CN103342940A - Low-temperature water-based glass paint and preparation method thereof - Google Patents
Low-temperature water-based glass paint and preparation method thereof Download PDFInfo
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- CN103342940A CN103342940A CN2013102609221A CN201310260922A CN103342940A CN 103342940 A CN103342940 A CN 103342940A CN 2013102609221 A CN2013102609221 A CN 2013102609221A CN 201310260922 A CN201310260922 A CN 201310260922A CN 103342940 A CN103342940 A CN 103342940A
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Abstract
The invention provides low-temperature water-based glass paint and a preparation method thereof. The low-temperature water-based glass paint disclosed by the invention is prepared from 20-60 parts of modified water-based epoxy resin, 5-10 parts of water-based polyurethane resin and 0-30 parts of auxiliaries. The low-temperature water-based glass paint disclosed by the invention has strong stability and good normal-temperature self-crosslinking property; the adhesive force between a coating and glass is increased; the low-temperature water-based glass paint is directly sprayed on the surface of a glass product at normal temperature to be thermally cured, and therefore, a high-quality glaze sealed glass wine product is produced.
Description
Technical field
The present invention relates to the painting technical field, be specifically related to a kind of aqueous environment protection coating for glass article surface and preparation method thereof
Technical background
Stupalith is because its exquisite outward appearance has application widely in people produce and live, as artwork, bottle, vase etc., but the high temperature gloss firing during its process for processing pottery need consume a large amount of energy, from raw material be ground to 1,000 the degree more than the kiln high-temperature firing, polish under press then etc., these directly and have indirectly consumed a large amount of coals.And pottery is frangible, and the ceramic-like bottle uses later can't recycling, causes huge burden to environment.
In order to satisfy people for the pursuit of quality of the life, accomplish " the low-carbon (LC) life " of energy-saving and emission-reduction again, so people are chosen in vial outside surface sprayed coating, namely form the effect of envelope glaze at the outside surface of glass, thereby can substitute ceramic high temperature colored glaze bottle.This product innovation and application thereof have plurality of advantages such as low-carbon (LC), safety and environmental protection, can also save a large amount of energy, and seal the glaze glass wine bottle and can reclaim reprocessing, have very significant meaning for energy-saving and emission-reduction and environment protection.
Because at present glass paint mostly is solvent based coating greatly, need use during application the harmful benzene,toluene,xylene of human body and environment etc. is contained benzene solvent; In addition, the bonding strength of the coating that has is low, and is less to the sticking power of various glass material products, so the application of inapplicable glass material product.And there is water-fast poor, the high shortcoming of construction solidification value in present watersoluble modified epoxypaint on the market.
So the present invention studies a kind of aqueous environment protection glass with low thermo-paint, is the product that ceramic high temperature colored glaze and water-borne coatings mutually combine, and is two new results that the technology in the different field organically blends.Make this coating can be painted on glass article surface, thermofixation at normal temperatures, form high-quality envelope glaze glasswork.
Summary of the invention
The purpose of this invention is to provide a kind of low temperature water-based glass paint and preparation method thereof, reach the purpose that just can form the envelope glaze at low temperatures at the surface cure of glasswork.
Technical scheme of the present invention is as follows:
A kind of low temperature water-based glass paint is prepared from by following raw materials in parts by weight:
20 ~ 60 parts of modified aqueous epoxy resins
5 ~ 10 parts of waterborne polyurethane resins
0 ~ 30 part of auxiliary agent;
Described modified aqueous epoxy resin is to be made by Resins, epoxy, esters of acrylic acid and amino modified silane reaction.
Further, described modified aqueous epoxy resin is to be prepared from by following raw materials in parts by weight:
15.0 ~ 40.0 parts of Resins, epoxy
5.0 ~ 30.0 parts of esters of acrylic acids
0.1 ~ 5.0 part in amino modified silane.
Further, described auxiliary agent is one or more combinations in pigment, filler, catalyzer, flow agent, dispersion moisture agent, defoamer, conductive agent, adhesion promoter or the mask agent.
Wherein pigment can be selected from iron pigment, chromate pigments, the blue or green pigment of phthalein, titanium dioxide or metallized dye; Described filler is talcum powder, zinc sulfide white or flatting silica.
