CN103665271A - Acrylic acid-epoxy ester hybrid resin and coatings thereof - Google Patents
Acrylic acid-epoxy ester hybrid resin and coatings thereof Download PDFInfo
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Abstract
The invention provides an acrylic acid-epoxy ester hybrid resin. The acrylic acid-epoxy ester hybrid resin is prepared by reacting an epoxy resin and aliphatic acid under the action of a catalyst so as to prepare epoxy ester and then adding acrylic monomers and an initiator under certain conditions. A self-drying type antirust coating can be prepared with the acrylic acid-epoxy ester hybrid resin provided by the invention as a main film forming substance; a dried anticorrosive coating can also be prepared, especially coatings for curtain spraying sliver-coated mirrors, color films and aluminum mirrors; the coatings can meet coating process requirements of a wide-curtain spraying and coating production line with a maximum length of 3 m and are completely dried when baked at a temperature of 130 to 150 DEG C for 5 to 3 min, a film obtained after complete drying has excellent anticorrosion performance, can resist CASS, dampness, dryness and water with a temperature of 60 DEG C for more than 240 h, satisfy requirements of edging and texturing process of a downstream client and do not suffer from edge blackening and corrosion of clad layers.
Description
Technical field
The present invention relates to a kind of epoxy ester resin, relate in particular to a kind of vinylformic acid-epoxy ester hybrid resin, and the coating that contains this resin.
Background technology
Tradition mirror is pressed plated metallic reflector material and can be divided two large classes, i.e. silver mirror and aluminium mirror, along with scientific and technical development, occur plating other color metals and the decorating mirror that forms color is referred to as color film (color mirror) in recent years.Traditionally, the coating that employing curtain on mirror line processed is drenched to form of construction work in mirror industry processed is referred to as mirror back paint, by being divided into for base material: silver-colored mirror back lacquer, aluminium mirror back lacquer, color film paint and glass lacquer.
Silver mirror is divided into again has copper silver mirror and without bronze mirror; there is the production technique of copper silver mirror to be: by chemical method, at glass surface plating layer of metal silver, to be first reflecting layer; and then on silverskin, plate layer of copper; to increase the reflecting effect of silverskin and to protect silverskin, then be silver-colored mirror back lacquer at copper film surface-coated protective cover.Without bronze mirror production technique and have bronze mirror production technique suitable, only plate less layer of copper, be coated in without the coating on bronze mirror and be copper-free silver mirror back of the body paint, copper-free silver mirror relative environmental protection.
Aluminium mirror production method has two kinds: a kind of is evaporation plating aluminium, in the vacuum chamber of certain vacuum degree, glass surface deposition one deck aluminium is as reflecting layer, and when this method is produced, semi-continuous process is produced, production efficiency is on the low side and be easily subject to outside contamination, can use self-drying type or baking-type aluminium mirror back lacquer; Another is horizontal magnetron sputtering method, and electronics accelerates to fly in the process of substrate and bumps with ar atmo under the effect of electric field, ionizes out a large amount of argon ions and electronics, and electronics flies to substrate.Argon ion accelerates bombardment target under the effect of electric field; sputter a large amount of target atom; be neutral target atom (or molecule) and be deposited on film forming on substrate; form reflecting layer; magnetron sputtering method is that serialization is produced; on market, mainly with aluminium target, be main, the protective cover being coated on aluminium film is aluminium mirror paint.
In recent years, on horizontal magnetic control line, use the various metals such as copper target, silver-colored target, nickel target and stainless target, different target interworkings or production technique change, and can form various colored plated films, as yellow in crystal, rich and honour Huang, powder mirror etc., the general color film (color mirror) that claims, this coloured silk film reflecting layer is owing to being mainly copper metal, and character is active, very easily oxidation.
Along with the development of mirror industry processed, no matter silver mirror, aluminium mirror or color mirror need high temperature drying after the complete paint of showering, for saving workshop length, saving, toast energy, enhance productivity, after the lower sheet of oven dry, pack, need to use quick-drying mirror back lacquer; Reflecting layer (containing protective layer) metal (especially depositing up by horizontal line plated film Physical), all easily by atomospheric corrosion, needs good corrosion resistance; After having produced, need through complete processings such as cutting and edgings, in the course of processing, for guaranteeing not fall paint, need mirror back lacquer to there is good sticking power; In edging process, emery wheel high speed rotating, local temperature can reach more than 600 ℃, for cooling emery wheel, need to use water cooling, after glass and sand milling medium contact, partial hydrolysis, recycles rear water and is alkalescence, therefore needs mirror back lacquer to have good water tolerance and alkali resistance.
