CN1814663A - Thermo-setting acrylic-acid emulsion, its preparing method and paint containing same - Google Patents

Thermo-setting acrylic-acid emulsion, its preparing method and paint containing same Download PDF

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CN1814663A
CN1814663A CN 200510033137 CN200510033137A CN1814663A CN 1814663 A CN1814663 A CN 1814663A CN 200510033137 CN200510033137 CN 200510033137 CN 200510033137 A CN200510033137 A CN 200510033137A CN 1814663 A CN1814663 A CN 1814663A
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monomer
acrylic
emulsion
consumption
water
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CN100363421C (en
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唐靖
黄光燕
陈兴耀
陈勇
李晨隽
唐泉
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Guangzhou Huigu New Materials Technology Co ltd
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HUIGU CHEMCIAL CO Ltd GUANGZHOU
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Abstract

This invention discloses a thermoset crylic acid latex and its preparation method and a corrosion resistant bottom coat containing such latex and used in the Al fins of the heat converter of air conditioners, in which, said latex includes a crylic acid kind monomers, an ionic vinyl monomers, an ethene monomers, a vinyl silane coupler, a crosslink monomers, a surface active agent and an initiator to be got by seed latex and semi-continuous drop technology. Said bottom coat includes said thermoset crylic acid latex, water-base coating resin, water-base cross-linker, booster solvent, neutralization agent, a water-base adhesive force accelerant, a catalyst and water.

Description

A kind of thermoset acrylics emulsion and preparation method thereof and the coating that contains this emulsion
Technical field
The present invention relates to paint field, particularly a kind of thermoset acrylics emulsion and preparation method thereof and contain this emulsion and be used for the corrosion-resistant bottom-coating of air-condition heat exchanger aluminium fin.
Background technology
Along with global warming, the market demand of all kinds of air-conditionings is increasing; And the energy-intensive situation impels air-conditioning to develop towards the direction of lightweight, miniaturization, high energy efficiency ratio.One of effective measure that realize conditioner lightweight, miniaturization, high energy efficiency ratio be reduce the thickness of air-condition heat exchanger aluminium fin, reduce between the aluminium fin spacing, increase the heat interchanging area of interchanger unit weight.The aluminum foil thickness that is used for the aluminium fin has at present reduced to about 0.1mm, and the aluminium spacing of fin is contracted to below the 2mm.If the aluminium fin surface is untreated, a large amount of water of condensation that produce during air-conditioning refrigeration can form the globule because of capillary effect accumulates in the aluminium fin surface.Because the spacing between the aluminium fin very little (2mm is following), the globule on the adjacent aluminium fin can form " water bridge " and stop up the air channel, and blast increases when causing operation of air conditioner, and noise becomes big when the heat exchanger effectiveness of reduction air-conditioning and running.In addition, the water of condensation of aluminium fin surface is understood the airborne impurity of adsorpting aggregation and is formed oxygen concentration cell at aluminium foil surface, quickens the corrosion of aluminium fin, produces " white powder " (main component is Al2O33H2O) and blows out contaminate environment with warm braw." water bridge " and " white powder " phenomenon have had a strong impact on the working efficiency of air-condition heat exchanger, even make the perforation that is corroded of aluminium fin, shorten the work-ing life of air-conditioning greatly.
In order to address the above problem, be necessary that heat exchanging device aluminium fin handles, method is that aluminium foil surface is carried out anticorrosion and hydrophilicity-imparting treatment preferably.Aluminium fin surface possess hydrophilic property after treatment, water of condensation is drawout rapidly, can not condense and forms the water bridge at the aluminium fin surface; Corrosion-resistance treatment can improve the antiseptic property of aluminium fin, prolongs the work-ing life of air-conditioning.
In the sixties in 20th century, people adopt chromic salt that aluminium foil is carried out surface treatment, the hydrophilic angle of aluminium foil surface after the processing is 50～60 °, film certain erosion resistance and wetting ability, but because adhesive force of coatings is poor, effect is unsatisfactory, and air-conditioning the problems referred to above can occur again after using for some time.Enter the eighties, along with developing rapidly of air-conditioning industry, it is the coating processing air-condition heat exchanger aluminium fin of main component that developed countries such as Japan begin to adopt with silicate, but dust and peculiar smell in the easy absorbed air of the coating of silicate systems, operation of air conditioner can produce peculiar smell after for some time, and because silicate has stronger alkalescence, the aluminium fin is had corrosive nature, this method that singly is coated with can't reach anticorrosion and hydrophilic purpose simultaneously.Begin the nineties so far, people adopt the two technologies that are coated with of two bakings progressively to replace and singly are coated with technology, promptly are coated with the primary coat of one deck preservative property on aluminium foil in air condition heat exchanger earlier, are coated with one deck wetting ability face after the oven dry again and are coated with, and reach not only anticorrosion but also hydrophilic purpose.
Because it is the thickness of heat exchanger of air conditioner aluminium fin is more and more thinner, more and more higher to the erosion resistance requirement of primary coat.In oceanic climate, the more area of acid rain, envrionment conditions is higher to the erosion resistance requirement of air-condition heat exchanger aluminium fin, requires salt spray resistance to reach more than 1000 hours, and existing product also can't reach requirement.
The line speed of the pre-tenaplate of air-condition heat exchanger aluminium fin has reached 100 meters/minute at present, this just require coating particularly primary coat be still or low bubble, good stability, directly cause the coatingsurface downgrade otherwise can produce a large amount of foams in process of production, even can't continue to produce.In addition, the punch press speed that is used for punching out interchanger aluminium fin reaches more than 200 times/minute, and in order to improve the heat exchanger effectiveness of interchanger, need go out complicated shapes such as window shutter in perforate of aluminium fin surface and punching out, this just require coating can not be when the high speed punching out dry linting or come off, the machining property of coating is required very high, particularly the sticking power that sticking power, primary coat and the face of the snappiness of primary coat and primary coat and aluminium foil surface is coated with requires very high; And, the aluminium fin of punch forming when assembling is welded into interchanger, require coating can not be because of high-temperature soldering xanthochromia; In order not influence air-condition heat exchanger aluminium heat exchange efficiency of fins, also require the thickness of coating can not be too thick, be generally 1～2um.
Commercially available organic primary coat at present is main with acrylic acid series and Resins, epoxy, the main problem that exists has the following aspects: (1) corrosion resistance of coating is undesirable, general single-layer coating will reach more than the 1.5um, and salt spray resistance also can only reach 9.5 grades even lower rank; (2) paint stability is bad, and the product that has is easy to generate throw out and influences coating quality in coating process; The coating that has life-span after preparation has only tens hours, if too many or too much for use, remainder just can't re-use, and waste greatly; The coating that also has in use physical and chemical performance changes, and is apparent that especially viscosity increases along with the prolongation of coating process, causes coating thickness uncontrollable, and coating performance descends.Cause the major cause of these problems to be that selected resin self stability difference and formulation for coating material are unreasonable.
Chinese patent CN 95117439.8 discloses a kind of aqueous epoxy phenolic paint, and this coating is made by resol, aqueous epoxy resins and water.Wherein, resol is made by phenol, formaldehyde and dimethylaminoethanol, and aqueous epoxy resins is made by Resins, epoxy, methyl methacrylate, vinylbenzene, benzoyl peroxide, dimethylaminoethanol, phosphoric acid and water etc.Though this aqueous epoxy phenolic paint is reducing the discharging of organic solvent, is preventing that aspects such as blast and fire from having made improvement, be adapted at using on the iron flask head, but its alkaline-resisting, corrosion-resistant and high temperature resistant xanthochromia is general, therefore is not suitable for the coating as aluminium foil base material very thin on the air-condition heat exchanger.
A kind of hydrophilic coating is disclosed among the Chinese patent application 02151903.X, this hydrophilic coating comprises modified epoxy, acrylate copolymer, aminoresin and sulfonate surfactant, wherein, modified epoxy is meant acrylic modified epoxy resin, anhydride modified Resins, epoxy and/or amino modified Resins, epoxy.This prescription belongs to singly coating, and its advantage is to have good hydrophilicity, but corrosion resistance is relatively poor.
