CN111269391A - Alkali-resistant water-based polyurethane aluminized protective coating material and preparation method thereof - Google Patents
Alkali-resistant water-based polyurethane aluminized protective coating material and preparation method thereof Download PDFInfo
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
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- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/30—Low-molecular-weight compounds
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- C08G18/30—Low-molecular-weight compounds
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- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
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- C08G18/40—High-molecular-weight compounds
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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- C09D—COATING 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
Abstract
The invention relates to an alkali-resistant polyurethane aluminized protective coating material and a preparation method thereof, wherein the alkali-resistant polyurethane aluminized protective coating material comprises the following components in percentage by mass through the operations of preparation of prepolymer NCO, dilution, salt formation, dispersion and de-ketonization of the prepolymer: polyether glycol: 10 to 30 percent; isocyanate: 5 to 11 percent; a crosslinking agent: 2.5 to 4 percent; hydrophilic chain extender: 1.0-2.2%; small-molecule chain extender: 0.1 to 3.6 percent; a post chain extender: 0.1 to 1.8 percent; deionized water: 60-70% of coating material, have solved the products of the prior art and resisted the alkaline, water-fast deficiency; the system of the invention is easy to form crystals, which is beneficial to improving the water resistance and alkali resistance of the resin; the system has no cyclic and side group structure, so that the compactness and cohesive strength after film forming are ensured, and the hydrophilic chain extender used in the system is a sulfonic acid type chain extender, so that compared with a carboxylic acid type chain extender, the dosage of the sulfonic acid type chain extender is less, the product stability is better, and the energy conservation and environmental protection are facilitated.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to an alkali-resistant polyurethane aluminized protective coating material and a preparation method thereof.
Background
The laser film is a novel functional film with higher technical content, is mainly applied to exquisite packages such as food, medicines, daily chemical products, cigarettes, wines, clothes, gift packages, decorative materials and the like, and has stronger decoration and anti-counterfeiting functions;
the laser film is a film with a laser holographic image prepared by a special production and processing technology and is used for producing composite laser card paper, transfer laser card paper and the like; at present, the most widely applied laser films in the market mainly comprise laser dielectric films, laser aluminum washing films, laser aluminum plating films, laser rainbow films and the like. Wherein, the laser aluminum washing film is an aluminum plating laser film: the aluminum washing film of the product formed by the production processes of printing, aluminum washing, coating and the like has higher technical content and more attractive visual effect, and the appearance is more exquisite;
however, the aluminum washing process needs to be carried out under a higher-temperature alkaline condition, so that a protective coating needs to be coated to carry out pre-protection on laser aluminum washing, in the prior art, a pre-protection coating protective coating product is basically a solvent-based product, so that the ecological damage is large, and along with the vigorous implementation of an environmental protection policy, a more environment-friendly waterborne design is adopted for a coating protective coating resin product, so that the method becomes very important;
in addition, the water resistance of the resin after film formation is poor due to the addition of the carboxylic acid type micromolecule hydrophilic chain extender in the preparation process of the common waterborne polyurethane resin, and the alkali resistance of the waterborne polyurethane also has certain defects; therefore, the development of the high-temperature-resistant alkaline waterborne polyurethane resin under the high-temperature condition is a problem to be solved by laser aluminum film washing.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the alkali-resistant polyurethane aluminized protective coating material and the preparation method thereof.
