CN1803913A - Nano grade polymer micro-emulsion for ink-jet printing and method for preparing the same - Google Patents
Nano grade polymer micro-emulsion for ink-jet printing and method for preparing the same Download PDFInfo
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Abstract
The disclosed preparation method for nano-polymer microemulsion in ink-jet printing comprises: using soft monomer butyl acrylate as main polymonomer for well film-forming flexible; adding comonomer with cross-linkging group to form three-dimensional space network structure and fix the color particle hard on textile fabric to prevent film tacky and endow the fabric with well resistance ability; adding polymerisable surfactant to let the polymer microemulsion have super stability even with much soft monomer and average size less than 100nm hard to agglomeration. This invention can obtain the product with small size and narrow distribution.
Description
Technical field
The present invention relates to the tackiness agent that printing in textiles is used, relate in particular to a kind of nano grade polymer micro-emulsion that is used for textile inkjet printing and preparation method thereof.
Background technology
Ink-jet printed technology is a kind of brand-new printing in textiles technology, and it is to contain the printing ink of pigment (dyestuff or pigment), prints on the matrix to quilt via the nozzle ejection of ink-jet decorating machine, forms floral designs by computer by design requirements control.According to the performance of printing ink, obtain the PRINTED FABRIC of certain fastness and vividness through suitable aftertreatment processing.Compare with traditional stamp mode, ink-jet printed have can print the high precision personalized pattern, satisfy the many variety production of the textiles short run many advantages such as province ground and environmental protection that require, respond fast, save time.
One of ink-jet printed core technology is an ink-jet printing ink.Ink-jet printing ink commonly used has two types: dye type printing ink and pigmented ink.At present, the production technique of dye-type ink-jet printing ink is ripe, and commercial ink-jet printing ink belongs to this type substantially on the market.Yet dye type printing ink has specificity and disadvantages such as selectivity, fabric pretreatment and aftertreatment technology complexity to the textile fiber kind.For example, reactive dyestuffs only are applicable to cellulosic fibre and silk fabrics, and matching stain can only be used for silk, hair, polyamide fabric, and dispersed dye only are applicable to polyester piece good; Fabric must carry out pre-treatment (going up alkali and thickener) ink-jet printed, and decatize is adopted in aftertreatment.And painting ink-jetting printing oil ink is not subjected to the restriction of fabric types, be applicable to any fabric, the seal back only needs simple aftertreatment (curing or uviolizing), therefore, painting ink-jetting printing oil ink is being represented the developing direction of ink-jet printing ink, is considered to follow-on ink-jet printing ink.
But pigment particles is poor to the avidity of fiber, must could paint to fiber by the tackiness agent effect, and keep suitable fastness.And traditional stamp is bigger with the tackiness agent size, can not directly use on ink-jet decorating machine.Simultaneously change for a short time for the feel that makes ink-jet printed back fabric especially flexibility, it is soft to also have crucial requirement to be exactly that its film forming is wanted to tackiness agent.
It is principal monomer with the divinyl that Chinese patent CN98100930.1 (1998.03.19) discloses a kind of, adopt the ultra micro emulsion copolymerization method to prepare tackiness agent, its particle diameter is at 40～50nm, and it is mainly used in the traditional coating textile printing, does not see its application in ink-jet printed.U.S. Pat P6117939 (2000.09.12) and USP6365675 (2002.04.02) adopt low emulsification pretreatment and add cosurfactant and prepare the thermoplastic acrylic ester microemulsion, but the solid content of preparation is lower, can not form self-crosslinking and film, also not see its application in ink-jet printed.Chinese patent CN03113855.1 (2003.03.06) discloses high-solid content acrylic acid ester microemulsion and its production and application, the median size of its microemulsion is less than 100nm, but soft monomer and the ratio of the weight of hard monomer are less than 1 in the microemulsion, and film forming is harder, and Application Areas is a woodwork coating.Chinese patent CN98120818.5 (1998.9.30) discloses a kind of textile inkjet printing method, it has invented a kind of ink, comprising the printing ink that contains aqueous carrier medium, pigment and superpolymer, described superpolymer has acid, alkali, epoxy and hydroxy functional group, and textiles contains hydroxyl, amine, acyl ammonia, carboxylic group, and linking agent is organometallic reagent or isocyanic ester.When the image of printing during to the extra power exposure, the polymer reaction in described linking agent and textiles and the printing ink, acquisition weather resistance, all improved image of water tolerance and washing fastness.But its superpolymer is the structure superpolymer, as block polymer, graftomer or branched polymer, preparation process is loaded down with trivial details, will remove after polymerization is finished and desolvate, and the ratio of soft monomer and the weight of hard monomer is less than 1 in the polymkeric substance, polymkeric substance is only as the dispersion agent of pigment particles, be applied to when ink-jet printed, fabric needs to carry out pre-treatment with linking agent earlier, dry spray printing, the complex procedures of carrying out again afterwards.
Summary of the invention
The purpose of this invention is to provide a kind of nano grade polymer micro-emulsion that is used for textile inkjet printing and preparation method thereof.
The nano grade polymer micro-emulsion that is used for textile inkjet printing is to be main polymerization single polymerization monomer with the soft monomer butyl acrylate, the unsaturated hard monomer of at least a vinyl, at least a unsaturated vinyl monomer and the polymerizable surfactants that has crosslinked group is comonomer, wherein butyl acrylate accounts for 60～85% of total monomer weight, the unsaturated hard monomer of vinyl accounts for 5～25% of total monomer weight, the unsaturated vinyl monomer that has crosslinked group accounts for 5～15% of total monomer weight, polymerizable surfactants accounts for 2～4% of total monomer weight, and total monomer weight accounts for 20～40% of weight of microemulsion.
