Ink quick-drying styrene-butadiene latex and preparation method thereof
By introducing the synergistic effect of hydroxyethyl methacrylate phosphate and unsaturated carboxylic acid into styrene-butadiene latex, a fast-drying styrene-butadiene latex for inks was prepared, solving the problem of insufficient ink drying speed on high-speed printing presses, achieving comprehensive performance optimization of the coating, and meeting the requirements of high-speed printing.
Patent Information
- Application Number
- CN202511996091.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-26
- Publication Date
- 2026-02-06
AI Technical Summary
Existing styrene-butadiene latex is difficult to meet the ink drying speed requirements on high-speed printing presses, resulting in problems such as smudging, smudging, and blurry printing. Furthermore, the polymer design is either too dense or lacks sufficient hydrophilicity, which affects the ink solvent absorption and locking ability of the coated paper.
By utilizing the synergistic effect of hydroxyethyl methacrylate phosphate (PEM) and unsaturated carboxylic acids, quick-drying styrene-butadiene latex for inks is prepared through emulsion polymerization, forming a microporous structure that promotes rapid ink penetration, and improving coating strength and gloss through a covalent cross-linking network.
It achieves rapid ink drying, ensures good compatibility between latex and coating, improves the dry and wet rubbing strength, gloss and smoothness of the coating, is suitable for high-speed printing needs, and has excellent water resistance.
Smart Images
Figure SMS_1
Abstract
Description
Technical Field
[0001] This invention belongs to the technical field of styrene-butadiene latex, and relates to a quick-drying styrene-butadiene latex for ink and its preparation method. Background Technology
[0002] Styrene-butadiene latex is a high-molecular polymer formed by emulsion polymerization of butadiene and styrene as the main monomers. Due to its advantages such as strong adhesion, good film-forming properties, and low cost, it is widely used in industries such as papermaking, carpet making, textiles, and construction. In the manufacturing process of white cardboard, carboxylated styrene-butadiene latex is the most critical adhesive in the coating formulation, and its performance directly affects key indicators such as printability, surface strength, and gloss of the white cardboard.
[0003] With the upgrading of consumption and the rapid development of the printing industry, the market has placed more stringent demands on the color saturation and quality consistency of printed materials on white cardboard packaging. At the same time, to improve production efficiency, printing plants are constantly increasing the speed of printing presses. However, excessively high printing speeds pose a serious challenge to the ink drying performance of white cardboard. When the ink is not dried sufficiently, problems such as ink smudging, blurring, and uneven printing can occur, severely affecting printing quality and efficiency.
[0004] As the primary adhesive in the coating of white cardboard, especially the topcoat, latex's microstructure (such as polymer chain rigidity, hydrophilicity, and glass transition temperature Tg) significantly influences the absorption and penetration rate of ink solvents by the coated paper, i.e., the ink drying speed. Currently, the mainstream styrene-butadiene latex used for white cardboard topcoat often features a dense polymer design or poor hydrophilicity to balance bond strength, gloss, and mechanical stability. This limits its ability to absorb and lock in ink solvents, making it difficult to meet the requirements of modern high-speed printing presses for instantaneous ink drying. Summary of the Invention
[0005] The purpose of this invention is to provide a fast-drying styrene-butadiene latex for ink and its preparation method. This invention improves the drying speed of ink by synergistic effect of PEM and unsaturated carboxylic acids, while ensuring good compatibility between the latex and pigments in the coating, as well as the required dry and wet rubbing strength, gloss and smoothness of the coating.
[0006] The objective of this invention can be achieved through the following technical solutions: A quick-drying styrene-butadiene latex ink comprises the following components in parts by weight: The composition includes 50-70 parts butadiene, 30-50 parts styrene, 2.5-6.0 parts composite monomer, 0.1-0.5 parts molecular weight regulator, 1-4 parts emulsifier, 0.2-1.0 parts initiator, and 110-130 parts deionized water.
[0007] As a preferred embodiment of the present invention, the composite monomer is prepared by compounding unsaturated carboxylic acid monomer and hydroxyethyl methacrylate phosphate in a mass ratio of 1:1.4-1.8, wherein the hydroxyethyl methacrylate phosphate is also known as 2-methyl-2-acrylic-2-hydroxyethyl phosphate.
[0008] As a preferred technical solution of the present invention, the preparation method of the unsaturated carboxylic acid monomer includes the following steps: mixing 2-furan acrolein and pure ethanol, stirring to form a mixture, adding acidic amino acids for ultrasonic treatment, heating and stirring, and rotary evaporating to remove the reaction solvent to obtain the unsaturated carboxylic acid monomer.
