EAA hybrid acrylic emulsion for PVC water-based ink and preparation method of EAA hybrid acrylic emulsion

Abstract

The invention discloses an EAA hybrid acrylic emulsion for PVC water-based ink and a preparation method of the EAA hybrid acrylic emulsion, and belongs to the field of preparation of water-based ink binders. The coating is composed of an EAA emulsion, a defoaming agent, an emulsifier, an initiator, methacrylic acid, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, a self-crosslinking monomer, an organosilicon monomer, a functional monomer, a preservative and the like. According to the emulsion for the PVC furniture film ink, the ethylene-acrylic copolymer emulsion is used as a seed emulsion, and polyethylene flexible chains and a large amount of carboxyl are introduced into emulsion particles, so that the adhesive force to a PVC film is improved. The product takes water as a dispersion medium, is convenient to use and has no pollution to the environment.

Description

Technical Field

[0001] The invention relates to a preparation technology of a functional acrylic emulsion, in particular to an EAA hybrid acrylic emulsion for PVC water-based ink and a preparation method thereof. Background Art

[0002] PVC is one of the most widely used general-purpose plastics with good water-proof properties. It can be used for packaging food, seasonings, beverages, etc., soft packaging for various items, beer bottle caps and beverage bottle cap linings, furniture and wallpaper, etc. Traditional PVC printing mostly uses solvent-based inks for printing effects and adhesion considerations. The volatilization of the solvent will cause health damage to printing operators and people who come into contact with the printed material.

[0003] In addition, PVC used for packaging or printing is a non-absorbent substrate, and due to the special nature of PVC materials, a certain amount of plasticizer needs to be added during its manufacture to improve its toughness. Therefore, general water-based emulsions will exhibit the characteristics of hot stickiness and cold brittleness. Moreover, since the surface tension of PVC film materials is low, the adhesion between ink and substrate is poor. In water-based inks, the water-based binder plays a vital role.

[0004] PVC color film industry is an important basic material for floor decoration. Color film can be used to produce floor and wallpaper materials with various patterns. Among them, ink is a key material for preparing PVC, and its quality directly affects the stability of color film quality. In recent years, the demand for decoration has increased dramatically, especially in Europe and the United States. On the other hand, traditional inks are oily and contain a lot of solvents, which cause environmental pollution. Therefore, accelerating the water-based ink is an important way to solve the oil pollution. However, there is a big gap between water-based and oil-based inks in drying speed and printing quality. The following factors cause these gaps: film-forming resin, pigment, additives, and PVC color film.

[0005] After printing, the PVC furniture film industry needs to undergo a short-time high-temperature bonding process with the PVC wear-resistant layer (160-170℃, 6-15 seconds, no specific pressure requirements). The wear-resistant layer mainly protects the printed film from scratches, scrapes, water and oil stains. Furniture films bonded with PVC wear-resistant layers are generally used for indoor furniture panels, door panels, etc., but due to the limited weather resistance of the PVC wear-resistant layer itself, it is difficult to use this kind of furniture film bonded with PVC wear-resistant layer in outdoor places. Summary of the invention

[0006] In order to solve the above problems, the present invention designs the process and structure around the problems encountered in the synthesis and application of the ink emulsion used on the above PVC substrate, so that the connecting material and the substrate can be better contacted and attached, and the water resistance of the product is improved. Specifically, an acrylic emulsion for water-based ink on a PVC substrate and a preparation method thereof are provided. The emulsion uses water as a dispersion medium, is easy to use, has no pollution to the environment, and has no pollution to the bonded materials. It has the characteristics of curing at room temperature, high bonding strength, and good water resistance, heat resistance, and aging resistance. The synthesis method has the characteristics of simple operation and high preparation efficiency.

[0007] To achieve the above object, the present invention adopts the following technical solutions:

[0008] An EAA hybrid acrylic emulsion for PVC water-based ink comprises the following components in parts by weight:

[0009]

[0010] Wherein, the functional monomer is an acrylate with a tetrahydrofuran ring, and the organosilicon monomer is a polyorganosiloxane with vinyl and alkyl functional groups.

