CN1927901A - High weatherability resin, preparation method thereof and coating composition containing the same - Google Patents
High weatherability resin, preparation method thereof and coating composition containing the same Download PDFInfo
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- CN1927901A CN1927901A CN 200610139283 CN200610139283A CN1927901A CN 1927901 A CN1927901 A CN 1927901A CN 200610139283 CN200610139283 CN 200610139283 CN 200610139283 A CN200610139283 A CN 200610139283A CN 1927901 A CN1927901 A CN 1927901A
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Abstract
The present invention relates to one kind of high weather resistance resin prepared through reaction of modified hydroxyl radical-containing vinyl chloride-vinyl acetate copolymer resin, polyisocyanate(s) and assistant in some organic solvent. The high weather resistance resin has excellent light resistance, violet resistance and hydrolysis stability, no free TDI contained, simple synthesis process and high performance/cost ratio. The present invention also relates to the preparation process of the high weather resistance resin and paint composition containing the high weather resistance resin. The paint composition has not only excellent yellowing resistance and high weather resistance, but also physical and chemical performance similar to that of white PU surface paint.
Description
Technical field
The present invention relates to a kind of high-weatherability resin, in particular for the high-weatherability macromolecule copolymer resin of preparation coatings with high weatherability and the solvent-borne type white finish paint of anti-the xanthochromia.The invention still further relates to the preparation method and the coating composition that contains this resin of this high-weatherability resin.
Background technology
At present white paint and obtained consumers in general's approval based on the light painting effect of white on the coating market has become the popular style of decoration paint industry.Traditional solvent-borne type white finish paint has three kinds: common alkyd colored paint, urethane colored paint and NC colored paint.Common alkyd colored paint easily wears out, ftractures, comes off; The easy flavescence of filming of urethane colored paint, the finishing effect can not be lasting; And NC colored paint construction solids content is low, and the application paint film is plentiful inadequately.Also having a kind of is exactly the white finish paint that is used for painting dressing automobiles, though good anti-xanthochromia effect and film performance are arranged, cost is too high, and the resistance of promoting in civilian finishing field is very big.
Therefore need a kind of not macromolecule copolymer resin of xanthochromia white finish paint of solvent-borne type that is used on the market, require its weather resistance extremely excellent, and show synthesis technique and excellent physical chemistry easily, prior is exactly to have very high cost performance.
Summary of the invention
Study by extensive analysis, we think, part of hydroxyl by the sealing vinyl chloride-vinyl acetate copolymer, just can prepare a kind of energy by chain extending reaction and satisfy the low-cost resin of making coatings with high weatherability and the white finish paint of anti-xanthochromia requirement, thereby improve the yellowing resistance of selecting for use raw-material anti-yellowing property raising to film by resin modified.
The inventor is through secular experiment experience accumulation and consulting various correlation technique documents, starting material selection and technology to synthetic this type of high-weatherability polymer copolymerization resin have been carried out intensive research, have been found that, want to make the coating that makes to reach not xanthochromic requirement, will start with from following three aspects theoretically: at first be exactly that selected starting material can not contain the chromophoric group that forms the quinoid structure; Secondly be exactly the used main film forming substance-resin of system lacquer, can not contain unsaturated double-bond; Moreover be exactly to contain heteroatoms etc. in system lacquer and the sclerosis properties-correcting agent.The last inventor adopts hydroxyl vinyl chloride-vinyl acetate copolymer and aliphatic polyisocyante can synthesize together to have the excellent anti-natural light or even the copolymer resin of UV-light and hydrolysis stability.
Therefore, one aspect of the present invention relates to a kind of high-weatherability resin, and it comprises modification vinyl chloride-vinyl acetate copolymer resin VAGH and one or more aliphatic polyisocyantes.Wherein said modification vinyl chloride-vinyl acetate copolymer resin VAGH contains the vinylchlorid of 85-95wt%, the vinyl acetate between to for plastic of 3-5wt%; The content of hydroxyl activity functional group is 1-10wt% in this resin, and the scope of its hydroxyl value is 60-100mgKOH/g.Preferably contain the hydroxyl activity functional group of 2-5wt%, the scope of its hydroxyl value is 70-90mgKOH/g.