The preparation method who is used for the nano grade polymer micro-emulsion of textile inkjet printing adds earlier 70～90% water, whole emulsifying agent, 30～60% initiator and 20～40% polymerization single polymerization monomer at polymeric kettle, stirs 10～40 minutes in 40～60 ℃ of constant temperature; Append residue initiator and water after being warming up to 65～90 ℃, drip remaining polymerization single polymerization monomer again, the control rate of addition dripped off polymerization single polymerization monomer in 2～8 hours.Insulation reaction 0.5～3 hour, cooling promptly gets with the translucent microemulsion of the oyster white of blue light.
Be applicable to ink-jet printed tackiness agent, should make the aqueous binder particle grain size little, good stability does not stop up the nozzle of ink-jet decorating machine, realizes that again the spray printing fabric has good colour fastness and pleasant softness simultaneously.Nano grade polymer micro-emulsion of the present invention, with the butyl acrylate is principal monomer, the second-order transition temperature that adds the unsaturated hard monomer telomerized polymer of vinyl, adding the unsaturated vinyl monomer and the polymerizable surfactants that have crosslinked group is functional monomer, has following advantage:
At first, introduce crosslinkable groups in the microemulsion, behind the fabric spray printing when curing, crosslinked group reacts, form the polymeric film of solid space network structure, pigment particles securely attached on the fabric fibre, is prevented that film forming is clamminess, give ink-jet printed fabric good water-fast washing and colour fastness such as rub resistance.
Secondly, in order to improve the film forming flexibility of polymkeric substance, the soft monomer butyl acrylate accounts for more than 60% of total monomer weight in the microemulsion of the present invention, but the soft monomer ratio is too high, the bad stability that will cause microemulsion becomes big as particle diameter, takes place easily between particle to reunite etc.The present invention has added polymerisable surfactant toxilic acid monoesters in polymerization system, one end of toxilic acid monoesters molecule is hydrophilic carboxyl, the other end is lipophilic long alkyl chain, therefore its adding, increased the stability of microemulsion on the one hand, and particle diameter is diminished, can improve the flexibility of polymeric film on the other hand.
The present invention adopts improved microemulsion polymerization method---and the hungry reinforced polymerization of monomer prepares the nano level microemulsion, promptly in polymeric kettle, add a spot of monomer earlier, form the micro-emulsion polymerization seed, slowly drip residual monomer then, the control monomer grows up seed in the seed-coat polymerization, obtains the nano level microemulsion.The advantage of this method is, the first, and can regulate and control polymerization rate by the speed that changes monomer dropping, thereby accurately control the particle diameter of microemulsion; The second, the residual monomer of dropping generally can only carry out polymerization at seed-coat, can not form new polymerization seed, the microemulsion narrow diameter distribution that obtains so basically.The polymer micro-emulsion that utilizes the present invention to obtain, its average particle size is below 100nm, minimum grain size is greater than 20nm, maximum particle diameter is less than 120nm, can not stop up the nozzle of ink-jet decorating machine, spray printing to the fabric after, the microemulsion particle infiltrates in fabric relatively deeply and evenly, ink-jet printed back fabric color nature; And can form small discontinuous phase behind the polymer film forming, make the film forming softness, have good hand feeling more; Its good stability was at room temperature placed 6 months, and size distribution is constant substantially.
Nano grade polymer micro-emulsion of the present invention, viscosity little (≤15mPaS), surface tension big (〉=25mN/m), good with various auxiliary agent consistencies in the printing ink, therefore can directly mix with dispersible pigment color paste, add an amount of wetting Agent for Printing Inks, water and other auxiliary agents again, the surface tension of simple adjustment printing ink and viscosity can be mixed with painting ink-jetting printing oil ink, and is simple for process, the ink-jet printed fabric of gained, have good water-fastly wash, rub resistance and colour fastness to light.
Embodiment
The ink-jet printed nano grade polymer micro-emulsion of using of the present invention, by high-load soft monomer butyl acrylate, the unsaturated hard monomer of at least a vinyl, at least a unsaturated vinyl monomer and the polymerizable surfactants copolymerization that has crosslinked group form, wherein
Butyl acrylate accounts for 60～85% of total monomer weight, and preferred 70～80%;
The unsaturated hard monomer of vinyl is vinyl acetate and vinylbenzene, and ester and carboxylic acid with following general formula: CH
2=CR-COOR ', wherein R is-CH
3,-H; R ' is H or C
1-2Alkyl.Preferred monomers is methyl methacrylate, vinylbenzene and methacrylic acid.Hard monomer accounts for 5～25% of total monomer weight, and preferred 12～20%;
The unsaturated vinyl monomer that has crosslinked group is the unsaturated monomer that contains hydroxyl, amido, N-methylol or N-hydroxymethyl alkyl active group, as Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, acrylamide, N hydroxymethyl acrylamide, N-methylol-butyl acrylamide etc., preferred N hydroxymethyl acrylamide and Hydroxyethyl acrylate.Monomer whose content accounts for 5～15% of total monomer weight;
Polymerizable surfactants is the toxilic acid monoesters that has long alkyl chain, and chemical structural formula is: HOOC-CH=CH-COOR, wherein R is C
12-16Alkyl.Preferred monomers is a maleic anhydride lauryl alcohol monoesters.Monomer whose content accounts for 2～4% of total monomer weight.
