CN114163924A - Modified polyurethane resin water-based paint with good flexibility - Google Patents
Modified polyurethane resin water-based paint with good flexibility Download PDFInfo
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- CN114163924A CN114163924A CN202111595001.1A CN202111595001A CN114163924A CN 114163924 A CN114163924 A CN 114163924A CN 202111595001 A CN202111595001 A CN 202111595001A CN 114163924 A CN114163924 A CN 114163924A
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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Abstract
The invention relates to a modified polyurethane resin water-based paint with good flexibility, which comprises the following components in parts by weight: 60.0-150.0 parts of hydroxyl-terminated liquid polybutadiene rubber modified waterborne polyurethane resin, 0.4-1.0 part of flatting agent, 0.2-1.2 parts of dispersing agent, 0.4-1.0 part of defoaming agent, 0.5-1.0 part of wetting agent, 3.0-7.0 parts of ethylene glycol, 1.5-5.0 parts of propylene glycol butyl ether, 1.5-5.0 parts of propylene glycol methyl ether acetate, 0.0-35.0 parts of pigment and filler, 0.5-1.0 part of sodium carboxymethylcellulose, 1.0-3.0 parts of polyvinyl alcohol, 0.4-1.0 part of sodium bicarbonate and 10.0-40.0 parts of deionized water; the modified polyurethane resin water-based paint with good flexibility is environment-friendly, has good sagging resistance, good impact resistance, high crosslinking density, good flexibility and other properties, and can be used for substrates of wood furniture, steel structures and the like.
Description
Technical Field
The invention relates to a modified polyurethane resin water-based paint, in particular to a modified polyurethane resin water-based paint with good flexibility, belonging to the technical field of water-based functional paints.
Background
At present, the paint is developing towards the environment-friendly direction, and the reduction of volatile organic compounds in the paint becomes a hotspot for research and development of the paint by people at present. The water-based coating is one of the best methods for reducing VOC in the coating, the appearance of the advantages and the disadvantages of the traditional water-based polyurethane coating is shown, various methods for improving the performance of the water-based polyurethane coating through modification are more and more concerned, at present, the modification of the water-based polyurethane resin is more and more, such as silicon modification, fluorine modification and the like, meanwhile, the water-based polyurethane coating needs to be baked at a high temperature in order to achieve good hardness and flexibility, and the self-drying water-based coating is difficult to have excellent hardness and flexibility at the same time, and the popularization of the water-based polyurethane coating is limited due to the defects.
Chinese patent CN104725942A discloses a high-flexibility water-based paint, which comprises the following components in percentage by weight: 35-50% of polymer emulsion; 20-40% of a filler; 2-5% of a film-forming assistant; 1-8% of functional auxiliary agent; make up to 100% with water. The styrene-acrylic emulsion and the acrylic emulsion are selected as main film forming substances, so that the water-based paint has the characteristic of good flexibility, and the flexibility of the paint is mainly provided by the styrene-acrylic emulsion and the acrylic emulsion.
Chinese patent CN102559030A discloses a high-hardness high-flexibility water-based paint and a preparation method thereof, wherein the paint comprises the following components in parts by weight: 40-60 parts of organic silicon epoxy resin modified polyurethane, 10-20 parts of wax-coated aluminum magnesium silicate, 0.2-0.5 part of dispersing agent, 0.2-0.5 part of defoaming agent, 0-40 parts of titanium dioxide (TiO2), 2-5 parts of dipropylene glycol butyl ether, 2-5 parts of propylene glycol monobutyl ether, 5-35 parts of water, 0.2-0.5 part of wetting agent, 0.2-0.5 part of wax and 0.2-0.5 part of polyamide wax. The flexibility is provided by the organosilicon epoxy resin modified polyurethane.
Disclosure of Invention
In order to solve the technical problems, the hydroxyl-terminated liquid polybutadiene rubber modified aqueous polyurethane resin is used as a main film forming substance, the hydroxyl-terminated liquid polybutadiene rubber modified aqueous polyurethane resin has good flexibility, and the hydroxyl-terminated liquid polybutadiene rubber is connected with the polyurethane resin through chemical bonds, so that the performance is stable and durable.