In a preferred embodiment of high-weatherability resin of the present invention, the molecular-weight average of the modification vinyl chloride-vinyl acetate copolymer resin VAGH of use is 738, and the content of vinylchlorid is about 90wt%, and the content of vinyl acetate between to for plastic is about 4wt%; The content of hydroxyl activity functional group is 2.3wt% in this resin, and its hydroxyl value is 76mgKOH/g.
The reason of selecting above-mentioned modification vinyl chloride-vinyl acetate resin for use is that on the one hand this resin contains a spot of hydroxyl value, can by with isocyanate reaction partially end-blocked-OH base and chain extension reaches the purpose that improves dryness and eliminate optical property; This resin is formed by the vinyl chloride-vinyl acetate copolymerization on the other hand, and this structure does not contain two keys, thereby stable paradigmatic structure can be resisted the irradiation of UV-light; Select for use the resin that hangs down hydroxyl value when the chain extension polymerization, can consume the monomer of isocyanic ester less more on the one hand.
Another aspect of the present invention relates to the preparation method of the weather-proof resin of height noted earlier, and this method comprises the steps:
1) in the four-hole bottle that thermometer, reflux exchanger, electric mixer, water trap are housed, adds modification vinyl chloride-vinyl acetate copolymer resin above-mentioned, organic solvent and auxiliary agent;
2) the electricity consumption heating jacket is heated to 150-200 ℃ to these mixtures by room temperature, dewaters then 0.5-1 hour;
3) cool under the 80-120 ℃ of condition, add a certain amount of aliphatic polyisocyante come enclosure portion-the OH group;
4) continue to keep at a certain temperature reaction, the certain hour of being separated by to detect once corresponding hydroxyl value, acid number and viscosity.When hydroxyl value less than 15, acid number is less than 5, viscosity is stopped reaction when 70-80KU;
5) it is even to add an amount of stirring solvent again, cooling, filters and promptly gets this high-weatherability macromolecule resin.
The amount ranges of various compositions is in above-mentioned preparation process:
1) organic solvent: 10-30 mass parts;
2) modification vinyl chloride-vinyl acetate copolymer resin: 30-80 mass parts;
3) auxiliary agent: 0.1-0.8 mass parts;
4) polyisocyanates: 2-20 mass parts.
In the preparation method of high-weatherability resin of the present invention, above-mentioned modification vinyl chloride-vinyl acetate copolymer resin VAGH contains the vinylchlorid of 85-95wt%, the vinyl acetate between to for plastic of 3-5wt%; Contain the hydroxyl activity functional group of 1-10wt% in this resin, the scope of its hydroxyl value is 60-100mgKOH/g.Preferably contain the hydroxyl activity functional group of 2-5wt%, the scope of its hydroxyl value is 70-90mgKOH/g.
In a preferred embodiment of high-weatherability process for preparing resins of the present invention, the molecular-weight average of above-mentioned modification vinyl chloride-vinyl acetate copolymer resin VAGH is 738, and the content of vinylchlorid is about 90wt%, and the content of vinyl acetate between to for plastic is about 4wt%; The content of hydroxyl activity functional group is 2.3wt% in this resin, and its hydroxyl value is 76mgKOH/g.
In the preparation method of high-weatherability resin of the present invention, the consumption of described modification vinyl chloride-vinyl acetate copolymer resin is the 30-80 mass parts, preferred 40-60 mass parts, more preferably 45-55 mass parts.
In the preparation method of high-weatherability resin of the present invention, described aliphatic polyisocyante is hexa-methylene methyl vulcabond (HDI) and/or isophorone diisocyanate (IPDI), and its consumption is the 2-20 mass parts, preferred 5-15 mass parts.
