CN104861780A - Dispersed resin solution and ink used on glass substrate - Google Patents
Dispersed resin solution and ink used on glass substrate Download PDFInfo
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- CN104861780A CN104861780A CN201510168577.8A CN201510168577A CN104861780A CN 104861780 A CN104861780 A CN 104861780A CN 201510168577 A CN201510168577 A CN 201510168577A CN 104861780 A CN104861780 A CN 104861780A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- Engineering & Computer Science (AREA)
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- Wood Science & Technology (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
Abstract
The invention discloses a dispersed resin solution and an ink used on a glass substrate. An average molecular weight of the resin of the dispersed resin solution is 1,000-10,000. The components of the dispersed resin solution are ammonium-containing acrylate, piperidinyl methacrylate, alkyl acrylate, an initiator, a polymerization molecular weight regulator and water. When the dispersed resin solution is blended and ground with an organic pigment, the dispersed resin solution can be highly efficiently combined with the organic pigment, such that organic pigment light fastness is effectively improved. The resin is coated on the surface of the pigment, such that pigment stability is greatly improved. The ink is a water-based ink, and can be firmly bonded on the glass substrate. The light fastness reaches 6-7 level, and the color is bright and full.
Description
Technical field
The present invention relates to a kind of resin for water-based jet ink and water-based jet ink, particularly a kind of dispersion resin liquid and ink being applicable to glass baseplate.
Background technology
Traditional analog printing need through imaging, color separation, plate-making to being printed on the machine this tediously long production process consuming time and technical process, the timely transmission limiting merchandise news with exchange, the restriction of minimum batch printing starting point also makes production cost effectively reduce.Digital printing is in conjunction with computer technology, traditional printing making is replaced directly to export, its personalization, timelyization, short run and the feature upgraded fast make press there occurs revolutionary change, impel typography from simulated to totally digitilized future development, growing with each passing day of digital printing Application Areas determines the broad mass market prospect of digital spray printing ink.
Along with the raising of people's living standard and the pursuit of personalization, people are to various glass decoration articles for use, and the decoration effect as light fixture, wineglass, bottle, vase, glass door and window etc. proposes more and more higher requirement.Domestic printing (comprising ink jet printing) on the glass substrate at present first on glass, carries out pre-treatment, namely first goes up precoated layer to improve the sticking power to glass, then impressing pattern, last spraying protective layer.This process is complicated, and great majority use solvent based coating, and have a large amount of VOC volatilizations, technique is loaded down with trivial details and unfriendly to environment.CN102492330A discloses a kind of UV photo-curing ink-jet ink for glass baseplate, its can directly spray printing on the glass substrate, strong to glass attachment power, warm water soaking does not come off, do not whiten.But cured film hardness is lower, easy scratch, boiling water soaks and comes off in the form of sheets, and UV ink-jet also exists the front monomer smell weight of solidification, high in cost of production unfavorable factor.Water-based jet ink owing to using water as solvent, nontoxic, do not fire not quick-fried, almost non-volatility organic gas produce, environmental protection.But due to the smooth surface atresia of glass baseplate, and surface tension is low, and the wettability of therefore general ink for ink-jet print to glass baseplate is poor, and sticking power is low.
Pigment dyestuff is bright-colored, strong coloring force, and chromatogram is complete, but most pigment dyestuff exists the shortcoming that light fastness and resistance to migration can differ from, therefore needs to improve light fastness by photostabilizer.Both at home and abroad in the polymer coloration course of processing, remain and pigment dyestuff and photostabilizer are added use respectively, because the molecular weight of pigment dyestuff and photostabilizer is relatively little, thus cause the rising of tooling cost, and the simple light fastness of mechanically mixing to pigment is raised the efficiency not quite.
Develop the dispersion resin liquid that is applicable to glass baseplate and ink has very actual meaning.
Summary of the invention
The object of the present invention is to provide a kind of dispersion resin liquid for glass baseplate.
Another object of the present invention is to provide a kind of water-based jet ink for glass baseplate.
The technical solution used in the present invention is:
A kind of dispersion resin liquid for glass baseplate, wherein the molecular-weight average of resin is 1000 ~ 10000, its constitutive material is following mass parts: 1.5 ~ 5 parts of category-A acrylate, 1.5 ~ 10 parts of piperidino methyl acrylate, 16 ~ 19 parts of category-B acrylate, appropriate initiator, appropriate polymerizable molecular amount conditioning agents, suitable quantity of water;
Wherein, category-A acrylate is the acrylate containing ammonium ion, and category-B acrylate is at least one in methyl methacrylate, butyl acrylate, Isooctyl acrylate monomer, octadecyl acrylate, octadecyl methacrylate, vinylformic acid, methacrylic acid.
