ink prepared by the method has smooth and flat surface, good adhesion and gloss, and strong adhesion;

[0026] (2) The acid and alkali resistant ink prepared by the method contains diphenyl ether aldehyde ketone resin and organic titanium aldehyde ketone resin mixture, has good acid and alkali resistance, no obvious color difference on the surface of the ink, and no cracking and falling of the ink layer. DETAILED DESCRIPTION

[0027] The following examples are only descriptive, not limiting, and cannot limit the protection scope of the present application.

[0028] Test the acid and alkali resistance of the ink: after sintering, the ink sample is placed in 0.1 mol / L H2SO4 solution, soaked in 80℃ water bath for 72h, and placed in 0.5% NaOH solution at room temperature for 80h, observe whether there is color difference on the surface of the ink before and after soaking, and observe whether there is cracking and falling phenomenon on the surface of the ink layer by using ultra-depth microscope.

[0029] Example 1

[0030] A preparation method of an acid and alkali resistant ink for battery film, the operation steps are:

[0031] A1: weigh 15g of acid and alkali resistant ketone aldehyde resin, 1g of acrylic resin, 1g of epoxy resin, 0.1g of dispersing agent, 0.5g of leveling agent, 0.1g of thixotropic agent, and 40g of solvent, and stir for 30min;

[0032] A2: continue to add 3g of pigment and 15g of solvent, and stir for 20min to obtain the acid and alkali resistant ink for battery film.

[0033] The dispersing agent is TEGODispers 610.

[0034] The leveling agent is isophorone.

[0035] The thixotropic agent is organic bentonite.

[0036] The pigment is titanium dioxide.

[0037] The solvent is terpineol.

[0038] The preparation method of the acid and alkali resistant ketone aldehyde resin is:

[0039] H1: add 20g of finely ground aldehyde ketone resin, 200g of dichloromethane, 6g of allyl isocyanate, and 0.4g of dibutyl tin oxide into a reaction kettle, and react at 80℃ for 30min;

[0040] H2: add 0.05g 4,4'-dithiodiphenyl ether, 0.4g tetramethyl guanidine, start the stirrer, 70℃ for 20 minutes, then add 0.07g mercapto organic titanium complex, 70℃ for 30 minutes, reaction is completed; evaporate dichloromethane under reduced pressure to obtain acid and alkali resistant ketone aldehyde resin.

[0041] The preparation method of the mercapto organic titanium complex is:

[0042] Add 11g 2-mercaptopyridine, 14g titanium chloride, 200g dichloromethane in a stirred tank, stir for 30 minutes at 30℃, distill off dichloromethane to obtain mercapto organic titanium complex.

[0043] Example 2

[0044] A method for preparing acid and alkali resistant ink for battery film, the operation steps are:

[0045] A1: weigh 16g acid and alkali resistant ketone aldehyde resin, 2g acrylic resin, 2g epoxy resin, 0.5g dispersant, 1g leveling agent, 0.5g thixotropic agent, 45g solvent, stir for 50 minutes;

[0046] A2: continue to add 4g pigment, 18g solvent, stir for 25 minutes to obtain acid and alkali resistant ink for battery film.

[0047] The dispersant is TEGO Dispers 610S.

[0048] The leveling agent is diacetone alcohol.

[0049] The thixotropic agent is hydrogenated castor oil.

[0050] The pigment is carbon black.

[0051] The solvent is silicone oil.

[0052] The preparation method of the acid and alkali resistant ketone aldehyde resin is:

[0053] H1: add 25g finely ground aldehyde ketone resin, 240g dichloromethane, 7g allyl isocyanate, 1g dibutyl tin oxide in a reaction kettle, 85℃ for 40 minutes;

[0054] H2: add 0.2g 4,4'-dithiodiphenyl ether, 1g tetramethyl guanidine, start the stirrer, 75℃ for 25 minutes, then add 0.2g mercapto organic titanium complex, 75℃ for 40 minutes, reaction is completed; evaporate dichloromethane under reduced pressure to obtain acid and alkali resistant ketone aldehyde resin.

[0055] The preparation method of the mercapto organic titanium complex is:

[0056] A stirring kettle is added with 16 g of 2-mercapto pyridine, 18 g of titanium chloride, 205 g of dichloromethane, stirred at 35℃ for 35 minutes, and dichloromethane is removed by distillation to obtain a mercapto organic titanium complex.