The ink-jet printed nano grade polymer micro-emulsion of using of the present invention adopts the hungry reinforced polymerization preparation of monomer, and its preparation process is:
Add earlier 70～90% water, whole emulsifying agent, 30～60% initiator and 20～40% polymerization single polymerization monomer in the polymeric kettle, stirred 10～40 minutes in 40～60 ℃ of constant temperature.Append residue initiator and water after being warming up to 65～90 ℃, begin to drip remaining polymerization single polymerization monomer, the control rate of addition dripped off polymerization single polymerization monomer in 2～8 hours.Insulation reaction 0.5～3 hour, cooling promptly gets with the translucent microemulsion of the oyster white of blue light.Wherein
Emulsifying agent is the compound of aniorfic surfactant and nonionic surface active agent, described aniorfic surfactant is one or more the mixture in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium laurylsulfonate, alkyl diphenyl ether disodium sulfonate salt, oxyethyl group disodium sulfosuccinate, sodium vinyl sulfonate, the alkyl amido sodium vinyl sulfonate, preferred Sodium dodecylbenzene sulfonate and sodium lauryl sulphate; Nonionic surface active agent is one or more the mixture in alkylphenol polyoxyethylene (as OP-10), the fatty alcohol-polyoxyethylene ether (as AEO9) etc., preferred OP-10; The ratio of aniorfic surfactant and nonionic surface active agent is 1: 4～4: 1 (weight ratio), preferred 1: 2～2: 1; The composite emulsifier gross weight accounts for 2～15% of total monomer weight, and preferred 6～10%;
Initiator is the mixture of 1: 1 (weight ratio) of Potassium Persulphate, ammonium persulphate or sodium bisulfite and ferrous sulfate, initiator system of ammonium persulfate; Initiator weight accounts for 0.1～1% of total monomer weight, and preferred 0.4～0.8%;
The weight of water is 150～400% of total monomer weight.
Nano grade polymer micro-emulsion of the present invention can directly be used for disposing painting ink-jetting printing oil ink, and process for preparation is as follows:
Dispersible pigment color paste is joined in the stirring tank, under the middling speed agitation condition, slowly join an amount of nano level microemulsion in the dispersible pigment color paste, stir after 5～10 minutes, slowly add an amount of wetting Agent for Printing Inks, sanitas and tensio-active agent, stir after 10～30 minutes, the pH value of regulating printing ink with the pH regulator agent is 6.5～7.5, and discharging, filtration promptly get painting ink-jetting printing oil ink.Wherein
Dispersible pigment color paste is pigment particles the stable dispersions in water of particle diameter less than 1000nm, can adopt the commercialization dispersible pigment color paste on the market, and as the dispersible pigment color paste of red, yellow, blue, black four primary colours of Cabot company, trade(brand)name is respectively Cab-O-Jet
TM260 Magenta Colorant, Cab-O-Jet
TM270 YellowColorant, Cab-O-Jet
TM250 Cyan Colorant, Cab-O-Jet
TM200 Black Colorant, the particle diameter of pigment particles is less than 500nm in the mill base, and median size is 165nm, and solid content is 10% (weight).Dispersible pigment color paste accounts for 30～60% of ink-jet printing ink gross weight;
Nano grade polymer micro-emulsion accounts for 30～60% of ink-jet printing ink gross weight;
Wetting Agent for Printing Inks is water miscible high boiling organic solvent, as one or more mixtures in ethylene glycol, propylene glycol, glycerol, glycol ether, dipropylene glycol, Triethylene glycol, tripropylene glycol, polyoxyethylene glycol, hexalin, N-Methyl pyrrolidone, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, butyl glycol ether, Diethylene Glycol butyl ether, propylene glycol monomethyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, tripropylene glycol ether, the triethylene glycol methyl ether etc.Wetting Agent for Printing Inks accounts for 5～30% of ink-jet printing ink gross weight;
Sanitas is the KATHON LXE and the KATHON LEX of Rhom and Hass, the mixture of one or more in the TROYSAN 174 of Te Luoyi company, TROYSAN 186, TROYSAN 192 and the formaldehyde etc., its content accounts for 0.1～0.6% of ink-jet printing ink gross weight;
Tensio-active agent is one or more the mixture in sodium lauryl sulphate, sodium laurylsulfonate, the Sodium dodecylbenzene sulfonate etc., and its content accounts for 0.1～2% of ink-jet printing ink gross weight;
The pH regulator agent is Trimethylamine 99, triethylamine, trolamine, aniline and ammoniacal liquor etc.;
The weight of water is 5～20% of ink-jet printing ink gross weight.
The following examples are used to describe the present invention.Remove explanation in addition, the temperature that provides is a centigradetemperature, and umber is a weight part, the size of microemulsion and the 90Plus type dynamic light scattering analyser test that distributes and adopt BrookHaven Instruments company; The viscosity of microemulsion with the Ubbelohde viscometer test, is primary standard with water in 20 ℃ of Water Tanks with Temp.-controlled; The surface tension of microemulsion is tested with the OCA 20 type video light contact angle measurements of Dataphysics company; Adopt the digital conduction band spray-jet printing machine of DBP-1600C type of Hangzhou Honghua Digical Code Science ﹠ Technology Co. Ltd. to carry out ink-jet printed test; The colour fastness to washing of ink-jet printed fabric, colour fastness to rubbing and color fastness to daylight are tested by standard GB/T3921-1997, GB/T3920-1997 and GB/T8427-1997.
Embodiment 1
Set of monomers becomes butyl acrylate, methyl methacrylate, methacrylic acid, N hydroxymethyl acrylamide, maleic anhydride lauryl alcohol monoesters, and its component prescription is as shown in table 1.
Table 1 nano grade polymer micro-emulsion prescription
| Sequence number | Form | Umber |
| 1 2 3 4 5 6 7 8 9 | Butyl acrylate methyl methacrylate methacrylic acid N hydroxymethyl acrylamide maleic anhydride lauryl alcohol monoesters lauryl sodium sulfate OP-10 ammonium persulfate deionized water | 77 10 5 5 3 3.2 3.2 0.5 230 |
With whole emulsifying agents (sodium lauryl sulphate and OP-10), maleic anhydride lauryl alcohol monoesters and 200 parts of deionized waters place polymeric kettle, high-speed stirring 10 minutes, be warmed up to 50 ℃, adding is by 16 parts of butyl acrylates, 2.5 part methyl methacrylate, 1.25 part methacrylic acid and 1.25 parts of mixtures that N hydroxymethyl acrylamide is formed, pH value with ammoniacal liquor conditioned reaction system is 6.5～7.0, continued stirring and emulsifying 30 minutes, be warming up to 60 ℃ then, add 30 parts of water dissolution of 0.25 part of usefulness good initiator (ammonium persulphate) solution carries out micro-emulsion polymerization in reaction system, continues to be stirred to microemulsion and the mazarine opalescence occurs.Be warmed up to 78 ℃ then, add remaining initiator, and begin to drip residual monomer, all drip in 4 hours, continue insulation 1.0 hours, cooling, cooling discharging filters, and promptly gets translucent oyster white nano level microemulsion.
