CN1330719C - Low-temperature solidified polyester surface paint for procoating metal coiled material and its preparing method - Google Patents
Low-temperature solidified polyester surface paint for procoating metal coiled material and its preparing method Download PDFInfo
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- CN1330719C CN1330719C CNB2005100408562A CN200510040856A CN1330719C CN 1330719 C CN1330719 C CN 1330719C CN B2005100408562 A CNB2005100408562 A CN B2005100408562A CN 200510040856 A CN200510040856 A CN 200510040856A CN 1330719 C CN1330719 C CN 1330719C
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- 239000003973 paint Substances 0.000 title claims abstract description 41
- 239000000463 material Substances 0.000 title claims abstract description 38
- 229920000728 polyester Polymers 0.000 title claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 36
- 239000002184 metal Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title description 4
- 239000000049 pigment Substances 0.000 claims abstract description 46
- 229920001225 polyester resin Polymers 0.000 claims abstract description 25
- 239000004645 polyester resin Substances 0.000 claims abstract description 25
- -1 glycidyl ester Chemical class 0.000 claims abstract description 20
- 239000012046 mixed solvent Substances 0.000 claims abstract description 20
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 229920003180 amino resin Polymers 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims description 39
- OZCWUNHGNVXCCO-UHFFFAOYSA-N oxiran-2-ylmethyl hydrogen carbonate Chemical group OC(=O)OCC1CO1 OZCWUNHGNVXCCO-UHFFFAOYSA-N 0.000 claims description 29
- 230000004048 modification Effects 0.000 claims description 21
- 238000012986 modification Methods 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 20
- 230000009257 reactivity Effects 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- 125000001931 aliphatic group Chemical group 0.000 claims description 11
- 238000001723 curing Methods 0.000 claims description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 9
- 150000002576 ketones Chemical class 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 8
- 239000000975 dye Substances 0.000 claims description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 7
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- IBMRTYCHDPMBFN-UHFFFAOYSA-N Mono-Me ester-Pentanedioic acid Natural products COC(=O)CCCC(O)=O IBMRTYCHDPMBFN-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Polymers C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- 238000013035 low temperature curing Methods 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 6
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229940100573 methylpropanediol Drugs 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 239000013530 defoamer Substances 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical class CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 3
- XFQHIELVPOKJIM-UHFFFAOYSA-N 1,4-dioxacyclotetradecane-5,14-dione Chemical compound O=C1CCCCCCCCC(=O)OCCO1 XFQHIELVPOKJIM-UHFFFAOYSA-N 0.000 claims description 3
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical group COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Polymers COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 claims description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 3
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 claims description 3
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 3
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical group O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical class [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 239000001038 titanium pigment Substances 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 3
- 239000000203 mixture Substances 0.000 claims 3
- QOFLTGDAZLWRMJ-UHFFFAOYSA-N 2-methylpropane-1,1-diol Chemical compound CC(C)C(O)O QOFLTGDAZLWRMJ-UHFFFAOYSA-N 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- 150000005690 diesters Chemical class 0.000 claims 1
- 235000006408 oxalic acid Nutrition 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 18
- 239000011248 coating agent Substances 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 229910000831 Steel Inorganic materials 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000010959 steel Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 125000005586 carbonic acid group Chemical group 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000011161 development Methods 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- XVMLNCGLTNHHTC-UHFFFAOYSA-N C(C)OCCO.C(C)(=O)OCCCCC Chemical compound C(C)OCCO.C(C)(=O)OCCCCC XVMLNCGLTNHHTC-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 2
- HZHMMLIMOUNKCK-UHFFFAOYSA-N dipropyl oxalate Chemical compound CCCOC(=O)C(=O)OCCC HZHMMLIMOUNKCK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920004935 Trevira® Polymers 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000007520 diprotic acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- HFEZEKQQHCPHDU-UHFFFAOYSA-N hexane-1,6-diol;terephthalic acid Chemical compound OCCCCCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 HFEZEKQQHCPHDU-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
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- 238000010561 standard procedure Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 238000011179 visual inspection Methods 0.000 description 1
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Abstract
The present invention relates to the technical field of polyester resin paint, particularly to low-temperature solidified polyester surface paint for pro-coating metal coiling materials and a preparation method thereof. The low-temperature solidified polyester surface paint is prepared in such a manner that linear polyester resin with high activity, which is modified from the glycidyl ester of tertiary carbonic acid, is used as film forming resin; amino resin is used as a firming agent, and pigment slurry, an auxiliary agent and a mixed solvent are added to the film forming resin and the firming agent, wherein the content of the solid weight of a finished product is from 40 to 80%, four cups of the paint having the viscosity of 30 to 200 seconds is coated at the temperature of 23 DEG C, and the paint can be solidified into a film after the paint is solidified for 30 to 60 seconds and the temperature of a base plate is from 200 to 216DEG C. The low-temperature solidified polyester surface paint for pro-coating metal coiling materials can meet various technical indexes of coiling steel, lower the temperature (PMT) of the base plate for solidifying the paint film by about 25 DEG C and lower the temperature of a drying tunnel by 50 to 80 DEG C. Thereby, the energy consumption is reduced, and the production cost of pre-coating coiling materials is lowered. Thus, the low-temperature solidified polyester surface paint has favorable economical and social benefits.