U.S. Pat 5389704 discloses a kind of preparation method and a kind of steel plate galvanized rot-resistant coating composition that is used for of epoxy group(ing) phosphate resins, and this coating composition comprises epoxy group(ing) phosphate resins, acrylic resin or vibrin and at least a solidifying agent.In this coating composition, the content of epoxy group(ing) phosphate resins is up to more than 70%, and high-load epoxy group(ing) phosphoric acid ester like this is unfavorable for the high temperature resistant xanthochromia and the alkali resistance of coating; And unexposed this coating composition is used for the anticorrosion required coat-thickness of steel plate galvanized in specification sheets.
China Patent No. is that 03105296.7 " water-borne coatings " discloses a kind of water-borne coatings that comprises that primary coat and face are coated with, primary coat and face are coated with and are used in combination, elder generation coats primary coat on aluminium and then the face that is coated with is coated with, wherein bottom-coating is made up of acrylic resin polymer emulsion, water soluble resin solidifying agent, anticorrosive agent, aqueous color paste, water-based defoamer, water-based flow agent etc., and points out that the acrylic resin polymer emulsion can be benzene emulsion, vinyl acetate emulsion and pure-acrylic emulsion.Owing to contain more defoamer and flow agent in this primary coat, directly influence the coating stability of bottom-coating, the ply adhesion between primary coat and face are coated with also can produce considerable influence; And the sticking power of this patent between post-treatment, primary coat and the face of the stability of primary coat, undercoat not being coated with is tested and is estimated.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the prior art, the thermoset acrylics emulsion of low, the low bubble of a kind of surfactant content, strong adhesion is provided.
Another object of the present invention is to provide a kind of preparation method of above-mentioned thermoset acrylics emulsion.
A further object of the present invention is to provide a kind of corrosion-resistant primary coat that is used for air-condition heat exchanger aluminium fin that contains above-mentioned thermoset acrylics emulsion, this primary coat good stability, coating performance is good, the strong adhesion of coating and base material, excellent corrosion resistance, the matching capacity that is coated with commercially available wetting ability face is good.
Purpose of the present invention is achieved through the following technical solutions:
A kind of thermoset acrylics emulsion comprises following component:
(1) one or more acrylic monomers, consumption are 58%～99.5% of all total monomer weights; Described acrylic monomer comprises carboxy acrylic class monomer and hydroxyl acrylic class monomer and other acrylic monomers, wherein carboxy acrylic class monomer accounts for 0.8%～8% of all total monomer weights, and hydroxyl acrylic class monomer accounts for 10%～30% of all total monomer weights;
(2) one or more ionic olefinic class monomers, consumption is 0.5～4.0% of all total monomer weights;
(3) vinyl monomer, consumption are 0～35% of all total monomer weights;
(4) olefinic one type of silane coupling agent, consumption are 0～1.5% of all total monomer weights;
(5) cross-linking monomer contains two two keys at least in its molecular structure, consumption is 0～4% of all total monomer weights;
(6) tensio-active agent, consumption are 0.1～1.5% of all total monomer weights;
(7) initiator, consumption are 0.5～3% of all total monomer weights;
Above-mentioned all components weight is solid weight; Described all monomers are made up of the listed monomer in above-mentioned (1)～(5).
Described one or more acrylic monomers comprise carboxy acrylic class monomer and hydroxyl acrylic class monomer and other acrylic monomers.Preferred (methyl) vinylformic acid of described carboxy acrylic class monomer.The preferred acrylic acid or the like hydroxyalkyl ester monomer of described hydroxyl acrylic class monomer, preferred (methyl) Hydroxyethyl acrylate of described acrylic acid or the like hydroxyalkyl ester monomer, (methyl) Propylene glycol monoacrylate.Described other acrylic monomers are acrylic acid or the like soft or hard monomer and acrylic functional monomer; The preferred acrylic acid or the like alkyl ester monomer of wherein said acrylic acid or the like soft or hard monomer; Described acrylic functional monomer preferred amide base acrylic monomer, epoxy group(ing) acrylic monomer, the basic acrylic monomer of phosphoric acid (ester), aminoacrylic acid class monomer etc.Preferred (methyl) methyl acrylate of described acrylic acid or the like alkyl ester monomer, ethyl propenoate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, Isooctyl acrylate monomer, (methyl) lauryl acrylate, (methyl) vinylformic acid norborneol ester etc.; More preferably methyl methacrylate, (methyl) butyl acrylate, lauryl acrylate, Isooctyl acrylate monomer.Preferred (methyl) acrylamide of described amide group acrylic monomer, N-hydroxyalkyl acrylamide.The preferred tertiary carbonic acid glycidyl ester of described epoxy group(ing) acrylic monomer, glycidyl methacrylate.Preferred (methyl) vinylformic acid phosphoric acid ester of the basic acrylic monomer of described phosphoric acid (ester).Described aminoacrylic acid class monomer preferable methyl dimethylaminoethyl acrylate.
The consumption of described acrylic monomer is preferably 70%～98% of all total monomer weights; Wherein, the monomeric consumption of carboxy acrylic class is preferably 1.5%～4.0% of all total monomer weights, and the monomeric consumption of hydroxyl acrylic class is preferably 15%～25% of all total monomer weights.
Described ionic olefinic class monomer is carboxylate salt, sulfonic acid (salt) and the quaternary ammonium salt that contains two keys; Preferred vinyl sodium sulfonate, allyl group hydroxypropyl azochlorosulfonate acid sodium, (methyl) sodium allyl sulfonate, to styryl sodium sulfonate, alkyl vinylformic acid-2-ethanesulfonic acid sodium, acrylamide sodium stearate, octadecyl dimethyl vinyl phenyl ammonium chloride, methylacryoyloxyethyl trimethyl ammonium chloride, contain two keys the long-chain sulfonate ammonium, contain the alkyl succinic acid ester sodium sulfonate of two keys.The monomeric consumption of described ionic olefinic class is preferably all total monomer weights 1～2%.Comprise two keys in the monomeric structure of described ionic olefinic class, this pair key can participate in reaction, enter in the macromolecular structure unit of emulsion by radical and other monomeric copolyreaction, can guarantee that emulsion has certain surfactivity and is beneficial to emulsion-stabilizing on the one hand, can reduce the consumption of conventional surfactant on the other hand, alleviate the bubble-related issues that conventional surfactant causes, and the migration of reduction conventional surfactant in coating, alleviate or avoid the recoat problem, help improving the water tolerance and the erosion resistance of coating simultaneously.
Described vinyl monomer can be vinylbenzene, vinyl acetate, vinylchlorid, chlorinated polyvinyl chloride or vinyl tertiary carbon acid esters; Consumption is preferably 0～25% of all total monomer weights.
Described olefinic one type of silane coupling agent can be the silane coupling agent that contains acryl or contain vinyl; Preferred γ-methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl-three (2-methoxy ethoxy) silane and vinyl methyl dimethoxysilane etc.; Consumption is preferably 0～1.0% of all total monomer weights.
The preferred trimethylolpropane allyl ether of described cross-linking monomer, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, two (methyl) vinylformic acid binaryglycol ester, two (methyl) vinylformic acid triglycol ester, two (methyl) vinylformic acid TEG ester or (methyl) polyalkylene glycol acrylate ester etc.; Consumption is preferably 0～3% of all total monomer weights.Described cross-linking monomer is to contain two above many double bond compounds of two keys, can be monomer crosslinked by radical and other, improve the molecular weight of emulsion on the one hand, and reduce free monomer simultaneously.
