CN103351758B - Primer coating compositions for polypropylene substrate and preparation method thereof - Google Patents
Primer coating compositions for polypropylene substrate and preparation method thereof Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 91
- 239000002987 primer (paints) Substances 0.000 title claims abstract description 51
- 239000012462 polypropylene substrate Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 86
- 229920005989 resin Polymers 0.000 claims abstract description 86
- 239000000853 adhesive Substances 0.000 claims abstract description 67
- 230000001070 adhesive effect Effects 0.000 claims abstract description 67
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- 240000000972 Agathis dammara Species 0.000 claims abstract description 15
- 229920002871 Dammar gum Polymers 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- 239000004925 Acrylic resin Substances 0.000 claims description 23
- 229920000178 Acrylic resin Polymers 0.000 claims description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 23
- 238000005660 chlorination reaction Methods 0.000 claims description 18
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 9
- 239000000049 pigment Substances 0.000 claims description 9
- 239000003973 paint Substances 0.000 abstract description 118
- 230000037452 priming Effects 0.000 abstract description 25
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 21
- 239000004952 Polyamide Substances 0.000 abstract description 18
- 229920002647 polyamide Polymers 0.000 abstract description 18
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 abstract description 16
- 239000004743 Polypropylene Substances 0.000 description 14
- 229920001155 polypropylene Polymers 0.000 description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 7
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 7
- 239000004744 fabric Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 235000010215 titanium dioxide Nutrition 0.000 description 7
- 229910052726 zirconium Inorganic materials 0.000 description 7
- 239000003085 diluting agent Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical class CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 239000002966 varnish Substances 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- XUBKPYAWPSXPDZ-UHFFFAOYSA-N [Ba].OS(O)(=O)=O Chemical compound [Ba].OS(O)(=O)=O XUBKPYAWPSXPDZ-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical class CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000052 vinegar Substances 0.000 description 3
- 235000021419 vinegar Nutrition 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IDQBJILTOGBZCR-UHFFFAOYSA-N 1-butoxypropan-1-ol Chemical compound CCCCOC(O)CC IDQBJILTOGBZCR-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- MOOWGTBDSGXGJW-UHFFFAOYSA-N C(C=C/C(=O)O)(=O)O.C(C)(=O)O.C(=C)Cl Chemical compound C(C=C/C(=O)O)(=O)O.C(C)(=O)O.C(=C)Cl MOOWGTBDSGXGJW-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical class CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 241000123611 Dipterocarpaceae Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 241001312741 Gekko swinhonis Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- HOCVBLVNCCMUAT-UHFFFAOYSA-N acetic acid;chloroethene;ethene Chemical group C=C.ClC=C.CC(O)=O HOCVBLVNCCMUAT-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000013615 primer Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Paints Or Removers (AREA)
Abstract
A kind of primer coating compositions for polypropylene substrate contains matrix resin and solvent, and wherein, said composition promotes resin possibly together with adhesive force, and it is one or more in amino polyamide, vinyl chloride-vinyl acetate resin and gum dammar that this adhesive force promotes resin.The preparation method that present invention also offers this primer coating compositions.Owing to primer coating compositions provided by the invention promotes resin possibly together with described adhesive force, the adhesive force between the priming paint paint film therefore formed by said composition and finish paint paint film is greatly improved.
Description
Related application
The divisional application of Chinese invention patent application that the application is application number is 200710152529.5, the applying date is JIUYUE in 2007 27 days, denomination of invention is " primer coating compositions for polypropylene substrate and preparation method thereof ".
Technical field
The present invention is about a kind of coating and preparation method thereof, more specifically about a kind of primer coating compositions for polypropylene substrate and preparation method thereof.
Background technology
At present, due to plastics have compared with metal material that light weight, manufacturing process are simple, corrosion-resistant, performance degree of amplitude modulation big, can the plurality of advantages such as injection molded, therefore metal all can be replaced to play a role in a lot of places, for instance polyolefin and other plastic material have been widely used as the raw material of the molded items such as auto parts, engineering plastics, toy, container.Wherein, polypropylene (PP) plastics due to its relatively low material cost, lightweight, high tenacity, the feature such as use again capable of circulation, there is in some field the advantage of its uniqueness, for instance it has become the main flow of automobile bumper material.
