CN1267517C - Organic silicon modified water double-component polyurethane coating and preparing method thereof - Google Patents
Organic silicon modified water double-component polyurethane coating and preparing method thereof Download PDFInfo
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- CN1267517C CN1267517C CN 200410042723 CN200410042723A CN1267517C CN 1267517 C CN1267517 C CN 1267517C CN 200410042723 CN200410042723 CN 200410042723 CN 200410042723 A CN200410042723 A CN 200410042723A CN 1267517 C CN1267517 C CN 1267517C
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Abstract
The present invention relates to an organic silicon modified water double-component polyurethane coating and a preparing method thereof. The organic silicon modified water double-component polyurethane coating is made from 100 parts by weight of organic silicon modified acrylic ester emulsion containing hydroxy groups, 0.05 to 1 part by weight of defoaming agents, 0.05 to 1 part by weight of wetting agents, 0 to 30 parts by weight of water, and 5 to 50 parts by weight of hydrophilic modified polyisocyanate which are uniformity mixed and stirred, wherein the organic silicon modified acrylic ester emulsion containing hydroxy groups is formed by that 20 to 50 parts by weight of acrylic ester monomer mixtures, 0.5 to 5 parts by weight of organic silicon monomers, 0.2 to 2 parts by weight of emulsifying agents, 0.2 to 0.5 part by weight of initiating agents, 49 to 79 parts by weight of water, 0.1 to 0.3 part by weight of buffering agents and right amount of neutralizing agents are polymerized by raising temperature and are neutralized by reducing temperature, the pH value is adjusted between 7 and 8.5, and the material is sieved and discharged. The present invention has the advantages that the coating has the characteristics of easy mix, self dryness under normal temperature, no toxicity, no taste and no environment pollution, and has the advantages of high hardness and good water resistance.
Description
Technical field
The present invention relates to a kind of organic silicon modified aqueous bicomponent polyurethane coating and preparation method.
Background technology
Polyurethane paint has the performance of many excellences, as strong adhesion, wear resistance is good, elasticity is adjustable, can be made into and arrive utmost point softish coating extremely firmly, have performances such as excellent acid, alkaline-resisting, high-low temperature resistant, therefore obtained using widely at aspects such as national defence, building, chemical industry, vehicle, woodenware, aircrafts.Traditional polyurethane paint contains to human body and the deleterious volatile organic compounds of environment, as toluene, dimethylbenzene etc.Along with the enhancing of people's Environmental awareness and the foundation of environmental regulation, its application more and more is restricted.
Aqueous polyurethane coating, water have replaced poisonous and hazardous organic solvent, have nontoxic, fire-retardant, free from environmental pollution, save advantage such as the energy, progressively replacing traditional solvent reducible coatings, represented the direction of coating development.Mono-component aqueous polyurethane coating easy construction, but still can not reach the performance of solvent borne polyurethane coating at aspects such as many performances such as water tolerance, solvent resistance, chemical-resistant, wear resistance, hardness; And waterborne two-component polyurethane coating has improved the cross-linking density of coating greatly by using polyisocyanates as the linking agent crosslinking curing, and its performance can compare favourably with the solvent borne polyurethane coating.
Aqueous polyurethane coating with bi component has carried out number of research projects both at home and abroad.Hydroxy-containing component as aqueous polyurethane coating with bi component, patent CA2107957, CN1278539, EP792898, EP1065228, US5387642, US5830938, WO97-35898 etc. have applied for the hydroxyl polyurethane dispersions, patent CN1162964, CN1230971, EP959115, WO99-58589, US6225398, WO99-51658, WO01-04172 etc. have applied for the hydroxy acryl acid dispersion, patent EP562282, EP742239 etc. have applied for the hydroxy acryl acid polyurethane dispersions, these dispersions all exist hardness of paint film low, water resistance is poor, with shortcomings such as hydrophilically modified polyisocyanates compatibility differences, be difficult to reach the performance of solvent based coating.
Summary of the invention
The objective of the invention is to improve the shortcoming of prior art, and provide a kind of organic-silicon-modified hydroxy acryl acid emulsion and its to cooperate the modified aqueous polyurethane coating with bi component that makes its performance reach solvent borne polyurethane coating index with hydrophilically modified polyisocyanates.
Another object of the present invention is to and a kind of preparation method of organic silicon modified aqueous bicomponent polyurethane coating is provided.
