CN101386673B - Oil modified epoxy resins and precoating coiled material coatings containing above resins - Google Patents
Oil modified epoxy resins and precoating coiled material coatings containing above resins Download PDFInfo
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- CN101386673B CN101386673B CN 200810222985 CN200810222985A CN101386673B CN 101386673 B CN101386673 B CN 101386673B CN 200810222985 CN200810222985 CN 200810222985 CN 200810222985 A CN200810222985 A CN 200810222985A CN 101386673 B CN101386673 B CN 101386673B
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Abstract
The invention relates to an oil modified epoxy resin and precoating coiled material paint containing the oil modified epoxy resin. The resin is an esterification type epoxy resin which is formed through the following steps: oil and binary acid react to generate an acidolysis product; and the acidolysis product has an addition esterification reaction with an epoxy group of the epoxy resin to form the esterification type epoxy resin. The mol ratio of the oil to the binary acid is between 1 to 0.5 and 1.5; and the mol ratio of the carboxyl in the acidolysis product to the epoxy group in the epoxy resin is between 1 to 1 and 3. The precoating coiled material paint consists of 20 to 35 percent of a resin compound in solid form, 20 to 35 percent of pigment and filler, 0.5 to 5 percent of additive, and 25 to 50 percent of a solvent, wherein the resin compound consists of 30 to 90 percent of the oil modified epoxy resin, and 10 to 70 percent of a crosslinking resin (the percentage is counted as the solid weight of the resins). The precoating coiled material paint can be adapted to the requirements of coiled material painting construction and performance. The dosage of the epoxy resin and the paint cost are reduced, while the performance of the paint film is equivalent to that of the prior epoxy resin precoating coiled material paint.
Description
Technical field
The present invention relates to a kind of oily modified epoxy and contain the precoated coil coating of this resin.
Background technology
Precoated coil coating is a class coating that develops rapidly in recent years, and it can for example be coated in various coiled materials in advance: surfaces such as cold-rolled steel sheet, steel plate galvanized, aluminium, zinc-plated aluminium sheet and aluminium plating zinc plate make pre-coated coil.Because it is very convenient that pre-coated coil uses, therefore, market demand is very big.But, increasing along with the fast development of world economy to the demand of oil, and oil is a kind of Nonrenewable resources, unbalanced supply-demand has become the major cause that oil price rapidly goes up.Because many raw material sources of coatings industry are in petroleum products, so coating also goes up fast with raw-material price, thereby causes the profit of coating products to reduce greatly thereupon.Therefore, seek the substitute of petroleum products raw material, reduce coating has become coating industry to the dependence of petroleum products the task of top priority.Traditional epoxy resin precoated coil coating is badly in need of surrogate, and one of its approach is with oily modified epoxy instead of part Resins, epoxy, reaches the purpose that reduces content of epoxy resin.CN101007921A discloses a kind of anticorrosive coating that is used for chimney of electric plant, it has related to tung oil-modified Resins, epoxy, a kind of aluminium hydraulic pressed connecting pipe connection epoxy resin sealant is disclosed among the CN1706905A, related to cashew nut oil modified Resins, epoxy, but these two kinds of coating are two-component coating and can not satisfy the Influencing Performance of Coil Coatings requirement; A kind of epoxy ester resin of improvement is disclosed among the CN1563135A, relate in particular to a kind of with cis-butenedioic anhydride vegetables oil, the resin modified epoxy ester resin of apple anhydride dehydration and preparation method, but the resin solidification of this coating is to utilize two key oxidation dryings, can not be fit to the construction requirement of pre-coated coil application; The preparation method of a kind of stillingia oil toughening agent for epoxy resin and modified epoxy thereof is disclosed among the CN1058604A, its Chinese catalpa oil ring epoxy resins replaces a part of Resins, epoxy as toughner and is used for molding for epoxy resin processing, does not relate to the application in precoated coil coating; Traditional epoxy ester resin is exactly a kind of esterification type Resins, epoxy, and still, it is the reaction product of lipid acid and Resins, epoxy, and through prepared such as acidifying, neutralization, washings, technology is loaded down with trivial details, the cost height by oils for wherein used lipid acid.
