CN104194684A - Antiblocking and water-white-resistant acrylate emulsion and preparation method thereof - Google Patents
Antiblocking and water-white-resistant acrylate emulsion and preparation method thereof Download PDFInfo
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- CN104194684A CN104194684A CN201410397819.6A CN201410397819A CN104194684A CN 104194684 A CN104194684 A CN 104194684A CN 201410397819 A CN201410397819 A CN 201410397819A CN 104194684 A CN104194684 A CN 104194684A
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Abstract
The invention discloses an antiblocking and water-white-resistant acrylate emulsion which is characterized by comprising the following components in parts by mass: 100 parts of water, 20-40 parts of methyl methacrylate, 0-20 parts of butyl acrylate, 10-40 parts of silica sol, 2-10 parts of functional monomers, 2-6 parts of emulsifier and 1-5 parts of persulfate. The antiblocking and water-white-resistant acrylate emulsion disclosed by the invention not only has excellent antiblocking property, but also has favorable water white resistance.
Description
Technical field
The present invention relates to a kind of acrylic ester emulsion and preparation method thereof, is a kind of antiblocking, water-fast white acrylic ester emulsion and preparation method thereof specifically.
Background technology
ACRYLIC EMULSION is emulsion conventional in current aqueous paint, particularly especially extensive in the application of aqueous woodware paint varnish.Traditional acrylic ester emulsion exists resistance to blocking and the conflicting phenomenon of water-whitening resistance, its major cause is that acrylic ester emulsion is affected by self molecular structure, it has the glutinous cold short characteristic of heat, thereby acrylic ester emulsion there will be situation about being clamminess under the higher environment of temperature.In prior art, in order to address this problem, conventionally can adopt the mode that improves polymer particle surface hardness to overcome the defect that acrylic ester emulsion high temperature is clamminess.Yet along with polymer particle surface hardness improves, molecule chain rigidity also strengthens thereupon, the fragility of paint film is increased.In addition, due to molecular chain rigidity reinforced, under irradiate light, the photostabilization of molecular chain is poor, and transport phenomena easily appears in the group on molecular chain, has greatly reduced the water-whitening resistance energy of paint film.Resistance to blocking and water-whitening resistance are conflicting performances to acrylic ester emulsion, and the two can not get both.Therefore, how developing a kind of good resistance to blocking that both had, have again the acrylic ester emulsion of good water-whitening resistance, is one technical barrier of current acrylic ester emulsion industry.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of excellent resistance to blocking that both had is provided, there is again the acrylic ester emulsion of good water-whitening resistance.
Another goal of the invention of the present invention is to provide the method for the above-mentioned antiblocking of the simple preparation of a kind of technique, water-fast white acrylic ester emulsion.
Goal of the invention of the present invention is achieved in that a kind of antiblocking, water-fast white acrylic ester emulsion, it is characterized in that: described antiblocking, water-fast white acrylic ester emulsion comprise water, methyl methacrylate, butyl acrylate, silicon sol, function monomer, emulsifying agent and persulphate, and said components content is respectively by mass fraction: water: 100 parts; Methyl methacrylate: 20-40 part; Butyl acrylate: 0-20 part; Silicon sol: 10-40 part; Function monomer: 2-10 part; Emulsifying agent: 2-6 part; Persulphate: 1-5 part.
The dioxide-containing silica of described silicon sol is 20%-40%.
The silicon particle diameter of described silicon sol is 20-80 nanometer.
Described function monomer is diacetone-acryloamide(DAA) and adipic dihydrazide cross-linked polymer.
Described emulsifying agent is sodium laurylsulfonate.
Described persulphate is that a kind of or mentioned component in ammonium persulphate, Potassium Persulphate and Sodium Persulfate mixes in any proportion.
