CN102925002B - Preparation method of white paint ink used for textile inkjet printing - Google Patents

Abstract

The invention discloses a preparation method of white paint ink for ink-jet printing of textiles, which belongs to the fields of fine chemical industry and material science and technology. The inkjet printing white paint ink of the present invention is prepared by mixing and stirring the oxide/polymer nanocomposite particle dispersion with a water-soluble co-solvent, a surfactant and deionized water, and filtering it as a white colorant. The white paint ink has good dispersion stability and storage stability, and the white pigment ink preparation method of the present invention has the characteristics of small equipment investment, simple production process, stable product quality and suitable for large-scale production.

Description

A kind of preparation method of white paint ink for textile inkjet printing

technical field

The invention belongs to the technical fields of fine chemical industry and material science, and in particular relates to a preparation method of white paint ink for ink-jet printing of textiles.

technical background

Inkjet printing is a new technology for textile printing and dyeing that integrates computer, information, new materials, fine chemicals and other multidisciplinary fields. It has the advantages of high printing precision, flexible batches, and no waste of dyes and auxiliaries. However, in the past, textile inkjet printing was mainly aimed at white fabrics. In recent years, with the increase in the printing volume of non-white fabrics, the demand for white pigment inks has also increased, and it has become one of the important colors in textile inkjet printing.

Silicon oxide and titanium oxide are the main colorants of white pigment inks for textile inkjet printing, however, due to the high specificity of these pigments, particle sedimentation and clogging of nozzles are prone to occur during long-term storage in low-viscosity inkjet printing ink media , resulting in the impossibility of inkjet printing. Although reducing the particle size of the pigment or increasing the viscosity of the ink can improve the stability of the ink to a certain extent, there is still a big gap from the actual requirements of the inkjet ink. Therefore, white paint inks currently on the market still mainly rely on multinational companies such as DuPont and Epson. Data retrieval found that Chinese patents CN101652437A and CN201210180490.9 respectively disclose the preparation methods of solvent-based white paint inks, which are prepared by grinding white pigments with the assistance of dispersants. U.S. US2010/0190922A1 discloses the method for preparing stable inkjet printing ink by adopting silicon oxide, dispersant and emulsion particles as main components; Method; US2009/0087627A1 and US2006/0155005A1 respectively disclose the method of using white paint, dispersant, photoinitiator, and polymerizable monomer to form UV-curable paint ink.

Although there are many preparation methods for white paint ink, however, summarizing related patents, it is found that the pigments used in these methods are still prepared by high-speed dispersion of silicon oxide or titanium oxide with the assistance of a special structural dispersant. There are few reports about the composition of the white paint ink for inkjet printing of textiles using the polymer-coated oxide nanocomposite particles as the colorant disclosed in this patent.

Contents of the invention

The purpose of the present invention is to provide a preparation method of white paint ink for inkjet printing of textiles. The specific method is to use a silane coupling agent to graft and modify the nano-oxide, and then utilize the polymerizable group of the silane coupling agent and Copolymerize other monomers, introduce a polymer with dual functions of dispersion and stabilization on the surface of silicon oxide, prepare polymer-coated oxide nanocomposite particles, and use this as a colorant, add a variety of water-soluble co-solvents and related additives, After stirring evenly, filter to prepare white pigment ink for inkjet printing of textiles.

The technical scheme of the present invention: a preparation method of white paint ink for inkjet printing of textiles, adding polymer-coated oxide nanocomposite particle dispersion, water-soluble co-solvent and surfactant into deionized water in a certain proportion, After stirring and mixing evenly, adjust the pH of the ink, and finally filter through a 500nm filter membrane to prepare white paint ink. The specific preparation process is to add a mass fraction of 1-5% surfactant to 15-80% mass fraction of deionized water, and then add a mass fraction of 10-30% polymer-coated oxide nanocomposite particle dispersion and mass fraction 10-50% water-soluble co-solvent, 0.05-0.5% antibacterial agent, stir with a stirrer at a speed of 500-1000 rpm for 20-50 minutes, adjust the pH to 7-9, and then filter with a 500nm filter membrane, The white paint ink is prepared; experimental tests show that the viscosity of the prepared ink is 5-8cP, the surface tension is 28-35mN/m, and the particle size is 50-150nm.