The microemulsion of preparing does not have precipitation, median size 46.5nm, and maximum particle diameter is 71.7nm, and minimum grain size is 26.5nm, and viscosity is 10.2mPaS, and surface tension is 30.3mN/m, solids content is 25.8%.
Embodiment 2
Set of monomers becomes butyl acrylate, methyl methacrylate, methacrylic acid, N hydroxymethyl acrylamide, maleic anhydride lauryl alcohol monoesters, and its component prescription is as shown in table 2.
Table 2 nano grade polymer micro-emulsion prescription
| Sequence number | Form | Umber |
| 1 2 3 4 5 6 7 8 9 | Butyl acrylate methyl methacrylate methacrylic acid N hydroxymethyl acrylamide maleic anhydride lauryl alcohol monoesters lauryl sodium sulfate OP-10 ammonium persulfate deionized water | 77 10 5 5 3 3.5 3.5 0.5 210 |
Whole emulsifying agent (sodium lauryl sulphate and OP-10), maleic anhydride lauryl alcohol monoesters and 185 parts of deionized waters are placed polymeric kettle, and high-speed stirring 10 minutes is warmed up to 50 ℃, adds by 16 parts of propylene
Acid butyl ester, 2.5 parts of methyl methacrylates, 1.25 parts of methacrylic acids and 1.25 parts of mixtures that N hydroxymethyl acrylamide is formed, pH value with ammoniacal liquor conditioned reaction system is 6.5～7.0, continued stirring and emulsifying 30 minutes, be warming up to 60 ℃ then, add 25 parts of water dissolution of 0.25 part of usefulness good initiator (ammonium persulphate) solution carries out micro-emulsion polymerization in reaction system, continues to be stirred to microemulsion and the mazarine opalescence occurs.Be warmed up to 75 ℃ then, add remaining initiator, and begin to drip residual monomer, all drip in 4.5 hours, continue insulation 1 hour, cooling, cooling discharging filters, and promptly gets translucent oyster white nano level microemulsion.
The microemulsion of preparing does not have precipitation, median size 61.3nm, and maximum particle diameter is 93.5nm, and minimum grain size is 47.2nm, and viscosity is 12.5mPaS, and surface tension is 28.4mN/m, solids content is 27.1%.
Embodiment 3
Set of monomers becomes butyl acrylate, methyl methacrylate, methacrylic acid, N hydroxymethyl acrylamide, maleic anhydride lauryl alcohol monoesters, and its component prescription is as shown in table 3.
Table 3 nano grade polymer micro-emulsion prescription
| Sequence number | Form | Umber |
| 1 2 3 4 5 6 7 8 9 | Butyl acrylate methyl methacrylate methacrylic acid N hydroxymethyl acrylamide maleic anhydride lauryl alcohol monoesters lauryl sodium sulfate OP-10 ammonium persulfate deionized water | 77 10 5 5 3 3.5 3.5 0.7 190 |
With whole emulsifying agents (sodium lauryl sulphate and OP-10), maleic anhydride lauryl alcohol monoesters and 175 parts of deionized waters place polymeric kettle, high-speed stirring 10 minutes, be warmed up to 50 ℃, adding is by 16 parts of butyl acrylates, 2.5 part methyl methacrylate, 1.25 part methacrylic acid and 1.25 parts of mixtures that N hydroxymethyl acrylamide is formed, pH value with ammoniacal liquor conditioned reaction system is 6.5～7.0, continued stirring and emulsifying 30 minutes, be warming up to 60 ℃ then, add 15 parts of water dissolution of 0.35 part of usefulness good initiator (ammonium persulphate) solution carries out micro-emulsion polymerization in reaction system, continues to be stirred to microemulsion and the mazarine opalescence occurs.Be warmed up to 75 ℃ then, add remaining initiator, and begin to drip residual monomer, all drip in 5 hours, continue insulation 1.5 hours, cooling, cooling discharging filters, and promptly gets translucent oyster white nano level microemulsion.
The microemulsion of preparing does not have precipitation, median size 89.4nm, and maximum particle diameter is 127.8nm, and minimum grain size is 54.5nm, and viscosity is 13.9mPaS, and surface tension is 27.2mN/m, solids content is 30.4%.
Embodiment 4
Set of monomers becomes butyl acrylate, vinylbenzene, methacrylic acid, vinylformic acid, N hydroxymethyl acrylamide, maleic anhydride tetradecyl alcohol monoesters, and its component prescription is as shown in table 4.
Table 4 nano grade polymer micro-emulsion prescription
| Sequence number | Form | Umber |
| 1 2 3 4 5 6 7 8 9 10 | Butyl acrylate styrene metering system acid acrylic acid N hydroxymethyl acrylamide maleic anhydride tetradecyl alchohol monoesters lauryl sodium sulfate OP-10 potassium peroxydisulfate deionized water | 71 14.6 3.6 1.8 5.4 3.6 3.6 3.6 0.7 250 |
With whole emulsifying agents (sodium lauryl sulphate and OP-10), maleic anhydride tetradecyl alcohol monoesters and 215 parts of deionized waters place polymeric kettle, high-speed stirring 10 minutes, be warmed up to 50 ℃, adding is by 14 parts of butyl acrylates, 3.65 part vinylbenzene, 0.9 part methacrylic acid, 0.45 part vinylformic acid, 1.35 the mixture that part N hydroxymethyl acrylamide is formed, pH value with ammoniacal liquor conditioned reaction system is 6.5～7.0, continued stirring and emulsifying 30 minutes, heat up 60 ℃ then, add 35 parts of water dissolution of 0.35 part of usefulness good initiator (Potassium Persulphate) solution carries out micro-emulsion polymerization in reaction system, continues to be stirred to microemulsion and the mazarine opalescence occurs.Be warmed up to 80 ℃ then, add remaining initiator, and begin to drip residual monomer, all drip in 5 hours, continue insulation 1 hour, cooling, cooling discharging filters, and promptly gets translucent oyster white nano level microemulsion.