In another preferred embodiment of high-weatherability process for preparing resins of the present invention, described aliphatic polyisocyante is methyl vulcabond (HDI), and molecular formula is NCO-CH
2-CH
2-CH
2-CH
2-CH
2-CH
2-NCO, molecular weight are 168, and equivalent is 84.The monomer that to select this monomeric reason for use be isocyanic ester has a variety of, but most of band benzene ring structure and easily form the quinoid structure and flavescence, the HDI monomer is a C-C singly-bound structure, thereby stability is very good, so preferred HDI monomer comes chain extension.
In the preparation method of high-weatherability resin of the present invention, described organic solvent can be selected from vinyl acetic monomer, N-BUTYL ACETATE, dimethylbenzene, one or more in pimelinketone or the acetone.Preferred vinyl acetic monomer and N-BUTYL ACETATE, more preferably vinyl acetic monomer, because this solvent molecule amount is 88.10, boiling point is 77 ℃, is 5.25 with respect to the evaporation rate of N-BUTYL ACETATE, and solvent power is strong, and the solvency power parameter is (9.1cal/cm
3)
1/2, and viscosity is low, is 0.449mpas.The scope of above-mentioned consumption of organic solvent is the 10-30 mass parts, preferred 12-25 mass parts, more preferably 15-20 mass parts.
In the preparation method of high-weatherability resin of the present invention, described auxiliary agent comprises antioxidant and/or catalyst for trimerization, and wherein antioxidant comprises one or more of BHT, triphenyl phosphite and other analogues, preferred BHT and triphenyl phosphite; Catalyst for trimerization comprises tributyl phosphorus, Lithium Acetate, sodium hydroxide and other analogues, preferred tributyl phosphorus and Lithium Acetate.Two types of auxiliary agents can use separately, and use also capable of being combined can choose that two or more auxiliary agent is used in combination in two types of auxiliary agents wantonly, as long as can reach purpose of the present invention, its portfolio ratio is not particularly limited.
In another preferred embodiment of high-weatherability process for preparing resins of the present invention, described auxiliary agent is the composition of tributyl phosphorus, BHT and triphenyl phosphite.
The purpose of selecting above-mentioned auxiliary agent is the speed of control end capping and improves the yellowing resistance energy, according to this purpose, except above-mentioned auxiliary agent, can also select other similar auxiliary agents as known in the art, it is selected for this area professional and technical personnel is conspicuous.The scope of above-mentioned auxiliary dosage is the 0.1-0.8 mass parts, preferred 0.2-0.6 mass parts, more preferably 0.2-0.4 mass parts.
The characteristic parameter scope of the high-weatherability resin that obtains by above-mentioned preparation process is as follows:
| Interventions Requested | Detect index | The method of inspection | |
| Solids content (quality) | 70-90％ | GB1725-79(89) | |
| NCO content | 4-5 | / | |
| Viscosity (KU/25 ℃) | 70-80 | GB9269-88 | |
| Artificial ageing resistance | The variable color grade | ＜ΔE1.5 | GB/T9755-2001 |
| Chalk rating | ＜0 grade | GB/T9755-2001 | |
| Sticking power | ＜0 grade | GB/T1720-89 | |
| Snappiness | ＜12mm | GB/T1731-93 | |
| Hardness | HB | GB/T6739-86 | |
| Time of drying (tack-free) | 3h | GB/T1728-89 | |
When with above-mentioned high-weatherability resin as coating composition, especially the main film forming substance of xanthochromia white finish paint and be equipped with specific anti-aging stablizer and other are can improve the specific adjuvant of coating application performance the time not, the coating of making not only has good anti-yellowing property and weathering resistance, but also has the same physical and chemical performance of PU white finish paint.
Therefore, another aspect of the present invention relates to a kind of coating composition, comprise according to high-weatherability resin of the present invention and one or more anti-aging stablizers, and thinner.