The preparation method of the polymer-coated oxide nanocomposite particle dispersion according to the present invention: the mass fraction of 5-30% nano-oxide is dispersed in a mixed solvent composed of 40-90% ethanol and water ( The mass ratio of ethanol to water is 1:1), adding a silane coupling agent with a mass fraction of 1-6%, adjusting the pH to 8-9 with ammonia water, reacting at 20-60°C for 2-3 hours, adding The comonomer with a mass fraction of 5-20% and the emulsifier with a mass fraction of 0.5-2% are dispersed at a high speed to the nanometer level, transferred to a water bath, and nitrogen is blown for 30 minutes, and the stirring speed is 250-600 rpm The temperature was raised to 60-80° C. within minutes, and the initiator was added dropwise with a mass fraction of 0.5-3% to the monomer. After reacting for 2-8 hours, centrifuge at high speed to obtain polymer-coated oxide nanocomposite particles. Dissolve the dispersant with a mass fraction of 1-10% in 70-90% deionized water, adjust the pH to 7-9, add 10-20% polymer-coated oxide nanocomposite particles, and use ultrasonic waves for dispersion treatment 10-40 minute. The selected dispersant is a polymer of acrylic monomer with a molecular weight of 3000-10000. The oxide used for preparing the white paint ink for ink-jet printing of textiles is nano-silicon oxide or nano-titanium oxide. The comonomer is one or both of acrylic acid, methacrylic acid, acrylamide, itaconic acid, sodium p-styrene sulfonate; the selected initiator is ammonium persulfate, potassium persulfate, persulfuric acid One of sodium, azobisisobutylamidine hydrochloride, and azobisisopropylimidazoline hydrochloride; the selected emulsifiers are sodium lauryl sulfate and sodium dodecylbenzenesulfonate , sodium dodecylsulfonate, sodium alkylnaphthalenesulfonate or one or both.

The selected water-soluble co-solvents are ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, Diethylene glycol, triethylene glycol, tetraethylene glycol, polyvinyl alcohol 200, polyvinyl alcohol 400, polyethylene glycol 600, glycerol, triethanolamine, pentaerythritol, 2-pyrrolidone, N- Two or more of methyl-2-pyrrolidone.

The selected surfactant is anionic, nonionic or a combination of the two; anionic surfactants are sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, potassium oleate, alkylnaphthalenesulfonic acid One of sodium and sodium rosinate; the non-ionic such as polyoxyethylene alkylphenol condensate: OP-7, OP-10 or OP-15; polyoxyethylene fatty alcohol condensate: Pingping plus O- 10. Pingpingjia O-20, Pingpingjia O-25 or Pingpingjia A-20; polyoxyethylene polyol ether fatty acid esters: such as Tween40, Tween60, Tween65, Tween80; polyoxyethylene esters of fatty acids: such as SG- 10. SE-10, OE-15.

The pH regulator is one of sodium hydroxide, sodium carbonate, ammonia, and triethanolamine.

The antibacterial agent is one of vanillin or ethyl vanillin compounds, anilides, imidazoles, thiazoles, isothiazolone derivatives, quaternary ammonium salts, diquats, and phenols.

Beneficial effects of the present invention: the average particle size of the white paint ink prepared by the present invention is less than 180nm, and the polymer-coated oxide nanocomposite particles are used as the colorant, which has the advantages of good dispersion stability and high hiding power. The ink can be stored for a long time and can be directly used for inkjet printing of textiles.

Detailed ways

Below by implementing examples, the outstanding advantages and notable features of the present invention are further set forth, but the present invention is by no means limited to the implementing examples.