[0011] Further, the EAA emulsion Michelman ethylene acrylic acid copolymer Prime4983-40R and Prime 4990R or two thereof; the functional monomer is tetrahydrofurfuryl acrylate (THFA), the self-crosslinking monomer is Nanjing Baiju Technology's self-crosslinking monomer AT-208, and the silicone monomer is Siluoke 3572F5 is a polysiloxane with vinyl and alkyl functional groups.

[0012] Furthermore, the emulsifier may be one or more of AEO-9, COPS-1, CO-436, SVS, EXG-202, SR10 reactive emulsifiers,

[0013] Furthermore, the initiator may be ammonium persulfate, the defoamer may be BYK024, the wetting agent may be OT-75, and the preservative may be LXE fungicide.

[0014] A method for preparing an EAA hybrid acrylic emulsion for PVC water-based ink, the method comprising the following process steps:

[0015] a. Dissolve 0.1 parts by weight of an initiator in 6 parts by weight of deionized water to obtain a polymerization initiator solution;

[0016] b. Add 18 parts by weight of deionized water to the emulsifying kettle, add 1.0-1.2 parts by weight of emulsifier after dispersion and stirring; after uniform dispersion and stirring, add 1.5 parts by weight of methacrylic acid, 15.3 parts by weight of butyl acrylate, 8.6 parts by weight of isooctyl acrylate, 20.4 parts by weight of methyl methacrylate, 0.5-0.8 parts by weight of self-crosslinking monomer, 0.8-1.0 parts by weight of organosilicon monomer, and 3.0 parts by weight of functional monomer, and stir and disperse for 50 minutes to prepare a pre-emulsion;

[0017] c. Add 23.7 parts by weight of deionized water, 0.2-0.3 parts by weight of emulsifier, and 5-8 parts by weight of EAA emulsion to the reactor, heat to 80°C, add 3.4 parts by weight of the pre-emulsion prepared in step b, and 1.6 parts by weight of the initiator solution prepared in step a. After reacting for 30 minutes, add 65.7-66.4 parts by weight of the pre-emulsion of step b dropwise, and simultaneously add 4.5 parts by weight of the initiator solution prepared in step a dropwise, and the pre-emulsion and the initiator are dripped at the same time;

[0018] d. After the pre-emulsion and initiator are dripped, continue to react for 20 minutes, then raise the temperature to 85°C, keep the temperature for 90 minutes, then cool to below 50°C, add 0.1 parts by weight of defoamer, 0.1 parts by weight of preservative, 0.1 parts by weight of wetting agent, and 0.3 parts by weight of ammonia water, stir for 30 minutes, then evacuate, filter the material with gauze to obtain EAA hybrid acrylic emulsion.

[0019] The beneficial effects of the present invention are as follows: 1. The present invention uses ethylene acrylic acid copolymer emulsion as the core. Since it is a copolymer of ethylene and acrylic acid, the water resistance of the EAA hybrid acrylic emulsion is very good. At the same time, a flexible chain ethylene structure is introduced into the polymer chain structure, which increases the flexibility of the EAA hybrid acrylic emulsion, solves the effect of the expansion and contraction of the connecting material in the ink prepared by the EAA hybrid acrylic emulsion on the adhesive layer as the temperature changes, and at the same time, due to the low surface energy of ethylene, the wetting and spreading of the ink coating prepared by the EAA hybrid acrylic emulsion on the PVC film is increased. At the same time, due to the introduction of a large number of carboxyl groups and the generation of a large number of hydrogen bonds with other functional groups in the structure, the adhesion and water resistance of the ink coating prepared by the EAA hybrid acrylic emulsion are improved. At the same time, the crystallization of the polymer is inhibited and the linearity of the main chain is destroyed, thereby improving the transparency and toughness of EAA; 2. Self-crosslinking monomer AT-208, film-forming at room temperature, through Michael reaction, the enamine structure can react with aldehydes and hydrazides through chelation, improving the adhesion to the substrate layer, water resistance and solvent resistance; 3. Functional monomer THFA is an acrylate product with a tetrahydrofuran ring. Tetrahydrofuran is a class of heterocyclic organic compounds, a class of cyclic ethers with extremely strong polarity, and can be used as a medium-polarity solvent in chemical reactions and extractions. The strong polarity brought by the tetrahydrofuran group makes this product have strong adhesion to most materials, and even has a swelling effect on some plastics such as PVC, PC, PET, etc. THFA also has good weather resistance, yellowing resistance, water resistance, dilution resistance and flexibility; and the lone electron pair on the THFA ring can react with AT-208 to produce Michael reaction, so that the polymer chain changes from linear to three-dimensional; 4. Polysiloxanes with vinyl and alkyl functional groups are copolymerized with acrylates through free radicals on silicone, and the properties of silicone are introduced into the emulsion, which improves the product's slipperiness, wear resistance, waterproof and anti-fouling properties, and prevents the film from sticking back after film formation; the pH of the silicone decreases after the ammonia volatilizes, and the siloxane realizes interchain hydrolysis reaction to achieve spatial network crosslinking. DETAILED DESCRIPTION

