CN1212360C - Finish for pre-coating coiled material - Google Patents
Finish for pre-coating coiled material Download PDFInfo
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- CN1212360C CN1212360C CN 03132290 CN03132290A CN1212360C CN 1212360 C CN1212360 C CN 1212360C CN 03132290 CN03132290 CN 03132290 CN 03132290 A CN03132290 A CN 03132290A CN 1212360 C CN1212360 C CN 1212360C
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Abstract
The present invention relates to a finish for pre-coating coiled materials, which is a mixture prepared by uniformly mixing 10 to 50% of saturated polyester resin, 1 to 30% of amino resin, 1 to 30% of polyisocyanate, 40 to 87% of pigment slurry and 0.1 to 5.0% of assistant in a solvent, wherein the saturated polyester resin of which the acid value is less than 5 mgkoh/g has linear structure, or branch chain structure or linear and branch chain structure; the polyisocyanate is fully closed by at least two sealants with active hydrogen, and 2 to 55% of-NCO group in the polyisocyanate is closed by polyether sealants. The mixture is a colored viscous liquid in appearance, wherein the viscosity for coating four cups at the temperature of 23 DEG C is from 20 to 200 seconds, and the solid is divided into 40 to 80%. The percentage is measured in solid weight. The finish accords with the requirements of the production line of the existing pre-coating coiled materials. A dry film which is solidified by baking for 20 to 90 seconds at the temperature of 200 to 260 DEG C is 8 to 35 mu m in thickness, and the finish film properties can meet the requirements for finish of pre-coating coiled materials.
Description
Technical field
The present invention relates to a kind of pre-coated coil finish paint.
Background technology
Pre-coated coil enters industrialization so far from nineteen forties, constantly enlarges on consumption.Precoated coil coating also constantly develops along with the extensive application of pre-coated coil, and its kind develops into tens present kinds by initial single variety.In difference use field, require also inequality with coating property to pre-coated coil.The coating variety that is used for the pre-coated coil finish paint at present mainly is a polyester coating, according to different Application Areass many kinds of kinds is arranged.European patent EP 686678 discloses a kind of pre-coated coil finish paint with preparations such as vibrin, aminoresin or urea-formaldehyde resin, catalyzer, pigment, wax, polysiloxane, polyacrylic acid, though can obtain the thick film of 40～55 μ m, but, this finish paint solidification value is higher than 260 ℃, producing in the baker of pre-coated coil usually, can't make the paint film completely solidified.
Summary of the invention
The objective of the invention is to, a kind of pre-coated coil finish paint is provided, meets the requirement of existing precoating coil production line, 200～260 ℃ of bakings 20～90 seconds, solidifying the gained build is 8～35 μ m, and paint film property can satisfy the requirement of pre-coated coil to finish paint.
Realize the technical scheme of the object of the invention: a kind of pre-coated coil finish paint, it is the saturated polyester resin 10～50% of acid number less than 5mgKOH/g, aminoresin 1～30%, the totally enclosed polyisocyanates 1～30% of encapsulant with at least two kinds of band reactive hydrogens, pigment slurry 40～87% and auxiliary agent 0.1～5.0%, the mixture that in solvent, mixes, its outward appearance is colored viscous liquid, 23 ℃ are coated with-4 glasss of viscosity is 20～200 seconds, solid is divided into 40～80%, above-mentioned percentage number average is with solid weight meter, wherein said saturated polyester resin is that mixture by dibasic alcohol and the polyvalent alcohol more than the binary is as polyvalent alcohol, with the mixture of aromatic acid and aliphatic dibasic acid as polyprotonic acid, in the presence of catalyzer, the reacting by heating dehydration makes; Described polyisocyanates-2～55% being sealed of NCO base by the polyethers encapsulant.