Epoxy-amino-stoving varnish, it all has high-performance at aspects such as water-fast, chemical-resistant resistance and salt spray resistances after doing solid work.But its shortcoming is: 1) dry slow; 2) need to could solidify 170 ℃ of above long-time bakings; 3) need strong solvent, as ketones solvent could dissolve, to the solvency power of solvent, require higher.
In aluminium mirror, after aluminium plated film, can in air, form aluminum oxide, finer and close, be relatively not easy oxidation.In color mirror, metal be take Cu as main, and is to be deposited on glass baseplate by Physical, more loose between atoms metal, and air, moisture content etc. easily corrode color film by loose gap infiltration, so color coating is comparatively crucial.
Chinese Patent Application No. 200610049898.7 discloses a kind of preparation method and application of organosilicon epoxide acrylate water dispersion, first use epoxy resin and lipid acid to be reacted to after terminal under effect at catalyzer, then reduce the temperature to 160 ℃-180 ℃, add unsaturated acid anhydride, speed with 2 ℃ of-4 ℃/min is warmed up to 240 ℃-250 ℃, then be incubated 0.5h-1h, after esterification completes, reduce temperature to 100 ℃-120 ℃, add acrylic monomer, reaction neutralizes and adds water, discharging afterwards to terminal.This resin adds unsaturated acid anhydride in 160 ℃-180 ℃, more slowly heats up, and unsaturated acid anhydride is active large, under high temperature easily autohemagglutination or and lipid acid in two key copolymerization, very easily make to react gel and be difficult to control, have a big risk, industrialization difficulty is higher.
Chinese invention patent ZL200510016476.5 discloses a kind of mirror back lacquer resin and curtain showering material thereof, and this resin solid component comprises the medium oil alkyd of 50%-70%, the poly-hydroxy acrylic resin of 20%-40% and the urethane resin of 10%-20%.Produce in process resin in the middle of obtaining with medium oil alkyd and acrylamide, hydroxyethyl meth acrylate and butyl methacrylate monomer generation copolyreaction; Middle resin reacts with tolylene diisocyanate, forms mirror back lacquer resin.Although by this method, produce the mirror back lacquer obtaining film high rigidity and good water tolerance, in the middle of existing resin react with tolylene diisocyanate after the difficult control of terminal, easy gel; And tolylene diisocyanate is highly toxic substance, from the more difficult control of the processes such as materials procurement, preservation, exist easily water suction to cause product to have serious quality problems.And tolylene diisocyanate price is high, and cost is higher, be not suitable for the production of mirror back lacquer.
Chinese invention patent application 200810152804.8 discloses a kind of acrylic graft-modified high hydroxyl value dry oil short oil alkyd resin, the catalyzer that contains 28%-33% siccative oil, 26%-35% polyvalent alcohol, 26%-43% polyprotonic acid, 13%-20% Acrylic Acid Monomer, 1.2%-2% initiator and trace.This resin has net vertical body structure, can effectively improve the compactness of coating structure, makes chemical substance be difficult for infiltrating, and also has the performances such as low temperature fast setting and height are anticorrosion.But because matrix resin is alkyd, Corrosion Protection is poor, in problems such as aspect poor-performing such as wet-heat resisting, resistance to CASS and chance water softenings.
In order to be adapted to the wide market requirement, still have a kind of quick-drying of both having had that goes out to be developed, there is again the coating of high anticorrosion and high comprehensive performance, especially for the mirror back paint of color film.
Summary of the invention
One object of the present invention is to provide a kind of vinylformic acid-epoxy ester hybrid resin, considers that epoxy ester Corrosion Protection is better, but does solid work slower, do solid work the problems such as rear paint film is partially soft, introduce crosslinked group monomer, especially acrylate moiety, improve molecular chain, shorten time of drying; Introduce hard monomer, improve hardness of paint film; Introduce acrylic monomer, reduced the requirement that solvent is used.