As the PP ground of bumper material, for keeping it to have good mechanical property, it is common to use temperature should below 100 DEG C.Spray-applied primer coating, finish paint (colored paint) coating and coating varnish coating successively on the surface of PP ground, the baking temperature adopted is all between 60-80 DEG C, baking time is within 60 minutes, thus sequentially form priming paint paint film, finish paint paint film and varnish paint film on the surface of PP ground.
The finish paint kind being currently widely used in PP ground has bicomponent polyurethane paint, amine baking varnish and thermoplastic acrylic paint, and the varnish then overwhelming majority adopts bicomponent polyurethane paint.
Primer coating compositions then mainly adopts chlorination modified acrylic resin as matrix resin, the priming paint paint film that this paint base composition is formed is good with the adhesive force of PP ground, but the ply adhesion with finish paint paint film is poor, particularly when finish paint is amine baking varnish, priming paint paint film is worse with the ply adhesion of finish paint paint film.
The method of traditional hardness improving PP priming paint paint film is interpolation plasticizer in primer coating compositions, such as phthalic acid ester, epoxy soybean oil and chlorinated paraffin etc..Although they can make the hardness of paint film decline after solidifying, but such plasticizer is free in resin owing to molecular weight is too little or polarity is relatively low, thus more weakening the adhesive force of priming paint paint film and finish paint paint film.
The method of the conventional adhesive force improving PP priming paint paint film is to add chlorinated polyolefin resin (chloridized polyolefin etc. such as the CP series plastics of Yi Shiman, Japan's chemical conversion) in primer coating compositions, but add this resin and can only increase the priming paint paint film adhesive force to PP ground, do not increase the adhesive force between priming paint paint film and finish paint paint film, and the price of chlorinated polyolefin resin is high, adds coating cost.
Summary of the invention
The invention aims to overcome the shortcoming that the adhesive force between existing priming paint paint film and the finish paint paint film formed for the primer coating compositions of polypropylene substrate is poor, it is provided that a kind of primer coating compositions that can form the good priming paint paint film of adhesive force between finish paint paint film for polypropylene substrate.
The preparation method that another object of the present invention is to provide this primer coating compositions.
The invention provides a kind of primer coating compositions for polypropylene substrate, said composition contains matrix resin and solvent, wherein, said composition promotes resin possibly together with adhesive force, and it is one or more in amino polyamide, vinyl chloride-vinyl acetate resin and gum dammar that this adhesive force promotes resin.
The preparation method that present invention also offers this primer coating compositions, the method includes matrix resin, adhesive force are promoted resin and solvent mix homogeneously, and it is one or more in amino polyamide, vinyl chloride-vinyl acetate resin and gum dammar that this adhesive force promotes resin.
Owing to primer coating compositions provided by the invention promotes resin possibly together with described adhesive force, the adhesive force between the priming paint paint film therefore formed by said composition and finish paint paint film is greatly improved.
Detailed description of the invention
Primer coating compositions for polypropylene substrate provided by the invention contains matrix resin and solvent, wherein, said composition promotes resin possibly together with adhesive force, and it is one or more in amino polyamide, vinyl chloride-vinyl acetate resin and gum dammar that this adhesive force promotes resin.
Wherein, even if compositions contains minimal amount of described adhesive force promotes resin, the adhesive force between priming paint paint film and the finish paint paint film of formation also can increase, and therefore to the content of adhesive force enhancement resin, there is no particular limitation.Additionally, the content of described matrix resin and solvent can be respective customary amount.Under preferable case, with the matrix resin of 100 weight portions for benchmark, the content of described solvent can be 0.5-120 weight portion, it is preferred to 0.75-80 weight portion；It can be 2-100 weight portion that described adhesive force promotes the content of resin, it is preferred to 3-60 weight portion.
