CN109694639A - A kind of Water-based glass baking paint and preparation method thereof - Google Patents

A kind of Water-based glass baking paint and preparation method thereof Download PDF

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Publication number
CN109694639A
CN109694639A CN201811636434.5A CN201811636434A CN109694639A CN 109694639 A CN109694639 A CN 109694639A CN 201811636434 A CN201811636434 A CN 201811636434A CN 109694639 A CN109694639 A CN 109694639A
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raw material
water
agent
based glass
glass baking
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CN109694639B (en
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徐军
付允明
裘家升
顾卓韦
张莉莉
周昶吉
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ZHEJIANG ZHONGKE LIDE NEW MATERIALS Co Ltd
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ZHEJIANG ZHONGKE LIDE NEW MATERIALS Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/32Modified amine-aldehyde condensates
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20Diluents or solvents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The present invention relates to a kind of Water-based glass baking paints, it is characterized by comprising following weight percentage components: aqueous epoxy resins 20~60%, low-methoxyl etherified amino resins 10~40%, water-based acrylic resin modified polyurethane 0~18%, color essence dyestuff or colorant 3~30%, levelling agent 0.1~0.8%, wetting agent 0.1~1.0%, adhesive agent 0.1~0.8%, antioxidant 0.1~0.8%, defoaming agent 0.1~0.6%, fungicide 0.1~0.4%, pH adjusting agent 0.5~6%, remaining is deionized water.The invention also discloses the preparation methods of above-mentioned Water-based glass baking paint.Compared with prior art, the adhesive force of Water-based glass baking paint of the invention on the substrates such as glass is good and alcohol resistance, water resistance, high abrasion resistance, without in addition using organic solvent.And preparation method is simple, environmentally friendly.

Description

A kind of Water-based glass baking paint and preparation method thereof
Technical field
The invention belongs to technical field of coatings, and in particular to a kind of Water-based glass baking paint and preparation method thereof.
Background technique
The coating protection of glass and glassware and decoration industry and civil field have extensive demand, as bottle, Bottle for cosmetics, scent flask, lamp decoration, house ornamentation glassware and glass apparatus etc. require surface it is armor coated and decoration apply Layer.Currently, the glass coating of domestic application is mostly solvent based product, relative maturity and popularize, when using oiliness glass baking varnish, Need to be added 50% or more organic solvent (toluene, dimethylbenzene, industrial alcohol etc.), these solvents are readily volatilized, irritant Smell and murder by poisoning to human body various degrees, constantly evaporate into sky in production process, application process and drying process It in gas or is absorbed by the body, seriously welding, injures human health.
With the raising of people's environmental consciousness and perfecting for environmentally friendly laws and regulations, water paint is a small amount of due to being free of or containing only Organic solvent and on glass application have been attached great importance.Using polyurethane aqueous dispersion body, water-soluble polypropylene acid tree There are adhesive force, resistance to alcohol in glass substrate for the mono-component aqueous glass lacquer of the acrylic resin preparation of rouge, urethane type and modification Property, water resistance, abrasion performance difference and the disadvantages such as hardness is low.Aqueous dual-component room temperature curing glass lacquer is too short in the construction process Working life can cause certain difficulty to construction, while the waste of paint vehicle and construction site also being caused to mix unequal problem.
In order to overcome defect existing for above-mentioned water paint, application No. is the applications for a patent for invention of CN201510703522.2 " a kind of Water-based glass baking paint " (application publication number CN106609080A) discloses a kind of Water-based glass baking paint, with parts by weight Meter, including 40~70 parts of water soluble acrylic resin, 2~5 parts of isopropanol, 1~5 part of triethanolamine, low-methoxyl etherified amino resins 10~15 parts, 2~5 parts of ethyl alcohol, 0.2~0.9 part of titanium dioxide.The Water-based glass baking paint has good adhesion strength, tinting strength, tinting power, There is stronger adhesive force to glass surface, improves decorative performance.But water soluble acrylic resin often occurs with dyestuff Reaction, and influence the color of baking vanish.
For another example application No. is the application for a patent for invention of CN201711146705.4 " a kind of Water-based glass baking paint ", (application is public The number of opening is CN107815192A) a kind of Water-based glass baking paint is disclosed, by weight percentage, comprising: water-base resin 60- 80%, acid catalyst 0.3-0.8%, pH adjusting agent 0.7-5.5%, thickener 0.1-0.5%, cosolvent 1-8%, wetting agent 0.1-1%, coalescing agent 1-9%, pigment 0-20%, water 5-25%.Wherein water-base resin is Hydroxylated acrylic resin, epoxy The mixture of one or more of acrylic resin, melamine resin, polyamide and inorganic polysiloxane.It is obtained Glass baking varnish has high gloss, high rigidity and strong weatherability.But it needs that base could be promoted by additionally addition acid catalyst Body resin Quick cross-linking reduces solidification temperature, improves curing degree;Though more or less being needed in addition, being water-based stoving paint Add certain organic solvent (i.e. cosolvent).
