CN1800225A - Latex type hydroxy acryl acid resin possessing core-shell configuration - Google Patents
Latex type hydroxy acryl acid resin possessing core-shell configuration Download PDFInfo
- Publication number
- CN1800225A CN1800225A CN 200510134997 CN200510134997A CN1800225A CN 1800225 A CN1800225 A CN 1800225A CN 200510134997 CN200510134997 CN 200510134997 CN 200510134997 A CN200510134997 A CN 200510134997A CN 1800225 A CN1800225 A CN 1800225A
- Authority
- CN
- China
- Prior art keywords
- monomer
- vinyl monomer
- acid
- acid resin
- hydroxy acryl
- 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.)
- Granted
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to an emulsion type hydroxy acrylic resin with core-shell configuration which is merged by four ene-type base on the condition of exploder and diversity. 1) the ene-type base 60%-80% (by weight rate)without other functionality functional group; 2) the ene-type base 20%-40% with hydroxyl; 3) the ene-type base 2%-8% with epoxy radicals; 4) the ene-type base 1%-5% with carboxyl, wherein 20~40% base 1) is as core base, other base 1) mixes with the base 2), 3), 4) as case base to form core-shell configuration.
Description
Technical field
The present invention relates to a kind of latex type hydroxy acryl acid resin, be particularly suitable in bi-component waterborne woodwork coating, watery anti-corrosion paint etc., being used as hydroxy component with core-shell configuration.
Background technology
Along with the strictness day by day of environmental requirement in the global range, the water-borne coatings product is used on a large scale.But be subjected to the restriction of itself preparating mechanism, resistance to medium of filming and hardness are difficult to effectively be improved according to a conventional method.In this case, people have begun the research of water-based hydroxyl resin that can be crosslinked to the adding solidifying agent.Latex type hydroxy acryl acid resin is compared with solvent method synthetic, salifiable, the aqueous dispersion type hydroxy resin of neutralization and aqurous ployurethane hydroxy resin, and cost is low, and solids content is higher, and key is that volatile organic compounds (VOC) content is few.Now obtain the extensive concern of domestic and international research unit and coating producer and played an active part in research and development.U.S. Pat 5641829 is made monomer with Hydroxyethyl acrylate, butyl acrylate and vinylformic acid, under solvent, carry out polymerization, after reacting completely, with alkali neutralization, water-dispersion, form the hydroxy resin of aqueous dispersion type, get its 243.0 parts and 39.8 parts of linking agents (trade(brand)name Cymel 327), crosslinking curing in the presence of the phosphoric acid ester catalyzer, the formed resistance to medium of filming is good.But because the hydroxy resin of this aqueous dispersion type is polymerized with solvent method, VOC content is higher, and solids content is lower.International Patent Application WO 01-72909 relates to a kind of water-based hydroxyl polymer-containing, it divides three phases in polymerization process: fs monomer ratio of components is methyl methacrylate/butyl acrylate/methacrylic acid 441.6/147.2/11.9, subordinate phase monomer ratio of components is methyl methacrylate/butyl acrylate/Hydroxyethyl acrylate 71.0/35.0/6.9, and phase III monomer ratio of components is methyl methacrylate/butyl acrylate/Hydroxyethyl acrylate/methacrylic acid 12.3/30.8/40.2/22.7; Get 165 parts of this hydroxyl latex emulsions, the aluminium powder paint film performance that 150 parts of aluminum pastes and 112 parts of mixing of polyurethane dispersions obtain is good, but the synthesis technique of this emulsion is comparatively numerous and diverse, and the various patience that gained is filmed still can not be satisfactory.Chinese patent application 200410051550.2 disclosed hydroxyl acrylic emulsions with microgel nuclear structure, it is earlier with vinyl silicane coupling agent and acrylate monomer copolymerization, obtain having the nuclear of microgel structure, carry out hydroxyl vinyl monomer and acrylic ester monomer copolymerization on the nuclear surface then, nuclear inside can self-crosslinking, and the hydroxyl on the shell is used for external crosslinking, increased cross-linking set, improve the hardness and the patience of filming, but can cause filming becoming fragile the snappiness variation; All synthetic with conventional emulsifier, easily bubble and influence water-resistance property of coating; Its microgel structure can make the system increased activity, and the work-ing life of preparation coating is shorter, has only 3～6 hours.
Summary of the invention
The objective of the invention is to, a kind of latex type hydroxy acryl acid resin with core-shell configuration is provided, its VOC content is low, solids content is high, and formed hardness of film, snappiness and various patience are improved.
