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

Preparation method of white paint ink used for textile inkjet printing Download PDF

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Publication number
CN102925002B
CN102925002B CN201210486821.1A CN201210486821A CN102925002B CN 102925002 B CN102925002 B CN 102925002B CN 201210486821 A CN201210486821 A CN 201210486821A CN 102925002 B CN102925002 B CN 102925002B
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sodium
preparation
ink
water
massfraction
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CN102925002A (en
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付少海
白福顺
关玉
龙晓霞
王春霞
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Kunshan Yijia Ju Textile Co ltd
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Jiangnan University
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Abstract

The invention relates to a preparation method of white paint ink used for textile inkjet printing and belongs to the technical fields of fine chemical industry and material science. The white paint ink used for inkjet printing provided by the invention is formed by the steps of mixing oxide/polymer nano composite particle dispersoid serving as a white colouring agent with a water-soluble cosolvent, a surface active agent and deionized water, stirring and filtering. The white paint ink prepared by adopting the preparation method provided by the invention has good dispersion stability and storage stability, and the preparation method of white pigment ink provided by the invention has the characteristics of low equipment investment, simple production process, stable product quality and the like and is suitable for mass production.

Description

The preparation method of whitewash ink for a kind of textile inkjet printing
Technical field
The invention belongs to fine chemistry industry and materials science field, be specifically related to the preparation method of a kind of textile inkjet printing whitewash ink.
Technical background
Ink-jet printed is the fabrics printing and dyeing New Machining Technology that integrates the multidisciplinary fields such as computer, information, novel material and fine chemistry industry, have stamp fineness high, in batches flexibly, without advantages such as dyestuff and auxiliary agent wastes.But textile inkjet printing was mainly for white fabrics in the past, along with the increase of non-white fabrics stamp amount, the demand of whitewash ink is also increasing in recent years, becomes one of color important in textile inkjet printing.
Silicon oxide and titanium oxide are the main tinting materials of textile inkjet printing whitewash ink, but, because the ratio of these pigment is great, while depositing for a long time in low viscosity ink-jet printing ink medium, easily there is particles settling and stop up the phenomenons such as shower nozzle, causing ink-jet printed cannot carrying out.Although reduce the particle diameter of pigment, or increase the viscosity of ink and can improve to a certain extent the stability of ink, but still have very large gap apart from ink for ink-jet print actual requirement.Therefore, whitewash ink still mainly depends on the multinational enterprise such as Du Pont, Epson in the market.Data-searching finds that Chinese patent CN101652437A and CN201210180490.9 disclose respectively the preparation method of solvent-borne type whitewash ink, its way be by white pigment under dispersion agent is assisted, form by attrition process.U.S. US2010/0190922A1 discloses and adopted silicon oxide, dispersion agent and emulsion particle is the method that ink-jet printing ink is stablized in main ingredient preparation; US2010/0039463A1 discloses the method for improving whitewash stability of ink by the method for titanium oxide content in raising ink; US2009/0087627A1 and US2006/0155005A1 disclose respectively the method with whitewash, dispersion agent and light trigger, polymerisable monomer composition ultraviolet-curing paint ink.
Although preparation method is a lot of about whitewash ink, but, to sum up relevant patent and find, the pigment adopting in these methods remains silicon oxide or titanium oxide under the assistance of special construction dispersion agent, is prepared from by high speed dispersion.Use the report of whitewash ink less about the disclosed textile inkjet printing that forms taking polymer overmold oxidate nano composite particles as tinting material of this patent.
Summary of the invention
