A water-based cast composite resin and its preparation method and water-based cast composite ink

Abstract

The present invention provides a water-based cast composite resin for water-based cast composite ink and a preparation method thereof, belonging to the technical field of ink binders. The resin is a chemically modified copolymer of polyvinyl butyral, a high-softening-point polyamide resin, a disproportionated rosin resin, and a hydrogenated ketone-aldehyde resin. The preparation method comprises the following steps: weighing the above four resins, thoroughly mixing them, and recording them as component A, and monoethanolamine as component B; adding ethyl acetate, water, and ethanol, then adding component A and modified nano zinc oxide / magnesium oxide particles, heating the reaction, adding component B dropwise while stirring, and reacting at a constant temperature; after the reaction is completed, cooling the reaction to stop the reaction, and collecting the product. The present invention utilizes the heat-resistant water-based cast composite ink resin provided by the present invention as a binder for water-based inks, and has good acid resistance, alkali resistance, and water resistance, high adhesion and peel strength, and good high-temperature resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of ink binders, and in particular to a water-based cast composite resin and a preparation method thereof, and a water-based cast composite ink. Background Art

[0002] As an environmentally friendly ink, water-based ink has become increasingly important in various printing industries, particularly in demanding sectors such as food, pharmaceuticals, tobacco, and alcohol packaging. Water-based ink has become the preferred printing material. Compared to other printing inks, water-based inks do not contain volatile, toxic organic solvents, thus minimizing the health risks to press operators during the printing process. Water-based inks are formulated using water as a solvent, a water-based polymer resin as a binder, and pigments and additives through a physical and chemical process. The binder, the continuous phase of the ink, is the fluid component and a key factor influencing its printing performance. The quality of the binder directly impacts the ink's performance.

[0003] Water-based cast tape composite ink resin not only possesses the advantages of organic solvent-based resins, such as excellent gloss, acid and alkali resistance, good weather resistance, and excellent printability, but also offers advantages such as low price, safe use, energy conservation, and reduced environmental pollution and hazards. It is a VOC-free, green and environmentally friendly material. Due to its diverse range and excellent physical and chemical properties, water-based cast tape composite ink resin has become the optimal choice for water-based ink binders.

[0004] The inks currently used in the market have poor outdoor weather resistance. For example, outdoor advertising is subject to long-term damage from adverse factors such as ultraviolet rays, acidity, alkali, and high temperatures. Generally, within a year, they will experience severe yellowing and discoloration. To meet the needs of inks used in various high-temperature or complex environments, it is necessary to develop ink materials with better heat resistance. As a key binder in inks, the heat resistance of water-based cast composite ink resins is crucial to the performance of the ink. Therefore, the high-temperature resistance of water-based cast composite ink resins improves the high-temperature resistance of the ink, meeting the needs of its use in complex environments. Summary of the Invention

[0005] The invention provides a water-based cast composite resin and a preparation method thereof, and a water-based cast composite ink, which solve the problems of poor outdoor weather resistance of existing inks and the tendency to suffer from relatively serious yellowing and discoloration.

[0006] In order to solve the above technical problems, the technical solution of the present invention is:

[0007] The present invention provides a water-based cast composite resin for water-based cast composite ink, which is a chemically modified copolymer of polyvinyl butyral, high-softening-point polyamide resin, disproportionated rosin resin and hydrogenated ketone-aldehyde resin; the copolymer is prepared by chemically modifying the following components in parts by weight:

[0008] 15-23.5 parts of polyvinyl butyral resin;

[0009] 0-2.5 parts of high softening point polyamide resin;

[0010] 1-10 parts of disproportionated rosin resin;

[0011] 2-8 parts of hydrogenated ketone-aldehyde resin;

[0012] 15-40 parts of ethanol;

[0013] 3-10 parts of monoethanolamine;

[0014] 5-15 parts of ethyl acetate;

[0015] 20-35 parts of deionized water;

[0016] Among them, a water-based cast composite resin for water-based cast composite ink is prepared by chemical reaction modification of the following components, calculated by weight:

[0017] 15-18.6 parts of polyvinyl butyral resin;

[0018] 1-1.5 parts of high softening point polyamide resin;

[0019] 1-5 parts of disproportionated rosin resin;

[0020] 3-6 parts of hydrogenated ketone-aldehyde resin;

[0021] 20-35 parts of ethanol;

[0022] 6-8 parts of monoethanolamine;

[0023] 8-10 parts of ethyl acetate;

[0024] 25-32 parts of deionized water.

