CN1353151A - Resin dedicated for coating on polypropylene plastics - Google Patents
Resin dedicated for coating on polypropylene plastics Download PDFInfo
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- CN1353151A CN1353151A CN 01137350 CN01137350A CN1353151A CN 1353151 A CN1353151 A CN 1353151A CN 01137350 CN01137350 CN 01137350 CN 01137350 A CN01137350 A CN 01137350A CN 1353151 A CN1353151 A CN 1353151A
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Abstract
A special-purpose resin for coating it on surface of polypropylene plastics is prepared from chlorinated polypropylene resin (5-50 wt.%), epoxy resin (0-30), monomer containing unsaturated bi-bond able to partiapate copolymerzation (20-90) and copolymer of organic compound of special element containing bi-bond (0.1-5) through the conventional solution method. Its coated film features high adhesion, weatherability and the resistance to water and solvent.
Description
Technical field
The present invention relates to a kind of resin dedicated for coating on polypropylene plastics.
Background technology
Along with the development of society, progress of industry, the effect of plastics in people's life is increasing.Acrylic plastering because have easy-formation, proportion is little, price is low, mechanical property, superiority such as reusable preferably, add nontoxicity, thereby be widely used in fields such as automobile, motorcycle, household electrical appliances, daily necessities, wrapping material.Yet acrylic plastering is low because of its degree of crystallinity height, polarity, thus poor because of coating and its surface adhesion force for a long time, exist problems such as being difficult to application, printing always.For addressing this problem, the past, the general methods such as polishing, chromic acid oxidation, corona that adopt were handled the acrylic plastering surface, but in these pre-treatment processes, or need specific equipment, or environment is polluted, thereby all be subjected to certain restriction.Adopt chlorinated polypropylene, though can remove the pre-treatment on acrylic plastering surface from, by the coating of this resin formation and the poor adhesive force between top coat layer, practicality is relatively poor.Present existing acrylate modified chlorinated polypropylene, cis-butenedioic anhydride modified chlorinated polypropylene resin, though the sticking power to the acrylic plastering surface is improved, but the matching capacity of they and other finish paints still has very big limitation, applicable surface is narrower, particularly prepare these resins and still have following difficulty: when 1. preparing acrylic acid modified chlorinated polypropylene, the cl content of Chlorinated Polypropylene III was greater than 35% o'clock, graft copolymerization takes place easily with Acrylic Acid Monomer, the reaction conversion ratio height, but the affinity of gained resin and acrylic plastering is very poor; The chlorination of Chlorinated Polypropylene III contains and is lower than at 30% o'clock, though the sticking power of gained resin and acrylic plastering is good, under this condition, the transformation efficiency of copolyreaction is extremely low and gained resin package stability is poor, so there is not practicality; When 2. preparing cis-butenedioic anhydride modified chlorinated polypropylene resin, usually must adopt melt phase polycondensation with cis-butenedioic anhydride and polypropylene polymerization, chlorination makes again, this complex process and be difficult to control, the water tolerance of gained resin, weathering resistance are also undesirable, and comparatively easy solution polymerization process is difficult to finish this copolyreaction.
Summary of the invention
The objective of the invention is to, a kind of resin dedicated for coating on polypropylene plastics is provided, and it can adopt the preparation of conventional soln polymerization, shelf-stable, use its coatings formulated, can directly be coated with and be contained in acrylic plastering surface and its film good sticking power, water tolerance, solvent resistance, weathering resistance.
The technical scheme that realizes the object of the invention is: a kind of resin dedicated for coating on polypropylene plastics, it is that component (A) chlorinated polypropylene, component (B) Resins, epoxy, component (C) can participate in the monomer that contains unsaturated double-bond of copolymerization and the multipolymer of the double bond containing special element organic compound of component (D), it is faint yellow to brown that its outward appearance is, solid is divided into 20%～50% (weight), under 25 ± 1 ℃, the viscosity of 50% solution is 1000～6000cps, and each component shared weight percent in this resin solids is as follows:
Component (A) 5%～50%
Component (B) 0%～30%
Component (C) 20%～90%
Component (D) 0.1%～5%.