Realize the technical scheme of the object of the invention: a kind of latex type hydroxy acryl acid resin with core-shell configuration, it is that following 4 kinds of vinyl monomers are in the presence of initiator and emulsifying agent, letex polymerization forms, and monomeric species and each monomer consumption shared per-cent in the monomer total amount are as follows: the vinyl monomer 60～80% that does not 1. contain other functional functional group; 2. the vinyl monomer 20～40% of hydroxyl; 3. the vinyl monomer 2～8% that contains epoxy group(ing); 4. carboxylic vinyl monomer 1～5%;
Described initiator amount is 0.2～0.7% of a monomer total amount;
Described emulsifying agent is a reactive emulsifier, or reactive emulsifier and conventional small-molecular emulsifier, and the weight ratio of the two consumption is 7.5～15.0: 1; The total consumption of emulsifying agent is 0.3～2.0% of a monomer total amount;
During letex polymerization, 1. 20～40% monomer at first aggregates into the seed emulsion as nuclear, and 2., 3., 4. 1. residual monomers mix as becoming shell monomer with monomer again, becomes shell, the formation core-shell configuration at the surface aggregate of established nuclear particle;
Above per-cent all is weight percentage.
1. described monomer is: two or more in esters of acrylic acid or methyl acrylic ester monomer, the aromatic series vinyl monomer.For example, (methyl) acrylic ester monomers such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) 2-EHA, (methyl) cyclohexyl acrylate and (methyl) lauryl acrylate; Aromatic series vinyl monomers such as vinylbenzene, vinyl toluene, Vinyl toluene.
Above-mentioned emulsion type hydroxy acryl acid resin, wherein, following monomer consumption shared per-cent in the monomer total amount is preferably: the vinyl monomer of hydroxyl 2. 22～26%; The vinyl monomer that contains epoxy group(ing) 3. 3～5%; Carboxylic vinyl monomer 4. 1～2%.
Above-mentioned emulsion type hydroxy acryl acid resin, wherein, 2. the vinyl monomer of described hydroxyl is: one or more in the hydroxyl esters monomer of acrylic or methacrylic acid.For example, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate etc.
Above-mentioned emulsion type hydroxy acryl acid resin, wherein, 3. the described vinyl monomer that contains epoxy group(ing) is: one or more in the Racemic glycidol esters monomer of acrylic or methacrylic acid.For example, (methyl) glycidyl acrylate, allyl glycidyl etc.
Above-mentioned emulsion type hydroxy acryl acid resin, wherein, 4. described carboxylic vinyl monomer is: one or more in vinylformic acid, methacrylic acid, butenoic acid, methylene-succinic acid, toxilic acid, the fumaric acid.
Above-mentioned emulsion type hydroxy acryl acid resin, wherein, described reactive emulsifier is one or more in the reactive emulsified monomer of anionic or non-ionic type, as: Methacrylamide sodium isopropyl xanthate, SE-10N, NE-10 etc., described conventional small-molecular emulsifier, as: sodium lauryl sulphate, Sodium dodecylbenzene sulfonate etc.
Above-mentioned emulsion type hydroxy acryl acid resin, wherein, described initiator is the persulfuric acid salt, as: ammonium persulphate, Potassium Persulphate etc.
Above-mentioned emulsion type hydroxy acryl acid resin, its outward appearance is the little blue light liquid of oyster white, viscosity 200～2000Mpas, solids content 42～46%, pH value 7.0～8.5, particle diameter 0.05～0.2 μ m, volatile organic compounds VOC content＜0.1%, hydroxy radical content 2.5～3.5%, storage period is more than 6 months.
Latex type hydroxy acryl acid resin of the present invention can be with existing emulsion polymerization equipment production.
When preparation resin of the present invention, heating in the presence of emulsifying agent and initiator earlier, make 20～40% monomer 1. polymerization form the nuclear emulsion, again under same temperature, drip simultaneously emulsifying agent and initiator and residual monomer 1. with monomer 2., monomer 3., monomer mixture 4., make them in the particle surface polymerization, formation contains the shell of hydroxyl, epoxy group(ing) and carboxyl, neutralization back carboxyl salify, keep functional functional group (hydroxyl and epoxy group(ing)) in the shell, formed the latex type hydroxy acryl acid resin with core-shell configuration of the present invention at last.