Above-mentioned finish paint, dibasic alcohol as polyvalent alcohol is ethylene glycol, a condensed ethandiol, propylene glycol, methyl propanediol, neopentyl glycol or 2,2, the 4-neopentyl glycol, the above polyvalent alcohol of binary that is used as polyvalent alcohol is glycerine, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol, mannitol or Sorbitol Powder; Aromatic acid as polyprotonic acid is Tetra hydro Phthalic anhydride, terephthalic acid, m-phthalic acid, trimellitic acid or trimellitic anhydride, and the aliphatic dibasic acid that is used as polyprotonic acid is hexanodioic acid, nonane diacid or sebacic acid.
Above-mentioned finish paint, described aminoresin are commercially available methyl-etherified, butyl etherization, methyl alcohol and ethanol complex etherified or methyl alcohol and the complex etherified aminoresin of butanols.
Above-mentioned finish paint, described totally enclosed polyisocyanates is by aliphatic polyisocyante, with the encapsulants of at least two kinds of band reactive hydrogens, in the presence of catalyzer, reacts to nco value and makes less than 0.5%.The aliphatic polyisocyante that is used to prepare totally enclosed polyisocyanates is tripolymer, isophorone diisocyanate, the Trimerization of Isophorone Diisocyanate body of hexamethylene diisocyanate, hexamethylene diisocyanate, or their mixture; The encapsulant that is used for preparing the band reactive hydrogen of totally enclosed polyisocyanates is the mixture of at least two kinds of alcohols, pure ethers, amides, ketoxime class, malonic ester class or polyethers.Alcohols as encapsulant is ethanol, butanols, amylalcohol, hexanol or octanol; The alcohol ethers is ethylene glycol ethyl ether, butyl glycol ether, diethylene glycol ether, Diethylene Glycol butyl ether or propylene glycol monomethyl ether; Amides is a hexanolactam; The ketoxime class is methyl ethyl ketoxime or cyclohexanone-oxime; The malonic ester class is methyl aceto acetate, diethyl malonate or methyl ethyl diketone; Polyethers is dihydroxyl polyoxygenated propyl ether, trihydroxy-oxidation propyl ether, polytetrahydrofuran dibasic alcohol, polycaprolactone polyol or polycarbonate diol.
Above-mentioned finish paint, described pigment slurry be by pigment with finish paint prescription in the identical resin of saturated polyester resin, than mixing, dispersion grinding to fineness was made less than 10 μ m by 1: 20～5: 1 solid weights.Used pigment is selected organic or inorganic pigment commonly used such as titanium white, phthalocyanine blue, carbon black, red iron oxide, medium chrome yellow medium yellow etc. according to actual needs for use; Corrosion-inhibiting pigment such as zinc-chrome yellow, zinc phosphate, yellow ultramarine etc.; Pigment extender such as lime carbonate, barium sulfate, talcum powder, china clay etc.Preparation process can add auxiliary agent and solvent as required.
Above-mentioned finish paint, described auxiliary agent are one or more in dispersion agent, siccative, flow agent, anti-settling agent or the defoamer.
Above-mentioned finish paint, described solvent are benzene,toluene,xylene or the high boiling aromatic hydrocarbon solvents in the arene; Sherwood oil in the fat hydrocarbon, industrial naptha or hexanaphthene; Ethanol in the alcohols, butanols, amylalcohol, hexanol or octanol; Ethylene glycol ethyl ether, butyl glycol ether, diethylene glycol ether, Diethylene Glycol butyl ether or propylene glycol monomethyl ether in the alcohol ethers; Acetone in the ketone, methylethylketone, pimelinketone or hydroxyacetone; Ethyl acetate in the ester class, butylacetate or hexyl acetate.
With above-mentioned finish paint with the solvent latting drown to the viscosity that is fit to apply, be coated in through pre-treatment and apply on the galvanized sheet of pre-coated coil priming paint (epoxies or polyester), between 200～260 ℃, toasted 20～90 seconds, form the finish paint paint film of 8～35 μ m.