Another object of the present invention is to provide a kind of vinylformic acid-epoxy ester hybrid resin, consider later stage Acrylic Acid Monomer percentage of grafting problem, in epoxy ester building-up process, added unsaturated fatty acids, unsaturated double-bond can with two key copolymerization in acrylic monomer, this resin is from epoxy ester synthetic, be equipped with relevant Acrylic Acid Monomer, carry out radical polymerization and obtain, there is good sticking power with selecting amino resin crosslinked realization again, and can be at a lower temperature with the short period in curing coating.
A further object of the present invention is to provide a kind of thing coating that vinylformic acid-epoxy ester hybrid resin is main film forming of take, and as protective system, especially mirror back lacquer is applied to mirror industry processed.
Another object of the present invention is to provide a kind of coating for mirror back curtain drenching, various vinylformic acid-epoxy ester the hybrid resin provided by the invention of take is main film forming matter, take alcohol etherified amino resins or urea-formaldehyde resin as linking agent, paint film density is increased, strengthen erosion resistance, wet-heat resisting, resistance to acids and bases and the water tolerance of paint film.
Vinylformic acid-epoxy ester hybrid resin provided by the invention, to generate epoxy ester resin by the epoxy group(ing) in epoxy resin and the carboxyl esterification in lipid acid, by regulating lipid acid (as: polyunsaturated vegetable oil acid) kind and consumption, and introduce appropriate two keys, utilize this pair of key and acrylic monomer copolymerization to form macromolecular compound.
The present invention's polymerization technique used belongs to the general operation technical ability that those of ordinary skills should possess, also can be according to < < coating process (third edition) > > (coating process editorial committee volume, Chemical Industry Press, 1997) guidance of a book prepares.
The epoxy ester resin of preparing propone of the present invention acid modification, i.e. vinylformic acid-epoxy ester hybrid resin, acrylic monomer consumption used is the 90wt%-400wt% of epoxy ester resin solid content.
Lipid acid adopt main plant-derived lipid acid as: but be not limited only to eleostearic acid, linolenic acid, behenic acid, dehydrated castor oleic acid, vegetable seed oleic acid, tall oil acid, cocinic acid, ricinolic acid and talloleic acid.These lipid acid can be used separately, also can select arbitrarily several being used in combination.Preferential selection, lipid acid is comprised of the first lipid acid and the second lipid acid.
The first lipid acid as: but be not limited only to eleostearic acid and linolenic acid.These lipid acid can be used separately, also can select two kinds to be used in combination, and it is used for preferentially selecting the 5wt%-60wt% of total fatty acids consumption.
The second lipid acid as: but be not limited only to behenic acid, dehydrated castor oleic acid, vegetable seed oleic acid, tall oil acid, cocinic acid, ricinolic acid and talloleic acid.These lipid acid can be used separately, also can select arbitrarily several being used in combination.
Epoxy resin as: but be not limited only to E-51, E-44, E-20, E-12 and the E-06(epoxy resin trade mark, according to GB/T1630-1989, name).These resins can be used separately, also can select arbitrarily several applied in any combination in the present invention.
Acrylic monomer as: but be not limited only to vinylformic acid (AA), methacrylic acid (MAA), vinylbenzene (ST), methyl methacrylate (MMA), butyl acrylate (BA), butyl methacrylate (BMA), methacrylic acid (MAA), methacrylic acid hydroxyl ethyl ester (HEMA) and Hydroxyethyl Acrylate (EHA), Propylene glycol monoacrylate (HPA) and N-Hexyl methacrylate (HMA), Rocryl 410 vinyl trichloro silane and methyl ethylene dichlorosilane.Common two kinds of the selections arbitrarily of these monomers and two or more applied in any combination are in the present invention.
High temperature esterification catalyzer is can be 160 ℃ of chemical substances that are catalyzed into above ester, as: but be not limited only to lithium hydroxide, zinc oxide and plumbous oxide.These materials can be applied to the present invention alone or in combination.