Further, described amino modified silane is γ-aminopropyl methyldiethoxysilane, γ-An Bingjisanyiyangjiguiwan or N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane.
Further, described esters of acrylic acid is isobornyl acrylate, glycidyl acrylate, methyl acrylate, Isooctyl acrylate monomer, vinylformic acid fluorinated ester, Hydroxyethyl acrylate or Propylene glycol monoacrylate.
Another object of the present invention provides a kind of preparation as above-mentioned water at low temperature glass paint, may further comprise the steps:
(1) preparation modified aqueous epoxy resin:
By proportioning Resins, epoxy is dissolved in the solvent, temperature rises to 80 ~ 120 ℃, drips the esters of acrylic acid that is dissolved with initiator then and dropwises back insulation 1 ~ 5 hour, gets modified epoxy grafted propylene acid resin; Cool to 45 ~ 65 ℃ again, adding neutralizing agent and amino modified silane carried out the chain extension modified-reaction 1 ~ 6 hour in modified epoxy grafted propylene acid resin, added water at last, obtained modified aqueous epoxy resin;
(2) preparation low temperature water-based glass paint:
Be mixed together by modified aqueous epoxy resin and waterborne polyurethane resin, auxiliary agent, the solvent of proportioning with (1) preparation, mix afterwards material with evenly disperse in the sand mill low temperature water-based glass paint.
Further, the dropping temperature of mix monomer is 60 ~ 150 ℃ in the described step (1), and the time is 1 ~ 4 hour.
Further, initiator is at least a in azo-bis-isobutyl cyanide, benzoyl peroxide, dicumyl peroxide, methylethyl ketone peroxide, di-cyclohexylperoxy dicarbonate, tertbutyl peroxide, the azo-bis-iso-dimethyl in the described step (1);
Described neutralizing agent is NaHCO
3, ammoniacal liquor, triethylamine, N, N-dimethylethanolamine or 2-amino-2-methyl-1-propanol;
Further, the solvent in described step (1) and (2) is propyl carbinol, butyl glycol ether, 2-Butoxyethyl acetate, propylene glycol monomethyl ether, 1-Methoxy-2-propyl acetate, Virahol, ethanol.
Waterborne polyurethane resin is a kind of superfine aliphatic polyurethane dispersion liquid, is mainly used in promoting the then property of covering with paint, has the ultra-fine film that causes and extend, excellent winter hardiness, and the present invention is preferably water-based negatively charged ion or non-ionic polyurethane resin.The complex etherified aminoresin of the preferred high imido fundamental mode of aminoresin can add corresponding pigment according to client's needs and prepare the former coating of different colours, pigment iron clad series pigments such as red iron oxide, iron oxide yellow, iron oxide black among the present invention; Chromate pigments such as lead-chrome yellow, molybdenum red and chrome green; The blue or green pigment of phthalein, titanium dioxide, metallized dye etc.Filler and auxiliary agent also are to carry out selectivity according to the performance of processing needs and the finished product to add.
The present invention provides a kind of novel aqueous glass coating, with one or more pure ether solvent heating for dissolving Resins, epoxy, drip the acrylate monomer grafting Resins, epoxy that the mixing that is dissolved with initiator contains functional group then, obtain modified epoxy grafted propylene acid resin; With neutralizing agent this grafting Resins, epoxy that neutralizes, carry out the open loop epoxy reaction with amino modified silane more then, chain extension branching grafting Resins, epoxy obtains modified aqueous epoxy resin.Be the main body film-forming resin at last again with the modified aqueous epoxy resin, auxiliary other waterborne polyurethane resins, aminoresin, color stuffing and auxiliary agent, modulation obtains the good aqueous glass coating of workability.
So the present invention has following beneficial effect:
1, the aqueous glass coating of the present invention's preparation, thermofixation is carried out on the surface that can be painted on glasswork at normal temperatures, can produce high-quality envelope glaze glasswork, reduces its construction temperature.
2, owing to adopt the acrylic ester monomer grafting Resins, epoxy that contains functional group among the present invention, introduce multiple functional group in the grafted monomer, these functional groups not only can realize the Water-borne modification of epoxy, and has good ambient self-crosslinking character, need not to add solidifying agent such as aminoresin, modified amine and can obtain the splendid paint coatings of over-all properties, improve the stability of coating.