In order to achieve the purpose, the invention provides an alkali-resistant polyurethane aluminized protective coating material and a preparation method thereof, wherein the alkali-resistant polyurethane aluminized protective coating material comprises the following components in parts by weight:
an alkaline water-resistant polyurethane aluminized protective coating material comprises the following components in percentage by mass:
① polyether diol 10-30%;
as an illustration, the polyether glycol is: polytetrahydrofuran ether glycols of the same molecular weight or a combination of polytetrahydrofuran ether glycols of different molecular weights;
② isocyanate 5-11%;
as an illustration, the isocyanate is: hexamethylene diisocyanate;
③ cross-linking agent 2.5-4%;
as an illustration, the crosslinking agent is: one or a combination of hexamethylene diisocyanate trimer or trimethylolpropane with different isocyanate group contents;
④ hydrophilic chain extender, 1.0-2.2%;
as an illustration, the hydrophilic chain extender is: one or a combination of micromolecule sulfonate diol or sodium diaminosulfonate;
⑤ small molecular chain extender, 0.1-3.6%;
as an illustration, the small molecule chain extender is: one or a combination of 1, 4-butanediol or diethylene glycol;
⑥ rear chain extender, 0.1-1.8%;
as an illustration, the post-chain extender is ethylene diamine;
⑦ deionized water 60-70%;
a preparation method of an alkaline water-resistant polyurethane aluminized protective coating material comprises the following steps:
step one, preparation of prepolymer NCO: carrying out vacuum dehydration on polyether diol at 120 ℃ for 1 hour, cooling to 50 ℃ after dehydration, adding isocyanate, heating to 85 ℃, keeping the temperature for 2 hours, adding micromolecule sulfonate diol, a cross-linking agent and a micromolecule chain extender into the system, keeping the temperature at 85 ℃, and keeping the temperature for 3 hours;
step two, dilution of the prepolymer: sampling and testing the mass percent of NCO of the prepolymer, cooling after meeting the required mixture ratio, adding butanone accounting for 30 percent of the mass of the prepolymer when the temperature is reduced to 50 ℃, and stirring for 30 minutes to obtain the diluted prepolymer;
step three, salt forming operation: pouring the diluted prepolymer into a dispersion cylinder, adding sodium diaminosulfonate after the temperature of the diluted prepolymer in the fine dispersion cylinder is reduced to be below 40 ℃, and salifying for 30 minutes under the stirring of a dispersion machine, wherein the rotating speed of the dispersion machine is 300 rpm/min;
step four, a dispersing process: adjusting the rotation speed of a dispersion machine to 1000rpm/min, adding metered deionized water with the temperature below 10 ℃ into the system, adding a rear chain extender after the prepolymer is dispersed, and continuing to disperse for 30 minutes to obtain a polyurethane dispersion liquid;
as an example, the mass of the metered deionized water is 115-180% of the mass of the diluted prepolymer;
step five, ketone removal operation: and (3) carrying out de-ketonization on the polyurethane dispersion liquid at the temperature of 45-55 ℃ and the atmospheric pressure of-0.08 MPa to obtain the waterborne polyurethane laser aluminum-washing protective coating resin, namely the alkaline-resistant polyurethane aluminum-plating protective coating material.
Has the advantages that:
1. the invention adopts a polytetrahydrofuran ether glycol and hexamethylene diisocyanate system and a small amount of micromolecular diol chain extender, and well solves the defects of poor alkali resistance and water resistance of the product in the prior art; compared with a polyester system, the polyether body has more excellent water resistance because of no ester group, and the system of the invention is easy to form crystal, thereby being beneficial to improving the water resistance and alkali resistance of the resin;
2. the system of the invention has no ring and side group structure, thus ensuring the compactness after film forming, and in addition, the system introduces hexamethylene diisocyanate trimer to form an internal crosslinking structure, thus increasing the cohesive strength of the system and improving the alkali resistance;
3. the hydrophilic chain extender used in the system is sulfonic acid type, and experiments and detection prove that compared with the carboxylic acid type chain extender in the prior art, the use amount of the sulfonic acid type chain extender is less, the product stability is better, and the energy conservation and environmental protection are facilitated.