Technique effect of the present invention: the latex type hydroxy acryl acid resin with core-shell configuration of technical solution of the present invention has following beneficial effect: the first is because resin of the present invention is an emulsion-type, when formulating of recipe, with water is dispersion medium, do not add any organic solvent, thereby compare with the Hydroxylated acrylic resin (VOC content surpasses 10%) of the aqueous dispersion type that forms with the solvent method polymerization of present domestic use, safety, nontoxic, environmental protection (VOC content is lower than 0.1%), in addition, owing to use the Hydroxylated acrylic resin of the aqueous dispersion type of solvent method polymerization formation to have the problem at dilution peak, solids content is lower than 40%, and the solids content of resin of the present invention can reach 46%, can improve operating efficiency indirectly.It two uses reactive emulsified monomer or reactive emulsified monomer to add the emulsifying agent of the conventional small-molecular emulsifier of minute quantity as system, and its advantage is that emulsion has low bubble property, and the water tolerance of filming and transparency are improved.It three is core-shell configurations that resin of the present invention has standard, and owing to when formulating of recipe, determined with the vinyl monomer that contains appropriate functional functional group as becoming nuclear monomer; Determined each monomer consumption; Never contain in the vinyl monomer of other functional functional groups, determined that appropriate quantity makes nuclear monomer; During enforcement, after the polymerization nucleation, the remaining vinyl monomer that does not conform to functional functional group, add with vinyl monomer, the carboxylic vinyl monomer of hydroxyl, the vinyl monomer that contains epoxy group(ing) again, therefore, after letex polymerization became shell, having just, normal functional functional group (hydroxyl and epoxy group(ing)) can be distributed in the latex particle top layer.When making the hydroxy component of two-component coating with resin of the present invention, the hydroxyl of shell just can fully participate in reaction, improve the cross-linking efficiency of filming that forms, thereby improve hardness of film and various patience, polymkeric substance as nuclear does not participate in crosslinking reaction when the film forming, and giving films has good snappiness; Polymer active as nuclear is low simultaneously, makes coatings formulated have long work-ing life (＞24 hours).It four is the various resistance to medium that further increased hardness of film and filmed in the epoxy group(ing) that shell is introduced.
Embodiment
Below in conjunction with embodiment the present invention is further described in detail, but is not limited to this.
Part in embodiment and the comparative example prescription is weight part; Unless otherwise indicated, all raw materials are the commercially available industrial goods of coating level; Deionized water meets among the GB6682-92 requirement (pH:5.0～7.5, the specific conductivity≤0.50mS/m) of three grades of water regulations.
Embodiment 1～3:
Prescription sees Table 1
Table 1
| Stock number | Material name | Embodiment 1 (part) | Embodiment 2 (part) | Embodiment 3 (part) | |
| 1 (medium) | Deionized water | 160.0 | 160.0 | 140.0 | |
| 2 (emulsifying agent and initiators) | Deionized water | 20.0 | 20.0 | 20.0 | |
| SE-10N | / | 0.6 | 0.3 | ||
| NE-10 | / | / | 0.3 | ||
| AMPS (effective constituent 50%) | 1.2 | / | / | ||
| Sodium lauryl sulphate | 0.2 | / | / | ||
| Ammonium persulphate | 0.3 | 0.3 | 0.3 | ||
| 3 (becoming nuclear monomer 1.) | Methyl methacrylate | 20.0 | 10.0 | 2.0 | |
| Butyl acrylate | 15.0 | 20.0 | 15.0 | ||
| Vinylbenzene | / | / | 12.0 | ||
| 4 (emulsifying agent and initiators) | Deionized water | 30.0 | 30.0 | 30.0 | |
| SE-10N | / | 1.2 | 1.0 | ||
| NE-10 | / | / | 1.0 | ||
| AMPS (effective constituent 50%) | 2.8 | / | / | ||
| Ammonium persulphate | 0.5 | 0.5 | 0.5 | ||
| 5 (one-tenth shell monomers) | Monomer 1. | Methyl methacrylate | 45.0 | 30.0 | 5.0 |
| Butyl acrylate | 35.0 | 50.0 | 40.0 | ||
| Vinylbenzene | / | / | 35.0 | ||
| Monomer 2. | Propylene glycol monoacrylate | 30.0 | / | / | |
| Hydroxyethyl methylacrylate | / | 35.0 | 40.0 | ||
