CN104861780B - A kind of dispersion resin liquid and ink for glass baseplate - Google Patents
A kind of dispersion resin liquid and ink for glass baseplate Download PDFInfo
- Publication number
- CN104861780B CN104861780B CN201510168577.8A CN201510168577A CN104861780B CN 104861780 B CN104861780 B CN 104861780B CN 201510168577 A CN201510168577 A CN 201510168577A CN 104861780 B CN104861780 B CN 104861780B
- Authority
- CN
- China
- Prior art keywords
- acrylate
- classes
- resin liquid
- dispersion resin
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
Abstract
The invention discloses a kind of dispersion resin liquid and ink for glass baseplate, the mean molecule quantity of dispersion resin liquid resin is 1000~10000, and its constitutive material is the acrylate containing ammonium, piperidino methyl acrylate, alkyl acrylate, initiator, polymerizable molecular amount conditioning agent and water.The dispersion resin liquid of the present invention, is blended with organic pigment and grinds, can efficiently be combined with organic pigment, effectively improve the fastness to light of organic pigment, while resin-coating can be made in surface of pigments, the stability of pigment improves a lot.Ink is water-base ink, can be firmly bonded on glass baseplate, and fastness to light is up to 6~7 grades, bright and full color.
Description
Technical field
The present invention relates to a kind of resin and water-based jet ink for water-based jet ink, more particularly to one kind is applied to
The dispersion resin liquid and ink of glass baseplate.
Background technology
Traditional analog printing need to be by imaging, color separation, plate-making to being printed on the machine this tediously long time-consuming production process and technique
Flow, limits the timely transmission of merchandise news and exchanges, and the limitation of minimum batch printing starting point also makes production cost not have
Effect reduction.Digital printing combination computer technology, with directly export substitution traditional printing make, its personalization, timelyization, in small batches
The characteristics of amount and quick renewal, makes press there occurs revolutionary change, promotes typography from simulated to total digitalization
Direction is developed, the broad mass market prospect growing day by day for determining digital spray printing ink of digital printing application field.
With the improvement of people ' s living standards and personalized pursuit, people are to various glass decoration articles for use, such as light fixture, wine
Decoration effect of cup, bottle, vase, glass door and window etc. proposes higher and higher requirement.The country is in glass baseplate at present
On printing（Including ink jet printing）It is that elder generation is pre-processed on glass, i.e., first goes up precoated shet to improve the attachment to glass
Power, then impressing pattern, last spraying protective layer.This process is complicated, and it is most of use solvent based coating, have substantial amounts of
VOC volatilizees, and technique is cumbersome and unfriendly to environment.CN102492330A discloses a kind of UV photocurings for glass baseplate
Ink-jet ink, its can directly spray printing it is on the glass substrate, strong to glass attachment power, warm water immersion does not fall off, not whitened.But solidification
Film hardness is relatively low, easy scratch, and boiling water immersion comes off in the form of sheets, and UV ink-jets have monomer smell weight, cost height etc. before solidification
Unfavorable factor.Water-based jet ink due to water as solvent, it is nontoxic, non-ignitable not quick-fried, almost without VOC
Produce, environmental protection.But be due to glass baseplate surface it is smooth non-porous, and surface tension is low, therefore general ink-jet ink
Wetability to glass baseplate is poor, and adhesive force is low.
Organic pigment is bright-colored, and strong coloring force, chromatogram is complete, but most organic pigments have fastness to light and resistance to migration
The shortcoming of poor performance, therefore need to improve fastness to light by light stabilizer.Both at home and abroad in polymer coloration process, still
It is so to be separately added into organic pigment and light stabilizer to use, because the molecular weight of organic pigment and light stabilizer is relatively small,
So as to cause the rising of processing cost, and simple mechanical mixture is little to the fastness to light raising efficiency of pigment.
The dispersion resin liquid and ink developed suitable for glass baseplate have very actual meaning.
The content of the invention
It is an object of the invention to provide a kind of dispersion resin liquid for glass baseplate.
It is another object of the present invention 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, the wherein mean molecule quantity of resin are 1000~10000, and it is constituted
Raw material is following mass parts：1.5~5 parts of A classes acrylate, 1.5~10 parts of piperidino methyl acrylate, 16~19 parts of B
Class acrylate, appropriate initiator, appropriate polymerizable molecular amount conditioning agent, suitable quantity of water；
Wherein, A classes acrylate is the acrylate containing ammonium ion, and B classes acrylate is methyl methacrylate, third
Olefin(e) acid butyl ester, Isooctyl acrylate monomer, octadecyl acrylate, octadecyl methacrylate, acrylic acid, methacrylic acid
At least one of.
As the further improvement of above-mentioned dispersion resin liquid, A classes acrylate is selected from acrylyl oxy-ethyl-trimethyl chlorination
Ammonium, N- carboxymethyls-N, N- dimethyl -2- [（2- methyl isophthalic acids-oxo -2- acrylic）- chloro] in acetamide inner salt at least one
Kind.
As the further improvement of above-mentioned dispersion resin liquid, the mean molecule quantity of resin is preferably 1000 in dispersion resin liquid
~8000,1000~5000, more preferably 1500~3000.