The microemulsion of preparing does not have precipitation, median size 54.7nm, and maximum particle diameter is 84.2nm, and minimum grain size 37.5nm is, and viscosity is 8.1mPaS, and surface tension is 32.0mN/m, solids content is 26.5%.
Embodiment 5
Set of monomers becomes butyl acrylate, methyl methacrylate, methacrylic acid, hydroxyethyl methylacrylate, N hydroxymethyl acrylamide, maleic anhydride lauryl alcohol monoesters, and its component prescription is as shown in table 5.
Table 5 nano grade polymer micro-emulsion prescription
| Sequence number | Form | Umber |
| 1 2 3 4 5 6 7 8 9 10 | Butyl acrylate methyl methacrylate methacrylic acid methyl hydroxy-ethyl acrylate N hydroxymethyl acrylamide maleic anhydride lauryl alcohol monoesters lauryl sodium sulfate OP-10 ammonium persulfate deionized water | 73 10.8 5.4 1.8 5.4 3.6 3.6 3.6 0.7 256 |
Whole emulsifying agent (sodium lauryl sulphate and OP-10) and 220 parts of deionized waters are placed polymeric kettle, high-speed stirring 10 minutes, be warmed up to 50 ℃, adding is by 15 parts of butyl acrylates, 2.7 part methyl methacrylate, 1.35 part methacrylic acid, 0.45 part hydroxyethyl methylacrylate and 1.35 parts of mixtures that N hydroxymethyl acrylamide is formed, pH value with ammoniacal liquor conditioned reaction system is 6.5～7.0, continued stirring and emulsifying 30 minutes, heat up 60 ℃ then, add 36 parts of water dissolution of 0.35 part of usefulness good initiator (ammonium persulphate) solution carries out micro-emulsion polymerization in reaction system, continues to be stirred to microemulsion and the mazarine opalescence occurs.Be warmed up to 78 ℃ then, add remaining initiator, and begin to drip residual monomer, all drip in 4 hours, continue insulation 1.0 hours, cooling, cooling discharging filters, and promptly gets translucent oyster white nano level microemulsion.
The microemulsion of preparing does not have precipitation, median size 64.2nm, and maximum particle diameter is 87.2nm, and minimum grain size is 47.5nm, and viscosity is 11.5mPaS, and surface tension is 34.1mN/m, solids content is 25.5%.
Embodiment 6
Press the formulated pigment jetting printing ink shown in the table 6.Compound method is as follows:
40 parts of dispersible pigment color pastes are joined in the stirring tank, nano level microemulsion with preparation among 40 parts of embodiment 1 under the middling speed agitation condition slowly joins in the dispersible pigment color paste, stir after 5～10 minutes, slowly add quantitative wetting Agent for Printing Inks, sanitas and tensio-active agent, stir after 10～30 minutes, the pH value of regulating printing ink with trolamine is 6.5～7.5, and discharging, filtration promptly get painting ink-jetting printing oil ink.
The performance of the ink-jet printing ink of preparing is: the pH value is 6.5～7.5, and solids content is 17～20%, and viscosity is 3～5mPaS, and surface tension is 25～35mN/m, and particle diameter is less than 500nm.
Table 6 ink-jet printing ink prescription
| Sequence number | Form | Umber |
| 1 2 3 4 5 6 7 | Nano grade polymer micro-emulsion Cab-O-Jet among the embodiment 1 TMDispersible pigment color paste glycerine KATHON LXE lauryl sodium sulfate pH adjusting agent deionized water amounts to | 40 40 8 0.1 0.4 0.5 11 100 |
Above-mentioned printing ink is joined in the continuous ink-supply system of ink-jet decorating machine, carry out the ink-jet printed test of cotton by following technology: ink-jet decorating machine stamp → oven dry (80 ℃, 3 minutes) → bake (160 ℃, 3 minutes) → finished product.
The result is that ink-jet printed test is stable, does not block shower nozzle, and spray back shower nozzle easy cleaning.The ink-jet printed fabrics feel soft of gained, decorative pattern are clear.The colour fastness of ink-jet printed fabric is: colour fastness to washing is 4 grades of variable colors, 4 grades of cotton staining, 4 grades of felt staining; Colour fastness to rubbing is unlubricated friction 3-4 level, wets and rub 3 grades; Colour fastness to light is 4 grades.
Embodiment 7
Press the formulated pigment jetting printing ink shown in the table 7.Compound method is as follows:
Table 7 ink-jet printing ink prescription
| Sequence number | Form | Mass percent, % |
| 1 2 3 4 5 6 7 | Nano grade polymer micro-emulsion Cab-O-Jet among the embodiment 4 TMDispersible pigment color paste 1,2-propylene glycol KATHON LEX Sodium dodecylbenzene sulfonate pH regulator agent deionized water amounts to | 40 40 8 0.1 0.4 0.5 11 100 |
40 parts of dispersible pigment color pastes are joined in the stirring tank, nano level microemulsion with preparation among 40 parts the embodiment 4 under the middling speed agitation condition slowly joins in the dispersible pigment color paste, stir after 5～10 minutes, slowly add quantitative wetting Agent for Printing Inks, sanitas and tensio-active agent, stir after 10～30 minutes, the pH value of regulating printing ink with trolamine is 6.5～7.5, and discharging, filtration promptly get painting ink-jetting printing oil ink.