In the above-mentioned resin, the Chlorinated Polypropylene III chlorinity that is used as component (A) is less than 35% (weight);
Resins, epoxy as component (B) is bisphenol A-type, and its epoxy equivalent (weight) is 200～2000;
As containing of participated in the copolymerization of component (C) unsaturated two strong monomers be methacrylic alkene esters of gallic acid, esters of acrylic acid, methacrylic acid, vinylformic acid, vinylbenzene or vinyl cyanide, can be wherein a kind of monomer, also can be the monomeric combination collocation more than a kind wherein;
As the double bond containing special element organic compound of component (D), its pair key is the two keys in the vinyl monomer, also can be the two keys in the unsaturated acid; Its special element is titanium, silicon or aluminium.
Technique effect of the present invention is: resin dedicated for coating on polypropylene plastics of the present invention is the multipolymer of A, B, C, four kinds of components of D, wherein component (A) can improve the sticking power with the acrylic plastering surface, proportion must not be lower than 5% (weight) in resin solid part of the present invention, otherwise sticking power is bad, also must not surpass 50% (weight), otherwise the over-all properties of coating is relatively poor; Component (B) can effectively improve the matching capacity of resin of the present invention and other resins, component (B) has copolymerization that the blend capacitive of resin of the present invention is improved with component (C) slightly, proportion can not be higher than 30% (weight) in resin solid part of the present invention, otherwise the package stability of resin of the present invention descends, and over-all properties is also not satisfactory, particularly component (B) surpasses that 30% (weight) has excessive epoxy group(ing) or hydroxyl is uncrosslinked, can influence its water tolerance significantly like this; Component (C) major function is to improve the workability of the coating of using resin formation of the present invention, dryness, hardness, water tolerance, solvent resistance, weathering resistance etc.According to the difference of actual user to above-mentioned performance requriements, can adopt wherein a kind of monomer, also can adopt the monomeric combination collocation more than a kind; Component (D) can improve with the sticking power of acrylic plastering and because hydrolytic condensation takes place in film process component (D), filming, it is partial cross-linked to take place, and can improve a series of over-all propertieies of coating such as water tolerance, solvent resistance, ageing resistance, chemical-resistant, mechanical property etc.In addition, this monomer is incorporated in the multipolymer of resin of the present invention, also can improve the wettability of resin to face, filler to a certain extent.Therefore, with resin of the present invention preparation coating, direct application acrylic plastering surface, and need not any pre-treatment, and the formed good sticking power of filming, over-all propertieies such as water tolerance, weathering resistance, oil-proofness also have improvement.In addition, resin of the present invention can adopt existing solution polymerization process, utilizes general initiator can finish in 3～12 hours 60～140 ℃ of reactions, so the simple control easily of polymerization process.
Specific implementation method
With following embodiment resin dedicated for coating on polypropylene plastics of the present invention is further described in detail, but is not limited thereto.
Be used to prepare the raw material of resin of the present invention among the following embodiment:
Component (A) Chlorinated Polypropylene III is a commercially available product, and wherein cl content is 27% (weight), and weight-average molecular weight is 50000;
The bisphenol A type epoxy resin that component (B) is produced for Wuxi resin processing plant, the trade mark is E-44, also can adopt E-51, E-20, E-12;
Component (C) is commercially available vinylformic acid, methyl methacrylate, butyl acrylate, Isooctyl acrylate monomer, vinylbenzene, vinyl cyanide;
Component (D) is for containing the grease class titanium compound of unsaturated double-bond, and its trade names are that TSC-1 (production of auxiliary reagent factory, the south of the River, Changzhou) structural formula is as follows:
Embodiment 1
Condenser is being housed, thermometer, in the four-hole boiling flask of dropping funnel and agitator, pack into 90 parts of solvents (toluene), press table 1 number of columns and add 6 parts of Chlorinated Polypropylene IIIs, 20 parts of E-44, be warming up to 80 ℃, drip 35 parts of methyl methacrylates then, 17 parts of butyl acrylates, 1 part in vinylformic acid, 20 parts of vinylbenzene, 1.1 parts of TSC-11 part and initiator Diisopropyl azodicarboxylates, be incubated 4 hours more at last, with 10 parts of toluene coolings, make resin of the present invention (P-1), its solid be divided into 50% in solids constituent component (A) Chlorinated Polypropylene III account for 6%, component (B) epoxy resin E-44 accounts for 20%, component (C) vinylformic acid, vinylbenzene, methyl methacrylate, the butyl acrylate total accounts for 72%, and component (D) TSC-1 accounts for 1%.
Embodiment 2-4
Synthesis technique is with embodiment 1, and each amounts of components is pressed table 1 adjustment, makes resin of the present invention (P-2)～(P-4), and its solid is divided into 50%.