Summary of the invention
First technical problem to be solved by this invention is the status for the prior art, provide a kind of adhesive force it is good, And alcohol resistance, water resistance, high abrasion resistance, environmentally protective Water-based glass baking paint.
Second technical problem to be solved by this invention is the status for the prior art, provide a kind of simple process, The preparation method of environment amenable above-mentioned Water-based glass baking paint.
The present invention solves technical solution used by above-mentioned first technical problem are as follows: a kind of Water-based glass baking paint, it is special Sign is to include following weight percentage components:
Aqueous epoxy resins 20~60%, low-methoxyl etherified amino resins 10~40%, the modified poly- ammonia of water-based acrylic resin Ester 0~18%, color essence dyestuff or colorant 3~30%, levelling agent 0.1~0.8%, wetting agent 0.1~1.0%, adhesive agent 0.1~0.8%, antioxidant 0.1~0.8%, defoaming agent 0.1~0.6%, fungicide 0.1~0.4%, pH adjusting agent 0.5 ~6%, remaining is deionized water.
The low-methoxyl etherified amino resins are preferably high imine part low-methoxyl etherified amino resins.
The water-based acrylic resin modified polyurethane is preferably aromatic isocyanate type aqueous polyurethane.
In the above scheme, the color essence dyestuff or colorant be preferably transparent pigment, azo pigments, pearlescent pigment, At least one of carbon black, titanium dioxide;The levelling agent is preferably acrylic compounds levelling agent, silicone levelling agent, fluorine carbon At least one of compounds levelling agent;The wetting agent is preferably the profit such as acetylenic diols, fluorine class, acrylic compounds, organic silicon At least one of humectant;The adhesive agent preferably contain amino, double amino, methacrylate, epoxy group, ethylene At least one of the silicone coupling agents of base, chlorination alkyl etc.;The antioxidant is preferably sodium formaldehyde sulfoxylate, sodium hydrogensulfite, grass Acid, phytic acid, ammonium hydroxide, hydrazine hydrate, ascorbic acid, tea polyphenols, tocopherol, flavonoids, butylated hydroxy anisole, dibutyl hydroxy At least one of toluene, tert-butyl hydroquinone;The defoaming agent is preferably polyethers, high-carbon alcohols, silicon class, polyether-modified At least one of silicon, self-emulsifying type, polysiloxane defoamer;The pH regulator is preferably N- aminopropyl monomethyl second Hydramine, 2-amino-2-methyl-1-propanol, butyl diethanolamine, N- methylethanolamine, -1,3 propylene glycol of 2- amino -2- ethyl, One of dimethylethanolamine, monoethanolamine, diethanol amine, triethanolamine, butylethanolamine, ammonium hydroxide.
In order to further increase the properties of baking vanish, the aqueous epoxy resins select it is water-soluble preferably, transparency compared with High aqueous epoxy resins, it is preferred that the aqueous epoxy resins include following weight percentage components: raw material a 5~ 15%;Raw material b 2~10%;Raw material c1~8%;Raw material d 26~47%;Raw material e 14~25%;Raw material f 5~10%; Remaining is deionized water;Wherein the raw material a is at least one of secondary amine or tertiary amine;The raw material b is esters of unsaturated carboxylic acids At least one of;The raw material c is alcamines, amides, aromatic amine, imines, at least one in azanol class raw material Kind;The raw material d is one of the epoxy resin of different epoxide equivalents;The raw material e is one of organic solvent;Institute Stating raw material f is one of acrylic monomer.
The raw material a is preferably triethylamine, diethanol amine, triethanolamine, diethylenetriamines, hexamethylene imine, six Methenamine, N, at least one of N- diethylaniline, the unsaturated bond being used to open in material b;The raw material b is excellent It is selected as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, Isobutyl methacrylate, metering system Tert-butyl acrylate, isooctyl methacrylate, n octyl methacrylate, cyclohexyl methacrylate, methacrylic acid trifluoro second The positive fourth of ester, glycidyl methacrylate, isobornyl methacrylate, methyl acrylate, ethyl acrylate, acrylic acid Ester, hydroxypropyl acrylate, Isooctyl acrylate monomer, ethylene carbonate, propene carbonate, lauryl acrylate and the different ice of acrylic acid At least one of piece ester;The raw material c is preferably monoethanolamine, diethanol amine, triethanolamine, 3- Propanolamine, acetamide, two Methylformamide, isobutyramide, aniline, o-phenylenediamine, 2,4- dimethylaniline, N, N- diethylaniline, para-fluoroaniline, neighbour Phthalimide, at least one of azanol, introduce polar group for being grafted;The raw material d is preferably that epoxide equivalent is 100~5000 epoxy resin;The raw material e be preferably propylene glycol methyl ether acetate, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, Propylene-glycol ethyl ether, propandiol butyl ether, isobutylvinyl ether, cyclohexyl vinyl ether, N- vinyl imidazole, N- vinyl are in oneself Amide, N- vinyl pyrrole ketone, vinyl ethyl ether, diethylene glycol divinyl ether, 1,4- cyclohexane dimethanol divinyl One kind of ether, hydroxy butyl vinyl ether, 1,4- cyclohexanediol mono vinyl ether, divinyl -1,4- butanediol ethere;The original Expect that f is preferably acrylic acid, methacrylic acid, Alpha-hydroxy methacrylic acid, maleic acid, 2- acrylamide -2- methyl-prop sulphur One kind of acid increases the hardness and water resistance of aqueous annular resin to improve the degree of cross linking.
