CN101469194B - Coating composition for polypropylene substrate and method for preparation thereof - Google Patents
Coating composition for polypropylene substrate and method for preparation thereof Download PDFInfo
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- CN101469194B CN101469194B CN2007101257198A CN200710125719A CN101469194B CN 101469194 B CN101469194 B CN 101469194B CN 2007101257198 A CN2007101257198 A CN 2007101257198A CN 200710125719 A CN200710125719 A CN 200710125719A CN 101469194 B CN101469194 B CN 101469194B
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Abstract
The invention relates to a coating composition for polypropylene bottom materials and a preparation method thereof. The composition contains chlorinated acrylic resin, pigment, a filling material, an addition agent and a solvent, and also contains nano calcium carbonate and a zirconium coupling agent. Based on the amount of the nano calcium carbonate, the zirconium coupling agent accounts for 1-10 wt% of the nano calcium carbonate. The zirconium coupling agent is a zirconium aluminate inorganic polymer containing two organic groups, wherein one organic group is hydroxyl, and the other organic group is fatty acid or methacrylic acid. A paint film formed after curing of the coating composition has excellent shock resistance, good adsorption force to the polypropylene bottom materials, and good appearance; and the coating cost is reduced greatly.
Description
Technical field
The present invention relates to a kind of coating composition that is used for polypropylene substrate and preparation method thereof.
Background technology
Nano particles of calcium carbonate is a kind of novel ultrafine solids material that grows up the eighties in 20th century.The nano-calcium carbonate calcium material is applied in the coating; Because film forming material, color stuffing and auxiliary agent equimolecular exist many active sites; These active sites may and the active site of nanoparticle surface between intensive takes place interacts; Thereby densification might be formed and stable coating significantly improves the physical and chemical performance of filming.In coatings industry, the nano-calcium carbonate Heat stability is good, cheap, in film forming matter, play skeleton function, can replace expensive white titanium pigment in a large number, reduce the base-material adhesive consumption simultaneously, reduce cost remarkable in economical benefits significantly.Therefore, being applied in the coating nano-calcium carbonate in the hope of improving coating property is one of hot issue of paying close attention to of coating circle.Yet the surface treatment agent of nano-calcium carbonate adopts hard ester acid and its esters mostly at present, is applied in the coating, has following defective: particle surface energy is high, is in the thermodynamic instability state, very easily reunites; Dispersing property in organic medium is also bad, is prone to form boundary defect, causes film performance to descend.
Summary of the invention
The technical problem that the present invention will solve provides a kind ofly to be had excellent in impact resistance and can have good sticking power simultaneously behind film-forming, be applicable to the coating composition of Vestolen PP 7052 (PP) ground.
A kind of coating composition; Said composition contains chlorination modified vinyl resin, pigment, filler, auxiliary agent and solvent, and said composition also contains nano-calcium carbonate and zirconium class coupling agent, is benchmark with the amount of nano-calcium carbonate; Zirconium class coupling agent accounts for the 1-10 weight % of nano-calcium carbonate; Said zirconium class coupling agent is the zirconium aluminate inorganic polymer that contains two kinds of organic groups, and a kind of organic group wherein is a hydroxyl, and another kind of organic group is lipid acid or methylacrylic acid.
Preferably, the skin of nano-calcium carbonate particles is coated with zirconium class coupling agent.
Wherein, Total amount with compsn is a benchmark; The content of said chlorination modified vinyl resin is 15-70 weight %, and the content of said nano-calcium carbonate is 5-50 weight %, and the total content of said pigment and filler is 10-60 weight %; The content of said auxiliary agent is 0.2-10 weight %, and the content of said solvent is 5-60 weight %.
The zirconium aluminate inorganic polymer is the zirconium aluminate inorganic polymer of known, is preferably the low molecule inorganic polymer of zirconium aluminate, molecular weight 200-1000.