Described preparation method comprises the following steps:
A: take raw material for standby according to said ratio;
B: add water, methyl methacrylate, butyl acrylate, function monomer and silicon sol under normal temperature state and be stirred well to evenly in reactor;
C: the mixture of b step is warming up to 80-90 ℃, adds the emulsifying agent of persulphate and 10-20% proportional quantity and be stirred well to evenly;
D: the mixture temperature in c step remains on 75-85 ℃ and lasting stirring, reaction times 15-35 minute;
E: the mixture obtaining in d step is remained on to 80-85 ℃, and drip remaining emulsifying agent, continue to stir, time for adding is 3-5 hour;
F: be warming up to 90-95 ℃ after e step is added dropwise to complete, and is incubated 1-3 hour;
G: obtain adding redox agent in mixture in f step, be cooled to 60-70 ℃, and be incubated 10-20 minute;
H: again add redox agent in the mixture making toward g step, be cooled to 50-60 ℃, and be incubated 10-20 minute;
I: the mixture that g step is made is cooled to 40-50 ℃, obtains acrylic ester emulsion after filtration.
The present invention has the following advantages:
1, in antiblocking of the present invention, water-fast white acrylic ester emulsion, added silicon sol, the moisture of silicon sol solution is when evaporation, and silicon sol micelle, because self is active and aggregation generation dehydration condensation, forms reticulated structure.And silicon sol micelle infiltrates in the macromolecular chain structure of reaction system when reacting, make can merge at faster speed between the particle of polymkeric substance and particle, can effectively shorten time of drying of filming, making to film has excellent antiblocking performance.
2, in antiblocking of the present invention, water-fast white acrylic ester emulsion, added function monomer, this function monomer adopts diacetone-acryloamide(DAA) and adipic dihydrazide cross-linked polymer (being DAAM/ADH).In molecular chain due to diacetone-acryloamide(DAA) and adipic dihydrazide cross-linked polymer, have more active group, there is a large amount of crosslinking reactions with methyl methacrylate or butyl acrylate in active group in reaction system, forms cross linking membrane.Thereby diacetone-acryloamide(DAA) and adipic dihydrazide cross-linked polymer can improve the cross-linking density and the bond energy that molecular chain group is connected of acrylic ester emulsion reaction system greatly, make emulsion have good water-whitening resistance.
3, antiblocking of the present invention, water-fast white acrylic ester emulsion adopt the autoreaction legal system of heating standby, and whole reaction is carried out at 40-95 ℃ of temperature, so whole reaction system can be carried out under relatively gentle environment, have guaranteed the stability of reaction.Whole reaction simultaneously is all carried out in reactor, and only need heat and stir and can prepare, and its manufacturing procedure is very simple, greatly reduces the tooling cost of acrylic ester emulsion.
Embodiment
Antiblocking of the present invention, water-fast white acrylic ester emulsion comprise water, methyl methacrylate, butyl acrylate, silicon sol, function monomer, emulsifying agent and persulphate, and said components content is respectively by mass fraction: water: 100 parts; Methyl methacrylate: 20-40 part; Butyl acrylate: 0-20 part; Silicon sol: 10-40 part; Function monomer: 2-10 part; Emulsifying agent: 2-6 part; Persulphate: 1-5 part.Methyl methacrylate and butyl acrylate are added to the water, and using persulphate and carry out polyreaction as initiator, and the emulsifying effect that is aided with emulsifying agent forms acrylic ester emulsion.
Silicon sol dioxide-containing silica of the present invention is 20%-40%, and silicon particle diameter is 20-80 nanometer.In whole chemical reaction, silicon sol micelle, because of self active and aggregation generation dehydration condensation, forms reticulated structure, and micelle infiltrates in the macromolecular chain structure of reaction system, makes can merge at faster speed between the particle of polymkeric substance and particle.
Function monomer of the present invention adopts diacetone-acryloamide(DAA) and adipic dihydrazide cross-linked polymer, in molecular chain due to diacetone-acryloamide(DAA) and adipic dihydrazide cross-linked polymer, there is more active group, there is a large amount of crosslinking reactions with methyl methacrylate or butyl acrylate in active group, form cross linking membrane in reaction system.
