Water-based ink acrylate emulsion for PVC and its preparation method

Abstract

The embodiment of the present application discloses a kind of PVC water-based ink acrylate emulsion and preparation method thereof.Its raw materials include, by weight fraction: isomerized tridecanol polyoxyethylene ether (40) 4-5 parts, alcohol ether sulfosuccinic acid monoester disodium salt 2-3 parts, glycidyl methacrylate 4-6 parts, hydroxyethyl methacrylate 3-5 parts, methacrylic acid 5-7 parts, glycerol acetonide acrylate 5-7 parts, butyl acrylate 30-40 parts, methyl acrylate 50-60 parts, methyl methacrylate 20-25 parts, 3-(2,3 epoxy propoxy) propyl methyldiethoxysilane 4-6 parts, potassium persulfate 1.2-1.5 parts, alcohol ether sulfosuccinic acid monoester disodium salt 5-7 parts, deionized water 265-300 parts.The PVC water-based ink acrylate emulsion provided by the present application has the advantages of environmental protection, high transparency, good gloss, light, heat and water resistance, no tackback, strong adhesion, high stability and good application prospect.

Description

TECHNICAL FIELD

[0001] The embodiment of the present application relates to the technical field of acrylic emulsion, and particularly relates to a water-based ink acrylic emulsion for PVC and a preparation method thereof. BACKGROUND

[0002] The ink is an important material for printing, which displays patterns and characters on the printing material by printing or spraying. The ink is composed of resin, pigment, filler, additive and solvent. The ink is used for various printing such as books, package decoration, building decoration and the like. With the increase of social demand, the variety and output of the ink are also expanded and increased.

[0003] With the development of human civilization and the printing industry, the ink process is more sophisticated, and the types of ink products are continuously increased. The concept of green environmental protection has led to the reselection of ink raw materials and the reform of manufacturing process, such as water-based ink and UV ink. Compared with the traditional solvent-based ink, the water-based ink has become the main development direction of the ink industry.

[0004] The current ink for the base material PVC is generally solvent-based, and the solvent-based ink has good adhesion and water resistance, high transparency and anti-sticking. However, the solvent-based ink is not environmentally friendly. The quality of the water-based ink mainly depends on the quality of the resin. At present, the acrylic emulsion has been widely used in the base material PVC due to its advantages of good gloss, weather resistance and rheological property. However, the ink prepared by the acrylic resin still has the disadvantages of low stability, poor transparency and heat resistance, poor anti-sticking, poor water resistance, poor adhesion and the like. Therefore, it is necessary to develop the acrylic emulsion for the base material PVC, which has high transparency, good gloss, light resistance, heat resistance, water resistance, anti-sticking, high stability and good adhesion. SUMMARY

[0005] Therefore, the embodiment of the present application provides a water-based ink acrylic emulsion for PVC and a preparation method thereof.

[0006] In order to achieve the above object, the embodiment of the present application provides the following technical scheme.

[0007] According to the first aspect of the embodiment of the present application, the present application provides a water-based ink acrylic emulsion for PVC, and the raw materials thereof include, by weight fraction, isomeric tridecanol polyoxyethylene ether (40) 4-5 parts, alcohol ether sulfosuccinic acid monoester disodium salt 2-3 parts, glycidyl methacrylate 4-6 parts, hydroxyethyl methacrylate 3-5 parts, methacrylic acid 5-7 parts, propylene glycol ketals acrylate 5-7 parts, butyl acrylate 30-40 parts, methyl acrylate 50-60 parts, methyl methacrylate 20-25 parts, 3-(2,3-epoxypropoxy) propyl methyldiethoxysilane 4-6 parts, potassium persulfate 1.2-1.5 parts, alcohol ether sulfosuccinic acid monoester disodium salt 5-7 parts and deionized water 265-300 parts.