Described amino polyamide can be conventional various amino polyamides, it is preferred to low molecular weight amino polyamide.The number-average molecular weight of amino polyamide is preferably 200-10000, more preferably 500-3000.Described amino polyamide is commercially available, for instance, Henkel(Henkel) company Versamid series, such as Versamid115, Versamid125 etc.；May be used without Cognis (section is peaceful) or sieve Rhodia(ground be sub-) the Versamid series of products of company.
Described vinyl chloride-vinyl acetate resin can be the terpolymer of the bipolymer of vinyl chloride and vinyl acetate or vinyl chloride, vinyl acetate and other dicarboxylic acids (ester), it is preferred to one or more in Chlorovinyl-acetate vinyl, vinyl chloride-acetate-hydroxy acrylate, vinyl chloride-acetate-maleate and vinyl chloride-acetate-ethylene alcohol ester.With the total amount of vinyl chloride-vinyl acetate resin for benchmark, in vinyl chloride-vinyl acetate resin, the content of vinyl chloride can be 40-99 weight %, it is preferred to 50-90 weight %；The content of vinyl acetate can be 1-60 weight %, it is preferred to 9-40 weight %；The content of hydroxy acrylate can be 0-20 weight %, it is preferred to 0.5-10 weight %；The content of vinyl alcohol can be 0-20 weight %, it is preferred to 0.5-10 weight %；The content of maleic acid can be 0-10 weight %, it is preferred to 0.5-10 weight %.The number-average molecular weight of vinyl chloride-vinyl acetate resin can be 10000-150000, it is preferred to 13000-80000.Vinyl chloride-vinyl acetate resin is commercially available, for instance, binary vinyl chloride-vinyl acetate resin can select H40/43, H14/36 etc. that Wa Ke company of Germany produces or the SOLBINC series of products of SHIN-ETSU HANTOTAI of Japan chemical industry；Ternary chlorine vinegar resin can select E15/45 or LL4320 etc. of Wa Ke company of Germany or the SOLBINM series of products of SHIN-ETSU HANTOTAI of Japan chemical industry.
Described gum dammar is a kind of Dipterocarpaceae plant secretion thing originating in Southeast Asia one band.Gum dammar is commercially available, for instance, it is possible to select the A level of Indonesia's product of Guangzhou Xiang Fu trading firm agency or superfine gum dammar.
Described amino polyamide, vinyl chloride-vinyl acetate resin and gum dammar can be used alone or combine use, when used in combination, the adhesive force between priming paint paint film and finish paint paint film can be further enhanced, therefore, described adhesive force promote resin be preferably in amino polyamide, vinyl chloride-vinyl acetate resin and gum dammar any two or three combination.In the combination of any two or three, the weight ratio that any two kinds of adhesive force promote resin can be 1:0.1-10, it is preferred to 1:0.2-5.
Described matrix resin can be the matrix resin of the conventional various primer coating compositions for polypropylene substrate, for instance, it is possible to for chlorination modified acrylic resin.Chlorination modified acrylic resin has been conventionally known to one of skill in the art.The number-average molecular weight of chlorination modified acrylic resin can be 2000-100000, it is preferred to 4000-50000；Chlorinity can be 2-20 weight %, it is preferred to 5-15 weight %.Commercially available chlorination modified acrylic resin is usually chlorination modified acrylic resin soln, and the solid content (being generally the content of chlorination modified acrylic resin) of this solution is 30-60 weight %.In this manual, unless stated otherwise, the amount of chlorination modified acrylic resin refers to the amount of chlorination modified acrylic resin soln.The solvent of chlorination modified acrylic resin soln can be the various solvents for primer coating compositions.
Described solvent can be the solvent of the conventional various primer coating compositions for polypropylene substrate, for example, it is possible to be one or more in toluene, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, ethanol, n-butyl alcohol, cyclohexanone, dimethylbenzene, hexone, acetone, butanone, butyl glycol ether, propandiol butyl ether.