In the present invention, initiator is applied for realizing Raolical polymerizable, those skilled in the art just can realize and selecting being applicable to initiator type and the consumption of reaction according to the guidance of textbook or laboratory manual, as: but be not limited only to Diisopropyl azodicarboxylate (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide (BPO), dilauroyl peroxide, peroxide-2-ethyl hexanoic acid tert-butyl, peroxidation-2 ethyl hexanoic acid tert-pentyl ester, tert-butyl peroxy acetate, peroxidized t-butyl perbenzoate (TBPB), peroxidation-3, 5, the 5-tri-methyl hexanoic acid tert-butyl ester, tertbutyl peroxide (TBHP), isopropyl benzene hydroperoxide, ditertiary butyl peroxide (DTBP), percarbonic acid two cyclohexyls and percarbonic acid two (2-ethylhexyl).These initiators can be applied to the present invention alone or in combination.
Various vinylformic acid-epoxy ester hybrid resin provided by the invention, by the following method preparation:
Step 1: by lipid acid and epoxy resin by weight 0.5: 1-1: 1 mixes, add esterifying catalyst, being warming up to temperature is 160 ℃-240 ℃ insulations 3 hours-6 hours, detect acid number termination reaction when 4mgKOH/g-8mgKOH/g, being diluted to solid part is 50% ± 1%, and viscosity controller obtains epoxy ester at 60s-250s;
Step 2: the epoxy ester first step 1 being made drops into reactor, and temperature rises to initiator kick off temperature, drips the mixed solution of acrylic acid or the like and initiator, at 3 hours-4 hours, dropwise, then be incubated 1 hour, then add initiator, be incubated 1 hour, add again initiator, be incubated 1 hour-2 hours, being diluted to solid part is 50% ± 1%, regulates 25 ℃ of viscosity 2000mPas-5000mPas, discharging, makes vinylformic acid-epoxy ester hybrid resin.
Take silicon-containing acrylic-acid-modified epoxy ester resin provided by the invention as main film forming matter, add aminoresin (as: urea-formaldehyde resin) as linking agent, to make the coating that drenches glass for curtain.According to actual needs, can also coordinate materials such as adding various pigment, filler, dispersion agent, flow agent and siccative.
A coating, by weight, its component is as follows:
Primer composition and proportioning are as follows:
Finish paint component and proportioning are as follows:
The use of linking agent is not necessary, and makes paint dry voluntarily at normal temperatures, but it adds and can at high temperature realize better crosslinkedly, accelerates set time.At this, linking agent applicatory as: but be not limited only to melamine resin or the urea-formaldehyde resin of alcohol etherificate.
Pigment as: but be not limited only to titanium white, carbon black, phthalocyanine blue, phthalein viridescent and iron pigment, these materials can be applied to the present invention alone or in combination.
Filler as: but be not limited only to barium sulfate, talcum powder, calcium carbonate, mica and kaolin, these materials can be applied to the present invention alone or in combination.
Auxiliary agent as: but be not limited only to wetting dispersing agent, flow agent, defoamer, anti skinning agent, naphthenic acid metallic soap or isocaprylic acid metallic soap.According to actual needs, these materials can be applied to the present invention alone or in combination.
Solvent as: but be not limited only to alcoholic solvent and high boiling solvent.Alcoholic solvent as: but be not limited only to Virahol, propyl carbinol, isopropylcarbinol and phenylcarbinol.High boiling solvent as: but be not limited only to trimethylbenzene, petroleum naphtha, raffinate oil, propandiol butyl ether, Diethylene Glycol butyl ether and pimelinketone.Above-mentioned alcoholic solvent and high boiling solvent all can be used alone, or mix mutually, or the mixture forming with dimethylbenzene.
Various coating provided by the invention; be applicable to the protection that curtain drenches the mirror back of the body; when curtain drenches on streamline, can meet the wide curtain of the longest 3m and drench the requirement of finishing line coating process; the constantly special construction technique of curtain of accomplishing to film when curtain drenches; 130 ℃-150 ℃ bakings, within 5 minutes-3 minutes, can reach complete drying; filming of being dried guarantees hardness and snappiness balance, makes glass there will not be depainting phenomenon in deep processing edging, punching and sandblast.And there is good chemical resistance.
Term involved in the present invention is identical with its universal.
Described " solid content " refers to the weight percentage of contained resin solid in resin.