[0020] The present invention is described in detail below with reference to specific embodiments.

[0021] Embodiment 1 formula:

[0022]

[0023] Production process:

[0024] a. Dissolve 0.1 kg of ammonium persulfate in 6 kg of deionized water to obtain 6.1 kg of ammonium sulfate solution for polymerization;

[0025] b. Add 18 kg of deionized water to the emulsifying kettle, disperse and stir and add 0.4 kg of AEO-9, 0.4 kg of SVS, and 0.2 kg of EXG-202; disperse and stir for 5 minutes and then add 1.5 kg of methacrylic acid, 15.3 kg of butyl acrylate, 8.6 kg of isooctyl acrylate, 20.4 kg of methyl methacrylate, 0.5 kg of self-crosslinking monomer AT-208, and 0.8 kg of 3572F5 polysiloxane with vinyl and alkyl functional groups and 3.0 kg of tetrahydrofurfuryl acrylate were stirred and dispersed for 50 minutes to prepare a pre-emulsion.

[0026] c. Add 23.7 kg of deionized water, 0.1 kg of SVS, 0.1 kg of EXG-202, and 5 kg of Prime 4983-40R ethylene acrylic acid copolymer emulsion was heated to 80°C, 3.4 kg of the pre-emulsion prepared in step b and 1.6 kg of the ammonium persulfate solution prepared in step a were added, and after reacting for 30 minutes, 65.7 kg of the pre-emulsion prepared in step b was added dropwise, and 4.5 kg of the ammonium persulfate solution prepared in step a was added dropwise simultaneously, and the addition time was 4.0 hours, and the pre-emulsion and the initiator were dripped at the same time;

[0027] d. After the pre-emulsion and initiator are dripped, continue to react for 20 minutes, then raise the temperature to 85°C, keep the temperature for 90 minutes, then cool down to below 50°C, add 0.1 kg BYK024, 0.1 kg LXE fungicide, 0.1 kg OT-75, and 0.3 kg ammonia water, stir for 30 minutes, then evacuate, filter the material with gauze to obtain EAA hybrid acrylic emulsion.

[0028] Embodiment 2 formula:

[0029]

[0030] Production process:

[0031] a. Dissolve 0.1 kg of ammonium persulfate in 6 kg of deionized water to obtain 6.1 kg of ammonium sulfate solution for polymerization;

[0032] b. Add 18 kg of deionized water to the emulsifying kettle, disperse and stir and add 0.4 kg of AEO-9, 0.4 kg of SR-10, and 0.3 kg of EXG-202; disperse and stir for 5 minutes and then add 1.5 kg of methacrylic acid, 15.3 kg of butyl acrylate, 8.6 kg of isooctyl acrylate, 20.4 kg of methyl methacrylate, 0.6 kg of self-crosslinking monomer AT-208, and 0.9 kg of 3572F5 polysiloxane with vinyl and alkyl functional groups and 3.0 kg of tetrahydrofurfuryl acrylate were stirred and dispersed for 50 minutes to prepare a pre-emulsion.