Example 1

Preparation of nano-silica composite particles: Weigh 15g of nano-silica, 29.5g of water, and 29.5g of ethanol, mix well, add 5g of KH-570, adjust the pH to 8-9 with ammonia solution, and react at 40°C After 2 hours, 10 g of sodium p-styrene sulfonate and 1 g of sodium dodecyl sulfate were added, and after thorough stirring, the solution was transferred to an ultrasonic pulverizer with a power of 1100 W for 15 minutes of sonication. Then it was transferred to a water bath, heated to 65° C. at a stirring speed of 500 rpm after passing nitrogen gas for 30 minutes, and 10 g of ammonium persulfate solution with a mass fraction of 10% was added dropwise and reacted for 4 hours. The silica/polystyrene sodium sulfonate nanocomposite particles can be obtained by high-speed centrifugation and precipitation.

Take 2g of maleic anhydride-methyl methacrylate copolymer (Mn=8000, maleic anhydride:methyl methacrylate=1:1), add 0.20g of sodium hydroxide, 85.8g of deionized water, and stir until completely dissolved , and then add 12 g of silica/sodium polystyrene sulfonate nanocomposite particles, and use ultrasonic dispersion for 30 minutes to obtain a dispersion of silica/sodium polystyrene sulfonate nanocomposite particles.

Get sodium lauryl sulfate 1.2g and OP-10 emulsifier 1g and dissolve in 41.7g deionized water, add nanocomposite particle dispersion 30g, 1,6-hexanediol 10g, tetraethylene glycol 12g successively, 4 g of n-butanol, 0.1 g of aniline antibacterial agent were stirred with a stirrer at 500 r/min for 30 min, then the pH value was adjusted to 9 with sodium hydroxide solution, and finally the water-based white pigment ink was obtained by filtering with a 500 nm microporous membrane. The indexes of physical ink are as follows: surface tension σ=34.6mN/m, viscosity η=7.67cP, Z-average particle diameter d=154.2nm.

Example 2

Nano-composite particle dispersion is prepared with example 1, gets sodium cetylbenzene sulfonate 1.5g, 0.5g Tween 80 is dissolved in 42.7g deionized water, adds nano-silicon composite particle dispersion 25g, n-propanol 10g, one 10g of diethylene glycol, 10g of pentaerythritol and 0.3g of thiazole antibacterial agent, stirred with a stirrer at 1000r/min for 50min, then adjusted the pH value to 8 with sodium hydroxide, and finally filtered with a 500nm microporous membrane to obtain water-based white pigment ink , The ink index is as follows: surface tension σ=31.2mN/m, viscosity η=8.91cP, Z-average particle size d=158.6nm.

Example 3

Preparation of nano-titanium dioxide composite particles: Weigh 30g of nano-titanium dioxide, 11g of water, and 11g of ethanol. After mixing evenly, add 6g of KH-570, adjust the pH to 8-9 with ammonia solution, and add 20g of methacrylic acid and 2g of Sodium dodecyl sulfonate, after fully stirring, transfer it to a high-speed emulsifier for emulsification for 15 minutes. Transfer to a water bath, blow nitrogen for 30 minutes, then raise the temperature to 75° C. at a stirring speed of 250 rpm, start to add 20 g of 10% sodium persulfate solution dropwise, and react for 5 hours. The titanium dioxide/polymethacrylic acid nanocomposite particles can be obtained by high-speed centrifugation and precipitation.

Take 3g of styrene-butyl acrylate copolymer (Mn=5000, styrene: butyl acrylate=3:1), add 6g of 20% ammonia water, 71g of deionized water, stir until completely dissolved, then add 20g of nanocomposite particles, The titanium dioxide/polymethacrylic acid nanocomposite particle dispersion was prepared by ultrasonic dispersion for 10 minutes.

Take Pingpingjia O-251g and dissolve it in 48.5g deionized water, add 20g of nano-titanium dioxide composite particle dispersion, 5g of isopropanol, 20010g of polyvinyl alcohol, 15g of 1,4-butanediol and 0.5g of isothiazolone, and use a mixer Stir at 700 rpm for 40 minutes, then adjust the pH value to 8 with 20% ammonia water, and finally filter with a 500nm microporous membrane to obtain water-based white pigment ink. The physical properties are as follows: surface tension σ=28.4mN/m, viscosity η= 6.15cP, Z-average particle size d=162.2nm.