Preferably, the aqueous epoxy resins the preparation method comprises the following steps:
Raw material a and raw material b is added, is warming up to 40~60 DEG C, stirs 2~7h;80~130 DEG C are then heated to, is added former Expect c and raw material d, stirs 3~10h;Then raw material e, raw material f and deionized water is added, continues 0.5~4.5h of heat preservation, is cooled to After room temperature, pH to 7~8 is adjusted, filtering obtains aqueous epoxy resins.
Since aqueous epoxy resins are using water as primary solvent, the volatilization of solvent is reduced in production process, reduces VOC Discharge, while using water as primary solvent, preparation process is environmentally friendly, preparation process is simple;And in preparation method first Raw material a and b are reacted, so that the unsaturated bond in raw material b is opened, raw material c and d are added, so that the ring in raw material d Oxygen groups are opened, and are carried out graft crosslinking, are eventually adding raw material e, f and deionized water, further increase the crosslinking journey of polymer Degree, in this way, so that the aqueous epoxy resins performance produced is more excellent, and having preferable water-soluble by reaction layer by layer Property, it can be soluble in water without other organic solvents.
The present invention solves technical solution used by above-mentioned second technical problem are as follows: a kind of aqueous glass as described above The preparation method of baking vanish, it is characterised in that include the following steps:
Wetting agent, defoaming agent, deionized water are mixed and stirred for uniformly;Then aqueous epoxy resins, low-methoxyl etherificate are added Amino resins, water-based acrylic resin modified polyurethane add levelling agent, adhesive agent, antioxidant, fungicide, pH and adjust Agent is uniformly mixed, and obtains mixed solution, and color essence dyestuff or colorant are added as needed, defoams and adjusts to required It is filtered after viscosity, obtains Water-based glass baking paint.
As an improvement, the mixed solution being added before color essence dyestuff or colorant is transparence solution, it is viscous at 25 DEG C Degree is 10~1000 centipoises, is more preferably 90~500 centipoises.
The solid content of Water-based glass baking paint obtained above is 25~75%, is more preferably 30~50%.
Compared with the prior art, the advantages of the present invention are as follows: aqueous epoxy resins and low-methoxyl etherified amino resins etc. pass through Cross-linking reaction can form complicated three-dimensional net structure, so that applicator becomes more continuous fine and close, can effectively prevent solvent Migration and swelling of the small molecule into polymer molecular chain, to improve the water-fast alcohol resistance of paint film, cohesive force, low coating Viscosity and high mechanical strength, the pencil hardness of manufactured paint film are scratch resistance with enamel film, wear-resisting up to 3H or more Performance;And the fixing of dye will not react and influence the color of dyestuff with aqueous epoxy resins on baking vanish;Aqueous acrylamide While the addition of acid resin modified polyurethane can be further improved baking vanish paint film toughness, moreover it is possible to prevent sunlight irradiation to paint film Influence, prevent film aging;Further, since using water-soluble preferable aqueous epoxy resins so that the present invention using water as Solvent avoids the volatilization of solvent without adding organic solvent in production process, reduce the discharge of volatile organic matter VOC, It takes water as a solvent simultaneously, preparation process is environmentally friendly, preparation process is simple;Water-based glass baking paint of the invention is suitable for The products such as bottle, bottle for cosmetics, scent flask, lamp decoration, plastics, house ornamentation glassware and glass apparatus make surface protection decoration, It is applied widely.
Specific embodiment
Present invention is further described in detail with reference to embodiments.
Embodiment 1:
A kind of Water-based glass baking paint, including following weight percentage components:
Aqueous epoxy resins 30% (select the water of the model GS-5000C of Changzhou Guang Shu Chemical Industry Science Co., Ltd production Property epoxy resin), low-methoxyl etherified amino resins 18% (select high imine part low-methoxyl etherified amino resins), aqueous acrylamide Acid resin modified polyurethane 6.4% (selects aromatic isocyanate type aqueous polyurethane), color essence dyestuff or colorant 13% (selecting red color essence dyestuff), levelling agent 0.4% (selects silicone oil), organic silicon wetting agent 0.3%, (the choosing of adhesive agent 0.3% With double amino silicane coupling agents), antioxidant 0.5% (selects sodium hydrogensulfite), polyether antifoam agent 0.2%, fungicide 0.2%, pH adjusting agent 1.4% (selects 2-amino-2-methyl-1-propanol), remaining is deionized water.