[0009] As a preferred embodiment of the present invention, the ratio of 2-furan acrolein, pure ethanol, and acidic amino acids is 1.5-1.8g:20-30mL:1.35-1.46g; the ultrasonic treatment power is 300-400W and the treatment time is 10-15min; the heating and stirring temperature is 60-65℃ and the stirring time is 4-5h; the acidic amino acid is one or more of aspartic acid and glutamic acid; the introduced carboxyl group (-COOH) not only provides crosslinking points, enhancing the adhesive strength and mechanical stability of the latex, but also promotes the rapid absorption of water in the ink through its hydrophilicity.
[0010] As a preferred embodiment of the present invention, the molecular weight regulator is tert-dodecyl mercaptan.
[0011] As a preferred embodiment of the present invention, the emulsifier is a compound of anionic and nonionic emulsifiers; the mass ratio of the anionic and nonionic emulsifiers is (2-3):1, and the anionic emulsifier is any one of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, or sodium allyloxyhydroxypropyl sulfonate; the nonionic emulsifier is alkylphenol polyoxyethylene ether (OP-10) or fatty alcohol polyoxyethylene ether (AEO-9); the compound emulsifier can form more stable and denser micelles, which is beneficial to the smooth progress of the polymerization reaction and the control of latex particle size.
[0012] As a preferred embodiment of the present invention, the initiator is any one of ammonium persulfate, potassium persulfate, and tert-butyl hydroperoxide.
[0013] As a preferred embodiment of the present invention, a method for preparing a quick-drying styrene-butadiene latex ink includes the following steps: a. Preparation of pre-emulsion: Mix 80wt% deionized water, 80wt% emulsifier, butadiene, styrene and composite monomer, and stir to form a stable pre-emulsion; b. Seed emulsion preparation: Add the remaining deionized water, remaining emulsifier and 15wt% initiator to the polymerization reactor, heat to 85-90℃, add 10wt% of the pre-emulsion to react and form a seed emulsion; c. Droplet polymerization: The remaining pre-emulsion, molecular weight regulator and remaining initiator are added dropwise into the polymerization reactor at a uniform rate and simultaneously over 3-5 hours, while controlling the reaction temperature at 85-90℃. d. Incubation and maturation: After the addition is complete, incubate at 95-100℃ for 1-2 hours; e. Cooling and post-processing: Cool to below 40℃, adjust pH to 6.0-8.0, and filter out the material.
[0014] The beneficial effects of this invention are: 1. Excellent ink drying properties: This invention creatively selects hydroxyethyl methacrylate phosphate (PEM) as a functional comonomer. The phosphate groups in the PEM molecule have moderate hydrophilicity and excellent polarity. When introduced into the styrene-butadiene latex polymer molecular chain, it can form a microporous structure in the coating that is more conducive to the rapid penetration of ink solvents. At the same time, its polar groups can interact with the components in the ink, accelerating the curing and drying of the ink. Compared with latexes using SSS or AMPS, PEM ensures fast drying while having less negative impact on the water resistance of the coating.
[0015] 2. Balanced overall performance: Through the synergistic effect of hydroxyethyl methacrylate phosphate and unsaturated carboxylic acid, the ink drying speed is improved while ensuring good compatibility between latex and pigments in coatings (such as kaolin and calcium carbonate), as well as the required dry and wet rubbing strength, gloss and smoothness of the coating.
[0016] 3. Feasible process and easy to industrialize: The preparation method of this invention is based on conventional emulsion polymerization process, which does not require special equipment. The reaction conditions are mild and controllable, making it suitable for large-scale industrial production. Detailed Implementation
[0017] To further illustrate the technical means and effects of the present invention in achieving its intended purpose, the following detailed description of the specific implementation methods, structures, features, and effects of the present invention, in conjunction with embodiments, is provided below.
[0018] Example 1 A quick-drying styrene-butadiene latex ink comprises the following components in parts by weight: 50 parts butadiene, 30 parts styrene, 2.5 parts composite monomer, 0.1 parts molecular weight regulator, 1 part emulsifier, 0.2 parts initiator and 110 parts deionized water; The composite monomer is prepared by compounding an unsaturated carboxylic acid monomer and hydroxyethyl methacrylate phosphate in a mass ratio of 1:1.4. The preparation method of the unsaturated carboxylic acid monomer includes the following steps: mixing 2-furan acrolein and pure ethanol, stirring to form a mixture, adding acidic amino acids, treating with ultrasonic power of 300W for 10 min, stirring at 60℃ for 4 h, and removing the reaction solvent by rotary evaporation to obtain the unsaturated carboxylic acid monomer; the ratio of 2-furan acrolein, pure ethanol and acidic amino acids is 1.5g:20mL:1.35g, and the acidic amino acid is glutamic acid; The molecular weight regulator is tert-dodecyl mercaptan; The emulsifier is a compound of sodium dodecyl sulfate and alkylphenol polyoxyethylene ether in a mass ratio of 2:1. The initiator is ammonium persulfate.
