CN106752362A - A kind of waterborne glass ink and preparation method thereof - Google Patents
A kind of waterborne glass ink and preparation method thereof Download PDFInfo
- Publication number
- CN106752362A CN106752362A CN201710142924.9A CN201710142924A CN106752362A CN 106752362 A CN106752362 A CN 106752362A CN 201710142924 A CN201710142924 A CN 201710142924A CN 106752362 A CN106752362 A CN 106752362A
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- glass ink
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- waterborne glass
- waterborne
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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
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
-
- 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
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- 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
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
Abstract
The present invention relates to ink area, a kind of waterborne glass ink and preparation method thereof is disclosed.The waterborne glass ink, is made up of the watersoluble modified acrylic acid polymer and the auxiliary material of 30.5 ~ 55 weight portions of 50 65 weight portions, and the auxiliary material is made up of the component of following weight portion：1 ~ 5 part of coupling agent；2 ~ 8 parts of curing agent, 0.5 ~ 1 part of defoamer；1 ~ 3 part of levelling agent；8 ~ 10 parts of organic pigment；6 ~ 8 parts of inorganic fillings；12 ~ 20 parts of solvent.Waterborne glass ink of the invention favorable solubility in water, without the solvent that the toxicity such as benzene are larger, and it is low to prepare reaction temperature, overcomes problem of environmental pollution, largely alleviates the environmental protection pressure of environment, the pollution to worker laboring environment to external world.The waterborne glass ink adhesive force is good, gloss is high, corrosion-resistant, hardness is high and need not toast, and is a kind of green and environment-friendlyglass glass ink.
Description
Technical field
The present invention relates to ink area, specifically a kind of waterborne glass ink and preparation method thereof.
Background technology
The ink for making glass decoration pattern is generally the solvent-based ink of high temperature sintering ink and low-temperature setting, but this two
There is very big defect in the preparation method for planting ink：The sintering temperature of high temperature sintering ink is up to 600~800 DEG C, produces
Flyash is produced in journey, and the solvent-based ink of low-temperature setting needs to use the larger organic solvent of toxicity.Both the above ink
There is heavier pollution in process of production, it is big to human body toxic.
With the development of society, our people accelerates China's organic solvent for the continuous reinforcement of environmental protection concept
The development process of ink hydrotropism's ink.In response to the call of the big policy of energy-conserving and environment-protective, the research to water-based ink is also being got over
Come more, such as number of patent application 200810194816.7 discloses a kind of preparation of the waterborne glass ink resin of enhanced water resistance
Method, number of patent application 200710134937.8 discloses a kind of self-drying glass ink and preparation method thereof, but these ink
Still need to add the larger solvent of some toxicity, could not meet the requirement of environmental protection.
The content of the invention
The present invention is intended to provide a kind of waterborne glass ink.
Preparation method another object of the present invention is to disclose above-mentioned waterborne glass ink.
The present invention to achieve the above object, takes following technical scheme to be achieved：
A kind of waterborne glass ink, the watersoluble modified acrylic acid polymer by 50~65 weight portions is auxiliary with 30.5~55 weight portions
Material composition, the auxiliary material is made up of the component of following weight portion：
1~5 part of coupling agent；2~8 parts of curing agent, 0.5~1 part of defoamer；1~3 part of levelling agent；8~10 parts of organic pigment；Nothing
6~8 parts of machine inserts；12~20 parts of solvent.
Preferably, the watersoluble modified acrylic acid polymer is obtained by the raw material of following weight portion through condensation reaction：Methyl
15~20 parts of methyl acrylate, butyl acrylate 5~10,10~18 parts of hydroxyethyl methacrylate, 3~5 parts of methacrylic acid,
34~50 parts of epoxy resin, 1~2 part of azodiisobutyronitrile.
Preferably, the coupling agent is silane coupler.Silane coupler is that a class contains two kinds not simultaneously in the molecule
With the organo-silicon compound of chemical property group, its classical product can be represented with formula YSiX3.In formula, Y is non-hydrolytic group,
Generally organo-functional group, reacts and combines with organic substance, and X is hydrolyzable groups, and silanol is generated during hydrolysis, with inorganic substances
With reference to.Due to this special construction, equivalent to molecule bridge is erected between organic matter and inorganic matter, can two attributes are poor
Not very big material is combined together, so as to improve the performance of composite, can be used for surface treatment.