As the further improvement of above-mentioned dispersion resin liquid, category-A acrylate is selected from acrylyl oxy-ethyl-trimethyl salmiac, N-carboxymethyl-N, at least one in N-dimethyl-2-[(2-methyl isophthalic acid-oxo-2-propenyl)-chloro] ethanamide inner salt.
As the further improvement of above-mentioned dispersion resin liquid, in dispersion resin liquid, the molecular-weight average of resin is preferably 1000 ~ 8000, and 1000 ~ 5000, be more preferred from 1500 ~ 3000.
As the further improvement of above-mentioned dispersion resin liquid, polymerizable molecular amount conditioning agent is selected from least one in lauryl mercaptan, hexadecyl mercaptan, the different monooctyl ester of 3-thiohydracrylic acid.
As the further improvement of above-mentioned dispersion resin liquid, initiator is selected from water soluble persulfates initiator.
A kind of preparation method of dispersion resin liquid, comprise: in reactor, add water, be warming up to 65 ~ 80 DEG C, drip the mixture of category-A acrylate, piperidino methyl acrylate, category-B acrylate and polymerizable molecular amount conditioning agent, add initiator in dropping process simultaneously in batches, insulation reaction obtains dispersion resin liquid, and wherein, the raw material composition of dispersion resin liquid as mentioned above.
A kind of water-based jet ink for glass baseplate, be made up of the raw material of following mass parts: 1 ~ 6 part of pigment, 1 ~ 7 part of dispersion resin liquid, 6 ~ 18 parts of organosilicon-modified acrylic epoxy resin, 0.9 ~ 1.5 part of auxiliary agent, appropriate aqueous solvent, wherein, dispersion resin liquid is above-mentioned dispersion resin liquid.
Organosilicon-modified acrylic epoxy resin is hud typed machine fluorine-silicon modified acrylic epoxy resin, its quality constitutive material is: 0.2 ~ 1.1 part of positive silicon ester, 0.3 ~ 0.8 part of 3-(methacryloxypropyl) propyl trimethoxy silicane, 24 ~ 28 parts of category-B acrylate, 8 ~ 15 parts of C class acrylate, 6 ~ 18 parts of D class acrylate, 0.8 ~ 2 part of emulsifying agent, 0.2 ~ 0.3 part of buffer reagent, 0.2 ~ 0.3 part of initiator, 0.2 ~ 1.5 part of pH adjusting agent, 10 ~ 23 parts of ethanol, suitable quantity of water, wherein, category-B acrylate is methyl methacrylate, butyl acrylate, Isooctyl acrylate monomer, octadecyl acrylate, octadecyl methacrylate, vinylformic acid, at least one in methacrylic acid, C class acrylate is the acrylate containing ring, and D class acrylate is epoxy acrylate.
The preparation method of organosilicon-modified acrylic epoxy resin comprises the steps:
1) add positive silicon ester, pH adjusting agent, deionized water and ethanol in a kettle., stirring at room temperature is obtained by reacting silicon sol;
2) slowly 3-(methacryloxypropyl is dripped) mixed solution of propyl trimethoxy silicane and ethanol, dropwise and continue to react completely, generate the MPS-SiO of band double bond
2;
3) get category-B acrylate, C class acrylate, D class acrylate, mix, add emulsifying agent and deionized water, stir and obtain pre-emulsion;
4) at MPS-SiO
2in add emulsifying agent, buffer reagent and deionized water, dispersed with stirring, be warmed up to 70 ~ 85 DEG C, drip above-mentioned pre-emulsion and initiator solution simultaneously, pre-emulsion dripped off in 2 ~ 4 hours, and initiator solution dropwised in the half an hour after pre-emulsion drips off, and temperature raises 3 ~ 5 DEG C, be incubated 0.5 ~ 1 hour, to obtain organosilicon be core acrylic acid epoxy resin is the organosilicon-modified acrylic epoxy resin of shell.
As the further improvement of above-mentioned water-based jet ink, C class acrylate is selected from isobornyl acrylate, vinylformic acid hexahydro--4,7-methylene radical-1H-indenyl ester, vinylformic acid octahydro-4, at least one in 7-methylene radical-1H-indenyl ester, methacrylic acid three ring [5.2.1.02,6]-8-base in last of the ten Heavenly stems ester.