The invention aims to provide a modified polyurethane resin water-based paint with good flexibility.
In order to solve the technical problems, the invention adopts the following technical scheme: the invention relates to a modified polyurethane resin water-based paint with good flexibility, which comprises the following components in parts by weight: 60.0-150.0 parts of hydroxyl-terminated liquid polybutadiene rubber modified waterborne polyurethane resin, 0.4-1.0 part of flatting agent, 0.2-1.2 parts of dispersing agent, 0.4-1.0 part of defoaming agent, 0.5-1.0 part of wetting agent, 3.0-7.0 parts of ethylene glycol, 1.5-5.0 parts of propylene glycol butyl ether, 1.5-5.0 parts of propylene glycol methyl ether acetate, 0.0-35.0 parts of pigment and filler, 0.5-1.0 part of sodium carboxymethylcellulose, 1.0-3.0 parts of polyvinyl alcohol, 0.4-1.0 part of sodium bicarbonate and 10.0-40.0 parts of deionized water.
The pigment and filler is one or a combination of more of mica powder, zinc oxide, silica type transparent powder, kaolin, calcium carbonate, bentonite, titanium dioxide and water-based color paste.
The hydroxyl-terminated liquid polybutadiene rubber modified waterborne polyurethane resin comprises the following components in parts by weight: 100.0-200.0 parts of diisocyanate, 10.0-18.0 parts of 1, 4-butanediol, 3.0-8.0 parts of trimethylolpropane, 75.0-180.0 parts of oligomer polyol, 9.0-18.0 parts of dimethylolpropionic acid, 0.02-0.1 part of dibutyltin dilaurate, 2.5-4.0 parts of crosslinking monomer, 10.0-20.0 parts of hydroxyl-terminated liquid polybutadiene rubber, 2.0-6.0 parts of ethanol, 50.0-100.0 parts of acetone, 7.0-20.0 parts of neutralizer and 500.0-900.0 parts of deionized water.
The oligomer dihydric alcohol is one or a combination of more of polytetrahydrofuran ether glycol, polycarbonate dihydric alcohol, polycaprolactone dihydric alcohol and polyethylene glycol polyhydric alcohol with the molecular weight of 1000-4000.
The neutralizing agent is one or a combination of more of triethylamine, ammonia water and dimethylethanolamine.
The crosslinking monomer is one or the combination of two of hydroxyethyl acrylate and hydroxypropyl acrylate.
The diisocyanate is one or a combination of toluene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.
The preparation method of the hydroxyl-terminated liquid polybutadiene rubber modified waterborne polyurethane resin comprises the following steps:
a. sequentially adding 1, 4-butanediol, trimethylolpropane, oligomer polyalcohol and dimethylolpropionic acid in parts by weight of a formula into a multifunctional reaction kettle, stirring, heating to 110-115 ℃, carrying out vacuum dehydration for 2.0h, and cooling;
b. then dropwise adding diisocyanate, after dropwise adding is completed within 0.5h, adding dibutyltin dilaurate, controlling the temperature to be 82-84 ℃, stirring and reacting for 2h, then adding a crosslinking monomer and hydroxyl-terminated liquid polybutadiene rubber, continuing to react and stir for 1.5h, adding acetone according to the system viscosity, and determining the NCO value until the NCO value is close to the designed value;
c. and cooling, adding ethanol, slowly dropwise adding a neutralizing agent under the stirring condition, adding a calculated amount of deionized water, continuously stirring and dispersing, removing acetone, and filtering to obtain the hydroxyl-terminated liquid polybutadiene rubber modified waterborne polyurethane resin.
The modified polyurethane resin water-based paint with good flexibility is environment-friendly, has good sagging resistance, good impact resistance, high crosslinking density, good flexibility and other properties, and can be used for substrates of wood furniture, steel structures and the like.
