High gloss resin ink and method of making same

Abstract

The application discloses a high-gloss resin ink and a preparation method thereof. The high-gloss resin ink comprises the following raw material components in mass fractions: carboxymethyl cellulose acetate butyrate 3-50 parts; water-based ink 25-95 parts; surfactant 0-10 parts; organic solvent 1.5-100 parts; water 1-10 parts; wherein the weight percentage of the carboxymethyl cellulose acetate butyrate in the total solid of the high-gloss resin ink is 3-50%. The high-gloss resin ink can significantly improve the ink drying speed, adhesion and gloss of the printed matter and does not need additional preparation cost.

Description

Technical Field

[0001] This application relates to the field of polymer materials technology, and in particular to a high-gloss resin ink and its preparation method. Background Technology

[0002] Ink is an essential material used in printing, which transfers patterns and text onto a substrate through printing or inkjet printing. Ink consists of main and auxiliary components, which are uniformly mixed and repeatedly rolled to form a viscous, colloidal fluid. Gloss is a crucial indicator affecting the printing effect of ink.

[0003] Currently, improving ink gloss primarily involves selecting and formulating the raw materials for the ink emulsion or additives. For example, acrylic resin is used as the ink emulsion to leverage its gloss-retaining and color-retaining properties to enhance ink printing gloss. Alternatively, high-whiteness, abrasion-resistant fillers such as mica and titanium dioxide, or color-retaining agents such as light stabilizers, are used as additives to improve ink printing gloss. However, while acrylic resin is effective in enhancing ink gloss, adding additives incurs additional preparation costs. Summary of the Invention

[0004] This application provides a high-gloss resin ink and its preparation method to solve the technical problem of limited gloss enhancement effect of ink-printed products or the need for additional preparation costs.

[0005] This application provides a high-gloss resin ink comprising the following raw material components in parts by weight:

[0006] 3 to 50 parts of cellulose carboxymethyl acetate butyrate;

[0007] Water-based ink: 25-95 parts;

[0008] 0 to 10 parts of surfactant;

[0009] Organic solvent: 1.5 to 100 parts;

[0010] 1 to 10 parts water;

[0011] Cellulose carboxymethyl acetate butyrate accounts for 3% to 50% of the total solids in high-gloss resin inks by weight.

[0012] Carboxylated cellulose is a chemical substance used for thickening, emulsifying, and stabilizing. It is commonly used as an emulsifier and stabilizer in the food industry, and as a stabilizer and thickener in pharmaceuticals and cosmetics.

[0013] Carboxymethyl cellulose acetate butyrate (CMCAB) is a compound synthesized by esterification of carboxymethyl cellulose (CMC) with acetic anhydride and butyric anhydride. It combines the advantages of both carboxymethyl cellulose and cellulose acetate butyrate (CAB), exhibiting a high glass transition temperature (Tg) and a relatively high molecular weight (MW). It is dispersible in water and soluble in a variety of organic solvents, providing a wide range of solvent options. It also benefits coating applications by slowing the release rate of highly water-soluble compounds and increasing the solubility of poorly soluble compounds.

[0014] This application utilizes the thickening, adhesive, and film-forming properties of carboxymethyl acetate butyrate (CMA) to effectively control ink emulsion viscosity, improve ink adhesion and film-forming properties. Furthermore, it leverages the rheological properties of CMA, similar to cellulose acetate butyrate (CAB), to provide water-based inks with better flowability, leveling, and anti-sagging properties. This improves the elimination of printing pinholes, accelerates solvent release from the paint film, and reduces ink contact time (better flowability and faster contact drying result in higher gloss), thereby enhancing the gloss of printed materials. Compared to traditional inks that offer limited gloss enhancement or require additional manufacturing costs, this application significantly improves ink drying speed, adhesion, and gloss without incurring additional manufacturing costs.

[0015] Preferably, the mass ratio of the carboxymethyl acetate butyrate cellulose to the organic solvent is 1:(0.5-2).

[0016] Preferably, the raw material components include the following parts by weight:

[0017] 10 to 50 parts of cellulose carboxymethyl acetate butyrate;

[0018] 45 to 85 parts of water-based resin;

[0019] 0 to 5 parts of surfactant;

[0020] Organic solvent: 5 to 100 parts;

[0021] 5 to 10 parts water;

[0022] The weight percentage of cellulose carboxymethyl acetate butyrate in the total solids of high-gloss resin ink is 10% to 50%.