Above-mentioned Water-based glass baking paint the preparation method comprises the following steps: wetting agent, defoaming agent, deionized water are mixed and stirred for uniformly; Then be added aqueous epoxy resins, low-methoxyl etherified amino resins, water-based acrylic resin modified polyurethane, add levelling agent, Adhesive agent, antioxidant, fungicide, pH adjusting agent are uniformly mixed, and the mixed solution of clear solution shape are obtained, 25 Viscosity at DEG C is 500 centipoises, and color essence dyestuff or colorant is added, and defoaming (waiting physical defoaming methods by vacuumizing) is simultaneously adjusted It is filtered after whole to required viscosity, obtains Water-based glass baking paint.
The solid content of Water-based glass baking paint obtained is 45%.
Embodiment 2:
A kind of Water-based glass baking paint, including following weight percentage components:
Aqueous epoxy resins 38% (select the water of the model WE-8216 of the auspicious three Chemical Industry Science Co., Ltd production in Shandong Property epoxy resin), low-methoxyl etherified amino resins 13% (select high imine part low-methoxyl etherified amino resins), aqueous acrylamide Acid resin modified polyurethane 13% (selects aromatic isocyanate type aqueous polyurethane), and color essence dyestuff or colorant 6% (are selected Green color essence dyestuff), levelling agent 0.3% (selects acrylate leveling agent), acetylenic diols wetting agent 0.3%, adhesive agent 0.3% (selecting the silicone coupling agents containing methacrylate), antioxidant 0.5% (select oxalic acid), high-carbon alcohols Defoaming agent 0.2%, fungicide 0.2%, pH adjusting agent 1.2% (select N- methylethanolamine), remaining is deionized water.
Above-mentioned Water-based glass baking paint the preparation method comprises the following steps: wetting agent, defoaming agent, deionized water are mixed and stirred for uniformly; Then be added aqueous epoxy resins, low-methoxyl etherified amino resins, water-based acrylic resin modified polyurethane, add levelling agent, Adhesive agent, antioxidant, fungicide, pH adjusting agent are uniformly mixed, and the mixed solution of clear solution shape are obtained, 25 Viscosity at DEG C is 300 centipoises, and color essence dyestuff or colorant is added, defoams and filters after adjusting to required viscosity, obtain Water-based glass baking paint.
The solid content of Water-based glass baking paint obtained is 30%.
Embodiment 3:
A kind of Water-based glass baking paint, including following weight percentage components:
Water-based acrylic resin 22% (selects the model HOMAAC of Jin Tuan Chemical Company productionTM- 5201 Water soluble acrylic acid baking vanish resin), low-methoxyl etherified amino resins 26% (select high imine part low-methoxyl etherified amino resins), Water-based acrylic resin modified polyurethane 5.5% (selects aromatic isocyanate type aqueous polyurethane), color essence dyestuff or coloring Agent 21% (selects blue color essence dyestuff), and levelling agent 0.3% (selects fluorine carbon levelling agent), and acrylic compounds wetting agent 0.3% is close Agent 0.3% (select the silicone coupling agents containing epoxy group), antioxidant 0.5% (select ammonium hydroxide), silicon class defoaming agent 0.2%, fungicide 0.2%, pH adjusting agent 1.2% (selects dimethylethanolamine), remaining is deionized water.
Above-mentioned Water-based glass baking paint the preparation method comprises the following steps: wetting agent, defoaming agent, deionized water are mixed and stirred for uniformly; Then be added aqueous epoxy resins, low-methoxyl etherified amino resins, water-based acrylic resin modified polyurethane, add levelling agent, Adhesive agent, antioxidant, fungicide, pH adjusting agent are uniformly mixed, and the mixed solution of clear solution shape are obtained, 25 Viscosity at DEG C is 10 centipoises, and color essence dyestuff or colorant is added, defoams and filters after adjusting to required viscosity, obtain Water-based glass baking paint.
The solid content of Water-based glass baking paint obtained is 25%.
Embodiment 4:
A kind of Water-based glass baking paint, including following weight percentage components:
Aqueous epoxy resins 41% (select Qingdao beautiful jade can Trade Co., Ltd. provide model YT-02 aqueous tree Rouge), low-methoxyl etherified amino resins 13% (select high imine part low-methoxyl etherified amino resins), and water-based acrylic resin changes Property polyurethane 5.5% (select aromatic isocyanate type aqueous polyurethane), color essence dyestuff or colorant 15% (select titanium white Mill base), levelling agent 0.3% (selects acrylic acid levelling agent), and fluorine class wetting agent 0.5%, (selection contains ethylene to adhesive agent 0.3% The silicone coupling agents of base), antioxidant 0.5% (selects hydrazine hydrate), self-emulsifying type defoaming agent 0.2%, fungicide 0.2%, PH adjusting agent 1.2% (selects monoethanolamine, diethanol amine, triethanolamine, butylethanolamine, butyl diethyl also can be selected certainly Hydramine etc.), remaining is deionized water.