Preferably, the curing agent be dimethylaminopropylamine, TEPA, IPD, pyridine etc. it is a kind of or
Two or more mixtures.Curing agent is essential additive in resin curing process, and otherwise epoxy resin can not solidify.
Preferably, the curing agent is TEPA.
Preferably, the inorganic fillings are one or two mixtures in barium sulfate, calcium carbonate.
Preferably, the solvent is the mixture of alcohols solvent and ether solvent, the volume ratio of the alcohol and ether for 30~
60:40~70, the alcohols solvent is one or more mixing of ethanol, isopropanol, n-butanol, isobutanol, ethylene glycol
Thing, the ether solvent is ethylene glycol monobutyl ether, the double butyl ether of ethylene glycol, diethyl ether, one or more mixing of isopropyl ether
Thing.
Preparation method another object of the present invention is to disclose above-mentioned waterborne glass ink, comprises the following steps：
S91:By the weight portion, by watersoluble modified acrylic acid polymer, coupling agent, blocked curing agent, defoamer, levelling
Agent, organic pigment, inorganic fillings, stirring solvent 20min；
S92：Frosted to fineness in mixture feeding skin grinder obtained in step S91 is less than 15 microns, filtering and discharging, packaging.
Preferably, the preparation of the watersoluble modified acrylic acid polymer is comprised the following steps：
S101:By the weight portion, by methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate, metering system
Acid, azodiisobutyronitrile mix to dissolving；
S102:By in the isopropanol of epoxy resin 15~25 weight portions of addition, it is heated to being warming up to after epoxy resin is completely dissolved
100~120 DEG C, obtained mixture in S101 steps is added dropwise in 2~3h, is added dropwise to complete rear insulation reaction 2-3h, cooling is obtained final product.
The present invention be the single-component water-based glass ink of normal temperature cure, in involved solvent, ethanol, isopropanol, n-butanol,
Isobutanol etc. is the less solvent of toxicity, and the favorable solubility in water, without the solvent that the toxicity such as benzene are larger, and instead
Answer temperature low, overcome problem of environmental pollution, largely alleviate to external world the environmental protection pressure of environment, to workman's work ring
The pollution in border；It is a kind of green and the waterborne glass ink adhesive force is good, gloss is high, corrosion-resistant, hardness is high and need not toast
Colour circle protects glass ink.
Specific embodiment
In the present invention, defoamer (is abbreviated as KEPER- for the KEPER-706 type defoamers of Jin Tuan Chemical Companies
706), one or two mixtures in DC-65 types defoamer (being abbreviated as DC-65) of Dow Corning Corporation；Levelling agent is rolled into a ball for gold
KEPER-191 types levelling agent (being abbreviated as KEPER-191) of Chemical Company, the BYK-410 type streams of Bi Ke companies of Germany
One or two mixtures in flat agent (being abbreviated as BYK-410)；The wherein preferred DC-65 of defoamer, the preferred BYK- of levelling agent
410.Organic pigment is red iron oxide 130 S or iron oxide yellow 313.Inorganic fillings are calcium carbonate or barium sulfate.Below in conjunction with specific
Embodiment is next, and the present invention is further illustrated.
Embodiment 1
1. the preparation method of watersoluble modified acrylic acid polymer is comprised the following steps：
S11：Under stirring, the weight portion as described in table 1, by methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate,
Methacrylic acid, azodiisobutyronitrile mix to dissolving；
S12：It is added dropwise in epoxy resin addition isopropanol, being heated to being warming up to after epoxy resin is completely dissolved in 110 DEG C, 3h
Obtained mixture in S11 steps, is added dropwise to complete rear insulation reaction 3h, and cooling is obtained final product.
The ＞ of ＜ tables 1
| Material name | Weight portion |
| Methyl methacrylate | 20 |
| Butyl acrylate | 7 |
| Hydroxyethyl methacrylate | 10 |
| Methacrylic acid | 3 |
| Epoxy resin | 39 |
| Azodiisobutyronitrile | 1 |
| Isopropanol | 20 |
Gained watersoluble modified acrylic acid polymer outward appearance is light yellow clear liquid, and viscosity is 5500mPa.s/25 DEG C, pH value
8.2, amount of solid content is 80%.