As the further improvement of above-mentioned dispersion resin liquid, polymerizable molecular amount conditioning agent is selected from lauryl mercaptan, 16
At least one of alkyl hydrosulfide, 3- isooctyl mercaptopropionates.
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, including：Water is added in reactor, 65~80 DEG C are warming up to, A classes are added dropwise
Acrylate, piperidino methyl acrylate, the mixture of B classes acrylate and polymerizable molecular amount conditioning agent, during dropwise addition
Initiator is added portionwise simultaneously, insulation reaction obtains dispersion resin liquid, wherein, the raw material composition of dispersion resin liquid is as described above.
A kind of water-based jet ink for glass baseplate, is made up of the raw material of following mass parts：1~6 part of pigment, 1~7
Part dispersion resin liquid, 6~18 parts of organosilicon-modified acrylic epoxy resin, 0.9~1.5 part of auxiliary agent, appropriate aqueous solvent, its
In, 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
For：0.2~1.1 part of positive esters of silicon acis, 0.3~0.8 part of 3-（Methacryloxypropyl）Propyl trimethoxy silicane, 24~28 parts of B classes
Acrylate, 8~15 parts of C classes acrylate, 6~18 parts of D classes acrylate, 0.8~2 part of emulsifying agent, 0.2~0.3 part of buffering
Agent, 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, B class acrylate is
Methyl methacrylate, butyl acrylate, Isooctyl acrylate monomer, octadecyl acrylate, octadecyl methacrylate,
At least one of acrylic acid, methacrylic acid；C classes acrylate is the acrylate containing ring, and D classes acrylate is epoxy third
Olefin(e) acid ester.
The preparation method of organosilicon-modified acrylic epoxy resin comprises the following steps：
1) positive esters of silicon acis, pH adjusting agent, deionized water and ethanol are added in a kettle., and reaction is stirred at room temperature, and to obtain silicon molten
Glue；
2) 3- is slowly added dropwise（Methacryloxypropyl）The mixed liquor of propyl trimethoxy silicane and ethanol, completion of dropping continues
Reaction is complete, generates the MPS-SiO with double bond2；
3) B classes acrylate, C classes acrylate, D class acrylate are taken, is well mixed, emulsifying agent and deionization is added
Water, stirring obtains pre-emulsion；
4) in MPS-SiO2Middle addition emulsifying agent, buffer and deionized water, dispersed with stirring, are warming up to 70~85 DEG C, together
When above-mentioned pre-emulsion and initiator solution is added dropwise, pre-emulsion was dripped off in 2~4 hours, initiator solution pre-emulsion drip
Completion of dropping in half an hour after complete, temperature raises 3~5 DEG C, is incubated 0.5~1 hour, obtains organosilicon for 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 classes acrylate is selected from isobornyl acrylate, acrylic acid
Hexahydro -4,7- methylene -1H- indenyls ester, acrylic acid octahydro -4,7- methylene -1H- indenyls ester, the ring of methacrylic acid three
At least one of [5.2.1.02,6] decyl- 8- base esters.
As the further improvement of above-mentioned water-based jet ink, auxiliary agent is selected from defoamer, surface tension modifier, sterilizes and prevent
One or more mixtures in rotten agent, pH adjusting agent；Aqueous solvent is selected from ethylene glycol, diethylene glycol (DEG), propane diols, ethylene glycol fourth
One or more mixtures in ether, butyl, glycerine, 2-Pyrrolidone, deionized water.
The beneficial effects of the invention are as follows：
The dispersion resin liquid of the present invention, is blended with organic pigment and grinds, can efficiently be combined, effectively improved with organic pigment
The fastness to light of organic pigment, while resin-coating can be made in surface of pigments, the stability of pigment improves a lot.
The water-based jet ink of the present invention, original is used as using the acrylate containing ammonium ion and piperidino methyl acrylate
Material, synthesizes existing ammonium group, has the dispersion resin of hindered amine group again, the grinding for organic pigment.Ammonium ion base
Group has strong anchorage effect to granules of pigments, so as to improve the dispersion stabilization and resistance to migration of organic pigment.By ammonium from
Subbase group is firmly distributed in surface of pigments, plays a part of light stabilizer, effectively to the anchorage effect of pigment, hindered amine group
Ground improves the fastness to light of organic pigment.
The water-based jet ink of the present invention, by accessing vinyl group on positive esters of silicon acis, and with acrylate, containing ring
Acrylate, epoxy acrylate carry out radical polymerization, and synthesizing organo-silicon is the nucleocapsid breast that core acrylic acid epoxy resin is shell
Liquid.In emulsion drying process, the interphase interaction of organosilicon, formed through acrylic acid epoxy resin network structure, organosilicon,
Epoxide group reacts to form close chemical constitution with glass substrate, firmly by pigment adhesion on the glass substrate there is provided
Good attachment fastness.
The water-based jet ink of the present invention, introduces the acrylic acid containing ring in organosilicon-modified acrylic epoxy resin
Ester, its cyclic structure not only increases the close work and adhesive force of resin, pigment is adhered better on glass；And improve
The weatherability and transparency of resin, makes ink-jet colour developing more bright-coloured.