Described tensio-active agent can be various conventional surfactants, comprises anion surfactant, nonionogenic tenside, anionic and nonionic tensio-active agent, cats product; Consumption is preferably 0.2～0.8% of all total monomer weights.Described anion surfactant can be alkyl-sulphate, hydrocarbyl sulfonate, phosphoric acid salt, carboxylate salt; Preferably sodium dodecyl sulfate, Sodium dodecylbenzene sulfonate, potassium oleate (sodium), succinate sodium sulfonate, alkyl phosphate diethanolamine salt.Described nonionogenic tenside can be glycerin fatty acid ester, Fatty Alcohol(C12-C14 and C12-C18) oleic acid/stearate, fatty alcohol-polyoxyethylene ether, polyoxyethylene carboxylate, alkylphenol polyoxyethylene; Preferably glycerine stearate, oleic acid glyceride, ethoxylated dodecyl alcohol, lauric acid polyoxyethylene ester, polyoxyethylene oleic acid ester, polyoxyethylene nonylphenol ether, sapn series non-ionic surfactants such as sorbitan monooleate and Span60, tween series non-ionic surfactants such as polyoxyethylene sorbitan stearate and polyoxyethylene sorbitan oleic acid ester.Described anionic and nonionic tensio-active agent can be fatty alcohol-polyoxyethylene ether potassiumphosphate (sodium), polyoxyethylenated alcohol sodium sulfate, alkyl phenol polyethenoxy ether sodium sulfate; Preferred isooctyl alcohol Soxylat A 25-7 sodium sulfonate, ethoxylated dodecyl alcohol sodium sulfonate, polyoxyethylene nonylphenol ether sodium sulfonate.Described cats product can be quaternary ammonium salt; Preferred 12/16/octadecyl benzyl dimethyl ammonium chloride.Described tensio-active agent plays emulsification, solublization in emulsion is synthetic, the stability of emulsion is played an important role; Do not participate in free radical reaction, do not enter in the macromolecular structure unit of emulsion by copolyreaction with described all monomers; Their consumption is less because consumption too conference produce foam and recoat problem.
Described initiator can be water soluble starter, preferred persulphate or azo compound; Persulphate can be Sodium Persulfate, Potassium Persulphate and ammonium persulphate; Azo compound can be 4, the two 4-cyanopentanoic acids (sodium), 4 of 4-azo, the two 4-cyano group amylalcohols and 2 of 4-azo, 2-azo two NSC 18620 dihydrochlorides.The consumption of described initiator is preferably 0.8～1.5% of all total monomer weights.
In addition, can in emulsion, add the pH regulator agent, the pH value of cation emulsion is adjusted to 4～7, the pH value of anionic emulsion is adjusted to 7～9.For anionic emulsion, described pH regulator agent is conventional anionic emulsion neutralizing agent, as ammoniacal liquor or organic amine, and preferred high boiling point organic amine, preferred especially N, N diethanolamine, trolamine, N, N dimethylethanolamine and 2-methyl-2 aminopropanol.For cation emulsion, described pH regulator agent is conventional organic acid or mineral acid, preferred dilute hydrochloric acid, dilute sulphuric acid, rare nitric acid, phosphoric acid and acetic acid etc.Described anionic emulsion be when emulsion is synthetic, adopt one or more anion surfactant or/and anionic and nonionic tensio-active agent or anion surfactant or/and anionic and nonionic tensio-active agent and nonionogenic tenside; Described cation emulsion is cats product or cation surface activating and the nonionogenic tenside that adopts one or more when emulsion is synthetic.
In addition, also can in described thermoset acrylics emulsion, add other conventional emulsions additive synthesis, as protection glue, pH stablizer etc.Described protection glue can be water soluble polymers such as polyvinyl alcohol, ether of cellulose/ester, polyacrylic acid and polyacrylamide.Described pH stablizer can be yellow soda ash, sodium bicarbonate etc.
The preparation process of described thermoset acrylics emulsion is:
(1) described ionic olefinic type monomers, described tensio-active agent and deionized water and stirring are mixed, be heated to 40～85 ℃, make mixture A;
(2) described acrylic monomer, described vinyl monomer, described olefinic one type of silane coupling agent and described cross-linking monomer are mixed, make mixture B;
(3) described 1～10% (weight) mixture B is added among the mixture A, under 40～85 ℃ of temperature, stirred 5～15 minutes, make mixture C;
(4) described 10～50% (weight) initiator is added in the mixture C, under 75～85 ℃ of temperature, reacted 20～60 minutes,, make seed emulsion D until no tangible monomers flow back;
(5) be added dropwise among the seed emulsion D remaining mixture B, remaining initiator are semicontinuous respectively simultaneously, under 75～85 ° of temperature, dripped 2～3.5 hours, kept 75～85 ° of temperature then 1～2 hour;
(6) with the pH regulator agent pH value of emulsion is transferred to required pH value, with deionized water the solid content of emulsion is transferred to 25～35% then, make the thermoset acrylics emulsion.
Above-mentioned institute in steps in, can adopt nitrogen protection.
In the described step (3), preferred 3～8% (weight) of the consumption of mixture B.
In the described step (3), preferred 15～35% (weight) of the consumption of initiator.
The median size of prepared thermoset acrylics emulsion is 0.1～2 μ m, preferred 0.1-1 μ m; Number-average molecular weight is 1000～50000, preferred 2000～30000; Second-order transition temperature is-15～40 ℃, preferred 0～30 ℃; Solid content is 20～40%, preferred 25～35%; Viscosity is 10 seconds～16 seconds (20 ℃ are coated with 4 glasss), preferred 11～14 seconds.
The bottom-coating that is used for air-condition heat exchanger aluminium fin comprises following component:
(1) above-mentioned thermoset acrylics emulsion, consumption is 20～60 weight parts;
(2) water-base resin, consumption are 0.5～20 weight part, and described water-base resin is one or more mixtures in water-dispersion acrylic resin, aqueous epoxy resins, aqueous acrylic modified Resins, epoxy, the water-based saturated polyester resin;
(3) water cross-linking agent, consumption are 2～15 weight parts;
(4) solubility promoter, consumption are 5～15 weight parts;
(5) neutralizing agent, consumption are 0.05～0.5 weight part;
(6) water-based adhesion promoter, consumption are 0～5 weight part;
(7) catalyzer, consumption are 0.1～0.5 weight part;
(8) water, surplus;
The said components gross weight is 100 weight parts.
Preferred 30～50 weight parts of the consumption of described thermoset acrylics emulsion.
Add described water-base resin in primary coat, it is more tough that one side can assist the curing of primary coat that it is filmed, and can improve the primary coat adhesive force of coatings on the other hand, makes it tightr with contacting of aluminium foil base material.
Described water-dispersion acrylic resin and water-based saturated polyester resin, all preferred acid number is 50～200mgKOH/g, more preferably acid number is 80～120mgKOH/g.Because acid number is lower than 50mgKOH/g, can influence the adherence of filming, the too high viscosity that will cause again of acid number is too high, is unfavorable for operation construction and scumbling coating.
Described aqueous epoxy resins and aqueous acrylic modified Resins, epoxy, its molecular skeleton feature is bisphenol A-type, and weight-average molecular weight is 200～30000, preferred 200～15000.If molecular weight is too high, on the one hand bad with the compatibility of ACRYLIC EMULSION, cause on the other hand that viscosity is too high to be unfavorable for that operation construction and scumbling are coated with; Otherwise molecular weight is too low, can influence the obdurability and the adherence of filming, and is unfavorable for continuing preservative activity.
Described water cross-linking agent can be aminoresin, water-based isocyanate.
Described solubility promoter can be one or more in ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, propyl carbinol, isopropylcarbinol, propylene glycol monobutyl ether, the diethylene glycol monobutyl ether, preferred ethylene glycol monobutyl ether.
Described neutralizing agent can be low molecular amine, as ammoniacal liquor, N, and N-dimethylethanolamine, diethanolamine, trolamine, 2-methyl 2-aminopropanol etc.; Preferred N, N-dimethylethanolamine, 2-methyl 2-aminopropanol.
Described water-based adhesion promoter can be the EP-1300 of Degussa, the Halox 570 of Hammond Group Inc., the Borcher HMP of Byers.
Described catalyzer can be p-methyl benzenesulfonic acid, dinonylnaphthalene disulfonic acid, phosphoric acid, Witco 1298 Soft Acid, dibutyl tin laurate, zinc naphthenate etc.
In addition, in primary coat, also can add aqueous promoter, as defoamer, mould inhibitor, sanitas, coupling agent etc.; These aqueous promoters need have good intermiscibility, and do not influence the recoatability and the yellowing resistance of bottom-coating.