Drawings
FIG. 1 is a flow chart of a preparation process of an alkaline-resistant polyurethane aluminized protective coating material and a preparation method thereof
Detailed Description
A preferred embodiment of the present invention will now be described in detail with reference to the accompanying drawings, shown in FIG. 1, wherein:
an alkali-resistant polyurethane aluminized protective coating material and a preparation method thereof are disclosed, wherein:
an alkaline water-resistant polyurethane aluminized protective coating material comprises the following components in percentage by mass:
① polyether diol 10-30%;
as an illustration, the polyether glycol is: polytetrahydrofuran ether glycols of the same molecular weight or a combination of polytetrahydrofuran ether glycols of different molecular weights;
② isocyanate 5-11%;
as an illustration, the isocyanate is: hexamethylene diisocyanate;
③ cross-linking agent 2.5-4%;
as an illustration, the crosslinking agent is: one or a combination of hexamethylene diisocyanate trimer or trimethylolpropane with different isocyanate group contents;
④ hydrophilic chain extender, 1.0-2.2%;
as an illustration, the hydrophilic chain extender is: one or a combination of micromolecule sulfonate diol or sodium diaminosulfonate;
⑤ small molecular chain extender, 0.1-3.6%;
as an illustration, the small molecule chain extender is: one or a combination of 1, 4-butanediol or diethylene glycol;
⑥ rear chain extender, 0.1-1.8%;
as an illustration, the post-chain extender is ethylene diamine;
⑦ deionized water 60-70%;
a preparation method of an alkaline water-resistant polyurethane aluminized protective coating material comprises the following steps:
step one, preparation of prepolymer NCO: carrying out vacuum dehydration on polyether diol at 120 ℃ for 1 hour, cooling to 50 ℃ after dehydration, adding isocyanate, heating to 85 ℃, keeping the temperature for 2 hours, adding micromolecule sulfonate diol, a cross-linking agent and a micromolecule chain extender into the system, keeping the temperature at 85 ℃, and keeping the temperature for 3 hours;
step two, dilution of the prepolymer: sampling and testing the mass percent of NCO of the prepolymer, cooling after meeting the required mixture ratio, adding butanone accounting for 30 percent of the mass of the prepolymer when the temperature is reduced to 50 ℃, and stirring for 30 minutes to obtain the diluted prepolymer;
step three, salt forming operation: pouring the diluted prepolymer into a dispersion cylinder, adding sodium diaminosulfonate after the temperature of the diluted prepolymer in the fine dispersion cylinder is reduced to be below 40 ℃, and salifying for 30 minutes under the stirring of a dispersion machine, wherein the rotating speed of the dispersion machine is 300 rpm/min;
step four, a dispersing process: adjusting the rotation speed of a dispersion machine to 1000rpm/min, adding metered deionized water with the temperature below 10 ℃ into the system, adding a rear chain extender after the prepolymer is dispersed, and continuing to disperse for 30 minutes to obtain a polyurethane dispersion liquid;
step five, ketone removal operation: and (3) carrying out de-ketonization on the polyurethane dispersion liquid at the temperature of 45-55 ℃ and the atmospheric pressure of-0.08 MPa to obtain the waterborne polyurethane laser aluminum-washing protective coating resin, namely the alkaline-resistant polyurethane aluminum-plating protective coating material.