Described " tinting pigment ", " rust-stabilising pigment " " filler ", " auxiliary agent " and " solvent " are material conventional in paint field.
The beneficial effect that technical solution of the present invention realizes:
Vinylformic acid-epoxy ester hybrid resin provided by the invention, in epoxy ester is synthetic, the feed intake proportioning of middle lipid acid and epoxy resin of adjusting, control esterification yield, retain certain oh group, and the monomer that adds hydroxyl in acrylic acid modified process of later stage, oh group distribution uniform on molecular chain, it not only can be with amino resin crosslinked, and hydroxyl is that polar group and polarity are larger, can produce Chemical bond power with adjacent smooth interface, thus this resin not only rate of drying is fast, and sticking power is good.Overcome general epoxy ester degree of esterification too high, reaction latter temperature higher (210 ℃-230 ℃), reacts wayward, easily gel, and residual hydroxyl is very little, with the crosslinked inadequate defect of amino.
The present invention introduces lipid acid in resin is synthetic, i.e. and " soft section ", the hardness of balance coating and snappiness, have good wettability, can not add or add less wetting dispersing agent, improves the sand milling efficiency in sand milling painting process.Avoid falling to paint risk in the course of processing, meet the deep processing requirement of mirror back paint.Simultaneously also introduced conjugated double bond, for later stage free yl graft polymerization provides grafting site, and it can be at room temperature and the crosslinked film forming of oxygen, has from dryness energy.
The present invention is in resin is synthetic, add (methyl) vinylformic acid, control resinous acid value in certain limit, carboxyl is polar group, can produce Chemical bond power with adjacent smooth interface, improved the sticking power to base material, both improved the wetting dispersion efficiency of sand milling, again can be crosslinked with linking agent, the reaction of all right catalysis oh group and linking agent, improve dryness, improve paint film density.
Vinylformic acid-epoxy ester hybrid resin of the present invention, resin heterozygosis the advantage of vinylformic acid, epoxy and three kinds of resins of alkyd, inferior position is complementary.As: epoxy resin exists, physical strength is high, antiseptic property is good and sticking power is good, but weathering resistance is poor, as: the acrylate moiety of being introduced, increased molecular weight, improve drying property, there is, the weather-proof and corrosion-resistant advantage of look shallow, weakened the weathering resistance of epoxy resin; The sticking power of Synolac is good, bright, plentiful and from dryness energy, integrates various resin advantages.
Embodiment
Below describe technical scheme of the present invention in detail.The embodiment of the present invention is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement the technical scheme of invention, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in claim scope of the present invention.
If the present invention's reagent used does not clearly indicate, use technical grade.
Embodiment 1 preparing propone acid-epoxy ester hybrid resin
Step 1: prepare epoxy ester: as table 1 formula, by epoxy resin E-12, behenic acid, linolenic acid and zinc oxide drop into reactor, the backflow dimethylbenzene that adds 80kg, after being warming up to 150 ℃-160 ℃, crawl stirs, motor starts stirring when abnormal, to temperature, be that 180 ℃-200 ℃ insulations start to detect acid value and viscosity for 4 hours, when being about 6mgKOH/g, acid number is reaction end, be discharged to thinning vessel, cooling limit, limit is (50 ± 1) % with dimethylbenzene latting drown to solid part, control viscosity for (being coated with four glasss in 120s left and right simultaneously, 25 ℃), filtration discharging is standby,
Step 2: prepare vinylformic acid-epoxy hybrid resins: as table 1 formula, 1000kg epoxy ester, getting 16kgAIBN mixes with the Acrylic Acid Monomer in formula, then get 250kg mix monomer and drop into bottoming in reactor, be warming up to 80 ℃ and start insulation, control holding temperature 30min at 80 ℃ ± 2 ℃, residue mix monomer at the uniform velocity dripped off in 3 hours, after be incubated 1 hour, add 2kgAIBN, be incubated 1 hour, add again 2kgAIBN insulation 1 hour, with dimethylbenzene latting drown to solid part, be (50 ± 1) %, adjusting viscosity is at 3000mPas-4000mPas(25 ℃), discharging, make vinylformic acid-epoxy ester hybrid resin.