The present invention compared with prior art has following advantage and effect:
(1) surfactant content of described thermoset acrylics emulsion is low, and foam is few, strong adhesion;
(2) contain the high-speed and continuous coating that primary coat good stability, the foam volume of this thermoset acrylics emulsion is low, be applicable to air-condition heat exchanger aluminium fin aluminium foil;
(3) because in this primary coat, surfactant content is low, thereby reduce its water-absorbent, contain higher hydroxyl, carboxyl and epoxy group(ing)/epoxy phosphate base isopolarity group simultaneously, make this primary coat coating tightr, improve protection and the lasting erosion resistance of primary coat coating aluminium foil surface with contacting of aluminium foil surface;
(4) after the aluminium foil surface of air-condition heat exchanger aluminium fin applies this primary coat, the formed coating that is heating and curing has favorable mechanical processibility and erosion resistance;
(5) apply described primary coat and the coating that forms has good recoatability at aluminium foil surface, can be coated with by the multiple commercially available or homemade wetting ability face of supporting coating, between primary coat coating and the face coating layer good ply adhesion is arranged.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description, but embodiments of the present invention are not limited thereto.
Embodiment 1
Prescription (1):
Sodium vinyl sulfonate (25% aqueous solution) 8.0g
Sodium lauryl sulphate (5% aqueous solution) 4.0g
Deionized water 150g
Prescription (2):
Methyl methacrylate 35.5g
Isooctyl acrylate monomer 15.0g
Butyl acrylate 18.4g
Vinylformic acid 1.5g
Hydroxyethyl acrylate 25g
A-174 (silane portion of GE company) 1.0g
Vinyl tertiary carbon acid esters (EXXON company) 1.5g
Trimethylolpropane allyl ether 0.1
Prescription (3):
Potassium Persulphate (5% aqueous solution) 16g
The preparation process of thermoset acrylics emulsion is as follows:
(1) under the condition of nitrogen protection, in 1 liter of reaction flask that agitator, thermometer, condenser are housed, add each material in the prescription (1) successively, mix, be heated to 40 ℃, make mixture A:
(2) in beaker, add all monomers in the prescription (2) successively, mix, make mixture B;
(3) the mixture B with 1% (weight) adds among the mixture A, stirs 15 minutes under 40 ℃ of temperature, makes mixture C;
(4) material in the prescription (3) of 50% (weight) is added mixture C, reacted 20 minutes down, make seed emulsion D at 85 ℃;
(5) be added dropwise among the seed emulsion D material is semicontinuous respectively simultaneously among the remaining mixture B, remaining prescription (3), under 85 ℃ of temperature, dripped 2.5 hours, drip the back and be incubated 1 hour down at 85 ℃, with trolamine emulsion being neutralized to the pH value then is 7～8, with deionized water the solid content of emulsion is adjusted to 35% at last, makes negatively charged ion thermoset acrylics emulsion.
Embodiment 2
Prescription (1):
25% ammonia soln of AMPS (Lubrizol company) *4.0g
Sodium lauryl sulphate (5% aqueous solution) 16.0g
Deionized water 150g
Prescription (2):
Methyl methacrylate 42.95g
Isooctyl acrylate monomer 20.0g
Butyl acrylate 14.0g
Methacrylic acid 4.0g
Hydroxyethyl methylacrylate 15g
Witco A-172 (silane portion of GE company) 1.5g
Glycidyl methacrylate 1.5g
Trimethylolpropane trimethacrylate 0.05
Prescription (3):
Potassium Persulphate (5% aqueous solution) 30g
( *The preparation of AMPS 25% ammonia soln: the AMPS solid is made into 30% aqueous solution with deionized water, regulates pH to 5-6 with ammoniacal liquor then, regulate effectively part with deionized water again, count 25% with AMPS.)
The preparation process of thermoset acrylics emulsion is as follows:
(1) under the condition of nitrogen protection, in 1 liter of reaction flask that agitator, thermometer, condenser are housed, add each material in the prescription (1) successively, mix, be heated to 85 ℃, make mixture A:
(2) in beaker, add all monomers in the prescription (2) successively, mix, make mixture B;
(3) the mixture B with 10% (weight) adds among the mixture A, stirs 5 minutes under 85 ℃ of temperature, makes mixture C;
(4) material in the prescription (3) of 10% (weight) is added mixture C, reacted 20 minutes down, make seed emulsion D at 85 ℃;
(5) be added dropwise among the seed emulsion D material is semicontinuous respectively simultaneously among the remaining mixture B, remaining prescription (3), under 85 ℃ of temperature, dripped 2 hours, drip the back and be incubated 2 hours down at 85 ℃, with ammoniacal liquor emulsion being neutralized to the pH value then is 7～8, with deionized water the solid content of emulsion is adjusted to 25% at last, makes negatively charged ion thermoset acrylics emulsion.
Embodiment 3
Prescription (1):
AMPS (NH3) (Lubrizol company) (25% aqueous solution) 16.0g
Sodium lauryl sulphate (5% aqueous solution) 2.0g
Deionized water 150g
Prescription (2):
Methyl methacrylate 40.3g
Isooctyl acrylate monomer 16.0g
Butyl acrylate 21.0g
Vinylformic acid 8.0g
Hydroxyethyl acrylate 10g
A-151 (silane portion of GE company) 0.5g
Viscoat 295 0.2g
Prescription (3):
Potassium Persulphate (5% aqueous solution) 60g
The preparation process of thermoset acrylics emulsion is as follows:
(1) under the condition of nitrogen protection, in 1 liter of reaction flask that agitator, thermometer, condenser are housed, add each material in the prescription (1) successively, mix, be heated to 70 ℃, make mixture A;
(2) in beaker, add all monomers in the prescription (2) successively, mix, make mixture B;
(3) the mixture B with 5% (weight) adds among the mixture A, stirs 10 minutes under 70 ℃ of temperature, makes mixture C;
(4) material in the prescription (3) of 30% (weight) is added mixture C, reacted 30 minutes down, make seed emulsion D at 80 ℃;
(5) be added dropwise among the seed emulsion D material is semicontinuous respectively simultaneously among the remaining mixture B, remaining prescription (3), under 80 ℃ of temperature, dripped 2.5 hours, drip the back and be incubated 1 hour down at 80 ℃, with diethanolamine emulsion being neutralized to the pH value then is 7～8, with deionized water the solid content of emulsion is adjusted to 30% at last, makes negatively charged ion thermoset acrylics emulsion.
Embodiment 4
Prescription (1):
AMPS (Na) (Lubrizol company) (25% aqueous solution) 8.0g
Ethoxylated dodecyl alcohol sodium sulfonate (25% aqueous solution) 6.0g
Deionized water 150g
Prescription (2):
Methyl methacrylate 14.0g
Isooctyl acrylate monomer 11.15g
Butyl acrylate 38.0g
Vinylformic acid 0.8g
Hydroxyethyl acrylate 30g
A-172 (silane portion of GE company) 0.05g
Dimethacrylate macrogol ester 4.0g
Prescription (3):
Potassium Persulphate (5% aqueous solution) 10g
The preparation process of thermoset acrylics emulsion is as follows:
(1) in 1 liter of reaction flask that agitator, thermometer, condenser are housed, add each material in the prescription (1) successively, mix, be heated to 50 ℃, make mixture A;
(2) in beaker, add all monomers in the prescription (2) successively, mix, make mixture B;
(3) the mixture B with 4% (weight) adds among the mixture A, stirs 10 minutes under 75 ℃ of temperature, makes mixture C;
(4) material in the prescription (3) of 25% (weight) is added mixture C, reacted 60 minutes down, make seed emulsion D at 75 ℃;
(5) be added dropwise among the seed emulsion D material is semicontinuous respectively simultaneously among the remaining mixture B, remaining prescription (3), under 75 ℃ of temperature, dripped 3.5 hours, dripping the back is incubated 1 hour down at 75 ℃, is incubated 1 hour down at 80 ℃ again, use N then, it is 7～8 that the N dimethylethanolamine is neutralized to the pH value with emulsion, with deionized water the solid content of emulsion is adjusted to 30% at last, makes negatively charged ion thermoset acrylics emulsion.