2. the preparation of waterborne glass ink is comprised the following steps：
S21：The weight portion as described in table 2, by watersoluble modified acrylic acid polymer, silane coupler, TEPA, DC-65,
The double butyl ether stirring 20min of BYK-410, red iron oxide 130 S, barium sulfate, isopropanol, ethylene glycol；
S22：Frosted to fineness in mixture feeding skin grinder obtained in step S21 is less than 15 microns, filtering and discharging, packaging.
The ＞ of ＜ tables 2
| Material name | Weight portion |
| Watersoluble modified acrylic acid polymer | 53.5 |
| Silane coupler | 5 |
| TEPA | 5 |
| DC-65 | 0.5 |
| BYK-410 | 2 |
| Red iron oxide 130 S | 8 |
| Barium sulfate | 6 |
| Isopropanol | 10 |
| The double butyl ether of ethylene glycol | 10 |
Embodiment 2
1. the preparation method of watersoluble modified acrylic acid polymer is comprised the following steps：
S11：Under stirring, the weight portion as described in table 3, by methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate,
Methacrylic acid, azodiisobutyronitrile mix to dissolving；
S12：It is added dropwise in epoxy resin addition isopropanol, being heated to being warming up to after epoxy resin is completely dissolved in 100 DEG C, 3h
Obtained mixture in S11 steps, is added dropwise to complete rear insulation reaction 3h, and cooling is obtained final product.
The ＞ of ＜ tables 3
| Material name | Weight portion |
| Methyl methacrylate | 17 |
| Butyl acrylate | 7 |
| Hydroxyethyl methacrylate | 13 |
| Methacrylic acid | 3 |
| Epoxy resin | 34 |
| Azodiisobutyronitrile | 1 |
| Isopropanol | 25 |
Gained watersoluble modified acrylic acid polymer outward appearance is light yellow clear liquid, and viscosity is 5300mPa.s/25 DEG C, pH value
8.3, amount of solid content is 75%.
2. the preparation of waterborne glass ink is comprised the following steps：
S21：The weight portion as described in table 4, by watersoluble modified acrylic acid polymer, silane coupler, TEPA, DC-65,
The double butyl ether stirring 20min of BYK-410, red iron oxide 130 S, barium sulfate, isopropanol, ethylene glycol；
S22：Frosted to fineness in mixture feeding skin grinder obtained in step S21 is less than 15 microns, filtering and discharging, packaging.
The ＞ of ＜ tables 4
| Material name | Weight portion |
| Watersoluble modified acrylic acid polymer | 50 |
| Silane coupler | 5 |
| TEPA | 2 |
| DC-65 | 0.5 |
| BYK-410 | 1 |
| Red iron oxide 130 S | 8 |
| Barium sulfate | 6 |
| Isopropanol | 10 |
| The double butyl ether of ethylene glycol | 10 |
Embodiment 3
1. the preparation method of watersoluble modified acrylic acid polymer is comprised the following steps：
S11：Under stirring, the weight portion as described in table 5, by methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate,
Methacrylic acid, azodiisobutyronitrile mix to dissolving；
S12：It is added dropwise in epoxy resin addition isopropanol, being heated to being warming up to after epoxy resin is completely dissolved in 110 DEG C, 3h
Obtained mixture in S11 steps, is added dropwise to complete rear insulation reaction 3h, and cooling is obtained final product.
The ＞ of ＜ tables 5
| Material name | Weight portion |
| Methyl methacrylate | 20 |
| Butyl acrylate | 5 |
| Hydroxyethyl methacrylate | 15 |
| Methacrylic acid | 3 |
| Epoxy resin | 37 |
| Diimide bis-isobutyronitrile | 1 |
| Isopropanol | 25 |
Gained watersoluble modified acrylic acid polymer outward appearance is light yellow clear liquid, and viscosity is 5000mPa.s/25 DEG C, pH value
8.3, amount of solid content is 75%.
2. the preparation of waterborne glass ink is comprised the following steps：
S21：The weight portion as described in table 6, by watersoluble modified acrylic acid polymer, silane coupler, TEPA, DC-65,
The double butyl ether stirring 20min of BYK-410, iron oxide yellow 313, calcium carbonate, isopropanol, ethylene glycol；
S22：Frosted to fineness in mixture feeding skin grinder obtained in step S21 is less than 15 microns, filtering and discharging, packaging.
