CN113308182A - Aqueous two-component polyurethane coating for TR-90 base material and preparation method and use method thereof - Google Patents
Aqueous two-component polyurethane coating for TR-90 base material and preparation method and use method thereof Download PDFInfo
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- CN113308182A CN113308182A CN202110659452.0A CN202110659452A CN113308182A CN 113308182 A CN113308182 A CN 113308182A CN 202110659452 A CN202110659452 A CN 202110659452A CN 113308182 A CN113308182 A CN 113308182A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/633—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polymers of compounds having carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/638—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers characterised by the use of compounds having carbon-to-carbon double bonds other than styrene and/or olefinic nitriles
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Abstract
The invention relates to the technical field of TR-90 substrate coatings, in particular to a waterborne two-component polyurethane coating for a TR-90 substrate, and a preparation method and a use method thereof. The aqueous two-component polyurethane coating for the TR-90 substrate comprises the following raw materials, 50-60% of an isocyanate curing agent, 20-30% of hydroxyl acrylic resin ester, 10-15% of epoxybutene, 5-6% of fluorostyrene, 1-3% of an emulsifier, 0.1-1% of an initiator and 0.2-2% of a cross-linking agent, wherein the hydroxyl acrylic resin ester consists of methyl methacrylate, hydroxypropyl acrylate and acrylic resin; the solid content of the two-component polyurethane coating is 40-50%, and the coating has the advantages of good toughness, no delamination, good adhesive force and good anti-fouling performance.
Description
Technical Field
The invention relates to the technical field of TR-90 substrate coatings, in particular to a waterborne two-component polyurethane coating for a TR-90 substrate, and a preparation method and a use method thereof.
Background
The TR-90 material has the characteristics of memory function, super toughness, collision resistance, wear resistance, low friction coefficient and the like, and light weight, so the TR-90 material is an excellent material for the ultralight mirror frame.
As the spectacles manufacturing industry uses TR-90 plastics as the material of the spectacle frame, the surface of the injection-molded part is coated with the plastics in order to further improve the decoration and durability of the injection-molded part. In practical application, because the TR-90 material has large surface compactness and small surface tension, the common coating is difficult to be directly coated on the surface of the TR-90 material, and for the reason, the coating process adopted by the prior art in the industry is as follows: the special solvent-type bi-component paint is used as a primer as an adhesion promoting coating, and then the bi-component finishing paint or UV radiation curing finishing paint is coated. The scheme is multi-coating construction, the required processing time is long, and the production efficiency is low; meanwhile, a large amount of solvent volatilization is generated in the construction process, which is harmful to the environment.
At present, the water-based two-component polyurethane coating is widely applied because the water-based two-component polyurethane coating is environment-friendly, the curing agent can be well compatible, and the water-based two-component polyurethane coating has high hydroxyl functional groups. However, the existing aqueous two-component polyurethane coating still has limitations for application in TR-90:
1. the traditional water-based two-component polyurethane coating has poor adhesive force on a TR-90 base material, cannot be used independently and needs a primer;
2. the traditional water-based double-component polyurethane coating is a multilayer coating, so that a paint film is thick, the paint film cracks after the workpiece is bent and deformed (at an included angle of 45 degrees), and the coating cannot be well applied to the field of mirror frames.
3. The water-based pigment is easy to generate the problems of flooding and re-agglomeration in the storage process, so that the phenomena of floating, uneven color distribution and small particles of the coating are caused.
In the prior art, a macrocyclic high-steric-hindrance monomer is introduced into a hydroxy acrylic resin to reduce the viscosity of a water-based two-component polyurethane coating, but the existence of the macrocyclic high-steric-hindrance monomer in a large amount can reduce the toughness of the coating and influence the dispersion of pigments in the coating, so that the function of the coating is influenced.
Disclosure of Invention
The invention aims to avoid the defects in the prior art and provides the aqueous two-component polyurethane coating for the TR-90 base material, which has the advantages of good toughness, no delamination, good adhesive force and good anti-fouling performance.