Described compositions can also contain one or more in pigment, filler, levelling agent, dispersant and anti-settling agent.With the matrix resin of 100 weight portions for benchmark, the content of pigment can be 0-150 weight portion, it is preferred to 5-120 weight portion, more preferably 20-100 weight portion；The content of filler can be 0-120 weight portion, it is preferred to 5-100 weight portion, more preferably 10-80 weight portion；The content of levelling agent can be 0-10 weight portion, it is preferred to 0.2-8 weight portion, more preferably 0.5-5 weight portion；The content of dispersant can be 0-10 weight portion, it is preferred to 0.2-8 weight portion, more preferably 0.5-5 weight portion；The content of anti-settling agent can be 0-10 weight portion, it is preferred to 0.2-8 weight portion, more preferably 0.5-5 weight portion.
Described pigment can be the pigment of the conventional various primer coating compositions for polypropylene substrate, for instance, it is possible to for titanium dioxide (also referred to as titanium dioxide) or carbon black.Primer composition is mainly given white by titanium dioxide, for keeping coating weatherability, it is preferable that Rutile type titanium dioxide.Titanium dioxide is commercially available, for instance can select CR-826 and the CR-828 of Ke Maiqi and R-706 and the R-902 of Du Pont.Primer composition is mainly given black by white carbon black.Carbon black can also be commercially available, for instance can select the FW-200 and special 6 of Degussa.
Described filler can be the filler of the conventional various primer coating compositions for polypropylene substrate, for instance, it is possible to for one or several in Pulvis Talci, barium sulfate, Kaolin, mica powder and magnesium carbonate.Filler has been mainly filling effect, can reduce the cost of coating simultaneously.
Described levelling agent can improve the surface effect of paint film, it is possible to use the levelling agent that this area is conventional, for instance can be selected from one or more in EFKA-3777, EFKA-3670, EFKA-3600, BYK-358N and BYK-333.
Described dispersant can improve the dispersion effect of coating composition, it is possible to use the dispersant that this area is conventional, for instance can be selected from one or more in EFKA-4010, EFKA-4015, BYK-110, BYK-163 and BYK-2000.EFKA series is Holland's Ai Fuka Products, and BYK series is BYK Products, and its trade mark above is conventionally known to one of skill in the art.
Described anti-settling agent can use the anti-settling agent that this area is conventional, it is preferred to one or more of organobentonite, aerosil, Tissuemat E and polyamide wax.Described anti-settling agent is commercially available, for instance, organobentonite can select Bentone-38, SD-2 of Britain Hai Mingsi, the BT series of products of Anji County, Zhejiang Province Gekko Swinhonis organic Peng Run soil company limited.Aerosil can select the M-5 of the R-972 of Degussa, Cabot Co., Ltd.Tissuemat E and polyamide wax can select the part wax product of SANYE company of the U.S., such as S-363D, U-675A.
The preparation method of compositions provided by the invention includes matrix resin, adhesive force are promoted resin and solvent mix homogeneously, and it is one or more in amino polyamide, vinyl chloride-vinyl acetate resin and gum dammar that this adhesive force promotes resin.
With the matrix resin of 100 weight portions for benchmark, the consumption of described solvent can be 0.5-120 weight portion, it is preferred to 0.75-80 weight portion；It can be 2-100 weight portion that described adhesive force promotes the consumption of resin, it is preferred to 3-60 weight portion.
Described matrix resin, solvent and adhesive force are promoted resin and are described in detail hereinbefore, do not repeat them here.
By in the process of matrix resin, adhesive force enhancement resin and solvent mixing or after mixing, it is also possible to add one or more in pigment, filler, levelling agent, dispersant and anti-settling agent.With the matrix resin of 100 weight portions for benchmark, the consumption of pigment can be 0-150 weight portion, it is preferred to 5-120 weight portion, more preferably 20-100 weight portion；The consumption of filler can be 0-120 weight portion, it is preferred to 5-100 weight portion, more preferably 10-80 weight portion；The consumption of levelling agent can be 0-10 weight portion, it is preferred to 0.2-8 weight portion, more preferably 0.5-5 weight portion；The consumption of dispersant can be 0-10 weight portion, it is preferred to 0.2-8 weight portion, more preferably 0.5-5 weight portion；The consumption of anti-settling agent can be 0-10 weight portion, it is preferred to 0.2-8 weight portion, more preferably 0.5-5 weight portion.