Embodiment
A kind of dispersion resin liquid for glass baseplate, the wherein mean molecule quantity of resin are 1000~10000, and it is constituted
Raw material is following mass parts：1.5~5 parts of A classes acrylate, 1.5~10 parts of piperidino methyl acrylate, 16~19 parts of B
Class acrylate, appropriate initiator, appropriate polymerizable molecular amount conditioning agent, suitable quantity of water；
Wherein, A classes acrylate be containing the acrylate containing ammonium ion, B classes acrylate be methyl methacrylate,
Butyl acrylate, Isooctyl acrylate monomer, octadecyl acrylate, octadecyl methacrylate, acrylic acid, metering system
At least one of acid.
As the further improvement of above-mentioned dispersion resin liquid, A classes acrylate is selected from acrylyl oxy-ethyl-trimethyl chlorination
Ammonium, N- carboxymethyls-N, N- dimethyl -2- [（2- methyl isophthalic acids-oxo -2- acrylic）- chloro] in acetamide inner salt at least one
Kind.The use of these monomers, can be such that dispersion resin is preferably combined with pigment.Ammonium ion is to pigment contained by A class acrylate
Particle has strong anchorage effect, so that the dispersion stabilization of pigment is improved, in addition, ammonium group has stronger hydrophily,
Dissolubility of the dispersion resin in water can be improved, so as to form the uniform dispersion resin aqueous solution, it is to avoid polymer precipitation.
Ink-jet ink typically requires that viscosity is less than 10 mpas, and above-mentioned dispersion resin liquid uses polymerisation in solution, if molecular weight is too
Conference causes polymeric solution viscosity too high, in addition, molecular weight is excessive also to influence ammonium ion to the anchorage effect of pigment.As upper
The mean molecule quantity for stating resin in the further improvement of dispersion resin liquid, dispersion resin liquid is preferably 1000~8000,1000~
5000, more preferably 1500~3000.
The effect of polymerizable molecular amount conditioning agent is the size for controlling molecular resin amount, can use those skilled in the art
Known polymerizable molecular amount conditioning agent.As the further improvement of above-mentioned dispersion resin liquid, polymerizable molecular amount conditioning agent is selected from
At least one of lauryl mercaptan, hexadecyl mercaptan, 3- isooctyl mercaptopropionates.The consumption of polymerizable molecular amount conditioning agent
It can be adjusted as needed, based on the proportioning of above-mentioned dispersion resin liquid, its addition can be 1~2 part.It can also combine
Regulate and control reaction condition, control the molecular weight of polymer.
The initiator that initiator is well known to those skilled in the art, selected from water soluble persulfates initiator, such as over cure
Sour ammonium, sodium peroxydisulfate and potassium peroxydisulfate.The consumption of initiator can be adjusted as needed, based on above-mentioned dispersion resin liquid
Proportioning, its addition can be 0.3~0.6 part.
In resin dispersion liquid, water is used as solvent, and its consumption can be adjusted as needed.Based on above-mentioned scattered
The proportioning of resin liquid, its addition can be 70~75 parts.
A kind of preparation method of dispersion resin liquid, including：Water is added in reactor, 65~80 DEG C are warming up to, A classes are added dropwise
Acrylate, piperidino methyl acrylate, the mixture of B classes acrylate and polymerizable molecular amount conditioning agent, during dropwise addition
Initiator is added portionwise simultaneously, insulation reaction obtains dispersion resin liquid, wherein, the raw material composition of dispersion resin liquid is as described above.
A kind of water-based jet ink for glass baseplate, is made up of the raw material of following mass parts：1~6 part of pigment, 1~7
Part dispersion resin liquid, 6~18 parts of organosilicon-modified acrylic epoxy resin, 0.9~1.5 part of auxiliary agent, appropriate aqueous solvent, its
In, dispersion resin liquid is above-mentioned dispersion resin liquid.It is preferred that, 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
For：0.2~1.1 part of positive esters of silicon acis, 0.3~0.8 part of 3-（Methacryloxypropyl）Propyl trimethoxy silicane, 24~28 parts of B classes
Acrylate, 8~15 parts of C classes acrylate, 6~18 parts of D classes acrylate, 0.8~2 part of emulsifying agent, 0.2~0.3 part of buffering
Agent, 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, B class acrylate is
Methyl methacrylate, butyl acrylate, Isooctyl acrylate monomer, octadecyl acrylate, octadecyl methacrylate,
At least one of acrylic acid, methacrylic acid；C classes acrylate is the acrylate containing ring, and D classes acrylate is epoxy third
Olefin(e) acid ester.
The preparation method of organosilicon-modified acrylic epoxy resin comprises the following steps：
1) positive esters of silicon acis, pH adjusting agent, deionized water and ethanol are added in a kettle., and reaction is stirred at room temperature, and to obtain silicon molten
Glue；
2) 3- is slowly added dropwise（Methacryloxypropyl）The mixed liquor of propyl trimethoxy silicane and ethanol, completion of dropping continues
Reaction is complete, generates the MPS-SiO with double bond2；
3) B classes acrylate, C classes acrylate, D class acrylate are taken, is well mixed, emulsifying agent and deionization is added
Water, stirring obtains pre-emulsion；
4) in MPS-SiO2Middle addition emulsifying agent, buffer and deionized water, dispersed with stirring, are warming up to 70~85 DEG C, together
When above-mentioned pre-emulsion and initiator solution is added dropwise, pre-emulsion was dripped off in 2~4 hours, initiator solution pre-emulsion drip
Completion of dropping in half an hour after complete, temperature raises 3~5 DEG C, is incubated 0.5~1 hour, obtains organosilicon for core acrylic acid epoxy
Resin is the organosilicon-modified acrylic epoxy resin of shell.