In order to achieve one of the above-mentioned objects of the invention,
provides a waterborne two-component polyurethane coating for a TR-90 base material, which comprises the following raw materials,
50 to 60 percent of isocyanate curing agent
20 to 30 percent of hydroxyl acrylic resin ester
10 to 15 percent of epoxy butylene
5 to 6 percent of fluorine styrene
1 to 3 percent of emulsifier
0.1 to 1 percent of initiator
0.2 to 2 percent of cross-linking agent;
wherein the hydroxy acrylic resin ester consists of methyl methacrylate, hydroxypropyl acrylate and acrylic resin;
the solid content of the two-component polyurethane coating is 40-50%.
In the raw materials, epoxybutene and fluorostyrene are used as macrocyclic high steric hindrance monomers, and vinyl groups in the epoxybutene and the fluorostyrene can be bonded with double bonds in methyl methacrylate, hydroxypropyl acrylate and acrylic resin in hydroxy acrylic resin ester, so that epoxy rings and the fluorostyrene are connected into the hydroxy acrylic resin ester, and the repulsion force among resin molecules in the hydroxy acrylic resin ester is increased, the viscosity of the coating is reduced, the coating can be conveniently dispersed on a TR-90 substrate, and the pigment can be conveniently and uniformly dispersed in the coating.
In addition, the invention adopts two macrocyclic high steric hindrance monomers of epoxybutene and fluorostyrene, the two high steric hindrance monomers play a complementary role, as the rigidity of the fluorostyrene is stronger, but the steric hindrance of the fluorostyrene is better and more stable, but if a large amount of fluorostyrene is used, the pigment is difficult to disperse in the whole paint, while the epoxybutene is only adopted, the epoxybutene is not good enough in stability, so that the pigment cannot have better steric hindrance performance. The invention combines the epoxybutene and the fluorostyrene, thus not only reducing the viscosity of the coating, but also reducing the use of phenyl so as to avoid influencing the dispersion of the coating and influencing the toughness of the coating. And under the condition of sufficient steric hindrance, epoxybutene can open the ring at a certain temperature, so that the steric hindrance of the coating is reduced, the pigment can be further dispersed in the coating, and the toughness of the coating is improved.
The invention adopts the fluorostyrene as the macrocyclic steric hindrance unit, the surface energy of the fluorine element is lower, and the fluorine element reduces the anti-fouling performance of the whole coating, which plays an important role in the TR-20 material applied to the base material of the spectacle frame, so that the cleanliness of the spectacle frame is higher.
Wherein the isocyanate curing agent is one or a mixture of any two or more of hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate.
Wherein the initiator is one or a mixture of two of azodiisobutanedinitrile and azodiisoheptanecarbonitrile. Such initiators have fewer side reactions.
Wherein the cross-linking agent is one or a mixture of two of 3-hydroxypropionic acid and 2, 3-dihydroxypropionic acid.
Wherein the emulsifier is SR-10 emulsifier.
The waterborne two-component polyurethane coating for the TR-90 base material has the beneficial effects that:
(1) as the high steric hindrance units at the large ring positions in epoxybutene and fluorostyrene, vinyl groups in the epoxybutene and the fluorostyrene can be bonded with double bonds in methyl methacrylate, hydroxypropyl acrylate and acrylic resin in the hydroxy acrylic resin ester, so that the epoxy ring and the fluorostyrene are connected into the hydroxy acrylic resin ester, the repulsion force among resin molecules in the hydroxy acrylic resin ester is increased, the viscosity of the coating is reduced, the coating is convenient to disperse among TR-90, and the pigment is convenient to disperse uniformly in the coating.
(2) The invention adopts two macrocyclic high steric hindrance monomers of epoxybutene and fluorostyrene, the two high steric hindrance monomers play a complementary role, the rigidity of the fluorostyrene is stronger, but the steric hindrance of the fluorostyrene is better and more stable, but if a large amount of fluorostyrene is used, the pigment is difficult to disperse in the whole paint, while if epoxybutene is used only, the steric hindrance performance cannot be better because the stability of epoxybutene is not good enough. The invention combines the epoxybutene and the fluorostyrene, thereby reducing phenyl, further reducing the viscosity of the paint and better dispersing the pigment in the paint. When the epoxy butene is uniformly dispersed under the condition of sufficient steric hindrance, the epoxy butene opens the ring at a certain temperature, so that the steric hindrance of the paint is reduced, and the pigment can be further dispersed in the paint.