The temperature of described mixing can be conventional mixing temperature, for instance, it is possible at room temperature carry out.
After mixing, it is also possible to mixture obtained above is ground, then filters, obtain coating composition.Described grinding can use the various Ginding process of routine, for instance, add grinding bead.Grinding bead is grinding bead commonly used in this field, for instance can be zirconium pearl and/or bead.The condition ground makes fineness of grind be less than 20 microns, it is preferred to 8-18 micron.Fineness of grind method of testing carries out according to GB/T1724.Described filtration can adopt the filter cloth of 400 orders.
It is more fully described the present invention by the examples below.
Embodiment 1
This embodiment is used for primer coating compositions provided by the invention and preparation method thereof is described.
By the above-mentioned 100 chlorination modified acrylic resins of the weight portion (SRE-168A of east commission agent, solid content is 50 weight %, number-average molecular weight is 6000-8000, chlorinity is 8-10 weight %) and 12 weight portion adhesive force promotion resin (amino polyamide Versamid-115, number-average molecular weight is 5000-6000) join in 33 parts by weight solvent toluene and the dimethylbenzene of 1:1 (volume ratio be), at room temperature mix homogeneously.Then 35 weight portion titanium dioxides (Du Pont R-706), 16 parts by weight kaolin clay, 2 parts per weight dispersing agent (EFKA-4010), 0.8 weight portion levelling agent (EFKA-3670) and 1 weight portion anti-settling agent (Bentone-38 of Britain Hai Mingsi) it are added thereto to again, and at room temperature mix homogeneously.By the mixture that obtains with stirring under 200 revs/min 10 minutes, being subsequently adding zirconium pearl, to be ground to fineness be 15 microns, afterwards with the filter-cloth filtering of 400 orders, obtains primer coating compositions T1.
Embodiment 2
This embodiment is used for primer coating compositions provided by the invention and preparation method thereof is described.
By the above-mentioned 100 chlorination modified acrylic resin of the weight portion (ZJ-440 of Suzhou Sheng Jia Resins Corporation, solid content is 38 weight %, number-average molecular weight is 7000-8000, chlorinity is 7-9 weight %) and 10 weight portion adhesive force promotion resin (the ternary chlorine vinegar resin E15/45 of Wa Ke company, number-average molecular weight is 50000-60000) join in 1 parts by weight solvent ethyl acetate, at room temperature mix homogeneously.Then 25 part by weight of carbon black (FW-200 of Degussa), 12 weight portion Pulvis Talci, 1 parts per weight dispersing agent (EFKA-4010), 0.5 weight portion levelling agent (EFKA-3777) and 0.5 weight portion anti-settling agent (Bentone-38 of Britain Hai Mingsi) it are added thereto to again, and at room temperature mix homogeneously.By the mixture that obtains with stirring under 300 revs/min 15 minutes, being subsequently adding zirconium pearl, to be ground to fineness be 15 microns, afterwards with the filter-cloth filtering of 400 orders, obtains primer coating compositions T2.
Embodiment 3
This embodiment is used for primer coating compositions provided by the invention and preparation method thereof is described.
By the above-mentioned 100 weight portion chlorination modified acrylic resin (PPS-35 of Lu Ou, solid content is 40 weight %, number-average molecular weight is about 7000, chlorinity is about 10 weight %) and 25 weight portion adhesive force promotion resin (the binary vinyl chloride-vinyl acetate resin H40/43 of Wa Ke company, number-average molecular weight is 40000-50000) join in 40 parts by weight solvent ethyl acetate, at room temperature mix homogeneously.Then 30 weight portion titanium dioxides (CR-826 of Ke Maiqi) and 35 parts sulfuric acid barium it are added thereto to again, and at room temperature mix homogeneously.By the mixture that obtains with stirring under 100 revs/min 20 minutes, being subsequently adding zirconium pearl, to be ground to fineness be 15 microns, afterwards with the filter-cloth filtering of 400 orders, obtains primer coating compositions T3.
Embodiment 4
This embodiment is used for primer coating compositions provided by the invention and preparation method thereof is described.