Summary of the invention
First purpose of the present invention is: the oily modified epoxy that a kind of cost is low, be fit to the precoated coil coating use is provided.
The technical scheme that realizes first purpose of the present invention is: a kind of oily modified epoxy, its characteristics are, it is the acidolysis thing that generates with oil and diprotic acid reaction and the esterification type Resins, epoxy of the epoxy group(ing) addition esterification formation of Resins, epoxy, the mol ratio of used oil and diprotic acid is 1:0.5～1.5, and the mol ratio of the epoxide group that carboxyl that used acidolysis thing contains and used Resins, epoxy contain is 1:1～3.
Above-mentioned oily modified epoxy, its oil is 260～280 ℃ with the temperature of reaction of diprotic acid; The temperature of the epoxy group(ing) addition esterification of its acidolysis thing and Resins, epoxy is 140～160 ℃.
Above-mentioned oily modified epoxy, its oil is 1:0.7～1.0 with the mol ratio of diprotic acid, the mol ratio of the epoxide group that carboxyl that the acidolysis thing contains and Resins, epoxy contain is 1:1.5～2.5.The diprotic acid consumption is too low, and oleic acid is separated not exclusively, influences the transparency of follow-up acid hydrolysate and Resins, epoxy reaction gained resin; The diprotic acid consumption is too high, and acid can not complete reaction and is residual, so can not obtain uniform acid hydrolysate.The acid hydrolysate consumption is too high, hardness and the wiping properties of anti-MEK that influence is finally filmed; The acid hydrolysate consumption is too low, does not then have the modifying function to Resins, epoxy.
Above-mentioned oily modified epoxy, described oil are coating with semi-drying oil or nondrying oil, and the typical example of its semi-drying oil has soya-bean oil, Trisun Oil R 80, oleum gossypii seminis, tallol etc.; The typical example of nondrying oil has Viscotrol C, Oleum Cocois, rice bran wet goods.Described diprotic acid is coating aromatic acid, aliphatic dibasic acid or an alicyclic diprotic acid, preferred aliphat diprotic acid or alicyclic diprotic acid, the typical example of its aromatic acid has phthalic anhydride, tetrahydrophthalic anhydride, HHPA, m-phthalic acid, terephthalic acid etc.; The typical example of its aliphatic dibasic acid has propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid, dodecyl diacid etc.; The typical example of its alicyclic diprotic acid has 1,3-cyclohexane cyclohexanedimethanodibasic, 1,4 cyclohexanedicarboxylic acid etc.Described Resins, epoxy is that epoxy equivalent (weight) that precoated coil coating is used is 200～4000 bisphenol-type epoxy resin, for example: the domestic standard model be E-03, E-06, E-12, E-14, E-20, E-31, E-35, E-44 Resins, epoxy and with the corresponding various imported products of above-mentioned standard model, wherein, the home made article typical example has CYD-134, CYD-011, CYD-001, CYD-014, CYD-017, the CYD-019 etc. of Yueyang general petrochemicals factory; The imported product typical example has EPON828, EPON1001, EPON1004, EPON1007, EPON1009 of Shell Co. Ltd etc.
Second purpose of the present invention is: a kind of precoated coil coating that contains above-mentioned oily modified epoxy is provided, and low and coating property of cost and traditional epoxy resin precoated coil coating are suitable.
The technical scheme that realizes second purpose of the present invention is: a kind of characteristics that contain the precoated coil coating of above-mentioned oily modified epoxy are: each component and weight percentage thereof are as follows:
Resin combination is in solid: 20%～35%; Auxiliary agent: 0.5～5%;
Pigment and filler: 20～35%; Solvent: 25～50%;
Described resin combination is made up of above-mentioned oily modified epoxy 30%～90% and cross-linked resin 10%～70%, and described percentage number average is with the solid weight meter of resin.