[0008] According to a second aspect of the embodiments of the present application, the present application provides a preparation method of the water-based ink acrylate emulsion for PVC as described above, which comprises the following steps:

[0009] (1) isomerized tridecanol polyoxyethylene ether (40) 4-5 parts, alcohol ether sulfosuccinic acid monoester disodium salt 2-3 parts, glycidyl methacrylate 4-6 parts, hydroxyethyl methacrylate 3-5 parts, methacrylic acid 5-7 parts, glycerol acetonide acrylate 5-7 parts, butyl acrylate 30-40 parts, methyl acrylate 50-60 parts, methyl methacrylate 20-25 parts, 3-(2,3 epoxy propoxy) propyl methyldiethoxysilane 4-6 parts and deionized water 90-100 parts are mixed, and a pre-emulsion is obtained by fully stirring and emulsifying, and is ready for use;

[0010] (2) potassium persulfate 1.2-1.5 parts and deionized water 25-30 parts are mixed to obtain a potassium persulfate aqueous solution, which is ready for use;

[0011] (3) in a reaction kettle, deionized water 150-170 parts, alcohol ether sulfosuccinic acid monoester disodium salt 5-7 parts, and the pre-emulsion of step (1) 12-15 parts are added, and the temperature is raised to 78-80°C, then the potassium persulfate aqueous solution in step (2) 5-7 parts is added to initiate the reaction; when the emulsion appears blue light and the temperature is 80-82°C, the remaining pre-emulsion and the remaining potassium persulfate aqueous solution are added dropwise to carry out the reaction;

[0012] (4) after the reaction is completed, the temperature is lowered to 30-40°C, neutralized, the pH value is adjusted to 7±1, and the solid content of the emulsion is adjusted to 30±1% with deionized water to obtain the water-based ink acrylate emulsion for PVC.

[0013] Further, in step (1), the stirring conditions are: 800-1000 rpm, 30-50 minutes.

[0014] Further, in step (3), the remaining pre-emulsion and the remaining potassium persulfate aqueous solution are added dropwise for 3-3.5 hours, and the temperature of the reaction system is controlled at 80-82°C during the dropwise addition.

[0015] Further, in step (3), after the dropwise addition is completed, the reaction system is incubated at 80-82°C for 2-2.5 hours.

[0016] Further, in step (4), the neutralization is carried out with ammonia water with a concentration of 24-28%.

[0017] The embodiments of the present application have the following advantages:

[0018] The ink for PVC of the present application is a water-based environment-friendly acrylate resin, which selects emulsifier alcohol ether sulfosuccinic acid monoester disodium salt, which contains carboxylic acid group and sulfonic acid group in the molecule, has good hydrophilic property, and also contains long-chain alkyl ether oxyethylene group, which has good hydrophobic property, thus having dual surface chemical properties of non-ionic emulsifier and anionic emulsifier, and is used together with non-ionic emulsifier isomeric tridecanol polyoxyethylene ether (40), so that the stability of the obtained polymer emulsion is good.

[0019] In the reaction kettle, the emulsifier alcohol ether sulfosuccinic acid monoester disodium salt is added, and the process and the monomer ratio are adjusted to control the particle size of the polymer, so that the obtained polymer emulsion has high transparency, alcohol resistance, and good stability. The emulsion dry film is transparent, heat-resistant, light-resistant, and water-resistant.

[0020] The present application selects functional monomer glycidyl methacrylate, which contains carbon-carbon double bond and epoxy group in the molecule, and can be polymerized in the form of functional group or ionically. The two polymerization reaction modes are used to improve and improve the water resistance and adhesion of the polymer film. At the same time, the selected functional monomers, such as methacrylic acid and hydroxyethyl methacrylate, improve the compactness and adhesion of the polymer film after crosslinking reaction, so that the heat resistance, light resistance and water resistance of the obtained polymer are further enhanced.

[0021] The 3-(2,3 epoxypropoxy) propyl methyldiethoxysilane is selected in the formula of the present application, which is a kind of special low molecular organic silicon compound, and has strong reaction ability with different matrix resins, so that the obtained polymer has excellent temperature resistance and water resistance, and improves the adhesion of the product to the substrate; by adjusting the proportion of the selected monomers butyl acrylate, methyl acrylate and methyl methacrylate, and under the synergistic action of 3-(2,3 epoxypropoxy) propyl methyldiethoxysilane, the polymer film has no tackback, high transparency and good dryness.