Description
Technical field
The present invention relates to the Polyester resin lacquer technical field, especially a kind of low-temperature solidified polyester surface paint for procoating metal coiled material and preparation method thereof.
Background technology
The precoating metal coiled material is a continuous coating organic coating and through high temperature rapid curing on the metal original tape of advancing, a kind of organic materials/metallic composite panel of making.Nineteen thirty-five Joe Hunter has built up the thick 0.2mm of article one application in the world in the U.S., the precoating metal winding production line of wide 50mm steel band.After World War II finishes, the precoating metal coiled material obtains very big development as light-duty, cheap material of construction, simultaneously along with economic recovery and progress of science and technology after the war, good material and technical foundation is provided for again the development of precoating metal coiled material, be starting point the 1950's with the U.S., begun precoating metal coiled material fast-developing period, become an emerging industry very soon in American-European developed country.The maximum purposes of precoating metal coiled material is as material of construction, and its consumption accounts for the over half of precoating metal coiled material ultimate production.It cooperates with light-weight steel cage structure, is suitable for building exterior wall wooden handcart, curtain wall, roof boarding, indoor partition wall, rolling screen door, garage door and the mat shelter etc. of industrial premises, public utility, single-family dwelling, station, booth etc.Except that building materials, the inside fitting from the shell of vehicle, liner to boats and ships; From household appliances shell to culinary frying pan and baking tray; To various package packing supplies, it can both provide of all kinds, colourful product for people from art metal furniture.
Late 1920s Kienle reacts with glycerine and phthalic anhydride and has synthesized Synolac the earliest with the unsaturated fatty acids modification.Carothers has started the research and development of vibrin with the research of the synthetic line polymer of hexylene glycol terephthalic acid afterwards.Nineteen forty-one Whenfielt Dikson has made the trevira with practical value.Expiring the beginning of the sixties just occurs coating vibrin and polyester coating, and becomes the main body of pre-coated coil with coating very soon.The coating of using because of the precoating metal coiled material must satisfy its production technique and process the requirement of using two aspects, requirement from production technique, have fast forward, roller coat applies, high temperature, short time baking and the sharply characteristics of cooling of back of coming out of the stove, from requirement to paint film property, finish paint should have good opacifying power and ornamental, and identical product gloss relative error should be not more than 0.5%, aberration Δ E＜1, to have good toughness and hardness simultaneously, to satisfy processing and service requirements.Therefore Polyester resin lacquer is a topmost kind in the at present pre-coating.Have the well balanced of snappiness and hardness through amino resin crosslinked paint film, and other good over-all properties.Coating is mainly formed through the esterification condensation by diprotic acid (comprising aromatic acid, aliphatic dibasic acid and alicyclic diprotic acid) and polyvalent alcohol (mainly being the pure and mild alicyclic dibasic alcohol of binary aliphatic) with vibrin.By selecting the kind of raw material acid and raw alcohol, can synthesize the different vibrin of performance, and then prepare and satisfy the coating that different use propertieies require.The Ministry of Chemical Industry's coatings industry institute and the Shanghai magnificent coating factory of shaking successfully develops and introduces pre-coated coil respectively with amino curing polyester finish paint in the eighties in last century.Along with the development of pre-coated coil industry, a lot of coating producer releases one after another multiple pre-coated coil with amino curing polyester finish paint.