As the further improvement of above-mentioned water-based jet ink, auxiliary agent is selected from one or more the mixture in defoamer, surface tension modifier, fungicidal preservative, pH adjusting agent; Aqueous solvent is selected from one or more the mixture in ethylene glycol, glycol ether, propylene glycol, butyl glycol ether, butyl, glycerine, 2-Pyrrolidone, deionized water.
The invention has the beneficial effects as follows:
Dispersion resin liquid of the present invention, grinding blended with pigment dyestuff, efficiently can be combined with pigment dyestuff, effectively improves the light fastness of pigment dyestuff, and resin-coated can be made in surface of pigments, the stability of pigment improves a lot simultaneously.
Water-based jet ink of the present invention, adopts the acrylate and piperidino methyl acrylate that contain ammonium ion as starting material, synthesizes existing ammonium group, have again the dispersion resin of hindered amine group, for the grinding of pigment dyestuff.Ammonium group has strong anchorage effect to granules of pigments, thus improves dispersion stabilization and the resistance to migration of pigment dyestuff.By the anchorage effect of ammonium group to pigment, hindered amine group is distributed in surface of pigments firmly, plays the effect of photostabilizer, effectively improves the light fastness of pigment dyestuff.
Water-based jet ink of the present invention, by accessing vinyl group on positive silicon ester, and with acrylate, carry out radical polymerization containing the acrylate of ring, epoxy acrylate, the core-shell emulsion of synthesizing organo-silicon to be core acrylic acid epoxy resin be shell.In emulsion drying process, the interphase interaction of organosilicon, form the network structure running through acrylic acid epoxy resin, organosilicon, epoxide group all react with glass substrate and form chemical structure closely, firmly by paint adhesion on the glass substrate, good attachment fastness is provided.
Water-based jet ink of the present invention, introduces the acrylate containing ring in organosilicon-modified acrylic epoxy resin, and its ring texture not only increases close outstanding property and the sticking power of resin, and pigment is attached on glass better; And improve weathering resistance and the transparency of resin, ink-jet is developed the color more bright-coloured.
Embodiment
A kind of dispersion resin liquid for glass baseplate, wherein the molecular-weight average of resin is 1000 ~ 10000, its constitutive material is following mass parts: 1.5 ~ 5 parts of category-A acrylate, 1.5 ~ 10 parts of piperidino methyl acrylate, 16 ~ 19 parts of category-B acrylate, appropriate initiator, appropriate polymerizable molecular amount conditioning agents, suitable quantity of water;
Wherein, category-A acrylate is that category-B acrylate is at least one in methyl methacrylate, butyl acrylate, Isooctyl acrylate monomer, octadecyl acrylate, octadecyl methacrylate, vinylformic acid, methacrylic acid containing the acrylate containing ammonium ion.
As the further improvement of above-mentioned dispersion resin liquid, category-A acrylate is selected from acrylyl oxy-ethyl-trimethyl salmiac, N-carboxymethyl-N, at least one in N-dimethyl-2-[(2-methyl isophthalic acid-oxo-2-propenyl)-chloro] ethanamide inner salt.The use of these monomers, can make dispersion resin be combined with pigment better.Contained by category-A acrylate, ammonium ion has strong anchorage effect to granules of pigments, thus improves the dispersion stabilization of pigment, in addition, ammonium group has stronger wetting ability, the solvability of dispersion resin in water can be improved, thus form the uniform dispersion resin aqueous solution, avoid polymkeric substance and separate out.
Ink for ink-jet print general requirement viscosity is less than 10 mpas, and above-mentioned dispersion resin liquid adopts solution polymerization, if molecular weight too conference cause polymeric solution viscosity too high, in addition, molecular weight is excessive also can affect the anchorage effect of ammonium ion to pigment.As the further improvement of above-mentioned dispersion resin liquid, in dispersion resin liquid, the molecular-weight average of resin is preferably 1000 ~ 8000, and 1000 ~ 5000, be more preferred from 1500 ~ 3000.
The effect of polymerizable molecular amount conditioning agent is the size controlling molecular resin amount, can use polymerizable molecular amount conditioning agent well-known to those skilled in the art.As the further improvement of above-mentioned dispersion resin liquid, polymerizable molecular amount conditioning agent is selected from least one in lauryl mercaptan, hexadecyl mercaptan, the different monooctyl ester of 3-thiohydracrylic acid.The consumption of polymerizable molecular amount conditioning agent can regulate as required, and based on the proportioning of above-mentioned dispersion resin liquid, its addition can be 1 ~ 2 part.Also in conjunction with regulation and control reaction conditions, the molecular weight of polymkeric substance can be controlled.
