Preparation method of high-adhesion and quick-drying green water-based ink and application of high-adhesion and quick-drying green water-based ink in low-surface-energy base material

Abstract

The invention discloses a preparation method of high-adhesion and quick-drying green water-based ink and application of the high-adhesion and quick-drying green water-based ink in a low-surface-energy base material. The ink is prepared from the following raw materials in parts by weight: 6.16% of deionized water, 9.8% of resin liquid, 0.28% of a stabilizer, 0.7% of a wetting agent, 0.14% of a defoaming agent, 52.92% of environment-friendly polyacrylate emulsion and 30% of color paste. The high-adhesion and quick-drying green water-based ink takes alkyl glycoside as an emulsifier, is low in toxicity and good in biodegradability, is applied to low-surface-energy base materials such as PET (polyethylene terephthalate), PA (polyamide), PVC (polyvinyl chloride) and PE (polyethylene) films, the adhesion fastness reaches 97% or above, the adhesion fastness on the PET film reaches 100%, and the initial drying property of the ink reaches the drying speed of contrast ink. The renewable alkyl glycoside used for preparing the water-based ink does not threaten the environment and human health, and is more in line with the trend of modern science and technology development.

Description

Technical Field

[0001] The invention relates to the technical field of water-based inks, and in particular to a preparation method of a high-adhesion and quick-drying green water-based ink and application thereof in a low-surface-energy substrate. Background Art

[0002] Inks are divided into solvent-based inks and water-based inks. Unlike traditional solvent-based inks, water-based inks produce volatile organic compounds (VOCs) during preparation and use. Its volatile substances are water vapor, which is safe for the environment. The development of water-based inks has become an important choice for the ink industry to turn to environmentally friendly printing inks.

[0003] Water-based ink is mainly composed of resin binder, color pigment slurry, solvent and additives. It is an ink with water as the main solvent. Although water-based ink has very obvious advantages, it also has disadvantages such as slow drying and curing speed and poor adhesion to low-grade substrates due to the slow evaporation of water, which greatly inhibits its application in traditional industrial inks. Resin binder is the most important component that provides various properties of ink such as viscosity and adhesion. Therefore, the modification research of resin binder is of great significance to promote the industrial application of ink.

[0004] At present, the most studied resin binder in printing ink is water-based polyacrylate emulsion, which has the advantages of high stability, good gloss, good printing adaptability and good rheology. However, the surface tension of polyacrylate emulsion is large, while the polarity of non-polar substrates such as PA, PVC and PE is small, resulting in poor adhesion of acrylic-based water-based ink on non-polar substrates.

[0005] Therefore, the present invention mainly modifies the polyacrylate emulsion from the perspective of emulsifier, optimizes the resin binder, synthesizes the formula of water-based ink, and prepares a water-based ink with fast drying speed and good adhesion on low-surface substrates. Summary of the invention

[0006] Based on the technical problems existing in the background technology, the present invention proposes a preparation method of a high-adhesion and fast-drying green water-based ink and its application in a low-surface-energy substrate.

[0007] The problem to be solved by the present invention is that the polyoxyethylene octylphenol emulsifier OP-10 is bioaccumulative and persistent in the environment, which is harmful to human health; and the water-based ink has the problems of slow drying and curing speed and poor adhesion to low-grade substrates due to the slow evaporation of water, and cannot meet the requirements of high-speed printing process of polyethylene terephthalate (PET), polyamide (PA), polyvinyl chloride (PVC) and polyethylene (PE) films.

[0008] The present invention forms an environmentally friendly polyacrylate emulsion by selecting the type of emulsifier, so that the emulsion can form a film at room temperature and is transparent and has a blue fluorescence; and designs L9(3 4 ) The optimal synthesis conditions of emulsion polymerization were obtained by orthogonal experiment: the mass ratio of MMA to BA was 5:4, and the dosages of AA, APG / SDS and potassium persulfate KPS were 2%, 6% and 0.4% respectively; at the same time, the influence of the mass ratio of APG to SDS on the properties of the emulsion (such as glass transition temperature, solid content, viscosity, particle size, water absorption, gel rate, contact angle, stability, etc.) was studied, and the optimal ratio was determined to be 2:1; in addition, the obtained polyacrylate emulsion was further used as a binder for preparing water-based inks, and its printing performance was compared with the ink prepared by the OP-10 / SDS emulsification system. The results show that the initial drying properties of the two prepared water-based inks are basically the same, and they all show good adhesion on PET, PA, PVC and PE films, especially the adhesion on PE film reaches 100%.