For achieving the above object, the present invention takes following design: described organic-silicon-modified hydroxy acryl acid ester emulsion is made up of following materials based on weight:
Acrylate monomer blend 20～50 emulsifying agents 0.2～2
Initiator 0.2～0.5 water 49～79
Buffer reagent 0.1～0.3 neutralizing agent is an amount of
Organosilane monomer 0.5～5
Described acrylate monomer blend, its solid acid number scope is at 5～50mgKOH/g, and solid hydroxyl value scope is at 50～250mgKOH/g; Described an amount of neutralizing agent, its be in right amount make the preparation emulsion the pH value be 7～8.5.Described acrylate monomer blend can with hydroxy acryl acid ester monomer and not the acrylate monomer copolymerization of hydroxyl make.Described hydroxy acryl acid ester monomer is (methyl) Hydroxyethyl acrylate or (methyl) Propylene glycol monoacrylate; The acrylate monomer of described not hydroxyl comprises (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA or other (methyl) higher hydrocarbyl acrylate.The acrylate monomer of described not hydroxyl is (methyl) vinylformic acid also.Described emulsifying agent is the mixing of anionic emulsifier and nonionic emulsifying agent.The mixed weight ratio of described anionic emulsifier and nonionic emulsifying agent is 2: 8～8: 2.Described initiator is water miscible, as Potassium Persulphate or ammonium persulphate etc.Described water is distilled water or deionized water.Described buffer reagent is a sodium bicarbonate.Described neutralizing agent is methyldiethanolamine, dimethylethanolamine, triethylamine or ammoniacal liquor etc.Described organosilane monomer is double bond containing organo-siloxane, as vinyltrimethoxy silane, vinyltriethoxysilane, propenyl Trimethoxy silane or gamma-methyl allyl acyloxypropyl trimethoxysilane etc.
Described organic-silicon-modified hydroxy acryl acid ester emulsion preparation step is as follows: earlier water, emulsifying agent, buffer reagent sodium bicarbonate etc. are mixed the back and add in the reactor, be warmed up to 65～85 ℃, drip the mixture of the initiator, acrylate monomer and the organosilane monomer that are mixed with the aqueous solution respectively, after in 1～3 hour, dripping off, kept 0.5～1.5 hour, make the complete polymerization of acrylate monomer, be cooled to 40～60 ℃, add neutralizing agent, adjust pH, excessively discharging behind at least 80 eye mesh screens 7～8.5.
The organic silicon modified aqueous bicomponent polyurethane coating of the present invention is made up of following materials based on weight:
Hydroxy-containing component:
Organic-silicon-modified hydroxy acryl acid ester emulsion 100 defoamers 0.05～1
Wetting agent 0.05～1, water 0～30
Curing agent component: hydrophilically modified polyisocyanates 5～50
Organic silicon modified aqueous bicomponent polyurethane coating preparation process is as follows: various raw materials in the hydroxy-containing component are mixed, add curing agent component, by hand or mechanical stirring even, be the inventive method product.
During use, can adopt conventional coating method, this coating is coated on the ground that needs, as timber, metal, plastics or paper etc. as brushing, spraying, roller coat, showering, dip-coating etc.This coating can be used as priming paint, in be coated with and finish paint etc.
Advantage of the present invention is: this coating have mix easily, normal temperature self-drying, characteristics nontoxic, tasteless, free from environmental pollution, hardness height, water-tolerant.
Embodiment
Embodiment 1:
Organic-silicon-modified hydroxy acryl acid ester emulsion is made up of following materials based on weight:
Acrylate monomer blend 50 emulsifying agents 2
Initiator 0.5 water 79
Sodium bicarbonate 0.3 neutralizing agent is an amount of
Organosilane monomer 3
Organic-silicon-modified hydroxy acryl acid ester emulsion preparation step is as follows:
In container, add distilled water, compound emulsifying agent MS-1/OP-10 (1: 1) and buffer reagent sodium bicarbonate, be warming up to 85 ℃, drip the aqueous solution (10%) and acrylate monomer blend (the monomer weight ratio: Rocryl 410 23 of initiator ammonium persulfate, methacrylic acid 3, butyl acrylate 40, methyl methacrylate 34) and organosilane monomer vinyltrimethoxy silane mixture.After in 1 hour, dripping off, kept 1.5 hours, be cooled to 40 ℃, add neutralizing agent ammoniacal liquor, adjust the pH value, excessively discharging behind 80 eye mesh screens 8.5.