[0023] Further, the carboxymethyl acetate butyrate cellulose is prepared by the following steps:

[0024] Step 1: Acidify sodium carboxymethyl cellulose (CMC-Na) to convert CMC-Na into free acid form, to obtain carboxymethyl cellulose hydrogen (CMC-H);

[0025] Step 2: Activate CMC-H to obtain active wet butyric acid CMC-H solid; Esterify the active wet butyric acid CMC-H solid using acetic anhydride solution and butyric anhydride solution to obtain a mixture;

[0026] Step 3: Hydrolyze, neutralize, precipitate, filter and dry the mixture to obtain cellulose carboxymethyl acetate butyrate (CMCAB).

[0027] Preferably, step 1 specifically involves: soaking CMC-Na in a 2% to 20% sulfuric acid aqueous solution at 27℃ to 60℃, stirring for 10 min to 120 min, filtering, washing with water to remove acid, and recovering CMC-H, wherein the mass percentage of CMC-Na to the sulfuric acid aqueous solution is 1:20 to 30.

[0028] Preferably, step 2 specifically involves: transferring the CMC-H recovered in step 1 to a filter funnel, draining the water to a concentration of 20%–40% active solid; using 1 part by mass of CMC-Na as a reference, dehydrating the active solid with 3 parts by mass of acetic acid, and then washing with 3–4 parts by mass of butyric acid to obtain 40% active butyric acid wet CMC-H solid; esterifying the active butyric acid wet CMC-H solid at 0–15°C using 0.31 parts by mass of acetic anhydride solution and 2.53 parts by mass of butyric anhydride solution to obtain an esterified solution; slowly adding a catalyst solution containing 0.0344 parts by mass of sulfuric acid and 0.0344 parts by mass of acetic acid to the esterified solution at a temperature of 30°C–35°C for 60–150 min; then raising the temperature to 45°C–60°C and maintaining it for 2–6 h until the active butyric acid wet CMC-H solid is completely dissolved to obtain a mixture.

[0029] Preferably, step 3 specifically comprises: at 40℃~45℃, using 1 part by mass of CMC-Na as a reference, adding 0.95 parts by mass of water, 0.95 parts by mass of acetic acid, and 0.02 parts by mass of sulfuric acid solution dropwise to the mixture obtained in step 2 within 30min~45min, and heating to 60℃~72℃ for hydrolysis for 2h~4.5h; dissolving 0.0753 parts by mass of magnesium acetate tetrahydrate in 0.25 parts by mass of water and 0.25 parts by mass of acetic acid, and then pouring it into the mixture to neutralize the excess sulfuric acid; filtering the liquid in the mixture to obtain a precipitate; washing the precipitate with water to remove excess organic acids and inorganic salts; and vacuum drying at 60℃ to obtain an acidic white granular powder of cellulose carboxymethyl acetate butyrate.

[0030] This application uses the above steps to prepare cellulose carboxymethyl acetate butyrate, which can effectively control the acyl content of CMCAB. Furthermore, hydrolysis can improve the compatibility of the ink formulation with other resins and obtain more free hydroxyl groups, providing crosslinking sites for ink emulsion applications. By neutralizing strong acids, the final CMCAB product has better thermal stability and hydrolytic stability, thereby providing better rheological modification for ink systems.

[0031] Preferably, the waterborne resin comprises waterborne acrylic resin and waterborne polyurethane in a mass ratio of (3.5-4.5):1. Using waterborne acrylic resin ensures the basic gloss of the printed ink, while using waterborne polyurethane improves the high composite strength of the ink.

[0032] Preferably, the surfactant comprises one of alkylbenzene sulfonate, sodium dodecyl sulfate, and sodium alkyl polyether sulfate; the solvent comprises one or more of isopropanol, butanone, ethyl acetate, butyl hexanoate, and ethylene glycol.

[0033] This application also provides a method for preparing the high-gloss resin ink as described above, comprising:

[0034] Weigh the raw materials according to the mass fraction; dissolve cellulose carboxymethyl acetate butyrate in an organic solvent to form solution A; mix the aqueous resin and surfactant with solution A to form solution B; add water to solution B and stir evenly to obtain high-gloss resin ink.