The object of the invention is to provide the preparation method of a kind of textile inkjet printing whitewash ink, specific practice is first to adopt silane coupling agent to carry out graft modification to nano-oxide, then utilize polymerizable groups and other monomer copolymerization of silane coupling agent, introduce the polymkeric substance with dispersion and stable dual function at silicon oxide surface, preparation polymer overmold oxidate nano composite particles, and as tinting material, add multiple water-soluble cosolvent and relevant auxiliary agent, after stirring, filter, prepare textile inkjet printing whitewash ink.
Technical scheme of the present invention: the preparation method of whitewash ink for a kind of textile inkjet printing, polymer overmold oxidate nano composite particle dispersions, water-soluble cosolvent and tensio-active agent are joined in deionized water by a certain percentage, after being uniformly mixed, regulate the pH of ink, finally use the membrane filtration of 500nm, prepare whitewash ink.Concrete preparation process is that the tensio-active agent of massfraction 1~5% is added to massfraction is in 15~80% deionized waters, then adding massfraction 10~30% polymer overmold oxidate nano composite particle dispersions and massfraction is 10~50% water-soluble cosolvent, 0.05~0.5% antiseptic-germicide, stir 20~50 minutes with the speed of 500~1000 revs/min with stirrer, adjusting pH is 7-9, then use the membrane filtration of 500nm, prepare whitewash ink; Experiment test shows the viscosity 5~8cP of prepared ink, surface tension 28~35mN/m, particle diameter 50-150nm.
The preparation method of polymer overmold oxidate nano composite particle dispersions of the present invention: massfraction is distributed in the mixed solvent that massfraction forms for 40~90% second alcohol and waters (mass ratio of second alcohol and water is 1: 1) for 5~30% nano-oxides, adding massfraction is 1~6% silane coupling agent, with ammoniacal liquor adjusting pH to 8~9, under 20-60 DEG C of condition, react after 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 is after 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 0.5~3% to monomer mass mark.React high speed centrifugation after 2-8 hour, can obtain polymer overmold oxidate nano composite particles.Be that 1~10% dispersion agent is dissolved in 70~90% deionized waters by massfraction, regulating pH is 7~9, adds 10~20% polymer overmold oxidate nano composite particless, uses ultrasonic wave to carry out dispersion treatment 10~40 minutes.Selected dispersion agent is the polymkeric substance of molecular weight at 3000~10000 acrylic monomers.The described oxide compound of preparing textile inkjet printing whitewash ink is nano silicon oxide or nano-titanium oxide.Described comonomer is one or both in vinylformic acid, methacrylic acid, acrylamide, methylene-succinic acid, sodium p styrene sulfonate; Selected initiator is the one in ammonium persulphate, Potassium Persulphate, Sodium Persulfate, azo diisobutyl amidine hydrochloride, azo di-isopropyl imidazoline salt hydrochlorate; Selected emulsifying agent is one or both in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, sodium alkyl naphthalene sulfonate.
Selected water-soluble cosolvent 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.
Selected tensio-active agent is anionic, non-ionic type or both are composite; Aniorfic surfactant is the one in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, potassium oleate, sodium alkyl naphthalene sulfonate, sodium abietate; Described non-ionic type is as polyoxyethylene alkylphenol condenses: OP-7, OP-10 or OP-15; Polyoxyethylene fatty alcohol condenses: paregal O-10, paregal O-20, peregal O-25 or peregal A-20; Polyoxyethylene polyols ether fatty acid ester: as Tween40, Tween60, Tween65, Tween80; The polyoxyethylene ester class of lipid acid: as SG-10, SE-10, OE-15.
Described pH adjusting agent is the one in sodium hydroxide, sodium carbonate, ammoniacal liquor, trolamine.
Described antiseptic-germicide is the one in Vanillin or vanillal compounds, anilid class, imidazoles, thiazoles, isothiazolones derivative, quaternary ammonium salt, two croak class, phenols.
Beneficial effect of the present invention: whitewash ink median size prepared by the present invention is less than 180nm, adopting polymer overmold oxidate nano composite particles is tinting material, has dispersion stabilization good, opacifying power advantages of higher.This ink can be stored for a long time, and can be directly used in the ink-jet printed of textiles.
Embodiment
Below by examples of implementation, further set forth outstanding advantages of the present invention and distinguishing feature, but the present invention is in no way limited to examples of implementation.
Example 1