(3) The invention adopts the fluorostyrene as the macrocyclic steric hindrance unit, the surface energy of the fluorine element is lower, the anti-fouling performance of the whole coating is reduced, and the coating plays an important role in the TR-20 material applied to the base material of the spectacle frame, so that the cleanliness of the spectacle frame is higher.
(4) According to the invention, epoxybutene and fluorostyrene are used, so that the viscosity of the aqueous two-component polyurethane coating is reduced, the adhesive force on the TR-90 substrate of the aqueous two-component polyurethane coating is improved, and the aqueous two-component polyurethane coating can be independently used.
(5) According to the invention, the macrocyclic steric hindrance monomer is added into the water-based two-component polyurethane coating, so that the strength and the density of the water-based two-component polyurethane coating are enhanced, and the water-based two-component polyurethane coating is thin in coating layer and does not cause cracking of a paint film after TR-90 is bent and deformed because no primer is needed; the water-based two-component polyurethane coating has good toughness and can prevent the coating from cracking.
In order to achieve the second object of the present invention,
the preparation method of the aqueous two-component polyurethane coating for the TR-90 base material is also provided, and the raw materials of the aqueous two-component polyurethane coating for the TR-90 base material are adopted, and the preparation method comprises the following steps:
s1: putting methyl methacrylate, hydroxypropyl acrylate, acrylic resin, epoxybutene, fluorostyrene and an emulsifier into a reactor, reacting under the protection of nitrogen, and stirring at 80-90 ℃ to react to prepare a hydroxyl polyacrylate prepolymer;
s2: cooling the hydroxyl polyacrylate prepolymer to 50-60 ℃, adding sodium hydroxide into the hydroxyl polyacrylate prepolymer for neutralization, then adding the neutralized hydroxyl polyacrylate prepolymer into water, and continuously stirring to obtain a polyacrylate prepolymer aqueous dispersion with the solid content of 40-50%;
s3: stirring and mixing the aqueous dispersion of the polyacrylate prepolymer in the formula amount and the isocyanate curing agent in the formula amount, and reacting for a certain time to obtain the aqueous two-component polyurethane coating for the TR-90 base material.
Wherein in the S1, the weight ratio of the methyl methacrylate to the hydroxypropyl acrylate to the acrylic resin is 1: 1-2: 1 to 2.
In the S2, the concentration of sodium hydroxide is 5%, the adding amount of sodium hydroxide is 3% -5%, and the stirring time is 4-5 h.
In the step S3, the time for stirring and mixing the polyacrylate prepolymer aqueous dispersion with the formula amount and the isocyanate curing agent with the formula amount is 1-3 h.
The preparation method of the aqueous two-component polyurethane coating for the TR-90 base material has the beneficial effects that:
(1) the invention adds water once, so that the paint is converted from oil-in-water state to water-in-oil state, and the dispersion uniformity of the paint is kept.
In order to achieve the third object of the present invention,
the application method of the aqueous two-component polyurethane coating for the TR-90 base material is characterized by adding the pigment into the aqueous two-component polyurethane coating for the TR-90 base material, uniformly stirring, directly coating the aqueous two-component polyurethane coating on the TR-90 base material in a 70-80% humidity environment within 4-5 h, wherein the environmental temperature is 40-45 ℃, and then coating a layer of carboxylic acid end-capping agent to obtain a coating film.
The application method of the waterborne two-component polyurethane coating for the TR-90 base material has the beneficial effects that:
(1) the stability of the coating can be ensured by using the aqueous two-component polyurethane coating within 4-5 h, the coating disclosed by the invention is coated in a relatively wet environment, the hydrophilic group in the coating is favorably utilized to perform a hydrophilic reaction with water, so that the flowing of the coating is accelerated, the coating temperature is increased, the flowability of the coating can be improved, and the coating effect is improved.