[0025] Among them, a water-based cast composite resin for water-based cast composite ink is prepared by chemical reaction modification of the following components, in parts by weight:

[0026] Polyvinyl butyral resin: 18.6 parts;

[0027] 1.5 parts of high softening point polyamide resin;

[0028] 1 part of disproportionated rosin resin;

[0029] 3.5 parts of hydrogenated ketone-aldehyde resin;

[0030] 25 parts of ethanol;

[0031] 8 parts of monoethanolamine;

[0032] 8 parts of ethyl acetate;

[0033] 30.4 parts of deionized water.

[0034] The invention also includes 0.1-0.3 parts of modified nano zinc oxide / magnesium oxide particles.

[0035] The modified nano zinc oxide / magnesium oxide particles are prepared by the following preparation method:

[0036] Vinyl triethoxysilane is added to anhydrous ethanol, ammonia water is added dropwise, and then nano zinc oxide particles or nano magnesium oxide particles are added. The mixture is stirred at a speed of 300-500 r / min for 5-10 hours, centrifuged, washed with anhydrous ethanol, and dried to obtain modified nano zinc oxide / magnesium oxide particles.

[0037] Wherein, the mass ratio of the vinyltriethoxysilane to the nano zinc oxide particles or nano magnesium oxide particles is 1:1-5.

[0038] The present invention also provides a method for preparing a water-based cast composite resin, comprising the following steps:

[0039] (1) Weigh polyvinyl butyral resin, polyamide resin, disproportionated rosin resin and hydrogenated ketone-aldehyde resin, mix them thoroughly and record them as component A, and monoethanolamine as component B;

[0040] (2) Add ethyl acetate, water, and 50% of the total amount of ethanol to a reaction vessel, then add component A and modified nano zinc oxide / magnesium oxide particles, and stir to mix; then heat to 30-40°C and stir for 15-30 minutes; while stirring, heat to 50-60°C and react for 15-30 minutes;

[0041] (3) Raise the temperature to 80-90°C, add component B dropwise while stirring, and complete the addition within 30 minutes. Then add the remaining ethanol and continue the reaction at a constant temperature for 2-5 hours.

[0042] (4) After the reaction is completed, the temperature is lowered to 35°C to stop the reaction and collect the product.

[0043] A water-based cast composite ink comprises an additive, a pigment, water and the water-based cast composite ink resin or the water-based cast composite ink resin prepared by the above-mentioned preparation method.

[0044] Disproportionated rosin, or DMR, is a modified rosin product obtained through the esterification of rosin with alcohols such as methanol or butanol. It retains the natural properties of rosin while also improving its solubility and application range through modification.

[0045] Polyvinyl butyral (PVB) is a multifunctional resin synthesized by the chemical reaction of polyvinyl alcohol and butyraldehyde. It has extremely high transparency, excellent toughness, flexibility, low-temperature resistance, and is resistant to UV rays, water, oil, and aging. It has strong adhesion to a variety of materials such as glass, metal, plastic, wood, leather, etc.

[0046] High softening point polyamide resin is a polyamide resin with special properties. Its softening point is higher than that of ordinary polyamide resins. Unlike other thermoplastic resins, this resin does not solidify rapidly when the temperature is slightly below the melting point, but has a narrower softening point range.

[0047] Hydrogenated ketone-aldehyde resin, also known as polyketone resin or ketone-aldehyde resin, is a neutral, non-saponifiable resin with high brightness and light resistance. Its use in inks can significantly improve gloss, adhesion, quick-drying properties, leveling, pigment wettability, and solids content.