[0009] The technical solution of the present invention is:

[0010] The formula of a high adhesion and fast drying green water-based ink is as follows:

[0011] Table 1: Water-based ink formula

[0012]

[0013] The raw materials of the self-made polyacrylate emulsion include kettle liquid, seed emulsion and initiator solution; in terms of percentage by total weight of the environmentally friendly polyacrylate emulsion raw materials, the kettle liquid is composed of 1.6%-2.4% of a surfactant, 0.2% of a buffer NaHCO3 and 36% of water, the seed emulsion is composed of 20% of a mixed monomer and 20% of an initiator solution, and the initiator solution is composed of 0.16% of potassium persulfate and 20% of water.

[0014] The surfactants are sodium dodecyl sulfate SDS, alkyl polyglycoside APG and polyoxyethylene octylphenol emulsifier OP-10, and the mass ratio of the nonionic surfactant to the anionic surfactant is 2:1.

[0015] The mixed monomers include a hard monomer methyl methacrylate, a soft monomer butyl acrylate and a functional monomer acrylic acid, and the mass ratio of the hard monomer to the soft monomer is 5:4.

[0016] The environmentally friendly polyacrylate emulsion of the invention has a solid content of 40%-45% and a theoretical glass transition temperature of 12.56°C.

[0017] The method for preparing the renewable alkyl polyglycoside emulsified polyacrylate emulsion specially used for green water-based ink is characterized by comprising the following steps:

[0018] 1) Preparation of environmentally friendly polyacrylate emulsion

[0019] (1) Weigh and measure the composite emulsifier, buffer and most of the deionized water according to the raw material formula, stir at 400 rpm, wait until they are completely dissolved, raise the temperature to 80° C., and continue stirring at 200 rpm;

[0020] (2) Slowly drop 1 / 5 of the mixed monomer into the reaction vessel according to the raw material formula and stir thoroughly to emulsify it. Then add 1 / 5 of the initiator aqueous solution to initiate seed emulsion polymerization;

[0021] (3) When the emulsion shows a blue phase, the remaining mixed monomers are evenly added, and the initiator aqueous solution is added from time to time; the mixed monomers are added in 2.5-3 hours, and the initiator aqueous solution is added slightly later than the monomers;

[0022] (4) After the addition is completed, the temperature is raised to 90°C and kept for 2 hours. Finally, after the temperature drops below 40°C, the pH value of the emulsion is adjusted to 8-9 with ammonia water, and the mixture is naturally cooled and filtered to obtain an environmentally friendly polyacrylate emulsion.

[0023] 2) Preparation of a high-adhesion and fast-drying green water-based ink

[0024] (1) Preparation of color paste: First, add dispersant and other additives into water for dispersion, and then add pigment for high-speed dispersion to make it evenly dispersed and set aside.

[0025] (2) Preparation of green water-based ink: Add water, resin liquid, stabilizer, wetting agent and other additives to the mixing tank in accordance with the formula, disperse at a low speed, and then add the ink vehicle (self-made polyacrylic acid emulsion). Then, add the color paste under high-speed stirring, and filter with a 200-mesh filter cloth to obtain the water-based ink.

[0026] Preferably, the stirring speed in step (1) is continued at 200 rpm; in step (3), the blue phase of the emulsion is maintained for 30 minutes, and the mixed monomer is controlled to be added in 2.5-3 hours, and the initiator aqueous solution is added slightly later than the monomer; and the pH value of the emulsion is adjusted to 8-9 in step (4) by using ammonia water.