[0022] The present application selects acetone glycerol acrylate, which is proved by experiments to have extremely strong adhesion to the substrate PVC. It is used together with 3-(2,3 epoxypropoxy) propyl methyldiethoxysilane to further enhance the reaction ability to the substrate PVC.

[0023] The present application selects thermal decomposition initiator potassium persulfate for emulsion polymerization reaction, which has an initiation temperature of 78-80℃, and a reaction temperature of 80-82℃, and cooperates with the selected monomers and additives, so that the particle size and particle size distribution, molecular weight and molecular weight distribution of the obtained polymer meet the requirements of the present application. The selected monomers and additives of the present application are environment-friendly, and the obtained water-based polymer emulsion is also environment-friendly.

[0024] Therefore, the PVC water-based ink acrylate emulsion has the advantages of environmental protection, high transparency, good gloss, light resistance, heat resistance, water resistance, no tackiness, good adhesion and high stability. DETAILED DESCRIPTION

[0025] The embodiments of the present application will be described in detail by the following specific examples, and other advantages and effects of the present application can be easily understood by those skilled in the art from the contents disclosed in the specification. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the scope of protection of the present application.

[0026] Example 1

[0027] The present embodiment provides a PVC water-based ink acrylate emulsion, and the preparation method thereof comprises the following steps:

[0028] (1) 4 parts of isomeric tridecanol polyoxyethylene ether (40), 2 parts of alcohol ether sulfosuccinic acid monoester disodium salt, 4 parts of glycidyl methacrylate, 3 parts of hydroxyethyl methacrylate, 5 parts of methyl acrylate, 30 parts of butyl acrylate, 50 parts of methyl acrylate, 20 parts of methyl methacrylate, 4 parts of 3-(2,3-epoxypropoxy) propyl methyldiethoxysilane and 90 parts of deionized water are mixed to obtain a pre-emulsion, which is emulsified at 1000 rpm for 30 min.

[0029] (2) 1.2 parts of potassium persulfate and 25 parts of deionized water are mixed to obtain a potassium persulfate aqueous solution, which is used.

[0030] (3) In a reaction kettle, 150 parts of deionized water, 5 parts of alcohol ether sulfosuccinic acid monoester disodium salt and 12 parts of the pre-emulsion are added, and the temperature is raised to 78-80°C. Then 5 parts of the potassium persulfate aqueous solution is added to initiate the reaction. When the emulsion appears blue light and the temperature is at 80-82°C, the remaining pre-emulsion and the remaining potassium persulfate aqueous solution are added dropwise. The dropwise addition is completed in 3-3.5 hours, and the temperature is controlled at 80-82°C during the reaction. After the dropwise addition is completed, the temperature is maintained for 2 hours.

[0031] (4) After the temperature maintenance is completed, the temperature is lowered to 30-40°C, and the emulsion is neutralized with 26% ammonia water, and the pH value is adjusted to 7±1. Then the solid content of the emulsion is adjusted to 30±1% with deionized water to obtain product A.

[0032] Example 2

[0033] The present embodiment provides a PVC water-based ink acrylate emulsion, and the preparation method thereof comprises the following steps:

[0034] (1) Mix isomerized tridecanol polyoxyethylene ether (40) 4.2 parts, alcohol ether sulfosuccinic acid monoester disodium salt 2.2 parts, glycidyl methacrylate 4.4 parts, hydroxyethyl methacrylate 3.4 parts, methacrylic acid 5.4 parts, acetone glycerol acrylate 5.4 parts, butyl acrylate 32 parts, methyl acrylate 52 parts, methyl methacrylate 21 parts, 3-(2,3-epoxypropoxy)propyl methyldiethoxysilane 4.4 parts, and deionized water 92 parts, emulsify at 1000 rpm for 30 min to obtain a pre-emulsion, and wait for use.

[0035] (2) Mix potassium persulfate 1.26 parts and deionized water 26 parts to obtain a potassium persulfate aqueous solution, and wait for use.