By the above-mentioned 100 chlorination modified acrylic resin of weight portion (Hangzhou moral still chemical industry DSP-8160-TS, solid content is 50 weight %, number-average molecular weight is about 9000, chlorinity is about 10 weight %) and 30 weight portion adhesive force promote that resin (Indonesia produce superfine gum dammar) joins in 20 parts by weight solvent hexone and the Ketohexamethylene of 1:1 (volume ratio be), at room temperature mix homogeneously.Then 45 parts by weight kaolin clay, 1 weight portion anti-settling agent (R-972), 2 parts per weight dispersing agent (BYK-110) and 3 weight portion levelling agents (BYK-333) it are added thereto to again, and at room temperature mix homogeneously.By the mixture that obtains with stirring under 400 revs/min 20 minutes, being subsequently adding zirconium pearl, to be ground to fineness be 15 microns, afterwards with the filter-cloth filtering of 400 orders, obtains primer coating compositions T4.
Embodiment 5
This embodiment is used for primer coating compositions provided by the invention and preparation method thereof is described.
The above-mentioned 100 chlorination modified acrylic resins of weight portion (Hangzhou moral still chemical industry DSP-8160-TS), 10 weight portion adhesive force are promoted that resin (the ternary chlorine vinegar resin E15/45 of Wa Ke company) and 30 weight portion adhesive force promotion resin (amino polyamide Versamid-115) join in 20 parts by weight solvent hexone and the Ketohexamethylene of 1:1 (volume ratio be), at room temperature mix homogeneously.Then 35 parts sulfuric acid barium, 1 weight portion anti-settling agent (R-972), 1 parts per weight dispersing agent (BYK-110) and 1 weight portion levelling agent (BYK-333) it are added thereto to again, and at room temperature mix homogeneously.By the mixture that obtains with stirring under 200 revs/min 20 minutes, being subsequently adding zirconium pearl, to be ground to fineness be 15 microns, afterwards with the filter-cloth filtering of 400 orders, obtains primer coating compositions T5.
Embodiment 6
This embodiment is used for primer coating compositions provided by the invention and preparation method thereof is described.
The above-mentioned 100 chlorination modified acrylic resins of weight portion (Hangzhou moral still chemical industry DSP-8160-TS), 10 weight portion adhesive force are promoted that resin (the binary vinyl chloride-vinyl acetate resin H40/43 of Wa Ke company), 20 weight portion adhesive force promotion resin (amino polyamide Versamid-115) and 10 weight portion adhesive force promotion resin (Indonesia produces superfine gum dammar) join in 50 parts by weight solvent ethyl acetate, at room temperature mix homogeneously.Then 35 parts sulfuric acid barium, 20 parts by weight kaolin clay, 1 weight portion anti-settling agent (R-972), 1 parts per weight dispersing agent (BYK-110) and 1 weight portion levelling agent (BYK-333) it are added thereto to again, and at room temperature mix homogeneously.By the mixture that obtains with stirring under 200 revs/min 20 minutes, being subsequently adding zirconium pearl, to be ground to fineness be 15 microns, afterwards with the filter-cloth filtering of 400 orders, obtains primer coating compositions T6.
Comparative example 1
This comparative example is for illustrating the existing primer coating compositions for polypropylene substrate.
Primer coating compositions D1 is prepared according to the method identical with embodiment 1, the difference is that, it does not have use described adhesive force to promote resin.
Comparative example 2
This comparative example is for illustrating the existing primer coating compositions for polypropylene substrate.
Primer coating compositions D2 is prepared according to the method identical with embodiment 1, the difference is that, use 12 weight portion dioctyl phthalates (DOP) to replace described adhesive force to promote resin.
Comparative example 3
This comparative example is for illustrating the existing primer coating compositions for polypropylene substrate.
Primer coating compositions D3 is prepared according to the method identical with embodiment 1, the difference is that, use 12 weight portion chlorinated polypropylenes (CP343-3 of Yi Shiman) to replace described adhesive force to promote resin.
Embodiment 7-12
Embodiment 7-12 is for the performance of the primer coating compositions that testing example 1-6 prepares respectively.