Wherein, the cl content in the said chlorination modified vinyl resin is 5-20 weight %.
Wherein, said filler is selected from one or more in talcum powder, permanent white, water-ground limestone, kaolin, mica powder, the magnesiumcarbonate, and said auxiliary agent is one or more in dispersion agent, flow agent, the anti-settling agent.
Wherein, said solvent is selected from one or more in toluene, ETHYLE ACETATE, butylacetate, isobutyl acetate, propyl acetate, ethanol, propyl carbinol, pimelinketone, YLENE, hexone, acetone, methylethylketone, butyl glycol ether, the Ucar 35 butyl ether.
The preparation method of aforementioned coating composition, this method may further comprise the steps:
(1) nano-calcium carbonate is added in the mixing machine, heat to 70-120 ℃, and add a certain amount of zirconium class coupling agent, mix, cooling obtains the nano-calcium carbonate that zirconium class coupling agent coats;
(2) nano-calcium carbonate that the zirconium class coupling agent that chlorination modified vinyl resin and step (1) is obtained coats joins in a mixing bowl of dispersion machine, at room temperature mixes, and obtains first mixture;
(3) first mixture and pigment, filler, auxiliary agent, the solvent that step (2) are obtained evenly obtain second mixture;
(4) second mixture that step (3) is obtained is ground to the scraper plate fineness less than 20 microns, filters second mixture after grinding with 400 purpose stainless (steel) wires, obtains coating composition.
The nano-calcium carbonate that the present invention adopts is the common nano-calcium carbonate in this area, can be to adopt Triple Pressed Stearic Acid or resinous acid to do the surface-treated nano-calcium carbonate, also can adopt the not nano-calcium carbonate of coating processing.
In the present invention; The nano-calcium carbonate that adopts zirconium class coupling agent to coat replaces ordinary titanium powder; Zirconium class coupling agent wherein is the low molecule inorganic polymer of zirconium aluminate that contains two kinds of organic groups, and organic group wherein is a kind of to be hydroxyl, and another kind of organic group is lipid acid or methylacrylic acid.Nano-calcium carbonate is sent in the mixing machine in the step (1); Heat to 70-120 ℃; And adding a certain amount of zirconium class coupling agent, after mixing for some time, hydroxyl of one of organic group and nano-calcium carbonate molecule are with covalent linkage or hydrogen bonded in the zirconium class coupling agent.After mixing for some time in chlorination modified vinyl resin and the dispersion machine of said mixture in step (2), another kind of organic group lipid acid in the zirconium class coupling agent or methylacrylic acid then produce with chlorination modified vinyl resin molecule and attract or tangle.Like this, Nano particles of calcium carbonate is that interlude is connected with chlorination modified vinyl resin with zirconium class coupling agent just, and nano-calcium carbonate is also just wrapped up by chlorination modified vinyl resin molecule, and the high surface energy of calcium carbonate particles has obtained greatly reducing.Therefore its thermodynamic stability has obtained improving greatly.Because of the nano-calcium carbonate molecule is wrapped up by zirconium class coupling agent and chlorination modified vinyl resin; When mixing with other components of the coating composition that is used for polypropylene substrate; Be difficult for forming boundary defect, so nano-calcium carbonate also just is easy to be dispersed in the organic medium.
Therefore; Comparing tradition interpolation white titanium pigment is that coating composition color stuffing, that be used for polypropylene substrate is compared; With low cost and the impact resistance of the nano paint compsn of gained of the present invention is excellent, and all improves a lot with the bonding force of PP ground and finish paint.
Embodiment
The nano paint compsn that is used for the PP material provided by the invention; It contains chlorination modified vinyl resin, pigment, filler, auxiliary agent and solvent; Wherein, said composition also contains nano-calcium carbonate and zirconium class coupling agent, is benchmark with the amount of nano-calcium carbonate; Zirconium class coupling agent accounts for the 1-10 weight % of nano-calcium carbonate; Said zirconium class coupling agent is the zirconium aluminate inorganic polymer that contains two kinds of organic groups, and a kind of organic group wherein is a hydroxyl, and another kind of organic group is lipid acid or methylacrylic acid.