Example 4

Nano-composite particle dispersion is prepared with example 2, gets SE-10 1g and is dissolved in 45.7g deionized water, adds nano-silicon composite particle dispersion 25g, isopropanol 6g, diethylene glycol 10g, 2-pyrrolidone 12g and Stir 0.3g of double quail antibacterial agent with a mixer at 1000r/min for 30min, then adjust the pH value to 9 with triethanolamine, and finally filter with a 500nm microporous membrane to obtain water-based white pigment ink. The physical properties are as follows: surface tension σ=30.5mN /m, viscosity η=6.97cP, Z-average particle diameter d=152.4nm.

Claims (3)

1. the preparation method of a textile inkjet printing use whitewash ink, it is characterized in that being become by following components in mass portion array: 10～30 parts of polymer overmold oxidate nano composite particle dispersions, 10～50 parts of water-soluble cosolvent, 1～5 part, tensio-active agent, 0.05～0.5 part of antiseptic-germicide, add 100 parts of deionized water ad pond oms, in deionized water, add successively polymer overmold oxidate nano composite particle dispersions by formula, water-soluble cosolvent, tensio-active agent and antiseptic-germicide, after being uniformly mixed, regulating ink pH is 7～9, finally use the membrane filtration of 500nm, prepare whitewash ink, here polymer overmold oxidate nano composite particle dispersions is prepared as follows: be that to be distributed to massfraction be that 40～90% mass ratioes are in the mixed solvent of 1: 1 second alcohol and water for 5～30% nano silicon oxides or nano-titanium oxide by massfraction, then adding massfraction is 1～6% silane coupling agent KH570, with ammoniacal liquor adjusting pH to 8～9, under 20-60 DEG C of condition, react 2-3 hour, adding massfraction is the emulsifying agent that 5～20% comonomer and massfraction are 0.5-2%, high speed dispersion is to nano level, transfer is put in water-bath, logical nitrogen 30 minutes, low whipping speed is to be warming up to 60-80 DEG C under 250-600 rev/min, start to drip the initiator that is 0.5～5% to monomer mass mark, react high speed centrifugation after 2-8 hour, obtain polymer overmold oxidate nano composite particles, be that 1～10% molecular weight is dissolved in 70～90% deionized waters at 3000～10000 acrylic polymerss by massfraction, regulating pH is 7～9, add 10～20% polymer overmold oxidate nano composite particless, carry out dispersion treatment 10～40 minutes by ultrasonic wave, here the comonomer adopting is one or both in vinylformic acid, methacrylic acid, acrylamide, methylene-succinic acid, sodium p styrene sulfonate, initiator is the one in ammonium persulphate, Potassium Persulphate, Sodium Persulfate, azo diisobutyl amidine hydrochloride, azo di-isopropyl imidazoline salt hydrochlorate, emulsifying agent is one or both in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, sodium alkyl naphthalene sulfonate.

2. preparation method as claimed in claim 1, it is characterized in that water-soluble cosolvent used is ethanol, n-propyl alcohol, Virahol, propyl carbinol, ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 1, two or more in 6-hexylene glycol, glycol ether, Triethylene glycol, tetraethylene-glycol, polyvinyl alcohol 200, polyvinyl alcohol 400, Polyethylene Glycol-600, glycerol, trolamine, tetramethylolmethane, 2-Pyrrolidone, METHYLPYRROLIDONE.

3. preparation method as claimed in claim 1, is characterized in that tensio-active agent used is anionic, non-ionic type or both are composite; Described anionic is sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, potassium oleate, sodium alkyl naphthalene sulfonate, sodium abietate; Described non-ionic type is polyoxyethylene alkylphenol condenses: OP-7, OP-10 or OP-15, polyoxyethylene fatty alcohol condenses: peregal 0-10, paregal O-20, peregal O-25 or peregal A-20; Polyoxyethylene polyols ether fatty acid ester: Tween40, Tween60, Tween65, Tween80; The polyoxyethylene ester class of lipid acid: SG-10, SE-10, OE-1.