For better illustration of the design principle of the present invention, the following embodiments are specifically described; example 1:
the embodiment provides an alkali-resistant polyurethane aluminized protective coating material and a preparation method thereof, wherein the alkali-resistant polyurethane aluminized protective coating material comprises the following components in parts by weight:
an alkali-resistant polyurethane aluminized protective coating material comprises the following components in percentage by mass: 24.2 percent of 1000 molecular weight polytetrahydrofuran ether glycol, 8.1 percent of hexamethylene diisocyanate, 3 percent of hexamethylene diisocyanate tripolymer N3300 with 21.8 percent of isocyanate group, 1.8 percent of small molecular sulfonate glycol, 0.5 percent of diethylene glycol, 0.4 percent of ethylenediamine and 62 percent of deionized water;
the preparation method of the alkali-resistant polyurethane aluminized protective coating material comprises the following steps:
step one, preparation of prepolymer NCO: carrying out vacuum dehydration on 1000 molecular weight polytetrahydrofuran ether glycol at 120 ℃ for 1 hour, cooling to 50 ℃ after dehydration, adding hexamethylene diisocyanate, heating to 85 ℃, preserving heat for 2 hours, adding micromolecular sulfonate glycol, hexamethylene diisocyanate tripolymer N3300 with 21.8% of isocyanate group and diethylene glycol into an image system after heat preservation, keeping the temperature at 85 ℃, and continuously preserving heat for 3 hours;
step two, sampling to test that the mass percent of the NCO in the prepolymer is qualified, cooling, reducing the temperature to 50 ℃, adding butanone accounting for 30 percent of the mass of the prepolymer, and stirring for 30 minutes to obtain the diluted prepolymer;
pouring the diluted prepolymer into a dispersion cylinder, reducing the temperature of the prepolymer to be below 40 ℃, regulating the rotation speed of a dispersion machine to be 1000rpm/min, adding metered deionized water with the temperature below 10 ℃ into the system, dispersing the diluted prepolymer, adding ethylenediamine, and continuing to disperse for 30 minutes to obtain a polyurethane dispersion liquid;
and step four, de-ketonizing the dispersion liquid at the temperature of 45-55 ℃ and under the pressure of-0.08 MPa to obtain the alkali-resistant polyurethane aluminized protective coating material.
Example 2
The embodiment provides an alkali-resistant polyurethane aluminized protective coating material and a preparation method thereof, wherein the alkali-resistant polyurethane aluminized protective coating material comprises the following components in parts by weight:
an alkali-resistant polyurethane aluminized protective coating material comprises the following components in percentage by mass: 20% of 1000 molecular weight polytetrahydrofuran ether glycol, 10% of hexamethylene diisocyanate, 2% of hexamethylene diisocyanate tripolymer N3300 with 21.8% of isocyanate group content and 1.8% of trimethylolpropane as cross-linking agents, 1.5% of BY-3306, 0.5% of diethylene glycol, 1.2% of ethylenediamine and 62% of deionized water;
a preparation method of an alkaline water-resistant polyurethane aluminized protective coating material comprises the following steps:
step one, preparation of prepolymer NCO: carrying out vacuum dehydration on 1000 molecular weight polytetrahydrofuran ether glycol at 120 ℃ for 1 hour, cooling to 50 ℃ after dehydration, adding hexamethylene diisocyanate, heating to 85 ℃, preserving heat for 2 hours, adding micromolecular sulfonate glycol, hexamethylene diisocyanate tripolymer N3300 with 21.8% of isocyanate group and diethylene glycol into an image system after heat preservation, keeping the temperature at 85 ℃, and continuously preserving heat for 3 hours;
step two, sampling to test that the mass percent of the NCO in the prepolymer is qualified, cooling, reducing the temperature to 50 ℃, adding butanone accounting for 30 percent of the mass of the prepolymer, and stirring for 30 minutes to obtain the diluted prepolymer;
pouring the diluted prepolymer into a dispersion cylinder, reducing the temperature of the prepolymer to be below 40 ℃, adjusting the rotation speed of a dispersion machine to be 1000rpm/min, adding metered deionized water with the temperature below 10 ℃ into the system, adding ethylenediamine after dispersing prepolymer NCO, and continuing to disperse for 30 minutes to obtain polyurethane dispersion liquid;
and step four, de-ketonizing the dispersion liquid at the temperature of 45-55 ℃ and under the pressure of-0.08 MPa to obtain the waterborne polyurethane laser aluminum-washing protective coating resin.