[0033] c. Add 23.7 kg of deionized water, 0.1 kg of AEO-9, 0.1 kg of SR-10, 0.1 kg of EXG-202, 4 kg of Prime 4990R, 3 kg of Prime 4983-40R ethylene acrylic acid copolymer emulsion was heated to 80°C, 3.4 kg of the pre-emulsion prepared in step b and 1.6 kg of the ammonium persulfate solution prepared in step a were added, and after reacting for 30 minutes, 66 kg of the pre-emulsion prepared in step b was added dropwise, and 4.5 kg of the ammonium persulfate solution prepared in step a was added dropwise simultaneously, and the addition time was 4.0 hours, and the pre-emulsion and the initiator were dripped at the same time;

[0034] d. After the pre-emulsion and initiator are dripped, continue to react for 20 minutes, then raise the temperature to 85°C, keep the temperature for 90 minutes, then cool down to below 50°C, add 0.1 kg BYK024, 0.1 kg LXE fungicide, 0.1 kg OT-75, and 0.3 kg ammonia water, stir for 30 minutes, then evacuate, filter the material with gauze to obtain EAA hybrid acrylic emulsion.

[0035] Embodiment three formula:

[0036]

[0037] Production process:

[0038] a. Dissolve 0.1 kg of ammonium persulfate in 6 kg of deionized water to obtain 6.1 kg of ammonium sulfate solution for polymerization;

[0039] b. Add 18 kg of deionized water to the emulsifying kettle, disperse and stir and add 0.5 kg of AEO-9, 0.4 kg of SVS, and 0.3 kg of EXG-202; disperse and stir for 5 minutes and then add 1.5 kg of methacrylic acid, 15.3 kg of butyl acrylate, 8.6 kg of isooctyl acrylate, 20.4 kg of methyl methacrylate, 0.8 kg of self-crosslinking monomer AT-208, and 1 kg 3572F5 polysiloxane with vinyl and alkyl functional groups and 3.0 kg of tetrahydrofurfuryl acrylate were stirred and dispersed for 50 minutes to prepare a pre-emulsion.

[0040] c. Add 23.7 kg of deionized water, 0.1 kg of SVS, 0.1 kg of EXG-202, 2 kg of Prime 4990R, and 6 kg of Prime 4983-40R ethylene acrylic acid copolymer emulsion was heated to 80°C, 3.4 kg of the pre-emulsion prepared in step b and 1.6 kg of the ammonium persulfate solution prepared in step a were added, and after reacting for 30 minutes, 66.4 kg of the pre-emulsion prepared in step b was added dropwise, and 4.5 kg of the ammonium persulfate solution prepared in step a was added dropwise simultaneously, and the addition time was 4.0 hours, and the pre-emulsion and the initiator were dripped at the same time;

[0041] d. After the pre-emulsion and initiator are dripped, continue to react for 20 minutes, then raise the temperature to 85°C, keep the temperature for 90 minutes, then cool down to below 50°C, add 0.1 kg BYK024, 0.1 kg LXE fungicide, 0.1 kg OT-75, and 0.3 kg ammonia water, stir for 30 minutes, then evacuate, filter the material with gauze to obtain EAA hybrid acrylic emulsion.

[0042] Comparative Example (5 kg Prime 4983-40R in Example 1, 0.8 kg The amount of 3572F5 is replaced by butyl acrylate and methyl methacrylate) formula:

[0043]

[0044] a. Dissolve 0.1 kg of ammonium persulfate in 6 kg of deionized water to obtain 6.1 kg of ammonium sulfate solution for polymerization;

[0045] b. Add 18 kg of deionized water to the emulsifying kettle, add 0.4 kg of AEO-9, 0.4 kg of SVS, and 0.2 kg of EXG-202 with dispersion and stirring; after dispersion and stirring for 5 minutes, add 1.5 kg of methacrylic acid, 18.2 kg of butyl acrylate, 8.6 kg of isooctyl acrylate, 23.3 kg of methyl methacrylate, 0.5 kg of self-crosslinking monomer AT-208, and 3.0 kg of tetrahydrofurfuryl acrylate in sequence, and stir and disperse for 50 minutes to prepare a pre-emulsion.

[0046] c. Add 23.7 kg of deionized water, 0.1 kg of SVS, and 0.1 kg of EXG-202 to the reactor, heat to 80°C, add 3.4 kg of the pre-emulsion prepared in step b, and 1.6 kg of the ammonium persulfate solution prepared in step a. After reacting for 30 minutes, add 70.7 kg of the pre-emulsion in step b dropwise, and simultaneously add 4.5 kg of the ammonium persulfate solution prepared in step a dropwise, the addition time is 4.0 hours, and the pre-emulsion and the initiator are dripped at the same time;

[0047] d. After the pre-emulsion and initiator are dripped, continue to react for 20 minutes, then raise the temperature to 85°C, keep the temperature for 90 minutes, then cool down to below 50°C, add 0.1 kg BYK024, 0.1 kg LXE fungicide, 0.1 kg OT-75, and 0.3 kg ammonia water, stir for 30 minutes, then evacuate, filter the material with gauze to obtain EAA hybrid acrylic emulsion.