The initiator that initiator is well known to those skilled in the art, is selected from water soluble persulfates initiator, as ammonium persulphate, Sodium Persulfate and Potassium Persulphate.The consumption of initiator can regulate as required, and based on the proportioning of above-mentioned dispersion resin liquid, its addition can be 0.3 ~ 0.6 part.
In resin dispersion liquid, water uses as solvent, can regulate its consumption as required.Based on the proportioning of above-mentioned dispersion resin liquid, its addition can be 70 ~ 75 parts.
A kind of preparation method of dispersion resin liquid, comprise: in reactor, add water, be warming up to 65 ~ 80 DEG C, drip the mixture of category-A acrylate, piperidino methyl acrylate, category-B acrylate and polymerizable molecular amount conditioning agent, add initiator in dropping process simultaneously in batches, insulation reaction obtains dispersion resin liquid, and wherein, the raw material composition of dispersion resin liquid as mentioned above.
A kind of water-based jet ink for glass baseplate, be made up of the raw material of following mass parts: 1 ~ 6 part of pigment, 1 ~ 7 part of dispersion resin liquid, 6 ~ 18 parts of organosilicon-modified acrylic epoxy resin, 0.9 ~ 1.5 part of auxiliary agent, appropriate aqueous solvent, wherein, dispersion resin liquid is above-mentioned dispersion resin liquid.Preferably, the consumption of aqueous solvent is 67 ~ 92 parts.
Organosilicon-modified acrylic epoxy resin is hud typed machine fluorine-silicon modified acrylic epoxy resin, its quality constitutive material is: 0.2 ~ 1.1 part of positive silicon ester, 0.3 ~ 0.8 part of 3-(methacryloxypropyl) propyl trimethoxy silicane, 24 ~ 28 parts of category-B acrylate, 8 ~ 15 parts of C class acrylate, 6 ~ 18 parts of D class acrylate, 0.8 ~ 2 part of emulsifying agent, 0.2 ~ 0.3 part of buffer reagent, 0.2 ~ 0.3 part of initiator, 0.2 ~ 1.5 part of pH adjusting agent, 10 ~ 23 parts of ethanol, suitable quantity of water, wherein, category-B acrylate is methyl methacrylate, butyl acrylate, Isooctyl acrylate monomer, octadecyl acrylate, octadecyl methacrylate, vinylformic acid, at least one in methacrylic acid, C class acrylate is the acrylate containing ring, and D class acrylate is epoxy acrylate.
The preparation method of organosilicon-modified acrylic epoxy resin comprises the steps:
1) add positive silicon ester, pH adjusting agent, deionized water and ethanol in a kettle., stirring at room temperature is obtained by reacting silicon sol;
2) slowly 3-(methacryloxypropyl is dripped) mixed solution of propyl trimethoxy silicane and ethanol, dropwise and continue to react completely, generate the MPS-SiO of band double bond
2;
3) get category-B acrylate, C class acrylate, D class acrylate, mix, add emulsifying agent and deionized water, stir and obtain pre-emulsion;
4) at MPS-SiO
2in add emulsifying agent, buffer reagent and deionized water, dispersed with stirring, be warmed up to 70 ~ 85 DEG C, drip above-mentioned pre-emulsion and initiator solution simultaneously, pre-emulsion dripped off in 2 ~ 4 hours, and initiator solution dropwised in the half an hour after pre-emulsion drips off, and temperature raises 3 ~ 5 DEG C, be incubated 0.5 ~ 1 hour, to obtain organosilicon be core acrylic acid epoxy resin is the organosilicon-modified acrylic epoxy resin of shell.
Also well-known to those skilled in the art other can be adopted glass baseplate to be had to the hud typed machine fluorine-silicon modified acrylic epoxy resin of high adhesive force.
As the further improvement of above-mentioned water-based jet ink, C class acrylate is selected from isobornyl acrylate, vinylformic acid hexahydro--4,7-methylene radical-1H-indenyl ester, vinylformic acid octahydro-4, at least one in 7-methylene radical-1H-indenyl ester, methacrylic acid three ring [5.2.1.02,6]-8-base in last of the ten Heavenly stems ester.The use of C class acrylate, can make the organosilicon-modified acrylic epoxy resin prepared have better water-fast thermotolerance, contribute to increasing its sticking power simultaneously, improve its transparency.