[0035] The preparation method of this application is simple to operate and requires no special equipment, which further reduces the preparation cost. Detailed Implementation

[0036] To make the above-mentioned objects, features, and advantages of the present invention more apparent and understandable, specific embodiments of the present invention are described in detail below. Many specific details are set forth in the following description to provide a thorough understanding of the present invention. However, the present invention can be practiced in many other ways different from those described herein, and those skilled in the art can make similar modifications without departing from the spirit of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0037] As used herein, the terms “prepared from” and “comprising” are synonymous. The terms “comprising,” “including,” “having,” “containing,” or any other variations thereof, as used herein, are intended to cover non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such composition, step, method, article, or apparatus.

[0038] When a quantity, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1 to 5” is disclosed, the described range should be interpreted as including the ranges “1 to 4”, “1 to 3”, “1 to 2”, “1 to 2 and 4 to 5”, “1 to 3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range.

[0039] Furthermore, the indefinite articles “a” and “an” preceding the elements or components of this invention do not impose any limitation on the quantity requirement (i.e., the number of times) of the elements or components. Therefore, “an” or “a” should be interpreted as including one or at least one, and the singular form of an element or component also includes the plural form, unless the quantity clearly refers to the singular form.

[0040] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0041] Preparation Example 1

[0042] The preparation method of cellulose carboxymethyl acetate butyrate includes the following steps:

[0043] Step 1: At 45°C, CMC-Na is soaked in a 15% sulfuric acid aqueous solution and stirred for 60 minutes. After filtration, the solution is washed with water to remove the acid and recover CMC-H. The mass percentage of CMC-Na to the sulfuric acid aqueous solution is 1:25.

[0044] Step 2: Transfer the CMC-H recovered in Step 1 to a filter funnel, drain the water until it contains 40% active solid; using 1 part by mass of CMC-Na as a reference, dehydrate the active solid with 3 parts by mass of acetic acid, and then wash with 3 parts by mass of butyric acid to obtain 40% active butyric acid wet CMC-H solid; esterify the active butyric acid wet CMC-H solid at 10°C with 0.31 parts by mass of acetic anhydride solution and 2.53 parts by mass of butyric anhydride solution to obtain an esterified solution; slowly add a catalyst solution containing 0.0344 parts by mass of sulfuric acid and 0.0344 parts by mass of acetic acid to the esterified solution at 35°C for 100 min; then increase the temperature to 55°C and maintain for 4 h until the active butyric acid wet CMC-H solid is completely dissolved to obtain a mixture.

[0045] Step 3: At 40°C, using 1 part by mass of CMC-Na as a reference, 0.95 parts by mass of water, 0.95 parts by mass of acetic acid, and 0.02 parts by mass of sulfuric acid solution were added dropwise to the mixture obtained in Step 2 over 40 minutes, and the mixture was heated to 65°C for hydrolysis for 3 hours. 0.0753 parts by mass of magnesium acetate tetrahydrate was dissolved in 0.25 parts by mass of water and 0.25 parts by mass of acetic acid, and then poured into the mixture to neutralize the excess sulfuric acid. The liquid in the mixture was filtered to obtain a precipitate. Excess organic acids and inorganic salts in the precipitate were washed with water. The precipitate was then vacuum dried at 60°C to obtain an acidic white granular powder of cellulose carboxymethyl acetate butyrate.

[0046] Example 1

[0047] A high-gloss resin ink comprises the following raw material components in parts by weight:

[0048] Three portions of cellulose carboxymethyl acetate butyrate prepared in Example 1;

[0049] 74 parts of waterborne acrylic resin with a solid content of 60%;

[0050] 21 parts of waterborne polyurethane with a solid content of 40%;

[0051] Two parts of sodium dodecyl sulfate;

[0052] 6 parts of methyl ethyl ketone;

[0053] 10 parts water;

[0054] Preparation method of high-gloss resin ink: Weigh the raw materials according to the mass parts; dissolve cellulose carboxymethyl acetate butyrate in an organic solvent to form solution A; mix water-based resin and surfactant with solution A to form solution B; add water to solution B and stir evenly to obtain high-gloss resin ink.