Embodiment 2 preparing propone acid-epoxy ester hybrid resins
Step 1: prepare epoxy ester: as table 2 formula, epoxy resin E-12, behenic acid, eleostearic acid, linolenic acid and zinc oxide are dropped into reactor, the backflow dimethylbenzene that adds 84kg, be warming up to 180 ℃-200 ℃ insulations and within 4 hours, start to detect acid value and viscosity, during to the about 7mgKOH/g of acid number, be reaction end, be discharged to thinning vessel, cooling limit, limit is (50 ± 1) % with dimethylbenzene latting drown to solid part, the about 150s of adjusting viscosity, standby;
Step 2: prepare vinylformic acid-epoxy hybrid resins: as table 2 formula, 2000kg epoxy ester is dropped into reactor, heat up.Getting 18kgBPO mixes with Acrylic Acid Monomer, then get 200kg mix monomer and drop into bottoming in reactor, be warming up to 98 ℃ and start insulation, control holding temperature 30min at 100 ℃ ± 2 ℃, residue mix monomer at the uniform velocity dripped off in 3 hours, after be incubated 1 hour, add 2kgBPO, be incubated 1 hour, then add 2kgBPO, be incubated 1 hour, with dimethylbenzene latting drown to solid part, be (50 ± 1) %, adjusting viscosity is at 4000mPas-5000mPas(25 ℃), filter discharging, make vinylformic acid-epoxy ester hybrid resin.
Table 1
Table 2
Embodiment 3 preparing propone acid-epoxy ester hybrid resins
Step 1: prepare epoxy ester: as table 3 formula, epoxy resin E-12, dehydrated castor oleic acid, linolenic acid and plumbous oxide are dropped into reactor, add 60kg backflow dimethylbenzene, be warming up to 180 ℃-200 ℃ insulations and within 4 hours, start to detect acid value and viscosity, during to the about 5mgKOH/g of acid number, be reaction end, be discharged to thinning vessel, cooling limit, limit is (50 ± 1) % with dimethylbenzene latting drown to solid part, the about 110s of adjusting viscosity, standby;
Step 2: prepare vinylformic acid-epoxy ester hybrid resin: as table 3 formula, by 1500kg epoxy ester, getting 12kg tert-butyl hydroperoxide benzoyl mixes with Acrylic Acid Monomer, then get kg mix monomer and drop into bottoming in reactor, be warming up to 130 ℃ and start insulation, control holding temperature 30min at 130 ℃-135 ℃, residue mix monomer at the uniform velocity dripped off in 3 hours, after be incubated 1 hour, add 1.5kg tert-butyl hydroperoxide benzoyl, be incubated 1 hour, add again 2kg tert-butyl hydroperoxide benzoyl, be incubated 1 hour, with dimethylbenzene latting drown to solid part, be (50 ± 1) %, adjusting viscosity is at 2000mPas-3000mPas(25 ℃), filter discharging, make vinylformic acid-epoxy ester hybrid resin.
Table 3
In the following example 4-embodiment 8, those skilled in the art according to actual needs, and just can select applicable siccative kind and consumption according to the guidance of textbook or laboratory manual.Siccative is one or more of naphthenic acid metallic soap and isocaprylic acid metallic soap.
Those skilled in the art according to actual needs, and just can select applicable anti skinning agent kind and consumption according to the guidance of textbook or laboratory manual.Anti skinning agent is one or more of methyl ethyl ketoxime, butyraldehyde oxime or kautschin.
The color film priming paint of embodiment 4 preparation
Press the proportioning of listed each component raw material in table 4, vinylformic acid-epoxy ester hybrid resin, anti skinning agent, pigment, filler are mixed to high speed dispersion 30min, then crossing sand mill, to be ground to fineness be below 25 μ m, after be added into linking agent, solvent and auxiliary agent and stir, after the assay was approved, filter metering, packing.
The color film base paint formulation of table 4 (weight percent)
Embodiment 5: prepare silver mirror priming paint
Press the proportioning of listed each component raw material in table 5, vinylformic acid-epoxy ester hybrid resin, anti skinning agent, pigment, filler are mixed to high speed dispersion 30min, then crossing sand mill, to be ground to fineness be below 25 μ m, after be added into linking agent, solvent and auxiliary agent and stir, after the assay was approved, filter, measure and packing.