As the further improvement of above-mentioned water-based jet ink, D class acrylate is selected from 3, at least one in 4-epoxycyclohexyl-methyl acrylate, 3,4-epoxycyclohexyl-methyl methacrylic esters, vinylformic acid tetrahydro furfuryl ester, methacrylic acid tetrahydro furfuryl ester.The use of D class acrylate effectively can improve the sticking power of ink film to glass, and compared with the glycidyl methacrylate used with tradition, the polymerization stability of D class acrylate is higher, is not easy gel.
As the further improvement of above-mentioned water-based jet ink, auxiliary agent is selected from one or more the mixture in defoamer, surface tension modifier, fungicidal preservative, pH adjusting agent; Aqueous solvent is selected from one or more the mixture in ethylene glycol, glycol ether, propylene glycol, butyl glycol ether, butyl, glycerine, 2-Pyrrolidone, deionized water.
Below in conjunction with specific embodiment, the present invention is further explained, but embodiments of the present invention is not limited in any way.Unless stated otherwise, involved in embodiment reagent, method are the conventional reagent in this area and method.
The performance test of water-based jet ink: measure ink jet viscosity with reference to the rotational method in GB/T 10247-2008; GB/T 19077.1-2008 measures the median size of ink-jet.Water-based jet ink direct spraying is on glass baseplate, and 180 DEG C of bakings are dry, according to the GB/T 13217.7-2009 liquid ink attachment fastness method of inspection, measures ink-jet to the attachment fastness of glass; Evaluate photostabilization according to GB/T 22771-2008 printing technology printed matter and printing-ink optical filtering xenon arc lamp, measure the light fastness of ink for ink-jet print.
embodiment 1:
the preparation of dispersion resin liquid:
Add 70g deionized water in a kettle., increase the temperature to 70 DEG C, drip the mixture of 1.5g acrylyl oxy-ethyl-trimethyl salmiac, 10.0g piperidino methyl acrylate, 14.2g butyl acrylate, 2.0g vinylformic acid and 2.0g lauryl mercaptan, drip off in 2 hours; In dropping process, divide 3 batches and add ammonium persulphate, often criticize 0.1g, insulation reaction 1.5 hours, obtains dispersion resin liquid.
Gained dispersion resin liquid is micro-yellow half penetrating, and solid content is that at 29.6%, 25 DEG C, viscosity is 35.6mpa.s, and number-average molecular weight is 1740.
the synthesis of organosilicon-modified acrylic epoxy resin
Add 0.2g methyl silicate, 0.25g ammoniacal liquor, 2.0g deionized water and 8.0g ethanol in a kettle., stirring at room temperature reacts 8 hours.Slow dropping 0.3g 3-(methacryloxypropyl) mixed solution of propyl trimethoxy silicane and 2g ethanol, drip off in 1 hour, continue reaction 24 hours, generate the MPS-SiO of band double bond
2;
Take 9.0g butyl acrylate, 5.0g octadecyl acrylate, 9.0g methyl methacrylate, 1.0g vinylformic acid, 8.0g methacrylic acid three ring [5.2.1.02,6] last of the ten Heavenly stems-8-base ester and 18.0g3,4-epoxycyclohexyl-methyl acrylate, mix, add 0.6g anionic emulsifier CO436,0.3g nonionic emulsifying agent TO-10 and 22.0g deionized water, 500rmp high-speed stirring obtains pre-emulsion.
Gained organosilicon-modified acrylic epoxy resin latex is creamy white, blueing light, and solid content is that at 49.8%, 25 DEG C, viscosity is 210mpa.s.
the preparation of water-based jet ink
Take 40g ethylene glycol, 55g glycol ether, 182g deionized water, 2.0g defoamer TEGO Foamex 810,1.2g Monoethanolamine MEA BASF, stir, add the above-mentioned dispersion resin liquid of 60g respectively, 60gC.I. Pigment red 53,1200rmp dispersed with stirring 0.5 hour, employing sand mill grinds, and successively by the membrane filtration of 1.0 μm, 0.45 μm, can obtain red pigment mill base to mill base;
Take 12.5g glycerine, 20g glycol ether, 7.5g butyl, 1.6g2-pyrrolidone, 44.8g deionized water, 0.2g surface tension modifier TEGO Wet 510,0.001g biocide mildewcide XF-2,0.7g Monoethanolamine MEA BASF, after mixing, add 6.0g above-mentioned organosilicon-modified acrylic epoxy resin, the above-mentioned red pigment mill base of 6.7g respectively, dispersed with stirring is even, namely obtains the water-based jet ink for glass baseplate.