Organic silicon modified aqueous bicomponent polyurethane coating is made up of following materials based on weight:
Hydroxy-containing component:
Organic-silicon-modified hydroxy acryl acid ester emulsion 100 defoamers 0.05
Wetting agent 0.1, water 30
Curing agent component: hydrophilically modified polyisocyanates 50
Organic silicon modified aqueous bicomponent polyurethane coating preparation process is as follows: in above-mentioned organic-silicon-modified hydroxy acryl acid emulsion, add defoamer Byk028, wetting agent Byk346, stir evenly the back and add hydrophilic polyisocyanate WT2102, stir, add entry, stir evenly, be product of the present invention.
Embodiment 2:
Organic-silicon-modified hydroxy acryl acid ester emulsion is made up of following materials based on weight:
Acrylate monomer blend 20 emulsifying agents 0.2
Initiator 0.2 water 49
Sodium bicarbonate 0.1 neutralizing agent is an amount of
Organosilane monomer 0.5
Organic-silicon-modified hydroxy acryl acid ester emulsion preparation step is as follows:
In container, add deionized water, compound emulsifying agent sodium lauryl sulphate/OP-10 (6: 4) and buffer reagent sodium bicarbonate, be warming up to 65 ℃, drip the aqueous solution (10%) and acrylate monomer blend (the monomer weight ratio: hydroxyethyl methylacrylate 20 of initiator ammonium persulfate simultaneously, methacrylic acid 3, butyl acrylate 40, methyl methacrylate 37) with the mixture of organosilane monomer vinyltriethoxysilane.After in 2 hours, dripping off, kept 1 hour, be cooled to 50 ℃, add the neutralizing agent methyldiethanolamine, adjust the pH value, excessively discharging behind 100 eye mesh screens 7.
Organic silicon modified aqueous bicomponent polyurethane coating is made up of following materials based on weight:
Hydroxy-containing component:
Organic-silicon-modified hydroxy acryl acid ester emulsion 100 defoamers 0.2
Wetting agent 1 water 10
Curing agent component: hydrophilically modified polyisocyanates 25
Organic silicon modified aqueous bicomponent polyurethane coating preparation process is as follows: in above-mentioned organic-silicon-modified hydroxy acryl acid emulsion, add defoamer Byk028, wetting agent Byk346, stir evenly the back and add hydrophilic polyisocyanate WT2102, stir, add entry, stir evenly, be product of the present invention.
Embodiment 3:
Organic-silicon-modified hydroxy acryl acid ester emulsion is made up of following materials based on weight:
Acrylate monomer blend 30 emulsifying agents 1
Initiator 0.3 water 60
Sodium bicarbonate 0.2 neutralizing agent is an amount of
Organosilane monomer 5
Organic-silicon-modified hydroxy acryl acid ester emulsion preparation step is as follows:
In container, add distilled water, compound emulsifying agent sodium lauryl sulphate/OP-10 (6: 4) and buffer reagent sodium bicarbonate, be warming up to 75 ℃, drip the aqueous solution (10%) and acrylate monomer blend (the monomer weight ratio: hydroxyethyl methylacrylate 20 of initiator potassium persulfate simultaneously, methacrylic acid 3, propyl methacrylate 40, methyl methacrylate 37) with the mixture of organosilane monomer gamma-methyl allyl acyloxypropyl trimethoxysilane.After in 3 hours, dripping off, kept 0.5 hour, be cooled to 60 ℃, add the neutralizing agent triethylamine, adjust the pH value, excessively discharging behind 100 eye mesh screens 8.
Organic silicon modified aqueous bicomponent polyurethane coating is made up of following materials based on weight:
Hydroxy-containing component:
Organic-silicon-modified hydroxy acryl acid ester emulsion 100 defoamers 1
Wetting agent 0.05 water 0
Curing agent component: hydrophilically modified polyisocyanates 5
Organic silicon modified aqueous bicomponent polyurethane coating preparation process is as follows: in above-mentioned organic-silicon-modified hydroxy acryl acid emulsion, add defoamer Byk028, wetting agent Byk346, stir evenly the back and add hydrophilic polyisocyanate WT2102, stir, add entry, stir evenly, be product of the present invention.