[0048] The physical and performance indicators of the products of Examples 1 to 3 and Comparative Examples were tested according to HJ / T220-2005, GB / T18583-2008 and HG / T2727-2010 standards. The standard test results are shown in the table.

[0049]

[0050]

[0051] In order to evaluate the performance of the EAA hybrid acrylic emulsion obtained in the above examples and the comparative examples as a binder in PVC water-based ink, the following experiment was conducted: 50 parts of the EAA hybrid acrylic emulsion (acrylic emulsion) obtained in each example (comparative example), 22 parts of vinyl chloride vinyl acetate emulsion, 8 parts of film-forming aid ethylene glycol ether, 4 parts of quick-drying agent, 3 parts of pigment, 0.2 parts of leveling agent, 0.2 parts of wetting agent, 0.3 parts of dispersant, 5 parts of titanium dioxide, 7.3 parts of deionized water. After a certain dispersion and grinding between the components, PVC gravure water-based ink was obtained, and the performance test was performed as shown in Table 2:

[0052] Table 2 Performance test of EAA hybrid acrylic composite emulsion binder for PVC gravure water-based ink

[0053]

[0054] It can be seen from the test data in Table 2 that the present invention utilizes the EAA hybrid acrylic composite emulsion to compound into a water-based ink for PVC, which has small fineness, bright color, and good pattern gloss and color rendering.

[0055] If the water-based gravure printing ink prepared by the composite emulsion obtained by using Examples 1-3 and Comparative Examples is printed on a PVC film and then thermally laminated, it is instantaneously laminated at 160-180°C, and then the performance test of the printed product is as shown in Table 3. In the plasticizer migration test, according to ISO 177:2016, the printed PVC film is prepared into a sample with a size of 60mm*60mm and a thickness of at least 0.5mm and weighed (the weight is recorded as m0), and the test sample is placed between two polyvinyl acetate sheets (containing no additives) that can absorb plasticizers and in close contact with them, with the axes aligned to form a sandwich structure, and placed in an environment of a constant temperature of 70°C±2°C under a pressure of 5kg, and the sample is taken out after 24h and its mass (m1) is measured.

[0056] Table 3 Performance test of water-based gravure printing ink prepared by composite emulsion

[0057]

[0058]

[0059] As can be seen from Table 3, the water-based ink prepared by the composite emulsions of Examples 1-3 of the present invention has good adhesion, corrosion resistance, and waterproof performance on the PVC substrate, and can effectively improve the durability of the printing ink. The present invention uses ethylene acrylic acid copolymer emulsion as the core. Since it is a copolymer of ethylene and acrylic acid, the water resistance of the EAA hybrid acrylic emulsion is very good. At the same time, a flexible chain ethylene structure is introduced into the polymer chain structure, which increases the flexibility of the EAA hybrid acrylic emulsion and solves the effect of the expansion and contraction of the connecting material in the ink prepared by the EAA hybrid acrylic emulsion on the adhesive layer as the temperature changes. At the same time, due to the low surface energy of ethylene, the wetting and spreading of the ink coating prepared by the EAA hybrid acrylic emulsion on the PVC film are increased. At the same time, due to the introduction of a large number of carboxyl groups and the generation of a large number of hydrogen bonds with other functional groups in the structure, the adhesion and water resistance of the ink coating prepared by the EAA hybrid acrylic emulsion are improved. At the same time, the crystallization of the polymer is suppressed, and the linearity of the main chain is destroyed, thereby improving the transparency and toughness of EAA. The organosiloxane with vinyl and alkyl functional groups is copolymerized with acrylates through free radicals on the organosilicone, and the properties of the organosilicone are introduced into the emulsion, which improves the product's slipperiness, wear resistance, waterproofness and antifouling properties, and prevents the film from sticking back after film formation. The pH of the organosiloxane decreases after the ammonia volatilizes, and the siloxane realizes interchain hydrolysis reaction to achieve spatial network crosslinking. Ether chains are introduced into the macromolecular chain to form a complex interaction force with the hydroxyl group in the structure or the lone electron pair in the PVC substrate, slowing down the plasticizer that migrates to the inner surface and continues to diffuse and volatilize outward.