The performance of the ink-jet printing ink of preparing is: the pH value is 6.5～7.5, and solids content is 17～20%, and viscosity is 3～5mPaS, and surface tension is 25～35mN/m, and particle diameter is less than 500nm.
Above-mentioned printing ink is joined in the ink-jet decorating machine continuous ink-supply system, wash/the ink-jet printed test of cotton (TC65/35) cloth: ink-jet decorating machine stamp → oven dry (80 ℃, 3 minutes) → bake (160 ℃, 3 minutes) → finished product by following technology.
The result is that ink-jet printed test is stable, does not block shower nozzle, and spray back shower nozzle easy cleaning.The ink-jet printed fabrics feel soft of gained, decorative pattern are clear.The colour fastness of ink-jet printed fabric is: colour fastness to washing is 4 grades of variable colors, 4 grades of cotton staining, 4 grades of felt staining; Colour fastness to rubbing is unlubricated friction 3-4 level, wets and rub 3 grades; Colour fastness to light is 4 grades.
Embodiment 8
Press the formulated pigment jetting printing ink shown in the table 8.Compound method is as follows:
40 parts of dispersible pigment color pastes are joined in the stirring tank, nano level microemulsion with preparation among 40 parts the embodiment 5 under the middling speed agitation condition slowly joins in the dispersible pigment color paste, stir after 5～10 minutes, slowly add quantitative wetting Agent for Printing Inks, sanitas and tensio-active agent, stir after 10～30 minutes, the pH value of regulating printing ink with trolamine is 6.5～7.5, and discharging, filtration promptly get painting ink-jetting printing oil ink.
The performance of the ink-jet printing ink of preparing is: the pH value is 6.5～7.5, and solids content is 17～20%, and viscosity is 3～5mPaS, and surface tension is 25～35mN/m, and particle diameter is less than 500nm.
Table 8 ink-jet printing ink prescription
| Sequence number | Form | Mass percent, % |
| 1 2 3 4 5 6 7 | Nano grade polymer micro-emulsion Cab-O-Jet among the embodiment 5 TMDispersible pigment color paste 1-METHYLPYRROLIDONE TROYSAN 174 dodecyl sodium sulfate pH adjusting agent deionized waters amount to | 40 40 8 0.1 0.4 0.5 11 100 |
Above-mentioned printing ink is joined in the ink-jet decorating machine continuous ink-supply system, carry out the ink-jet printed test of polyamide fabric by following technology: ink-jet decorating machine stamp → oven dry (80 ℃, 3 minutes) → bake (160 ℃, 3 minutes) → finished product.
The result is that ink-jet printed test is stable, does not block shower nozzle, and spray back shower nozzle easy cleaning.The ink-jet printed fabrics feel soft of gained, decorative pattern are clear.The colour fastness of ink-jet printed fabric is: colour fastness to washing is 4 grades of variable colors, 4 grades of cotton staining, 4 grades of felt staining; Colour fastness to rubbing is unlubricated friction 3-4 level, wets and rub 3 grades; Colour fastness to light is 4 grades.
Comparing embodiment 1
Set of monomers becomes butyl acrylate, methyl methacrylate, methacrylic acid, N hydroxymethyl acrylamide, and its component prescription is as shown in table 9.
Table 9 polymer micro-emulsion prescription
| Sequence number | Form | Umber |
| 1 2 3 4 5 6 7 8 | Butyl acrylate methyl methacrylate methacrylic acid N hydroxymethyl acrylamide lauryl sodium sulfate OP-10 ammonium persulfate deionized water | 80 10 5 5 3.2 3.2 0.5 235 |
Whole emulsifying agent (sodium lauryl sulphate and OP-10) and 200 parts of deionized waters are placed polymeric kettle, high-speed stirring 10 minutes, be warmed up to 50 ℃, adding is by 16 parts of butyl acrylates, 2.5 part methyl methacrylate, 1.25 part methacrylic acid and 1.25 parts of mixtures that N hydroxymethyl acrylamide is formed, pH value with ammoniacal liquor conditioned reaction system is 6.5～7.0, continued stirring and emulsifying 30 minutes, be warming up to 60 ℃ then, add 35 parts of water dissolution of 0.25 part of usefulness good initiator (ammonium persulphate) solution carries out micro-emulsion polymerization in reaction system, continues to be stirred to microemulsion and the mazarine opalescence occurs.Be warmed up to 78 ℃ then, add remaining initiator, and begin to drip residual monomer, all drip in 4 hours, continue insulation 1.0 hours, cooling, cooling discharging filters.
In the above-mentioned preparation process, when monomer dropping time to 2 hour, former semi-transparent zone blue light microemulsion becomes white gradually, forms white emulsion then, and has a large amount of condensation products to generate, and emulsion is placed the back layering of spending the night.Obviously the gained emulsion can not be used.
Comparing embodiment 2
Set of monomers becomes butyl acrylate, methyl methacrylate, methacrylic acid, and its component prescription is as shown in table 10.
Table 10 polymer micro-emulsion prescription
| Sequence number | Form | Umber |
| 1 2 3 4 5 6 7 | Butyl acrylate methyl methacrylate methacrylic acid lauryl sodium sulfate OP-10 ammonium persulfate deionized water | 50 40 10 3.2 3.2 0.5 235 |
Whole emulsifying agent (sodium lauryl sulphate and OP-10) and 200 parts of deionized waters are placed polymeric kettle, high-speed stirring 10 minutes, be warmed up to 50 ℃, adding is by 12.5 parts of butyl acrylates, 10 parts of methyl methacrylates, 2.5 parts of mixtures that methacrylic acid is formed, pH value with ammoniacal liquor conditioned reaction system is 6.5～7.0, continued stirring and emulsifying 30 minutes, be warming up to 60 ℃ then, add 35 parts of water dissolution of 0.25 part of usefulness good initiator (ammonium persulphate) solution carries out micro-emulsion polymerization in reaction system, continues to be stirred to microemulsion and the mazarine opalescence occurs.Be warmed up to 78 ℃ then, add remaining initiator, and begin to drip residual monomer, all drip in 4 hours, continue insulation 1.0 hours, cooling, cooling discharging filters, and promptly gets translucent oyster white nano level microemulsion.