[0055] Example 2

[0056] A high-gloss resin ink comprises the following raw material components in parts by weight:

[0057] 10 portions of cellulose carboxymethyl acetate butyrate prepared in Example 1;

[0058] 36.8 parts of waterborne acrylic resin with a solid content of 60%;

[0059] 8.2 parts of waterborne polyurethane with a solid content of 40%;

[0060] 5 parts sodium dodecyl sulfate;

[0061] 10 parts isopropanol;

[0062] 5 parts water;

[0063] The preparation method of the high-gloss resin ink is the same as in Example 1.

[0064] Example 3

[0065] A high-gloss resin ink comprises the following raw material components in parts by weight:

[0066] 35 parts of cellulose carboxymethyl acetate butyrate prepared in Example 1;

[0067] 20 parts of waterborne acrylic resin with a solid content of 60%;

[0068] Five parts of waterborne polyurethane with a solid content of 40%;

[0069] 10 parts of sodium alkyl polyether sulfate;

[0070] 17.5 parts of butyl hexanoate;

[0071] 1 part water;

[0072] The preparation method of the high-gloss resin ink is the same as in Example 1.

[0073] Example 4

[0074] A high-gloss resin ink comprises the following raw material components in parts by weight:

[0075] 50 parts of cellulose carboxymethyl acetate butyrate prepared in Example 1;

[0076] 40 parts of waterborne acrylic resin with a solid content of 60%;

[0077] 10 parts of waterborne polyurethane with a solid content of 40%;

[0078] Sodium alkyl polyether sulfate 0 parts;

[0079] 25 parts of methyl ethyl ketone;

[0080] 1 part water;

[0081] The preparation method of the high-gloss resin ink is the same as in Example 1.

[0082] Example 5

[0083] A high-gloss resin ink comprises the following raw material components in parts by weight:

[0084] 50 parts of cellulose carboxymethyl acetate butyrate prepared in Example 1;

[0085] 68 parts of waterborne acrylic resin with a solid content of 60%;

[0086] 17 parts of waterborne polyurethane with a solid content of 40%;

[0087] 5 parts sodium dodecyl sulfate;

[0088] 100 parts of methyl ethyl ketone (MEK);

[0089] 1 part water;

[0090] The preparation method of the high-gloss resin ink is the same as in Example 1.

[0091] Comparative Example 1

[0092] The difference from Example 2 is that CMC-Na is used instead of CMCAB, otherwise it is the same as Example 2.

[0093] Comparative Example 2

[0094] The difference from Example 2 is that CAB is used instead of CMCAB, otherwise it is the same as Example 2.

[0095] Comparative Example 3

[0096] The difference from Example 2 is that light stabilizer 1130 is used instead of CMCAB, otherwise it is the same as Example 2.

[0097] Gloss test:

[0098] Reference standard: GB / T 9754; Testing instrument: HG268 digital gloss meter; Test angle: 60° incident angle.

[0099] The inks prepared in Examples 1-5 and Comparative Examples 1-3 were used to print the same pattern to create patterned printed products. The gloss of each patterned printed product from the examples and comparative examples was tested using an HG268 analyzer. The gloss levels of the top left, bottom left, center, top right, and bottom right corners of each patterned printed product were measured, and the average values ​​were taken. The test results are shown in Table 1 below:

[0100] Table 1. Glossiness Test Results

[0101]

[0102] As shown in Table 1, the gloss of Examples 1 to 5 is better than that of Comparative Examples 1 to 3, indicating that CMCAB can improve the gloss of printed inks. Comparing Example 2 with Comparative Examples 1 and 2, it can be seen that the use of CMCAB has a more significant effect on improving the gloss of printed inks than the use of CMC or CAB alone. Comparing Example 2 with Comparative Example 3, the use of CMCAB also has a better gloss improvement effect than the use of a single additive with light stabilizer.

[0103] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0104] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of this application. It should be understood that the above descriptions are merely specific embodiments of this application and are not intended to limit the scope of protection of this application. In particular, it should be noted that any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the scope of protection of this application for those skilled in the art.