Above-mentioned Water-based glass baking paint the preparation method comprises the following steps: wetting agent, defoaming agent, deionized water are mixed and stirred for uniformly; Then be added aqueous epoxy resins, low-methoxyl etherified amino resins, water-based acrylic resin modified polyurethane, add levelling agent, Adhesive agent, antioxidant, fungicide, pH adjusting agent are uniformly mixed, and the mixed solution of clear solution shape are obtained, 25 Viscosity at DEG C is 1000 centipoises, and color essence dyestuff or colorant is added, defoams and filters after adjusting to required viscosity, that is, make Obtain Water-based glass baking paint.
The solid content of Water-based glass baking paint obtained is 75%.
Embodiment 5:
A kind of Water-based glass baking paint, including following weight percentage components:
(the model PRO-4200's of Beijing Comens New Materials Co., Ltd.'s production is aqueous for aqueous epoxy resins 52% Resin), low-methoxyl etherified amino resins 15% (select high imine part low-methoxyl etherified amino resins), water-based acrylic resin Modified polyurethane 5% (selects aromatic isocyanate type aqueous polyurethane), and color essence dyestuff or colorant 30% (select carbon black Mill base), levelling agent 0.4% (selects acrylic acid levelling agent), and fluorine class wetting agent 0.5%, (selection contains chlorination to adhesive agent 0.3% The silicone coupling agents of alkyl), antioxidant 0.5% (selects tea polyphenols, tocopherol, flavonoids, anti-bad also can be selected certainly Other antioxidants such as hematic acid), polyether-modified silicon class defoaming agent 0.2%, fungicide 0.2%, pH adjusting agent 1.2% (selects 2- Amino -2- ethyl -1,3 propylene glycol), remaining is deionized water.
Above-mentioned Water-based glass baking paint the preparation method comprises the following steps: wetting agent, defoaming agent, deionized water are mixed and stirred for uniformly; Then be added aqueous epoxy resins, low-methoxyl etherified amino resins, water-based acrylic resin modified polyurethane, add levelling agent, Adhesive agent, antioxidant, fungicide, pH adjusting agent are uniformly mixed, and the mixed solution of clear solution shape are obtained, 25 Viscosity at DEG C is 700 centipoises, and color essence dyestuff or colorant is added, defoams and filters after adjusting to required viscosity, obtain Water-based glass baking paint.
The solid content of Water-based glass baking paint obtained is 50%.
Embodiment 6:
It is substantially the same manner as Example 1, it distinguishes in Water-based glass baking paint in this present embodiment, including following weight percent Component:
Aqueous epoxy resins 20%, low-methoxyl etherified amino resins 40% (select high imine part low-methoxyl etherified amino tree Rouge), color essence dyestuff or colorant 3% (selecting pearlescent pigment mill base), levelling agent 0.1% (select silicone oil), organic silicon wetting Agent 0.1%, adhesive agent 0.1% (select double amino silicane coupling agents), and antioxidant 0.1% (selects sodium hydrogensulfite), polyethers Defoaming agent 0.1%, fungicide 0.1%, pH adjusting agent 6% (select 2-amino-2-methyl-1-propanol), remaining is deionization Water.
The solid content of Water-based glass baking paint is 40%.
Embodiment 7:
It is substantially the same manner as Example 1, it distinguishes in Water-based glass baking paint in this present embodiment, including following weight percent Component:
Aqueous epoxy resins 60%, low-methoxyl etherified amino resins 10% (select high imine part low-methoxyl etherified amino tree Rouge), color essence dyestuff or colorant 4% (selecting azo pigments mill base), levelling agent 0.8% (select silicone oil), organic silicon wetting Agent 1.0%, adhesive agent 0.8% (select double amino silicane coupling agents), and antioxidant 0.8% (selects sodium hydrogensulfite), polyethers Defoaming agent 0.6%, fungicide 0.4%, pH adjusting agent 0.5% (select 2-amino-2-methyl-1-propanol), remaining is deionization Water.
The solid content of Water-based glass baking paint is 55%.
Embodiment 8:
It is substantially the same manner as Example 1, it distinguishes in Water-based glass baking paint in this present embodiment, including following weight percent Component:
Aqueous epoxy resins 20%, low-methoxyl etherified amino resins 10% (select high imine part low-methoxyl etherified amino tree Rouge), water-based acrylic resin modified polyurethane 18% (select aromatic isocyanate type aqueous polyurethane), color essence dyestuff or Colorant 30% (selects metallic pigments mill base), and levelling agent 0.8% (selects silicone oil), organic silicon wetting agent 1.0%, adherence Agent 0.8% (selects double amino silicane coupling agents), and antioxidant 0.8% (selects sodium hydrogensulfite), polyether antifoam agent 0.6%, Fungicide 0.4%, pH adjusting agent 0.5% (select 2-amino-2-methyl-1-propanol), remaining is deionized water.
The solid content of Water-based glass baking paint is 30%.