Detailed Description
The following examples are provided to further describe a modified polyurethane resin aqueous coating material having good flexibility according to the present invention. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
Example 1
A hydroxyl-terminated liquid polybutadiene rubber modified waterborne polyurethane resin A is prepared by the following process:
the hydroxyl-terminated liquid polybutadiene rubber modified waterborne polyurethane resin A of the embodiment comprises the following components in parts by weight: 180.0 parts of isophorone diisocyanate, 14.0 parts of 1, 4-butanediol, 6.0 parts of trimethylolpropane, 150.0 parts of polytetrahydrofuran ether glycol, 16.0 parts of dimethylolpropionic acid, 0.08 part of dibutyltin dilaurate, 3.0 parts of hydroxypropyl acrylate, 18.0 parts of hydroxyl-terminated liquid polybutadiene rubber, 5.0 parts of ethanol, 90.0 parts of acetone, 15.0 parts of triethylamine and 880.0 parts of deionized water.
The preparation method of the hydroxyl-terminated liquid polybutadiene rubber modified waterborne polyurethane resin A described in the embodiment comprises the following steps:
a. sequentially adding 1, 4-butanediol, trimethylolpropane, polytetrahydrofuran ether glycol and dimethylolpropionic acid in parts by weight of a formula into a multifunctional reaction kettle, stirring, heating to 110-115 ℃, vacuum dehydrating for 2.0h, and cooling;
b. then, dripping isophorone diisocyanate, after dripping is finished for 0.5h, adding dibutyltin dilaurate, controlling the temperature to be 82-84 ℃, stirring and reacting for 2h, then adding a crosslinking monomer and hydroxyl-terminated liquid polybutadiene rubber, continuing to react and stir for 1.5h, adding acetone according to the system viscosity, and measuring the NCO value until the NCO value is close to the designed value;
c. and cooling, adding ethanol, slowly dropwise adding triethylamine under the stirring condition, adding a calculated amount of deionized water, continuously stirring and dispersing, removing acetone, and filtering to obtain the hydroxyl-terminated liquid polybutadiene rubber modified waterborne polyurethane resin A.
Example 2
A hydroxyl-terminated liquid polybutadiene rubber modified waterborne polyurethane resin B is prepared by the following process:
the hydroxyl-terminated liquid polybutadiene rubber modified waterborne polyurethane resin B comprises the following components in parts by weight: 130.0 parts of hexamethylene diisocyanate, 12.0 parts of 1, 4-butanediol, 5.0 parts of trimethylolpropane, 120.0 parts of polycaprolactone diol, 12.0 parts of dimethylolpropionic acid, 0.08 part of dibutyltin dilaurate, 3.5 parts of hydroxyethyl acrylate, 14.0 parts of hydroxyl-terminated liquid polybutadiene rubber, 4.0 parts of ethanol, 70.0 parts of acetone, 15.0 parts of dimethylethanolamine and 650.0 parts of deionized water.
The preparation method of the hydroxyl-terminated liquid polybutadiene rubber modified waterborne polyurethane resin B comprises the following steps:
a. sequentially adding 1, 4-butanediol, trimethylolpropane, polycaprolactone diol and dimethylolpropionic acid in parts by weight of a formula into a multifunctional reaction kettle, stirring, heating to 110-115 ℃, carrying out vacuum dehydration for 2.0h, and cooling;
b. then dropwise adding hexamethylene diisocyanate, after dropwise adding is completed within 0.5h, adding dibutyltin dilaurate, controlling the temperature to be 82-84 ℃, stirring and reacting for 2h, then adding hydroxyethyl acrylate and hydroxyl-terminated liquid polybutadiene rubber, continuing to react and stirring for 1.5h, adding acetone according to the system viscosity, and measuring the NCO value until the NCO value is close to the designed value;
c. and cooling, adding ethanol, slowly dropwise adding dimethylethanolamine under the stirring condition, adding a calculated amount of deionized water, continuously stirring for dispersion, removing acetone, and filtering to obtain the hydroxyl-terminated liquid polybutadiene rubber modified waterborne polyurethane resin B.
Comparative example 1
The conventional modified waterborne polyurethane resin X comprises the following components in parts by weight: 176.0 parts of isophorone diisocyanate, 15.4 parts of 1, 4-butanediol, 5.2 parts of trimethylolpropane, 165.0 parts of polyethylene glycol polyol, 16.0 parts of dimethylolpropionic acid, 0.08 part of dibutyltin dilaurate, 3.4 parts of hydroxypropyl acrylate, 5.0 parts of ethanol, 90.0 parts of acetone, 15.0 parts of triethylamine and 850.0 parts of deionized water.