The microemulsion of preparing has a small amount of condensation product, median size 65.4nm, and maximum particle diameter is 74.6nm, and minimum grain size is 32.3nm, and viscosity is 8.2mPaS, and surface tension is 31.5mN/m, solids content is 25.3%.
Comparing embodiment 3
Set of monomers becomes butyl acrylate, methyl methacrylate, methacrylic acid, N hydroxymethyl acrylamide, and its component prescription is as shown in table 11.
Table 11 polymer micro-emulsion prescription
| Sequence number | Form | Umber |
| 1 2 3 4 5 6 7 8 | Butyl acrylate methyl methacrylate methacrylic acid N hydroxymethyl acrylamide lauryl sodium sulfate OP-10 ammonium persulfate deionized water | 50 40 5 5 3.2 3.2 0.5 235 |
Whole emulsifying agent (sodium lauryl sulphate and OP-10) and 200 parts of deionized waters are placed polymeric kettle, high-speed stirring 10 minutes, be warmed up to 50 ℃, adding is by 12.5 parts of butyl acrylates, 10 parts of methyl methacrylates, 1.25 part methacrylic acid and 1.25 parts of mixtures that N hydroxymethyl acrylamide is formed, pH value with ammoniacal liquor conditioned reaction system is 6.5～7.0, continued stirring and emulsifying 30 minutes, be warming up to 60 ℃ then, add 35 parts of water dissolution of 0.25 part of usefulness good initiator (ammonium persulphate) solution carries out micro-emulsion polymerization in reaction system, continues to be stirred to microemulsion and the mazarine opalescence occurs.Be warmed up to 78 ℃ then, add remaining initiator, and begin to drip residual monomer, all drip in 4 hours, continue insulation 1.0 hours, cooling, cooling discharging filters, and promptly gets translucent oyster white nano level microemulsion.
The microemulsion of preparing has a small amount of condensation product, median size 60.5nm, and maximum particle diameter is 77.6nm, and minimum grain size is 22.3nm, and viscosity is 8.4mPaS, and surface tension is 31.1mN/m, solids content is 26.3%.
Comparing embodiment 4
Press the formulated pigment jetting printing ink shown in the table 12.Compound method is as follows:
40 parts of dispersible pigment color pastes are joined in the stirring tank, nano level microemulsion with preparation in 40 parts the comparing embodiment 2 under the middling speed agitation condition slowly joins in the dispersible pigment color paste, stir after 5～10 minutes, slowly add quantitative wetting Agent for Printing Inks, sanitas and tensio-active agent, stir after 10～30 minutes, the pH value of regulating printing ink with trolamine is 6.5～7.5, and discharging, filtration promptly get painting ink-jetting printing oil ink.
The performance of the ink-jet printing ink of preparing is: the pH value is 6.5～7.5, and solids content is 17～20%, and viscosity is 3～5mPaS, and surface tension is 25～35mN/m, and particle diameter is less than 500nm.
Table 12 ink-jet printing ink prescription
| Sequence number | Form | Umber |
| 1 2 3 4 5 6 7 | Nano grade polymer micro-emulsion Cab-O-Jet in the comparing embodiment 2 TMDispersible pigment color paste glycerine KATHON LXE lauryl sodium sulfate pH adjusting agent deionized water amounts to | 40 40 8 0.1 0.4 0.5 11 100 |
Above-mentioned printing ink is joined in the continuous ink-supply system of ink-jet decorating machine, carry out the ink-jet printed test of cotton by following technology: ink-jet decorating machine stamp → oven dry (80 ℃, 3 minutes) → bake (160 ℃, 3 minutes) → finished product.
The result is that ink-jet printed test is stable, does not block shower nozzle, and spray back shower nozzle easy cleaning.The ink-jet printed fabric feeling of gained is harder, and it is very serious to fade behind the fabric washing.
Comparing embodiment 5
Press the formulated pigment jetting printing ink shown in the table 13.Compound method is as follows:
40 parts of dispersible pigment color pastes are joined in the stirring tank, nano level microemulsion with preparation in 40 parts the comparing embodiment 3 under the middling speed agitation condition slowly joins in the dispersible pigment color paste, stir after 5～10 minutes, slowly add quantitative wetting Agent for Printing Inks, sanitas and tensio-active agent, stir after 10～30 minutes, the pH value of regulating printing ink with trolamine is 6.5～7.5, and discharging, filtration promptly get painting ink-jetting printing oil ink.
Table 13 ink-jet printing ink prescription
| Sequence number | Form | Umber |
| 1 2 3 4 5 6 7 | Nano grade polymer micro-emulsion Cab-O-Jet in the comparing embodiment 3 TMDispersible pigment color paste glycerine KATHON LXE lauryl sodium sulfate pH adjusting agent deionized water amounts to | 40 40 8 0.1 0.4 0.5 11 100 |
The performance of the ink-jet printing ink of preparing is: the pH value is 6.5～7.5, and solids content is 17～20%, and viscosity is 3～5mPaS, and surface tension is 25～35mN/m, and particle diameter is less than 500nm.
Above-mentioned printing ink is joined in the continuous ink-supply system of ink-jet decorating machine, carry out the ink-jet printed test of cotton by following technology: ink-jet decorating machine stamp → oven dry (80 ℃, 3 minutes) → bake (160 ℃, 3 minutes) → finished product.