The nano paint compsn that is used for the PP material provided by the invention; Its matrix resin is chlorination modified vinyl resin, and interpolation Nano particles of calcium carbonate and zirconium class coupling agent are material modified as PP priming paint, and it is formed and content is the chlorination modified vinyl resin of 15-70 weight %; The surperficial coated nano calcium carbonate of 5-45 weight %; The color stuffing of 10-60 weight %, the auxiliary agent of 0.2-10 weight %, the solvent of said 5-60 weight %.Wherein nano-calcium carbonate surface coats zirconium class coupling agent and obtains coated nano calcium carbonate, and in the amount of the nano-calcium carbonate of untreated zirconium class coupling agent, zirconium class coupling agent accounts for the 1-10 weight % of the nano-calcium carbonate that is untreated.In addition, in the present invention, all resins all are as the criterion with solid, and the solvent in the resin counts in the solvent part of whole prescription.
Among the present invention nano-calcium carbonate being carried out surface-treated zirconium class coupling agent is the low molecule inorganic polymer of zirconium aluminate that contains two kinds of organic coordination bases, and organic group wherein is a kind of to be hydroxyl, and another kind is lipid acid or methylacrylic acid.
Total amount with coating composition is as the criterion, and the content of Nano particles of calcium carbonate accounts for the 5-45 weight % of total amount, does not then have very little to improve paint film impact resistance and the effect that reduces cost, and is too many then can make enamelled coating of the present invention loss of adhesion to the PP ground.Amount to zirconium class coupling agent among the present invention is also wanted strict control, and in the amount of nano-calcium carbonate, zirconium class coupling agent accounts for 1-10 weight %.The amount of zirconium class coupling agent then can not form effective coating to nano-calcium carbonate very little, and the PP primary coat that makes does not reach requirement to the sticking power of PP ground or top coat layer.Then cause waste too much, unfavorable in cost.The specification of the nano-calcium carbonate that is adopted among the present invention does not have special demands; As can select the product such as CC-R, CCR-100, CCR-300 of Guangdong Enping Gavin Chemical Industrial Enterprise Co., Ltd. for use, also can adopt the model such as J-13233, J-13319 of Shanghai Zhuoyue Nanometer Material Co., Ltd.Zirconium class coupling agent wherein can adopt the products such as MANCHEM F.FPM, MANCHEM-1 or MANCHEM-MPG in the MANCHEM series that French Rhone-poulenc company releases.
Chlorination modified vinyl resin as main film forming substance of the present invention does not have special restriction, can select for use Suzhou to contain the ZJ-440 of good resin company, ZJ-441; The Hangzhou moral is one or more among chemical industry DSP-8160-TS, DSP-8260, PPS-35, SRE-168A and the SRE-169 still.
Filler described in the present invention is this area customary fillers, mainly has been filling effect, can reduce the cost of coating simultaneously, can be selected from talcum powder, permanent white, water-ground limestone, kaolin, mica powder, the magnesiumcarbonate one or more.
Auxiliary agent described in the present invention is this area auxiliary agent commonly used, like dispersion agent, preferably contains flow agent and anti-settling agent.
The solvent that coating composition of the present invention adopted is this area organic solvent commonly used, can be selected from toluene, ETHYLE ACETATE, butylacetate, isobutyl acetate, propyl acetate, ethanol, propyl carbinol, pimelinketone, YLENE, hexone, acetone, methylethylketone, butyl glycol ether, the Ucar 35 butyl ether one or more.
The NHG series product that the mixing machine equipment that is adopted in the coating manufacture craft among the present invention can adopt Rugao, Jiangsu machine works to produce, this equipment have the mixing efficiency height, easy and simple to handle, volume is little.