[0036] (3) Add deionized water 154 parts, alcohol ether sulfosuccinic acid monoester disodium salt 5.4 parts, and pre-emulsion 12.6 parts to a reaction kettle, heat to 78-80°C, then add potassium persulfate aqueous solution 5.4 parts to initiate the reaction; when blue light appears in the emulsion and the temperature is 80-82°C, drop the remaining pre-emulsion and the remaining potassium persulfate aqueous solution, and complete the drop in 3-3.5 hours; control the temperature at 80-82°C during the reaction, and keep the temperature for 2 hours after the drop is completed;

[0037] (4) After the temperature keeping is completed, cool to 30-40°C, neutralize with 26% ammonia water, adjust the pH value to 7±1, and adjust the solid content of the emulsion to 30±1% with deionized water to obtain product B.

[0038] Example 3

[0039] The present embodiment provides a water-based ink acrylate emulsion for PVC, and a preparation method thereof, which comprises the following steps:

[0040] (1) Mix isomerized tridecanol polyoxyethylene ether (40) 4.4 parts, alcohol ether sulfosuccinic acid monoester disodium salt 2.4 parts, glycidyl methacrylate 4.8 parts, hydroxyethyl methacrylate 3.8 parts, methacrylic acid 5.8 parts, acetone glycerol acrylate 5.8 parts, butyl acrylate 34 parts, methyl acrylate 54 parts, methyl methacrylate 22 parts, 3-(2,3-epoxypropoxy)propyl methyldiethoxysilane 4.8 parts, and deionized water 94 parts, emulsify at 1000 rpm for 30 min to obtain a pre-emulsion, and wait for use.

[0041] (2) Mix potassium persulfate 1.32 parts and deionized water 27 parts to obtain a potassium persulfate aqueous solution, and wait for use.

[0042] (3) In the reaction kettle, add deionized water 158 parts, alcohol ether sulfobutyl succinic acid monoester disodium salt 5.8 parts, pre-emulsion 13.2 parts, heat to 78-80℃, then add potassium persulfate aqueous solution 5.8 parts, initiate the reaction; When the emulsion appears blue light and the temperature is at 80-82℃, add the remaining pre-emulsion and the remaining potassium persulfate aqueous solution, and the temperature is controlled at 80-82℃ during the reaction. Dropwise addition is completed in 3-3.5 hours, and the reaction is kept for 2 hours after dropping;

[0043] (4) After the end of the heat preservation, cool to 30-40℃, neutralize with 26% ammonia water, adjust the pH value to 7±1, and adjust the solid content of the emulsion to 30±1% with deionized water to obtain product C.

[0044] Example 4

[0045] The present embodiment provides a PVC water-based ink acrylate emulsion, and its preparation method comprises the following steps:

[0046] (1) Mix isomeric tridecanol polyoxyethylene ether (40) 4.6 parts, alcohol ether sulfobutyl succinic acid monoester disodium salt 2.6 parts, glycidyl methacrylate 5.2 parts, hydroxyethyl methacrylate 4.2 parts, methacrylic acid 6.2 parts, propylene glycol acetone acrylate 6.2 parts, butyl acrylate 36 parts, methyl acrylate 56 parts, methyl methacrylate 23 parts, 3-(2,3 epoxypropoxy) propyl methyldiethoxysilane 5.2 parts and deionized water 96 parts, and emulsify for 30 minutes at 1000 rpm to obtain a pre-emulsion, which is ready for use.

[0047] (2) Mix potassium persulfate 1.38 parts and deionized water 28 parts to obtain a potassium persulfate aqueous solution, which is ready for use.

[0048] (3) In the reaction kettle, add deionized water 162 parts, alcohol ether sulfobutyl succinic acid monoester disodium salt 6.2 parts, pre-emulsion 13.8 parts, heat to 78-80℃, then add potassium persulfate aqueous solution 6.2 parts, initiate the reaction; When the emulsion appears blue light and the temperature is at 80-82℃, add the remaining pre-emulsion and the remaining potassium persulfate aqueous solution, and the temperature is controlled at 80-82℃ during the reaction. Dropwise addition is completed in 3-3.5 hours, and the reaction is kept for 2 hours after dropping;

[0049] (4) After the end of the heat preservation, cool to 30-40℃, neutralize with 26% ammonia water, adjust the pH value to 7±1, and adjust the solid content of the emulsion to 30±1% with deionized water to obtain product C.