Among the P-2: component A accounts for 6%, and B component accounts for 20%, and component C accounts for 73%, and component D accounts for 1%;
Among the P-3: component A accounts for 6%, and B component accounts for 20%, and component C accounts for 73.5%, and component D accounts for 0.5%;
Among the P-4: component A accounts for 6%, and B component accounts for 20%, and component C accounts for 73.5%, and component D accounts for 0.5%.
Embodiment 5～8
Remove temperature of reaction and change reflux temperature into, initiator is used instead outside the dibenzoyl peroxide, and all the other are operated all with embodiment 1, and each raw material consumption makes resin of the present invention (P-5)～(P-8) by table 1 adjustment, and solids constituent is 50%.
Among the P-5: component A accounts for 15%, and B component accounts for 6%, and component C accounts for 78.5%, and component D accounts for 0.5%;
Among the P-6: component A accounts for 15%, and B component accounts for 0%, and component C accounts for 84.5%, and component D accounts for 0.5%;
Among the P-7: component A accounts for 15%, and B component accounts for 6%, and component C accounts for 78%, and component D accounts for 1.0%;
Among the P-8: component A accounts for 15%, and B component accounts for 0%, and component C accounts for 84%, and component D accounts for 1.0%;
Above-mentioned (P-1)～(P-8) resin is stored 12 monthly no changes at 40 ℃.
With the resin of the present invention (P-1)～(P-8) that the foregoing description 1～8 makes, press the prescription of table 2, grind decentralized system through sand milling and get colored paint, and to transfer to viscosity (being coated with-4 glasss) be 11～16 seconds, can adopt ordinary method directly to be coated with and be contained in the acrylic plastering surface.During as the priming paint base-material, adopt dip-coating or spraying, coating thickness is about 8～10 μ m.Behind the surface drying 10min, 70 ℃ are toasted 30min again.List above-mentioned correlated performance of filming in the table 3, film performance is estimated as follows.
Outward appearance---range estimation
Sticking power---GB9286-88
Water tolerance---GB1733-91
Anti-gasoline---120# gasoline, 25 ± 1 ℃ of immersions
Ethanol-tolerant---industrial spirit, 25 ± 1 ℃ of immersions
Weathering resistance---GB1865-80,500 hours weather resistance tests
Film with resin coatings formulated application acrylic plastering gained of the present invention as can be seen from Table 3 have good sticking power, water tolerance, ethanol-tolerant, anti-gasoline, weathering resistance, over-all properties is better.And As time goes on existing various the resin dedicated of acrylic plastering surface that directly be coated on, form one, after two months filming, and it is very fast that adhesive force of coatings descends, and stripping strength descends.Table 1
Table 2
Annotate: 1. the JB-3 resin is a hydroxyl acrylic, and China Chemical Industry Costruction Head Co.,Ltd. Changzhou Coating Chemical Industry Research Institute produces
| Resin of the present invention is formed | Example | |||||||
| ?1 | ?2 | ?3 | 4 | 5 | ?6 | 7 | ??8 | |
| ?P1 | ?P2 | ?P3 | P4 | P5 | ?P6 | P7 | ??P8 | |
| Chlorinated Polypropylene III (component A) | ?6 | ?6 | ?6 | 6 | 15 | ?15 | 15 | ??15 |
| E-44 (B component) | ?20 | ?20 | ?20 | 20 | 6 | ?- | 6 | ??- |
| TSC-1 (component D) | ?1 | ?1 | ?0.5 | 0.5 | 0.5 | ?0.5 | 1 | ??1 |
| Vinylformic acid (component C) | ?1 | ?1 | ?1 | 1 | 1.0 | ?- | 1.0 | ??- |
| Vinylbenzene (component C) | ?20 | ?15 | ?- | 13 | 12 | ?16 | 10 | ??7 |
| Methyl methacrylate (component C) | ?35 | ?57 | ?54 | 53.5 | 61.5 | ?63 | 46 | ??48 |