Example 3
The embodiment provides an alkali-resistant polyurethane aluminized protective coating material and a preparation method thereof, wherein the alkali-resistant polyurethane aluminized protective coating material comprises the following components in parts by weight:
an alkali-resistant polyurethane aluminized protective coating material comprises the following components in percentage by mass: 20% of 2000 molecular weight polytetrahydrofuran ether glycol, 8% of hexamethylene diisocyanate, 3% of hexamethylene diisocyanate tripolymer N3600 with 23% of isocyanate group content, 1.5% of small molecular sulfonate glycol, 0.4% of sodium diaminosulfonate, 2% of 1, 4-butanediol, 0.3% of ethylenediamine and 65% of deionized water;
a preparation method of an alkaline water-resistant polyurethane aluminized protective coating material comprises the following steps:
step one, preparation of prepolymer NCO: carrying out vacuum dehydration on 2000 molecular weight polytetrahydrofuran ether glycol at 120 ℃ for 1 hour, cooling to 50 ℃ after dehydration, adding hexamethylene diisocyanate, heating to 85 ℃, preserving heat for 2 hours, adding micromolecular sulfonate glycol, hexamethylene diisocyanate trimer N3600 with 23% of isocyanate group content and micromolecular chain extender into an image system after heat preservation, keeping the temperature at 85 ℃, and continuing to preserve heat for 3 hours;
step two, sampling to test that the mass percent of the NCO in the prepolymer is qualified, cooling, reducing the temperature to 50 ℃, adding butanone accounting for 30 percent of the mass of the prepolymer, and stirring for 30 minutes to obtain the diluted prepolymer;
pouring the diluted prepolymer into a dispersion cylinder, reducing the temperature of the prepolymer to be below 40 ℃, adding sodium diaminosulfonate into the dispersion cylinder, stirring the mixture in a dispersion machine, and forming salt for 30 minutes, wherein the rotating speed of the dispersion machine is 300 rpm/min;
after salifying, regulating the rotation speed of a dispersion machine to 1000rpm/min, adding metered deionized water into the system, adding deionized water at the temperature of below 10 ℃, dispersing the prepolymer, adding a rear chain extender, and continuing to disperse for 30 minutes to obtain a polyurethane dispersion liquid;
and step five, de-ketonizing the dispersion liquid at the temperature of 45-55 ℃ and under the pressure of-0.08 MPa to obtain the waterborne polyurethane laser aluminum washing protective coating resin.
Further, is resistant to alkaliThe test method comprises the following steps: the waterborne polyurethane aluminum-washing protective coating resin prepared by the invention is coated on the aluminum-plated surface of an aluminum-washing film, and the coating weight is 1.5g/m2Baking the coated film in an oven at 80 ℃ for 20 minutes, taking out and placing at room temperature; and (3) putting the aluminizer coated with the protective coating into an alkali solution with the temperature of 25 ℃ and the concentration of 2% sodium hydroxide for 1 minute, and taking out to observe the aluminizing corrosion condition. The operation time of the aluminum washing process is basically within 20 seconds, and the protective coating has a protective effect without failure within 1 minute of soaking time;
according to the alkali-resistant test method, the alkali-resistant polyurethane aluminized protective coating material disclosed in the embodiments 1 to 3 does not lose effectiveness in an alkali-resistant test within 1 minute, and has a protective effect.
The invention adopts a polytetrahydrofuran ether glycol and hexamethylene diisocyanate system and a small amount of micromolecular diol chain extender, and well solves the defects of poor alkali resistance and water resistance of the product in the prior art; compared with a polyester system, the polyether body has more excellent water resistance because of no ester group, and the system of the invention is easy to form crystal, thereby being beneficial to improving the water resistance and alkali resistance of the resin; the system of the invention has no ring and side group structure, thus ensuring the compactness after film forming, and in addition, the system introduces hexamethylene diisocyanate trimer to form an internal crosslinking structure, thus increasing the cohesive strength of the system and improving the alkali resistance; the hydrophilic chain extender used in the system is sulfonic acid type, and experiments and detection prove that compared with the carboxylic acid type chain extender in the prior art, the use amount of the sulfonic acid type chain extender is less, the product stability is better, and the energy conservation and environmental protection are facilitated.