[0050] Example 5

[0051] The present embodiment provides a PVC water-based ink acrylate emulsion, and its preparation method comprises the following steps:

[0052] (1) Mix 4.8 parts of isomeric tridecanol polyoxyethylene ether (40), 2.8 parts of disodium salt of alcohol ether sulfosuccinate, 5.6 parts of glycidyl methacrylate, 4.6 parts of hydroxyethyl methacrylate, 6.6 parts of methacrylic acid, 6.6 parts of acetone glycerol acrylate, 38 parts of butyl acrylate, 58 parts of methyl acrylate, 24 parts of methyl methacrylate, 5.6 parts of 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane and 98 parts of deionized water, stir and emulsify at 1000 rpm for 30 minutes to obtain a pre-emulsion for use.

[0053] (2) Mix 1.44 parts of potassium persulfate and 29 parts of deionized water to obtain a potassium persulfate aqueous solution for later use.

[0054] (3) Add 166 parts of deionized water, 6.6 parts of disodium salt of alcohol ether sulfosuccinate, and 14.4 parts of pre-emulsion into the reactor, raise the temperature to 78-80°C, and then add 6.6 parts of potassium persulfate aqueous solution to initiate the reaction; when the emulsion emits a blue light and the temperature is 80-82°C, add the remaining pre-emulsion and the remaining potassium persulfate aqueous solution dropwise, and complete the addition in 3-3.5 hours. During the reaction, the temperature is controlled at 80-82°C, and the temperature is kept for 2 hours after the addition is completed;

[0055] (4) After the insulation is completed, the temperature is lowered to 30-40°C, neutralized with 26% ammonia water, and the pH value is adjusted to 7±1. The solid content of the emulsion is adjusted to 30±1% with deionized water to obtain product E.

[0056] Example 6

[0057] This embodiment provides a water-based ink acrylic emulsion for PVC, and the preparation method thereof comprises the following steps:

[0058] (1) Mix 5 parts of isomeric tridecanol polyoxyethylene ether (40), 3 parts of disodium salt of alcohol ether sulfosuccinate, 6 parts of glycidyl methacrylate, 5 parts of hydroxyethyl methacrylate, 7 parts of methacrylic acid, 7 parts of acetone glycerol acrylate, 40 parts of butyl acrylate, 60 parts of methyl acrylate, 25 parts of methyl methacrylate, 6 parts of 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane and 100 parts of deionized water, stir and emulsify at 1000 rpm for 30 minutes to obtain a pre-emulsion for use.

[0059] (2) Mix 1.5 parts of potassium persulfate and 30 parts of deionized water to obtain a potassium persulfate aqueous solution for later use.

[0060] (3) In the reactor, add 170 parts of deionized water, 7 parts of alcohol ether sulfobutane acid monoester disodium salt, 15 parts of pre-emulsion, and heat to 78-80°C. Then add 7 parts of potassium persulfate aqueous solution to initiate the reaction. When the emulsion appears blue light and the temperature is at 80-82°C, drop the remaining pre-emulsion and the remaining potassium persulfate aqueous solution. The dropping is completed in 3-3.5 hours, and the temperature is controlled at 80-82°C during the reaction. After dropping, keep warm for 2 hours.

[0061] (4) After the end of the warm-up, cool down to 30-40°C, neutralize with 26% ammonia water, adjust the pH value to 7±1, and adjust the solid content of the emulsion to 30±1% with deionized water to obtain product F.

[0062] Test Example

[0063] Take 100 grams of products A, B, C, D, E, and F, and 0.5 grams of film-forming aid alcohol ester twelve, 0.2 grams of wetting agent silok8000, and 0.3 grams of defoaming agent silok4635, and stir evenly. Then add an appropriate amount of thickening agent HB-139, and after thickening, add 4 grams of color paste BASF Dispers 6900. Stir evenly and filter with 120 mesh filter cloth. Roll coat on PVC with a glass rod, and dry at 80-100°C.

[0064] Emulsion appearance: visually observe whether the emulsion has gel, whether it is transparent, and its color.