[0048] Compared with the prior art, the present invention has the following beneficial effects:

[0049] The present invention provides a polyvinyl butyral / high softening point polyamide resin / disproportionated rosin resin / hydrogenated ketone-aldehyde resin copolymer with a reasonable combination of components. The preparation method of the present invention is used to synthesize the polyvinyl butyral / high softening point polyamide resin / disproportionated rosin resin / hydrogenated ketone-aldehyde resin copolymer, achieving more precise control of the synthesis route and process conditions. Test results show that the water-based cast composite ink resin of the present invention has a high solid content. In addition, the polyvinyl butyral / high softening point polyamide resin / disproportionated rosin resin / hydrogenated ketone-aldehyde resin copolymer of the present invention also shows good high-temperature resistance and can withstand temperatures as high as 140°C or above. Therefore, it can maintain better stability and strength in high-temperature environments. In addition, the present invention adds nano-magnesium oxide particles or magnesium oxide particles modified by vinyltriethoxysilane to the chemical reaction, further improving the high-temperature resistance of the copolymer.

[0050] The heat-resistant water-based cast composite ink resin provided by the present invention, that is, the polyvinyl butyral / high softening point polyamide resin / disproportionated rosin resin / hydrogenated ketone-aldehyde resin copolymer is used as a binder for water-based ink, has good acid resistance, alkali resistance and water resistance, high adhesion and peel strength, and has good high temperature resistance, which can meet the use requirements of complex external environments. DETAILED DESCRIPTION

[0051] The following will be combined with specific embodiments of the present invention to clearly and completely describe the technical solutions of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0052] Example 1

[0053] This embodiment provides a water-based cast composite resin for water-based cast composite ink, which is a chemically modified copolymer of polyvinyl butyral, high softening point polyamide resin, disproportionated rosin resin, and hydrogenated ketone-aldehyde resin; the copolymer is prepared by chemically modifying the following components in parts by weight:

[0054] Polyvinyl butyral resin: 18.6 parts;

[0055] 1.5 parts of high softening point polyamide resin;

[0056] 1 part of disproportionated rosin resin;

[0057] 3.5 parts of hydrogenated ketone-aldehyde resin;

[0058] 25 parts of ethanol;

[0059] 8 parts of monoethanolamine;

[0060] 8 parts of ethyl acetate;

[0061] 30.4 parts of deionized water;

[0062] 0.2 parts of modified nano zinc oxide particles.

[0063] The modified nano zinc oxide particles are prepared by the following preparation method:

[0064] Vinyltriethoxysilane was added to anhydrous ethanol, ammonia was added dropwise, and then nano-zinc oxide particles were added. The mixture was stirred at 400 r / min for 8 hours, centrifuged, washed with anhydrous ethanol, and dried to obtain modified nano-zinc oxide particles. The mass ratio of vinyltriethoxysilane to nano-zinc oxide particles was 1:3.

[0065] This embodiment also provides a method for preparing a water-based cast composite resin, comprising the following steps:

[0066] (1) Weigh polyvinyl butyral resin, polyamide resin, disproportionated rosin resin and hydrogenated ketone-aldehyde resin, mix them thoroughly and record them as component A, and monoethanolamine as component B;

[0067] (2) Add ethyl acetate, water, and 50% of the total amount of ethanol to a reaction vessel, then add component A and modified nano-zinc oxide particles, and stir to mix; then heat to 35°C and stir for 10 minutes; while stirring, heat to 55°C and react for 25 minutes;

[0068] (3) Raise the temperature to 80-90°C, add component B dropwise while stirring, and complete the addition within 30 minutes. Then add the remaining ethanol and continue the reaction at a constant temperature for 3.5 hours.

[0069] (4) After the reaction is completed, the temperature is lowered to 35°C to stop the reaction and collect the product.