Emulsifying agent of the present invention adopts sodium laurylsulfonate, and sodium laurylsulfonate is anion surfactant, has good emulsifying, foaming, infiltration, decontamination and dispersing property.
Vitriol of the present invention adopts a kind of or mentioned component in ammonium persulphate, Potassium Persulphate and Sodium Persulfate to mix as initiator in any proportion.Because mentioned component is water-based persulphate, after completing, chemical reaction can give the water tolerance that emulsion is good.
Antiblocking of the present invention, water-fast white acrylic ester emulsion preparation method comprise the following steps:
A: take raw material for standby according to said ratio;
B: add water, methyl methacrylate, butyl acrylate, function monomer and silicon sol under normal temperature state and be stirred well to evenly in reactor;
C: the mixture of b step is warming up to 80-90 ℃, adds the emulsifying agent of persulphate and 10-20% proportional quantity and be stirred well to evenly;
D: the mixture temperature in c step remains on 75-85 ℃ and lasting stirring, reaction times 15-35 minute;
E: the mixture obtaining in d step is remained on to 80-85 ℃, and drip remaining emulsifying agent, continue to stir, time for adding is 3-5 hour;
F: be warming up to 90-95 ℃ after e step is added dropwise to complete, and is incubated 1-3 hour;
G: obtain adding redox agent in mixture in f step, be cooled to 60-70 ℃, and be incubated 10-20 minute;
H: again add redox agent in the mixture making toward g step, be cooled to 50-60 ℃, and be incubated 10-20 minute;
I: the mixture that g step is made is cooled to 40-50 ℃, obtains acrylic ester emulsion after filtration.
The redox agent adding in g step and h step, can adopt the Oxidizing and Reducing Agents that Potassium Persulphate, sodium bisulfite etc. are conventional to form redox system.
By water-fast white test (sample is filmed after abundant being dried, and soaks sample 1-5 hour in 10-50 ℃ of distilled water, sees whether paint film bubbles, comes off, fades), acrylic ester emulsion of the present invention is that microvesicle to still, nothing comes off, colour-fast.And test by resistance to blocking, (sample is filmed after abundant being dried, on sample, cover test paper, sample is positioned over to 2-6 hour under 40-60 ℃ of environment, then take off test paper, seeing sample films to film whether to have after whether having adhesive power and taking off test paper comes off), acrylic ester emulsion of the present invention is for without adhering to, without coming off.
Below in conjunction with table, a pair of each embodiment is elaborated, but does not therefore limit the invention in described scope of embodiments:
Embodiment 1
Antiblocking of the present invention, water-fast white acrylic ester emulsion comprise water, methyl methacrylate, silicon sol, function monomer, emulsifying agent and ammonium persulphate, and said components content is respectively by mass fraction: water: 100 parts; Methyl methacrylate: 20 parts; Silicon sol: 10 parts; Function monomer: 2 parts; Emulsifying agent: 2 parts; Ammonium persulphate: 1 part.Wherein, in silicon sol, dioxide-containing silica is 20%, and the silicon particle diameter of silicon sol is 20 nanometers.Function monomer is diacetone-acryloamide(DAA) and adipic dihydrazide cross-linked polymer, and emulsifying agent is sodium laurylsulfonate.Methyl methacrylate is added to the water, and usings ammonium persulphate and carry out polyreaction as initiator, the emulsifying effect that is aided with emulsifying agent forms acrylic ester emulsion.