The precoated coil coating of above-mentioned oil-containing modified epoxy, in its resin combination: cross-linked resin is one or both in aminoresin, the blocked polyisocyanates resin.The typical example of its aminoresin has: CYMEL303, CYMEL300, the CYMEL325 of the special company of cyanogen; Resimene-747, the Resimene-717 etc. of head promise company; The typical example of its blocked polyisocyanates resin has: the BL3175 of Beyer Co., Ltd; BI7960, the BI7982 etc. of Baxenden Chemicals Limited; BIN-10, the BIN-7 that Jiangsu Hongye Coating Science and Technology Industry Co., Ltd. produces, HY-C-01 closure, CX resin etc.
The precoated coil coating of above-mentioned oil-containing modified epoxy, its described pigment is corrosion-inhibiting pigment and/or tinting pigment, described filler is anti-heavy filler.Wherein, the typical example of tinting pigment has carbon black, titanium dioxide, iron oxide red, iron oxide yellow etc.; The typical example of corrosion-inhibiting pigment has strontium yellow, zinc yellow, zinc phosphate, zinc oxide, aluminium triphosphate or some novel protection against corrosion color stuffings (typical example is the Shieldex303 of W. R. Grace ﹠ Co) etc.; The typical example of anti-heavy filler has organobentonite (for example MP250), aerosil (for example R-972) etc.
The precoated coil coating of above-mentioned oil-containing modified epoxy, its described auxiliary agent be in dispersion agent, defoamer, flow agent, adhesion promoter, the curing catalysts any one or several arbitrarily.
The precoated coil coating of above-mentioned oil-containing modified epoxy, its described solvent be in dimethylbenzene, cyclohexanone, N-BUTYL ACETATE, S-1000, ethylene glycol ether acetate, 1-Methoxy-2-propyl acetate, DBE, methyl iso-butyl ketone (MIBK), the butyl glycol ether any one or several arbitrarily.
The preparation of the present invention's oil modified epoxy can adopt Synolac to use synthesis device always, and the coating preparation that contains this resin can be adopted coating production technique commonly used and equipment.Coating of the present invention is applicable to various coiled materials, for example cold-rolled steel sheet, steel plate galvanized, aluminium, zinc-plated aluminium sheet and aluminium plating zinc plate etc.
Technique effect of the present invention is: the oily modified epoxy of technical solution of the present invention is a kind of esterification type Resins, epoxy that directly adopts oils rather than adopt the fatty acid modification, therefore, saved the operation of technologies such as oils acidifying, neutralization, washing being made lipid acid, cost is low, do not have in the reaction process by product and suitable precoated coil coating to use; Adopt the precoated coil coating that contains the present invention's oil modified epoxy of technical solution of the present invention, because oily modified epoxy of the present invention can satisfy pre-coated coil application condition, and each component of coating cooperates appropriate, therefore, can replace parts of traditional Resins, epoxy with the Resins, epoxy of this renewable resources modification of natural oils, both reduced content of epoxy resin, reduced the coating cost, and during as the front priming paint of pre-coated coil and back side lacquer, its performance and traditional epoxy resin precoated coil coating are suitable.
Embodiment
Below in conjunction with embodiment the present invention is further described in detail, but is not limited to this.
The used raw material of embodiment and comparative example all can be buied by commercial sources.