Table 5 silver mirror base paint formulation (weight percent)
Embodiment 6: prepare aluminium mirror priming paint
Press the proportioning of listed each component raw material in table 6, vinylformic acid-epoxy ester hybrid resin, anti skinning agent, pigment, filler are mixed to high speed dispersion 30min, then crossing sand mill, to be ground to fineness be below 25 μ m, after be added into linking agent, solvent and auxiliary agent and stir, after the assay was approved, filter, measure and packing.
Table 6 aluminium mirror base paint formulation (weight percent)
Embodiment 7: prepare mirror back curtain drenching coating (finish paint)
Press the proportioning of listed each component raw material in table 7, the auxiliary agents such as vinylformic acid-epoxy ester hybrid resin, anti skinning agent, pigment, filler are mixed to high speed dispersion 30min, then crossing sand mill, to be ground to fineness be below 25 μ m, after be added into linking agent, solvent and auxiliary agent and stir, check viscosity is filtered admittedly after waiting qualified, metering, packing.
Table 7 finish paint formula (weight percent)
Embodiment 8: prepare rust-inhibiting paint
Press the proportioning of listed each component raw material in table 8, the auxiliary agents such as vinylformic acid-epoxy ester hybrid resin, anti skinning agent, pigment, filler are mixed to high speed dispersion 30min, then crossing sand mill, to be ground to fineness be below 45 μ m, after be added into solvent and auxiliary agent stirs, check viscosity is filtered admittedly after waiting qualified, metering, packing.
Table 8 rust-inhibiting paint formula (weight percent)
Paint film preparation technology:
At mirror line processed scene, this mirror back curtain drenching coating is diluted to working viscosity with solvent xylene, showering is to color film/silver mirror/aluminium mirror, 150 ℃-130 ℃ (plate temperature) baking 3 minutes-5 minutes, priming paint film thickness is controlled at 25 μ m-30m, finish paint paint film total thickness is controlled at 20 μ m-25 μ m, after rolling off the production line 24 hours, detects performance as table 9 and table 10.
Table 9 paint film property assay
Table 10
Claims (17)
1. vinylformic acid-epoxy ester hybrid resin, is prepared from by following steps:
Step 1: by lipid acid and epoxy resin by weight 0.5: 1-1: 1 mixes, add esterifying catalyst, being warming up to temperature is 160 ℃-240 ℃ insulations 3 hours-6 hours, detects acid number termination reaction when 4mgKOH/g-8mgKOH/g, dilution, obtains epoxy ester;
Step 2: the epoxy ester first step 1 being made drops into reactor, is warming up to initiator kick off temperature, drips the mixed solution of acrylic acid or the like and initiator, at 3 hours-4 hours, dropwise, then be incubated 1 hour, then add initiator, be incubated 1 hour, add again initiator, be incubated 1 hour-2 hours, dilution, regulates 25 ℃ of viscosity, discharging, makes vinylformic acid-epoxy ester hybrid resin;
Described lipid acid is selected from one or several of eleostearic acid, linolenic acid, behenic acid, dehydrated castor oleic acid, vegetable seed oleic acid, tall oil acid, cocinic acid, ricinolic acid and talloleic acid.
2. vinylformic acid-epoxy ester hybrid resin according to claim 1, is characterized in that described epoxy resin is selected from one or more of E-51, E-44, E-20, E-12 and E-06.
3. vinylformic acid-epoxy ester hybrid resin according to claim 1, it is characterized in that described lipid acid is comprised of the first lipid acid and the second lipid acid, described the first lipid acid is selected from one or more of eleostearic acid and linolenic acid, and described the second lipid acid is selected from one or several of behenic acid, dehydrated castor oleic acid, vegetable seed oleic acid, tall oil acid, cocinic acid, ricinolic acid and talloleic acid.
4. vinylformic acid-epoxy ester hybrid resin according to claim 1, is characterized in that described the first lipid acid accounts for the 5wt%-60wt% of total fatty acids consumption.
5. vinylformic acid-epoxy ester hybrid resin according to claim 1, is characterized in that described acrylic monomer consumption is the 90wt%-400wt% of described epoxy ester resin solid content.