Polymer substance is owing in use inevitably contact with oxygen and light, and variation of temperature, causes them to change on outward appearance, structure and performance, also promptly wears out.Data shows that the interpolation of antioxidant, photostabilizer and/or ultraviolet absorbers can both obviously improve the stability of polymkeric substance.Antioxidant is a kind ofly can suppress or slow down the material of macromolecular material autoxidation speed of response.The antioxidant kind has following several: amine, phenols, phosphorous acid esters; Ultraviolet absorbers has following several: salicylate class, benzotriazole category and benzophenone.Therefore, at the preparation coating composition, especially during solvent based coating, yellowing resistance and weathering resistance according to resin, often add one or more above-mentioned reagent as anti-aging stablizer, improving the yellowing resistance and the weathering resistance of resin, and improve the stability of resin simultaneously.
Therefore, in coating composition of the present invention, described anti-aging stablizer comprises antioxidant, photostabilizer, UV light absorber, in concrete the use, can select wherein one or more mixture as the anti-aging stablizer in the coating composition, as long as can reach purpose of the present invention, any combination of mentioned reagent is included within the scope of the present invention.
In a preferred embodiment of coating composition of the present invention, described anti-aging auxiliary agent comprises the combination of antioxidant, photostabilizer and UV light absorber, the preferred phosphorous acid esters of wherein said antioxidant, more preferably bis-phosphite; The preferred hindered amine of photostabilizer, the preferred benzotriazole category of UV light absorber, more preferably benzotriazole.
It should be understood that the thinner that uses in coating composition of the present invention can use routine to be used for the thinner of solvent based coating, it is selected for this area professional and technical personnel is conspicuous, also can use commercially available product.
In a preferred embodiment of coating composition of the present invention, this coating composition further comprises one or more reagent that are selected from flow agent, defoamer, wetting dispersing agent, anti-settling agent and the matting agent.Mentioned reagent can be used commercially available product, flow agent such as TEGO450 (German Di Gao company), HX3130 (Guangdong China company); Defoamer such as BYK066N (German Bi Ke chemistry), HX2300 (Guangdong China company); Anti-settling agent such as 6900-HV (Supreme Being Si clings to the gallery), or the like.
In yet another aspect, the invention still further relates to the coating that the aforementioned coating composition construction obtains.The coating composition made from resin of the present invention also has outstanding weathering resistance simultaneously, and the coating that adopts this coating composition construction to obtain has excellent characteristic at aspects such as paint film appearance, sticking power, snappiness, hardness, opacifying powers.
Conventional PU white finish paint host main component is the Synolac of a kind of containing-OH, by contain with another-component of NCO functional group mixes film forming after the crosslinking reaction of back by a certain percentage.And of the present invention and the high-weatherability macromolecule copolymer resin be that hydroxyl and chain extension by partially enclosed hydroxyl vinyl chloride-vinyl acetate copolymer makes; the resin that makes so not only has good anti-yellowing property and physical and chemical performance; and only contain the free monomer of minute quantity; especially anything but it is this to the great material of human injury to contain free TDI, thereby has fundamentally also solved environment protection and human body health problem.
Based on above-mentioned theory basis and practice, in a preferred embodiment of the invention, adopt the performance of the white finish paint of anti-xanthochromia of high-weatherability resin of the present invention exploitation can improve 5-6 doubly than popular PU white finish paint tint retention on the market, simultaneously price is more cheap many than automobile finish, thus can large-scale promotion application in house decoration.
Embodiment
Use embodiment to help further to understand the present invention below, this area professional and technical personnel it should be understood that the present invention is not limited to these embodiment, as long as can reach purpose of the present invention, these embodiment can carry out various variations.
Embodiment 1
The preparation of high-weatherability macromolecule resin (one)
In the 2000ml four-hole bottle of thermometer, reflux exchanger, electric mixer, water trap was housed, (molecular-weight average was 738, and the content of vinylchlorid is about 90wt%, and the content of vinyl acetate between to for plastic is about 4wt% to add modification vinyl chloride-vinyl acetate copolymer resin VAGH; The content of hydroxyl activity functional group is 2.3wt% in this resin, and its hydroxyl value is 76mgKOH/g) 950g, solvent vinyl acetic monomer 295g and tributyl phosphorus 2g, BHT 2g and triphenyl phosphite 1g.The electricity consumption heating jacket is heated to 200 ℃ to these mixtures by room temperature, dewaters then 0.5 hour, cools under 120 ℃ of conditions, adds HDI 250g.After this under 65-75 ℃ of temperature, keep reaction 2 hours, detected once corresponding hydroxyl value, acid number and viscosity then every 0.5 hour, when hydroxyl value less than 15, acid number is less than 5, viscosity is stopped reaction when 70-80KU; , it is even to add an amount of stirring solvent again, cooling, filters and promptly gets this high-weatherability macromolecule resin.