Embodiment 5
Prescription (1):
COPS-1 (the 8.0g of Rhodia company (25% aqueous solution)
Sodium lauryl sulphate (5% aqueous solution) 4.0g
Deionized water 150g
Prescription (2):
Vinylbenzene 32g
Vinyl acetate 3g
Butyl acrylate 36.5g
Methacrylic acid 1.5g
Hydroxyethyl methylacrylate 25g
Prescription (3):
Potassium Persulphate (5% aqueous solution) 16g
The preparation process of thermoset acrylics emulsion is as follows:
(1) in 1 liter of reaction flask that agitator, thermometer, condenser are housed, add each material in the prescription (1) successively, mix, be heated to 60 ℃, make mixture A;
(2) in beaker, add all monomers in the prescription (2) successively, mix, make mixture B;
(3) the mixture B with 5% (weight) adds among the mixture A, stirs 10 minutes under 80 ℃ of temperature, makes mixture C;
(4) material in the prescription (3) of 30% (weight) is added mixture C, reacted 30 minutes down, make seed emulsion D at 80 ℃;
(5) be added dropwise among the seed emulsion D material is semicontinuous respectively simultaneously among the remaining mixture B, remaining prescription (3), under 80 ℃ of temperature, dripped 2 hours, dripping the back is incubated 1 hour down at 80 ℃, is incubated 1 hour down at 85 ℃ again, with 2-methyl 2-aminopropanol emulsion being neutralized to the pH value then is 7～8, with deionized water the solid content of emulsion is adjusted to 30% at last, makes negatively charged ion thermoset acrylics emulsion.
Embodiment 6
Prescription (1):
Sodium dodecylbenzene sulfonate (5% aqueous solution) 10g
To styryl sodium sulfonate (5% aqueous solution) 40g
Deionized water 150g
Prescription (2):
Vinylbenzene 17g
Isooctyl acrylate monomer 14.5g
Butyl acrylate 30g
Lauryl acrylate 18.4g
Methacrylic acid 4.0g
Hydroxyethyl methylacrylate 11g
Glycidyl methacrylate 2.0g
Diacrylate TEG ester 1.0g
A-2171 (silane portion of GE company) 0.1g
Prescription (3):
Sodium Persulfate (5% aqueous solution) 20g
The preparation process of thermoset acrylics emulsion is as embodiment 3.
Embodiment 7
Prescription (1):
AP-065 (Rhodia company) (5% aqueous solution) 10g
JS-2 (Mitsubishi Chemical) (5% aqueous solution) 40g
Deionized water 150g
Prescription (2):
Vinylbenzene 20g
Isooctyl acrylate monomer 10g
Butyl acrylate 41.0g
Lauryl acrylate 8.9g
Vinylformic acid 4.0g
Hydroxyethyl acrylate 11g
2-methacryloyl oxyethyl group phosphoesterase 30 .5g
Dimethacrylate triglycol ester 2.0g
A-151 (silane portion of GE company) 0.1g
Prescription (3):
Sodium Persulfate (5% aqueous solution) 16g
The preparation process of thermoset acrylics emulsion is as embodiment 4.
Embodiment 8
Prescription (1):
Sodium lauryl sulphate (5% aqueous solution) 4.0g
DNS-10 (two key chemistry, 30% aqueous solution) 3.7g
Bvconc (Clariant) (50% aqueous solution) 0.4g
V5127 (Clariant) (100% effective part) 0.3g
AMPS (Na) (Lubrizol company) (50% aqueous solution) 0.4g
Deionized water 150g
Prescription (2):
Methyl methacrylate 18g
Vinylbenzene 24.7g
Butyl acrylate 22.8g
Vinylformic acid 1g
Propylene glycol monoacrylate 16g
Hydroxyethyl methylacrylate 11.0g
PEG400DMA (Bisomer company) (long-chain cross-linking monomer) 3.0g
DV-6280 (Rhodia company) 3.0g
Prescription (3):
Sodium Persulfate (5% aqueous solution) 60g
The preparation process of thermoset acrylics emulsion is as embodiment 3.
Embodiment 9
Prescription (1):
Sodium dodecylbenzene sulfonate (5% aqueous solution) 4g
Polyoxyethylene nonylphenol ether (25% aqueous solution) 2.4g
AMPS (Na) (Lubrizol company) (50% aqueous solution) 2.0g
Deionized water 150g
Prescription (2):
Methyl methacrylate 26.8g
Butyl acrylate 42.7g
Vinylformic acid 2.0g
Propylene glycol monoacrylate 18g
Hydroxyethyl methylacrylate 9.0g
A-172 (silane portion of GE company) 0.5g
Prescription (3):
Ammonium persulphate (5% aqueous solution) 20g
The preparation process of thermoset acrylics emulsion is as embodiment 4.
Embodiment 10
Prescription (1):
Dodecyl benzyl dimethyl ammonium chloride (20% aqueous solution) 7.5g
Methylacryoyloxyethyl trimethyl ammonium chloride (25% aqueous solution) 4g
Deionized water 150g
Prescription (2):
Vinylbenzene 17g
Isooctyl acrylate monomer 16.5g
Butyl acrylate 29g
Lauryl acrylate 19g
Methacrylic acid 4.0g
Hydroxyethyl methylacrylate 11g
Glycidyl methacrylate 2.0g
Diacrylate binaryglycol ester 0.5g
Prescription (3):
2,2-azo two (2-amidine propane) dihydrochloride (5% aqueous solution) 16g
The preparation process of thermoset acrylics emulsion is as follows:
(1) under the condition of nitrogen protection, in 1 liter of reaction flask that agitator, thermometer, condenser are housed, add each material in the prescription (1) successively, mix, be heated to 70 ℃, make mixture A;
(2) in beaker, add all monomers in the prescription (2) successively, mix, make mixture B;
(3) the mixture B with 5% (weight) adds among the mixture A, stirs 10 minutes under 70 ℃ of temperature, makes mixture C;
(4) material in the prescription (3) of 25% (weight) is added mixture C, reacted 30 minutes down, make seed emulsion D at 75 ℃;
(5) be added dropwise among the seed emulsion D material is semicontinuous respectively simultaneously among the remaining mixture B, remaining prescription (3), under 75 ℃ of temperature, dripped 3 hours, drip the back and be incubated 1 hour down at 75 ℃, be incubated 1 hour down at 80 ℃ again, with 3N hydrochloric acid emulsion being acidified to the pH value then is 5～6.With deionized water the solid content of emulsion is adjusted to 30% at last, makes positively charged ion thermoset acrylics emulsion.
Embodiment 11
Prescription (1):
Hexadecyl benzyl dimethly ammonium chloride (5% aqueous solution) 8g
Polyoxyethylene nonylphenol ether (5% aqueous solution) 8g
Methylacryoyloxyethyl trimethyl ammonium chloride (25% aqueous solution) 8g
Deionized water 150g
Prescription (2):
Methyl methacrylate 12.6g
Isooctyl acrylate monomer 25.0g
Butyl acrylate 40.0g
Vinylformic acid 4.0g
Hydroxyethyl acrylate 15g
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 1.0g
WitcoA-2171 (silane portion of GE company) 0.2g
Trimethylolpropane trimethacrylate 0.2g
Prescription (3):
4, two 4-cyanopentanoic acid sodium (5% aqueous solution) 60g of 4-azo
The preparation process of thermoset acrylics emulsion is as follows:
(1) under the condition of nitrogen protection, in 1 liter of reaction flask that agitator, thermometer, condenser are housed, add each material in the prescription (1) successively, mix, be heated to 70 ℃, make mixture A;
(2) in beaker, add all monomers in the prescription (2) successively, mix, make mixture B;
(3) the mixture B with 5% (weight) adds among the mixture A, stirs 10 minutes under 70 ℃ of temperature, makes mixture C;
(4) material in the prescription (3) of 25% (weight) is added mixture C, reacted 30 minutes down, make seed emulsion D at 80 ℃;
(5) be added dropwise among the seed emulsion D material is semicontinuous respectively simultaneously among the remaining mixture B, remaining prescription (3), under 80 ℃ of temperature, dripped 2.5 hours, dripping the back is incubated 1 hour down at 80 ℃, is incubated 1 hour down at 85 ℃ again, with acetic acid emulsion being acidified to the pH value then is 5～6, with deionized water the solid content of emulsion is adjusted to 30% at last, makes positively charged ion thermoset acrylics emulsion.