| Monomer 3. | Glycidyl methacrylate | 3.0 | 6.0 | 4.0 | |
| Monomer 4. | Vinylformic acid | 3.2 | / | / | |
| Methacrylic acid | / | 2.2 | 1.6 | ||
| 6 (middle mixture) | Ammoniacal liquor | 2.6 | 1.6 | 1.0 |
Annotate:
Embodiment 1: 1. monomer accounts for 76.06%; 2. monomer accounts for 19.84%; 3. monomer accounts for 1.98%; 4. monomer accounts for 2.12%; Emulsifying agent accounts for 1.46% of monomer total amount; Initiator accounts for 0.53% of monomer total amount;
Embodiment 2: 1. monomer accounts for 71.80%; 2. monomer accounts for 22.84%; 3. monomer accounts for 3.92%; 4. monomer accounts for 1.44%; Emulsifying agent accounts for 1.17% of monomer total amount; Initiator accounts for 0.52% of monomer total amount;
Embodiment 3: 1. monomer accounts for 70.51%; 2. monomer accounts for 25.87%; 3. monomer accounts for 2.59%; 4. monomer accounts for 1.03%; Emulsifying agent accounts for 1.68% of monomer total amount; Initiator accounts for 0.52% of monomer total amount;
AMPS is the reactive emulsified monomer of anionic of U.S. Lubrizol Corp. in the table:
Molecular formula: CH
2=CH-CO-NH-C (CH
3)
2-CH
2-SO
3Na, (Methacrylamide sodium isopropyl xanthate) 50% effective ingredient;
SE-10N is the reactive emulsified monomer of anionic of the electrochemical company of the Japanese rising sun in the table:
Molecular formula:
100% effective ingredient;
NE-10 is the reactive emulsified monomer of non-ionic type of the electrochemical company of the Japanese rising sun in the table
Molecular formula:
100% effective ingredient.
Synthesis technique:
Take into account in the 500ml there-necked flask of condensing works being furnished with heat riser, whipping appts, temperature, the formula ratio of pressing table 1 adds material 1, is warming up to 80 ℃ and adds materials 2, then drips material 3 in 1 hour, drips off insulation 0.5 hour, generates the nucleus of the seed emulsion.Under said temperature, drip material 4 and material 5 then simultaneously, in 3 hours, drip off.Drip off back insulation 2 hours.Be cooled to 50 ℃ then, add material 6 neutralizations, the after-filtration discharging that stirs makes the resin of the present invention of embodiment 1～3 respectively, and its technical indicator sees Table 2.
Comparative example
Comparative example is with conventional small-molecular emulsifier, the hydroxy acryl acid resin of emulsion polymerization technique preparation routinely, and do not add the vinyl monomer that has epoxy group(ing) in the prescription.
Prescription: 1. deionized water is 160.0 parts, 2. 50.0 parts of deionized waters, 1.6 parts of sodium lauryl sulphate and ammonium persulphate are 0.6 part, 3. 65.0 parts of methyl methacrylates, 55.0 parts of butyl acrylates, 30 parts of Propylene glycol monoacrylates and vinylformic acid are 2.7 parts, and 4. ammoniacal liquor is 2.0 parts;
Take into account in the 500ml there-necked flask of condensing works being furnished with heat riser, whipping appts, temperature, add material 1., be warming up to 80 ℃ drip simultaneously material 2. with material 3., in 3 hours, drip off.Drip off back insulation 2 hours.Be cooled to 50 ℃ then, add material and 4. neutralize, the after-filtration discharging that stirs makes the comparative example hydroxy acryl acid resin, and its technical indicator sees Table 2.
Table 2
| Index | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example |
| Outward appearance | Milky white little blue light | The opal blue light intensity | The opal blue light intensity | The opal blue light intensity |
| The cohesion rate, % | ＜0.2 | ＜0.1 | ＜0.2 | ＜0.2 |
| Viscosity, Mpas | 300 | 360 | 1200 | 680 |
| Solids content, % | 42.1 | 42.5 | 44.2 | 42.2 |
| Hydroxy radical content, % | 2.6 | 3.0 | 3.4 | 2.6 |
| The pH value | 8.3 | 7.8 | 8.0 | 8.2 |
| Median size, μ m | 0.15 | 0.08 | 0.10 | 0.10 |
| VOC content, % | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 |
| Storage period, month | ＞6 | ＞6 | ＞6 | ＞6 |
Film performance check after the film forming
With the above-mentioned resin of 100g as hydroxy component and 10g polyisocyanate component B 2336 (BAYER companies, NCO content is 18%) be made into the polyurethane coating (at least 24 hours work-ing life of coating of embodiment 1～3) of two-pack, be coated on the tinplate, thickness is 20 μ m (dry film), under 25 ℃, the environment of humidity 50% after dry 10 days, detect film performance, the results are shown in Table 3.