Antiblocking of the present invention, water-fast white acrylic ester emulsion preparation method comprise the following steps:
A: take raw material for standby according to said ratio;
B: add water, methyl methacrylate, function monomer and silicon sol under normal temperature state and be stirred well to evenly in reactor;
C: the mixture of b step is warming up to 80 ℃, adds the emulsifying agent of ammonium persulphate and 10% proportional quantity and be stirred well to evenly;
D: the mixture temperature in c step remains on 75 ℃ and lasting stirring, 15 minutes reaction times;
E: the mixture obtaining in d step is remained on to 80 ℃, and drip remaining emulsifying agent, continue to stir, time for adding is 3 hours;
F: be warming up to 90 ℃ after e step is added dropwise to complete, and is incubated 1 hour;
G: obtain adding redox agent in mixture in f step, be cooled to 60 ℃, and be incubated 10 minutes;
H: again add redox agent in the mixture making toward g step, be cooled to 50 ℃, and be incubated 10 minutes;
I: the mixture that g step is made is cooled to 40 ℃, obtains acrylic ester emulsion after filtration.
After tested, the water-fast white test of antiblocking of the present invention, water-fast white acrylic ester emulsion (10 ℃ of distilled water, 1 hour) is microvesicle, without coming off, colour-fast; Resistance to blocking test (40 ℃, 2 hours) is for coming off without adhesion, nothing.
Embodiment 2
Antiblocking of the present invention, water-fast white acrylic ester emulsion comprise water, methyl methacrylate, butyl acrylate, silicon sol, function monomer, emulsifying agent, Potassium Persulphate and Sodium Persulfate, and said components content is respectively by mass fraction: water: 100 parts; Methyl methacrylate: 25 parts; Butyl acrylate: 5 parts; Silicon sol: 18 parts; Function monomer: 4 parts; Emulsifying agent: 3 parts; Potassium Persulphate: 1 part; Sodium Persulfate: 1 part.Wherein, in silicon sol, dioxide-containing silica is 25%, and the silicon particle diameter of silicon sol is 40 nanometers.Function monomer is diacetone-acryloamide(DAA) and adipic dihydrazide cross-linked polymer, and emulsifying agent is sodium laurylsulfonate.Methyl methacrylate and butyl acrylate are added to the water, and using Potassium Persulphate and Sodium Persulfate mixture and carry out polyreaction as initiator, the emulsifying effect that is aided with emulsifying agent forms acrylic ester emulsion.
Antiblocking of the present invention, water-fast white acrylic ester emulsion preparation method comprise the following steps:
A: take raw material for standby according to said ratio;
B: add water, methyl methacrylate, butyl acrylate, function monomer and silicon sol under normal temperature state and be stirred well to evenly in reactor;
C: the mixture of b step is warming up to 83 ℃, adds the emulsifying agent of Potassium Persulphate and Sodium Persulfate mixture and 13% proportional quantity and be stirred well to evenly;
D: the mixture temperature in c step remains on 78 ℃ and lasting stirring, 20 minutes reaction times;
E: the mixture obtaining in d step is remained on to 82 ℃, and drip remaining emulsifying agent, continue to stir, time for adding is 3.5 hours;
F: be warming up to 93 ℃ after e step is added dropwise to complete, and is incubated 1.5 hours;
G: obtain adding redox agent in mixture in f step, be cooled to 63 ℃, and be incubated 12 minutes;
H: again add redox agent in the mixture making toward g step, be cooled to 52 ℃, and be incubated 13 minutes;
I: the mixture that g step is made is cooled to 43 ℃, obtains acrylic ester emulsion after filtration.
After tested, the water-fast white test of antiblocking of the present invention, water-fast white acrylic ester emulsion (20 ℃ of distilled water, 2 hours) for still, without coming off, colour-fast; Resistance to blocking test (45 ℃, 4 hours) is for coming off without adhesion, nothing.