[0019] A method for preparing a quick-drying styrene-butadiene latex ink includes the following steps: a. Preparation of pre-emulsion: Mix 80wt% deionized water, 80wt% emulsifier, butadiene, styrene and composite monomer, and stir to form a stable pre-emulsion; b. Seed emulsion preparation and initiation: Add the remaining deionized water, remaining emulsifier and 15wt% initiator to the polymerization reactor, heat to 85°C, add 10wt% of the pre-emulsion to react and form a seed emulsion; c. Droplet polymerization: The remaining pre-emulsion, molecular weight regulator and remaining initiator are added dropwise to the polymerization reactor at a uniform rate and simultaneously over 3 hours, while controlling the reaction temperature at 85°C; d. Incubation and maturation: After the addition is complete, incubate at 95℃ for 1 hour; e. Cooling and post-processing: Cool to below 40℃, adjust pH to 6.0, and filter out the material.
[0020] Example 2 A quick-drying styrene-butadiene latex ink comprises the following components in parts by weight: The composition consists of 60 parts butadiene, 40 parts styrene, 4.2 parts composite monomer, 0.3 parts molecular weight regulator, 2 parts emulsifier, 0.6 parts initiator, and 120 parts deionized water. The composite monomer is prepared by compounding an unsaturated carboxylic acid monomer and hydroxyethyl methacrylate phosphate in a mass ratio of 1:1.6. The preparation method of the unsaturated carboxylic acid monomer includes the following steps: mixing 2-furan acrolein and pure ethanol, stirring to form a mixture, adding acidic amino acids, treating with ultrasonic power of 350W for 12 min, stirring at 62℃ for 4.5 h, and removing the reaction solvent by rotary evaporation to obtain the unsaturated carboxylic acid monomer; the ratio of 2-furan acrolein, pure ethanol and acidic amino acids is 1.6 g: 25 mL: 1.4 g, and the acidic amino acid is glutamic acid; The molecular weight regulator is tert-dodecyl mercaptan; The emulsifier is a compound of sodium dodecyl sulfate and alkylphenol polyoxyethylene ether in a mass ratio of 2.5:1; The initiator is ammonium persulfate.
[0021] A method for preparing a quick-drying styrene-butadiene latex ink includes the following steps: a. Preparation of pre-emulsion: Mix 80wt% deionized water, 80wt% emulsifier, butadiene, styrene and composite monomer, and stir to form a stable pre-emulsion; b. Seed emulsion preparation and initiation: Add the remaining deionized water, remaining emulsifier and 15wt% initiator to the polymerization reactor, heat to 88°C, add 10wt% of the pre-emulsion to react and form a seed emulsion; c. Droplet polymerization: The remaining pre-emulsion, molecular weight regulator and remaining initiator are added dropwise to the polymerization reactor at a uniform rate and simultaneously over 4 hours, while controlling the reaction temperature at 88°C. d. Incubation and maturation: After the addition is complete, incubate at 98℃ for 1.5 hours; e. Cooling and post-processing: Cool to below 40℃, adjust pH to 7, and filter out the material.
[0022] Example 3 A quick-drying styrene-butadiene latex ink comprises the following components in parts by weight: 70 parts butadiene, 50 parts styrene, 6.0 parts composite monomer, 0.5 parts molecular weight regulator, 4 parts emulsifier, 1.0 part initiator and 130 parts deionized water; The composite monomer is prepared by compounding an unsaturated carboxylic acid monomer and hydroxyethyl methacrylate phosphate in a mass ratio of 1:1.8. The preparation method of the unsaturated carboxylic acid monomer includes the following steps: mixing 2-furan acrolein and pure ethanol, stirring to form a mixture, adding acidic amino acids, treating with ultrasonic power at 400W for 15 min, stirring at 65℃ for 5 h, and removing the reaction solvent by rotary evaporation to obtain the unsaturated carboxylic acid monomer; the ratio of 2-furan acrolein, pure ethanol and acidic amino acids is 1.8 g: 30 mL: 1.46 g, and the acidic amino acid is glutamic acid; The molecular weight regulator is tert-dodecyl mercaptan; The emulsifier is a compound of sodium dodecyl sulfate and alkylphenol polyoxyethylene ether in a mass ratio of 3:1. The initiator is ammonium persulfate.