Table 3
| Test item | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example | Detection method |
| Outward appearance | Transparent, smooth | Transparent, smooth | Transparent, smooth | Transparent, smooth | Range estimation |
| Sticking power, level | 0～1 | 0～1 | 0～1 | 0～1 | GB/T9286-1998 |
| Snappiness, mm | 1 | 1 | 1 | 2 | GB/T1731-93 |
| Pencil hardness | 2H | H | 2H | H | GB/T6739-1996 |
| Water tolerance, 72h | No change | No change | No change | Whiting | Annotate 1 |
| The acetone extract rate, % | ＜10 | ＜10 | ＜10 | ＞30 | Annotate 2 |
Annotate 1: the water tolerance detection method
The different emulsion polymer of coating on the sheet glass of 8cm * 12cm is made thick the filming of about 20 μ m respectively,, after 7 days it is soaked in the deionized water 25 ℃ of dryings, observes paint film whiting, foaming and dropping situations.
Annotate 2: acetone extract rate detection method
Is m with emulsion in weight
0Sheet glass on after film forming solidifies, (m weighs
1), immerse a large amount of acetone solns then and place after 7 days, take out oven dry, (m weighs
2), be calculated as follows acetone extract rate (f).
Owing to used reactive emulsified monomer, improved the water tolerance of filming, the core-shell configuration of latex particle, shell hydroxyl and epoxy-based functional functional group fully participate in crosslinking reaction, improved the degree of crosslinking and the hardness of filming, the inner nuclear layer polymkeric substance does not participate in crosslinking reaction, gives the good snappiness of filming, therefore compare with comparative example, the degree of crosslinking of filming, snappiness and the water tolerance of resin formation of the present invention are significantly improved.Latex type hydroxy acryl acid resin of the present invention, can be used as the hydroxyl component and prepare various two two-component coatings of packing, 120-180 ℃ of baking-curing, also normal temperature solidified, be widely used in multiple base material, as: the application on surface such as timber, plastics, metal, glass and concrete.Alternative traditional solvent-borne type dual-component polyurethane self-drying paint and solvent-borne type amino-stoving varnish.
Claims (7)
1, a kind of latex type hydroxy acryl acid resin with core-shell configuration, it is characterized in that: it is that following 4 kinds of vinyl monomers are in the presence of initiator and emulsifying agent, letex polymerization forms, and monomeric species and each monomer consumption shared per-cent in the monomer total amount are as follows: the vinyl monomer 60～80% that does not 1. contain other functional functional group; 2. the vinyl monomer 20～40% of hydroxyl; 3. the vinyl monomer 2～8% that contains epoxy group(ing); 4. carboxylic vinyl monomer 1～5%;
Described initiator amount is 0.2～0.7% of a monomer total amount;
Described emulsifying agent is a reactive emulsifier, or reactive emulsifier and conventional small-molecular emulsifier, and the weight ratio of the two consumption is 7.5～15.0: 1; The total consumption of emulsifying agent is 0.3～2.0% of a monomer total amount;
During letex polymerization, 1. 20～40% monomer at first aggregates into the seed emulsion as nuclear, and 2., 3., 4. 1. residual monomers mix as becoming shell monomer with monomer again, becomes shell, the formation core-shell configuration at the surface aggregate of established nuclear particle;
1. described monomer is two or more in esters of acrylic acid or methyl acrylic ester monomer, the aromatic series vinyl monomer;
Above per-cent all is weight percentage.
2, latex type hydroxy acryl acid resin according to claim 1 is characterized in that: following monomer consumption shared per-cent in the monomer total amount is preferably: the vinyl monomer of hydroxyl 2. 22～26%; The vinyl monomer that contains epoxy group(ing) 3. 3～5%; Carboxylic vinyl monomer 4. 1～2%.
3, latex type hydroxy acryl acid resin according to claim 1 and 2 is characterized in that: 2. the vinyl monomer of described hydroxyl is one or more in the hydroxyl esters monomer of acrylic acid or methacrylic acid.
4, latex type hydroxy acryl acid resin according to claim 1 and 2 is characterized in that: one or more in the Racemic glycidol esters monomer that 3. the described vinyl monomer that contains epoxy group(ing) is acrylic acid or methacrylic acid.