Technique effect of the present invention: after adopting technical scheme of the present invention, determined each component and proportioning thereof are guaranteed the paint film property after the finish paint film forming of the present invention, meet the requirement of pre-coated coil with finish paint.Particularly owing to adopt totally enclosed polyisocyanates and two kinds of cured resins of aminoresin to mix use, make that the paint film of finish paint of the present invention can be at 200～260 ℃, completely solidified in 20～90 seconds, meet the requirement of existing precoating coil production line, gained dry film thickness range broad requires different multiple products applicable to the finish paint paint film thickness is approached like this at 8～35 μ m.In addition owing to selected polyprotonic acid and polyvalent alcohol rightly, the linear structure of gained saturated polyester resin, the collocation of branched chain type structure rationally, the degree of branching is suitable, thereby the snappiness of paint film and hardness are suitable.
Embodiment
Below in conjunction with embodiment the present invention is further described in detail, but is not limited to this.
Embodiment 1 preparation saturated polyester resin A
1. prescription sees Table 1
Table 1
| Component | Raw material | Consumption (kg) | |
| Title | Specification | ||
| The trivalent alcohol dibasic alcohol | The TriMethylolPropane(TMP) propylene glycol | The industrial goods industrial goods | 46 318 |
| The aromatic acid aliphatic dibasic acid | The m-phthalic acid hexanodioic acid | The industrial goods industrial goods | 500 147 |
| Catalyzer | Dibutyl tin laurate | Analytical pure | 1 |
| Solvent | High boiling aromatic hydrocarbon solvent oil 1500# | Industrial goods | 272 |
| High boiling aromatic hydrocarbon solvent oil 2000# | Industrial goods | 272 | |
2. technology
In the clean reactor that thermometer, agitator, reflux exchanger, header tank are housed, all the other components except that catalyzer in the prescription are all added in the reactor, logical carbon dioxide is warmed up to 180 ℃ in 1 hour, start stirring.Add dibutyl tin laurate,, be warming up to 205 ℃ and kept 30 minutes, continue to be warming up to 230 ℃ 180 ℃ of insulations 1 hour, insulation, dehydration reaction to acid number less than 5mgKOH/g, get final product cooling discharge, it is standby to keep in Dark Place.Gained saturated polyester resin A, solid is divided into 65%.
The totally enclosed polyisocyanates A of embodiment 2 preparations
1. prescription sees Table 2
Table 2
| Component | Raw material | Consumption (kg) | |
| Title | Specification | ||
| Aliphatic polyisocyante | N3390 (HDI tripolymer) | Germany Bayer company produces | 100 |
| Encapsulant | Hexanolactam | Industrial goods | 21 |
| Ethylene glycol ethyl ether | Industrial goods | 16.71 | |
| Polyethers N-220 (dihydroxyl polyoxygenated propyl ether) | Industrial goods | 92.86 | |
| Catalyzer | Dibutyl tin laurate | Analytical pure | 1 |
| Solvent | Dimethylbenzene | Industrial goods, dehydration | 124.1 |
2. technology
In the clean reactor that thermometer, agitator, reflux exchanger, header tank are housed, adding dimethylbenzene, N3390 and dibutyl tin laurate stirs, follow disposable adding hexanolactam, be incubated with frozen water, make temperature of reaction be lower than 50 ℃, then be incubated 2～3 hours, guarantee to react completely.Then drip ethylene glycol ethyl ether and control rate of addition, guarantee that temperature is lower than 50 ℃, add polyethers N-220 at last, be warmed up to 100～120 ℃, be incubated 2～3 hours, measure nco value less than 0.5% o'clock, it is qualified to be, cooling discharge, and it is standby to keep in Dark Place.The NCO base of the totally enclosed isocyanic ester 19% of gained is sealed by polyethers N-220, and solid is divided into 65.1%.