The coating process of coating composition of the present invention is: with ground coating composition of the present invention and thinner according to 1: after the dilution proportion of 0.8-1.2, be sprayed on the PP material surface; Toasted 10-20 minute down at 60-80 ℃ then, obtain the coating that thickness is 15-20 μ m.
Said thinner of the present invention is this area small molecules organic solvent commonly used, can be selected from toluene, ETHYLE ACETATE, butylacetate, isobutyl acetate, propyl acetate, ethanol, propyl carbinol, pimelinketone, YLENE, hexone, acetone, methylethylketone, butyl glycol ether, the Ucar 35 butyl ether one or more.
Come to describe in more detail the present invention through embodiment below.
Embodiment 1
This embodiment is used for explaining coating composition of the present invention and preparation method thereof.
The step of making coating composition is:
(1) (CC-R type, median size are 60nm, the surface fat s.t. to get nano-calcium carbonate; Guangdong Enping Gavin Chemical Industrial Enterprise Co., Ltd. product) sends in the mixing machine (NHG-5 type, Rugao, Jiangsu machine works produces) for 100 parts, heat to 80 ℃; Then add 5 parts of zirconium class coupling agents (model MANCHEM F.FPM, organo-functional group are ten tetra-carbonics, and Rhone-poulenc company produces); (1000-1200 rev/min) mixed 20 minutes at a high speed, and mixed slurry is taken out, cooling;
(2) mixture that obtains of above-mentioned steps (1) is got 30 parts; And get chlorination modified vinyl resin (SRE-168A; Admittedly contain 50 weight %, all the other are solvent, and Suzhou is contained good resin company and produced) 60 parts join dispersion machine (TSO.75 model; The Jiangsu mechanical ltd of diligent industry produces) a mixing bowl in, at room temperature (25 ± 5 ℃) at a high speed (1000-1200 rev/min) mixed 20-30 minute;
(3) in said mixture, add Degussa FW-200 carbon black 0.1g, kaolin filler 8g, EFKA-4010 dispersion agent 1g; EFKA-3670 flow agent 0.4g; The Bentone-38 anti-settling agent 0.5g of Hai Mingsi adopts 200-500 rev/min of speed to disperse, and jitter time is 10-20 minute;
(4) add grinding bead and grind, and test its scraper plate fineness, when the scraper plate fineness promptly stops to grind less than 20 microns;
(5) adopt 400 purpose stainless (steel) wires to filter, get coating composition.
Embodiment 2
Except that the temperature in the step 1 is changed into 60 ℃, all the other are identical with the method for embodiment 1.
Embodiment 3
Remove and change zirconium class coupling agent in the step 1 (model MANCHEM F.FPM, organo-functional group are ten tetra-carbonics, and Rhone-poulenc company produces) into 2 parts, all the other are identical with the method for embodiment 1.
Embodiment 4
Remove and change zirconium class coupling agent in the step 1 (model MANCHEM F.FPM, organo-functional group are ten tetra-carbonics, and Rhone-poulenc company produces) into 9 parts, all the other are identical with the method for embodiment 1.
Embodiment 5
The model of removing zirconium class coupling agent in the step 1 changes into outside the MANCHEM MPG (organo-functional group is a methylacrylic acid, and Rhone-poulenc company produces), and all the other are identical with the method for embodiment 1.
Embodiment 6
The model of removing nano-calcium carbonate in the step 1 changes into outside the CC-100 type (median size is 40nm, surface fat s.t., Guangdong Enping Gavin Chemical Industrial Enterprise Co., Ltd. product), and all the other are identical with the method for embodiment 1.
Embodiment 7
The weight of removing the chlorination modified acrylic resin SRE-168A in the step 2 among the embodiment 1 (admittedly contain 50 weight %, all the other are solvent) changes 45g into, and the nano-calcium carbonate of zirconium class coupling agent treatment is changed into outside the 45g, and all the other are identical with the method for embodiment 1.