5, latex type hydroxy acryl acid resin according to claim 1 and 2 is characterized in that: 4. described carboxylic vinyl monomer is one or more in vinylformic acid, methacrylic acid, butenoic acid, methylene-succinic acid, toxilic acid, the fumaric acid.
6, latex type hydroxy acryl acid resin according to claim 1 and 2 is characterized in that: described reactive emulsifier is one or more in the reactive emulsified monomer of anionic or non-ionic type.
7, the latex type hydroxy acryl acid resin of stating according to claim 1 or 2, it is characterized in that: its outward appearance is the little blue light liquid of oyster white, viscosity 200～2000Mpas, solids content 42～46%, pH value 7.0～8.5, particle diameter 0.05～0.2 μ m, volatile organic compounds VOC content＜0.1%, hydroxy radical content 2.5～3.5%, storage period is more than 6 months.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101349970A CN100376607C (en) | 2005-12-28 | 2005-12-28 | Latex type hydroxy acryl acid resin possessing core-shell configuration |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101349970A CN100376607C (en) | 2005-12-28 | 2005-12-28 | Latex type hydroxy acryl acid resin possessing core-shell configuration |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1800225A true CN1800225A (en) | 2006-07-12 |
| CN100376607C CN100376607C (en) | 2008-03-26 |
Family
ID=36810466
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101349970A Active CN100376607C (en) | 2005-12-28 | 2005-12-28 | Latex type hydroxy acryl acid resin possessing core-shell configuration |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100376607C (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100451042C (en) * | 2006-11-08 | 2009-01-14 | 吉林大学 | Fluoride core-shell acrylic-resin emulsion, its production and use |
| CN101914185A (en) * | 2010-09-08 | 2010-12-15 | 廊坊金汇利工业涂料有限公司 | Hydroxy acrylic resin aqueous dispersion and water-based coating prepared therefrom |
| CN101586010B (en) * | 2008-05-23 | 2011-05-11 | 北京京都大成化工有限公司 | Preparation method of dry composite crylic acid resin aqueous adhesive |
| CN101585898B (en) * | 2008-05-23 | 2012-05-30 | 东丽纤维研究所（中国）有限公司 | Resin microparticle in multilayered structure, dispersion liquid and preparation method thereof |
| CN102936386A (en) * | 2012-11-09 | 2013-02-20 | 广州市高士实业有限公司 | Fluororubber master batch and preparing method thereof |
| CN103319965A (en) * | 2013-07-02 | 2013-09-25 | 中国海洋石油总公司 | Aqueous metal glossy lacquer for cars and preparation method thereof |
| CN106243273A (en) * | 2016-07-29 | 2016-12-21 | 肇庆浩城树脂科技有限公司 | A kind of hydroxyl acrylic emulsion with nucleocapsid structure and preparation method and application |
| CN107722186A (en) * | 2017-10-27 | 2018-02-23 | 常州华科聚合物股份有限公司 | Hydroxylated acrylic resin dispersion and the water paint with its preparation |
| CN109776715A (en) * | 2019-01-18 | 2019-05-21 | 上海巴德富实业有限公司 | A kind of bi-component acrylic cover lotion and preparation method thereof |
| CN109929067A (en) * | 2017-12-16 | 2019-06-25 | 万华化学（宁波）有限公司 | A kind of core-shell structure acrylic acid ester emulsion and its preparation method and application |
| CN109970905A (en) * | 2019-03-12 | 2019-07-05 | 煤科集团杭州环保研究院有限公司 | Integral ceiling veneer coating aqueous high molecular lotion and preparation method thereof |
| CN110511388A (en) * | 2019-08-23 | 2019-11-29 | 湖北双键精细化工有限公司 | A kind of modified hydroxyl acrylic emulsion and preparation method thereof for aqueous coatings for tin plate printing |
| CN110628289A (en) * | 2019-09-26 | 2019-12-31 | 万华化学集团股份有限公司 | Water-based woodware stain-resistant white finish and preparation method thereof |
| CN111116831A (en) * | 2020-01-07 | 2020-05-08 | 黄禹 | Preparation method of hydroxyl acrylic emulsion |
| CN112063281A (en) * | 2020-07-31 | 2020-12-11 | 广东海特高新材料有限公司 | Water-based two-component wood paint and preparation method thereof |
| CN112573885A (en) * | 2020-12-12 | 2021-03-30 | 南京霄祥工程技术有限公司 | Self-leveling mortar and preparation method thereof |