[0060] Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived therefrom are still within the scope of protection of the present invention.

Claims

1. A modified hybrid acrylic emulsion for PVC water-based ink, characterized in that: The modified hybrid acrylic emulsion for PVC water-based ink is prepared from raw materials containing the following mass contents: Wherein, the functional monomer is an acrylate with a tetrahydrofuran ring, and the organosilicon monomer is a polyorganosiloxane with vinyl and alkyl functional groups.

2. The modified hybrid acrylic emulsion for PVC water-based ink according to claim 1, characterized in that: The initiator is ammonium persulfate.

3. The modified hybrid acrylic emulsion for PVC water-based ink according to claim 1, characterized in that: The EAA emulsion is an ethylene acrylic acid copolymer emulsion, the functional monomer is tetrahydrofurfuryl acrylate, the self-crosslinking monomer is the self-crosslinking monomer AT-208, and the silicone monomer is 3572F5 is a polysiloxane with vinyl and alkyl functional groups.

4. The modified hybrid acrylic emulsion for PVC water-based ink according to claim 1, characterized in that: The defoamer is BYK024, the preservative is Clariant NIPACIDE CI 15HS, and the wetting agent is Cytec OT-75.

5. A method for preparing the modified hybrid acrylic emulsion for PVC water-based ink according to claim 1, characterized in that: The steps include: a. Dissolve 0.1 parts by weight of an initiator in 6 parts by weight of deionized water to obtain a polymerization initiator solution; b. Add 18 parts by weight of deionized water to the emulsifying kettle, add 1.0-1.2 parts by weight of emulsifier after dispersion and stirring; after uniform dispersion and stirring, add 1.5 parts by weight of methacrylic acid, 15.3 parts by weight of butyl acrylate, 8.6 parts by weight of isooctyl acrylate, 20.4 parts by weight of methyl methacrylate, 0.5-0.8 parts by weight of self-crosslinking monomer, 0.8-1.0 parts by weight of organosilicon monomer, and 3.0 parts by weight of functional monomer, and stir and disperse for 50 minutes to prepare a pre-emulsion; c. Add 23.7 parts by weight of deionized water, 0.2-0.3 parts by weight of emulsifier, and 5-8 parts by weight of EAA emulsion to the reactor, heat to 80°C, add 3.4 parts by weight of the pre-emulsion prepared in step b, and 1.6 parts by weight of the initiator solution prepared in step a. After reacting for 30 minutes, add 65.7-66.4 parts by weight of the pre-emulsion of step b dropwise, and simultaneously add 4.5 parts by weight of the initiator solution prepared in step a dropwise, and the pre-emulsion and the initiator are dripped at the same time; d. After the pre-emulsion and initiator are dripped, continue to react for 20 minutes, then raise the temperature to 85°C, keep the temperature for 90 minutes, then cool to below 50°C, add 0.1 parts by weight of defoamer, 0.1 parts by weight of preservative, 0.1 parts by weight of wetting agent, and 0.3 parts by weight of ammonia water, stir for 30 minutes, then evacuate, filter the material with gauze to obtain EAA hybrid acrylic emulsion.

6. The preparation method according to claim 1, characterized in that: The initiator is ammonium persulfate.

7. The preparation method according to claim 1, characterized in that: The EAA emulsion is an ethylene acrylic acid copolymer emulsion, the functional monomer is tetrahydrofurfuryl acrylate, the self-crosslinking monomer is the self-crosslinking monomer AT-208, and the silicone monomer is 3572F5 is a polysiloxane with vinyl and alkyl functional groups.

8. The preparation method according to claim 1, characterized in that: The defoamer is BYK024, the preservative is Clariant NIPACIDE CI 15HS, and the wetting agent is Cytec OT-75.

9. Use of the modified hybrid acrylic emulsion for PVC water-based ink according to claim 1 in the preparation of PVC water-based ink, characterized in that: The PVC water-based ink uses a modified hybrid acrylic emulsion as a connecting material.

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