Embodiment 3
Antiblocking of the present invention, water-fast white acrylic ester emulsion comprise water, methyl methacrylate, butyl acrylate, silicon sol, function monomer, emulsifying agent, ammonium persulphate and Sodium Persulfate, and said components content is respectively by mass fraction: water: 100 parts; Methyl methacrylate: 30 parts; Butyl acrylate: 10 parts; Silicon sol: 26 parts; Function monomer: 6 parts; Emulsifying agent: 4 parts; Ammonium persulphate: 1 part; Sodium Persulfate: 2 parts.Wherein, in silicon sol, dioxide-containing silica is 30%, and the silicon particle diameter of silicon sol is 50 nanometers.Function monomer is diacetone-acryloamide(DAA) and adipic dihydrazide cross-linked polymer, and emulsifying agent is sodium laurylsulfonate.Methyl methacrylate and butyl acrylate are added to the water, and using ammonium persulphate and Sodium Persulfate mixture and carry out polyreaction as initiator, the emulsifying effect that is aided with emulsifying agent forms acrylic ester emulsion.
Antiblocking of the present invention, water-fast white acrylic ester emulsion preparation method comprise the following steps:
A: take raw material for standby according to said ratio;
B: add water, methyl methacrylate, butyl acrylate, function monomer and silicon sol under normal temperature state and be stirred well to evenly in reactor;
C: the mixture of b step is warming up to 86 ℃, adds the emulsifying agent of ammonium persulphate and Sodium Persulfate mixture and 15% proportional quantity and be stirred well to evenly;
D: the mixture temperature in c step remains on 80 ℃ and lasting stirring, 25 minutes reaction times;
E: the mixture obtaining in d step is remained on to 83 ℃, and drip remaining emulsifying agent, continue to stir, time for adding is 4 hours;
F: be warming up to 94 ℃ after e step is added dropwise to complete, and is incubated 2 hours;
G: obtain adding redox agent in mixture in f step, be cooled to 65 ℃, and be incubated 16 minutes;
H: again add redox agent in the mixture making toward g step, be cooled to 55 ℃, and be incubated 15 minutes;
I: the mixture that g step is made is cooled to 45 ℃, obtains acrylic ester emulsion after filtration.
After tested, the water-fast white test of antiblocking of the present invention, water-fast white acrylic ester emulsion (30 ℃ of distilled water, 4 hours) for still, without coming off, colour-fast; Resistance to blocking test (50 ℃, 5 hours) is for coming off without adhesion, nothing.
Embodiment 4
Antiblocking of the present invention, water-fast white acrylic ester emulsion comprise water, methyl methacrylate, butyl acrylate, silicon sol, function monomer, emulsifying agent, ammonium persulphate and Potassium Persulphate, and said components content is respectively by mass fraction: water: 100 parts; Methyl methacrylate: 35 parts; Butyl acrylate: 15 parts; Silicon sol: 34 parts; Function monomer: 8 parts; Emulsifying agent: 5 parts; Ammonium persulphate: 2 parts; Potassium Persulphate: 2 parts.Wherein, in silicon sol, dioxide-containing silica is 35%, and the silicon particle diameter of silicon sol is 65 nanometers.Function monomer is diacetone-acryloamide(DAA) and adipic dihydrazide cross-linked polymer, and emulsifying agent is sodium laurylsulfonate.Methyl methacrylate and butyl acrylate are added to the water, and using ammonium persulphate and Potassium Persulphate mixture and carry out polyreaction as initiator, the emulsifying effect that is aided with emulsifying agent forms acrylic ester emulsion.
Antiblocking of the present invention, water-fast white acrylic ester emulsion preparation method comprise the following steps:
A: take raw material for standby according to said ratio;
B: add water, methyl methacrylate, butyl acrylate, function monomer and silicon sol under normal temperature state and be stirred well to evenly in reactor;
C: the mixture of b step is warming up to 88 ℃, adds the emulsifying agent of ammonium persulphate and Potassium Persulphate mixture and 18% proportional quantity and be stirred well to evenly;
D: the mixture temperature in c step remains on 83 ℃ and lasting stirring, 30 minutes reaction times;
E: the mixture obtaining in d step is remained on to 84 ℃, and drip remaining emulsifying agent, continue to stir, time for adding is 4.5 hours;
F: be warming up to 93 ℃ after e step is added dropwise to complete, and is incubated 2.5 hours;
G: obtain adding redox agent in mixture in f step, be cooled to 68 ℃, and be incubated 18 minutes;
H: again add redox agent in the mixture making toward g step, be cooled to 57 ℃, and be incubated 18 minutes;
I: the mixture that g step is made is cooled to 48 ℃, obtains acrylic ester emulsion after filtration.