Embodiment 8
Except that the Change Weight To 0.2g with the EFKA-4010 dispersion agent among the embodiment 1, all the other are identical with the method for embodiment 1.
Embodiment 9
Except that the Bentone-38 anti-settling agent that does not add Hai Mingsi, all the other are identical with the method for embodiment 1.
Comparative Examples 1
Remove the zirconium class coupling agent component of adding among the embodiment 1 is removed, implementation step 1, and nano-calcium carbonate is directly added in the chlorination modified vinyl resin, and all the other are identical with the method for embodiment 1.
Comparative Examples 2
Remove step 1, with the alternative nano-calcium carbonate of the zirconium class coupling agent treatment of amount equally of white titanium pigment (R-706, E.I.Du Pont Company produces) of 30 weight parts, all the other are identical with the method for embodiment 1.
Performance test
Testing method is as shown in table 1:
Table 1
| Test event | The method of inspection | Quality index |
| Sticking power | GB/T9286 | Being divided into is six grades, and 0,1,2 grade is qualified. |
| Impact resistance | GB/T1732; | Multilayer thickness requirement>=20KG * CM is qualified. |
| Paint film appearance | Range estimation | Paint film smooth smooth be qualified. |
(a) various performance tests behind the sprayed coating compsn on the polypropylene substrate
With above-mentioned coating respectively with thinner according to 1: after the dilution proportion of 0.8-1.2, be sprayed on the PP material surface, at 60-80 ℃ of following baking 10-20min, obtaining thickness is the PP primer coating of 15-20um.Then carry out each item performance test.
(b) various performance tests behind the topcoating
Get the sample behind the spray material compsn, the two component polyurethane finish paint of spraying band color (like silver color), 60-80 ℃ of baking 10-20min down obtains the topcoat that thickness is 20-30um.Dried paint film is then carried out each item performance test.
The coating composition that embodiment 1-9 and Comparative Examples 1-2 are obtained carries out corresponding performance test according to the method described above, and the result who records lists in the table 2.
Table 2
Can find out that from table 2 coating composition of the present invention can improve the impact resistance and its sticking power to PP bottom material and finish paint of priming paint; Shown in embodiment 1; Coating composition is 0 grade to the sticking power of PP ground and finish paint, and impact strength surpasses 30KG * CM, paint film layer smooth; In Comparative Examples 1, priming paint is the 2-3 level to the sticking power of PP material, be the 1-2 level to the sticking power of finish paint, and impact resistance is less than 30KG * CM.In Comparative Examples 2, priming paint is the 1-2 level to the sticking power of PP ground and finish paint, and impact resistance is less than 25KG * CM, and the paint film layer planeness is general, and slickness is also bad.Therefore, the coating composition that is used for polypropylene material provided by the invention has the excellent in impact resistance ability, and the adsorptive power of polypropylene substrate and finish paint is also obviously improved, and the paint film layer outward appearance is good, and the coating cost also reduces greatly simultaneously.
Claims (7)
1. coating composition, said composition contains chlorination modified vinyl resin, pigment, filler, auxiliary agent and solvent, it is characterized in that, and said composition also contains the nano-calcium carbonate particles that skin is coated with zirconium class coupling agent; Said zirconium class coupling agent is the zirconium aluminate inorganic polymer that contains hydroxyl and another kind of organic group, and another kind of organic group wherein is a lipid acid; Amount with nano-calcium carbonate is a benchmark, and said zirconium class coupling agent accounts for the 1-10 weight % of nano-calcium carbonate; Total amount with compsn is a benchmark; The content of said chlorination modified vinyl resin is 15-70 weight %; The content of said nano-calcium carbonate is 5-50 weight %; The total content of said pigment and filler is 10-60 weight %, and the content of said auxiliary agent is 0.2-10 weight %, and the content of said solvent is 5-60 weight %.