[0027] Step 2) After adding water, resin liquid, stabilizer, wetting agent and other additives, the rotation speed of the low-speed dispersion is 30-100 r / min; the time of the low-speed dispersion is 5-10 min; the rotation speed of the high-speed stirring is 500-900 r / min; the time of the high-speed stirring is 10-20 min.

[0028] Preferably, the dispersant is block polymer dispersant 9012; the resin liquid is resin HD-397A; the stabilizer is NH3·H2O; the wetting agent is acetylene alcohol wetting agent LZ-104E; and the defoamer is water-based defoamer LZ-8835.

[0029] The ink prepared by the APG / SDS emulsion prepared by the present invention has adhesion of 97.9%, 99.7%, 99.7% and 100% on PET, PA, PVC and PE films respectively, which is equivalent to the adhesion of the contrasting color ink of 99.7%, 100%, 98.2% and 100%. The initial drying property of the ink prepared by the emulsifier APG / SDS is 24mm / 30s, which is similar to the initial drying property of the ink prepared by the emulsifier OP-10 / SDS of 23mm / 30s.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] 1. The present invention selects an emulsifier in a polyacrylate emulsion to form an environmentally friendly polyacrylate emulsion binder, so that the emulsion can form a transparent film at room temperature and have a blue fluorescence; and designs L9(3 4 ) The orthogonal experiment obtained the optimal synthesis conditions of emulsion polymerization: the mass ratio of MMA to BA was 5:4, and the amounts of AA, APG / SDS and KPS were 2%, 6% and 0.4%, respectively.

[0032] 2. Based on the optimal synthesis conditions, the dosage of the composite emulsifier was determined to be 6%. The effect of the mass ratio of nonionic to anionic emulsifiers (APG / SDS) on the properties of polyacrylate emulsions (including particle size, gel fraction, water absorption, viscosity, contact angle and stability) was evaluated, and the mass ratio of APG / SDS was determined to be 2:1.

[0033] 3. The polyacrylate emulsion emulsified with APG / SDS has superior solid content, viscosity, surface tension, gel fraction and particle size compared with the emulsion prepared with OP-10 / SDS, proving that the green renewable APG nonionic emulsifier is a reliable choice for emulsion polymerization.

[0034] 4. The adhesion of the water-based ink prepared with the renewable emulsifier on PET, PA, PVC and PE films is comparable to that of the contrasting color ink, and the adhesion on the PET film can reach 100%; the initial drying property of the water-based ink prepared with APG / SDS is similar to that of the water-based ink prepared with OP-10 / SDS, further proving that the water-based ink prepared with the environmentally friendly nonionic emulsifier APG instead of the traditional OP-10 and SDS has broad application prospects.

[0035] 5. The solvent of the product of the present invention is water, and the emulsifier used is a renewable and environmentally friendly emulsifier alkyl polyglycoside. Compared with the water-based ink prepared by traditional OP-10, it has lower toxicity and better biodegradability, will not pose a threat to the environment and human health, and is more in line with the trend of contemporary scientific and technological development. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 (a) MMA, (b) BA, (c) AA, emulsified by (d) APG / SDS and (e) OP-10 / SDS, respectively

[0037] FTIR spectrum of polyacrylate emulsion;

[0038] Figure 2 TGA graphs of latex films prepared with different emulsifier combinations;

[0039] Figure 3 DSC curves of latex films prepared with different emulsifier combinations;

[0040] Figure 4 (A) Printing effects of inks prepared from (a) APG / SDS and (b) OP-10 / SDS emulsions on PET, PA, PVC, and PE films. (B) Adhesion of the two inks on PET, PA, PVC, and PE films, respectively;

[0041] Figure 5 Initial drying properties of inks emulsified using different emulsifier combinations. DETAILED DESCRIPTION

[0042] Embodiment 1:

[0043] 1. Preparation of environmentally friendly polyacrylate emulsion

[0044] (1) Weigh 3.6 g APG, 1.2 g SDS, 0.4 g NaHCO3 and 72.88 g deionized water, stir at 400 rpm until all of them are dissolved, raise the temperature to 80 °C, and continue stirring at 200 rpm;