The result is that ink-jet printed test is stable, does not block shower nozzle, and spray back shower nozzle easy cleaning.The ink-jet printed fabric feeling of gained is hard, decorative pattern is clear.The colour fastness of ink-jet printed fabric is: colour fastness to washing is 4 grades of variable colors, 4 grades of cotton staining, 4 grades of felt staining; Colour fastness to rubbing is 3～4 grades of unlubricated frictions, wets and rub 3 grades; Colour fastness to light is 4 grades.
Comparing embodiment and application are summed up
| Numbering | Outward appearance or stability | Median size (nm) | Fabric feeling | Fastness |
| Comparing embodiment 1 | White emulsion, instability | ～ | ～ | ～ |
| Comparing embodiment 2 | Band blue light microemulsion, stable | 65.4 | Soft | Washing is seriously faded |
| Comparing embodiment 3 | Band blue light microemulsion, stable | 60.5 | Harder | ≥3 |
Claims (9)
1. nano grade polymer micro-emulsion that is used for textile inkjet printing, it is characterized in that with the soft monomer butyl acrylate be main polymerization single polymerization monomer, the unsaturated hard monomer of at least a vinyl, at least a unsaturated vinyl monomer and the polymerizable surfactants that has crosslinked group is comonomer, wherein butyl acrylate accounts for 60～85% of total monomer weight, the unsaturated hard monomer of vinyl accounts for 5～25% of total monomer weight, the unsaturated vinyl monomer that has crosslinked group accounts for 5～15% of total monomer weight, polymerizable surfactants accounts for 2～4% of total monomer weight, and total monomer weight accounts for 20～40% of weight of microemulsion.
2. a kind of nano grade polymer micro-emulsion that is used for textile inkjet printing according to claim 1 is characterized in that the unsaturated hard monomer of said vinyl is vinyl acetate, vinylbenzene or ester and the carboxylic acid with following general formula: CH
2=CR-COOR ', wherein R is-CH
3,-H, R ' are H or C
1-2Alkyl.
3. a kind of nano grade polymer micro-emulsion that is used for textile inkjet printing according to claim 1 is characterized in that the said unsaturated vinyl monomer that has crosslinked group is Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, acrylamide, N hydroxymethyl acrylamide or N-methylol-butyl acrylamide.
4. a kind of nano grade polymer micro-emulsion that is used for textile inkjet printing according to claim 1, it is characterized in that said polymerizable surfactants is the toxilic acid monoesters that has long alkyl chain, its chemical structural formula is: HOOC-CH=CH-COOR, wherein R is C
12-16Alkyl.
5. preparation method who is used for the nano grade polymer micro-emulsion of textile inkjet printing according to claim 1, it is characterized in that, in polymeric kettle, add earlier 70～90% water, whole emulsifying agent, 30～60% initiator and 20～40% polymerization single polymerization monomer, stirred 10～40 minutes in 40～60 ℃ of constant temperature; Append residue initiator and water after being warming up to 65～90 ℃, drip remaining polymerization single polymerization monomer again, the control rate of addition dripped off polymerization single polymerization monomer in 2～8 hours.Insulation reaction 0.5～3 hour, cooling promptly gets with the translucent microemulsion of the oyster white of blue light.
6. a kind of preparation method who is used for the nano grade polymer micro-emulsion of textile inkjet printing according to claim 5, it is characterized in that said polymerization single polymerization monomer is a butyl acrylate, the unsaturated hard monomer of at least a vinyl, at least a unsaturated vinyl monomer of crosslinked group and the mixture of polymerizable surfactants of having, wherein butyl acrylate accounts for 60～85% of total monomer weight, the unsaturated hard monomer of vinyl accounts for 5～25% of total monomer weight, the unsaturated vinyl monomer that has crosslinked group accounts for 5～15% of total monomer weight, polymerizable surfactants accounts for 2～4% of total monomer weight, and total monomer weight accounts for 20～40% of weight of microemulsion.
7. a kind of preparation method who is used for the nano grade polymer micro-emulsion of textile inkjet printing according to claim 6 is characterized in that the unsaturated hard monomer of said vinyl is vinyl acetate, vinylbenzene or ester and the carboxylic acid with following general formula: CH
2=CR-COOR ', wherein R is-CH
3,-H, R ' are H or C
1-2Alkyl; The unsaturated vinyl monomer that has crosslinked group is an alkene acid amides in Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, acrylamide, N hydroxymethyl acrylamide or the N-methylol-butyl; Polymerizable surfactants is the toxilic acid monoesters that has long alkyl chain, and its chemical structural formula is: HOOC-CH=CH-COOR, wherein R is C
12-16Alkyl.
8. a kind of preparation method who is used for the nano grade polymer micro-emulsion of textile inkjet printing according to claim 5, it is characterized in that said emulsifying agent is the compound of aniorfic surfactant and nonionic surface active agent, wherein aniorfic surfactant is a Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium laurylsulfonate, alkyl diphenyl ether disodium sulfonate salt, the oxyethyl group disodium sulfosuccinate, sodium vinyl sulfonate, the mixture of one or more in the alkyl amido sodium vinyl sulfonate, nonionic surface active agent is an alkylphenol polyoxyethylene, the mixture of one or more in the fatty alcohol-polyoxyethylene ether, the weight ratio of aniorfic surfactant and nonionic surface active agent is 1: 4～4: 1, and the composite emulsifier gross weight accounts for 2～15% of total monomer weight;
9. a kind of preparation method who is used for the nano grade polymer micro-emulsion of textile inkjet printing according to claim 5, it is characterized in that said initiator is that the weight ratio of Potassium Persulphate, ammonium persulphate or sodium bisulfite and ferrous sulfate is 1: 1 a mixture, initiator weight accounts for 0.1～1% of total monomer weight.
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