After tested, the water-fast white test of antiblocking of the present invention, water-fast white acrylic ester emulsion (40 ℃ of distilled water, 5 hours) for still, without coming off, colour-fast; Resistance to blocking test (55 ℃, 6 hours) is for coming off without adhesion, nothing.
Embodiment 5
Antiblocking of the present invention, water-fast white acrylic ester emulsion comprise water, methyl methacrylate, butyl acrylate, silicon sol, function monomer, emulsifying agent, ammonium persulphate, Potassium Persulphate and Sodium Persulfate, and said components content is respectively by mass fraction: water: 100 parts; Methyl methacrylate: 40 parts; Butyl acrylate: 20 parts; Silicon sol: 40 parts; Function monomer: 10 parts; Emulsifying agent: 6 parts; Ammonium persulphate: 2 parts; Potassium Persulphate: 1 part; Sodium Persulfate: 2 parts.Wherein, in silicon sol, dioxide-containing silica is 40%, and the silicon particle diameter of silicon sol is 80 nanometers.Function monomer is diacetone-acryloamide(DAA) and adipic dihydrazide cross-linked polymer, and emulsifying agent is sodium laurylsulfonate.Methyl methacrylate and butyl acrylate are added to the water, and using ammonium persulphate, Potassium Persulphate and Sodium Persulfate mixture and carry out polyreaction as initiator, the emulsifying effect that is aided with emulsifying agent forms acrylic ester emulsion.
Antiblocking of the present invention, water-fast white acrylic ester emulsion preparation method comprise the following steps:
A: take raw material for standby according to said ratio;
B: add water, methyl methacrylate, butyl acrylate, function monomer and silicon sol under normal temperature state and be stirred well to evenly in reactor;
C: the mixture of b step is warming up to 90 ℃, adds the emulsifying agent of ammonium persulphate, Potassium Persulphate and Sodium Persulfate mixture and 20% proportional quantity and be stirred well to evenly;
D: the mixture temperature in c step remains on 85 ℃ and lasting stirring, 35 minutes reaction times;
E: the mixture obtaining in d step is remained on to 85 ℃, and drip remaining emulsifying agent, continue to stir, time for adding is 5 hours;
F: be warming up to 95 ℃ after e step is added dropwise to complete, and is incubated 3 hours;
G: obtain adding redox agent in mixture in f step, be cooled to 70 ℃, and be incubated 20 minutes;
H: again add redox agent in the mixture making toward g step, be cooled to 60 ℃, and be incubated 20 minutes;
I: the mixture that g step is made is cooled to 50 ℃, obtains acrylic ester emulsion after filtration.
After tested, the water-fast white test of antiblocking of the present invention, water-fast white acrylic ester emulsion (50 ℃ of distilled water, 5 hours) for still, without coming off, colour-fast; Resistance to blocking test (60 ℃, 6 hours) is for coming off without adhesion, nothing.
Claims (7)
1. an antiblocking, water-fast white acrylic ester emulsion, it is characterized in that: described antiblocking, water-fast white acrylic ester emulsion comprise water, methyl methacrylate, butyl acrylate, silicon sol, function monomer, emulsifying agent and persulphate, and said components content is respectively by mass fraction: water: 100 parts; Methyl methacrylate: 20-40 part; Butyl acrylate: 0-20 part; Silicon sol: 10-40 part; Function monomer: 2-10 part; Emulsifying agent: 2-6 part; Persulphate: 1-5 part.