There can also be the hud typed machine of high adhesion force to glass baseplate using well-known to those skilled in the art other
Fluorine-silicon modified acrylic epoxy resin.
As the further improvement of above-mentioned water-based jet ink, C classes acrylate is selected from isobornyl acrylate, acrylic acid
Hexahydro -4,7- methylene -1H- indenyls ester, acrylic acid octahydro -4,7- methylene -1H- indenyls ester, the ring of methacrylic acid three
At least one of [5.2.1.02,6] decyl- 8- base esters.The use of C class acrylate, can change the organosilicon prepared
Property acrylic acid epoxy resin there is more preferable water-fast heat resistance, while helping to increase its adhesive force, improve its transparency.
As the further improvement of above-mentioned water-based jet ink, D classes acrylate is selected from 3,4- epoxycyclohexyl-methyls third
In olefin(e) acid ester, 3,4- epoxycyclohexyl-methyls methacrylate, acrylic acid tetrahydro furfuryl ester, methacrylic acid tetrahydro furfuryl ester
At least one.The use of D class acrylate can effectively improve adhesive force of the ink film to glass, the metering system used with tradition
Acid glycidyl ester is compared, and the polymerization stability of D class acrylate is higher, it is not easy to gel.
As the further improvement of above-mentioned water-based jet ink, auxiliary agent is selected from defoamer, surface tension modifier, sterilization
One or more mixtures in preservative, pH adjusting agent；Aqueous solvent is selected from ethylene glycol, diethylene glycol (DEG), propane diols, ethylene glycol
One or more mixtures in butyl ether, butyl, glycerine, 2-Pyrrolidone, deionized water.
The present invention is further explained with reference to specific embodiment, but specific embodiment is not to the present invention
It is limited in any way.Unless stated otherwise, reagent involved in embodiment, method are reagent commonly used in the art and method.
The performance test of water-based jet ink：Ink jet viscosity is determined with reference to the rotary process in GB/T 10247-2008；GB/T
19077.1-2008 determines the average grain diameter of ink-jet.Water-based jet ink direct spraying is on glass baseplate, and 180 DEG C of bakings are dry
It is dry, according to the GB/T 13217.7-2009 liquid ink attachment fastness methods of inspection, determine attachment fastness of the ink-jet to glass；Press
Light resistance is evaluated with optical filtering xenon arc lamp according to GB/T 22771-2008 printing technologies printed matters and printing-ink, ink jet ink is determined
The fastness to light of water.
Embodiment 1：
The preparation of dispersion resin liquid：
70g deionized waters are added in a kettle., 70 DEG C are increased the temperature to, and 1.5g acrylyl oxy-ethyl-trimethyl chlorine is added dropwise
Change the mixed of ammonium, 10.0g piperidino methyls acrylate, 14.2g butyl acrylates, 2.0g acrylic acid and 2.0g lauryl mercaptans
Compound, is dripped off in 2 hours；During dropwise addition, point 3 batches of addition ammonium persulfates, every crowd of 0.1g, insulation reaction 1.5 hours is divided
Dissipate resin liquid.
Gained dispersion resin liquid is in micro- yellow half penetrating, and solid content is that viscosity is 35.6mpa.s at 29.6%, 25 DEG C, and number is divided equally
Son amount is 1740.
The synthesis of organosilicon-modified acrylic epoxy resin
0.2g methyl silicates, 0.25g ammoniacal liquor, 2.0g deionized waters and 8.0g ethanol are added in a kettle., and room temperature is stirred
Mix reaction 8 hours.0.3g 3- are slowly added dropwise（Methacryloxypropyl）The mixed liquor of propyl trimethoxy silicane and 2g ethanol, 1 is small
When it is interior drip off, continue react 24 hours, generate the MPS-SiO with double bond2；
Weigh 9.0g butyl acrylates, 5.0g octadecyl acrylates, 9.0g methyl methacrylates, 1.0g propylene
Acid, the ring of 8.0g methacrylic acids three [5.2.1.02,6] decyl- 8- base esters and 18.0g3,4- epoxycyclohexyl-methyl acrylate,
It is well mixed, 0.6g anion emulsifier CO436,0.3g nonionic emulsifier TO-10 and 22.0g deionized waters are added,
500rmp high-speed stirreds obtain pre-emulsion.
Gained organosilicon-modified acrylic epoxy resin latex is creamy white, blueing light, at solid content is 49.8%, 25 DEG C
Viscosity is 210mpa.s.