Embodiment 3 preparation pigment slurry A
1. prescription sees Table 3
Table 3
| Component | Raw material | Consumption (kg) | |
| Title | Specification | ||
| Saturated polyester resin | Embodiment 1 | Self-control, solids constituent 65% | 200 |
| Pigment | Rutile type 2310 | Kronos company produces | 400 |
| Dispersion agent | BYK180 | BYK company produces | 8 |
| Solvent | High boiling aromatic hydrocarbon solvent oil 1500# | Industrial goods | 100 |
2. technology
In the scuffing of cylinder bore of cleaning, add saturated polyester resin, pigment, dispersion agent and solvent in the prescription successively, carry out high speed dispersion with high speed dispersor, controlled temperature is below 40 ℃ simultaneously.Measure fineness after 1 hour, discharging during less than 10 μ m, it is standby to keep in Dark Place, and the solid of pigment slurry is divided into 75.9%, and resin-pigment ratio is 3: 1.
Embodiment 4 preparation pre-coated coil finish paint A
1. prescription sees Table 4
Table 4
| Component | Raw material | Consumption | ||
| Title | Specification | Weight (kg) | In the shared per-cent of solid (%) | |
| Saturated polyester resin | Embodiment 1 | Self-control, solids constituent 65% | 27.2 | 17.07 |
| Aminoresin | 303 (methyl-etherified terpolycyantoamino-formaldehyde resins) | CYTEC company produces | 3.9 | 3.77 |
| Totally enclosed polyisocyanates | Embodiment 2 | Self-control, solids constituent 65.1% | 5.8 | 3.65 |
| Pigment slurry | Embodiment 3 | Self-control, solids constituent 75.9% | 100.0 | 73.29 |
| Auxiliary agent | Dibutyl tin laurate (siccative) BYK-450 | Analytical pure | 0.3 | 2.22 |
| (dispersion agent) | BYK company produces | 2.0 | ||
| Solvent | High boiling aromatic hydrocarbon solvent oil 1500# | Industrial goods | 8.4 | |
| High boiling aromatic hydrocarbon solvent oil 2000 # | Industrial goods | 8.4 |
2. technology
In clean paint still, drop into pigment slurry, aminoresin, totally enclosed polyisocyanates, saturated polyester resin, auxiliary agent and solvent in the prescription successively, stir, filter, pack, make pre-coated coil finish paint A, its solid is divided into 64.8%, and viscosity is 97 seconds (being coated with-4 glasss, 23 ℃).
Embodiment 5 finish paint service checks
At the galvanized sheet through obtaining after the degreasing, cleaning, activation, oven dry pretreatment procedure, first primer coating (the product HY-C-01 of Jiangsu Hongye Coating Science and Technology Industry Co., Ltd. pre-coated coil priming paint) applies the finish paint A of embodiment 4 again.Applying used line plate is No. 22 line rods of RDS.Galvanized sheet after the coating, baking is 45 seconds in 220 ℃ of baking ovens, and the gained build is 25 μ m, and the visual inspection flat appearance is smooth.Press national standard method and detect, T is curved: 2T; Cupping: 6mm; Anti-methylethylketone wiping:＞100 times; Impact: 100cm; Pencil hardness: 2H.The above results shows that pre-coated coil can satisfy the requirement of pre-coated coil to finish paint fully with finish paint A and the supporting use of epoxies pre-coated coil priming paint.
Embodiment 6 preparation saturated polyester resin B
1. prescription sees Table 5
Table 5
| Component | Raw material | Consumption (kg) | |
| Title | Specification | ||
| The trivalent alcohol dibasic alcohol | TriMethylolPropane(TMP) propylene glycol neopentyl glycol | Industrial goods industrial goods industrial goods | 46 128 260 |
| The aromatic acid aliphatic dibasic acid | The m-phthalic acid hexanodioic acid | The industrial goods industrial goods | 435 199 |
| Catalyzer | Dibutyl tin laurate | Analytical pure | 0.8 |
| Solvent | High boiling aromatic hydrocarbon solvent oil 1500 # | Industrial goods | 298 |
| High boiling aromatic hydrocarbon solvent oil 2000 # | Industrial goods | 298 | |
2. technology
In the clean reactor that thermometer, agitator, reflux exchanger, header tank are housed, add all raw materials except that catalyzer in the prescription, feed carbon dioxide, be warmed up to 190 ℃ in 1 hour, start stirring.Add dibutyl tin laurate, 190 ℃ of insulations 1 hour, be warming up to 210 ℃, kept 40 minutes, be warming up to 230 ℃ again, insulation is dewatered, react to acid number less than 5mgKOH/g, get final product cooling discharge, it is standby to keep in Dark Place.Gained saturated polyester resin B, solid is divided into 64.2%.