The preparation method of the conventional modified waterborne polyurethane resin X described in the embodiment comprises the following steps:
a. sequentially adding 1, 4-butanediol, trimethylolpropane, polyethylene glycol polyol and dimethylolpropionic acid in parts by weight of the formula into a multifunctional reaction kettle, stirring, heating to 110-115 ℃, vacuum dehydrating for 2.0h, and cooling;
b. then, dripping isophorone diisocyanate, after dripping is finished for 0.5h, adding dibutyltin dilaurate, controlling the temperature to be 82-84 ℃, stirring and reacting for 2h, then adding hydroxypropyl acrylate, continuing to react and stirring for 1.5h, adding acetone according to the viscosity of the system, and measuring the NCO value until the NCO value is close to the designed value;
c. and cooling, adding ethanol, slowly dropwise adding triethylamine under the stirring condition, adding a calculated amount of deionized water, continuously stirring and dispersing, removing acetone, and filtering to obtain the conventional modified waterborne polyurethane resin X.
Example 3
A modified polyurethane resin water-based paint with good flexibility comprises the following components in parts by weight: 120.0 parts of hydroxyl-terminated liquid polybutadiene rubber modified waterborne polyurethane resin A, 0.6 part of flatting agent, 0.3 part of dispersing agent, 0.6 part of defoaming agent, 0.7 part of wetting agent, 6.0 parts of ethylene glycol, 3.5 parts of propylene glycol butyl ether, 3.5 parts of propylene glycol methyl ether acetate, 0.7 part of sodium carboxymethylcellulose, 2.0 parts of polyvinyl alcohol, 0.6 part of sodium bicarbonate and 15.0 parts of deionized water.
Example 4
A modified polyurethane resin water-based paint with good flexibility comprises the following components in parts by weight: 100.0 parts of hydroxyl-terminated liquid polybutadiene rubber modified waterborne polyurethane resin B, 0.7 part of flatting agent, 0.9 part of dispersing agent, 0.8 part of defoaming agent, 0.8 part of wetting agent, 5.0 parts of ethylene glycol, 3.0 parts of propylene glycol butyl ether, 3.0 parts of propylene glycol methyl ether acetate, 10.0 parts of bentonite, 10.0 parts of titanium dioxide, 0.6 part of sodium carboxymethylcellulose, 2.5 parts of polyvinyl alcohol, 0.8 part of sodium bicarbonate and 30.0 parts of deionized water.
Comparative example 2
A conventional modified polyurethane resin water-based paint comprises the following components in parts by weight: 110.0 parts of conventional modified waterborne polyurethane resin X, 0.7 part of flatting agent, 0.8 part of dispersing agent, 0.7 part of defoaming agent, 0.7 part of wetting agent, 5.5 parts of ethylene glycol, 3.0 parts of propylene glycol butyl ether, 3.0 parts of propylene glycol methyl ether acetate, 15.0 parts of silicon oxide type transparent powder, 5.0 parts of kaolin, 0.6 part of sodium carboxymethylcellulose, 2.0 parts of polyvinyl alcohol, 0.7 part of sodium bicarbonate and 25.0 parts of deionized water.
Examples 3 and 4 of the present invention were compared with comparative example 2 according to the relevant standards, and the measured performance indexes are shown in table 1.
Wherein, the adhesive force is as follows: testing was carried out as specified in GB/T1720-1988;
hardness: detecting according to the regulation of GB/T6739-2006;
water resistance: detecting according to the regulation of GB/T1733-93;
flexibility: detection is carried out according to the specification of GB/T1731-1993;
impact resistance: detecting according to the GB/T1732-2020;
sag resistance: detection was carried out according to the regulations of GB/T9264-2012.
Table 1: performance specification of coating
As can be seen from Table 1, the adhesion, flexibility, impact resistance and sag resistance of examples 3 and 4 of the present invention are significantly better than those of comparative example 2 (conventional modified polyurethane resin aqueous coating material); the result shows that the modified polyurethane resin water-based paint with good flexibility has good adhesion, flexibility, impact resistance, sag resistance and other properties.