The preparation of water-based jet ink
Weigh 40g ethylene glycol, 55g diethylene glycol (DEG)s, 182g deionized waters, 2.0g defoamer TEGO Foamex 810,1.2g
Monoethanolamine, stirs, and is separately added into the above-mentioned dispersion resin liquid of 60g, 60gC.I. paratoneres 53,1200rmp dispersed with stirring
0.5 hour, ground using sand mill, 1.0 μm, 0.45 μm of membrane filtration can be passed sequentially through to mill base, red pigment color is obtained
Slurry；
Weigh 12.5g glycerine, 20g diethylene glycol (DEG)s, 7.5g butyls, 1.6g2- pyrrolidones, 44.8g deionizations
Water, 0.2g surface tension modifier TEGO Wet 510,0.001g biocide mildewcides XF-2,0.7g monoethanolamine, mixing is equal
After even, the above-mentioned organosilicon-modified acrylic epoxy resin of 6.0g, the above-mentioned red pigment mill bases of 6.7g are separately added into, dispersed with stirring is equal
It is even, that is, obtain the water-based jet ink for glass baseplate.
Red water-based jet ink prepared by embodiment 1, viscosity is 5.43mpas at 25 DEG C, and average grain diameter is 270nm；Ink
Film is bright-colored, is not fallen off with 3M adhesive tape stripping films, attachment fastness 100%, 6 grades of fastness to light.
Embodiment 2：
The preparation of dispersion resin liquid：
Add 75g deionized waters in a kettle., increase the temperature to 65 DEG C, be added dropwise 5.0gN- carboxymethyls-N, N- dimethyl-
2-[（2- methyl isophthalic acids-oxo -2- acrylic）- chloro] acetamide Inner salt, 1.5g piperidino methyls acrylate, 4.5g methyl-props
E pioic acid methyl ester, 12.0g butyl acrylates, the mixture of 0.5g methacrylic acids and 1.0g hexadecyl mercaptans, drip in 2 hours
It is complete；During dropwise addition, point 5 batches of addition sodium peroxydisulfates, every crowd of 0.1g, insulation reaction 1 hour obtains dispersion resin liquid.
Gained dispersion resin liquid is in micro- yellow half penetrating, and solid content is that viscosity is 45.5mpa.s at 24.7%, 25 DEG C, and number is divided equally
Son amount is 2890.
The synthesis of organosilicon-modified acrylic epoxy resin
1.1g positive silicic acid propyl esters, 1.5g ammoniacal liquor, 7.0g deionized waters and 18.0g ethanol are added in a kettle., and room temperature is stirred
Mix reaction 12 hours.0.6g 3- are slowly added dropwise（Methacryloxypropyl）The mixed liquor of propyl trimethoxy silicane and 5g ethanol, 2
Dripped off in hour, continue to react 24 hours, generate the MPS-SiO with double bond2；
Weigh 15.0g butyl acrylates, 7.0g methyl methacrylates, 2.0g methacrylic acids, 15.0g acrylic acid eight
Hydrogen -4,7- methylene -1H- indenyls ester and 6.0g acrylic acid tetrahydro furfuryl esters, are well mixed, and add 0.5g anion emulsifiers
CO436,0.9g nonionic emulsifier TO-10 and 19.4g deionized water, 600rmp high-speed stirreds obtain pre-emulsion；
In MPS-SiO2It is middle to add 0.3gCO436,0.6gTO-10,0.2gNaHCO3Buffer, dispersed with stirring is warming up to 70
DEG C, while above-mentioned pre-emulsion is added dropwise and 0.2g is dissolved in sodium peroxydisulfate in 3.0g deionized waters, pre-emulsion was dripped off in 3 hours, drawn
Agent aqueous solution completion of dropping within the half an hour after pre-emulsion is dripped off is sent out, temperature raises 5 DEG C, is incubated 1 hour；Room temperature is down to, is used
Ammoniacal liquor regulation pH value is 7, filtering, and it is the organosilicon-modified acrylic asphalt mixtures modified by epoxy resin that core acrylic acid epoxy resin is shell to obtain organosilicon
Fat liquor.
Gained organosilicon-modified acrylic epoxy resin latex is creamy white, blueing light, at solid content is 46.3%, 25 DEG C
Viscosity is 195mpa.s.
The preparation of water-based jet ink
Weigh 45.5g ethylene glycol, 50g butyls, 172.2g deionized waters, 0.8g defoamers HY-206,1.5g
Monoethanolamine, stirs, and is separately added into the above-mentioned dispersion resin liquid of 70g, 60gC.I. pigment blue 15s, 1500rmp dispersed with stirring 1
Hour, ground using sand mill, 1.0 μm, 0.45 μm of membrane filtration can be passed sequentially through to mill base, blue pigment mill base is obtained；
Weigh 10.0g glycerine, 17.5g butyls, 2.0g2- pyrrolidones, 1.55g ethylene glycol, 10g deionizations
Water, 0.2g surface tension modifier TEGO Rad 2100,0.002g biocide mildewcides CF-S40,0.75g monoethanolamine is mixed
After closing uniformly, the above-mentioned organosilicon-modified acrylic epoxy resin of 18.0g, the above-mentioned red pigment mill bases of 40.0g are separately added into, is stirred
It is uniformly dispersed, that is, obtains the water-based jet ink for glass baseplate.
Blue water-based ink-jet ink prepared by embodiment 2, viscosity is 4.85mpas at 25 DEG C, and average grain diameter is 263nm；Ink
Film is bright-colored, is not fallen off with 3M adhesive tape stripping films, attachment fastness 100%, 7 grades of fastness to light.