Embodiment 9:
Substantially the same manner as Example 1, difference is made by oneself in aqueous epoxy resins in this present embodiment, including is weighed as follows Measure the component of percentage: raw material a 6.5% (triethylamine);Raw material b 7.8% (selects methyl methacrylate in the present embodiment As raw material b, ethyl methacrylate, isopropyl methacrylate, Isobutyl methacrylate, methyl also can be selected certainly Tert-butyl acrylate, isooctyl methacrylate, n octyl methacrylate, cyclohexyl methacrylate, methacrylic acid are different Norbornene ester etc., has the same effect);Raw material c 2.3% (selects monoethanolamine as raw material c, certainly in the present embodiment The hydramine substances such as the similar diethanol amine of property, triethanolamine can be selected);(the ring of 300 epoxide equivalents of raw material d 35.6% Oxygen resin);Raw material e 20.2% (propylene glycol methyl ether acetate);Raw material f 6.7% (acrylic acid);Remaining is deionized water.
Above-mentioned aqueous epoxy resins the preparation method comprises the following steps: in four-hole boiling flask be added raw material a raw material b, be warming up to 59 DEG C, 5h is stirred, then heats to 85 DEG C, raw material c, raw material d is added, raw material e, raw material f, deionized water is added after stirring 8h, continues 3h is kept the temperature, is cooled to room temperature, with neutralizer tune pH to 7, filtering obtains aqueous epoxy resins.Aqueous epoxy resins obtained For clear solution shape, the viscosity at 25 DEG C is 500 centipoises.
Embodiment 10:
Substantially the same manner as Example 1, difference is made by oneself in aqueous epoxy resins in this present embodiment, including is weighed as follows Measure the component of percentage: raw material a 11.2% (triethanolamine);Raw material b 4.5% (ethyl acrylate is selected in the present embodiment, As raw material b, methyl acrylate, n-butyl acrylate, hydroxypropyl acrylate, Isooctyl acrylate monomer etc. also can be selected certainly); Raw material c 5.1% (selects acetamide, can also use dimethylformamide, isobutyramide etc. certainly) in the present embodiment;Raw material d 27.9% (epoxy resin of 850 epoxide equivalents);(for ethylene glycol monobutyl ether, other ethers can also be used in raw material e 15.6% certainly Class raw material is as cosolvent);Raw material f 7.4% (methacrylic acid);Remaining is deionized water.
Above-mentioned aqueous epoxy resins the preparation method comprises the following steps: in four-hole boiling flask be added raw material a raw material b, be warming up to 43 DEG C, 3h is stirred, then heats to 94 DEG C, raw material c, raw material d is added, raw material e, raw material f, deionized water is added after stirring 6.2h, after Continue insurance temperature 3h, is cooled to room temperature, and with neutralizer tune pH to 8, filtering obtains aqueous epoxy resins.Water-base epoxy tree obtained Rouge is clear solution shape, and the viscosity at 25 DEG C is 300 centipoises.
Embodiment 11:
Substantially the same manner as Example 1, difference is made by oneself in aqueous epoxy resins in this present embodiment, including is weighed as follows Measure the component of percentage: raw material a 7.5% (hexamethylene imine);Raw material b 6.6% (the present embodiment selects ethylene carbonate, Certainly propene carbonate also can be selected);Raw material c 2.2% (aniline is selected in the present embodiment, can also be used certainly o-phenylenediamine, 2,4- dimethylaniline, N, N- diethylaniline, para-fluoroaniline etc.);(the asphalt mixtures modified by epoxy resin of 550 epoxide equivalents of raw material d 33.6% Rouge);Raw material e 16.6% (vinyl ethyl ether);Raw material f 9.7% (acrylic acid);Remaining is deionized water.
Above-mentioned aqueous epoxy resins the preparation method comprises the following steps: in four-hole boiling flask be added raw material a raw material b, be warming up to 56 DEG C, 4h is stirred, then heats to 88 DEG C, raw material c, raw material d is added, raw material e, raw material f, deionized water is added after stirring 5h, continues 3h is kept the temperature, is cooled to room temperature, with neutralizer tune pH to 8, filtering obtains aqueous epoxy resins.Aqueous epoxy resins obtained For clear solution shape, the viscosity at 25 DEG C is 800 centipoises.
Embodiment 12:
Substantially the same manner as Example 1, difference is made by oneself in aqueous epoxy resins in this present embodiment, including is weighed as follows Measure the component of percentage: raw material a 5.8% (N, N- diethylaniline);Raw material b 8.4% (lauryl acrylate);Raw material C1.5% (N, N- diethylaniline);Raw material d 26.3% (epoxy resin of 1200 epoxide equivalents);Raw material e 15.6% (third Glycol butyl ether);Raw material f 10% (maleic acid);Remaining is deionized water.
Above-mentioned aqueous epoxy resins the preparation method comprises the following steps: in four-hole boiling flask be added raw material a raw material b, be warming up to 51 DEG C, 4.4h is stirred, then heats to 114 DEG C, raw material c, raw material d is added, raw material e, raw material f, deionized water is added after stirring 7h, after Continue insurance temperature 3h, is cooled to room temperature, and with neutralizer tune pH to 8, filtering obtains aqueous epoxy resins.Water-base epoxy tree obtained Rouge is clear solution shape, and the viscosity at 25 DEG C is 150 centipoises.