(2) According to the invention, after the isocyanate curing agent reacts with the hydroxyl acrylic resin ester, the carboxylic acid end capping agent is coated, and the carboxylic acid end capping agent can cap redundant polyol, prevent VOC emission, reduce VOC emission amount, and prevent side reaction between hydroxyl in the polyol and isocyanate group, thereby avoiding generation of carbamate-based polymer, and further avoiding generation of CO2So as to influence the coating effect of the coating; and because the carboxylic acid-type end-capping agent is coated after the isocyanate curing agent reacts with the hydroxyl acrylic resin ester, the normal reaction of the isocyanate curing agent and the hydroxyl acrylic resin ester can be kept.
Detailed Description
The invention is further described with reference to the following examples.
Example 1
The embodiment discloses a waterborne two-component polyurethane coating for a TR-90 substrate, which comprises the following raw materials, 50% of an isocyanate curing agent, 30% of hydroxyl acrylic resin ester, 10% of epoxybutene, 5% of fluorostyrene, 1% of an emulsifier, 0.1% of an initiator and 0.2% of a cross-linking agent;
wherein the hydroxy acrylic resin ester consists of methyl methacrylate, hydroxypropyl acrylate and acrylic resin;
the solid content of the two-component polyurethane coating is 40%.
In this embodiment, the isocyanate curing agent is selected from hexamethylene diisocyanate.
In this embodiment, the initiator is selected from azobisisobutyronitrile.
In this example, the cross-linking agent is selected from a mixture of two of 3-hydroxypropionic acid and 2, 3-dihydroxypropionic acid.
In this example, the emulsifier is an SR-10 emulsifier.
The preparation method of the aqueous two-component polyurethane coating for the TR-90 base material comprises the following steps:
s1: putting methyl methacrylate, hydroxypropyl acrylate, acrylic resin, epoxybutene, fluorostyrene and an emulsifier into a reactor, reacting under the protection of nitrogen, and stirring at 80 ℃ to react to prepare a hydroxy polyacrylate prepolymer;
s2: cooling the hydroxyl polyacrylate prepolymer to 50 ℃, adding sodium hydroxide into the hydroxyl polyacrylate prepolymer for neutralization, then adding the neutralized hydroxyl polyacrylate prepolymer into water, and continuously stirring to obtain a polyacrylate prepolymer aqueous dispersion with the solid content of 40-50%;
s3: stirring and mixing the aqueous dispersion of the polyacrylate prepolymer in the formula amount and the isocyanate curing agent in the formula amount, and reacting for a certain time to obtain the aqueous two-component polyurethane coating for the TR-90 base material. In this embodiment, in S1, the weight ratio of the methyl methacrylate, the hydroxypropyl acrylate, and the acrylic resin is 1: 1: 1.
in this example, in S2, the concentration of sodium hydroxide was 5%, the amount of sodium hydroxide added was 3%, and the stirring time was 4 hours.
In this example, in S3, the amount of the aqueous dispersion of polyacrylate prepolymer and the amount of the isocyanate curing agent were mixed with stirring for 1 hour.
The application method of the aqueous two-component polyurethane coating for the TR-90 base material comprises the steps of adding the pigment into the aqueous two-component polyurethane coating for the TR-90 base material, uniformly stirring, directly coating the aqueous two-component polyurethane coating on the TR-90 base material within 4h under the environment of 70-80% humidity, wherein the environment temperature is 40 ℃, and then coating a layer of carboxylic acid end-capping agent to obtain a coating film.
In this embodiment, the carboxylic acid-based capping agent is formic acid.
Example 2
The embodiment discloses a waterborne two-component polyurethane coating for a TR-90 substrate, which comprises the following raw materials, 60% of an isocyanate curing agent, 30% of hydroxyl acrylic resin ester, 15% of epoxybutene, 6% of fluorostyrene, 3% of an emulsifier, 1% of an initiator and 2% of a cross-linking agent;
wherein the hydroxy acrylic resin ester consists of methyl methacrylate, hydroxypropyl acrylate and acrylic resin;
the solid content of the two-component polyurethane coating is 50%.
In this embodiment, the carboxylic acid-based capping agent is dicarboxylic acid or monoformic acid.