2. antiblocking, water-fast white acrylic ester emulsion according to claim 1, is characterized in that: the dioxide-containing silica of described silicon sol is 20%-40%.
3. antiblocking, water-fast white acrylic ester emulsion according to claim 1, is characterized in that: the silicon particle diameter of described silicon sol is 20-80 nanometer.
4. antiblocking, water-fast white acrylic ester emulsion according to claim 1, is characterized in that: described function monomer is diacetone-acryloamide(DAA) and adipic dihydrazide cross-linked polymer.
5. antiblocking, water-fast white acrylic ester emulsion according to claim 1, is characterized in that: described emulsifying agent is sodium laurylsulfonate.
6. antiblocking, water-fast white acrylic ester emulsion according to claim 1, is characterized in that: described persulphate is that a kind of or mentioned component in ammonium persulphate, Potassium Persulphate and Sodium Persulfate mixes in any proportion.
7. a preparation method for antiblocking, water-fast white acrylic ester emulsion as claimed in claim 1, is characterized in that: described preparation method comprises the following steps:
A: take raw material for standby according to said ratio;
B: add water, methyl methacrylate, butyl acrylate, function monomer and silicon sol under normal temperature state and be stirred well to evenly in reactor;
C: the mixture of b step is warming up to 80-90 ℃, adds the emulsifying agent of persulphate and 10-20% proportional quantity and be stirred well to evenly;
D: the mixture temperature in c step remains on 75-85 ℃ and lasting stirring, reaction times 15-35 minute;
E: the mixture obtaining in d step is remained on to 80-85 ℃, and drip remaining emulsifying agent, continue to stir, time for adding is 3-5 hour;
F: be warming up to 90-95 ℃ after e step is added dropwise to complete, and is incubated 1-3 hour;
G: obtain adding redox agent in mixture in f step, be cooled to 60-70 ℃, and be incubated 10-20 minute;
H: again add redox agent in the mixture making toward g step, be cooled to 50-60 ℃, and be incubated 10-20 minute;
I: the mixture that g step is made is cooled to 40-50 ℃, obtains acrylic ester emulsion after filtration.
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| CN104710561A (en) * | 2014-12-31 | 2015-06-17 | 佛山市顺德区巴德富实业有限公司 | Raindrop imprint-resisting pure acrylic emulsion and preparation method thereof |
| CN106010380A (en) * | 2015-11-16 | 2016-10-12 | 江苏景宏新材料科技有限公司 | Method for preparation of water blush resistant acrylic emulsion pressure sensitive adhesive by pickering emulsion polymerization |
| CN106608943A (en) * | 2016-11-22 | 2017-05-03 | 佛山市顺德区巴德富实业有限公司 | One-component acrylic ester matte core-shell emulsions with good anti-water-white performance and preparation method and application thereof |
| CN106749865A (en) * | 2016-11-28 | 2017-05-31 | 南通华润新材料有限公司 | The preparation method of anti-stick white high glaze Weak solvent digital inkjet printing coating emulsion high |
| CN107345121A (en) * | 2017-06-30 | 2017-11-14 | 常州创索新材料科技有限公司 | A kind of overlay film adhesive and preparation method thereof |
| CN113429912A (en) * | 2021-07-16 | 2021-09-24 | 西安汉港新材料科技有限公司 | Environment-friendly waterproof white latex and preparation method thereof |
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Effective date of registration: 20170209 Address after: 528441 Zhongshan City, the people of the town of Sha Sha Village, Sha Zi Road, No. 7 Patentee after: Zhongshan badefu Chemical Technology Co., Ltd. Address before: 528322 Shunde District, Guangdong, Foshan Leliu South Road, Zhenlong Patentee before: Badefu Industry Co., Ltd. Foshan City Shunde District |