[0057] Example 3

[0058] A preparation method of an acid and alkali resistant ink for a battery film, the operation steps of which are:

[0059] A1: 18 g of acid and alkali resistant ketone aldehyde resin, 2 g of acrylic resin, 2 g of epoxy resin, 0.8 g of dispersant, 1.5 g of leveling agent, 0.8 g of thixotropic agent, and 55 g of solvent are weighed, and stirred for 70 min;

[0060] A2: 6 g of pigment and 23 g of solvent are continuously added, stirred for 35 min, and an acid and alkali resistant ink for a battery film is obtained.

[0061] The dispersant is TEGO Dispers 630.

[0062] The leveling agent is diacetone alcohol.

[0063] The thixotropic agent is hydrogenated castor oil.

[0064] The pigment is organic red.

[0065] The solvent is diethylene glycol.

[0066] The preparation method of the acid and alkali resistant ketone aldehyde resin is:

[0067] H1: 35 g of finely ground aldehyde ketone resin, 280 g of dichloromethane, 9 g of allyl isocyanate, and 1.5 g of dibutyl tin oxide are added to a reaction kettle, and reacted at 85℃ for 60 min;

[0068] H2: 0.4 g of 4,4'-dithio diphenyl ether and 1.5 g of tetramethyl guanidine are further added, the stirrer is started, and reacted at 75℃ for 35 min, 0.5 g of mercapto organic titanium complex is further added, and reacted at 75℃ for 60 min, and the reaction is completed; dichloromethane is distilled out under reduced pressure to obtain an acid and alkali resistant ketone aldehyde resin.

[0069] The preparation method of the mercapto organic titanium complex is:

[0070] A stirring kettle is added with 20 g of 2-mercapto pyridine, 22 g of titanium chloride, and 215 g of dichloromethane, stirred at 35℃ for 45 min, and dichloromethane is removed by distillation to obtain a mercapto organic titanium complex.

[0071] Example 4

[0072] A preparation method of an acid and alkali resistant ink for a battery film, the operation steps of which are:

[0073] A1: take 20 g of acid and alkali resistant ketone aldehyde resin, 3 g of acrylic resin, 3 g of epoxy resin, 1 g of dispersant, 2 g of leveling agent, 1 g of thixotropic agent, 60 g of solvent, stir for 80 min;

[0074] A2: continue to add 7 g of pigment, 25 g of solvent, stir for 40 min, get acid and alkali resistant ink for battery film.

[0075] The dispersant is TEGO Dispers 760W.

[0076] The leveling agent is polydimethylsiloxane.

[0077] The thixotropic agent is polyamide wax.

[0078] The pigment is phthalocyanine blue.

[0079] The solvent is polyethylene glycol.

[0080] The preparation method of the acid and alkali resistant ketone aldehyde resin is:

[0081] H1: add 40 g of finely ground aldehyde ketone resin, 300 g of dichloromethane, 10 g of allyl isocyanate, 2 g of dibutyl tin oxide into the reaction kettle, react at 90 ℃ for 70 min;

[0082] H2: add 0.5 g of 4,4'-dithio diphenyl ether, 2 g of tetramethyl guanidine, start the stirrer, react at 80 ℃ for 40 min, then add 0.6 g of mercapto organic titanium complex, react at 80 ℃ for 70 min, the reaction is completed; distill off the dichloromethane under reduced pressure to obtain the acid and alkali resistant ketone aldehyde resin.

[0083] The preparation method of the mercapto organic titanium complex is:

[0084] Add 22 g of 2-mercaptopyridine, 26 g of titanium chloride, 220 g of dichloromethane into the stirred tank, stir at 40 ℃ for 50 min, distill off the dichloromethane to obtain the mercapto organic titanium complex.

[0085] Comparative example 1

[0086] In this example, no acid and alkali resistant ketone aldehyde resin is added during the preparation of the acid and alkali resistant ink, ordinary aldehyde ketone resin is added, and the others are the same as example 1.

[0087] Comparative example 2

[0088] In this example, no allyl isocyanate is added during the preparation of the acid and alkali resistant ketone aldehyde resin, and the others are the same as example 1.