The oily modified epoxy of embodiment 1 preparation
The first step synthetic acidolysis thing EAA-1, EAA-2 and EAA-3
With oil and diprotic acid is that raw material carries out acidolysis reaction formation acidolysis thing, and this acid hydrolysate is the mixture of monocarboxylic acid, di-carboxylic acid and tribasic carboxylic acid, but based on monocarboxylic acid, forms monocarboxylic reaction formula schematically as follows:
1, prescription and significant parameter see Table 1
Table 1
| Material name | Raw material specification | Consumption EAA-1 | Consumption EAA-2 | Consumption EAA-3 | |
| Oil | Soya-bean oil | Industrial goods, two floating | 90.93 | 88.26 | 85.74 |
| Diprotic acid | Hexanodioic acid | Industrial goods, 〉=99.5% | 9.07 | 11.74 | 14.26 |
| Significant parameter: oil/diprotic acid mol ratio acidolysis thing acid number (mgKOH/g) acidolysis thing is calculated equivalent (56100/ acid number) | 1/0.674.3?755 | 1/0.895.2?589.3 | 1/1 1144?490.4 |
2, synthesis technique
In the reaction vessel that agitator, thermometer, reflux exchanger, inert gas entrance are housed, press table 1 formula ratio and add soya-bean oil and hexanodioic acid, under protection of inert gas, slowly heat up and carry out acidolysis reaction: be warming up to 250 ℃ of reaction 30min with 1h, be warming up to 280 ℃ of reaction 3h again, the sampling observation is transparence and represents that acidolysis is qualified, be cooled to below 80 ℃, discharging promptly makes acidolysis thing EAA-1, EAA-2 and EAA-3 respectively, preserves standby;
The second step synthetic oil modified epoxy ME-1, ME-2, ME-3, ME-4 and ME-5
The epoxy group(ing) addition esterification of above-mentioned acidolysis thing EAA-1, EAA-2 and EAA-3 and Resins, epoxy is formed esterification type Resins, epoxy, its reaction formula schematically as follows:
1, prescription and significant parameter see Table 2
Table 2
| Material name | Raw material specification | Consumption ME-1 | Consumption ME-2 | Consumption ME-3 | Consumption ME-4 | Consumption ME-5 | |
| Resins, epoxy | CYD-014 EPON1009 | Epoxy equivalent (weight) 757.6 epoxy equivalent (weight)s 2700 | 83.77/ | 90.60/ | 130.00/ | / 123.15 | 125.66/ |
| Solvent | The dimethylbenzene pimelinketone | The industrial goods industrial goods | 50.0050.00 | 50.0050.00 | 67.5067.50 | 112.48112.48 | 50.0050.00 |
| The acidolysis thing | EAA-1～EAA-3 | The self-control of embodiment 1 the first step | 40.00 (EAA-3) | 30.28 (EAA-3) | 32.50 (EAA-2) | 26.85 (EAA-2) | 60.00 (EAA-1) |
| Catalyzer | Methylimidazole | Industrial goods | 0.12 | 0.12 | 0.18 | 0.16 | 0.18 |
| Resin parameter: carboxyl/epoxy group(ing) (mol ratio) resin solids (weight %) | 1/1.05 56.3 | 1/1.5 56.3 | 1/3 55.6 | 1/1 40.0 | 1/2 65.3 |
Annotate: CYD-014 is the intermediate molecular weight Resins, epoxy that Yueyang general petrochemicals factory produces;
EPON1009 is the high molecular expoxy resin that Shell Co. Ltd produces.
2, synthesis technique
In the reaction vessel that agitator, thermometer, reflux exchanger, inert gas entrance are housed, press table 2 formula ratio respectively and add Resins, epoxy, solvent xylene and pimelinketone, be warming up to 140 ℃ and be incubated to system transparent.Be cooled to below 120 ℃; add acidolysis thing and catalyzer methylimidazole; under protection of inert gas, slowly be warming up to 150 ℃ of about 3h of back flow reaction; sampling detecting acid number ≈ 0; be cooled to below 80 ℃; discharging promptly makes the present invention's oil modified epoxy ME-1, ME-2, ME-3, ME-4 and ME-5 respectively, preserves standby.
Embodiment 2 synthesizes traditional epoxy ester resin ME-6 (using for comparative example)
In the reaction vessel that stirring, thermometer, reflux exchanger, inert gas entrance are housed; add behenic acid 42.08g, CYD-014 Resins, epoxy 140.00g, dimethylbenzene and pimelinketone mixing solvent or diluent (1:1) 121.4g and catalyzer methylimidazole 0.20g; under protection of inert gas, slowly be warming up to 150 ℃ of about 3h of back flow reaction; sampling detecting acid number ≈ 0; be cooled to below 80 ℃, discharging promptly makes traditional epoxy ester resin ME-6; its resin solids 61.6 weight % preserve standby.