[0045] (2) Weigh 44.4 g MMA, 35.6 g BA, 1.6 g AA, 0.32 g KPS and 40 g water to obtain an initiator solution. Slowly drop 1 / 5 of the mixed monomers into the reaction container, stir thoroughly to emulsify, and control the dropwise addition to be completed within 15 min. Then add 1 / 5 of the initiator aqueous solution to initiate seed emulsion polymerization;

[0046] (3) When the emulsion shows a blue phase, keep it for 30 minutes, then evenly add the remaining mixed monomers, and add the initiator aqueous solution from time to time. The mixed monomers should be added within 2.5-3 hours, and the initiator aqueous solution should be added slightly later than the monomers.

[0047] (4) After the addition is completed, the temperature is raised to 90°C and kept for 2 hours. Finally, after the temperature drops below 40°C, the pH value of the emulsion is adjusted to 8-9 with ammonia water, and the mixture is naturally cooled and filtered to obtain an environmentally friendly polyacrylate emulsion.

[0048] 2. Preparation of a high-adhesion and fast-drying green water-based ink

[0049] (1) Preparation of color paste: First, add block polymer dispersant 9012 and other additives into water for dispersion, and then add phthalocyanine blue pigment for high-speed dispersion for 30 minutes to make it evenly dispersed and set aside.

[0050] (2) Preparation of green water-based ink: 3.08 g of water, 4.9 g of resin liquid, 0.14 g of stabilizer, 0.35 g of wetting agent, and 0.07 g of defoamer were added to the mixing tank in order according to the formula, dispersed at low speed for 5 min, and then 26.46 g of ink vehicle (self-made polyacrylic acid emulsion) was added. Then, the color paste was added at high speed, dispersed for 10 min, and filtered with a 200-mesh filter cloth to obtain the water-based ink.

[0051] Embodiment 2:

[0052] 1. Preparation of environmentally friendly polyacrylate emulsion

[0053] (1) Weigh 3.43 g APG, 1.37 g SDS, 0.4 g NaHCO3 and 72.88 g deionized water, stir at 400 rpm until all of them are dissolved, raise the temperature to 80 °C, and continue stirring at 200 rpm;

[0054] (2) Weigh 44.4 g MMA, 35.6 g BA, 1.6 g AA, 0.32 g KPS and 40 g water to obtain an initiator solution. Slowly drop 1 / 5 of the mixed monomers into the reaction container, stir thoroughly to emulsify, and control the dropwise addition to be completed within 15 min. Then add 1 / 5 of the initiator aqueous solution to initiate seed emulsion polymerization;

[0055] (3) When the emulsion shows a blue phase, keep it for 30 minutes, then evenly add the remaining mixed monomers, and add the initiator aqueous solution from time to time. The mixed monomers should be added within 2.5-3 hours, and the initiator aqueous solution should be added slightly later than the monomers.

[0056] (4) After the addition is completed, the temperature is raised to 90°C and kept for 2 hours. Finally, after the temperature drops below 40°C, the pH value of the emulsion is adjusted to 8-9 with ammonia water, and the mixture is naturally cooled and filtered to obtain an environmentally friendly polyacrylate emulsion.

[0057] 2. Preparation of a high-adhesion and fast-drying green water-based ink

[0058] (1) Preparation of color paste: First, add block polymer dispersant 9012 and other additives into water for dispersion, and then add phthalocyanine blue pigment for high-speed dispersion for 30 minutes to make it evenly dispersed and set aside.

[0059] (2) Preparation of green water-based ink: 3.08 g of water, 4.9 g of resin liquid, 0.14 g of stabilizer, 0.35 g of wetting agent, and 0.07 g of defoamer were added to the mixing tank in order according to the formula, dispersed at low speed for 5 min, and then 26.46 g of ink vehicle (self-made polyacrylic acid emulsion) was added. Then, the color paste was added at high speed, dispersed for 10 min, and filtered with a 200-mesh filter cloth to obtain the water-based ink.