The technical indicator of the resin that obtains by aforesaid method is as follows:
| Interventions Requested | Detected result | The method of inspection | |
| Solids content (quality) | 80％ | GB1725-79(89) | |
| NCO content | 4.8 | / | |
| Viscosity (KU/25 ℃) | 75 | GB9269-88 | |
| Artificial ageing resistance | The variable color grade | ΔE1.2 | GB/T9755-2001 |
| Chalk rating | 0 grade | GB/T9755-2001 | |
| Sticking power | 0 grade | GB/T1720-89 | |
| Snappiness | ＜12mm | GB/T1731-93 | |
| Hardness | HB | GB/T6739-86 |
| Time of drying (tack-free) | 3h | GB/T1728-89 |
Embodiment 2
The preparation of high-weatherability macromolecule resin (two)
In the 2000ml four-hole bottle of thermometer, reflux exchanger, electric mixer, water trap is housed, add modification vinyl chloride-vinyl acetate copolymer resin VAGH 1035g, the solvent vinyl acetic monomer 295g and tributyl phosphorus 2g, BHT 2g and the triphenyl phosphite 1g that use among the embodiment 1.The electricity consumption heating jacket is heated to 200 ℃ to these mixtures by room temperature, dewaters then 0.5 hour, cools under 120 ℃ of conditions, adds HDI 265g.After this under 65-75 ℃ of temperature, keep reaction 2 hours, detected once corresponding hydroxyl value, acid number and viscosity then every 0.5 hour, when hydroxyl value less than 15, acid number is less than 5, viscosity is stopped reaction when 70-80KU; , it is even to add an amount of stirring solvent again, cooling, filters and promptly gets this high-weatherability macromolecule resin.
The technical indicator of the resin that obtains by aforesaid method is as follows:
| Interventions Requested | Detected result | The method of inspection | |
| Solids content (quality) | 80％ | GB1725-79(89) | |
| NCO content | 4.6 | / | |
| Viscosity (KU/25 ℃) | 79 | GB9269-88 | |
| Artificial ageing resistance | The variable color grade | ΔE1.2 | GB/T9755-2001 |
| Chalk rating | 0 grade | GB/T9755-2001 | |
| Sticking power | 0 grade | GB/T1720-89 | |
| Snappiness | ＜12mm | GB/T1731-93 | |
| Hardness | HB | GB/T6739-86 | |
| Time of drying (tack-free) | 3h | GB/T1728-89 | |
Embodiment 3
The not preparation of xanthochromia white finish paint
In order to identify high-weatherability resin of the present invention and the performance that contains its coating composition, with synthetic high-weatherability resin among the embodiment 1 as main film forming substance, select some suitable anti-aging stablizers, according to the not xanthochromia white finish paint that makes as described below, and according to respective country coating examination criteria detection respective performances, performance test results table 1 is described.