Coating is coated on the metal sheet continuously through the high temperature rapid curing film forming, is one of production characteristics of precoating metal coiled material.The energy that high bake consumed occupies sizable ratio in the running cost of producing.Along with the fast development of China's pre-coated coil industry, the energy total amount that it consumed is also considerable in recent years.At present pre-coated coil with the condition of cure of amino curing polyester finish paint all 220～240 ℃ or higher/30～90 second.The pre-coated coil vibrin that a kind of condition of cure is 200～260 ℃/20～90 seconds a reduced solidification value is disclosed as China patent of invention CN1473898A, United States Patent (USP) 4140727 and 4229555 all is to solidify the linear polyester finish paint about pre-coated coil with amino, and condition of cure is 240～260 ℃/40 seconds.Paint film generally needs 224～241 ℃ of following baking-curings of roll bending temperature on the coil production line at present, and oven drying temperature is generally at 350～450 ℃, thereby a large amount of heat energy of needs, is example with 30 meters long electric ovens, and under 60 meters/minute of belt speed, per hour power consumption 1200 is spent.If can reduce the film curing temperature, then be significant saving the energy and reducing production costs.
Summary of the invention
Be to save the energy and reduce the pre-coated coil production cost, the purpose of this invention is to provide a kind of can be at 200～216 ℃ of substrate temperatures, the low-temperature solidified polyester surface paint for procoating metal coiled material of 30～60 seconds film-formings.
The technical solution adopted for the present invention to solve the technical problems is: a kind of low-temperature solidified polyester surface paint for procoating metal coiled material, high reactivity linear polyester resin by the tertiary carbonic acid glycidyl ester modification is that film-forming resin and aminoresin are solidifying agent, being equipped with pigment slurry, auxiliary agent, mixed solvent again makes, finished weight solid part 40%～80%, 23 ℃ are coated with 4 glasss of viscositys is 30～200 seconds, can be 200～216 ℃ of substrate temperatures, 30～60 seconds film-formings.
Further: in the described low-temperature solidified polyester surface paint for procoating metal coiled material finished product each component by weight hundred parts of content be respectively: through the high reactivity linear polyester resin 10%～50% of tertiary carbonic acid glycidyl ester modification, aminoresin 5%～20%, pigment slurry 20%～60%, auxiliary agent 0.1%～5.0%, all the other are mixed solvent.
Further: the high reactivity linear polyester resin of described tertiary carbonic acid glycidyl ester modification, it is the linear polyester resin that in the presence of catalyzer and thermo-stabilizer, makes by a kind of tertiary carbonic acid glycidyl ester, at least a dibasic alcohol and at least a aromatic acid and at least a aliphatic dibasic acid through esterification, its acid number is 0.1～10mgKOH/ gram, hydroxyl value 10～80mgKOH/ gram.
Further: described aminoresin is the urea-formaldehyde resin of methyl or methyl butyl etherificate or the terpolycyantoamino-formaldehyde resin of methyl or methyl butyl etherificate.
Further: described pigment slurry for through the high reactivity linear polyester resin of tertiary carbonic acid glycidyl ester modification and pigment by solid weight than 10: 1～1: 5, add less than the auxiliary agent of resin and total pigment weight 10% and mixed solvent and be dispersed to fineness≤15 micron through grinding, described pigment is mineral dye or pigment dyestuff, as titanium pigment, phthualocyanine pigment, chrome yellow series pigments, inorganic compounding pigment, carbon black pigment.
Further: described mixed solvent is made up of aromatic hydrocarbon solvent, ketones solvent, pure ether solvent, two esters solvents, and weight percentage aromatic hydrocarbon solvent 30%～80%, ketones solvent 0%～40%, pure ether solvent 0%～50%, two esters solvents 5%～40%.
Further: described auxiliary agent is high molecular polyurethane-modified acrylic acid class pigment dispersing agent, aerosil class anti-settling agent, polyacrylic ester defoamer, fluorine modified polyacrylate class flow agent, tosic acid class curing catalysts.