3, aqueous glass coating of the present invention is with amino modified silane chain extension graft type Resins, epoxy, introduces siloxane groups, greatly improves the sticking power of coating and glass.In addition, the high molecular expoxy resin after the chain extension has excellent mechanical property.
4, do not add any environmentally harmful benzene-type products in the formulation for coating material of the present invention, so it is harmless to environment-friendly.
Embodiment:
The present invention is further elaborated below in conjunction with embodiment.
Embodiment 1:
(1) preparation modified aqueous epoxy resin:
By proportioning 35 parts of Resins, epoxy are dissolved in 20 parts of propyl carbinols and the 10 parts of butyl glycol ether mixed solvents, temperature rises to 100 ℃, drip 5 parts of Hydroxyethyl acrylates that are dissolved with 0.01 part of initiator benzoyl peroxide, 4 parts of glycidyl acrylates, 6 parts of mixing esters of acrylic acids that methyl methacrylate is formed then, dropping temperature is 120 ℃, and the time is 2 hours; Dropwise back insulation 4 hours, get modified epoxy grafted propylene acid resin; Cool to 50 ℃ again, 4 parts of neutralizing agent triethylamines of adding and 2 parts of amino modified silane γ-aminopropyl methyldiethoxysilane were carried out the chain extension modified-reaction 4 hours in modified epoxy grafted propylene acid resin, added water at last, obtained modified aqueous epoxy resin;
(2) preparation low temperature water-based glass paint:
0.2 part of 50 parts of modified aqueous epoxy resins that will (1) prepare by proportioning and 5 parts of waterborne polyurethane resins, 15 parts of pigment, defoamer, 0.8 part, 13 parts alcohol solvent agent of wetting agent are mixed together, mix the back material with evenly disperse in the sand mill low temperature water-based glass paint.
Adopt spraying coating process to construct in the glass surface of cleaning the low temperature water-based glass paint that makes, condition of cure is 120 ℃ and toasted 30 minutes down.
Embodiment 2:
(1) preparation modified aqueous epoxy resin:
By proportioning 15 parts of Resins, epoxy are dissolved in 20 parts of Virahols, temperature rises to 80 ℃, drip 10 parts of butyl acrylates that are dissolved with 0.1. part initiator benzoyl peroxide, 8 parts of isobornyl methacrylates, 12 parts of mixtures that Isooctyl acrylate monomer is formed then, dropping temperature is 80 ℃, and the time is 3 hours; Dropwise back insulation 4 hours, get modified epoxy grafted propylene acid resin; Cool to 50 ℃ again, in modified epoxy grafted propylene acid resin, add 5 parts of neutralizing agent N, N-dimethylethanolamine and 2 parts of amino modified silane γ-An Bingjisanyiyangjiguiwans carried out the chain extension modified-reaction 2 hours, added water at last, obtained modified aqueous epoxy resin;
(2) preparation low temperature water-based glass paint:
0.2 part of 20 parts of modified aqueous epoxy resins that will (1) prepare by proportioning and 10 parts of waterborne polyurethane resins, 10 parts of pigment, 11 parts of talcum powders, defoamer, 0.8 part, 38 parts propylene glycol monomethyl ether solvents of wetting agent are mixed together, mix the back material with evenly disperse in the sand mill low temperature water-based glass paint.
Adopt spraying coating process to construct in the glass surface of cleaning the low temperature water-based glass paint that makes, warm condition from dried solidify envelope glaze glasswork.
Embodiment 3:
(1) preparation modified aqueous epoxy resin:
By proportioning 40 parts of Resins, epoxy are dissolved in 35 parts of propylene glycol monomethyl ether solvents, temperature rises to 80 ℃, drip 5 parts of Propylene glycol monoacrylates that are dissolved with 1.0 parts of initiator dicumyl peroxides, 4 parts of vinylformic acid fluorinated esters, 6 parts of mix monomers that Hydroxyethyl acrylate is formed then, dropping temperature is 120 ℃, and the time is 3 hours; Dropwise back insulation 3 hours, get modified epoxy grafted propylene acid resin; Cool to 45 ℃ again, 5 parts of neutralizing agent ammoniacal liquor of adding and 2 parts of amino modified silane γ-An Bingjisanyiyangjiguiwans carried out the chain extension modified-reaction 6 hours in modified epoxy grafted propylene acid resin, added water at last, obtained modified aqueous epoxy resin;
(2) preparation low temperature water-based glass paint:
0.8 part of 30 parts of modified aqueous epoxy resins that will (1) prepare by proportioning and 10 parts of pigment of 8 parts of waterborne polyurethane resins, 25 parts of filler talcum powder, defoamer, 1.2 parts, 25 parts ethanol of wetting agent are mixed together, mix the back material with evenly disperse in the sand mill low temperature water-based glass paint.