In this embodiment, the isocyanate curing agent is selected from a mixture of isophorone diisocyanate and dicyclohexylmethane diisocyanate.
In this embodiment, the initiator is selected from a mixture of azobisisonitrile and azobisisoheptonitrile.
In this example, the cross-linking agent is selected from 2, 3-dihydroxypropionic acid.
In this example, the emulsifier is an SR-10 emulsifier.
The preparation method of the aqueous two-component polyurethane coating for the TR-90 base material comprises the following steps:
s1: putting methyl methacrylate, hydroxypropyl acrylate, acrylic resin, epoxybutene, fluorostyrene and an emulsifier into a reactor, reacting under the protection of nitrogen, and stirring at 90 ℃ to react to prepare a hydroxy polyacrylate prepolymer;
s2: cooling the hydroxyl polyacrylate prepolymer to 60 ℃, adding sodium hydroxide into the hydroxyl polyacrylate prepolymer for neutralization, then adding the neutralized hydroxyl polyacrylate prepolymer into water, and continuously stirring to obtain a polyacrylate prepolymer aqueous dispersion with the solid content of 50%;
s3: stirring and mixing the aqueous dispersion of the polyacrylate prepolymer in the formula amount and the isocyanate curing agent in the formula amount, and reacting for a certain time to obtain the aqueous two-component polyurethane coating for the TR-90 base material.
In this embodiment, in S1, the weight ratio of the methyl methacrylate, the hydroxypropyl acrylate, and the acrylic resin is 1: 2: 2.
in this example, in S2, the concentration of sodium hydroxide was 5%, the amount of sodium hydroxide added was 5%, and the stirring time was 5 hours.
In this example, in S3, the time for stirring and mixing the aqueous dispersion of polyacrylate prepolymer in a prescribed amount and the isocyanate curing agent in a prescribed amount was 3 hours.
The application method of the aqueous two-component polyurethane coating for the TR-90 base material comprises the steps of adding the pigment into the aqueous two-component polyurethane coating for the TR-90 base material, uniformly stirring, directly coating the aqueous two-component polyurethane coating on the TR-90 base material within 5h under the environment of 70-80% humidity, wherein the environment temperature is 45 ℃, and then coating a layer of carboxylic acid end-capping agent to obtain a coating film.
In this embodiment, the carboxylic acid-based capping agent is formic acid.
Example 3
The aqueous two-component polyurethane coating for the TR-90 base material disclosed by the embodiment comprises the following raw materials, 55% of an isocyanate curing agent, 25% of hydroxyl acrylic resin ester, 16% of epoxybutene, 5.5% of fluorostyrene, 2% of an emulsifier, 0.8% of an initiator and 1.5% of a cross-linking agent;
wherein the hydroxy acrylic resin ester consists of methyl methacrylate, hydroxypropyl acrylate and acrylic resin;
the solid content of the two-component polyurethane coating is 40-50%.
In this embodiment, the carboxylic acid-based capping agent is dicarboxylic acid or monoformic acid.
In this embodiment, the isocyanate curing agent is selected from one or a mixture of any two or more of hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate.
In the embodiment, the initiator is one or two of azodiisobutanedinitrile and azodiisoheptanecarbonitrile.
In this embodiment, the cross-linking agent is selected from one or a mixture of two of 3-hydroxypropionic acid and 2, 3-dihydroxypropionic acid.
In this example, the emulsifier is an SR-10 emulsifier.
The preparation method of the aqueous two-component polyurethane coating for the TR-90 base material comprises the following steps:
s1: putting methyl methacrylate, hydroxypropyl acrylate, acrylic resin, epoxybutene, fluorostyrene and an emulsifier into a reactor, reacting under the protection of nitrogen, and stirring at 85 ℃ to react to prepare a hydroxyl polyacrylate prepolymer;
s2: cooling the hydroxyl polyacrylate prepolymer to 55 ℃, adding sodium hydroxide into the hydroxyl polyacrylate prepolymer for neutralization, then adding the neutralized hydroxyl polyacrylate prepolymer into water, and continuously stirring to obtain a polyacrylate prepolymer aqueous dispersion with the solid content of 45%;
s3: stirring and mixing the aqueous dispersion of the polyacrylate prepolymer in the formula amount and the isocyanate curing agent in the formula amount, and reacting for a certain time to obtain the aqueous two-component polyurethane coating for the TR-90 base material.