Further: described tertiary carbonic acid glycidyl ester is C
8-C
14Glycidyl ester; Described aliphatic dihydroxy alcohol is ethylene glycol, glycol ether, propylene glycol, methyl propanediol, neopentyl glycol, 2,2-methyl butyl neopentyl glycol; Described alicyclic dibasic alcohol is the cyclohexyl dimethanol; Described aromatic acid is Tetra hydro Phthalic anhydride, dimethyl terephthalate (DMT), phthalic acid, m-phthalic acid; Described aliphatic dibasic acid is hexanodioic acid, nonane diacid, sebacic acid; Described alicyclic diprotic acid is the cyclohexyl dioctyl phthalate.
Further: described aromatic hydrocarbon solvent is dimethylbenzene, S-100, S-150; Described ketones solvent is pimelinketone, mibk or diacetone alcohol; Described pure ether solvent is propylene glycol monomethyl ether, propylene glycol butyl ether or ethylene glycol ethyl ether amyl acetate; Described two esters solvents are diethyl oxalate, Ethanedioic acid, dipropyl ester, ethylene sebacate or its combination, dimethyl succinate, Methyl glutarate, dimethyl adipate or its combination.
The preparation method of above-mentioned low-temperature solidified polyester surface paint for procoating metal coiled material has following processing step:
A. the high reactivity linear polyester resin of tertiary carbonic acid glycidyl ester modification is synthetic,
Tertiary carbonic acid glycidyl ester with weight percentage 10-30%, the m-phthalic acid of 20-50%, the hexanodioic acid of 5-15%, the methyl propanediol of 25-40%, the organotin catalysts of 0.03-0.05%, triphenyl phosphite stablizer and the refluxing xylene solvent of 0.05-0.08% are put in the reaction kettle of the esterification, filling material in the vertical tube jacket condensator of this device, thermometer is equipped with at the top, under protection of inert gas, slowly be warmed up to 210 ℃～220 ℃, under this temperature, continue reaction then, controlling the vertical tube condenser overhead simultaneously steams the thing temperature and is no more than 101 ℃, steam the thing temperature until the top and reduce to 80 ℃, and reactant becomes limpid and acid number is reduced to 0.1～10mgKOH/ gram, cooling, add the latting drown mixed solvent, filter discharging;
B. pigment slurry preparation,
The high reactivity linear polyester resin of the tertiary carbonic acid glycidyl ester modification of weight percentage 20-60%, the pigment of 30-65%, the dispersing auxiliary of 0.5-2%, the mixed solvent of 5-10% are dropped into premix in the premix cylinder, again premix slurry is dispersed to fineness≤15 micron through grinding plant, filters discharging;
C. low-temperature curing polyester finish coat preparation,
Hundred parts of content are respectively by weight: 10%～50% the high reactivity linear polyester resin through the tertiary carbonic acid glycidyl ester modification, 5%～20% aminoresin, 20%～60% pigment slurry, 0.1%～5.0% auxiliary agent, mixed solvent surplus thorough mixing in paint mixing tank is even, discharging, packing.
The invention has the beneficial effects as follows, low-temperature solidified polyester surface paint for procoating metal coiled material of the present invention, satisfy under the prerequisite of the every technical indicator of coil in assurance, can make the substrate temperature (PMT) of film curing reduce about 25 ℃, 50～80 ℃ of the corresponding reductions of drying tunnel temperature.Reduce energy consumption, reduced the production cost of pre-coated coil, had good economic benefits and social benefit.
Embodiment
A kind of low-temperature solidified polyester surface paint for procoating metal coiled material, by high reactivity linear polyester resin 10%～50% and aminoresin 5%～20% through the tertiary carbonic acid glycidyl ester modification is solidifying agent, being equipped with pigment slurry 20%～60%, auxiliary agent 0.1%～5.0%, mixed solvent surplus again makes, finished weight solid part 40%～80%, 23 ℃ are coated with 4 glasss of viscositys is 30～200 seconds, can be 200～216 ℃ of substrate temperatures, 30～60 seconds film-formings.