Adopt the technology of dip-coating to construct in the glass surface of cleaning the low temperature water-based glass paint that makes, condition of cure is that baking must be sealed the glaze glasswork in 20 minutes under 150 ℃.
Embodiment 4:
(1) preparation modified aqueous epoxy resin:
By proportioning 40 parts of Resins, epoxy are dissolved in 10 parts of butyl glycol ethers, 10 parts of 2-Butoxyethyl acetates, the 11 parts of alcohol mixed solvents, temperature rises to 120 ℃, drip 3 parts of vinyl toluenes that are dissolved with 0.5 part of initiator tertbutyl peroxide then, in 25 parts of methyl acrylates, dropping temperature is 150 ℃, and the time is 2 hours; Dropwise back insulation 5 hours, get modified epoxy grafted propylene acid resin; Cool to 65 ℃ again, in modified epoxy grafted propylene acid resin, add 5 parts of neutralizing agent NaHCO
3Carry out the chain extension modified-reaction 1 hour with 2 parts of amino modified silane N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilanes, add water at last, obtain modified aqueous epoxy resin;
(2) preparation low temperature water-based glass paint:
Be dissolved in the butyl glycol ether solvent by proportioning 60 parts of modified aqueous epoxy resins and 6 parts of waterborne polyurethane resins with (1) preparation, mix, mix afterwards material with evenly disperse in the sand mill low temperature water-based glass paint.
Adopt the technology of roller coating to construct in the glass surface of cleaning the low temperature water-based glass paint that makes, condition of cure is that baking must be sealed the glaze glasswork in 8 minutes under 190 ℃.
The coating of above-described embodiment 1-4 preparation is applied to seals the glaze glasswork after glass surface solidifies, basic detection method according to the industry compares the performances such as adhesive force of coatings, water tolerance, ethanol-tolerant and hardness of sealing the glaze glasswork, shown in the table specific as follows:
| Item compared | Examination criteria | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Sticking power | GB/T1720-1989 | 0 grade | 0 grade | 0 grade | 0 grade |
| Water tolerance (hour) | GB/T1733-1993 | ≥?240 | ≥?240 | ≥?240 | ≥?240 |
| Ethanol-tolerant (hour) | GB/T1734 | ≥?24 | ≥?24 | ≥?24 | ≥?24 |
| Hardness | GB/T1730-2007 | 2?H | 2?H | 2?H | 2?H |
As can be seen from the above table, the coating of the present invention's preparation reaches 0 grade standard at strong adhesion on glass; And water tolerance is not less than 240 hours, will exceed more than 10 times than the water tolerance of reference examples; In addition, the ethanol-tolerant of coating of the present invention and hardness all are higher than reference examples.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (9)
1. low temperature water-based glass paint is characterized in that: be prepared from by following raw materials in parts by weight:
20 ~ 60 parts of modified aqueous epoxy resins
5 ~ 10 parts of waterborne polyurethane resins
0 ~ 30 part of auxiliary agent;
Described modified aqueous epoxy resin is to be made by Resins, epoxy, esters of acrylic acid and amino modified silane reaction.
2. according to the described low temperature water-based of claim 1 glass paint, it is characterized in that: described modified aqueous epoxy resin is to be prepared from by following raw materials in parts by weight:
15.0 ~ 40.0 parts of Resins, epoxy
5.0 ~ 30.0 parts of esters of acrylic acids
0.1 ~ 5.0 part in amino modified silane.
3. according to the described low temperature water-based of claim 1 glass paint, it is characterized in that: described auxiliary agent is one or more combinations in pigment, filler, catalyzer, flow agent, dispersion moisture agent, defoamer, conductive agent, adhesion promoter or the mask agent.