[0070] Example 2

[0071] This embodiment provides a water-based cast composite resin for water-based cast composite ink, which is a chemically modified copolymer of polyvinyl butyral, high softening point polyamide resin, disproportionated rosin resin, and hydrogenated ketone-aldehyde resin; the copolymer is prepared by chemically modifying the following components in parts by weight:

[0072] 15 parts of polyvinyl butyral resin;

[0073] 2.5 parts of high softening point polyamide resin;

[0074] 1 part of disproportionated rosin resin;

[0075] 8 parts of hydrogenated ketone-aldehyde resin;

[0076] 15 parts of ethanol;

[0077] 10 parts of monoethanolamine;

[0078] 5 parts of ethyl acetate;

[0079] 35 parts of deionized water;

[0080] 0.1 parts of modified nano zinc oxide particles.

[0081] The modified nano magnesium oxide particles are prepared by the following preparation method:

[0082] Vinyltriethoxysilane is added to anhydrous ethanol, ammonia is added dropwise, and then nano-zinc oxide particles or nano-magnesium oxide particles are added. The mixture is stirred at 300 r / min for 10 hours, centrifuged, washed with anhydrous ethanol, and dried to obtain modified nano-magnesium oxide particles. The mass ratio of vinyltriethoxysilane to nano-zinc oxide particles or nano-magnesium oxide particles is 1:1.

[0083] This embodiment also provides a method for preparing a water-based cast composite resin, comprising the following steps:

[0084] (1) Weigh polyvinyl butyral resin, polyamide resin, disproportionated rosin resin and hydrogenated ketone-aldehyde resin, mix them thoroughly and record them as component A, and monoethanolamine as component B;

[0085] (2) Add ethyl acetate, water, and 50% of the total amount of ethanol to a reaction vessel, then add component A and modified nano-magnesium oxide particles, and stir to mix; then heat to 30°C and stir for 15 minutes; while stirring, heat to 60°C and react for 15 minutes;

[0086] (3) Raise the temperature to 80-90°C, add component B dropwise while stirring, and complete the addition within 30 minutes. Then add the remaining ethanol and continue the reaction at a constant temperature for 2 hours.

[0087] (4) After the reaction is completed, the temperature is lowered to 35°C to stop the reaction and collect the product.

[0088] Example 3

[0089] This embodiment provides a water-based cast composite resin for water-based cast composite ink, which is a chemically modified copolymer of polyvinyl butyral, high softening point polyamide resin, disproportionated rosin resin, and hydrogenated ketone-aldehyde resin; the copolymer is prepared by chemically modifying the following components in parts by weight:

[0090] 23.5 parts of polyvinyl butyral resin;

[0091] 10 parts of disproportionated rosin resin;

[0092] 1.5 parts of high softening point polyamide resin;

[0093] 2 parts of hydrogenated ketone-aldehyde resin;

[0094] 40 parts of ethanol;

[0095] 3 parts of monoethanolamine;

[0096] 15 parts of ethyl acetate;

[0097] 20 parts of deionized water;

[0098] 0.3 parts of modified nano magnesium oxide particles.

[0099] The modified nano magnesium oxide particles are prepared by the following preparation method:

[0100] Vinyltriethoxysilane is added to anhydrous ethanol, ammonia is added dropwise, and then nano-magnesium oxide particles are added. The mixture is stirred at 500 r / min for 5 hours, centrifuged, washed with anhydrous ethanol, and dried to obtain modified nano-magnesium oxide particles. The mass ratio of the vinyltriethoxysilane to the nano-magnesium oxide particles or the nano-magnesium oxide particles is 1:5.

[0101] This embodiment also provides a method for preparing a water-based cast composite resin, comprising the following steps:

[0102] (1) Weigh polyvinyl butyral resin, polyamide resin, disproportionated rosin resin and hydrogenated ketone-aldehyde resin, mix them thoroughly and record them as component A, and monoethanolamine as component B;

[0103] (2) Add ethyl acetate, water, and 50% of the total amount of ethanol to a reaction vessel, then add component A and modified nano-magnesium oxide particles, and stir to mix; then heat to 40°C and stir for 12 minutes; while stirring, heat to 50°C and react for 30 minutes;

[0104] (3) Raise the temperature to 80-90°C, add component B dropwise while stirring, and complete the addition within 30 minutes. Then add the remaining ethanol and continue the reaction at a constant temperature for 5 hours.