Embodiment 3
The synthesis of dispersion resin liquid
70g deionized waters are added in a kettle., 80 DEG C are increased the temperature to, and 3.0g acrylyl oxy-ethyl-trimethyl chlorine is added dropwise
Change ammonium, 6.0g piperidino methyls acrylate, 5.1g methyl methacrylates, 12.0g butyl acrylates, 1.5g acrylic acid and
The mixture of 1.8g 3- isooctyl mercaptopropionates, is dripped off in 1 hour；During dropwise addition, point 3 batches of addition potassium peroxydisulfates, every batch
0.2g, insulation reaction 2 hours, obtains dispersion resin liquid.
Gained dispersion resin liquid is in micro- yellow half penetrating, and solid content is that viscosity is 40.0mpa.s at 28.8%, 25 DEG C, and number is divided equally
Son amount is 2650.
The synthesis of organosilicon-modified acrylic epoxy resin
0.4g tetraethyl orthosilicates, 1.0g ammoniacal liquor, 5.0g deionized waters and 10.0g ethanol are added in a kettle., and room temperature is stirred
Mix reaction 10 hours.0.8g 3- are slowly added dropwise（Methacryloxypropyl）The mixed liquor of propyl trimethoxy silicane and 5g ethanol,
Dripped off in 1.5 hours, continue to react 24 hours, generate the MPS-SiO with double bond2；
Weigh 11.0g Isooctyl acrylate monomers, 5.0g octadecyl methacrylates, 10.0g methyl methacrylates,
1.5g acrylic acid, 5.0g isobornyl acrylates, the ring of 3.5g methacrylic acids three [5.2.1.02,6] decyl- 8- base esters and
12.0g3,4- epoxycyclohexyl-methyl acrylate, are well mixed, add 0.3g anion emulsifiers EPA-073,0.2g it is non-from
Sub- emulsifying agent TO-7 and 22.0g deionized waters, 500rmp high-speed stirreds obtain pre-emulsion；
In MPS-SiO2Middle addition 0.2g EPA-073,0.1gTO-7,0.27gNaHCO3Buffer and 3.43g deionizations
Water, dispersed with stirring is warming up to 85 DEG C, while above-mentioned pre-emulsion is added dropwise and 0.3g is dissolved in ammonium persulfate in 3.0g deionized waters, in advance
Emulsion was dripped off in 2 hours, initiator solution completion of dropping within the half an hour after pre-emulsion is dripped off, and temperature raises 3 DEG C, was protected
Temperature 0.5 hour；Room temperature is down to, is 7 with ammoniacal liquor regulation pH value, filtering, it is that core acrylic acid epoxy resin is shell to obtain organosilicon
Organosilicon-modified acrylic epoxy resin latex.
Gained organosilicon-modified acrylic epoxy resin latex is creamy white, blueing light, at solid content is 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 specific preparation process is as follows：
Weigh 40g ethylene glycol, 60g diethylene glycol (DEG)s, 166g deionized waters, 1.0g defoamer TEGO Foamex 810,1.0g
Triethanolamine, stirs, and is separately added into the above-mentioned dispersion resin liquid of 72g, 60gC.I. pigment yellow 13s 8,1500rmp dispersed with stirring
45min, is ground using sand mill, and 1.0 μm, 0.45 μm of membrane filtration can be passed sequentially through to mill base, yellow uitramarine mill base is obtained；
Weigh 13.0g glycerine, 15.0g diethylene glycol (DEG)s, 8.5g butyl glycol ethers, 1.5g2- pyrrolidones, 20.2g deionizations
Water, 0.8g surface tension modifier TEGO Rad 2200N, 0.002g biocide mildewcide XF-2,0.5g triethanolamines, mixing
After uniform, the above-mentioned organosilicon-modified acrylic epoxy resin of 10.5g, the above-mentioned yellow uitramarine mill bases of 30g, dispersed with stirring are separately added into
Uniformly, that is, the water-based jet ink for glass baseplate is obtained.
Yellow water-based jet ink prepared by embodiment 3, viscosity is 5.30mpas at 25 DEG C, and average grain diameter is 258nm；Ink
Film is bright-colored, is not fallen off with 3M adhesive tape stripping films, attachment fastness 100%, 7 grades of fastness to light.
It was found from the data of embodiment, dispersion resin liquid of the invention can inclusion pigment well, water-base ink has
Excellent performance, is particularly suitable for use in the printing of glass baseplate.
Claims (7)
1. a kind of dispersion resin liquid for glass baseplate, the wherein number-average molecular weight of resin are 1000~10000, it constitutes former
Expect for following mass parts：1.5~5 parts of A classes acrylate, 1.5~10 parts of piperidino methyl acrylate, 16~19 parts of B classes
Acrylate, appropriate initiator, appropriate polymerizable molecular amount conditioning agent, suitable quantity of water；
Wherein, A classes acrylate be selected from acrylyl oxy-ethyl-trimethyl salmiac, N- carboxymethyls-N, N- dimethyl -2- [（2- first
Base -1- oxo -2- acrylic）- chloro] at least one of acetamide inner salt, B classes acrylate be methyl methacrylate,
Butyl acrylate, Isooctyl acrylate monomer, octadecyl acrylate, octadecyl methacrylate, acrylic acid, metering system
At least one of acid.