4. according to claim 1 or 2 described low temperature water-based glass paints, it is characterized in that: described amino modified silane is γ-aminopropyl methyldiethoxysilane, γ-An Bingjisanyiyangjiguiwan or N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane.
5. according to claim 1 or 2 described low temperature water-based glass paints, it is characterized in that: described esters of acrylic acid is isobornyl acrylate, glycidyl acrylate, methyl acrylate, Isooctyl acrylate monomer, vinylformic acid fluorinated ester, Hydroxyethyl acrylate or Propylene glycol monoacrylate.
6. one kind prepares low temperature water-based glass paint according to claim 1, it is characterized in that: may further comprise the steps:
(1) preparation modified aqueous epoxy resin:
By proportioning Resins, epoxy is dissolved in the solvent, temperature rises to 80 ~ 120 ℃, drips the esters of acrylic acid that is dissolved with initiator then and dropwises back insulation 1 ~ 5 hour, gets modified epoxy grafted propylene acid resin; Cool to 45 ~ 65 ℃ again, adding neutralizing agent and amino modified silane carried out the chain extension modified-reaction 1 ~ 6 hour in modified epoxy grafted propylene acid resin, added water at last, obtained modified aqueous epoxy resin;
(2) preparation low temperature water-based glass paint:
Be mixed together by modified aqueous epoxy resin and waterborne polyurethane resin, auxiliary agent, the solvent of proportioning with (1) preparation, mix afterwards material with evenly disperse in the sand mill low temperature water-based glass paint.
7. method according to claim 6 is characterized in that: the dropping temperature of mix monomer is 60 ~ 150 ℃ in the described step (1), and the time is 1 ~ 4 hour.
8. method according to claim 6 is characterized in that: initiator is at least a in azo-bis-isobutyl cyanide, benzoyl peroxide, dicumyl peroxide, methylethyl ketone peroxide, di-cyclohexylperoxy dicarbonate, tertbutyl peroxide, the azo-bis-iso-dimethyl in the described step (1);
Described neutralizing agent is NaHCO
3, ammoniacal liquor, triethylamine, N, N-dimethylethanolamine or 2-amino-2-methyl-1-propanol.
9. method according to claim 6, it is characterized in that: the solvent in described step (1) and (2) is propyl carbinol, butyl glycol ether, 2-Butoxyethyl acetate, propylene glycol monomethyl ether, 1-Methoxy-2-propyl acetate, Virahol, ethanol.
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| CN2013102609221A CN103342940A (en) | 2013-06-27 | 2013-06-27 | Low-temperature water-based glass paint and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327632A (en) * | 2014-10-14 | 2015-02-04 | 马鞍山市恒毅机械制造有限公司 | Long-lasting fade-proof aqueous coating for glass doors, and its preparation method |
| CN107936647A (en) * | 2017-12-06 | 2018-04-20 | 苏州铂邦胶业有限公司 | Scratch resistance waterborne polyurethane coating |
| CN108129953A (en) * | 2017-12-28 | 2018-06-08 | 苏州德达特种涂料有限公司 | A kind of bi-component waterborne glass lacquer and preparation method thereof |
| CN109096874A (en) * | 2018-07-13 | 2018-12-28 | 安徽康瑞高科新材料技术工程有限公司 | A kind of aqueous glass paint and preparation method thereof |
-
2013
- 2013-06-27 CN CN2013102609221A patent/CN103342940A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327632A (en) * | 2014-10-14 | 2015-02-04 | 马鞍山市恒毅机械制造有限公司 | Long-lasting fade-proof aqueous coating for glass doors, and its preparation method |
| CN107936647A (en) * | 2017-12-06 | 2018-04-20 | 苏州铂邦胶业有限公司 | Scratch resistance waterborne polyurethane coating |
| CN108129953A (en) * | 2017-12-28 | 2018-06-08 | 苏州德达特种涂料有限公司 | A kind of bi-component waterborne glass lacquer and preparation method thereof |
| CN109096874A (en) * | 2018-07-13 | 2018-12-28 | 安徽康瑞高科新材料技术工程有限公司 | A kind of aqueous glass paint and preparation method thereof |
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Application publication date: 20131009 |