Described high reactivity lienar for vibrin through the tertiary carbonic acid glycidyl ester modification, it is the linear polyester resin that in the presence of catalyzer and thermo-stabilizer, makes by a kind of tertiary carbonic acid glycidyl ester, at least a dibasic alcohol and at least a aromatic acid and at least a aliphatic dibasic acid through esterification, its acid number is 0.1～10mgKOH/ gram, hydroxyl value 10～80mgKOH/ gram.
Described aminoresin is the urea-formaldehyde resin of methyl or methyl butyl etherificate or the terpolycyantoamino-formaldehyde resin of methyl or methyl butyl etherificate.
Described pigment slurry be the tertiary carbonic acid glycidyl ester modification high reactivity lienar for vibrin and pigment by solid weight than 10: 1～1: 5, add less than the auxiliary agent of resin and total pigment weight 10% and mixed solvent and be dispersed to fineness≤15 micron through grinding, described pigment is mineral dye or pigment dyestuff, as titanium pigment, phthualocyanine pigment, chrome yellow series pigments, inorganic compounding pigment, carbon black pigment.
Described mixed solvent is made up of aromatic hydrocarbon solvent, ketones solvent, pure ether solvent, two esters solvents, and weight percentage aromatic hydrocarbon solvent 30%～80%, ketones solvent 0%～40%, pure ether solvent 0%～50%, two esters solvents 5%～40%.
Described auxiliary agent is high molecular polyurethane-modified acrylic acid class pigment dispersing agent, aerosil class anti-settling agent, polyacrylic ester defoamer, fluorine modified polyacrylate class flow agent, tosic acid class curing catalysts.
Described tertiary carbonic acid glycidyl ester is C
8-C
14Glycidyl ester; Described aliphatic dihydroxy alcohol is ethylene glycol, glycol ether, propylene glycol, methyl propanediol, neopentyl glycol, 2,2-methyl butyl neopentyl glycol; Described alicyclic dibasic alcohol is the cyclohexyl dimethanol; Described aromatic acid is Tetra hydro Phthalic anhydride, dimethyl terephthalate (DMT), phthalic acid, m-phthalic acid; Described aliphatic dibasic acid is hexanodioic acid, nonane diacid, sebacic acid; Described alicyclic diprotic acid is the cyclohexyl dioctyl phthalate.
Described aromatic hydrocarbon solvent is dimethylbenzene, S-100, S-150; Described ketones solvent is pimelinketone, mibk or diacetone alcohol; Described pure ether solvent is propylene glycol monomethyl ether, propylene glycol butyl ether or ethylene glycol ethyl ether amyl acetate; Described two esters solvents are diethyl oxalate, Ethanedioic acid, dipropyl ester, ethylene sebacate or its combination, dimethyl succinate, Methyl glutarate, dimethyl adipate or its combination.
A kind of preparation method of low-temperature solidified polyester surface paint for procoating metal coiled material has following processing step:
A. the high reactivity linear polyester resin of tertiary carbonic acid glycidyl ester modification is synthetic,
With 97.7 weight part tertiary carbonic acid glycidyl esters, 252.0 weight part m-phthalic acid, 73.9 weight part hexanodioic acid, 154.3 weight part methyl propanediol, 0.3 weight part organotin esterifying catalyst, 0.5 weight part triphenyl phosphite thermo-stabilizer and 25.0 weight part refluxing xylene solvents are put into thermometer are housed, agitator, the vertical tube condenser of thermometer band filler and chuck is equipped with at the top, in the reactor of condensation reflux unit, under protection of inert gas, slowly be warmed up to 210 ℃～220 ℃, under this temperature, continue reaction then, controlling the vertical tube condenser overhead simultaneously steams the thing temperature and is no more than 101 ℃, steam the thing temperature until the top and reduce to 80 ℃, and reactant becomes limpid and acid number is reduced to processing requirement, be cooled to 110 ℃, add 336.6 weight part latting drown mixed solvents, filter discharging, obtain the weight solids content and be 60% polyester resin solution;
B. pigment slurry preparation,
The high reactivity linear polyester resin of the above-mentioned tertiary carbonic acid glycidyl ester modification of 100.0 weight parts, the titanium white powder pigment of 120.0 weight parts, the dispersing auxiliary of 3.0 weight parts, the mixed solvent of 20.0 weight parts are dropped into premix in the premix cylinder, again premix slurry is dispersed to fineness≤15 micron through grinding plant, filter discharging, pigment slurry solid part is 75%;
C. low-temperature curing polyester finish coat preparation,
With the above-mentioned mill base of 100 weight parts, the high reactivity linear polyester resin through the tertiary carbonic acid glycidyl ester modification of 25.0 weight parts, the aminoresin of 10.2 weight parts, 1.6 the tosic acid class catalyzer of weight part, 1.0 the flow agent of weight part, the defoamer of 0.2 weight part, the mixed solvent of 4.8 weight parts joins in the paint mixing tank respectively, thorough mixing is even, filter, packing makes low-temperature solidified polyester surface paint for procoating metal coiled material, its solid part is 70%, 23 ℃, and to be coated with 4 glasss of viscositys be 95 seconds.