| Butyl acrylate (component C) | ?17 | ?- | ?- | - | - | ?- | - | ??21 |
| Isooctyl acrylate monomer (component C) | ?- | ?- | ?18 | - | - | ?- | 16 | ??- |
| Vinyl cyanide (component C) | ?- | ?- | ?- | 6 | 4 | ?5.5 | 5 | ??8 |
| Diisopropyl azodicarboxylate (initiator) | ?1.1 | ?1.1 | ?1.1 | 1.1 | - | ?- | - | ??- |
| Dibenzoyl peroxide (initiator) | ?- | ?- | ?- | - | 1.0 | ?1.0 | 1.0 | ??1.0 |
| 40 ℃ of resin package stabilities, December | No change | No change | No change | No change | No change | No change | No change | No change |
| Resin of the present invention | Example | ||||||||
| ??1 | ??2 | ??3 | ??4 | ??5 | ??6 | ??7 | ??8 | ||
| ??P-1 | ??P-2 | ??P-3 | ??P-4 | ??P-5 | ??P-6 | ??P-7 | ??P-8 | ||
| The colored paint prescription | Resin of the present invention (50%) | ??60 | ??60 | ??60 | ??60 | ??60 | ??60 | ??60 | ??60 |
| JB-3 resin (50%) | ??40 | ??40 | ??20 | ??- | ??40 | ??40 | ??- | ??20 | |
| 8043 resins (80%) | ??- | ??- | ??20 | ??25 | ??- | ??- | ??25 | ??20 | |
| Mica powder (1250 order) | ??35 | ??35 | ??40 | ??35 | ??35 | ??35 | ??35 | ??35 | |
| TiO 2(R-575) | ??45 | ??45 | ??45 | ??45 | ??45 | ??45 | ??45 | ??45 | |
| BYK-104s | ??1.6 | ??1.6 | ??1.7 | ??1.6 | ??1.6 | ??1.6 | ??1.6 | ??1.6 | |
| BYK-306 | ??2.4 | ??2.4 | ??2.4 | ??2.4 | ??2.4 | ??2.4 | ??2.4 | ??2.4 | |
| Dimethylbenzene | ??80 | ??80 | ??85 | ??70 | ??80 | ??80 | ??70 | ???70 | |
| Dibutyl tin laurate | ??0.0001 | ??0.0001 | ??0.0005 | ??0.0004 | ??0.0001 | ??0.0001 | ??0.0004 | ??0.0005 | |
| N-75 | ??7.0 | ??7.0 | ??13.0 | ??10 | ??7.0 | ???7.0 | ??10 | ??13.0 | |
2. 8043 resins are hydroxyl polyester, and moral modest company in Taiwan produces
3. N-75 is a solidifying agent
4. BYK-104S provides for dispersant B YK company
5. BYK-306 provides for flow agent BYK company
6. other raw materials are common commercially available prod
7. weight percentage is the solid submeter 3 of resin in the bracket
| Resin of the present invention | Example | ||||||||
| 1 | ?2 | ?3 | ?4 | 5 | ?6 | ?7 | ?8 | ||
| P-1 | ?P-2 | ?P-3 | ?P-4 | P-5 | ?P-6 | ?P-7 | ?P-8 | ||
| Film performance | Dryness, surface drying, min | 10 | ?8 | ?15 | ?8 | 10 | ?10 | ?10 | ?15 |
| Do solid work h | 24 | ?24 | ?24 | ?24 | 24 | ?24 | ?24 | ?24 | |
| Sticking power, the initial stage | 100/100 | ?100/100 | 100/100 | 100/100 | 100/100 | 100/100 | 100/100 | 100/100 | |
| After half a year | 100/100 | ?100/100 | 100/100 | 100/100 | 100/100 | 100/100 | 100/100 | 100/100 | |
| Water-fast, 10 days | No change | No change | No change | No change | No change | No change | No change | No change | |
| Petrol-resistance | 48 hours | 48 hours | 24 hours | 12 hours | % hour | 96 hours | 48 hours | 96 hours | |
| Weathering resistance | Very | Excellent | Excellent | Very | Very | Very | Very | Very | |
| Alcohol resistance | Very | Very | Excellent | Excellent | Excellent | Excellent | Excellent | Excellent | |
Claims (5)
1, a kind of resin dedicated for coating on polypropylene plastics, it is characterized in that: it is that component (A) chlorinated polypropylene, component (B) Resins, epoxy, component (C) can participate in the monomer that contains unsaturated double-bond of copolymerization and the multipolymer of the double bond containing special element organic compound of component (D), it is faint yellow to brown that its outward appearance is, solid is divided into 20%～50% (weight), under 25 ± 1 ℃, the viscosity of 50% solution is 1000～6000cps, and each component shared weight percent in this resin solids is as follows:
Component (A) 5%～50%
Component (B) 0%～30%
Component (C) 20%～90%
Component (D) 0.1%～5%.