Press CNS and detect performance, the paint film property detected result is as follows:
Surface drying: 1 hour
Do solid work: 5 hours
Gloss (60 °): 90
Pencil hardness: 2H
Snappiness: 2mm passes through
Sticking power (cross-hatching): 0
Shock strength: 50Kg.cm
Water-fast: as to pass through in 72 hours
Chemical-resistant (spot corrosion):
10%H
2SO
4By
10%HCl passes through
10%CH
3COOH passes through
Ethanol: by
Dimethylbenzene: by
Methylethylketone: by
Claims (9)
1, a kind of organic silicon modified aqueous bicomponent polyurethane coating, it is characterized in that: it is made up of following materials based on weight:
Hydroxy-containing component:
Organic-silicon-modified hydroxy acryl acid ester emulsion 100 defoamers 0.05～1
Wetting agent 0.05～1 water 0～30 He, curing agent component: hydrophilic polyisocyanate 5～50;
Organic-silicon-modified hydroxy acryl acid ester emulsion is made up of following materials based on weight in the described hydroxy-containing component:
Hydroxy acryl acid ester monomer and hydroxy acryl acid ester monomer 20～50 not
Contain two key organo-siloxane 0.5～5 water 49～79
Anionic emulsifier and nonionic emulsifying agent 0.2～2
Water soluble starter 0.2～0.5 buffer reagent sodium bicarbonate 0.1～0.3
Neutralizing agent is an amount of.
2, a kind of organic silicon modified aqueous bicomponent polyurethane coating according to claim 1 is characterized in that: described hydroxy acryl acid ester monomer is (methyl) Hydroxyethyl acrylate or (methyl) Propylene glycol monoacrylate; The acrylate monomer of described not hydroxyl is (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA or other (methyl) higher hydrocarbyl acrylate.
3, a kind of organic silicon modified aqueous bicomponent polyurethane coating according to claim 1 is characterized in that: the acrylate monomer of described not hydroxyl is (methyl) vinylformic acid.
4, a kind of organic silicon modified aqueous bicomponent polyurethane coating according to claim 1 is characterized in that: the mixed weight ratio of described anionic emulsifier and nonionic emulsifying agent is 2: 8～8: 2.
5, a kind of organic silicon modified aqueous bicomponent polyurethane coating according to claim 1, it is characterized in that: described water soluble starter is Potassium Persulphate or ammonium persulphate.
6, a kind of organic silicon modified aqueous bicomponent polyurethane coating according to claim 1 is characterized in that: described to contain two key organo-siloxanes be vinyltrimethoxy silane, vinyltriethoxysilane, propenyl Trimethoxy silane or gamma-methyl allyl acyloxypropyl trimethoxysilane.
7, a kind of organic silicon modified aqueous bicomponent polyurethane coating according to claim 1, it is characterized in that: described hydroxy acryl acid ester monomer and the solid acid number scope of hydroxy acryl acid ester monomer mixture is not at 5～50mgKOH/g, solid hydroxyl value scope is at 50～250mgKOH/g.
8, a kind of organic silicon modified aqueous bicomponent polyurethane coating according to claim 1, it is characterized in that: described neutralizing agent is methyldiethanolamine, dimethylethanolamine, triethylamine or ammoniacal liquor.
9, the preparation method of a kind of organic silicon modified aqueous bicomponent polyurethane coating according to claim 1 is characterized in that, and is as follows in steps: hydroxy-containing component is mixed, adds curing agent component, by hand or the mechanical stirring method mix.
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| CN 200410042723 CN1267517C (en) | 2004-05-24 | 2004-05-24 | Organic silicon modified water double-component polyurethane coating and preparing method thereof |
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| CN 200410042723 CN1267517C (en) | 2004-05-24 | 2004-05-24 | Organic silicon modified water double-component polyurethane coating and preparing method thereof |
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| CN1267517C true CN1267517C (en) | 2006-08-02 |
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| CN103031046B (en) * | 2011-09-29 | 2015-05-27 | 上海正欧实业有限公司 | Novel organosilicone acrylic acid bi-component polyurethane coating and preparation method thereof |
| CN103342956A (en) * | 2013-06-27 | 2013-10-09 | 天长市巨龙车船涂料有限公司 | Acrylic acid modified waterborne polyurethane paint and preparation method thereof |
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| CN110396342A (en) * | 2019-08-01 | 2019-11-01 | 苏晓辉 | A kind of self-cleaning coating and its construction technology |
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| CN112708031A (en) * | 2020-12-25 | 2021-04-27 | 嘉宝莉化工集团股份有限公司 | Water-based hydroxyl acrylic emulsion and preparation method and application thereof |
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