Red water-based jet ink prepared by embodiment 1, at 25 DEG C, viscosity is 5.43mpas, and median size is 270nm; Ink film is bright-colored, does not come off with 3M tape stripping film, attachment fastness 100%, light fastness 6 grades.
embodiment 2:
the preparation of dispersion resin liquid:
Add 75g deionized water in a kettle., increase the temperature to 65 DEG C, drip 5.0gN-carboxymethyl-N, the mixture of N-dimethyl-2-[(2-methyl isophthalic acid-oxo-2-propenyl)-chloro] ethanamide Inner salt, 1.5g piperidino methyl acrylate, 4.5g methyl methacrylate, 12.0g butyl acrylate, 0.5g methacrylic acid and 1.0g hexadecyl mercaptan, dripped off in 2 hours; In dropping process, divide 5 batches and add Sodium Persulfate, often criticize 0.1g, insulation reaction 1 hour, obtains dispersion resin liquid.
Gained dispersion resin liquid is micro-yellow half penetrating, and solid content is that at 24.7%, 25 DEG C, viscosity is 45.5mpa.s, and number-average molecular weight is 2890.
the synthesis of organosilicon-modified acrylic epoxy resin
Add the positive silicic acid propyl ester of 1.1g, 1.5g ammoniacal liquor, 7.0g deionized water and 18.0g ethanol in a kettle., stirring at room temperature reacts 12 hours.Slow dropping 0.6g 3-(methacryloxypropyl) mixed solution of propyl trimethoxy silicane and 5g ethanol, drip off in 2 hours, continue reaction 24 hours, generate the MPS-SiO of band double bond
2;
Take 15.0g butyl acrylate, 7.0g methyl methacrylate, 2.0g methacrylic acid, 15.0g vinylformic acid octahydro-4,7-methylene radical-1H-indenyl ester and 6.0g vinylformic acid tetrahydro furfuryl ester, mix, add 0.5g anionic emulsifier CO436,0.9g nonionic emulsifying agent TO-10 and 19.4g deionized water, 600rmp high-speed stirring obtains pre-emulsion;
At MPS-SiO
2in add 0.3gCO436,0.6gTO-10,0.2gNaHCO
3buffer reagent, dispersed with stirring, is warmed up to 70 DEG C, drip above-mentioned pre-emulsion and 0.2g is dissolved in Sodium Persulfate in 3.0g deionized water, pre-emulsion dripped off in 3 hours, and initiator solution dropwised in the half an hour after pre-emulsion drips off simultaneously, temperature raises 5 DEG C, is incubated 1 hour; Being down to room temperature, is 7 by ammoniacal liquor adjust ph, filters, and to obtain organosilicon be core acrylic acid epoxy resin is the organosilicon-modified acrylic epoxy resin latex of shell.
Gained organosilicon-modified acrylic epoxy resin latex is creamy white, blueing light, and solid content is that at 46.3%, 25 DEG C, viscosity is 195mpa.s.
the preparation of water-based jet ink
Take 45.5g ethylene glycol, 50g butyl, 172.2g deionized water, 0.8g defoamer HY-206,1.5g Monoethanolamine MEA BASF, stir, add the above-mentioned dispersion resin liquid of 70g respectively, 60gC.I. pigment Blue 15,1500rmp dispersed with stirring 1 hour, employing sand mill grinds, and successively by the membrane filtration of 1.0 μm, 0.45 μm, can obtain blue pigments mill base to mill base;
Take 10.0g glycerine, 17.5g butyl, 2.0g2-pyrrolidone, 1.55g ethylene glycol, 10g deionized water, 0.2g surface tension modifier TEGO Rad 2100,0.002g biocide mildewcide CF-S40,0.75g Monoethanolamine MEA BASF, after mixing, add 18.0g above-mentioned organosilicon-modified acrylic epoxy resin, the above-mentioned red pigment mill base of 40.0g respectively, dispersed with stirring is even, namely obtains the water-based jet ink for glass baseplate.
Blue water-based ink for ink-jet print prepared by embodiment 2, at 25 DEG C, viscosity is 4.85mpas, and median size is 263nm; Ink film is bright-colored, does not come off with 3M tape stripping film, attachment fastness 100%, light fastness 7 grades.
embodiment 3
the synthesis of dispersion resin liquid
Add 70g deionized water in a kettle., increase the temperature to 80 DEG C, drip the mixture of 3.0g acrylyl oxy-ethyl-trimethyl salmiac, 6.0g piperidino methyl acrylate, 5.1g methyl methacrylate, 12.0g butyl acrylate, 1.5g vinylformic acid and the different monooctyl ester of 1.8g 3-thiohydracrylic acid, drip off in 1 hour; In dropping process, divide 3 batches and add Potassium Persulphate, often criticize 0.2g, insulation reaction 2 hours, obtains dispersion resin liquid.