[0089] Comparative example 3

[0090] In this example, no mercapto organic titanium complex is added during the preparation of the acid and alkali resistant ketone aldehyde resin, and the others are the same as example 1.

[0091] The acid and alkali resistance test results of the above examples and comparative examples are shown in the following table:

[0092] resistance to acid and alkali Example 1 No color difference, no cracking, no peeling Example 2 No color difference, no cracking, no peeling Example 3 No color difference, no cracking, no peeling Example 4 No color difference, no cracking, no peeling Comparative Example 1 Color difference, peeling Comparative Example 2 Color difference, cracking Comparative Example 3 Color difference, cracking

[0093] Through the comparison of the above examples and comparative examples, the acid and alkali resistant ink prepared by the present application has good acid and alkali resistance, and the ink surface has no obvious color difference, and the ink layer has no cracking, falling off and other phenomena.

[0094] The above is only the preferred embodiment of the present application, it should be noted that for those skilled in the art, without departing from the technical principles of the present application, a number of improvements and refinements can be made, which should also be considered within the scope of the present application.

Claims

1.A method for preparing an acid and alkali resistant ink for battery film, comprising the following steps: A1: weighing 15-20 parts of acid and alkali resistant ketone aldehyde resin, 1-3 parts of acrylic resin, 1-3 parts of epoxy resin, 0.1-1 parts of dispersant, 0.5-2 parts of leveling agent, 0.1-1 parts of thixotropic agent, and 40-60 parts of solvent, and stirring for 30-80 min; A2: continuously adding 3-7 parts of pigment and 15-25 parts of solvent, and stirring for 20-40 min to obtain the acid and alkali resistant ink for battery film; wherein the acid and alkali resistant ketone aldehyde resin is prepared by the following method: H1: adding 20-40 parts of finely ground aldehyde ketone resin, 200-300 parts of dichloromethane, 6-10 parts of allyl isocyanate, and 0.4-2 parts of dibutyl tin oxide into a reaction kettle, and reacting at 80-90℃ for 30-70 min; H2: further adding 0.05-0.5 parts of 4,4"-dithioxyphenyl ether, 0.4-2 parts of tetramethyl guanidine, and starting a stirrer, and reacting at 70-80℃ for 20-40 min, and further adding 0.07-0.6 parts of mercapto organic titanium complex, and reacting at 70-80℃ for 30-70 min, and then stopping the reaction; and distilling dichloromethane under reduced pressure to obtain the acid and alkali resistant ketone aldehyde resin; wherein the mercapto organic titanium complex is prepared by the following method: adding 11-22 parts of 2-mercapto pyridine, 14-26 parts of titanium chloride, and 200-220 parts of dichloromethane into a stirring kettle, and stirring at 30-40℃ for 30-50 min, and distilling dichloromethane to obtain the mercapto organic titanium complex; wherein the dispersant is at least one selected from TEGO Dispers 610, TEGO Dispers 610S, TEGO Dispers 630, TEGO Dispers 655, TEGO Dispers 710, TEGO Dispers 740W, TEGO Dispers 750W, TEGO Dispers 755W, and TEGO Dispers 760W; wherein the leveling agent is at least one selected from isophorone, diacetone alcohol, and polydimethylsiloxane; wherein the thixotropic agent is at least one selected from organic bentonite, hydrogenated castor oil, and polyamide wax; wherein the pigment is at least one selected from titanium dioxide, carbon black, organic red, azo yellow, phthalo green, and phthalo blue; and wherein the solvent is at least one selected from terpineol, turpentine oil, silicone oil, diethylene glycol, and polyethylene glycol. ​ ​ ​ ​ ​ ​ ​ 2. The method for preparing acid and alkali resistant ink on the battery film according to claim 1, characterized in that: ​ 3. The method for preparing acid and alkali resistant ink for a battery film according to claim 1, characterized in that: ​ 4. The method for preparing acid and alkali resistant ink for battery films according to claim 1, characterized in that: ​ 5. The method for preparing acid and alkali resistant ink for battery films according to claim 1, characterized in that: ​ 6. The method for preparing acid and alkali resistant ink for a battery film according to claim 1, characterized in that: ​