[0105] (4) After the reaction is completed, the temperature is lowered to 35°C to stop the reaction and collect the product.

[0106] Example 4

[0107] This embodiment provides a water-based cast composite resin for water-based cast composite ink, which is a chemically modified copolymer of polyvinyl butyral, high softening point polyamide resin, disproportionated rosin resin, and hydrogenated ketone-aldehyde resin; the copolymer is prepared by chemically modifying the following components in parts by weight:

[0108] 15 parts of polyvinyl butyral resin;

[0109] 1.5 parts of high softening point polyamide resin;

[0110] 1 part of disproportionated rosin resin;

[0111] 6 parts of hydrogenated ketone-aldehyde resin;

[0112] 20 parts of ethanol;

[0113] 8 parts of monoethanolamine;

[0114] 8 parts of ethyl acetate;

[0115] 32 parts of deionized water;

[0116] 0.1 parts of modified nano zinc oxide particles.

[0117] Wherein, the modified nano zinc oxide is prepared by the following preparation method:

[0118] Vinyltriethoxysilane was added to anhydrous ethanol, ammonia was added dropwise, and then nano-zinc oxide particles were added. The mixture was stirred at 300 r / min for 10 hours, centrifuged, washed with anhydrous ethanol, and dried to obtain modified nano-zinc oxide particles. The mass ratio of vinyltriethoxysilane to nano-zinc oxide particles was 1:1.

[0119] This embodiment also provides a method for preparing a water-based cast composite resin, comprising the following steps:

[0120] (1) Weigh polyvinyl butyral resin, polyamide resin, disproportionated rosin resin and hydrogenated ketone-aldehyde resin, mix them thoroughly and record them as component A, and monoethanolamine as component B;

[0121] (2) Add ethyl acetate, water, and 50% of the total amount of ethanol to a reaction vessel, then add component A and modified nano-zinc oxide particles, and stir to mix; then heat to 30°C and stir for 14 minutes; while stirring, heat to 60°C and react for 15 minutes;

[0122] (3) Raise the temperature to 80°C, add component B dropwise with stirring, and complete the addition within 30 minutes. Then add the remaining ethanol and continue the reaction at a constant temperature for 5 hours.

[0123] (4) After the reaction is completed, the temperature is lowered to 35°C to stop the reaction and collect the product.

[0124] Example 5

[0125] This embodiment provides a water-based cast composite resin for water-based cast composite ink, which is a chemically modified copolymer of polyvinyl butyral, high softening point polyamide resin, disproportionated rosin resin, and hydrogenated ketone-aldehyde resin; the copolymer is prepared by chemically modifying the following components in parts by weight:

[0126] 18.6 parts of polyvinyl butyral resin;

[0127] 1 part of high softening point polyamide resin;

[0128] 5 parts of disproportionated rosin resin;

[0129] 3 parts of hydrogenated ketone-aldehyde resin;

[0130] 35 parts of ethanol;

[0131] 6 parts of monoethanolamine;

[0132] 10 parts of ethyl acetate;

[0133] 25 parts of deionized water;

[0134] 0.3 parts of modified nano zinc oxide particles.

[0135] The modified nano zinc oxide particles are prepared by the following preparation method:

[0136] Vinyltriethoxysilane was added to anhydrous ethanol, and ammonia was added dropwise. Then, nano-zinc oxide particles were added. The mixture was stirred at 500 r / min for 5 hours, centrifuged, washed with anhydrous ethanol, and dried to obtain modified nano-zinc oxide particles. The mass ratio of vinyltriethoxysilane to nano-zinc oxide particles was 1:5.

