Water-based tape-casting composite resin, preparation method thereof and water-based tape-casting composite ink

Abstract

The invention provides water-based tape-casting composite resin for water-based tape-casting composite ink and a preparation method of the water-based tape-casting composite resin, and belongs to the technical field of ink binders, and the water-based tape-casting composite resin is a copolymer formed by chemically modifying polyvinyl butyral, high-softening-point polyamide resin, disproportionated rosin resin and hydrogenated ketoaldehyde resin. The preparation method comprises the following steps: weighing the four resins, fully mixing, recording as a component A, and recording the monoethanolamine as a component B; adding ethyl acetate, water and ethanol, then adding the component A and the modified nano zinc oxide / magnesium oxide particles, carrying out heating reaction, dropwise adding the component B in a stirring state, and carrying out constant-temperature reaction; cooling and stopping reaction after reaction, and collecting the product. The temperature-resistant water-based tape-casting composite ink resin provided by the invention is used as a binder of water-based ink, has better acid resistance, alkali resistance and water resistance, higher adhesive force and peel strength, and has better high temperature resistance.

Description

Technical Field

[0001] The invention relates to the technical field of ink connecting materials, 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 played an increasingly important role in various printing industries, especially in industries with strict requirements such as food, medicine, tobacco, and alcohol packaging. Water-based ink has become the first choice for printing. Compared with other printing inks, water-based ink does not contain volatile toxic organic solvents, so it has no adverse effects on the health of printer operators during the printing process. Water-based ink uses water as a solvent, water-based polymer resin as a binder, and is mixed with pigments and additives through a physical and chemical process. Among them, the binder is the fluid part of the ink as the continuous phase of the ink. It is a key factor affecting the printing performance of the ink. The quality of the binder directly affects the performance of the ink.

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

[0004] The inks currently used in the market have poor outdoor weather resistance. For example, outdoor advertisements will be damaged by adverse factors such as ultraviolet rays, acid and alkali, and high temperature weather for a long time. Generally, they will become seriously yellowed and discolored if they cannot last for more than one year. In order to meet the use requirements of inks in different high temperature or complex environments, it is necessary to develop ink materials with better heat resistance. As an important binder in inks, the heat resistance of water-based cast composite ink resin is crucial to the performance of inks. Therefore, the high temperature resistance of water-based cast composite ink resin improves the high temperature resistance of inks and meets their use requirements 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 that the existing ink has poor outdoor weather resistance and is prone to 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 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 chemically modifying the following components by weight:

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

[0018] 1 to 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 chemically modifying the following components 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] Among them, 0.1-0.3 parts of modified nano zinc oxide / magnesium oxide particles are also included.

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

[0036] Add vinyl triethoxysilane to anhydrous ethanol, add ammonia water dropwise, then add nano zinc oxide particles or nano magnesium oxide particles, stir at a speed of 300-500r / min for 5-10h, centrifuge, wash with anhydrous ethanol, and dry to obtain modified nano zinc oxide / magnesium oxide particles.

[0037] Wherein, the mass ratio of the vinyl triethoxysilane 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) Weighing polyvinyl butyral resin, polyamide resin, disproportionated rosin resin and hydrogenated ketone-aldehyde resin, and mixing them thoroughly, recording them as component A, and monoethanolamine as component B;

[0040] (2) Add ethyl acetate, water and 50% of ethanol in total to a reaction container, 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 under stirring, and complete the addition within 30 minutes, then add the remaining ethanol, and then react 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 preparation method.

[0044] Disproportionated rosin, referred to as DMR, is a modified rosin product obtained by esterification of rosin with alcohols such as methanol or butanol. It not only retains the natural properties of rosin, but also improves 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 many materials such as glass, metal, plastic, wood, leather and other materials.

[0046] High softening point polyamide resin is a polyamide resin with special properties, and its softening point is higher than that of ordinary polyamide resin. This resin does not solidify sharply like other thermoplastic resins 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. In ink, it can significantly improve the gloss, adhesion, quick drying, leveling, pigment wettability and solid content of the product.