Embodiment 7 preparation pigment slurry B
Remove the saturated polyester resin B with embodiment 6 preparations, replace outside the saturated polyester resin A in embodiment 3 prescriptions, all the other (comprising prescription and technology) are all with embodiment 3.Gained pigment slurry B keeps in Dark Place standby, and its solid is divided into 75.8%, and resin-pigment ratio is 3: 1.
Embodiment 8 preparation pre-coated coil finish paint B
1. prescription sees Table 6
Table 6
| Component | Raw material | Consumption | ||
| Title | Specification | Weight (kg) | In the shared per-cent of solid (%) | |
| Saturated polyester resin | Embodiment 6 | Self-control, solids constituent 64.2% | 27.2 | 16.96 |
| Aminoresin | 303 (methyl-etherified terpolycyantoamino-formaldehyde resins) | CYTEC company produces | 2.8 | 2.72 |
| Totally enclosed polyisocyanates | Embodiment 2 | Self-control, solids constituent 65.1% | 7.5 | 4.74 |
| Pigment slurry | Embodiment 7 | Self-control, solids constituent 75.8% | 100.0 | 73.64 |
| Auxiliary agent | BYK-450 (dispersion agent) | BYK company produces | 2.0 | 1.94 |
| Solvent | High boiling aromatic hydrocarbon solvent oil 1500 # | Industrial goods | 7.8 | |
| High boiling aromatic hydrocarbon solvent oil 2000 # | Industrial goods | 7.8 | ||
2. technology
Adopt above-mentioned prescription, press the technological operation of embodiment 4, make pre-coated coil finish paint B, its solid is divided into 65.3%, and viscosity is 102 seconds (being coated with-4 glasss, 23 ℃).
Embodiment 9 finish paint service checks
At the galvanized sheet through obtaining after the degreasing, cleaning, activation, oven dry pretreatment procedure, first primer coating (Jiangsu Hongye Coating Science and Technology Industry Co., Ltd.'s product, HY-C-01 pre-coated coil priming paint) applies the finish paint B of embodiment 8 again.Applying used line plate is No. 16 line rods of RDS.Galvanized sheet after the coating, baking is 45 seconds in 260 ℃ of baking ovens, and the gained build is 15 μ m, and the visual inspection flat appearance is smooth.Press national standard method and detect, T is curved: 2T; Cupping: 6mm; Anti-methylethylketone wiping:＞100 times; Impact: 100cm; Pencil hardness: 2H.The above results shows that pre-coated coil can satisfy the requirement of pre-coated coil to finish paint fully with finish paint B and the supporting use of epoxies pre-coated coil priming paint.
Claims (9)
1, a kind of pre-coated coil finish paint, it is characterized in that: it is the saturated polyester resin 10～50% of acid number less than 5mgKOH/g, aminoresin 1～30%, the totally enclosed polyisocyanates 1～30% of encapsulant with at least two kinds of band reactive hydrogens, pigment slurry 40～87% and auxiliary agent 0.1～5.0%, the mixture that in solvent, mixes, its outward appearance is colored viscous liquid, 23 ℃ are coated with-4 glasss of viscosity is 20～200 seconds, solid is divided into 40～80%, above-mentioned percentage number average is with solid weight meter, wherein said saturated polyester resin is that mixture by dibasic alcohol and the polyvalent alcohol more than the binary is as polyvalent alcohol, with the mixture of aromatic acid and aliphatic dibasic acid as polyprotonic acid, in the presence of catalyzer, the reacting by heating dehydration makes; Described polyisocyanates-2～55% being sealed of NCO base by the polyethers encapsulant.