Adopt following method that the paint film after solidifying is carried out adhesive force test:
Draw the square lattice of 100 1 millimeter × 1 millimeter at sprayed surface by hundred grid, it is bonded on grid with the adhesive tape that model is 600 of Minnesota Mining and Manufacturing Company's production is smooth, do not stay a space, then vertically uncover with prestissimo, observe scratching edge place with or without depainting.If depainting amount is 5B between 0～5%, it is 4B between 5～10%, is 3B between 10～20%, be 2B between 20～30%, be B between 30～50%, be 0B more than 50%.
(1) priming paint paint film measures with the adhesive force of ground
Respectively by embodiment 1-6 prepare primer coating compositions T1 to T6 and diluent (diluent is toluene: dimethylbenzene: cyclohexanone: butanone: hexone=20:20:15:10:35(weight ratio)) mix by the weight ratio of 1:1 after, it is sprayed on PP surface of bottom material, toast 15 minutes at 70 DEG C, obtain the PP priming paint paint film that thickness is 15 microns.By adhesion test method, the adhesive force between priming paint paint film and PP ground being tested, result is as shown in table 1.Every kind of spray painting two set carries out subsequent experimental.
(2) adhesive force of priming paint paint film and finish paint paint film
Take the sample after above-mentioned spray-applied primer, the red two component polyurethane finish paint (being decided to be No. 1 finish paint) of spraying, toast 10 minutes at 75 DEG C, obtain the finish paint paint film that thickness is 20 microns.Dried paint film is carried out ply adhesion test, and test result is as shown in table 1.
Red two component polyurethane finish paint consist of red finish paint component A: curing agent component B: diluent=5:1:1(weight ratio).
Red finish paint component A processing technology is:
54 weight portion Hydroxylated acrylic resin FS2050(Deuchem companies are produced), 20.1 weight portion F3RK70 redness slurries, 10.8 weight portion 45SQ yellow pulp, 2.8 weight portion FW200 black slurry, 0.1 weight portion levelling agent BYK331,4 weight portion butyl acetates, 4 weight portion 2-Butoxyethyl acetates, 4.2 parts by weight of xylene mixing with 300 revs/min of stirrings 30 minutes.
Wherein, the processing technology of F3RK70 redness slurry is:
55 weight portion Hydroxylated acrylic resin 1753(NUPLEX companies are produced), 10 parts per weight dispersing agent BYK2000,15 weight portion red pigment F3RK70(Clariant Corporation produce), 20 weight portion 2-Butoxyethyl acetate mix homogeneously, and be ground to fineness less than 15 microns.
Wherein, the processing technology of 45SQ yellow pulp is:
30 weight portion Hydroxylated acrylic resin 1753(NUPLEX companies are produced), 5 parts per weight dispersing agent BYK100,52 weight portion yellow uitramarine 45SQ(Clariant Corporation produce), 13 weight portion 2-Butoxyethyl acetate mix homogeneously, and be ground to fineness less than 15 microns.
Wherein, the processing technology of FW200 black slurry is:
64 weight portion Hydroxylated acrylic resin 1753(NUPLEX companies are produced), 5.5 parts per weight dispersing agent BYK163,7 weight portion black pigment FW200(Clariant Corporation produce), 23.5 weight portion 2-Butoxyethyl acetate mix homogeneously, and be ground to fineness less than 15 microns.
The formula of curing agent component B is as follows:
55 weight portion trimer isocyanates N3390(Bayers produce), 0.59 weight portion water absorbing agent OF(Bayer produce), 0.16 weight portion water absorbing agent TI(Bayer produce), 44.25 weight portion butyl acetates.
Diluent formulation is toluene: dimethylbenzene: butyl acetate: Ketohexamethylene=30:30:25:15(weight ratio)
Separately take the sample after a set of spray-applied primer, spray the thermoset acrylics-tripolycyanamide one component amino baking finish (being decided to be No. 2 finish paints) of silver color thereon, toast 20 minutes at 60 DEG C, obtain the finish paint paint film that thickness is 30 microns.Dried paint film is carried out ply adhesion test, and test result is as shown in table 1.