[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, thereby achieving more precise control of the synthesis route and process conditions. The 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 a high temperature environment. In addition, in the present invention, nano magnesium oxide particles or magnesium oxide particles modified by vinyltriethoxysilane are added in the chemical reaction to further improve 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 connecting material for water-based ink, which has good acid resistance, alkali resistance and water resistance, high adhesion and peel strength, and has good high temperature resistance, and can meet the use requirements of complex external environments. DETAILED DESCRIPTION

[0051] The technical solution of the present invention will be clearly and completely described below in conjunction with the specific embodiments of the present invention. Obviously, the described embodiments 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 creative work are within the scope of protection of the present invention.

[0052] Example 1

[0053] The present 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; in parts by weight, it is prepared by chemically modifying the following components:

[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] Add vinyl triethoxysilane to anhydrous ethanol, add ammonia water, then add nano zinc oxide particles, stir at a speed of 400 r / min for 8 hours, centrifuge, wash with anhydrous ethanol, and dry to obtain modified nano zinc oxide particles. The mass ratio of vinyl triethoxysilane to nano zinc oxide particles is 1:3.

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

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

[0067] (2) Add ethyl acetate, water and 50% of ethanol in total 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 min; while stirring, heat to 55° C. and react for 25 min;

[0068] (3) Raise the temperature to 80-90°C, add component B dropwise under stirring, and complete the addition within 30 minutes, then add the remaining ethanol, and then react 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] The present 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; in parts by weight, it is prepared by chemically modifying the following components:

[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] Add vinyl triethoxysilane to anhydrous ethanol, add ammonia water, then add nano zinc oxide particles or nano magnesium oxide particles, stir at a speed of 300 r / min for 10 hours, centrifuge, wash with anhydrous ethanol, and dry to obtain modified nano magnesium oxide particles. The mass ratio of the vinyl triethoxysilane to the nano zinc oxide particles or nano magnesium oxide particles is 1:1.

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

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

[0085] (2) Add ethyl acetate, water and 50% of ethanol in total 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 under stirring, and complete the addition within 30 min, then add the remaining ethanol, and then keep the reaction at a constant temperature for 2 h;

[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] The present 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; in parts by weight, it is prepared by chemically modifying the following components:

[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] Add vinyl triethoxysilane to anhydrous ethanol, add ammonia water, then add nano magnesium oxide particles, stir at a speed of 500 r / min for 5 hours, centrifuge, wash with anhydrous ethanol, and dry to obtain modified nano magnesium oxide particles. The mass ratio of the vinyl triethoxysilane to the nano magnesium oxide particles or the nano magnesium oxide particles is 1:5.

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

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

[0103] (2) Add ethyl acetate, water and 50% of ethanol in total 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 under stirring, and complete the addition within 30 min, then add the remaining ethanol, and then keep the reaction at a constant temperature for 5 h;

[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] The present 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; in parts by weight, it is prepared by chemically modifying the following components:

[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] Add vinyl triethoxysilane to anhydrous ethanol, add ammonia water, then add nano zinc oxide particles, stir at a speed of 300 r / min for 10 hours, centrifuge, wash with anhydrous ethanol, and dry to obtain modified nano zinc oxide particles. The mass ratio of vinyl triethoxysilane to nano zinc oxide particles is 1:1.

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

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

[0121] (2) Add ethyl acetate, water and 50% of ethanol in total 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 while stirring, and complete the addition within 30 min. Then add the remaining ethanol and react at a constant temperature for 5 h.

[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] The present 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; in parts by weight, it is prepared by chemically modifying the following components:

[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] Add vinyl triethoxysilane to anhydrous ethanol, add ammonia water, then add nano zinc oxide particles, stir at a speed of 500 r / min for 5 hours, centrifuge, wash with anhydrous ethanol, and dry to obtain modified nano zinc oxide / particles. The mass ratio of vinyl triethoxysilane to nano zinc oxide particles is 1:5.

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

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

[0139] (2) Add ethyl acetate, water and 50% of ethanol in total 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 min; while stirring, heat to 50-60° C. and react for 15 min;

[0140] (3) Raise the temperature to 80-90°C, add component B dropwise under stirring, and complete the addition within 30 minutes, then add the remaining ethanol, and then react 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 the pigment, 0.2% of the dispersant, 0.2% of the leveling agent, 1% of the fumed silica, 2% of the plasticizer, and about 0.2% of the wetting agent, and then water and n-propanol are added to 100%. After weighing each component, add it to a container for mixing, pre-disperse it in a high-speed disperser, let it stand, and then grind it using a ball mill to obtain a water-based ink.