Embodiment 13:
Substantially the same manner as Example 1, difference is made by oneself in aqueous epoxy resins in this present embodiment, including is weighed as follows Measure the component of percentage: raw material a 12.5% (hexa);Raw material b 3.8% (glycidyl methacrylate); Raw material c 4.8% (phthalimide);Raw material d 40.3% (epoxy resin of 660 epoxide equivalents);Raw material e 16.4% (N- vinyl imidazole);Raw material f 5.5% (methacrylic acid);Remaining is deionized water.
Above-mentioned aqueous epoxy resins the preparation method comprises the following steps: in four-hole boiling flask be added raw material a raw material b, be warming up to 50 DEG C, 5.8h is stirred, then heats to 123 DEG C, raw material c, raw material d is added, raw material e, raw material f, deionized water is added after stirring 8h, after Continue insurance temperature 3h, is cooled to room temperature, and with neutralizer tune pH to 8, filtering obtains aqueous epoxy resins.Water-base epoxy tree obtained Rouge is clear solution shape, and the viscosity at 25 DEG C is 900 centipoises.
Embodiment 14:
Substantially the same manner as Example 1, difference is made by oneself in aqueous epoxy resins in this present embodiment, including is weighed as follows Measure the component of percentage: raw material a 5% (diethylenetriamines);Raw material b 2% (trifluoroethyl methacrylate);Raw material C1% (azanol);Raw material d 47% (epoxy resin of 100 epoxide equivalents);(divinyl -1,4- the butanediol of raw material e 14% Ether);Raw material f 5% (Alpha-hydroxy methacrylic acid);Remaining is deionized water.
Above-mentioned aqueous epoxy resins the preparation method comprises the following steps: in four-hole boiling flask be added raw material a raw material b, be warming up to 40 DEG C, 7h is stirred, then heats to 130 DEG C, raw material c, raw material d is added, raw material e, raw material f, deionized water is added after stirring 3h, continues 0.5h is kept the temperature, is cooled to room temperature, with neutralizer tune pH to 7.5, filtering obtains aqueous epoxy resins.Water-base epoxy obtained Resin is clear solution shape, and the viscosity at 25 DEG C is 1000 centipoises.
Embodiment 15:
Substantially the same manner as Example 1, difference is made by oneself in aqueous epoxy resins in this present embodiment, including is weighed as follows Measure the component of percentage: raw material a 15% (diethanol amine);Raw material b10% (isobornyl acrylate);(the 3- third of raw material c 8% Hydramine);Raw material d 26% (epoxy resin of 5000 epoxide equivalents);Raw material e 25% (N- caprolactam);Raw material f 5% (2- acrylamide-2-methyl propane sulfonic);Remaining is deionized water.
Above-mentioned aqueous epoxy resins the preparation method comprises the following steps: in four-hole boiling flask be added raw material a raw material b, be warming up to 60 DEG C, 2h is stirred, then heats to 80 DEG C, raw material c, raw material d is added, raw material e, raw material f, deionized water is added after stirring 10h, continues 4.5h is kept the temperature, is cooled to room temperature, with neutralizer tune pH to 7, filtering obtains aqueous epoxy resins.Water-base epoxy tree obtained Rouge is clear solution shape, and the viscosity at 25 DEG C is 90 centipoises.
Water-based glass baking paint paint film made from the various embodiments described above is detected, testing result is as shown in the table:

Claims (10)

1. a kind of Water-based glass baking paint, it is characterised in that including following weight percentage components:
Aqueous epoxy resins 20~60%, low-methoxyl etherified amino resins 10~40%, water-based acrylic resin modified polyurethane 0~ 18%, color essence dyestuff or colorant 3~30%, levelling agent 0.1~0.8%, wetting agent 0.1~1.0%, adhesive agent 0.1~ 0.8%, antioxidant 0.1~0.8%, defoaming agent 0.1~0.6%, fungicide 0.1~0.4%, pH adjusting agent 0.5~6%, Remaining is deionized water.
2. Water-based glass baking paint according to claim 1, it is characterised in that: the low-methoxyl etherified amino resins are high imines Type part low-methoxyl etherified amino resins.
3. Water-based glass baking paint according to claim 1, it is characterised in that: the water-based acrylic resin modified polyurethane For aromatic isocyanate type aqueous polyurethane.