[0137] This embodiment also provides a method for preparing a water-based cast composite resin, comprising the following steps:

[0138] (1) Weigh polyvinyl butyral resin, polyamide resin, disproportionated rosin resin and hydrogenated ketone-aldehyde resin, mix them thoroughly and record them as component A, and monoethanolamine as component B;

[0139] (2) Add ethyl acetate, water, and 50% of the total amount of ethanol to a reaction vessel, then add component A and modified nano-zinc oxide particles, and stir to mix; then heat to 30°C and stir for 30 minutes; while stirring, heat to 50-60°C and react for 15 minutes;

[0140] (3) Raise the temperature to 80-90°C, add component B dropwise while stirring, and complete the addition within 30 minutes. Then add the remaining ethanol and continue the reaction at a constant temperature for 2-5 hours.

[0141] (4) After the reaction is completed, the temperature is lowered to 35°C to stop the reaction and collect the product.

[0142] Example 6

[0143] This comparative example provides a water-based cast composite ink comprising the following components: 49.5% of the water-based cast composite ink resin prepared in Example 4 (prepared in Example 1), 15% of a pigment, 0.2% of a dispersant, 0.2% of a leveling agent, 1% of fumed silica, 2% of a plasticizer, and approximately 0.2% of a wetting agent. Water and n-propanol were then added to a total weight of 100%. The components were weighed and added to a container, mixed, pre-dispersed in a high-speed disperser, allowed to stand, and then ground using a ball mill to obtain a water-based ink.

[0144] Comparative Example 1

[0145] This embodiment provides a water-based cast composite resin for water-based cast composite ink and a preparation method thereof. In this embodiment, modified nano zinc oxide particles are not added, and other components, component amounts and preparation methods are the same as those in Example 1.

[0146] Comparative Example 2

[0147] This embodiment provides a water-based cast composite resin for water-based cast composite ink and a preparation method thereof. In this embodiment,

[0148] By weight, it is prepared by chemical reaction modification of the following components:

[0149] 25 parts of polyvinyl butyral resin;

[0150] 1 part of high softening point polyamide resin;

[0151] 12 parts of disproportionated rosin resin;

[0152] 1 part of hydrogenated ketone-aldehyde resin;

[0153] 25 parts of ethanol;

[0154] 8 parts of monoethanolamine;

[0155] 20 parts of ethyl acetate;

[0156] 55 parts of deionized water;

[0157] Comparative Example 3

[0158] This comparative example provides a water-based cast composite ink comprising the following components: 49.5% of the water-based cast composite ink resin prepared in Example 4 (prepared in Comparative Example 1), 15% of a pigment, 0.2% of a dispersant, 0.2% of a leveling agent, 1% of fumed silica, 2% of a plasticizer, and approximately 0.2% of a wetting agent. Water and n-propanol are then added to a total weight of 100%. The components are weighed and added to a container, mixed, pre-dispersed in a high-speed disperser, allowed to stand, and then ground using a ball mill to obtain a water-based ink.

[0159] Performance tests were performed on the products of Examples 1-6 and Comparative Examples 1-3 of the present invention:

[0160] 1. Test Method

[0161] 1. Determination of solid content

[0162] Determination of solid content: Weigh a certain amount of water-based cast composite ink resin sample, place it in a watch glass, and dry it in a drying oven at 105°C to constant weight. Calculate the solid content of the prepared resin according to the following formula:

[0163] P = (m2-m) ÷ (m1-m) × 100%.

[0164] Where: P is the solid content, %; m1 is the total mass of the watch glass and sample before drying, g; m is the mass of the watch glass, g; m2 is the total mass of the watch glass and sample after drying, g.

[0165] 2. Temperature resistance test

[0166] To test a product's heat distortion temperature, apply the prepared water-based cast composite ink resin onto a glass slide and place it in a drying oven to measure the product's heat distortion temperature. First, measure the resin's heat distortion temperature range roughly, then precisely measure the resin's heat distortion temperature.