[0144] Comparative Example 1

[0145] This embodiment provides an aqueous cast composite resin for aqueous 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 an aqueous cast composite resin for aqueous 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 about 0.2% of a wetting agent, and then water and n-propanol are added to 100%. Each component is weighed and added to a container for mixing, pre-dispersed in a high-speed disperser, allowed to stand, and then ground using a ball mill to obtain a water-based ink.

[0159] The 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, put it into 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 the sample before drying, g; m is the mass of the watch glass, g; m2 is the total mass of the watch glass and the sample after drying, g.

[0165] 2. Temperature resistance test

[0166] To test the heat deformation temperature of the product, you need to apply the prepared water-based cast composite ink resin on a glass slide, and then put it in a drying oven to measure the heat deformation temperature of the product. First, roughly measure the heat deformation temperature range of the resin, and then accurately measure the heat deformation temperature of the resin.

[0167] Rough measurement: Place the glass slide coated with resin in a drying oven, set the starting temperature to 80°C, increase the temperature by 10°C 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, the prepared water-based cast composite ink resin needs to be applied on a glass slide, dried in a drying oven at 50°C, and the drying time of the resin is recorded. The test is repeated 3 times to obtain the average value.

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

[0172] 5. Adhesion: According to the method specified in the national standard GB / T13217.7-91, use a wire rod applicator to evenly spread the ink on the plastic substrate (Bopp) film. After drying and forming a film, use 3M tape to measure its adhesion. The results are shown in Table 1. Test results: Cover the uncovered part with a 20mm wide translucent millimeter grid paper.

[0173] 2. Test Results

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

[0175] The test results of solid content, conversion rate, drying property and temperature resistance 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 than other water-based ink cast resin dimers, trimers and polymers. The water-based cast composite ink resin copolymer provided by Comparative Examples 1 and 2 has a lower solid content of the prepared tetrapolymer due to the more extensive ratio of each component and the preparation process, indicating that the copolymerization efficiency is low and more components fail to participate in the chemistry. The water-based cast composite ink resin provided by the present invention has a faster drying time and stronger tolerance to high temperatures. These differences in performance are directly related to the fine control of the type, ratio and preparation process of the monomers.

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

[0177]

[0178]

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

[0180] The present invention adopts an immersion method, that is, a dry ink scrape sample is soaked in acid, alkali and water of specified concentrations, and the scrape sample is taken out after a certain period of time. The scrape sample is rated according to the change of the scrape sample, as shown in Table 2, and the acid resistance, alkali resistance and water resistance of the ink are characterized by this. The higher the acid resistance, alkali resistance and water resistance of the ink, the better the performance.

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

[0182] level Scrape discoloration 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] Example 6 uses the water-based cast composite ink resin prepared in Example 1 to prepare water-based ink, and Comparative Example 3 uses the water-based cast composite ink resin prepared in Comparative Example 1 to prepare water-based ink, and the two water-based inks are tested for acid and alkali resistance, water resistance and cast composite strength, respectively. The results are shown in Table 3. As can be seen from Table 3, the ink provided in Example 6 has excellent acid and alkali resistance and water resistance, basically no color change, and high cast composite strength. The ink provided in Comparative Example 5 has very poor acid and alkali resistance, severe and obvious discoloration, and poor water resistance.

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

[0185] sample Acid resistance Alkali resistance Water resistance Casting 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 above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope 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 to 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 is 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: Add vinyl triethoxysilane to anhydrous ethanol, add ammonia water dropwise, then add nano zinc oxide particles or nano magnesium oxide particles, stir at a speed of 300-500r / min for 5-10h, centrifuge, wash with anhydrous ethanol, and dry 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 vinyl triethoxysilane 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) Weighing polyvinyl butyral resin, polyamide resin, disproportionated rosin resin and hydrogenated ketone-aldehyde resin, and mixing them thoroughly, recording them as component A, and monoethanolamine as component B; (2) Add ethyl acetate, water and 50% of ethanol in total to a reaction container, 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 under stirring, and complete the addition within 30 minutes, then add the remaining ethanol, and then react 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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