The precoated coil coating 1～5 of embodiment 3 preparation oil-containing modified epoxies
(1) coating 1～5 prescription sees Table 3
Table 3
| Coating composition | Material name | Raw material specification | Consumption, g coating 1 | Consumption, g coating 2 | Consumption, g coating 3 | Consumption, g coating 4 | Consumption, g coating 5 |
| Resin combination: oily modified epoxy cross-linking agent resin | ME-1～ME-5 HY-C-01 closure CX resin | Embodiment 1 self-control blocked isocyanate, solids constituent 50% sealing urethane, solids constituent 65% | 167.85(ME-1)81.00 / | 155.86(ME-2)/ 72.69 | 139.06(ME-3)66.27 / | 236.25(ME-4)81.00 / | 164.24(ME-5)115.5 / |
| Pigment and/or filler: | Zinc yellow strontium yellow titanium white talcum powder | Industrial goods industrial goods import industrial goods | 20.25 33.75 54.00 anatase titanium dioxides 27.00 | / 6.75 114.75 rutile-types 13.50 | 20.25 33.75 54.00 anatase titanium dioxides 27.00 | 20.25 33.75 54.00 anatase titanium dioxides 27.00 | 20.25 33.75 54.00 anatase titanium dioxides 27.00 |
| Auxiliary agent: dispersion agent flow agent | EFKA-4010 BYK-354 | Import, the product import of vapour crust EFKA company, German Bi Ke company product | 2.70 135? | 2.70 1.35 | 2.70 1.35 | 2.70 135? | 2.70 2.50 |
| Solvent | Dimethylbenzene/pimelinketone of mass ratio 1:1 | Industrial goods | 62.10 | 82.40 | 64.70 | 83.70 | 80.06 |
| The coating solids constituent, % | 60 | 60 | 60 | 50 | 60 |
Annotate 1:HY-C-01 closure and CX resin and be Jiangsu Hongye Coating Science and Technology Industry Co., Ltd.'s production;
Annotate 2: in the resin combination of coating 1～5, each resin demand is converted into solid by solids constituent and is calculated the weight percentage of each component (numerical value in the bracket) and lists in table 4 in the table 3;
Annotate 3: the weight percentage of each component of coating 1～5 is listed in table 5 in the table 3;
Table 4
| Component | Coating 1 | Coating 2 | Coating 3 | Coating 4 | Coating 5 |
| Resin combination (being converted into solid) by resin solids wherein, oily modified epoxy cross-linking agent resin | 135.00g 94.50g (70％) 40.50g(30％) | 135.00g 87.75g (65％) 47.25g(35％) | 110.45g 77.32g (70％) 33.14g(30％) | 135.00g 94.50g (70％) 40.50g(30％) | 165.00g 107.25g (65％) 57.75g(35％) |
Table 5
| Component | Coating 1 | Coating 2 | Coating 3 | Coating 4 | Coating 5 |
| Resin combination (being converted into solid) by resin solids | 135.00g(30％)? | 135.00g(30％)? | 110.45g(27％)? | 135.00g(25％)? | 165.00g(33％)? |
| Pigment and/or filler: | 135.00g(30％)? | 135.00g(30％)? | 135.00g(33％)? | 135.00g(25％)? | 135.00g(27％)? |
| Auxiliary agent | 4.05g (0.9％) | 4.05g (0.9％) | 4.05g (1.0％) | 4.05g (0.75％) | 5.20g (1.0％) |
| Solvent | 175.95g (39.10％) | 175.95g (39.10％) | 175.95g?(39.0％) | 265.95g (49.25％) | 175.95g?(39.0％) |
| Amount to | 450.00g | 450.00g | 409.08g | 540.00g | 500.00g |
Annotate: the solvent total amount of coating 1～5 comprises the solvent that adds in solvent that the resin solution of forming resin combination in the prescription is contained and the prescription in the table 5;
(2) preparation coating 1～5
1, takes by weighing each raw material respectively by formula ratio shown in the table 3;
2, get part embodiment 1 homemade oily modified epoxy, whole pigment and filler (titanium white, zinc yellow, strontium yellow, talcum powder), auxiliary agent (dispersion agent) and partial solvent by face/base than 3/1 (weight ratio) and put into clean beaker, after stirring with the high speed dispersion device, pour the laboratory into in the miniature sand mill, add an amount of zirconium pearl, grinding is distributed to scraper plate fineness≤20 μ m, discharging promptly obtains mill base 1 respectively
#～5
#, preserve standby; 3, in clean container, add mill base and remaining oily modified epoxy, linking agent HY-C-01 closure or CX resin, auxiliary agent (flow agent) BYK-354 and the residual solvent that makes, stir with the high speed dispersion device, obtain the precoated coil coating 1～5 of oil-containing modified epoxy of the present invention respectively.