| CN113242889A (en) * | 2018-12-25 | 2021-08-10 | 日涂汽车涂料有限公司 | Clear coating composition and method for forming clear coating film |
| CN115717014A (en) * | 2022-11-21 | 2023-02-28 | 河北工业大学 | Preparation method of easily-crosslinked core-shell type polyhydroxyacrylate emulsion coating |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1345905A (en) * | 2000-09-22 | 2002-04-24 | 吉林省纺织工业设计研究院 | Nano emlsion adhesion agent and preparation process and use thereof |
| CN1206251C (en) * | 2003-03-06 | 2005-06-15 | 华南理工大学 | Acrylate micro-emulsion with high solid content, its preparation method and use |
| CN1282677C (en) * | 2004-09-21 | 2006-11-01 | 华南理工大学 | Hydroxyl acrylic acid emulsion with microgel nuclear structure and preparation process and application thereof |
-
2005
- 2005-12-28 CN CNB2005101349970A patent/CN100376607C/en active Active
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100451042C (en) * | 2006-11-08 | 2009-01-14 | 吉林大学 | Fluoride core-shell acrylic-resin emulsion, its production and use |
| CN101586010B (en) * | 2008-05-23 | 2011-05-11 | 北京京都大成化工有限公司 | Preparation method of dry composite crylic acid resin aqueous adhesive |
| CN101585898B (en) * | 2008-05-23 | 2012-05-30 | 东丽纤维研究所（中国）有限公司 | Resin microparticle in multilayered structure, dispersion liquid and preparation method thereof |
| CN101914185A (en) * | 2010-09-08 | 2010-12-15 | 廊坊金汇利工业涂料有限公司 | Hydroxy acrylic resin aqueous dispersion and water-based coating prepared therefrom |
| CN102936386A (en) * | 2012-11-09 | 2013-02-20 | 广州市高士实业有限公司 | Fluororubber master batch and preparing method thereof |
| CN102936386B (en) * | 2012-11-09 | 2015-12-16 | 广州市高士实业有限公司 | Viton rubber master batch and preparation method thereof |
| CN103319965A (en) * | 2013-07-02 | 2013-09-25 | 中国海洋石油总公司 | Aqueous metal glossy lacquer for cars and preparation method thereof |
| CN103319965B (en) * | 2013-07-02 | 2015-12-23 | 中国海洋石油总公司 | A kind of automobile water-based property metal flash paint and preparation method thereof |
| CN106243273A (en) * | 2016-07-29 | 2016-12-21 | 肇庆浩城树脂科技有限公司 | A kind of hydroxyl acrylic emulsion with nucleocapsid structure and preparation method and application |
| CN106243273B (en) * | 2016-07-29 | 2019-04-16 | 肇庆浩城树脂科技有限公司 | A kind of hydroxyl acrylic emulsion and the preparation method and application thereof with core-shell structure |
| CN107722186A (en) * | 2017-10-27 | 2018-02-23 | 常州华科聚合物股份有限公司 | Hydroxylated acrylic resin dispersion and the water paint with its preparation |
| CN109929067A (en) * | 2017-12-16 | 2019-06-25 | 万华化学（宁波）有限公司 | A kind of core-shell structure acrylic acid ester emulsion and its preparation method and application |
| CN109929067B (en) * | 2017-12-16 | 2021-07-23 | 万华化学（宁波）有限公司 | Acrylate emulsion with core-shell structure and preparation method and application thereof |
| CN113242889A (en) * | 2018-12-25 | 2021-08-10 | 日涂汽车涂料有限公司 | Clear coating composition and method for forming clear coating film |
| CN109776715B (en) * | 2019-01-18 | 2021-02-26 | 上海巴德富实业有限公司 | Double-component acrylic acid cover emulsion and preparation method thereof |
| CN109776715A (en) * | 2019-01-18 | 2019-05-21 | 上海巴德富实业有限公司 | A kind of bi-component acrylic cover lotion and preparation method thereof |
| CN109970905B (en) * | 2019-03-12 | 2021-07-13 | 中煤科工集团杭州研究院有限公司 | Water-based polymer emulsion for integrated ceiling finishing coating and preparation method thereof |
| CN109970905A (en) * | 2019-03-12 | 2019-07-05 | 煤科集团杭州环保研究院有限公司 | Integral ceiling veneer coating aqueous high molecular lotion and preparation method thereof |
| CN110511388A (en) * | 2019-08-23 | 2019-11-29 | 湖北双键精细化工有限公司 | A kind of modified hydroxyl acrylic emulsion and preparation method thereof for aqueous coatings for tin plate printing |
| CN110628289A (en) * | 2019-09-26 | 2019-12-31 | 万华化学集团股份有限公司 | Water-based woodware stain-resistant white finish and preparation method thereof |