The ＞ of ＜ tables 6
| Material name | Weight portion |
| Watersoluble modified acrylic acid polymer | 53.5 |
| Silane coupler | 5 |
| Four ethene jade amine | 5 |
| DC-65 | 0.5 |
| BYK-410 | 2 |
| Iron oxide yellow 313 | 8 |
| Calcium carbonate | 6 |
| Isopropanol | 10 |
| The double butyl ether of ethylene glycol | 10 |
Embodiment 4
1. the preparation method of watersoluble modified acrylic acid polymer is comprised the following steps：
S11：Under stirring, the weight portion as described in table 7, by methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate,
Methacrylic acid, azodiisobutyronitrile mix to dissolving；
S12：It is added dropwise in epoxy resin addition isopropanol, being heated to being warming up to after epoxy resin is completely dissolved in 120 DEG C, 2h
Obtained mixture in S11 steps, is added dropwise to complete rear insulation reaction 2h, and cooling is obtained final product.
The ＞ of ＜ tables 7
| Material name | Weight portion |
| Methyl methacrylate | 15 |
| Butyl acrylate | 10 |
| Hydroxyethyl methacrylate | 18 |
| Methacrylic acid | 5 |
| Epoxy resin | 50 |
| Azodiisobutyronitrile | 2 |
| Isopropanol | 15 |
Gained watersoluble modified acrylic acid polymer outward appearance is light yellow clear liquid, and viscosity is 5300mPa.s/25 DEG C, pH value
8.3, amount of solid content is 80%.
2. the preparation of waterborne glass ink is comprised the following steps：
S21：The weight portion as described in table 8, by watersoluble modified acrylic acid polymer, silane coupler, TEPA, DC-65,
The double butyl ether stirring 20min of BYK-410, iron oxide yellow 313, calcium carbonate, isopropanol, ethylene glycol；
S22：Frosted to fineness in mixture feeding skin grinder obtained in step S21 is less than 15 microns, filtering and discharging, packaging.
The ＞ of ＜ tables 8
Effect example
Printing viscosity required for aqueous printing ink obtained in above-described embodiment 1~4 is diluted into printing, spraying or dip-coating, normal temperature
Lower solidification.The performance test results are as follows, and ink firmness over time on glass obtained in above-described embodiment 1~4
Can be increasingly stronger, a week can reach maximum firmness.
As a result of such scheme, the single-component water-based glass ink of obtained normal temperature cure overcomes tradition to the present invention
The shortcoming of glass ink, meets the requirement of " green, environmental protection, energy-conservation " that current country advocates, and product quality reaches both at home and abroad
The quality level of like product.The product with water as solvent, except with nonirritant gas, the spy such as green, environmental protection, energy-conservation
Point is outer, especially with advantages below：
(1) printing full color, glossiness are high；
(2) adhesive force is strong, hardness is high；
(3) anti-corrosion resistance and good.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention and is limited the interest field of the present invention.
Claims (10)
1. a kind of waterborne glass ink, it is characterised in that：By the watersoluble modified acrylic acid polymer of 50 ~ 65 weight portions and 30.5 ~
The auxiliary material composition of 55 weight portions, the auxiliary material is made up of the component of following weight portion：
1 ~ 5 part of coupling agent；2 ~ 8 parts of curing agent, 0.5 ~ 1 part of defoamer；1 ~ 3 part of levelling agent；8 ~ 10 parts of organic pigment；Inorganic fill
6 ~ 8 parts of material；12 ~ 20 parts of solvent.
2. a kind of waterborne glass ink according to claim 1, it is characterised in that the watersoluble modified acrylic acid polymer
Obtained through condensation reaction by the raw material of following weight portion：
15 ~ 20 parts of methyl methacrylate, butyl acrylate 5 ~ 10,10 ~ 18 parts of hydroxyethyl methacrylate, methacrylic acid 3 ~
5 parts, 34 ~ 50 parts of epoxy resin, 1 ~ 2 part of azodiisobutyronitrile.
3. a kind of waterborne glass ink according to claim 1, it is characterised in that：The coupling agent is silane coupler.