Embodiment 4 preparation comparative example coating 1～4
(1) comparative example coating 1～4 adopts the ME-6 of embodiment 2 preparations, traditional epoxy resin precoated coil coating to make film forming matter with Resins, epoxy (CYD-014 Resins, epoxy, EPON1009 Resins, epoxy) and cross-linked resin respectively, and concrete prescription sees Table 6.
Table 6
| Component | Material name | Specification | Consumption, g comparative example coating 1 | Consumption, g comparative example coating 2 | Consumption, g comparative example coating 3 | Consumption, g comparative example coating 4 |
| The cross linking of epoxy resin resin | Epoxy ester resin ME-6 CYD-014 Resins, epoxy, commercially available product EPON1009 Resins, epoxy, commercially available product HY-C-01 closure CX resin | Embodiment 2 self-control solids constituent 61.6% solids constituent 60%, solids constituent 40%, blocked isocyanate, solids constituent 50% sealing urethane, solids constituent 65% | 153.41 / / 81.00 / | / 157.5 / 81.00 / | / / 236.25 81.00 / | / / 219.38 / 72.69? |
| Pigment and/or filler: | Zinc yellow strontium yellow titanium white | The import of industrial goods industrial goods | 20.25 33.75 54.00 anatase titanium dioxides | 20.25 33.75 54.00 anatase titanium dioxides | 20.25 33.75 54.00 anatase titanium dioxides | / 6.75 114.75 rutile-types |
| Talcum powder | Industrial goods | 27.00 | 27.00 | 27.00 | 13.50 | |
| Auxiliary agent: dispersion agent flow agent | EFKA-4010 BYK-354 | Import, the product import of vapour crust EFKA company, German Bi Ke company product | 2.70 1.35 | 2.70 1.35 | 2.70 1.35 | 2.70 1.35 |
| Solvent | Dimethylbenzene/pimelinketone of mass ratio 1:1 | Industrial goods | 76.54 | 72.45 | 83.7 | 108.88 |
| The coating solids constituent, % | 60 | 60 | 50 | 50 |
Annotate: the Resins, epoxy commercially available prod CYD-014 Resins, epoxy and the EPON1009 Resins, epoxy that relate in table 6 prescription are solid form, during use, are prepared into the epoxy resin solution of described solid content with dimethylbenzene/cyclohexanone solvent of mass ratio 1:1.
(2) preparation comparative example coating 1～4
1, takes by weighing each raw material respectively by formula ratio shown in the table 6;
2, get part embodiment 2 homemade traditional epoxy ester resin ME-6 by face/base than 3/1 (weight ratio) or traditional epoxy resin precoated coil coating is put into clean beaker with Resins, epoxy (CYD-014 Resins, epoxy, EPON1009 Resins, epoxy), whole pigment and filler (titanium white, zinc yellow, strontium yellow, talcum powder), auxiliary agent (dispersion agent) and partial solvent, after stirring with the high speed dispersion device, pour the laboratory into in the miniature sand mill, add an amount of zirconium pearl, grinding is distributed to scraper plate fineness≤20 μ m, discharging promptly obtains comparative example mill base 1 respectively
#～4
#, preserve standby;
3, in clean container, add mill base and remaining epoxy ester resin ME-6 or traditional epoxy resin precoated coil coating Resins, epoxy (CYD-014 Resins, epoxy, EPON1009 Resins, epoxy), HY-C-01 closure or CX resin, auxiliary agent (flow agent) BYK-354 and the residual solvent that makes, stir with the high speed dispersion device, obtain containing the pre-coated coil comparative example coating 1～4 of epoxy ester resin ME-6 or CYD-014 Resins, epoxy or EPON1009 Resins, epoxy respectively.