Comparative Examples 1
Prescription (1):
Sodium lauryl sulphate (5% aqueous solution) 40g
AP-065 (30%) (Rhodia company) 2.0g
V5127 (100%) (Clariant) 2.0g
AMPS (NH3) (50% aqueous solution) (Lubrizol company) 6g
Deionized water 150g
Prescription (2):
Vinylbenzene 21g
Isooctyl acrylate monomer 15.3g
Butyl acrylate 31g
Lauryl acrylate 10g
Methacrylic acid 4.0g
Hydroxyethyl methylacrylate 11g
Glycidyl methacrylate 2.0g
Diacrylate TEG ester 0.5g
Witco A-172 (silane portion of GE company) 0.2
Prescription (3):
Sodium Persulfate (5% aqueous solution) 20g
Concrete preparation process is with embodiment 6.
Comparative Examples 2
Prescription (1):
Sodium lauryl sulphate (5% aqueous solution) 30g
Polyoxyethylene nonylphenol ether (5% aqueous solution) 30g
AMPS (NH3) (50% aqueous solution) 1.6g
Deionized water 150g
Prescription (2):
Vinylbenzene 40.0g
Butyl acrylate 42.2g
Vinylformic acid 3.0g
Hydroxyethyl methylacrylate 6.0g
Rhodia DV-6280 3.0g
Dimethacrylate triglycol ester 5.0g
Prescription (3):
Sodium Persulfate (5% aqueous solution) 20g
Concrete preparation process is with embodiment 2.
Comparative Examples 3
Prescription (1):
Sodium dodecylbenzene sulfonate (5% aqueous solution) 4.0g
DNS-10 (two key chemistry, 30% aqueous solution) 3.7g
Bvconc (50% aqueous solution) (Clariant company) 0.4g
V5127 (100%) (Clariant company) 0.3g
AMPS (Na) (Lubrizol company) (50% aqueous solution) 0.4g
Deionized water 150g
Prescription (2):
Methyl methacrylate 30g
Vinylbenzene 32g
Butyl acrylate 20.0g
Vinylformic acid 0.2g
Hydroxyethyl methylacrylate 15g
PEG400DMA (Bisomer company) 0.3g
A-174 (silane portion of GE company) 2.0g
Prescription (3):
Sodium Persulfate (5% aqueous solution) 20g
Concrete preparation process is with embodiment 3.
Comparative Examples 4
Prescription (1):
Sodium lauryl sulphate (5% aqueous solution) 4.0g
DNS-10 (two key chemistry, 30% aqueous solution) 3.7g
Clariant Bvconc (50% aqueous solution) 0.4g
Clariant V5127 (100% aqueous solution) 0.3g
AMPS (Na) (50% aqueous solution) 0.4g
Deionized water 150g
Prescription (2):
Methyl methacrylate 19.5g
Butyl acrylate 63g
Vinylformic acid 2.0g
Hydroxyethyl acrylate 15.0g
Prescription (3):
Sodium Persulfate (5% aqueous solution) 5g
Concrete preparation process is with embodiment 4.
Comparative Examples 5
Prescription (1):
Hexadecyl benzyl dimethly ammonium chloride (25% aqueous solution) 8g
Methylacryoyloxyethyl trimethyl ammonium chloride (25% aqueous solution) 20g
Deionized water 150g
Prescription (2):
Methyl methacrylate 24.6g
Isooctyl acrylate monomer 20.0g
Butyl acrylate 30.0g
Vinylformic acid 4.0g
Hydroxyethyl acrylate 15g
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 1.0g
Witco A-151 (silane portion of GE company) 0.2
Trimethylolpropane trimethacrylate 0.2g
Prescription (3):
4, two 4-cyanopentanoic acid sodium (5% aqueous solution) 60g of 4-azo
Concrete preparation process is with embodiment 11.
The physicals of the foregoing description 1～11,1～5 synthetic thermoset acrylics of Comparative Examples emulsion sees Table 1:
Table 1
Numbering Outward appearance Tg (℃) calculated value Freeze-thaw cycle (number of times) Mechanical stability Stability in storage Foam volume
Embodiment 1 Little blue emulsion 15 3 ○ ○ ◎
Embodiment 2 Little blue emulsion 40 2 ○ ○ ◎
Embodiment 3 Little blue emulsion 30 3 ○ ○ ◎
Embodiment 4 Little blue emulsion -15 3 ◎ ○ ◎
Embodiment 5 Little blue emulsion 15 3 ◎ ○ ◎
Embodiment 6 Blue phase emulsion 0 3 ○ ◎ ○
Embodiment 7 Blue phase emulsion -10 3 ○ ◎ ○
Embodiment 8 Blue phase emulsion 20 2 ◎ ◎ ○
Embodiment 9 Little blue emulsion 0 3 ○ ○ ○
Embodiment 10 Little blue emulsion 0 3 ○ ◎ ◎
Embodiment 11 Blue phase emulsion -10 3 ◎ ◎ ◎
Comparative Examples 1 Blue phase emulsion 0 3 ◎ ◎ ×
Comparative Examples 2 Blue phase emulsion 5 3 × × ×
Comparative Examples 3 Little blue phase emulsion 50 × × × ○
Comparative Examples 4 Blue phase emulsion -25 3 ◎ ◎ ×
Comparative Examples 5 Blue phase emulsion 15 3 ◎ ◎ ×
*The Tg of emulsion copolymers is calculated as follows and gets
1/Tg=W 1/ Tg 1+ W 2/ Tg 2+ ...+W i/ Tg i+ ...+W n/ Tg n, Tg wherein iThe second-order transition temperature of each monomer homopolymer of n kind monomer of polymkeric substance is formed in representative, with absolute temperature (L) expression, W iRepresent every kind of monomeric massfraction, that is: W 1+ W 2+ ...+W i+ ...+W n=1
*Freezing-thawing cycles ,-18 ℃ 12 hours, 25 ℃ were once circulation in 12 hours, breakdown of emulsion not, the viscosity that circulates each time change and are no more than 5 seconds
*Mechanical stability, 300 gram emulsions, 2000-3000 changes dispersion 15 minutes, and breakdown of emulsion is not stratified, does not reunite, and does not have particulate matter to appear as top grade and represents that with ◎ zero is good, and △ is general, * poor
*Foam volume, each 300 gram of each emulsion, the 2000-3000 commentaries on classics disperseed 15 minutes, compared what and lather collapse speed of foam volume, and the ◎ foam is few, disappears soon, and zero foam volume is less, disappears comparatively fast, and the △ foam volume is more, and it is slower to disappear, and * foam volume is many, and it is slow to disappear
*Stability in storage: 12 months emulsion no changes of room temperature condition storage time ◎, 06 months, △ 3 months, * less than 3 months
By table 1 as seen, hydroxyl, the low stable resin that all is unfavorable for of the consumption of carboxylic monomer and initiator, the ionic comonomer consumption surpasses 4% and also is unfavorable for emulsion-stabilizing, can be understood as hydroxyl, when carboxylic monomer content hangs down, the wetting ability of resin self is not enough, can not stable being dispersed in the water when low surfactant, in addition, hydroxyl, carboxylic monomer content is low, also is unfavorable for the cross-linking and curing reaction of emulsion and linking agent, and amount of initiator is too low, react inhomogeneous, also incomplete, and the ion monomer consumption is when high, because the ion monomer wetting ability is too strong, polarity is strong, be unfavorable for and the copolymerization in micella drop or emulsion droplet of other monomer, and tend to autohemagglutination in water, also be unfavorable for the stable of homogeneous reaction and emulsion; Second-order transition temperature is too high, and the freeze-thaw stability of emulsion is poor, and second-order transition temperature is too low, and curing speed is slow, is unfavorable for high-speed coating.The conventional surfactant consumption is big, though help the stable of emulsion, the foam that causes thus is unfavorable for high-speed coating, also is unfavorable for the preservative property of coating.Each composition described in the present invention is in preferable range, and the emulsion that obtains is not only steeped less, stablized, but suitability for industrialized production also
Embodiment 12～22
Be used for the corrosion-resistant primary coat of air-condition heat exchanger aluminium fin, by comprising that thermoset acrylics emulsion that embodiment 1～11 is prepared etc. forms, concrete component and content see Table 2.