[0023] A method for preparing a quick-drying styrene-butadiene latex ink includes the following steps: a. Preparation of pre-emulsion: Mix 80wt% deionized water, 80wt% emulsifier, butadiene, styrene and composite monomer, and stir to form a stable pre-emulsion; b. Seed emulsion preparation and initiation: Add the remaining deionized water, remaining emulsifier and 15wt% initiator to the polymerization reactor, heat to 90°C, add 10wt% of the pre-emulsion to react and form a seed emulsion; c. Droplet polymerization: The remaining pre-emulsion, molecular weight regulator and remaining initiator are added dropwise to the polymerization reactor at a uniform rate and simultaneously over 5 hours, while controlling the reaction temperature at 90°C. d. Incubation and maturation: After the addition is complete, incubate at 100℃ for 2 hours; e. Cooling and post-processing: Cool to below 40℃, adjust pH to 8.0, and filter out the material.
[0024] Example 4 Compared with Example 2, Example 4 differs in that the acidic amino acid is aspartic acid, while the other components, preparation steps and parameters are the same.
[0025] Comparative Example 1 Compared with Example 2, Comparative Example 1 differs in that sodium styrene sulfonate is used instead of hydroxyethyl methacrylate phosphate, while the other components, preparation steps and parameters are the same.
[0026] Comparative Example 2 Compared with Example 2, Comparative Example 2 differs in that it uses an equal amount of acrylamide-2-methylpropanesulfonic acid (AMPS) instead of hydroxyethyl methacrylate phosphate, while the other components, preparation steps and parameters are the same.
[0027] Comparative Example 3 Compared with Example 2, Comparative Example 3 differs in that it does not use hydroxyethyl methacrylate phosphate, while the other components, preparation steps and parameters are the same.
[0028] Comparative Example 4 Compared with Example 2, Comparative Example 4 differs in that the composite monomer is an unsaturated carboxylic acid monomer, while the other components, preparation steps and parameters are the same.
[0029] Comparative Example 5 Compared with Example 2, Comparative Example 5 differs in that the composite monomer is hydroxyethyl methacrylate phosphate, while the other components, preparation steps and parameters are the same.
[0030] Comparative Example 6 Compared with Example 2, Comparative Example 6 differs in that acrolein is used instead of 2-furan acrolein, while the other components, preparation steps and parameters are the same.
[0031] Comparative Example 7 Compared with Example 2, Comparative Example 6 differs in that 2-furan acrolein is used instead of the unsaturated carboxylic acid monomer, while the other components, preparation steps and parameters are the same.
[0032] The latexes obtained in Examples 1-4 and Comparative Examples 1-7 were used to formulate coatings according to the same coating formula.
[0033] The coating formulation uses a common white cardboard coating formulation. The top coat consists of 70 parts of grade 90 calcium carbonate, 30 parts of kaolin, 13 parts of latex (examples and comparative examples), and 0.1 parts of sodium polyacrylate dispersant. The intermediate and primer coats consist of 90 parts of grade 50 calcium carbonate, 10 parts of calcined kaolin, 11 parts of latex (examples and comparative examples), and 0.1 parts of sodium polyacrylate dispersant.
[0034] The base coat, intermediate coat, and top coat were applied to the white cardboard base paper to prepare coated white cardboard samples. Their performance was tested, and the results are shown in the table below: Test method description: Ink drying speed: After printing with a printability tester, the drying speed is measured with a drying instrument. The smaller the value, the faster the drying.
[0035] IGT roughening strength: Characterizes the surface strength of the coating; the higher the value, the better.
[0036] Gloss: Measured with a 75° angle gloss meter; the higher the value, the better.
[0037] Cobb value: Characterizes the water resistance of the coating; the lower the value, the better the water resistance.
[0038] Table 1
[0039] As shown in Table 1, compared with Comparative Examples 1-7, the white cardboard prepared using the latex of Examples 1-4 exhibits a significantly faster drying speed for its composite coating, fully meeting the requirements of high-speed printing. Furthermore, the latex of this invention demonstrates superior performance in key indicators such as coating strength (IGT value) and gloss, and its water resistance (Cobb value) is better than that of Comparative Examples 1-7. This indicates a synergistic effect between the unsaturated carboxylic acid monomer and hydroxyethyl methacrylate phosphate, achieving rapid drying while better balancing the overall performance of the coating.