Gained dispersion resin liquid is micro-yellow half penetrating, and solid content is that at 28.8%, 25 DEG C, viscosity is 40.0mpa.s, and number-average molecular weight is 2650.
the synthesis of organosilicon-modified acrylic epoxy resin
Add 0.4g tetraethoxy, 1.0g ammoniacal liquor, 5.0g deionized water and 10.0g ethanol in a kettle., stirring at room temperature reacts 10 hours.Slow dropping 0.8g 3-(methacryloxypropyl) mixed solution of propyl trimethoxy silicane and 5g ethanol, drip off in 1.5 hours, continue reaction 24 hours, generate the MPS-SiO of band double bond
2;
Take 11.0g Isooctyl acrylate monomer, 5.0g octadecyl methacrylate, 10.0g methyl methacrylate, 1.5g vinylformic acid, 5.0g isobornyl acrylate, 3.5g methacrylic acid three ring [5.2.1.02,6] last of the ten Heavenly stems-8-base ester and 12.0g3,4-epoxycyclohexyl-methyl acrylate, mix, add 0.3g anionic emulsifier EPA-073,0.2g nonionic emulsifying agent TO-7 and 22.0g deionized water, 500rmp high-speed stirring obtains pre-emulsion;
At MPS-SiO
2in add 0.2g EPA-073,0.1gTO-7,0.27gNaHCO
3buffer reagent and 3.43g deionized water, dispersed with stirring, be warmed up to 85 DEG C, drip above-mentioned pre-emulsion and 0.3g is dissolved in ammonium persulphate in 3.0g deionized water simultaneously, pre-emulsion dripped off in 2 hours, initiator solution dropwised in the half an hour after pre-emulsion drips off, and temperature raises 3 DEG C, was incubated 0.5 hour; Being down to room temperature, is 7 by ammoniacal liquor adjust ph, filters, and to obtain organosilicon be core acrylic acid epoxy resin is the organosilicon-modified acrylic epoxy resin latex of shell.
Gained organosilicon-modified acrylic epoxy resin latex is creamy white, blueing light, and solid content is that at 48.8%, 25 DEG C, viscosity is 190mpa.s.
the preparation of water-based jet ink
The water-based jet ink of the present embodiment, its concrete preparation process is as follows:
Take 40g ethylene glycol, 60g glycol ether, 166g deionized water, 1.0g defoamer TEGO Foamex 810,1.0g trolamine, stir, add the above-mentioned dispersion resin liquid of 72g respectively, 60gC.I. pigment yellow 13 8,1500rmp dispersed with stirring 45min, employing sand mill grinds, and successively by the membrane filtration of 1.0 μm, 0.45 μm, can obtain yellow ultramarine mill base to mill base;
Take 13.0g glycerine, 15.0g glycol ether, 8.5g butyl glycol ether, 1.5g2-pyrrolidone, 20.2g deionized water, 0.8g surface tension modifier TEGO Rad 2200N, 0.002g biocide mildewcide XF-2,0.5g trolamine, after mixing, add 10.5g above-mentioned organosilicon-modified acrylic epoxy resin, the above-mentioned yellow ultramarine mill base of 30g respectively, dispersed with stirring is even, namely obtains the water-based jet ink for glass baseplate.
Yellow water-based jet ink prepared by embodiment 3, at 25 DEG C, viscosity is 5.30mpas, and median size is 258nm; Ink film is bright-colored, does not come off with 3M tape stripping film, attachment fastness 100%, light fastness 7 grades.
From the data of embodiment, dispersion resin liquid of the present invention can inclusion pigment well, and water-base ink has excellent performance, is specially adapted to the printing of glass baseplate.
Claims (10)
1. the dispersion resin liquid for glass baseplate, wherein the molecular-weight average of resin is 1000 ~ 10000, its constitutive material is following mass parts: 1.5 ~ 5 parts of category-A acrylate, 1.5 ~ 10 parts of piperidino methyl acrylate, 16 ~ 19 parts of category-B acrylate, appropriate initiator, appropriate polymerizable molecular amount conditioning agents, suitable quantity of water;
Wherein, category-A acrylate is the acrylate containing ammonium ion, and category-B acrylate is at least one in methyl methacrylate, butyl acrylate, Isooctyl acrylate monomer, octadecyl acrylate, octadecyl methacrylate, vinylformic acid, methacrylic acid.