4. a kind of waterborne glass ink according to claim 1, it is characterised in that：The curing agent is dimethylamino third
One or more mixtures such as amine, TEPA, IPD, pyridine.
5. a kind of waterborne glass ink according to claim 4, it is characterised in that：The curing agent is TEPA.
6. a kind of waterborne glass ink according to claim 1, it is characterised in that：The inorganic fillings be barium sulfate,
One or two mixtures in calcium carbonate.
7. a kind of waterborne glass ink according to claim 1, it is characterised in that：The solvent is alcohols solvent and ethers
The mixture of solvent, the alcohol is 30 ~ 60 with the volume ratio of ether:40 ~ 70, the alcohols solvent is ethanol, isopropanol, positive fourth
Alcohol, isobutanol, one or more mixtures of ethylene glycol, the ether solvent are ethylene glycol monobutyl ether, the double fourths of ethylene glycol
Ether, diethyl ether, one or more mixtures of isopropyl ether.
8. waterborne glass ink according to claim 7, it is characterised in that：The solvent is that volume ratio is 1:1 isopropyl
The mixture of alcohol and butyl glycol ether.
9. a kind of preparation method of waterborne glass ink, it is characterised in that comprise the following steps：
S91:The weight portion as described in claim 1, by watersoluble modified acrylic acid polymer, coupling agent, blocked curing agent, disappears
Infusion, levelling agent, organic pigment, inorganic fillings, stirring solvent 20min；
S92：Frosted to fineness in mixture feeding skin grinder obtained in step S91 is less than 15 microns, filtering and discharging, packaging.
10. the preparation method of waterborne glass ink as claimed in claim 9, it is characterised in that the watersoluble modified acrylic acid gathers
The preparation of compound is comprised the following steps：
S101:The weight portion as described in claim 2, by methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate,
Methacrylic acid, azodiisobutyronitrile mix to dissolving；
S102:By in the isopropanol of epoxy resin 15 ~ 25 weight portions of addition, it is heated to being warming up to after epoxy resin is completely dissolved
100 ~ 120 DEG C, obtained mixture in S101 steps is added dropwise in 2-3h, drips rear 2 ~ 3h of insulation reaction, cooling is obtained final product.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710142924.9A CN106752362A (en) | 2017-03-10 | 2017-03-10 | A kind of waterborne glass ink and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710142924.9A CN106752362A (en) | 2017-03-10 | 2017-03-10 | A kind of waterborne glass ink and preparation method thereof |
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| Publication Number | Publication Date |
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| CN106752362A true CN106752362A (en) | 2017-05-31 |
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ID=58962147
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250837A (en) * | 2018-03-28 | 2018-07-06 | 许水仙 | A kind of preparation method of modified resin type glass ink |
| CN113028442A (en) * | 2021-03-15 | 2021-06-25 | 汪子友 | Ink stick raw materials apparatus for producing |
| CN116285492A (en) * | 2023-02-01 | 2023-06-23 | 玉林师范学院 | Water-based epoxy resin black ink and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092531A (en) * | 2007-07-19 | 2007-12-26 | 王兆进 | Low temperature solidified glass printing ink in single constituent |
| CN102358815A (en) * | 2011-07-25 | 2012-02-22 | 上海电动工具研究所 | One-component self-drying acrylic acid grafted epoxy ester aqueous dispersion coating and its preparation method |
-
2017
- 2017-03-10 CN CN201710142924.9A patent/CN106752362A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092531A (en) * | 2007-07-19 | 2007-12-26 | 王兆进 | Low temperature solidified glass printing ink in single constituent |
| CN102358815A (en) * | 2011-07-25 | 2012-02-22 | 上海电动工具研究所 | One-component self-drying acrylic acid grafted epoxy ester aqueous dispersion coating and its preparation method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250837A (en) * | 2018-03-28 | 2018-07-06 | 许水仙 | A kind of preparation method of modified resin type glass ink |
| CN113028442A (en) * | 2021-03-15 | 2021-06-25 | 汪子友 | Ink stick raw materials apparatus for producing |
| CN116285492A (en) * | 2023-02-01 | 2023-06-23 | 玉林师范学院 | Water-based epoxy resin black ink and preparation method thereof |
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