The above embodiments are only preferred embodiments of the present invention, and it should be understood that the above embodiments are only for assisting understanding of the method and the core idea of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalents and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. The alkaline water-resistant polyurethane aluminized protective coating material is characterized by comprising the following components in percentage by mass:
① polyether diol 10-30%;
② isocyanate 5-11%;
③ cross-linking agent 2.5-4%;
④ hydrophilic chain extender, 1.0-2.2%;
⑤ small molecular chain extender, 0.1-3.6%;
⑥ rear chain extender, 0.1-1.8%;
⑦ deionized water 60-70%.
2. The alkaline-resistant polyurethane aluminized protective coating material according to claim 1, characterized in that the polyether glycol is: polytetrahydrofuran ether glycols of the same molecular weight or a combination of polytetrahydrofuran ether glycols of different molecular weights.
3. The alkaline-resistant polyurethane aluminized protective coating material according to claim 1, characterized in that the isocyanate is: hexamethylene diisocyanate.
4. The alkaline-resistant polyurethane aluminized protective coating material according to claim 1, characterized in that the crosslinking agent is: one or a combination of hexamethylene diisocyanate trimer or trimethylolpropane with different isocyanate group content.
5. The alkali-resistant polyurethane aluminized protective coating material according to claim 1, characterized in that the hydrophilic chain extender is: one or a combination of small molecule sulfonate diol or sodium diaminosulfonate.
6. The alkali-resistant polyurethane aluminized protective coating material according to claim 1, characterized in that the small-molecule chain extender is: 1, 4-butanediol or diethylene glycol.
7. The alkaline-resistant polyurethane aluminized protective coating material according to claim 1, characterized in that the post-chain extender is ethylenediamine.
8. A preparation method of an alkaline water-resistant polyurethane aluminized protective coating material is characterized by comprising the following steps:
step one, preparation of prepolymer NCO: carrying out vacuum dehydration on polyether diol at 120 ℃ for 1 hour, cooling to 50 ℃ after dehydration, adding isocyanate, heating to 85 ℃, keeping the temperature for 2 hours, adding micromolecule sulfonate diol, a cross-linking agent and a micromolecule chain extender into the system, keeping the temperature at 85 ℃, and keeping the temperature for 3 hours;
step two, dilution of the prepolymer: sampling and testing the mass percent of NCO of the prepolymer, cooling after meeting the required mixture ratio, adding butanone accounting for 30 percent of the mass of the prepolymer when the temperature is reduced to 50 ℃, and stirring for 30 minutes to obtain the diluted prepolymer;
step three, salt forming operation: pouring the diluted prepolymer into a dispersion cylinder, adding sodium diaminosulfonate after the temperature of the diluted prepolymer in the fine dispersion cylinder is reduced to be below 40 ℃, and salifying for 30 minutes under the stirring of a dispersion machine, wherein the rotating speed of the dispersion machine is 300 rpm/min;
step four, a dispersing process: adjusting the rotation speed of a dispersion machine to 1000rpm/min, adding metered deionized water with the temperature below 10 ℃ into the system, adding a rear chain extender after the prepolymer is dispersed, and continuing to disperse for 30 minutes to obtain a polyurethane dispersion liquid;
step five, ketone removal operation: and (3) carrying out de-ketonization on the polyurethane dispersion liquid at the temperature of 45-55 ℃ and the atmospheric pressure of-0.08 MPa to obtain the waterborne polyurethane laser aluminum-washing protective coating resin, namely the alkaline-resistant polyurethane aluminum-plating protective coating material.
9. The preparation method of the alkali-resistant polyurethane aluminized protective coating material according to claim 8, wherein the mass of the metered deionized water is 115% -180% of the mass of the diluted prepolymer.
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