D. low-temperature curing polyester finish coat service check
Scribbling on the galvanized sheet of epoxy primer, with the low-temperature curing polyester finish coat among No. 60 coiling scraper coating embodiment, 260 ℃ of oven temperatures, storing time 30 seconds, 204 ℃ of substrate temperatures (PMT).The gained coating dry film is thick to be 25 microns, and the visual inspection flat appearance is smooth.Pressing national standard method detects.T is curved: 2T; Impact: 100cm, pencil hardness 2H, cupping: 6.5mm; Anti-MEK wiping: 〉=100 times.
The result shows that this low-temperature curing polyester finish coat can solidify under lower substrate temperature, performance satisfies the requirement of precoating metal coiled material with polyester finish coat fully.
Claims (10)
1, a kind of low-temperature solidified polyester surface paint for procoating metal coiled material, it is characterized in that: the high reactivity linear polyester resin by the tertiary carbonic acid glycidyl ester modification is a film-forming resin, aminoresin is solidifying agent, being equipped with pigment slurry, auxiliary agent, mixed solvent again makes, finished weight solid part 40%～80%, 23 ℃ are coated with 4 glasss of viscositys is 30～200 seconds, can be 200～216 ℃ of substrate temperatures, and 30～60 seconds film-formings; Described high reactivity linear polyester resin through the tertiary carbonic acid glycidyl ester modification, it is the linear polyesters resin that in the presence of catalyzer and thermo-stabilizer, makes by a kind of tertiary carbonic acid glycidyl ester, at least a dibasic alcohol and at least a aromatic acid and at least a aliphatic dibasic acid through esterification, its acid number is 0.1～10mgKOH/ gram, and hydroxyl value is 10～80mgKOH/ gram.
2, low-temperature solidified polyester surface paint for procoating metal coiled material according to claim 1, it is characterized in that: hundred parts of content of each constituent mass are for to be respectively in the finished product: through the high reactivity linear polyester resin 10%～50% of tertiary carbonic acid glycidyl ester modification, aminoresin 5%～20%, pigment slurry 20%～60%, auxiliary agent 0.1%～5.0%, all the other are mixed solvent.
3, low-temperature solidified polyester surface paint for procoating metal coiled material according to claim 1 is characterized in that: described aminoresin is the urea-formaldehyde resin of methyl or methyl butyl etherificate, or the terpolycyantoamino-formaldehyde resin of methyl or methyl butyl etherificate.
4, low-temperature solidified polyester surface paint for procoating metal coiled material according to claim 1, it is characterized in that: described pigment slurry for through the high reactivity linear polyester resin of tertiary carbonic acid glycidyl ester modification and pigment by solid weight than 10: 1～1: 5, add less than the auxiliary agent of resin and total pigment weight 10% and mixed solvent and be dispersed to fineness≤15 micron through grinding, described pigment is mineral dye or pigment dyestuff.
5, low-temperature solidified polyester surface paint for procoating metal coiled material according to claim 4 is characterized in that: described mineral dye or pigment dyestuff are titanium pigment, phthualocyanine pigment, chrome yellow series pigments, inorganic compounding pigment, carbon black pigment.