The preparation of nano silicon composite particles: take nano silicon 15g, water 29.5g, ethanol 29.5g, after mixing, add 5g KH-570, with ammonia soln adjusting pH to 8~9, react 2 hours under 40 DEG C of conditions after, add again 10g sodium p styrene sulfonate and 1g sodium lauryl sulphate, after fully stirring, solution is transferred under the ultrasonication instrument that power is 1100w to ultrasonic 15 minutes.And then be transferred in water-bath, logical nitrogen was warming up to 65 DEG C after 30 minutes under the stirring velocity of 500 revs/min, dripped the ammonium persulfate solution that 10g massfraction is 10%, reaction 4h.High speed centrifugation precipitation, can obtain silicon-dioxide/poly (sodium 4-styrenesulfonate) nano-complex particle.
Get 2g maleic anhydride-methylmethacrylate copolymer (Mn=8000, maleic anhydride: methyl methacrylate=1: 1), add 0.20g sodium hydroxide, deionized water 85.8g, be stirred to completely and dissolve, then add silicon-dioxide/poly (sodium 4-styrenesulfonate) nano-complex particle 12g, use ultrasonic echography to disperse to make for 30 minutes silicon-dioxide/sodium polystyrene sulfonate nano-complex particle dispersion.
Get sodium lauryl sulphate 1.2g and OP-10 emulsifying agent 1g is dissolved in 41.7g deionized water; add successively nano-complex particle dispersion 30g; 1; 6-hexylene glycol 10g; tetraethylene-glycol 12g, propyl carbinol 4g, anilid antiseptic-germicide 0.1g stirs 30min with stirrer 500r/min; sodium hydroxide solution regulates pH value to 9 again, finally obtains aqueous white paint ink with the filtering with microporous membrane of 500nm.Thing indicator ink is as follows: surface tension σ=34.6mN/m, viscosities il=7.67cP, the equal particle diameter d=154.2nm of Z.
Example 2
Nano-complex particle dispersion is prepared with example 1, get hexadecyl benzene sulfonic acid sodium salt 1.5g, 0.5g tween 80 is dissolved in 42.7g deionized water, add nano-silicon composite particle dispersions 25g, n-propyl alcohol 10g, glycol ether 10g, tetramethylolmethane 10g and thiazoles antiseptic-germicide 0.3g, with stirrer 1000r/min stirring 50min, regulate pH value to 8 with sodium hydroxide again, finally obtain aqueous white paint ink with the filtering with microporous membrane of 500nm, indicator ink is as follows: surface tension σ=31.2mN/m, viscosities il=8.91cP, the equal particle diameter d=158.6nm of Z.
Example 3
The preparation of nano titanium oxide composite particles: take nano titanium oxide 30g, water 11g, ethanol 11g, after mixing, add 6g KH-570, regulate pH to 8~9 with ammonia soln, reaction adds 20g methacrylic acid and 2g sodium laurylsulfonate after 3h again, is transferred in high-speed emulsifying machine emulsification 15 minutes after fully stirring.Be transferred in water-bath, logical nitrogen was warming up to 75 DEG C after 30 minutes under the stirring velocity of 250 revs/min, started to drip 20g massfraction and be 10% Sodium Persulfate solution, reaction 5h.High speed centrifugation precipitation, can obtain titanium dioxide/polymethyl acrylic acid nano-complex particle.
Get 3g Styrene And Butyl-acrylate multipolymer (Mn=5000, vinylbenzene: butyl acrylate=3: 1), add 20% ammoniacal liquor 6g, deionized water 71g, be stirred to completely and dissolve, then add nano-complex particle 20g, use ultrasonic echography to disperse to make for 10 minutes titanium dioxide/polymethyl acrylic acid nano-complex particle dispersion.
Getting peregal O-251g is dissolved in 48.5g deionized water, add nano titanium oxide composite particle dispersions 20g, Virahol 5g, polyvinyl alcohol 20010g, 1,4-butyleneglycol 15g and isothiazolones 0.5g, stir 40 minutes with 700 revs/min, stirrer, then by 20% ammoniacal liquor adjusting pH value to 8, finally obtain aqueous white paint ink with the filtering with microporous membrane of 500nm, physical index is as follows: surface tension σ=28.4mN/m, viscosities il=6.15cP, the equal particle diameter d=162.2nm of Z.
Example 4
Nano-complex particle dispersion is prepared with example 2, getting SE-10 1g is dissolved in 45.7g deionized water, add nano-silicon composite particle dispersions 25g, Virahol 6g, Diethylene Glycol 10g, 2-Pyrrolidone 12g and two croak class antiseptic-germicide 0.3g stir 30min with stirrer 1000r/min, regulate pH value to 9 with trolamine again, finally obtain aqueous white paint ink with the filtering with microporous membrane of 500nm, physical index is as follows: surface tension σ=30.5mN/m, viscosities il=6.97cP, the equal particle diameter d=152.4nm of Z.

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.
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