In this embodiment, in S1, the weight ratio of the methyl methacrylate, the hydroxypropyl acrylate, and the acrylic resin is 1: 1.5: 1.5.
in this embodiment, in S2, the concentration of sodium hydroxide is 5%, the addition amount of sodium hydroxide is 3% to 5%, and the stirring time is 4.5 hours.
In this example, in S3, the time for stirring and mixing the aqueous dispersion of polyacrylate prepolymer in a prescribed amount and the isocyanate curing agent in a prescribed amount was 2.5 hours.
The application method of the aqueous two-component polyurethane coating for the TR-90 base material comprises the steps of adding the pigment into the aqueous two-component polyurethane coating for the TR-90 base material, uniformly stirring, directly coating the aqueous two-component polyurethane coating on the TR-90 base material within 4.5h under the environment of 75% humidity, wherein the environment temperature is 43 ℃, and then coating a layer of carboxylic acid end-capping agent to obtain a coating film.
In this embodiment, the carboxylic acid-based end-capping agent is a dicarboxylic acid.
Comparative example 1
This example differs from example 1 in that epoxybutene and fluorostyrene are omitted, and the other starting materials and the methods of making and using them are the same as in example 1.
Comparative example 2
This example differs from example 1 in that fluorostyrene was omitted, and other starting materials, methods of making and using the same as example 1 are omitted and are not described further herein.
Comparative example 3
The difference between this example and example 1 is that the carboxylic acid-based capping agent is omitted, and other raw materials, the preparation method and the using method thereof are the same as those in example 1, and are not described again here.
Effect verification:
the following performance tests were conducted on the aqueous two-component polyurethane coating obtained in example 1 and the aqueous two-component polyurethane coatings obtained in comparative examples 1 to 3,
(1) and (3) testing VOC emission: detecting by a PID detection method;
(2) adhesion force: a single layer coating was applied to a TR-90 substrate, and after the coating was cured, a 10X10 grid was scribed at 2mm intervals on the coating, which was then taped and separated.
(3) Hardness: testing the hardness of the pencil;
(4) acid resistance: soaking in 0.1N HCl for 24 hours, and observing the change of a coating film;
(5) alkali resistance: soaking in 0.1N NaOH for 24 hours, and observing the change of a coating film;
(6) moisture resistance: testing at 47 +/-1) deg.C and 96 +/-2% relative humidity for 120 hr;
(7) bending resistance: after the workpiece is bent at an angle of 45 degrees, observing the change of a coating;
(8) water resistance: and soaking in distilled water for 240h to observe the change of the coating film.
The results are shown in Table 1.
TABLE 1 Performance Table for the coatings of example 1 and comparative examples 1-3
As can be seen from table 1, the aqueous two-component polyurethane coating of the present invention used on TR-90 substrates has better adhesion, hardness, acid resistance, alkali resistance, moisture resistance, bending resistance, and water resistance, and lower VOC emission, and the performance of the aqueous two-component polyurethane coating of the present invention used on TR-90 substrates is better than that of comparative example 1 in which styrene is omitted, comparative example 2 in which epoxybutene and styrene are omitted, and comparative example 3 in which carboxylic acid-type blocking agent is omitted, indicating that the addition of epoxybutene, styrene, and carboxylic acid blocking agent of the present application effectively improves the performance of the coating.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The waterborne two-component polyurethane coating for the TR-90 base material is characterized in that: comprises the following raw materials in percentage by weight,
50 to 60 percent of isocyanate curing agent
20 to 30 percent of hydroxyl acrylic resin ester
10 to 15 percent of epoxy butylene
5 to 6 percent of fluorine styrene
1 to 3 percent of emulsifier
0.1 to 1 percent of initiator
0.2 to 2 percent of cross-linking agent;
wherein the hydroxy acrylic resin ester consists of methyl methacrylate, hydroxypropyl acrylate and acrylic resin;
the solid content of the two-component polyurethane coating is 40-50%.