2, finish paint according to claim 1, it is characterized in that: the dibasic alcohol as polyvalent alcohol is ethylene glycol, a condensed ethandiol, propylene glycol, methyl propanediol, neopentyl glycol or 2,2, the 4-neopentyl glycol, the above polyvalent alcohol of binary that is used as polyvalent alcohol is glycerine, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol, mannitol or Sorbitol Powder; Aromatic acid as polyprotonic acid is Tetra hydro Phthalic anhydride, terephthalic acid, m-phthalic acid, trimellitic acid or trimellitic anhydride, and the aliphatic dibasic acid that is used as polyprotonic acid is hexanodioic acid, nonane diacid or sebacic acid.
3, finish paint according to claim 1 is characterized in that: described aminoresin is commercially available methyl-etherified, butyl etherization, methyl alcohol and ethanol complex etherified or methyl alcohol and the complex etherified aminoresin of butanols.
4, finish paint according to claim 1 is characterized in that: described totally enclosed polyisocyanates is by aliphatic polyisocyante, with the encapsulant of at least two kinds band reactive hydrogen, in the presence of catalyzer, reacts to nco value and makes less than 0.5%.
5, finish paint according to claim 4, it is characterized in that: the aliphatic polyisocyante that is used to prepare totally enclosed polyisocyanates is tripolymer, isophorone diisocyanate, the Trimerization of Isophorone Diisocyanate body of hexamethylene diisocyanate, hexamethylene diisocyanate, or their mixture; The encapsulant that is used for preparing the band reactive hydrogen of totally enclosed polyisocyanates is the mixture of at least two kinds of alcohols, pure ethers, amides, ketoxime class, malonic ester class or polyethers.
6, finish paint according to claim 5 is characterized in that: the alcohols as encapsulant is ethanol, butanols, amylalcohol, hexanol or octanol; The alcohol ethers is ethylene glycol ethyl ether, butyl glycol ether, diethylene glycol ether, Diethylene Glycol butyl ether or propylene glycol monomethyl ether; Amides is a hexanolactam; The ketoxime class is methyl ethyl ketoxime or cyclohexanone-oxime; The malonic ester class is methyl aceto acetate, diethyl malonate or methyl ethyl diketone; Polyethers is dihydroxyl polyoxygenated propyl ether, trihydroxy-oxidation propyl ether, polytetrahydrofuran dibasic alcohol, polycaprolactone polyol or polycarbonate diol.
7, finish paint according to claim 1 is characterized in that: described pigment slurry be by pigment with finish paint prescription in the identical resin of saturated polyester resin, than mixing, dispersion grinding to fineness was made less than 10 μ m by 1: 20～5: 1 solid weights.
8, finish paint according to claim 1 is characterized in that: described auxiliary agent is one or more in dispersion agent, siccative, flow agent, anti-settling agent or the defoamer.
9, finish paint according to claim 1 is characterized in that: described solvent is benzene,toluene,xylene or the high boiling aromatic hydrocarbon solvent in the arene; Sherwood oil in the fat hydrocarbon, industrial naptha or hexanaphthene; Ethanol in the alcohols, butanols, amylalcohol, hexanol or octanol; Ethylene glycol ethyl ether, butyl glycol ether, diethylene glycol ether, Diethylene Glycol butyl ether or propylene glycol monomethyl ether in the alcohol ethers; Acetone in the ketone, methylethylketone, pimelinketone or hydroxyacetone; Ethyl acetate in the ester class, butylacetate or hexyl acetate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03132290 CN1212360C (en) | 2003-08-08 | 2003-08-08 | Finish for pre-coating coiled material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03132290 CN1212360C (en) | 2003-08-08 | 2003-08-08 | Finish for pre-coating coiled material |
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| CN1473898A CN1473898A (en) | 2004-02-11 |
| CN1212360C true CN1212360C (en) | 2005-07-27 |
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2003
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| CN1473898A (en) | 2004-02-11 |
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