[0060] Embodiment three:

[0061] 1. Preparation of environmentally friendly polyacrylate emulsion

[0062] (1) Weigh 3.20 g APG, 1.60 g SDS, 0.4 g NaHCO3 and 72.88 g deionized water, stir at 400 rpm until all of them are dissolved, raise the temperature to 80 °C, and continue stirring at 200 rpm;

[0063] (2) Weigh 44.4 g MMA, 35.6 g BA, 1.6 g AA, 0.32 g KPS and 40 g water to obtain an initiator solution. Slowly drop 1 / 5 of the mixed monomers into the reaction container, stir thoroughly to emulsify, and control the dropwise addition to be completed within 15 min. Then add 1 / 5 of the initiator aqueous solution to initiate seed emulsion polymerization;

[0064] (3) When the emulsion shows a blue phase, keep it for 30 minutes, then evenly add the remaining mixed monomers, and add the initiator aqueous solution from time to time. The mixed monomers should be added within 2.5-3 hours, and the initiator aqueous solution should be added slightly later than the monomers.

[0065] (4) After the addition is completed, the temperature is raised to 90°C and kept for 2 hours. Finally, after the temperature drops below 40°C, the pH value of the emulsion is adjusted to 8-9 with ammonia water, and the mixture is naturally cooled and filtered to obtain an environmentally friendly polyacrylate emulsion.

[0066] 2. Preparation of a high-adhesion and fast-drying green water-based ink

[0067] (1) Preparation of color paste: First, add block polymer dispersant 9012 and other additives into water for dispersion, and then add phthalocyanine blue pigment for high-speed dispersion for 30 minutes to make it evenly dispersed and set aside.

[0068] (2) Preparation of green water-based ink: 3.08 g of water, 4.9 g of resin liquid, 0.14 g of stabilizer, 0.35 g of wetting agent, and 0.07 g of defoamer were added to the mixing tank in order according to the formula, dispersed at low speed for 5 min, and then 26.46 g of ink vehicle (self-made polyacrylic acid emulsion) was added. Then, the color paste was added at high speed, dispersed for 10 min, and filtered with a 200-mesh filter cloth to obtain the water-based ink.

[0069] Embodiment 4:

[0070] 1. Preparation of environmentally friendly polyacrylate emulsion

[0071] (1) Weigh 2.40 g APG, 2.40 g SDS, 0.4 g NaHCO3 and 72.88 g deionized water, stir at 400 rpm until all of them are dissolved, raise the temperature to 80°C, and continue stirring at 200 rpm;

[0072] (2) Weigh 44.4 g MMA, 35.6 g BA, 1.6 g AA, 0.32 g KPS and 40 g water to obtain an initiator solution. Slowly drop 1 / 5 of the mixed monomers into the reaction container, stir thoroughly to emulsify, and control the dropwise addition to be completed within 15 min. Then add 1 / 5 of the initiator aqueous solution to initiate seed emulsion polymerization;

[0073] (3) When the emulsion shows a blue phase, keep it for 30 minutes, then evenly add the remaining mixed monomers, and add the initiator aqueous solution from time to time. The mixed monomers should be added within 2.5-3 hours, and the initiator aqueous solution should be added slightly later than the monomers.

[0074] (4) After the addition is completed, the temperature is raised to 90°C and kept for 2 hours. Finally, after the temperature drops below 40°C, the pH value of the emulsion is adjusted to 8-9 with ammonia water, and the mixture is naturally cooled and filtered to obtain an environmentally friendly polyacrylate emulsion.

[0075] 2. Preparation of a high-adhesion and fast-drying green water-based ink

[0076] (1) Preparation of color paste: First, add block polymer dispersant 9012 and other additives into water for dispersion, and then add phthalocyanine blue pigment for high-speed dispersion for 30 minutes to make it evenly dispersed and set aside.

[0077] (2) Preparation of green water-based ink: 3.08 g of water, 4.9 g of resin liquid, 0.14 g of stabilizer, 0.35 g of wetting agent, and 0.07 g of defoamer were added to the mixing tank in order according to the formula, dispersed at low speed for 5 min, and then 26.46 g of ink vehicle (self-made polyacrylic acid emulsion) was added. Then, the color paste was added at high speed, dispersed for 10 min, and filtered with a 200-mesh filter cloth to obtain the water-based ink.