2. The waterborne two-component polyurethane coating for TR-90 substrates of claim 1, wherein: the isocyanate curing agent is one or a mixture of any two of hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate.
3. The waterborne two-component polyurethane coating for TR-90 substrates of claim 1, wherein: the initiator is one or two mixture of azodiisonitrile and azodiisoheptonitrile.
4. The waterborne two-component polyurethane coating for TR-90 substrates of claim 2, wherein: the cross-linking agent is one or a mixture of two of 3-hydroxypropionic acid and 2, 3-dihydroxypropionic acid.
5. The waterborne two-component polyurethane coating for TR-90 substrates of claim 2, wherein: the emulsifier is SR-10 emulsifier.
6. A preparation method of an aqueous two-component polyurethane coating for a TR-90 substrate is characterized by comprising the following steps: the starting material for the aqueous two-component polyurethane coating for TR-90 substrates according to any of claims 1 to 5, comprising the steps of:
s1: putting methyl methacrylate, hydroxypropyl acrylate, acrylic resin, epoxybutene, fluorostyrene and an emulsifier into a reactor, reacting under the protection of nitrogen, and stirring at 80-90 ℃ to react to prepare a hydroxyl polyacrylate prepolymer;
s2: cooling the hydroxyl polyacrylate prepolymer to 50-60 ℃, adding sodium hydroxide into the hydroxyl polyacrylate prepolymer for neutralization, then adding the neutralized hydroxyl polyacrylate prepolymer into water, and continuously stirring to obtain a polyacrylate prepolymer aqueous dispersion with the solid content of 40-50%;
s3: stirring and mixing the aqueous dispersion of the polyacrylate prepolymer in the formula amount and the isocyanate curing agent in the formula amount, and reacting for a certain time to obtain the aqueous two-component polyurethane coating for the TR-90 base material.
7. The method for preparing the aqueous two-component polyurethane coating for the TR-90 substrate as claimed in claim 6, wherein the method comprises the following steps: in the S1, the weight ratio of the methyl methacrylate to the hydroxypropyl acrylate to the acrylic resin is 1: 1-2: 1 to 2.
8. The method for preparing the aqueous two-component polyurethane coating for the TR-90 substrate as claimed in claim 6, wherein the method comprises the following steps: in the S2, the concentration of sodium hydroxide is 5%, the adding amount of sodium hydroxide is 3% -5%, and the stirring time is 4-5 h.
9. The method for preparing the aqueous two-component polyurethane coating for the TR-90 substrate as claimed in claim 6, wherein the method comprises the following steps: in the S3, the time for stirring and mixing the polyacrylate prepolymer aqueous dispersion with the formula amount and the isocyanate curing agent with the formula amount is 1-3 h.
10. A use method of an aqueous two-component polyurethane coating for a TR-90 base material is characterized by comprising the following steps: the aqueous two-component polyurethane coating for the TR-90 base material, which is disclosed by any one of claims 1-5, is adopted, a pigment is added into the aqueous two-component polyurethane coating for the TR-90 base material, the mixture is uniformly stirred, the aqueous two-component polyurethane coating for the TR-90 base material is used within 4-5 h, the aqueous two-component polyurethane coating is directly coated on the TR-90 base material in a humidity environment of 70-80%, the environment temperature is 40-45 ℃, the curing is carried out for 30-40 min, and then a layer of carboxylic acid end-capping agent is coated, so that a coating film is obtained.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6635341B1 (en) * | 2000-07-31 | 2003-10-21 | Ppg Industries Ohio, Inc. | Coating compositions comprising silyl blocked components, coating, coated substrates and methods related thereto |
| CN102292405A (en) * | 2008-10-24 | 2011-12-21 | 关西涂料株式会社 | Coating composition and method for forming coating film |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6635341B1 (en) * | 2000-07-31 | 2003-10-21 | Ppg Industries Ohio, Inc. | Coating compositions comprising silyl blocked components, coating, coated substrates and methods related thereto |
| CN102292405A (en) * | 2008-10-24 | 2011-12-21 | 关西涂料株式会社 | Coating composition and method for forming coating film |
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Application publication date: 20210827 |