4. Water-based glass baking paint according to claim 1, it is characterised in that: the color essence dyestuff or colorant are transparent At least one of pigment, azo pigments, pearlescent pigment, carbon black, titanium dioxide;The levelling agent be acrylic compounds levelling agent, At least one of silicone levelling agent, fluorocarbons class levelling agent;The wetting agent is acetylenic diols, fluorine class, acrylic acid At least one of class, organic silicon wetting agent;The adhesive agent are to contain amino, methacrylate, epoxy group, ethylene Base, chlorination alkyl silicone coupling agents at least one;The antioxidant is sodium formaldehyde sulfoxylate, sodium hydrogensulfite, oxalic acid, plant Acid, ammonium hydroxide, hydrazine hydrate, ascorbic acid, tea polyphenols, tocopherol, flavonoids, butylated hydroxy anisole, dibutyl hydroxy toluene, uncle At least one of butylhydroquinone;The defoaming agent be polyethers, high-carbon alcohols, silicon class, polyether-modified silicon, self-emulsifying type, At least one of polysiloxane defoamer;The pH adjusting agent is N- aminopropyl monomethyl ethanol amine, 2- amino -2- first Base -1- propyl alcohol, butyl diethanolamine, N- methylethanolamine, -1,3 propylene glycol of 2- amino -2- ethyl, dimethylethanolamine, Dan Yi One of hydramine, diethanol amine, triethanolamine, butylethanolamine, ammonium hydroxide.
5. Water-based glass baking paint according to claim 1, it is characterised in that: the aqueous epoxy resins include following weight The component of percentage: raw material a 5~15%;Raw material b 2~10%;Raw material c1~8%;Raw material d 26~47%;Raw material e 14 ~25%;Raw material f 5~10%;Remaining is deionized water;Wherein the raw material a is at least one of secondary amine or tertiary amine;Institute Stating raw material b is at least one of esters of unsaturated carboxylic acids;The raw material c is alcamines, amides, aromatic amine, imines, hydroxyl At least one of amine raw material;The raw material d is one of the epoxy resin of different epoxide equivalents;The raw material e is to have One of solvent;The raw material f is one of acrylic monomer.
6. Water-based glass baking paint according to claim 5, it is characterised in that: the raw material a be triethylamine, diethanol amine, Triethanolamine, diethylenetriamines, hexamethylene imine, hexa, N, at least one of N- diethylaniline;Institute Stating raw material b is methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, Isobutyl methacrylate, methyl Tert-butyl acrylate, isooctyl methacrylate, n octyl methacrylate, cyclohexyl methacrylate, methacrylic acid three Fluorine ethyl ester, glycidyl methacrylate, isobornyl methacrylate, methyl acrylate, ethyl acrylate, acrylic acid are just Butyl ester, hydroxypropyl acrylate, Isooctyl acrylate monomer, ethylene carbonate, propene carbonate, lauryl acrylate and the different ice of acrylic acid At least one of piece ester;The raw material c is monoethanolamine, diethanol amine, triethanolamine, 3- Propanolamine, acetamide, dimethyl methyl Amide, isobutyramide, aniline, o-phenylenediamine, 2,4- dimethylaniline, N, N- diethylaniline, para-fluoroaniline, phthalyl At least one of imines, azanol;The raw material e is propylene glycol methyl ether acetate, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, the third two Alcohol ether, propandiol butyl ether, isobutylvinyl ether, cyclohexyl vinyl ether, N- vinyl imidazole, N- caprolactam, N- vinyl pyrrole ketone, vinyl ethyl ether, diethylene glycol divinyl ether, 1,4- cyclohexane dimethanol divinyl ether, hydroxyl One kind of butyl vinyl ether, 1,4- cyclohexanediol mono vinyl ether, divinyl -1,4- butanediol ethere;The raw material f is third One kind of olefin(e) acid, methacrylic acid, Alpha-hydroxy methacrylic acid, maleic acid, 2- acrylamide-2-methyl propane sulfonic.
7. Water-based glass baking paint according to claim 5, it is characterised in that: the preparation method of the aqueous epoxy resins Are as follows:
Raw material a and raw material b is added, is warming up to 40~60 DEG C, stirs 2~7h;Then heat to 80~130 DEG C, be added raw material c and Raw material d stirs 3~10h;Then raw material e, raw material f and deionized water is added, continues 0.5~4.5h of heat preservation, is cooled to room temperature Afterwards, pH to 7~8 is adjusted, filtering obtains aqueous epoxy resins.
8. a kind of preparation method of the Water-based glass baking paint as described in any claim of claim 1~7, it is characterised in that including such as Lower step:
Wetting agent, defoaming agent, deionized water are mixed and stirred for uniformly;Then aqueous epoxy resins, low-methoxyl etherified amino are added Resin, water-based acrylic resin modified polyurethane add levelling agent, adhesive agent, antioxidant, fungicide, pH adjusting agent and stir It mixes uniformly mixed, obtains mixed solution, color essence dyestuff or colorant are added as needed, defoams and adjusts to required viscosity Filtering, obtains Water-based glass baking paint.
9. preparation method according to claim 8, it is characterised in that: the mixed solution before color essence dyestuff or colorant is added For transparence solution, the viscosity at 25 DEG C is 10~1000 centipoises.
10. preparation method according to claim 8, it is characterised in that: the solid content of Water-based glass baking paint obtained is 25 ~75%.
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