[0078] Embodiment five:

[0079] 1. Preparation of environmentally friendly polyacrylate emulsion

[0080] (1) Weigh 1.60 g APG, 3.20 g SDS, 0.4 g NaHCO3 and 72.88 g deionized water, stir at 400 rpm until all of them are dissolved, raise the temperature to 80 °C, and continue stirring at 200 rpm;

[0081] (2) Weigh 44.4 g MMA, 35.6 g BA, 1.6 g AA, 0.32 g KPS and 40 g water to obtain an initiator solution. Slowly drop 1 / 5 of the mixed monomers into the reaction container, stir thoroughly to emulsify, and control the dropwise addition to be completed within 15 min. Then add 1 / 5 of the initiator aqueous solution to initiate seed emulsion polymerization;

[0082] (3) When the emulsion shows a blue phase, keep it for 30 minutes, then evenly add the remaining mixed monomers, and add the initiator aqueous solution from time to time. The mixed monomers should be added within 2.5-3 hours, and the initiator aqueous solution should be added slightly later than the monomers.

[0083] (4) After the addition is completed, the temperature is raised to 90°C and kept for 2 hours. Finally, after the temperature drops below 40°C, the pH value of the emulsion is adjusted to 8-9 with ammonia water, and the mixture is naturally cooled and filtered to obtain an environmentally friendly polyacrylate emulsion.

[0084] 2. Preparation of a high-adhesion and fast-drying green water-based ink

[0085] (1) Preparation of color paste: First, add block polymer dispersant 9012 and other additives into water for dispersion, and then add phthalocyanine blue pigment for high-speed dispersion for 30 minutes to make it evenly dispersed and set aside.

[0086] (2) Preparation of green water-based ink: 3.08 g of water, 4.9 g of resin liquid, 0.14 g of stabilizer, 0.35 g of wetting agent, and 0.07 g of defoamer were added to the mixing tank in order according to the formula, dispersed at low speed for 5 min, and then 26.46 g of ink vehicle (self-made polyacrylic acid emulsion) was added. Then, the color paste was added at high speed, dispersed for 10 min, and filtered with a 200-mesh filter cloth to obtain the water-based ink.

[0087] Comparative Example 1:

[0088] The difference from the third embodiment is that OP-10 is used instead of APG, and the rest is the same as the third embodiment.

[0089] Performance Test:

[0090] The performance tests were performed on the polyacrylate emulsions and water-based inks prepared in Examples 1-5 and Comparative Example 1, respectively, and the test methods were as follows:

[0091] A Fourier transform infrared spectrometer (Nicolet Avater 370, Thermo Fisher Scientific, USA) recorded the wavelengths of 600–4000 cm -1 Fourier transform infrared spectroscopy in the wavelength range. The glass transition temperature (Tg) of the latex film was determined by a Q100 differential scanning calorimeter (DSC) (TA Instruments, USA). The sample was heated at a rate of 10°C / min in the temperature range of -20-150°C under a nitrogen environment. The thermal degradation behavior of the polyacrylate emulsion was estimated by a thermogravimetric analyzer (TA Instruments, USA) in a nitrogen environment, with a heating rate of 10°C / min and a test temperature range of 20-800°C. In addition, the curve of weight loss versus temperature was recorded. The particle size and particle size distribution of the emulsion at 25°C were determined using a laser particle size analyzer (Zetasizer Nano S, Malvern, UK). The contact angle (CA) formed by a water droplet on the latex film was measured using a contact angle tester (Kruss, Dataphysics, Germany). The larger the contact angle, the better the hydrophobicity, and the smaller the contact angle, the worse the hydrophobicity. The surface tension of the emulsion was measured at a test temperature of 25°C using a BP100 bubble pressure tensiometer (Kruss, Dataphysics, Germany), and the results of three measurements were averaged. When measuring the viscosity, a rotational viscometer (DSV+, Brookfield AMETEK, USA) was used, with a rotor of 62# and a rotation speed of 50r / min. The average of three measurements at 25°C was taken. The solid content of the emulsion was analyzed at 110°C using a CSY-G5 solid content tester (Shenfen Instrument Co., Ltd., China). The mechanical stability of the emulsion was tested by centrifugation at 4000r / min for 30min. The calcium ion stability of the emulsion was evaluated using 8mL of emulsion and 2mL of calcium chloride solution (concentration of 0.5wt%). The water absorption of the latex film was determined as follows: First, dry in an oven at 50°C for 24h and then cool to room temperature. Then, a uniform latex film with a size of 1.5cm×1.5cm and a thickness of 2mm was weighed. The resulting weight is marked as m1. Next, soak the sample in water for 24 hours, take it out, quickly wipe off the surface water with filter paper, and then weigh it. The weight obtained again is marked as m2. The water absorption rate of the latex film is calculated by the formula: The gel fraction of the emulsion is calculated as follows: Where m1 and m2 correspond to the mass of the gel g and the total mass of the added monomer g, respectively. The adhesion test uses a gravure ink printing proofer (AYDJ-B1, Shanghai Modern Environmental Engineering Technology Co., Ltd., China) to first apply the ink on PET, PA, PVC, and PE substrates, and then quickly blow dry with a hair dryer. The dried ink sample is fixed on a millimeter grid paper, and a 3M tape (width 1.9 cm) is tightly attached to the ink film, and then quickly pulled apart at an angle of 180°. After drying and curing, the adhesion is measured by the grid method, and the calculation is as follows: Wherein, S0 and S represent the total number of grids covered by the tape and the total number of grids stuck by the tape, respectively. According to the Chinese national standard GB / T13217.5-2008, the initial dryness is measured by the length (mm) of the ink film scraped off at 30 seconds.

[0092] The emulsion properties of the embodiments and comparative examples were tested according to the above test methods. The test results are shown in Table 2. The results show that, as can be seen from Table 2, the emulsion prepared by the present invention has excellent solid content, viscosity, surface tension, gel fraction and particle size.

[0093] Table 2 Emulsion performance test results of examples and comparative examples

[0094]

[0095] Note: ■ indicates that the emulsion is translucent with a blue glow, and √ indicates that the emulsion is stable.

[0096] The FTIR spectra of the emulsions prepared in Example 3 and Comparative Example 1 are as follows: Figure 1 As shown in Figure 2, the absorption peaks of the two polyacrylate emulsions emulsified by APG / SDS (curve d) and OP-10 / SDS (curve e) are similar to the monomer spectrum (curve ac). -1 The peak at 1732 cm belongs to the characteristic stretching of C–H (–CH3 and –CH2). -1 The peak at 1238cm belongs to the stretching vibration of C=O. -1 and 1144cm -1 The absorption band at 1600-1700cm is the stretching vibration peak of COC. -1 The stretching vibration in the range of 3000~3100cm -1 The characteristic absorption peak =C–H in the range disappeared, indicating that there was no C=C in the copolymer; all monomers participated in the reaction, and the polyacrylate emulsion was successfully synthesized. The infrared spectra of the products of other embodiments are similar to this example and are not provided one by one.

[0097] The TGA graphs of the latex films prepared in Example 3 and Comparative Example 1 are as follows: Figure 2The thermal performance data of the latex film under different emulsifier combinations are shown in Table 3. It can be seen that compared with the latex film prepared by OP-10 / SDS, the initial decomposition temperature of the latex film prepared by APG / SDS is increased from 373.28°C to 378.59°C, the total weight loss mass fraction is reduced from 98.42% to 97.58%, and the residual mass fraction is increased from 1.58% to 2.42%. The results show that the emulsion prepared by the present invention has good thermal stability.

[0098] Table 3 Effect of Examples and Comparative Examples on Thermal Properties of Latex Films

[0099]

[0100] The DSC curves of the latex films prepared in Example 3 and Comparative Example 1 are as follows: Figure 3 As shown, the glass transition temperature (Tg) of the latex film synthesized by APG / SDS is 26.36°C, and the glass transition temperature (Tg) of the latex film synthesized by OP-10 / SDS is 26.38°C, which are different from the Tg of BA homopolymer (-54°C) and MMA homopolymer (105°C), confirming that all monomers participated in the reaction and the polyacrylate emulsion was successfully prepared.