1. xanthochromia white finish paint host agent prescription not:
| Material name | Formula ratio | Manufacturer | Operating procedure |
| The high-weatherability resin | 600.00 | Add earlier and stir | |
| Solvent butyl acetate | 50.00 | The Tyson chemical industry | |
| Wetting dispersing agent BYK-110 | 10.00 | Germany Bi Ke chemistry | |
| Titanium dioxide R595 | 250.00 | Mei Lilian | The high speed dispersion state adds down, high speed dispersion 20 minutes |
| Aerosil TS-100 | 20.00 | Degussa company | |
| Flow agent TEGO450 | 2.00 | Germany Di Gao company | Adding stirs |
| Defoamer BYK066N | 2.00 | Germany Bi Ke chemistry | Adding stirs |
| Flow agent HX3130 | 3.00 | Guangdong China company | Adding stirs |
| Defoamer HX2300 | 2.00 | Guangdong China company | Adding stirs |
| Anti-settling agent 6900-HV | 10.00 | Supreme Being Si clings to the gallery | Adding stirs |
| The solvent vinyl acetic monomer | 51.00 | The Tyson chemical industry | Adjust viscosity |
| Add up to | 1000.00 |
2. anti-aging stabilizer formula:
| Material name | Formula ratio | Manufacturer | Operating procedure |
| The solvent vinyl acetic monomer | 300.00 | The Tyson chemical industry | Add and be stirred to dissolving fully |
| Bis-phosphite | 250.00 | ||
| Hindered amine | 200.00 | ||
| Benzotriazole | 250.00 |
3. diluent formulation
| Material name | Formula ratio | Manufacturer | Operating procedure |
| N-BUTYL ACETATE | 600.00 | The Tyson chemical industry | Adding stirs |
| Ethylene glycol ether acetate | 250.00 | The happy chemical industry that reaches | |
| Pimelinketone | 150.00 | The Great Wall chemical industry |
According to host: stablizer: construct after the mixed of thinner=100: 5: 75, the physical and chemical performance detected result of the coating of coating composition and acquisition thereof sees Table 1:
Table 1: the physical and chemical performance detected result of xanthochromia white finish paint coating composition not
| Interventions Requested | Detected result | The method of inspection | |
| Coating host solids content | 75％ | GB1725-79(89) | |
| Artificial ageing resistance | The variable color grade | ΔE1.2 | GB/T9755-2001 |
| Chalk rating | 0 grade | GB/T9755-2001 | |
| Paint film appearance | Do not have and bubble, do not come off | GB/T9755-2001 | |
| Sticking power | 0 grade | GB /T1720-89 | |
| Snappiness | ＜12mm | GB/T1731-93 | |
| Hardness | HB | GB/T6739-86 | |
| Former lacquer host outward appearance | The white thick liquid | GB/T1721-79 | |
| Paint film color and outward appearance | White, flat-satin | GB/T1729-79 | |
| Apparent viscosity | 120KU/25℃ | GB/T9751-88 | |
| Fineness | 25μm | GB/T1724-89 | |
| Opacifying power | 98g/m 2 | GB/T1726-89 | |
| Free TDI | Do not detect | GB/T18581-2001 | |
By the detected result of table 1 as can be seen, not xanthochromia white finish paint of being made by high-weatherability macromolecule resin prepared in accordance with the present invention and the coating that obtains have excellent weathering resistance and good physical and chemical performance, and do not contain free TDI.
The present invention is illustrated according to embodiment, will be appreciated that, the foregoing description is intended to explanation rather than restriction.According to above instruction, the present invention can exist many improvement and variation.Therefore, will be appreciated that except concrete narration, the present invention can implement within the scope of the appended claims.
Claims (9)
1. high-weatherability resin is characterized in that it comprises:
(1) modification vinyl chloride-vinyl acetate copolymer resin VAGH contains 85-95wt% vinylchlorid, the vinyl acetate between to for plastic of 3-5wt%;
(2) one or more aliphatic polyisocyantes.
2. according to the high-weatherability resin of claim 1, it is characterized in that the content of hydroxyl activity functional group among the described modification vinyl chloride-vinyl acetate copolymer resin VAGH is 1-10wt%, its hydroxyl value scope is 60-100mgKOH/g.
3. according to the high-weatherability resin of claim 2, it is characterized in that the content of hydroxyl activity functional group among the described modification vinyl chloride-vinyl acetate copolymer resin VAGH is 2-5wt%, its hydroxyl value scope is 70-90mgKOH/g.
4. according to the high-weatherability resin of claim 1, it is characterized in that described aliphatic polyisocyante is hexamethylene diisocyanate and/or isophorone diisocyanate.