| CN110628289B (en) * | 2019-09-26 | 2022-02-18 | 万华化学集团股份有限公司 | Water-based woodware stain-resistant white finish and preparation method thereof |
| CN111116831A (en) * | 2020-01-07 | 2020-05-08 | 黄禹 | Preparation method of hydroxyl acrylic emulsion |
| CN112063281A (en) * | 2020-07-31 | 2020-12-11 | 广东海特高新材料有限公司 | Water-based two-component wood paint and preparation method thereof |
| CN112573885A (en) * | 2020-12-12 | 2021-03-30 | 南京霄祥工程技术有限公司 | Self-leveling mortar and preparation method thereof |
| CN115717014A (en) * | 2022-11-21 | 2023-02-28 | 河北工业大学 | Preparation method of easily-crosslinked core-shell type polyhydroxyacrylate emulsion coating |
| CN115717014B (en) * | 2022-11-21 | 2023-10-24 | 河北工业大学 | Preparation method of easily-crosslinked core-shell polyhydroxyacrylate emulsion coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100376607C (en) | 2008-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1800225A (en) | Latex type hydroxy acryl acid resin possessing core-shell configuration | |
| CN1164706C (en) | Epoxy ester emulsion and water-thinned antirust primer with the said emulsion as base material | |
| CN108250347B (en) | Salt-fog-resistant phosphate modified acrylic core-shell emulsion | |
| CN1438253A (en) | Acrylate micro-emulsion with high solid content, its preparation method and use | |
| CN1995245B (en) | Method for preparing thermosetting acrylic ester emulsion coating under room temperature | |
| CN101348611B (en) | Acroleic acid modified polysiloxane resin and coating thereof | |
| CN103059212B (en) | Hydrogenated rosin modified acrylic ester hybridization emulsion and preparation method and application thereof | |
| CN102504623B (en) | Peeling layer composition and preparation method and application thereof | |
| CN1803942A (en) | Ultraviolet curing coating for metal plating surface protection | |
| EP2855579A1 (en) | Aqueous binder compositions | |
| CN1730547A (en) | Monocomponent self-cross-linking epoxy acrylic acid composite emulsion , its preparation method and uses | |
| CN102325797B (en) | Binder compositions comprising boric acid or boric acid salt | |
| CN107936746A (en) | A kind of organic-silicon-modified cation photocuring cycloaliphatic epoxy resin coating and its application | |
| CN101445681A (en) | Aqueous emulsion copolymer compositions | |
| CN101407568A (en) | High solid low viscosity acrylic resin and preparation thereof | |
| CN114316722A (en) | High-wear-resistance water-based gloss oil and preparation method thereof | |
| CN103694861A (en) | Dual-modified and dual-cured epoxy acrylate coating material | |
| CN106752741A (en) | Ultraviolet light polymerization alkali-resistant coating composition | |
| CN101445682A (en) | Aqueous composition with homopolymer | |
| CN102477119A (en) | Method for preparing environment-friendly pigment printing binder | |
| CN102807814B (en) | Nano silica-modified recoatable ultraviolet (UV) varnish used on plastic and preparation method for varnish | |
| CN1160427C (en) | Ultraviolet curing coating composite for cation electro-deposition | |
| CN1160426C (en) | Water-based metal paint | |
| CN1872923A (en) | Green environmental protection polyisoprene in high elasticity | |
| CN109180885A (en) | A kind of preparation method of water polyacrylic acid lotion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: CNOOC CHANGZHOU PAINT + COATINGS INDUSTRY RESEARCH Free format text: FORMER OWNER: CHANGZHOU INST OF PAINT CHEMICAL, CHINESE CHEMICAL BUILDING CORP. Effective date: 20120910 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20120910 Address after: 213016 Changzhou Zhong Road, Jiangsu Province, No. 22 Longjiang Road Patentee after: CNOOC Changzhou Paint & Coatings Industry Research Institute Address before: 213016, Jiangsu City, Changzhou province Bell Tower West Ring Road North intersection Patentee before: Changzhou Inst of Paint Chemical, Chinese Chemical Building Corp. |