6. vinylformic acid-epoxy ester hybrid resin according to claim 1, is characterized in that described acrylic monomer is selected from one or more of the acrylic monomers such as vinylformic acid, methacrylic acid, vinylbenzene, methyl methacrylate, butyl acrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, n-BMA, N-Hexyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410 vinyl trichloro silane and methyl ethylene dichlorosilane.
7. vinylformic acid-epoxy ester hybrid resin according to claim 1, is characterized in that described high temperature esterification catalyzer is selected from one or more of lithium hydroxide, zinc oxide and plumbous oxide.
8. vinylformic acid-epoxy ester hybrid resin according to claim 1, it is characterized in that described initiator is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, dilauroyl peroxide, peroxide-2-ethyl hexanoic acid tert-butyl, peroxidation-2 ethyl hexanoic acid tert-pentyl ester, tert-butyl peroxy acetate, peroxidized t-butyl perbenzoate, peroxidation-3, one or more of 5, the 5-tri-methyl hexanoic acid tert-butyl ester, tertbutyl peroxide, isopropyl benzene hydroperoxide, ditertiary butyl peroxide, percarbonic acid two cyclohexyls and percarbonic acid two (2-ethylhexyl).
9. a coating, the described vinylformic acid-epoxy ester hybrid resin of one of claim 1-8 of take is main film forming matter.
10. coating according to claim 9, is characterized in that also adding the melamine resin of alcohol etherificate or urea-formaldehyde resin as linking agent.
Take the coating that the described vinylformic acid-epoxy ester hybrid resin of one of claim 1-8 makes as main film forming matter for 11. 1 kinds, for protection and the decoration of silver mirror, aluminium mirror, color film and glass baseplate.
12. 1 kinds of coating, is characterized in that take that the described vinylformic acid-epoxy ester hybrid resin of one of claim 1-8 is the coating described in main film forming matter, and by weight, primer composition and proportioning are as follows:
Finish paint component and proportioning are as follows:
13. coating according to claim 12, is characterized in that described tinting pigment is selected from one or more of titanium dioxide, zinc sulfide white, carbon black, phthalocyanine blue, phthalein viridescent and iron pigment.
14. coating according to claim 12, is characterized in that described rust-stabilising pigment is selected from one or more of red iron oxide, zinc oxide, zinc powder, basic lead chromate, red lead, yellow lead and zinc-chrome yellow.
15. coating according to claim 12, is characterized in that described filler is selected from one or more of barium sulfate, talcum powder, calcium carbonate, mica and kaolin.
16. coating according to claim 12, is characterized in that described auxiliary agent is selected from one or more of wetting dispersing agent, flow agent, defoamer, anti skinning agent, naphthenic acid metallic soap and isocaprylic acid metallic soap.
17. coating according to claim 12, is characterized in that described solvent is selected from the mixture of alcoholic solvent, high boiling solvent and dimethylbenzene, and described alcoholic solvent is selected from one or more of Virahol, propyl carbinol, isopropylcarbinol and phenylcarbinol; Described high boiling solvent is selected from trimethylbenzene, petroleum naphtha, raffinates oil, propandiol butyl ether, Diethylene Glycol butyl ether and pimelinketone one or more.
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| CN106674441B (en) * | 2017-01-24 | 2019-07-23 | 湘江涂料科技有限公司 | A kind of water-soluble acrylic modified epoxy ester resin and preparation method thereof |
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| CN109266070A (en) * | 2018-08-02 | 2019-01-25 | 广东鑫皇冠新材料有限公司 | A kind of anti-flaming dope and preparation method thereof |
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| CN112442719B (en) * | 2019-08-28 | 2022-02-18 | 芜湖通潮精密机械股份有限公司 | Shielding method before anodic oxidation of aluminum and aluminum alloy sunken hole |
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| CN113351823A (en) * | 2021-05-26 | 2021-09-07 | 宁夏共享化工有限公司 | Sand mold reinforcing liquid and preparation and use methods thereof |
| CN113351823B (en) * | 2021-05-26 | 2023-04-28 | 共享新材料(山东)有限公司 | Sand mould reinforcing liquid and preparation and use methods thereof |
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