2. dispersion resin liquid according to claim 1, it is characterised in that：Polymerizable molecular amount conditioning agent is selected from dodecyl sulphur
At least one of alcohol, hexadecyl mercaptan, 3- isooctyl mercaptopropionates.
3. dispersion resin liquid according to claim 1, it is characterised in that：Initiator triggers selected from water soluble persulfates
Agent.
4. a kind of preparation method of dispersion resin liquid, including：Water is added in reactor, 65~80 DEG C are warming up to, A classes third are added dropwise
Olefin(e) acid ester, piperidino methyl acrylate, the mixture of B classes acrylate and polymerizable molecular amount conditioning agent, it is same during dropwise addition
When initiator is added portionwise, insulation reaction obtains dispersion resin liquid, wherein, the raw material of dispersion resin liquid composition such as claim 1
Described in~3 any one.
5. a kind of water-based jet ink for glass baseplate, is made up of the raw material of following mass parts：1~6 part of pigment, 1~7 part
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 of the dispersion resin liquid as described in claims 1 to 3 any one, or be prepared into by claim 4 methods described
The dispersion resin liquid arrived；
Wherein, organosilicon-modified acrylic epoxy resin is hud typed organosilicon-modified acrylic epoxy resin, its quality composition
Raw material is：0.2~1.1 part of positive esters of silicon acis, 0.3~0.8 part of 3-（Methacryloxypropyl）Propyl trimethoxy silicane, 24~28 parts
B classes acrylate, 8~15 parts of C classes acrylate, 6~18 parts of D classes acrylate, 0.8~2 part of emulsifying agent, 0.2~0.3 part delay
Electuary, 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, B class acrylate
For methyl methacrylate, butyl acrylate, Isooctyl acrylate monomer, octadecyl acrylate, methacrylic acid octadecyl
At least one of ester, acrylic acid, methacrylic acid；C classes acrylate be the acrylate containing ring, isobornyl acrylate,
Acrylic acid hexahydro -4,7- methylene -1H- indenyls ester, acrylic acid octahydro -4,7- methylene -1H- indenyls ester, methacrylic acid
At least one of three rings [5.2.1.02,6] decyl- 8- base esters；D classes acrylate is epoxy acrylate.
6. water-based jet ink according to claim 5, it is characterised in that：The system of organosilicon-modified acrylic epoxy resin
Preparation Method comprises the following steps：
1）Positive esters of silicon acis, pH adjusting agent, deionized water and ethanol are added in a kettle., and reaction is stirred at room temperature and obtains Ludox；
2）3- is slowly added dropwise（Methacryloxypropyl）The mixed liquor of propyl trimethoxy silicane and ethanol, completion of dropping continues to react
Completely, the MPS-SiO with double bond is generated2；
3）B classes acrylate, C classes acrylate, D class acrylate are taken, is well mixed, emulsifying agent and deionized water is added, stirs
Mix and obtain pre-emulsion；
4）In MPS-SiO2Middle addition emulsifying agent, buffer and deionized water, dispersed with stirring, are warming up to 70~85 DEG C, are added dropwise simultaneously
Initiator solution and above-mentioned pre-emulsion, pre-emulsion were dripped off in 2~4 hours, and initiator solution is after pre-emulsion is dripped off
Completion of dropping in half an hour, temperature raises 3~5 DEG C, is incubated 0.5~1 hour, it is that core acrylic acid epoxy resin is to obtain organosilicon
The organosilicon-modified acrylic epoxy resin of shell.
7. water-based jet ink according to claim 5, it is characterised in that：Auxiliary agent is selected from defoamer, surface tension adjustment
One or more mixtures in agent, sterilization antiseptic, pH adjusting agent；Aqueous solvent is selected from ethylene glycol, diethylene glycol (DEG), the third two
One or more mixtures in alcohol, butyl glycol ether, butyl, glycerine, 2-Pyrrolidone, deionized water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510168577.8A CN104861780B (en) | 2015-04-10 | 2015-04-10 | A kind of dispersion resin liquid and ink for glass baseplate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510168577.8A CN104861780B (en) | 2015-04-10 | 2015-04-10 | A kind of dispersion resin liquid and ink for glass baseplate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104861780A CN104861780A (en) | 2015-08-26 |
| CN104861780B true CN104861780B (en) | 2017-09-19 |
Family
ID=53907986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510168577.8A Expired - Fee Related CN104861780B (en) | 2015-04-10 | 2015-04-10 | A kind of dispersion resin liquid and ink for glass baseplate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104861780B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114806286A (en) * | 2022-05-27 | 2022-07-29 | 深圳市安力环保科技有限公司 | High-performance super-dispersion resin liquid and preparation method thereof |
| CN117024079B (en) * | 2023-08-15 | 2024-02-23 | 仪征河海工程建设有限公司 | Waterproof material for building engineering |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003055416A (en) * | 2001-08-22 | 2003-02-26 | Kansai Paint Co Ltd | Method for producing pigment dispersing resin |