Embodiment 5 preparations apply the model of front priming paint
Processing condition
The Huangshi galvanized sheet of 10cm * 6cm * 0.4mm after cleaning, is handled with the chromium treatment solution; After 120 ℃ of baking 30s dryings, take out, with 7
#The line rod precoated coil coating 1,3,4,5 and the comparative example coating 1～3 of blade coating oil-containing modified epoxy of the present invention is respectively made priming paint, and is by following baking condition baking, surperficial with 17 at each priming paint
#The line rod is scraped overpainting (the sea blue and lime finish paint of the HY-C-02 that all supporting use Jiangsu achievements of a ruler paint company is produced in this test) again, and oven dry obtains using model for detecting, and preserves standby; Baking condition-furnace temperature: 330 ℃; Storing time: 28～29s; Plate temperature: 224～232 ℃.
Model build: priming paint 3～4 μ m+ finish paints 9～11 μ m.
The model of embodiment 6 preparation coated back surface lacquers
Processing condition
The Huangshi galvanized sheet of 0cm * 6cm * 0.4mm after cleaning, is handled with the chromium treatment solution; After 120 ℃ of baking 30s dryings, take out, with 13
#The line rod precoated coil coating 2 and the comparative example coating 4 of blade coating oil-containing modified epoxy of the present invention is respectively made back side lacquer, by following baking condition baking, obtains using model for detecting, and preserves standby;
Baking condition-furnace temperature: 330 ℃; Storing time: 28～29s; Plate temperature: 224～232 ℃.
Model build: 5～7 μ m.
The check of embodiment 7 film performances
Testing above-mentioned model film performance by the GB method of inspection comprises: outward appearance, build, pencil hardness, sticking power, T are curved, anti-MEK wiping (back and forth, inferior) and salt fog performance etc.The result is as shown in table 7.
Table 7
The detected result of table 7 shows, the present invention is by introducing the oily modified epoxy that this renewable resources of natural fats and oils obtains, be used to prepare precoated coil coating and can adapt to coil painting construction and performance requriements, reduced content of epoxy resin, reduced the coating cost, and film performance and not second to traditional epoxy resin precoated coil coating.
Claims (9)
1. oily modified epoxy, it is characterized in that, it is the acidolysis thing that generates with oil and diprotic acid reaction and the esterification type Resins, epoxy of the epoxy group(ing) addition esterification formation of Resins, epoxy, the mol ratio of used oil and diprotic acid is 1: 0.5～1.5, and the mol ratio of the epoxide group that carboxyl that used acidolysis thing contains and used Resins, epoxy contain is 1: 1～3;
Described oil is coating with semi-drying oil or nondrying oil.
2. oily modified epoxy according to claim 1 is characterized in that, the temperature of reaction of described oil and diprotic acid is 260～280 ℃; The temperature of the epoxy group(ing) addition esterification of described acidolysis thing and Resins, epoxy is 140～160 ℃.
3. oily modified epoxy according to claim 1 is characterized in that, the mol ratio of described oil and diprotic acid is 1: 0.7～1.0, and the mol ratio of the epoxide group that carboxyl that the acidolysis thing contains and Resins, epoxy contain is 1: 1.5～2.5.
4. oily modified epoxy according to claim 1 and 2 is characterized in that, described diprotic acid is coating aromatic acid, aliphatic dibasic acid or an alicyclic diprotic acid; Described Resins, epoxy is that epoxy equivalent (weight) that precoated coil coating is used is 200～4000 bisphenol-type epoxy resin.
5. a precoated coil coating that contains the described oily modified epoxy of claim 1 is characterized in that, its each component and weight percentage thereof are as follows:
Resin combination is in solid: 20%～35%; Auxiliary agent: 0.5～5%;
Pigment and filler: 20～35%; Solvent: 25～50%;
Described resin combination is made up of described oily modified epoxy 30%～90% of claim 1 and cross-linked resin 10%～70%, and described percentage number average is with the solid weight meter of resin.
6. the precoated coil coating of oil-containing modified epoxy according to claim 5 is characterized in that, in the described resin combination: cross-linked resin is one or both in aminoresin, the blocked polyisocyanates resin.
7. the precoated coil coating of oil-containing modified epoxy according to claim 5 is characterized in that described pigment is corrosion-inhibiting pigment and/or tinting pigment, and described filler is anti-heavy filler.