Comparative Examples 6～10
Coating composition, by comprising that ACRYLIC EMULSION that Comparative Examples 1～5 is prepared etc. forms, concrete component and content see Table 2.
Table 2 (unit: g)
Embodiment Low soap ACRYLIC EMULSION Water-base resin Adhesion promoter Water cross-linking agent Catalyzer Neutralizing agent Solubility promoter Water
Embodiment 12 30(R01) 10(A) 0.5(E) 6(H) 0.2(L) 0.1(O) 14 39.2
Embodiment 13 45(R02) 2(C) 1.0(G) 9(I) 0.3(L) 0.2(P) 13 31.0
Embodiment 14 25(R03) 20(B) - 15(J) 0.2(M) 0.1(O) 10 27.9
Embodiment 15 60(R04) 1(D) 2.0(F) 7.5(H) 0.3(M) 0.2(P) 12 18.0
Embodiment 16 40(R05) 2(B) 2.0(F) 12(J) 0.3(L) 0.2(O) 6 37.8
Embodiment 17 35(R06) 2(A) 1.0(E) 12(H) 0.2(M) 0.1(P) 14 35.7
Embodiment 18 20(R07) 15(A) 0.5(G) 6(H) 0.2(M) 0.1(P) 15 43.2
Embodiment 19 35(R08) 10(C) - 10(J) 0.3(L) 0.2(P) 10 33.8
Embodiment 20 35(R09) 5(D) 1(F) 10(I) 0.3(N) 0.1(O) 15 34.6
Embodiment 21 35(R10) 10(B) 2(G) 5(K) 0.3(N) 0.2(Q) 12 35.5
Embodiment 22 50(R11) 1(D) 2(E) 8(K) 0.3(N) 0.2(Q) 13 25.5
Comparative Examples 6 25(COR1) 15(A) 1(D) 10(H) 0.3(L) 0.2(O) 10 38.5
Comparative Examples 7 35(COR2) 10(B) 2(E) 5(J) 0.3(L) 0.1(P) 15 35.4
Comparative Examples 8 45(COR3) 5(C) 3(F) 8(I) 0.3(L) 0.2(O) 12 26.5
Comparative Examples 9 45(COR4) 0.5(D) 2(E) 15(J) 0.3(L) 0.2(O) 13 22.5
Comparative Examples 10 40(COR5) 2(A) 2(E) 10(K) 0.3(N) 0.2(Q) 14 30.5
In the table 2:
The thermoset acrylics emulsion that R01～the R11 representative is prepared by embodiment 1～11;
The ACRYLIC EMULSION that COR1～the COR5 representative is prepared by Comparative Examples 1～5;
(1) water-base resin
A: aqueous epoxy resins 3520-WY-55Surface Speciality
B: water-based saturated polyester Uradil SZ255 DSM
C: the sharp chemical materials of water-base epoxy ester HD-E50 Beijing Jin Hui company limited
D: change among the water-based epoxy acrylic resin WY-12H and build Changzhou coating institute
(2) adhesion promoter
E：EP-1300 Degussa
F：Halox 570 Hammond Group Inc.
G：Borcher HMP Byers
(3) water cross-linking agent
H：Cymel 303 Cytec Co.，Ltd.
I：Cymel 1168 Cytec Co.，Ltd.
J Resimene 747 UCB-Grou p
K：Trixene B1 7986 Baxene Chemicals Ltd.
(4) catalyzer
L：Cycat 4040 Cytec Co.，Ltd
M：Cyact 500 Cytec Co.，Ltd
N: dibutyl tin laurate
(5) neutralizing agent
O:N, the N-dimethylethanolamine
P:2-methyl 2-aminopropanol
Q: acetate
Solubility promoter: ethylene glycol monobutyl ether
The corrosion-resistant primary coat that is used for air-condition heat exchanger aluminium fin of embodiment 12～22, the coating composition of Comparative Examples 6～10 are carried out performance test, and concrete parameter sees Table 3:
Model preparation: with the trade mark is 8011 or 1030B, and thickness is that the aluminium foil of 0.105～0.115mm soaks certain hour in alkaline defatting agent, removes the ROLLING OIL on surface, cleans successively once with tap water and deionized water then, again 1000 ℃ of oven dry.With line rod spreader the coating sample for preparing is coated on the above-mentioned aluminium foil that cleans up, toasts 20-25 second at 280 ℃.The control build is 0.8～1.0 micron.After treating the model cooling, apply the wetting ability face more in the above and be coated with, after being heating and curing, make model.
In the table 3, the index of each performance perameter is:
(1) alkali resistance: model soaked 10 minutes in 20% NaOH
◎: the non-foaming nothing of coating comes off
Zero: coating has a small amount of small bubbles
△: coating has more small bubbles
*: coating shedding or have a large amount of bubbles to produce
(2) sticking power: draw the lattice device with paint film and on model, mark 100 grid that are spaced apart 1mm, test sticking power, test the sticking power of primary coat and base material and face respectively and be coated with ply adhesion with primary coat with scotch tape
◎: coating does not have and comes off
Zero: the coating shedding area is less than 2%
△: coating shedding area 2-5%
*: the coating shedding area is greater than 5%
(3) salt fog resistance: test condition: 5%NaCl, 40 ℃, spraying continuously
◎: the salt spray resistance grade was 9.8 grades in 1000 hours
The salt spray resistance grade was 9.8 grades in zero: 500 hour
△: the salt spray resistance grade was 9.8 grades in 100 hours
*: 100 hours salt spray resistance grade＜9.8 grade
(4) humidity resistance: test condition: 400C relative humidity〉95%1000 hours
◎: model no change
Zero: there are indivedual tiny hot spots on the model surface
△: there is more tiny hot spot on the model surface
*: there is bigger hot spot on the model surface, or perforation
(5) water boiling resistance: model is boiled 30min in ebullient water, observe appearance of coat and change.
◎: model no change
Zero: model slightly turns white
△: model turns white, and can wipe off.
*: coating shedding
(6) yellowing resistance: model 300 ℃ of bakings 5 minutes, is observed appearance of coat and changed
◎: the slight xanthochromia of coating
Zero: coating becomes khaki color
△: coating becomes isabelline
*: coating becomes brown-black
(7) post-treatment
1.T it is curved: as, to investigate folding line place coating and have or not and come off with the doubling outwardly of cated model coating.
Nothing comes off: qualified
2. impact: model is placed on the paint film impactor, and the 1kg weight impacts model in 50 cm height free-fallings, and pros and cons is all tested, and coating does not have the cracking that comes off for qualified.
3. cupping: model is placed on the cupping instrument, voltage rise height 5mm, coating does not have coming off cracking for qualified on the model.