6, low-temperature solidified polyester surface paint for procoating metal coiled material according to claim 1, it is characterized in that: described mixture is made up of aromatic hydrocarbon solvent, ketones solvent, pure ether solvent, two esters solvents, and quality percentage composition aromatic hydrocarbon solvent 30%～80%, ketones solvent 0%～40%, pure ether solvent 0%～50%, two esters solvents 5%～40%.
7, low-temperature solidified polyester surface paint for procoating metal coiled material according to claim 1 is characterized in that: described to help the machine agent be polyurethane-modified acrylic acid class pigment dispersing agent, aerosil class anti-settling agent, polyacrylic ester defoamer, fluorine modified polyacrylate class flow agent, tosic acid class curing catalysts.
8, low-temperature solidified polyester surface paint for procoating metal coiled material according to claim 1 is characterized in that: described tertiary carbonic acid glycidyl ester is C
8-C
14Glycidyl ester; Described aliphatic dihydroxy alcohol is ethylene glycol, glycol ether, propylene glycol, 2-methyl propanediol, neopentyl glycol, 2,2-methyl butyl neopentyl glycol; Described alicyclic dibasic alcohol is the cyclohexyl dimethanol; Described aromatic acid is Tetra hydro Phthalic anhydride, dimethyl terephthalate (DMT), phthalic acid, m-phthalic acid; Described aliphatic dibasic acid is hexanodioic acid, nonane diacid, sebacic acid; Described alicyclic diprotic acid is the cyclohexyl dioctyl phthalate.
9, low-temperature solidified polyester surface paint for procoating metal coiled material according to claim 6 is characterized in that: described aromatic hydrocarbon solvent is dimethylbenzene, S-100, S-150; Described ketones solvent is pimelinketone, mibk or diacetone alcohol; Described pure ether solvent is propylene glycol monomethyl ether, propylene glycol butyl ether or ethylene glycol ether acetate; Described two esters solvents are oxalic acid second diester, ethylene sebacate or its combination, dimethyl succinate, Methyl glutarate, dimethyl adipate or its combination.
10, a kind of preparation method of low-temperature solidified polyester surface paint for procoating metal coiled material is characterized in that having following processing step:
A. the high reactivity linear polyester resin of tertiary carbonic acid glycidyl ester modification is synthetic,
The tertiary carbonic acid glycidyl ester of weight percentage 10-30%, the m-phthalic acid of 20-50%, the hexanodioic acid of 5-15%, the methyl propanediol of 25-40%, the organotin catalysts of 0.03-0.05%, triphenyl phosphite stablizer and the refluxing xylene solvent of 0.05-0.08% are put in the reaction kettle of the esterification; filling material in the vertical tube folder condenser of this device; the temperature agent is equipped with at the top, slowly is warmed up to 210 ℃～220 ℃ under protection of inert gas.Under this temperature, continue reaction then, control the vertical tube condenser overhead simultaneously and steam the thing temperature and be no more than 101 ℃, steam the thing temperature until the top and reduce to 80 ℃, and reactant becomes limpid and acid number is reduced to 0.1～10mgKOH/ gram, and cooling adds the latting drown mixed solvent, filter discharging;
B. the preparation of pigment slurry,
The high reactivity linear polyester resin of the tertiary carbonic acid glycidyl ester modification of weight percentage 20-60%, the pigment of 30-65%, the dispersing auxiliary of 0.5-2%, the mixed solvent of 5-10% are dropped into premix in the premix cylinder, again premix slurry is dispersed to fineness≤15 micron through grinding plant, filters discharging;
C. low-temperature curing polyester finish coat preparation,
Percentage composition is respectively by weight: the high reactivity linear polyester resin through the tertiary carbonic acid glycidyl ester modification of 10%-50%, 5%～20% aminoresin, 20%～60% pigment slurry, 0.1%～5.0% auxiliary agent, mixed solvent surplus thorough mixing in paint mixing tank is even, discharging, packing.
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| CN106009821A (en) * | 2016-06-23 | 2016-10-12 | 广西柳州鱼峰制漆股份有限公司 | Acrylic-modified polyester resin varnish for coating of light industrial products |
| CN106009822A (en) * | 2016-06-23 | 2016-10-12 | 广西柳州鱼峰制漆股份有限公司 | Acrylic-modified polyester resin varnish for coating of light industrial products |
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