8. the precoated coil coating of oil-containing modified epoxy according to claim 5 is characterized in that, described auxiliary agent be in dispersion agent, defoamer, flow agent, adhesion promoter, the curing catalysts any one or several arbitrarily.
9. the precoated coil coating of oil-containing modified epoxy according to claim 5, it is characterized in that, described solvent be in dimethylbenzene, pimelinketone, N-BUTYL ACETATE, S-1000, ethylene glycol ether acetate, 1-Methoxy-2-propyl acetate, DBE, methyl iso-butyl ketone (MIBK), the butyl glycol ether any one or several arbitrarily.
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| CN101885831B (en) * | 2010-07-14 | 2012-01-25 | 中国海洋石油总公司 | Preparation method of polyester modified epoxy resin for household electroplate primer |
| CN103436139B (en) * | 2013-08-14 | 2016-05-25 | 中华制漆（深圳）有限公司 | Acidproof food cans inner-wall paint of anti-sulphur and preparation method thereof |
| CN104293091A (en) * | 2014-09-16 | 2015-01-21 | 天长市银狐漆业有限公司 | Flame-retardant insulating paint capable of increasing hardness of paint film and preparation method thereof |
| CN105153793B (en) * | 2015-07-06 | 2017-03-01 | 深圳市容大感光科技股份有限公司 | Resin combination ink, its purposes and use its wiring board |
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| CN1043338A (en) * | 1988-12-10 | 1990-06-27 | 郑发纲 | The method for preparing epoxy derivative of fatty acid |
| CN1122145A (en) * | 1993-03-30 | 1996-05-08 | 国际壳牌研究有限公司 | Epoxidized vegetable oil modification of epoxy esters |
| CN1307606A (en) * | 1998-06-26 | 2001-08-08 | 范蒂科股份公司 | Heat-curable can-coating lacquer |
| US6509417B1 (en) * | 2000-10-31 | 2003-01-21 | Lilly Industries, Inc. | Coating of fatty acid-modified glycidyl copolymer, OH polymer and optional anhydride polymer |
| CN1603352A (en) * | 2002-12-07 | 2005-04-06 | 株洲市九华新材料涂装实业有限公司 | Epoxy modified unsaturated polyester resin special for putty and method for making same |
| CN1621430A (en) * | 2004-10-18 | 2005-06-01 | 常州市柏鹤涂料有限公司 | Modified dry oil alkyd resin for protective paint for metal coating on the back of the mirror and the curtain coating paint |
-
2008
- 2008-09-25 CN CN 200810222985 patent/CN101386673B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043338A (en) * | 1988-12-10 | 1990-06-27 | 郑发纲 | The method for preparing epoxy derivative of fatty acid |
| CN1122145A (en) * | 1993-03-30 | 1996-05-08 | 国际壳牌研究有限公司 | Epoxidized vegetable oil modification of epoxy esters |
| CN1307606A (en) * | 1998-06-26 | 2001-08-08 | 范蒂科股份公司 | Heat-curable can-coating lacquer |
| US6509417B1 (en) * | 2000-10-31 | 2003-01-21 | Lilly Industries, Inc. | Coating of fatty acid-modified glycidyl copolymer, OH polymer and optional anhydride polymer |
| CN1603352A (en) * | 2002-12-07 | 2005-04-06 | 株洲市九华新材料涂装实业有限公司 | Epoxy modified unsaturated polyester resin special for putty and method for making same |
| CN1621430A (en) * | 2004-10-18 | 2005-06-01 | 常州市柏鹤涂料有限公司 | Modified dry oil alkyd resin for protective paint for metal coating on the back of the mirror and the curtain coating paint |
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| Publication number | Publication date |
|---|---|
| CN101386673A (en) | 2009-03-18 |
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Address after: 100010 Dongcheng District, Chaoyangmen, North Street, No. 4705, No. 25, box office, Beijing Patentee after: CHINA NATIONAL OFFSHORE OIL Corp. Patentee after: CNOOC CHANGZHOU PAINT CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Dongcheng District, Chaoyangmen, North Street, No. 4705, No. 25, box office, Beijing Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC CHANGZHOU PAINT & COATINGS INDUSTRY Research Institute Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |
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Granted publication date: 20110907 |