[0065] Particle size test: test with Nano-ZS type nano particle size analyzer.

[0066] Mechanical stability test: use a centrifuge to test at 3000 r / min for 20 min at room temperature. If there is no precipitation, it means that the storage period exceeds 180 days.

[0067] Ink gloss test: test according to GB / T13217.2-91.

[0068] Adhesion test: use a 100 μm applicator to apply the prepared ink on PVC, dry at 80-100°C, and then test according to national standard GB / T9286-98. The adhesion level is divided into six levels, from 0 to 5, with 0 being the best and 5 being the worst.

[0069] Water resistance: dry the prepared ink on PVC to form a film, then soak in 25°C deionized water for 24 hours, and observe whether the latex film bubbles, becomes transparent, or whitens.

[0070] Ink fineness test: test according to GB / T13217.3-91.

[0071] Light resistance and weather resistance: according to GB / T 31899-2015 "Textiles-Weather resistance test-UV exposure-determination of standards" for detection.

[0072] Heat resistance: according to national standard GB / T.13767-1992 Textiles-Heat resistance test.

[0073] Alcohol dilution stability: 50 grams of emulsion is added with equal amount of ethanol, and placed at room temperature for 180 days, and the stability is observed.

[0074] The test results are shown in Table 1 below.

[0075] Table 1

[0076]

[0077] The test results show that the transparency, gloss, light resistance, heat resistance, water resistance, anti-back-sticking, adhesion, stability and other performance indicators of the product of the present application have obvious advantages compared with the same kind of products on the market.

[0078] Although the present application has been described in detail in the foregoing with general description and specific embodiments, some modifications or improvements can be made on the basis of the present application, which is obvious to those skilled in the art. Therefore, these modifications or improvements made on the basis of not deviating from the spirit of the present application, all belong to the scope of the present application claimed.

Claims

1. A method for preparing a water-based ink acrylic emulsion for PVC, characterized in that: The method comprises the following steps, wherein the following components are calculated in parts by weight: (1) Mix 4-5 parts of isomeric tridecanol polyoxyethylene ether 40, 2-3 parts of disodium salt of alcohol ether sulfosuccinate monoester, 4-6 parts of glycidyl methacrylate, 3-5 parts of hydroxyethyl methacrylate, 5-7 parts of methacrylic acid, 5-7 parts of acetone glycerol acrylate, 30-40 parts of butyl acrylate, 50-60 parts of methyl acrylate, 20-25 parts of methyl methacrylate, 4-6 parts of 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane and 90-100 parts of deionized water, stir well to emulsify and obtain a pre-emulsion for use; (2) Mix 1.2-1.5 parts of potassium persulfate and 25-30 parts of deionized water to obtain a potassium persulfate aqueous solution for later use; (3) Add 150-170 parts of deionized water, 5-7 parts of disodium salt of alcohol ether sulfosuccinate, and 12-15 parts of the pre-emulsion of step (1) into the reactor, raise the temperature to 78-80°C, and then add 5-7 parts of the potassium persulfate aqueous solution of step (2) to initiate the reaction; when the emulsion emits blue light and the temperature is 80-82°C, add the remaining pre-emulsion and the remaining potassium persulfate aqueous solution dropwise to carry out the reaction; (4) After the reaction is completed, the temperature is lowered to 30-40°C, neutralized, and the pH value is adjusted to 7±1. The solid content of the emulsion is adjusted to 30±1% with deionized water to obtain the PVC water-based ink acrylate emulsion; In step (3), the remaining pre-emulsion and the remaining potassium persulfate aqueous solution are added dropwise over 3-3.5 hours, and the temperature of the reaction system is controlled at 80-82°C during the addition process; after the addition is completed, the reaction system is kept at 80-82°C for 2-2.5 hours.

2. The method for preparing a water-based ink acrylic emulsion for PVC according to claim 1, wherein: In step (1), the stirring conditions are: 800-1000 rpm, 30-50 minutes.

3. The method for preparing the PVC water-based ink acrylic emulsion according to claim 1, wherein: In step (4), neutralize with ammonia water with a concentration of 24-28%.

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