(8) stability in storage: judgment criteria is with the stability of resin
The The performance test results of table 3 embodiment 12～22, Comparative Examples 6～10
Embodiment Primary coat sticking power Alkali resistance Salt fog resistance Humidity resistance Water boiling resistance Face is coated with sticking power Yellowing resistance Post-treatment Stability in storage
Embodiment 12 ◎ ◎ ◎ ◎ ○ ◎ ◎ ◎ ○
Embodiment 13 ◎ ○ ◎ ◎ ○ ◎ ◎ ◎ ○
Embodiment 14 ◎ ○ △ ○ ◎ ◎ ◎ ◎ ○
Embodiment 15 ◎ ◎ ◎ ◎ ○ ◎ ◎ ◎ ○
Embodiment 16 ◎ ○ ○ ○ ○ ◎ ◎ ◎ ○
Embodiment 17 ◎ ◎ ○ ○ ○ ○ ○ ◎ ◎
Embodiment 18 ◎ ○ △ △ ○ ○ ○ ◎ ◎
Embodiment 19 ◎ ○ ○ ◎ ○ ○ ○ ◎ ◎
Embodiment 20 ◎ ○ ○ ○ ○ ○ ○ ◎ ○
Embodiment 21 ◎ ○ ◎ ○ ◎ ◎ ○ ◎ ◎
Embodiment 22 ◎ ○ ◎ ○ ◎ ◎ ○ ◎ ◎
Comparative Examples 6 ◎ △ × × △ × ○ × ◎
Comparative Examples 7 ○ △ △ △ △ × ○ × △
Comparative Examples 8 ○ ○ △ △ △ × ○ × ×
Comparative Examples 9 ◎ ○ × △ △ △ ○ ○ ◎
Comparative Examples 10 ○ ◎ ○ △ × △ ○ ○ ◎
By table 3 as seen; employed conventional surfactant of emulsion among the present invention or emulsifier content are low; contain higher hydroxyl simultaneously; carboxyl; the water-base resin that cooperates other carboxylic water-based polyester/acrylic resin and contain epoxy group(ing)/epoxy phosphate base; formed water-borne coatings; when reducing foam volume, can make coating stable again; be convenient to the coating of coating high-speed and continuous; be used for the coating of air-condition heat exchanger aluminium fin; can make the contact more adherence of coating,, improve the lasting erosion resistance of undercoat to promote the protection of primary coat to base material to aluminium foil.Coating has good recoatability simultaneously, can be coated with by the multiple commodity hydrophilic surface of supporting coating, and good ply adhesion is arranged between undercoat and the finishing coat.Compare with inorganic chromaking primary coat, not only satisfied the over-all properties requirement of air-condition heat exchanger primary coat, and environmental friendliness.

Claims (19)

1, a kind of thermoset acrylics emulsion comprises following component:
(1) one or more acrylic monomers, consumption are 58%～99.5% of all total monomer weights; Described acrylic monomer comprises carboxy acrylic class monomer and hydroxyl acrylic class monomer and other acrylic monomers, wherein carboxy acrylic class monomer accounts for 0.8%～8% of all total monomer weights, and hydroxyl acrylic class monomer accounts for 10%～30% of all total monomer weights;
(2) one or more ionic olefinic class monomers, consumption is 0.5～4.0% of all total monomer weights;
(3) vinyl monomer, consumption are 0～35% of all total monomer weights;
(4) olefinic one type of silane coupling agent, consumption are 0～1.5% of all total monomer weights;
(5) cross-linking monomer contains two two keys at least in its molecular structure, consumption is 0～4% of all total monomer weights;
(6) tensio-active agent, consumption are 0.1～1.5% of all total monomer weights;
(7) initiator, consumption are 0.5～3% of all total monomer weights;
Above-mentioned all components weight is solid weight; Described all monomers are made up of the listed monomer in above-mentioned (1)～(5).
2, thermoset acrylics emulsion according to claim 1, it is characterized in that: the consumption of described acrylic monomer is 70%～98% of all total monomer weights, wherein, the monomeric consumption of carboxy acrylic class is 1.5%～4.0% of all total monomer weights, and the monomeric consumption of hydroxyl acrylic class is 15%～25% of all total monomer weights.
3, thermoset acrylics emulsion according to claim 1 is characterized in that: described other acrylic monomers are acrylic acid or the like soft or hard monomer and acrylic functional monomer.
4, thermoset acrylics emulsion according to claim 3 is characterized in that: described acrylic functional monomer is one or more mixtures in amide group acrylic monomer, epoxy group(ing) acrylic monomer, the basic acrylic monomer of phosphoric acid (ester), the aminoacrylic acid class monomer.
5, thermoset acrylics emulsion according to claim 1 is characterized in that: described ionic olefinic class monomer is carboxylate salt, sulfonic acid (salt) or the quaternary ammonium salt that contains two keys.
6, thermoset acrylics emulsion according to claim 1 is characterized in that: described vinyl monomer is vinylbenzene, vinyl acetate, vinylchlorid, chlorinated polyvinyl chloride or vinyl tertiary carbon acid esters.
7, thermoset acrylics emulsion according to claim 1 is characterized in that: described olefinic one type of silane coupling agent is the silane coupling agent that contains acryl or contain vinyl.
8, thermoset acrylics emulsion according to claim 1 is characterized in that: described cross-linking monomer is trimethylolpropane allyl ether, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, two (methyl) vinylformic acid binaryglycol ester, two (methyl) vinylformic acid triglycol ester, two (methyl) vinylformic acid TEG ester or (methyl) polyalkylene glycol acrylate ester.
9, thermoset acrylics emulsion according to claim 1 is characterized in that: described initiator is persulphate or azo compound.
10, the preparation method of each described thermoset acrylics emulsion of claim 1～9 comprises the steps:
(1) described ionic olefinic type monomers, described tensio-active agent and deionized water and stirring are mixed, be heated to 40～85 ℃, make mixture A;
(2) described acrylic monomer, described vinyl monomer, described olefinic one type of silane coupling agent and described cross-linking monomer are mixed, make mixture B;
(3) described 1～10% (weight) mixture B is added among the mixture A, under 40～85 ℃ of temperature, stirred 5～15 minutes, make mixture C;
(4) described 10～50% (weight) initiator is added in the mixture C, under 75～85 ℃ of temperature, reacted 20～60 minutes,, make seed emulsion D until no tangible monomers flow back;
(5) be added dropwise among the seed emulsion D remaining mixture B, remaining initiator are semicontinuous respectively simultaneously, under 75～85 ° of temperature, dripped 2～3.5 hours, kept 75～85 ℃ of temperature then 1～2 hour;
(6) regulate the pH value of emulsion with the pH regulator agent, with deionized water the solid content of emulsion is transferred to 25～35% then, make the thermoset acrylics emulsion.
11, the preparation method of thermoset acrylics emulsion according to claim 10 is characterized in that: in described step (1)～(6), adopt nitrogen protection.
12, the preparation method of thermoset acrylics emulsion according to claim 10 is characterized in that: the median size of prepared thermoset acrylics emulsion is 0.1～2 μ m; Number-average molecular weight is 1000～50000; Second-order transition temperature is-15～40 ℃; Solid content is 20～40%; Viscosity is 10 seconds～16 seconds.
13, be used for the corrosion-resistant primary coat of air-condition heat exchanger aluminium fin, comprise following component:
(1) each described thermoset acrylics emulsion of claim 1～9, consumption is 20～60 weight parts;
(2) water-base resin, consumption is 0.5～20 weight part, and described water-base resin is one or more mixtures in water-dispersion acrylic resin, aqueous epoxy resins, water-base epoxy phosphate resins, aqueous acrylic modified Resins, epoxy, the water-based saturated polyester resin;
(3) water cross-linking agent, consumption are 2～15 weight parts;
(4) solubility promoter, consumption are 5～15 weight parts;
(5) neutralizing agent, consumption are 0.05～0.5 weight part;
(6) water-based adhesion promoter, consumption are 0～5 weight part;
(7) catalyzer, consumption are 0.1～0.5 weight part;
(8) water, surplus;
The said components gross weight is 100 weight parts.
14, corrosion-resistant primary coat according to claim 13 is characterized in that: the consumption of described thermoset acrylics emulsion is 30～50 weight parts.
15, corrosion-resistant primary coat according to claim 13 is characterized in that: described water-dispersion acrylic resin and water-based saturated polyester resin, its acid number are 50～200mgKOH/g.
16, corrosion-resistant primary coat according to claim 13 is characterized in that: described aqueous epoxy resins and aqueous acrylic modified Resins, epoxy, and its molecular skeleton feature is bisphenol A-type, and weight-average molecular weight is 200～3000.
17, corrosion-resistant primary coat according to claim 13 is characterized in that: described water cross-linking agent is aminoresin or water-based isocyanate.
18, corrosion-resistant primary coat according to claim 13 is characterized in that: described solubility promoter is one or more mixtures in ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, propyl carbinol, isopropylcarbinol, propylene glycol monobutyl ether, the diethylene glycol monobutyl ether.
19, corrosion-resistant primary coat according to claim 13 is characterized in that: described neutralizing agent is ammoniacal liquor, N, N-dimethylethanolamine, diethanolamine, trolamine or 2-methyl 2-aminopropanol.
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