Claims

1. A high-gloss resin ink, characterized in that, The raw material components include the following parts by weight: 3 to 50 parts of cellulose carboxymethyl acetate butyrate; 25 to 95 parts of water-based resin; 0 to 10 parts of surfactant; Organic solvent: 1.5 to 100 parts; 1 to 10 parts water; The weight percentage of cellulose carboxymethyl acetate butyrate in the total solids of high-gloss resin ink is 3% to 50%. The mass ratio of cellulose carboxymethyl acetate butyrate to organic solvent is 1:(0.5~2). The carboxymethyl acetate butyrate cellulose is prepared by the following steps: Step 1: Acidify sodium carboxymethyl cellulose (CMC-Na) to convert CMC-Na into free acid form, to obtain carboxymethyl cellulose hydrogen (CMC-H); Step 2: Activate CMC-H to obtain active wet butyric acid CMC-H solid; Esterify the active wet butyric acid CMC-H solid using acetic anhydride solution and butyric anhydride solution to obtain a mixture; Step 3: Hydrolyze, neutralize, precipitate, filter and dry the mixture to obtain cellulose carboxymethyl acetate butyrate (CMCAB); Step 1 specifically involves: soaking CMC-Na in a 2% to 20% sulfuric acid aqueous solution at 27℃ to 60℃, stirring for 10 min to 120 min, filtering, washing with water to remove acid, and recovering CMC-H, wherein the mass percentage of CMC-Na to sulfuric acid aqueous solution is 1:20 to 30. Step 2 specifically involves: transferring the CMC-H recovered in Step 1 to a filter funnel, draining the water until it contains 20%–40% active solid; using 1 part by mass of CMC-Na as a reference, dehydrating the active solid with 3 parts by mass of acetic acid, and then washing with 3–4 parts by mass of butyric acid to obtain 40% active butyric acid wet CMC-H solid; esterifying the active butyric acid wet CMC-H solid at 0–15°C using 0.31 parts by mass of acetic anhydride solution and 2.53 parts by mass of butyric anhydride solution to obtain an esterified solution; slowly adding a catalyst solution containing 0.0344 parts by mass of sulfuric acid and 0.0344 parts by mass of acetic acid to the esterified solution at a temperature of 30°C–35°C for 60–150 min; then increasing the temperature to 45°C–60°C and maintaining it for 2–6 h until the active butyric acid wet CMC-H solid is completely dissolved to obtain a mixture; Step 3 specifically involves: at 40℃~45℃, using 1 part by mass of CMC-Na as a reference, adding 0.95 parts by mass of water, 0.95 parts by mass of acetic acid, and 0.02 parts by mass of sulfuric acid solution dropwise to the mixture obtained in step 2 within 30min~45min, and heating to 60℃~72℃ for hydrolysis for 2h~4.5h; dissolving 0.0753 parts by mass of magnesium acetate tetrahydrate in 0.25 parts by mass of water and 0.25 parts by mass of acetic acid, and then pouring it into the mixture to neutralize the excess sulfuric acid; filtering the liquid in the mixture to obtain a precipitate; washing the precipitate with water to remove excess organic acids and inorganic salts; and vacuum drying at 60℃ to obtain an acidic white granular powder of cellulose carboxymethyl acetate butyrate.

2. The high-gloss resin ink as described in claim 1, characterized in that, The raw material components include the following parts by weight: 10 to 50 parts of cellulose carboxymethyl acetate butyrate; 45 to 85 parts of water-based resin; 0 to 5 parts of surfactant; Organic solvent: 5 to 100 parts; 5 to 10 parts water; The weight percentage of cellulose carboxymethyl acetate butyrate in the total solids of high-gloss resin ink is 10% to 50%.

3. The high-gloss resin ink as described in claim 1, characterized in that, The waterborne resin comprises waterborne acrylic resin and waterborne polyurethane in a mass ratio of (3.5~4.5):

1.

4. The high-gloss resin ink as described in claim 1, characterized in that, The surfactant includes one of alkylbenzene sulfonate, sodium dodecyl sulfate, and sodium alkyl polyether sulfate; The solvent includes one or more of isopropanol, butanone, ethyl acetate, butyl hexanoate, and ethylene glycol.

5. A method for preparing a high-gloss resin ink as described in any one of claims 1 to 4, characterized in that, include: Weigh the raw materials according to the mass fractions; dissolve cellulose carboxymethyl acetate butyrate in an organic solvent to form solution A; Aqueous resin and surfactant are mixed with solution A to form solution B; water is added to solution B and stirred until homogeneous to obtain high-gloss resin ink.

Images