[0040] This invention utilizes a cross-linked network structure formed by unsaturated carboxyl monomers and hydroxyethyl methacrylate phosphate, combined with the rigid furan ring structure of the unsaturated carboxyl monomers, to jointly enhance the cohesive strength of the coating. The polycarboxyl groups of the unsaturated carboxyl monomers and the phosphate groups of the hydroxyethyl methacrylate phosphate synergistically enhance the interfacial adhesion to the substrate, thereby significantly improving the IGT (intensity gloss) strength of the coating. The hydrophobic effect of the furan ring of the unsaturated carboxyl monomers and the alkyl chain of the hydroxyethyl methacrylate phosphate ester reduces moisture residue. The covalent cross-linking reaction of the two accelerates the molecular chain entanglement and film formation. Combined with the hydrophilic effect of the carboxyl groups and phosphate groups of the unsaturated carboxyl monomers, the drying speed is accelerated, and the molecular chain arrangement is made more regular, reducing film defects. Combined with the high refractive index of the furan ring, the gloss is improved. When the two are used in combination, their high-density cross-linked network blocks water penetration, and the strong hydrophobicity of the furan ring and the (stable intermolecular) covalent bonding reduce the exposure of hydrophilic sites, greatly optimizing water resistance.
[0041] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any indirect modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.
Claims
1. A quick-drying styrene-butadiene latex ink, characterized in that, The following components are included by weight: The composition includes 50-70 parts butadiene, 30-50 parts styrene, 2.5-6.0 parts composite monomer, 0.1-0.5 parts molecular weight regulator, 1-4 parts emulsifier, 0.2-1.0 parts initiator, and 110-130 parts deionized water. The composite monomer is prepared by combining an unsaturated carboxylic acid monomer and hydroxyethyl methacrylate phosphate. The preparation method of the unsaturated carboxylic acid monomer includes the following steps: mixing 2-furan acrolein and pure ethanol, stirring to form a mixture, adding acidic amino acids and sonicating, heating and stirring, and rotary evaporating to remove the reaction solvent to obtain the unsaturated carboxylic acid monomer.
2. The quick-drying styrene-butadiene latex ink according to claim 1, characterized in that: The ratio of 2-furan acrolein, pure ethanol, and acidic amino acids is 1.5-1.8g: 20-30mL: 1.35-1.46g.
3. The quick-drying styrene-butadiene latex ink according to claim 1, characterized in that: The acidic amino acid is one or more of aspartic acid and glutamic acid.
4. The quick-drying styrene-butadiene latex ink according to claim 1, characterized in that: The ultrasonic treatment power is 300-400W and the treatment time is 10-15min. The heating and stirring temperature is 60-65℃ and the stirring time is 4-5h.
5. The quick-drying styrene-butadiene latex ink according to claim 1, characterized in that: The molecular weight regulator is tert-dodecyl mercaptan; the emulsifier is a mixture of anionic and nonionic emulsifiers.
6. The quick-drying styrene-butadiene latex ink according to claim 5, characterized in that: The anionic emulsifier is any one of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, or sodium allyloxyhydroxypropyl sulfonate; the nonionic emulsifier is alkylphenol polyoxyethylene ether or fatty alcohol polyoxyethylene ether.
7. The quick-drying styrene-butadiene latex ink according to claim 1, characterized in that: The initiator is any one of ammonium persulfate, potassium persulfate, and tert-butyl hydroperoxide.
8. A method for preparing quick-drying styrene-butadiene latex as described in any one of claims 1 to 7, characterized in that, The preparation method includes the following steps: a. Preparation of pre-emulsion: Mix 80wt% deionized water, 80wt% emulsifier, butadiene, styrene and composite monomer, and stir to form a stable pre-emulsion; b. Seed emulsion preparation: Add the remaining deionized water, remaining emulsifier and 15wt% initiator to the polymerization reactor, heat to 85-90℃, add 10wt% of the pre-emulsion to react and form a seed emulsion; c. Droplet polymerization: The remaining pre-emulsion, molecular weight regulator and remaining initiator are added dropwise to the polymerization reactor at a uniform rate and simultaneously over 3-5 hours, while controlling the reaction temperature at 85-90℃. d. Incubation and maturation: After the addition is complete, incubate at 95-100℃ for 1-2 hours; e. Cooling and post-processing: Cool to below 40℃, adjust pH to 6.0-8.0, and filter out the material.