| JP2006150796A (en) * | 2004-11-30 | 2006-06-15 | Dainippon Ink & Chem Inc | Resin composition for recording object material, and recording material and printed matter using the composition |
| CN1896151A (en) * | 2005-07-13 | 2007-01-17 | 关西涂料株式会社 | Cationic electrodeposition coating |
| KR20090115949A (en) * | 2007-03-06 | 2009-11-10 | 다이니치 세이카 고교 가부시키가이샤 | Copolymer and use thereof |
| CN101845122A (en) * | 2010-06-11 | 2010-09-29 | 成都达威化工科技有限公司 | Water-based polymer pigment dispersant and leather cationic pigment paste prepared from same |
| CN102002257A (en) * | 2009-08-31 | 2011-04-06 | 大日精化工业株式会社 | Acylic resin processed dye composition, dye dispersion fluid, manufacture methods and uses thereof |
| JP4829531B2 (en) * | 2005-05-26 | 2011-12-07 | 三菱レイヨン株式会社 | Water-based coating material |
| CN102731717A (en) * | 2012-07-18 | 2012-10-17 | 中国海洋石油总公司 | Waterborne dispersion resin containing hydroxyl and preparation method thereof |
-
2015
- 2015-04-10 CN CN201510168577.8A patent/CN104861780B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003055416A (en) * | 2001-08-22 | 2003-02-26 | Kansai Paint Co Ltd | Method for producing pigment dispersing resin |
| JP2006150796A (en) * | 2004-11-30 | 2006-06-15 | Dainippon Ink & Chem Inc | Resin composition for recording object material, and recording material and printed matter using the composition |
| JP4829531B2 (en) * | 2005-05-26 | 2011-12-07 | 三菱レイヨン株式会社 | Water-based coating material |
| CN1896151A (en) * | 2005-07-13 | 2007-01-17 | 关西涂料株式会社 | Cationic electrodeposition coating |
| KR20090115949A (en) * | 2007-03-06 | 2009-11-10 | 다이니치 세이카 고교 가부시키가이샤 | Copolymer and use thereof |
| CN102002257A (en) * | 2009-08-31 | 2011-04-06 | 大日精化工业株式会社 | Acylic resin processed dye composition, dye dispersion fluid, manufacture methods and uses thereof |
| CN101845122A (en) * | 2010-06-11 | 2010-09-29 | 成都达威化工科技有限公司 | Water-based polymer pigment dispersant and leather cationic pigment paste prepared from same |
| CN102731717A (en) * | 2012-07-18 | 2012-10-17 | 中国海洋石油总公司 | Waterborne dispersion resin containing hydroxyl and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104861780A (en) | 2015-08-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101724326B (en) | Waterborne organic silicon-acrylic acid self-stratifying coating | |
| CN103965730B (en) | A kind of zero VOC release water paint and preparation method thereof | |
| CN112029362B (en) | Preparation method of core-shell structure nano particles and hardened water-based acrylic resin coating | |
| CN102226051B (en) | Glaze coloring agent for waterborne woodenware coating and preparation method thereof | |
| CN107226883A (en) | A kind of core shell structure aqueous silicone acrylic emulsion and preparation method thereof | |
| CN102838953A (en) | Aqueous acrylate emulsion adhesive for paper pearl powder, and preparation method thereof | |
| CN105482027A (en) | Acrylic acid modified polysiloxane resin and application thereof to self-stratifying coating | |
| CN101838370A (en) | Aqueous concoction, aqueous polymer emulsion prepared from same and application thereof | |
| CN107177299B (en) | Aqueous middle painting coating composition and preparation method thereof for the vehicles | |
| CN104861780B (en) | A kind of dispersion resin liquid and ink for glass baseplate | |
| CN106478861A (en) | A kind of modified aqueous acrylic acid resin and the method preparing manually color sand using it | |
| CN109790397A (en) | With the aqueous copolymer dispersion for improving scrub performance | |
| CN102807814B (en) | Nano silica-modified recoatable ultraviolet (UV) varnish used on plastic and preparation method for varnish | |
| CN107384155A (en) | A kind of novel aqueous PE woodcare paints and preparation method thereof | |
| CN113025147A (en) | Water-based wall surface hand-sprayed paint and preparation method thereof | |
| CN106752540A (en) | A kind of high rigidity, wear-resistant aqueous woodware paint and preparation method thereof | |
| JPH0370763A (en) | Aqueous composition of acid-functional acrylsilanol polymer base | |
| CN107674528A (en) | A kind of high-performance multicolor finish and preparation method thereof | |
| CN106916493A (en) | A kind of nano-TiO2/ Nano-meter SiO_22Compound modified acrylic water paint and preparation method thereof | |
| CN106479343A (en) | A kind of preparation method of water paint | |
| CN114591665B (en) | Low-VOC emulsion type water-based aluminum mirror back coating | |
| CN109181546A (en) | A kind of production method for the water paint that waterproofness is high | |
| KR20200107394A (en) | Water soluble paint composition for a road marking with improved water-repellent | |
| CN112010589B (en) | Sand-in-sand multicolor paint and preparation method and application thereof | |
| CN112851882B (en) | Preparation method of epoxy resin modified styrene-acrylic emulsion for plastic ink |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PP01 | Preservation of patent right | ||
| PP01 | Preservation of patent right |
Effective date of registration: 20170928 Granted publication date: 20170919 |
|
| PD01 | Discharge of preservation of patent | ||
| PD01 | Discharge of preservation of patent |
Date of cancellation: 20200928 Granted publication date: 20170919 |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170919 |