2. dispersion resin liquid according to claim 1, it is characterized in that: category-A acrylate is selected from acrylyl oxy-ethyl-trimethyl salmiac, N-carboxymethyl-N, at least one in N-dimethyl-2-[(2-methyl isophthalic acid-oxo-2-propenyl)-chloro] ethanamide inner salt.
3. dispersion resin liquid according to claim 1, is characterized in that: polymerizable molecular amount conditioning agent is selected from least one in lauryl mercaptan, hexadecyl mercaptan, the different monooctyl ester of 3-thiohydracrylic acid.
4. dispersion resin liquid according to claim 1, is characterized in that: initiator is selected from water soluble persulfates initiator.
5. the preparation method of a dispersion resin liquid, comprise: in reactor, add water, be warming up to 65 ~ 80 DEG C, drip the mixture of category-A acrylate, piperidino methyl acrylate, category-B acrylate and polymerizable molecular amount conditioning agent, add initiator in dropping process simultaneously in batches, insulation reaction obtains dispersion resin liquid, and wherein, the raw material composition of dispersion resin liquid is as described in Claims 1 to 4 any one.
6. the water-based jet ink for glass baseplate, be made up of the raw material of following mass parts: 1 ~ 6 part of pigment, 1 ~ 7 part of dispersion resin liquid, 6 ~ 18 parts of organosilicon-modified acrylic epoxy resin, 0.9 ~ 1.5 part of auxiliary agent, appropriate aqueous solvent, wherein, dispersion resin liquid dispersion resin liquid as claimed in any one of claims 1 to 5, wherein.
7. water-based jet ink according to claim 6, it is characterized in that: organosilicon-modified acrylic epoxy resin is hud typed machine fluorine-silicon modified acrylic epoxy resin, its quality constitutive material is: 0.2 ~ 1.1 part of positive silicon ester, 0.3 ~ 0.8 part of 3-(methacryloxypropyl) propyl trimethoxy silicane, 24 ~ 28 parts of category-B acrylate, 8 ~ 15 parts of C class acrylate, 6 ~ 18 parts of D class acrylate, 0.8 ~ 2 part of emulsifying agent, 0.2 ~ 0.3 part of buffer reagent, 0.2 ~ 0.3 part of initiator, 0.2 ~ 1.5 part of pH adjusting agent, 10 ~ 23 parts of ethanol, suitable quantity of water, wherein, category-B acrylate is methyl methacrylate, butyl acrylate, Isooctyl acrylate monomer, octadecyl acrylate, octadecyl methacrylate, vinylformic acid, at least one in methacrylic acid, C class acrylate is the acrylate containing ring, and D class acrylate is epoxy acrylate.
8. water-based jet ink according to claim 7, is characterized in that: the preparation method of organosilicon-modified acrylic epoxy resin comprises the steps:
1) add positive silicon ester, pH adjusting agent, deionized water and ethanol in a kettle., stirring at room temperature is obtained by reacting silicon sol;
2) slowly 3-(methacryloxypropyl is dripped) mixed solution of propyl trimethoxy silicane and ethanol, dropwise and continue to react completely, generate the MPS-SiO of band double bond
2;
3) get category-B acrylate, C class acrylate, D class acrylate, mix, add emulsifying agent and deionized water, stir and obtain pre-emulsion;
4) at MPS-SiO
2in add emulsifying agent, buffer reagent and deionized water, dispersed with stirring, be warmed up to 70 ~ 85 DEG C, drip above-mentioned pre-emulsion and initiator solution simultaneously, pre-emulsion dripped off in 2 ~ 4 hours, and initiator solution dropwised in the half an hour after pre-emulsion drips off, and temperature raises 3 ~ 5 DEG C, be incubated 0.5 ~ 1 hour, to obtain organosilicon be core acrylic acid epoxy resin is the organosilicon-modified acrylic epoxy resin of shell.
9. water-based jet ink according to claim 6, is characterized in that: auxiliary agent is selected from one or more the mixture in defoamer, surface tension modifier, fungicidal preservative, pH adjusting agent; Aqueous solvent is selected from one or more the mixture in ethylene glycol, glycol ether, propylene glycol, butyl glycol ether, butyl, glycerine, 2-Pyrrolidone, deionized water.
10. the water-based jet ink according to claim 7 or 8, it is characterized in that: C class acrylate is selected from isobornyl acrylate, vinylformic acid hexahydro--4,7-methylene radical-1H-indenyl ester, vinylformic acid octahydro-4, at least one in 7-methylene radical-1H-indenyl ester, methacrylic acid three ring [5.2.1.02,6]-8-base in last of the ten Heavenly stems ester.
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