The foregoing description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed; it will be appreciated by a person skilled in the art that the scope of the invention as referred to in the present application is not limited to the embodiments with a specific combination of the above-mentioned features, but also covers other embodiments with any combination of the above-mentioned features or their equivalents without departing from the inventive concept. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.
Claims (2)
1. A modified polyurethane resin water-based paint with good flexibility is characterized in that: the modified polyurethane resin water-based paint with good flexibility comprises the following components in parts by weight: 60.0-150.0 parts of hydroxyl-terminated liquid polybutadiene rubber modified waterborne polyurethane resin, 0.4-1.0 part of flatting agent, 0.2-1.2 parts of dispersing agent, 0.4-1.0 part of defoaming agent, 0.5-1.0 part of wetting agent, 3.0-7.0 parts of ethylene glycol, 1.5-5.0 parts of propylene glycol butyl ether, 1.5-5.0 parts of propylene glycol methyl ether acetate, 0.0-35.0 parts of pigment and filler, 0.5-1.0 part of sodium carboxymethylcellulose, 1.0-3.0 parts of polyvinyl alcohol, 0.4-1.0 part of sodium bicarbonate and 10.0-40.0 parts of deionized water;
the hydroxyl-terminated liquid polybutadiene rubber modified waterborne polyurethane resin comprises the following components in parts by weight: 100.0-200.0 parts of diisocyanate, 10.0-18.0 parts of 1, 4-butanediol, 3.0-8.0 parts of trimethylolpropane, 75.0-180.0 parts of oligomer polyol, 9.0-18.0 parts of dimethylolpropionic acid, 0.02-0.1 part of dibutyltin dilaurate, 2.5-4.0 parts of crosslinking monomer, 10.0-20.0 parts of hydroxyl-terminated liquid polybutadiene rubber, 2.0-6.0 parts of ethanol, 50.0-100.0 parts of acetone, 7.0-20.0 parts of neutralizer and 500.0-900.0 parts of deionized water; the preparation method of the hydroxyl-terminated liquid polybutadiene rubber modified waterborne polyurethane resin comprises the following steps:
a. sequentially adding 1, 4-butanediol, trimethylolpropane, oligomer polyalcohol and dimethylolpropionic acid in parts by weight of a formula into a multifunctional reaction kettle, stirring, heating to 110-115 ℃, carrying out vacuum dehydration for 2.0h, and cooling;
b. then dropwise adding diisocyanate, after dropwise adding is completed within 0.5h, adding dibutyltin dilaurate, controlling the temperature to be 82-84 ℃, stirring and reacting for 2h, then adding a crosslinking monomer and hydroxyl-terminated liquid polybutadiene rubber, continuing to react and stir for 1.5h, adding acetone according to the system viscosity, and determining the NCO value until the NCO value is close to the designed value;
c. and cooling, adding ethanol, slowly dropwise adding a neutralizing agent under the stirring condition, adding a calculated amount of deionized water, continuously stirring and dispersing, removing acetone, and filtering to obtain the hydroxyl-terminated liquid polybutadiene rubber modified waterborne polyurethane resin.
2. The aqueous coating material of a modified polyurethane resin having good flexibility according to claim 1, wherein: the pigment and filler is one or a combination of more of mica powder, zinc oxide, silica type transparent powder, kaolin, calcium carbonate, bentonite, titanium dioxide and water-based color paste.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017529A (en) * | 2014-04-14 | 2014-09-03 | 江苏嘉娜泰有机硅有限公司 | Single-component epoxy resin conductive silver adhesive composition and preparation method thereof |
| CN112662296A (en) * | 2020-12-18 | 2021-04-16 | 合众（佛山）化工有限公司 | Polyphenylene sulfide ketone modified polyurethane resin water-based paint |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017529A (en) * | 2014-04-14 | 2014-09-03 | 江苏嘉娜泰有机硅有限公司 | Single-component epoxy resin conductive silver adhesive composition and preparation method thereof |
| CN112662296A (en) * | 2020-12-18 | 2021-04-16 | 合众（佛山）化工有限公司 | Polyphenylene sulfide ketone modified polyurethane resin water-based paint |
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