One component amino baking finish consist of silver color finish paint component: diluent=1:1(weight)
The processing technology of silver color finish paint component is:
37 weight portion thermosetting acrylic resin A354(DIC companies are produced), 5 weight portion resist sagging resin 91757(NUPLEX companies produce), 9 weight portion amino resins US138-70(NUPLEX companies produce), 8 weight portion CAB381-0.5 solution (25 weight %CAB solution, dissolve with butyl ester), 2.2 parts by weight of silver powder 8154 and 2.3 weight portion AP354(produce by Eckart GmbH & Co. KG), 15 weight portion BYK-8461 Tissuemat Es, 7 weight portion ethylene glycol ether acetates, 14.5 weight portion butyl acetate mixing and stirring.
Diluent formulation is butyl acetate: dimethylbenzene: 2-Butoxyethyl acetate: S150# solvent naphtha=15:28:22:35(weight ratio)
Comparative example 4-6
Comparative example 4-6 is for the performance of the primer coating compositions that test comparison example 1-3 prepares respectively.
Measure the adhesive force of the comparative example 1-3 primer coating compositions D1 to D3 the prepared priming paint paint film formed and ground and finish paint paint film according to the method identical with embodiment 7-12, test result is as shown in table 1.
Table 1
Can be seen that from the result shown in table 1, priming paint paint film and the adhesive force of ground that coating D1 to D3 is formed still may be used, but the adhesive force too low (being up to 3B) of priming paint paint film and finish paint paint film, when finish paint paint film is formed by one component amino baking finish, adhesive force lower (minimum for 0B)；Coating T1 to T6 promotes one or more in resin containing described adhesive force, the priming paint paint film formed and the adhesive force of finish paint paint film are greatly improved (being up to 5B), even if when finish paint paint film is formed by one component amino baking finish, adhesive force is also significantly high (minimum for 4B), thus illustrates that the primer coating compositions adopting the present invention can significantly improve the adhesive force between priming paint paint film and finish paint paint film.
In addition, compared with the coating T1 to T4 promoting resin containing only a kind of adhesive force, coating T5 contains two kinds of adhesive force enhancement resins, coating T6 and contains three kinds of adhesive force and promote resins, adhesive force between priming paint paint film and finish paint paint film that coating T5 and T6 is formed is better, even if when finish paint paint film is formed by one component amino baking finish, adhesive force is also 5B, illustrate when the combination of described amino polyamide, vinyl chloride-vinyl acetate resin and gum dammar uses, it is possible to further enhance the adhesive force between priming paint paint film and finish paint paint film.
Claims (3)
1. the primer coating compositions for polypropylene substrate, said composition contains matrix resin and solvent, it is characterized in that, said composition promotes resin possibly together with adhesive force, it is gum dammar that this adhesive force promotes resin, described matrix resin is chlorination modified acrylic resin, and the number-average molecular weight of this chlorination modified acrylic resin is 2000-100000, and chlorinity is 5-15 weight %；With the matrix resin of 100 weight portions for benchmark, the content of described solvent is 0.5-120 weight portion, and it is 2-100 weight portion that described adhesive force promotes the content of resin.
2. compositions according to claim 1, wherein, said composition is possibly together with pigment, filler, levelling agent, dispersant and anti-settling agent, with the matrix resin of 100 weight portions for benchmark, the content of pigment is 5-120 weight portion, and the content of filler is 5-100 weight portion, and the content of levelling agent is 0.2-8 weight portion, the content of dispersant is 0.2-8 weight portion, and the content of anti-settling agent is 0.2-8 weight portion.
3. the preparation method of the compositions described in claim 1, the method includes matrix resin, adhesive force are promoted resin and solvent mix homogeneously, and it is gum dammar that this adhesive force promotes resin；With the matrix resin of 100 weight portions for benchmark, the consumption of described solvent is 0.5-120 weight portion, and it is 2-100 weight portion that described adhesive force promotes the consumption of resin.
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| Study on synthesis and adhesiveness of modified chlorinated polypropylene with acrylic acid;FU He-qing等;《ZHANJIE》;20041231;第25卷(第4期);第8-10 * |
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