[0167] Rough test: Place the glass slide coated with resin in a drying oven, set the starting temperature to 80℃, and increase the temperature by 10℃ every 30 minutes. Observe and record the state of the sample until the result is obtained and the measurement is completed.

[0168] Precision measurement: Based on the rough measurement, within the variation range, increase the temperature by 1°C every 25 minutes, observe and record the state of the sample until the result is obtained and the measurement is completed.

[0169] 3. Dryness test

[0170] To test the drying speed of the product, apply the prepared water-based cast composite ink resin on a glass slide and dry it in a drying oven at 50°C. Record the drying time of the resin and take the average value of the test three times.

[0171] 4. Acid and alkali resistance test: Test in accordance with the method of "Determination of Alkali Resistance of Architectural Paint Coatings" (GB / T 9265-2009).

[0172] 5. Adhesion: According to the method specified in GB / T13217.7-91, the ink was evenly applied to a plastic substrate (Bopp) film using a wire rod applicator. After drying to form a film, the adhesion was measured using 3M tape. The results are shown in Table 1. Test Results: The exposed area was covered with 20 mm wide translucent millimeter grid paper.

[0173] 2. Test Results

[0174] 1. Solid content, drying properties and temperature resistance results

[0175] The solid content, conversion rate, drying property and temperature resistance test results of the water-based cast composite ink resin provided by the present invention are shown in Table 1. It can be seen that the test results of the acrylic resin of Examples 1-5 are significantly better than those of Comparative Examples 1-2. It can be seen that the water-based cast composite ink resin copolymer provided by the present invention is significantly better in performance than other water-based cast resin dimers, trimers and polymers. The water-based cast composite ink resin copolymers provided by Comparative Examples 1 and 2 have a lower solid content of the prepared tetrapolymer due to the more extensive ratio of the components and the preparation process, indicating that the copolymerization efficiency is relatively low and more components fail to participate in the chemical reaction. The water-based cast composite ink resin provided by the present invention has a faster drying time and a stronger tolerance to high temperatures. These differences in performance are directly related to the precise control of the type, ratio and preparation process of the monomers.

[0176] Table 1 Solid content, drying properties and temperature resistance

[0177]

[0178]

[0179] Ink acid resistance, alkali resistance, water resistance

[0180] The present invention uses an immersion method, whereby a scrape sample of dried ink is immersed in a specified concentration of acid, alkali, and water. After a certain period of time, the scrape sample is removed and graded based on the changes in the sample, as shown in Table 2. This is used to characterize the ink's acid, alkali, and water resistance. The higher the acid, alkali, and water resistance ratings, the better the ink's performance.

[0181] Table 2 Ink acid resistance, alkali resistance, casting composite strength, and water resistance levels

[0182] level Scrape discoloration degree Casting composite strength N / 15mm 1 Severe discoloration No peel strength 2 Obvious discoloration ≤0.3 3 Slightly discolored ≥0.6 4 Basically no discoloration ≥1.0 5 No color change ≥2.5

[0183] In Example 6, a water-based ink was prepared using the water-based cast composite ink resin prepared in Example 1. In Comparative Example 3, a water-based ink was prepared using the water-based cast composite ink resin prepared in Comparative Example 1. The two water-based inks were tested for acid and alkali resistance, water resistance, and cast composite strength. The results are shown in Table 3. As can be seen from Table 3, the ink provided in Example 6 exhibits excellent acid and alkali resistance, water resistance, and virtually no color change, and exhibits high cast composite strength. In contrast, the ink provided in Comparative Example 5 exhibits very poor acid and alkali resistance, exhibits severe and noticeable discoloration, and exhibits poor water resistance.

[0184] Table 3 Test results of ink acid, alkali and water resistance

[0185] sample Acid resistance Alkali resistance Water resistance Cast composite strength Example 6 5 4 4 5 Comparative Example 3 3 2 2 2

[0186] In summary, the water-based cast composite ink resin copolymer provided by the present invention has a high degree of synthesis, a fast drying speed, and is resistant to high temperatures. The water-based ink containing the water-based cast composite ink resin copolymer of the present invention has significant tolerance to acid, alkali, and water, and has better comprehensive performance.