2, resin dedicated for coating on polypropylene plastics according to claim 1 is characterized in that: the Chlorinated Polypropylene III chlorinity that is used as component (A) is less than 35% (weight).
3, resin dedicated for coating on polypropylene plastics according to claim 1 is characterized in that: the Resins, epoxy as component (B) is bisphenol A-type, and its epoxy equivalent (weight) is 200～2000.
4, resin dedicated for coating on polypropylene plastics according to claim 1, it is characterized in that: the monomer that contains unsaturated double-bond that is used as participated in the copolymerization of component (C) is methacrylic alkene esters of gallic acid, esters of acrylic acid, methacrylic acid, vinylformic acid, vinylbenzene or vinyl cyanide, can be wherein a kind of monomer, also can be the monomeric combination collocation more than a kind wherein;
5, resin dedicated for coating on polypropylene plastics according to claim 1 is characterized in that: as the double bond containing special element organic compound of component (D), its pair key is the two keys in the vinyl monomer, also can be the two keys in the unsaturated acid; Its special element is titanium, silicon or aluminium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011373504A CN1162484C (en) | 2001-12-01 | 2001-12-01 | Resin dedicated for coating on polypropylene plastics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011373504A CN1162484C (en) | 2001-12-01 | 2001-12-01 | Resin dedicated for coating on polypropylene plastics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1353151A true CN1353151A (en) | 2002-06-12 |
| CN1162484C CN1162484C (en) | 2004-08-18 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011373504A Expired - Fee Related CN1162484C (en) | 2001-12-01 | 2001-12-01 | Resin dedicated for coating on polypropylene plastics |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1162484C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423722B (en) * | 2007-10-31 | 2011-09-07 | 比亚迪股份有限公司 | Coating composition and preparation method thereof and polypropylene material |
| CN102492097A (en) * | 2011-12-05 | 2012-06-13 | 江苏柏鹤涂料有限公司 | Modified acrylic resin as well as paint and application thereof |
| CN101679645B (en) * | 2007-05-04 | 2012-10-10 | 阿克佐诺贝尔国际涂料股份有限公司 | Protective sealable coating compositions |
| CN102876270A (en) * | 2012-09-20 | 2013-01-16 | 吴江市天源塑胶有限公司 | Epoxy resin conducting adhesive with high bonding strength |
| CN102911388A (en) * | 2011-08-05 | 2013-02-06 | 日立空调·家用电器株式会社 | Method for manufacturing polypropylene coating member, and polypropylene coating member and home appliance using the coating member |
| CN114773920A (en) * | 2022-04-25 | 2022-07-22 | 广东深展实业有限公司 | Photo-thermal dual-curing vacuum coating paint for polypropylene plastic and preparation method thereof |
-
2001
- 2001-12-01 CN CNB011373504A patent/CN1162484C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101679645B (en) * | 2007-05-04 | 2012-10-10 | 阿克佐诺贝尔国际涂料股份有限公司 | Protective sealable coating compositions |
| CN101423722B (en) * | 2007-10-31 | 2011-09-07 | 比亚迪股份有限公司 | Coating composition and preparation method thereof and polypropylene material |
| CN102911388A (en) * | 2011-08-05 | 2013-02-06 | 日立空调·家用电器株式会社 | Method for manufacturing polypropylene coating member, and polypropylene coating member and home appliance using the coating member |
| CN102911388B (en) * | 2011-08-05 | 2015-09-30 | 日立空调·家用电器株式会社 | The manufacture method of polypropylene application parts and polypropylene application parts and use its household appliances |
| CN102492097A (en) * | 2011-12-05 | 2012-06-13 | 江苏柏鹤涂料有限公司 | Modified acrylic resin as well as paint and application thereof |
| CN102492097B (en) | 2011-12-05 | 2013-05-08 | 江苏柏鹤涂料有限公司 | Modified acrylic resin as well as paint and application thereof |
| CN102876270A (en) * | 2012-09-20 | 2013-01-16 | 吴江市天源塑胶有限公司 | Epoxy resin conducting adhesive with high bonding strength |
| CN102876270B (en) * | 2012-09-20 | 2013-09-25 | 吴江市天源塑胶有限公司 | Epoxy resin conducting adhesive with high bonding strength |
| CN114773920A (en) * | 2022-04-25 | 2022-07-22 | 广东深展实业有限公司 | Photo-thermal dual-curing vacuum coating paint for polypropylene plastic and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1162484C (en) | 2004-08-18 |
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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 |
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Granted publication date: 20040818 Termination date: 20181201 |