2. coating composition according to claim 1, wherein, said lipid acid is methylacrylic acid.
3. coating composition according to claim 1, wherein, the cl content in the said chlorination modified vinyl resin is 5-20 weight %.
4. coating composition according to claim 1; Wherein, Said filler is selected from one or more in talcum powder, permanent white, water-ground limestone, kaolin, mica powder, the magnesiumcarbonate, and said auxiliary agent is one or more in dispersion agent, flow agent, the anti-settling agent.
5. coating composition according to claim 1; Wherein, said solvent is selected from one or more in toluene, ETHYLE ACETATE, butylacetate, propyl acetate, ethanol, propyl carbinol, pimelinketone, YLENE, hexone, acetone, methylethylketone, butyl glycol ether, the Ucar 35 butyl ether.
6. the preparation method of the said coating composition of claim 1, this method may further comprise the steps:
(1) nano-calcium carbonate is added in the mixing machine, heating, and add a certain amount of zirconium class coupling agent, and mixing, cooling obtains the nano-calcium carbonate that zirconium class coupling agent coats;
The nano-calcium carbonate of the coating that (2) chlorination modified vinyl resin and step (1) is obtained mixes, and obtains first mixture;
(3) first mixture and pigment, filler, auxiliary agent, the solvent that step (2) are obtained evenly obtain second mixture;
(4) second mixture that step (3) is obtained grinds, filtration obtains coating composition.
7. preparation method according to claim 6, this method may further comprise the steps:
(1) nano-calcium carbonate is added in the mixing machine, heat to 70-120 ℃, and add a certain amount of zirconium class coupling agent, mix, cooling obtains the nano-calcium carbonate that zirconium class coupling agent coats;
(2) nano-calcium carbonate that the zirconium class coupling agent that chlorination modified vinyl resin and step (1) is obtained coats joins in a mixing bowl of dispersion machine, at room temperature mixes, and obtains first mixture;
(3) first mixture and pigment, filler, auxiliary agent, the solvent that step (2) are obtained evenly obtain second mixture;
(4) second mixture that step (3) is obtained is ground to the scraper plate fineness less than 20 microns, filters second mixture after grinding with 400 purpose stainless (steel) wires, obtains coating composition.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101257198A CN101469194B (en) | 2007-12-29 | 2007-12-29 | Coating composition for polypropylene substrate and method for preparation thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101257198A CN101469194B (en) | 2007-12-29 | 2007-12-29 | Coating composition for polypropylene substrate and method for preparation thereof |
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| CN101469194A CN101469194A (en) | 2009-07-01 |
| CN101469194B true CN101469194B (en) | 2012-06-06 |
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| CN2007101257198A Expired - Fee Related CN101469194B (en) | 2007-12-29 | 2007-12-29 | Coating composition for polypropylene substrate and method for preparation thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106349857A (en) * | 2016-08-31 | 2017-01-25 | 安徽士华机电设备科技有限公司 | Coating for running machine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001049581A (en) * | 1999-08-05 | 2001-02-20 | Yuken Chemical Kk | Coating material for sewn product, production of coating material for sewn product and processing of sewn product |
| CN1373164A (en) * | 2002-04-05 | 2002-10-09 | 中山大学 | Organic hybridization process for processing surface of nano CaCo3 |
| CN1872918A (en) * | 2006-06-27 | 2006-12-06 | 上海大学 | Oleophilic modificatioon method for tiny inorganic Nano powder |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001049581A (en) * | 1999-08-05 | 2001-02-20 | Yuken Chemical Kk | Coating material for sewn product, production of coating material for sewn product and processing of sewn product |
| CN1373164A (en) * | 2002-04-05 | 2002-10-09 | 中山大学 | Organic hybridization process for processing surface of nano CaCo3 |
| CN1872918A (en) * | 2006-06-27 | 2006-12-06 | 上海大学 | Oleophilic modificatioon method for tiny inorganic Nano powder |
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