[0101] The printing effect and adhesion test results of the ink prepared in Example 3 and Comparative Example 1 are as follows: Figure 4 As shown, the printing effects of the ink prepared with APG / SDS emulsion (Aa) and the ink prepared with OP-10 / SDS emulsion (Ab) on PET, PA, PVC and PE films are similar, especially the adhesion on PE film reaches 100%. Figure 4 (B) shows the adhesion test results of the two inks on the above four plastic substrates. The adhesion of the ink prepared with APG / SDS emulsion on the above four plastic substrates is 97.9%, 99.7%, 99.7%, and 100%, respectively, which is comparable to the adhesion of the comparative color ink of 99.7%, 100%, 98.2%, and 100%, indicating that it has good adhesion on the above substrates.

[0102] The initial drying properties of the ink prepared by Example 3 and Comparative Example 1 are as follows: Figure 5 As shown, the initial drying degree of the ink prepared by emulsifier APG / SDS is 24 mm / 30 s, which is similar to the initial drying degree of the ink prepared by emulsifier OP-10 / SDS (23 mm / 30 s), and has better drying performance.

Claims

1. A method for preparing a green water-based ink with high adhesion and quick drying and its application in a substrate with low surface energy. It is characterized in that: The binder of the water-based ink is a polyacrylate emulsion emulsified with renewable alkyl glycoside; the formula of the water-based ink is:

2. The method for preparing a high-adhesion and fast-drying green water-based ink according to claim 1, characterized in that The following steps are involved: (1) Preparation of color paste: First, add block polymer dispersant 9012 and other additives into water for dispersion, and then add phthalocyanine blue pigment for high-speed dispersion for 30 minutes to make it evenly dispersed and set aside. (2) Preparation of water-based ink: Add water, resin liquid, stabilizer, wetting agent, defoamer and other additives to the mixing tank in order according to the formula, disperse at a low speed for 5 minutes, and then add the ink vehicle (environmentally friendly polyacrylic acid emulsion). Then add the color paste under high-speed stirring, disperse for 10 minutes, and filter with a 200-mesh filter cloth to obtain the water-based ink.

3. The renewable alkyl glycoside emulsified polyacrylate emulsion according to claim 1, characterized in that: The preparation method of the environmentally friendly polyacrylate emulsion comprises: (1) Weigh the emulsifier, buffer and most of the deionized water, stir at 400 rpm until they are completely dissolved, raise the temperature to 80° C., and continue stirring; (2) Weigh MMA, BA and AA according to the formula; KPS and part of deionized water to obtain an initiator solution. Slowly drop 1 / 5 of the mixed monomers into the reaction container, stir thoroughly to emulsify, and control the dropwise addition to be completed within 15 minutes. Then add 1 / 5 of the initiator aqueous solution to initiate seed emulsion polymerization; (3) When the emulsion shows a blue phase, keep it for 30 minutes, then evenly add the remaining mixed monomers, and add the initiator aqueous solution from time to time. The mixed monomers should be added within 2.5-3 hours, and the initiator aqueous solution should be added slightly later than the monomers. (4) After the addition is completed, the temperature is raised to 90°C and kept for 2 hours. Finally, after the temperature drops below 40°C, the pH value of the emulsion is adjusted to 8-9 with ammonia water, and the mixture is naturally cooled and filtered to obtain an environmentally friendly polyacrylate emulsion.

4. The environmentally friendly polyacrylate emulsion according to claim 3, characterized in that: The nonionic emulsifier is renewable alkyl polyglycoside APG, and the mass ratio of APG to SDS is 2:

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5. The environmentally friendly polyacrylate emulsion according to claim 3, characterized in that: The best formula for emulsion synthesis is: the mass ratio of MMA to BA is 5:4, and the amounts of AA, APG / SDS and KPS are 2%, 6% and 0.4% respectively.

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