[0187] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A water-based cast composite resin for water-based cast composite ink, characterized in that A chemically modified copolymer of polyvinyl butyral, high softening point polyamide resin, disproportionated rosin resin and hydrogenated ketone-aldehyde resin; prepared by chemical reaction modification of the following components in parts by weight: 15-23.5 parts of polyvinyl butyral resin; 0-2.5 parts of high softening point polyamide resin; 1-10 parts of disproportionated rosin resin; 2-8 parts of hydrogenated ketone-aldehyde resin; 15-40 parts of ethanol; 3-10 parts of monoethanolamine; 5-15 parts of ethyl acetate; 20-35 parts of deionized water.

2. The aqueous cast composite resin for aqueous cast composite ink according to claim 1, characterized in that: By weight, it is prepared by chemical reaction modification of the following components: 15-18.6 parts of polyvinyl butyral resin; 1-1.5 parts of high softening point polyamide resin; 1-5 parts of disproportionated rosin resin; 3-6 parts of hydrogenated ketone-aldehyde resin; 20-35 parts of ethanol; 6-8 parts of monoethanolamine; 8-10 parts of ethyl acetate; 25-32 parts of deionized water.

3. The aqueous cast composite resin for aqueous cast composite ink according to claim 1, characterized in that: By weight, it is prepared by chemical reaction modification of the following components: Polyvinyl butyral resin: 18.6 parts; 1.5 parts of high softening point polyamide resin; 1 part of disproportionated rosin resin; 3.5 parts of hydrogenated ketone-aldehyde resin; 25 parts of ethanol; 8 parts of monoethanolamine; 8 parts of ethyl acetate; 30.4 parts of deionized water.

4. The aqueous cast composite resin for aqueous cast composite ink according to claim 1, characterized in that: Also included are 0.1-0.3 parts of modified nano zinc oxide / magnesium oxide particles.

5. The aqueous cast composite resin for aqueous cast composite ink according to claim 4, characterized in that: The modified nano zinc oxide / magnesium oxide particles are prepared by the following preparation method: Vinyl triethoxysilane is added to anhydrous ethanol, ammonia water is added dropwise, and then nano zinc oxide particles or nano magnesium oxide particles are added. The mixture is stirred at a speed of 300-500 r / min for 5-10 hours, centrifuged, washed with anhydrous ethanol, and dried to obtain modified nano zinc oxide / magnesium oxide particles.

6. The aqueous cast composite resin for aqueous cast composite ink according to claim 5, characterized in that: The mass ratio of the vinyltriethoxysilane to the nano zinc oxide particles or nano magnesium oxide particles is 1:1-5.

7. A method for preparing the water-based cast composite resin according to any one of claims 1 to 6, characterized in that The steps include: (1) Weigh polyvinyl butyral resin, polyamide resin, disproportionated rosin resin and hydrogenated ketone-aldehyde resin, mix them thoroughly and record them as component A, and monoethanolamine as component B; (2) Add ethyl acetate, water, and 50% of the total amount of ethanol to a reaction vessel, then add component A and modified nano zinc oxide / magnesium oxide particles, and stir to mix; then heat to 30-40° C. and stir for 15-30 minutes; while stirring, heat to 50-60° C. and react for 15-30 minutes; (3) Raise the temperature to 80-90°C, add component B dropwise while stirring, and complete the addition within 30 minutes. Then add the remaining ethanol and continue the reaction at a constant temperature for 2-5 hours. (4) After the reaction is completed, the temperature is lowered to 35°C to stop the reaction and collect the product.

8. A water-based cast composite ink, characterized in that: The invention comprises an auxiliary agent, a pigment, water and the water-based cast composite ink resin according to any one of claims 1 to 6 or the water-based cast composite ink resin prepared by the preparation method according to claim 7.

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