5. according to the preparation method of the high-weatherability resin of claim 1, it is characterized in that in reactor, add organic solvent and the modification vinyl chloride-vinyl acetate copolymer resin VAGH of 30-80 mass parts and one or more auxiliary agents of 0.1-0.8 mass parts of 10-30 mass parts.Temperature rising reflux reaction adds the aliphatic polyisocyante of 2-20 mass parts then, and insulation continues reaction, stopped reaction when reactant reaches certain hydroxyl value, acid number and viscosity, and it is even to add stirring solvent, cooling, filters and makes described resin.
6. a coating composition comprises high-weatherability resin and one or more anti-aging stablizers according to claim 1, and thinner.
7. according to the coating composition of claim 6, it is characterized in that further comprising being selected from flow agent, defoamer, wetting dispersing agent, anti-settling agent and the matting agent one or more.
8. according to the coating composition of claim 6, it is characterized in that wherein said anti-aging stablizer comprises antioxidant, photostabilizer and UV light absorber.
9. the coating that obtains according to the coating composition of claim 6-8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101392833A CN100390210C (en) | 2006-09-20 | 2006-09-20 | High weatherability resin, preparation method thereof and coating composition containing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101392833A CN100390210C (en) | 2006-09-20 | 2006-09-20 | High weatherability resin, preparation method thereof and coating composition containing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1927901A true CN1927901A (en) | 2007-03-14 |
| CN100390210C CN100390210C (en) | 2008-05-28 |
Family
ID=37858051
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101392833A Expired - Fee Related CN100390210C (en) | 2006-09-20 | 2006-09-20 | High weatherability resin, preparation method thereof and coating composition containing the same |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311687A (en) * | 2011-09-28 | 2012-01-11 | 天长市巨龙车船涂料有限公司 | Modified vinyl chloride-acetate copolymer heavy duty anticorrosion paint |
| CN105294912A (en) * | 2015-10-22 | 2016-02-03 | 江苏科技大学 | Amino acid-modified chloro-acetate-acrylate copolymer emulsion and preparation method thereof |
| CN108219599A (en) * | 2017-12-27 | 2018-06-29 | 山东恒联新材料股份有限公司 | A kind of coating solution of cellulose membrane |
| CN111154349A (en) * | 2020-01-16 | 2020-05-15 | 上海立邦长润发涂料有限公司 | PU (polyurethane) water-based refinishing paint and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1076593A (en) * | 1996-09-03 | 1998-03-24 | Daicel Chem Ind Ltd | Barrier composite film and its manufacture |
-
2006
- 2006-09-20 CN CNB2006101392833A patent/CN100390210C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311687A (en) * | 2011-09-28 | 2012-01-11 | 天长市巨龙车船涂料有限公司 | Modified vinyl chloride-acetate copolymer heavy duty anticorrosion paint |
| CN102311687B (en) * | 2011-09-28 | 2014-01-01 | 天长市巨龙车船涂料有限公司 | Modified vinyl chloride-acetate copolymer heavy duty anticorrosion paint |
| CN105294912A (en) * | 2015-10-22 | 2016-02-03 | 江苏科技大学 | Amino acid-modified chloro-acetate-acrylate copolymer emulsion and preparation method thereof |
| CN105294912B (en) * | 2015-10-22 | 2017-06-23 | 江苏科技大学 | A kind of copolymer emulsion of amino-acid modified chlorine vinegar third and preparation method thereof |
| CN108219599A (en) * | 2017-12-27 | 2018-06-29 | 山东恒联新材料股份有限公司 | A kind of coating solution of cellulose membrane |
| CN108219599B (en) * | 2017-12-27 | 2021-01-15 | 山东恒联新材料股份有限公司 | Coating solution of cellulose membrane |
| CN111154349A (en) * | 2020-01-16 | 2020-05-15 | 上海立邦长润发涂料有限公司 | PU (polyurethane) water-based refinishing paint and preparation method thereof |
| CN111154349B (en) * | 2020-01-16 | 2021-11-16 | 上海立邦长润发涂料有限公司 | PU (polyurethane) water-based refinishing paint and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN100390210C (en) | 2008-05-28 |
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