CN110804387B - Plant-based blue water-based photocureable coating and preparation method thereof - Google Patents

Abstract

The invention relates to a plant blue water-based photocureable coating and a preparation method thereof, wherein the coating comprises the following raw materials in parts by mass: 70-80 parts of modified blue waterborne polyurethane acrylate, 15-25 parts of reactive diluent, 2-4 parts of waterborne photoinitiator, 0.2-0.5 part of flatting agent and 5-10 parts of deionized water. Compared with the prior art, the waterborne light-cured coating prepared by the invention is sky blue, and after the waterborne light-cured coating is coated on a coated object, the sky blue is gradually changed into transparent color along with the progress of light curing, so that the original color attribute of the coated object is embodied, but the coated object can be endowed with high scratch and scratch resistance performance, the coated area and the uncoated area do not have obvious color difference, and the key of the technology is that the coating is changed into transparent color from the sky blue, namely, the curing is finished, and touch can be carried out.

Description

Plant-based blue water-based photocureable coating and preparation method thereof

Technical Field

The invention relates to the technical field of coatings, in particular to a plant series blue water-based photocureable coating and a preparation method thereof.

Background

With the improvement of living standard of people, the household product has higher appeal. In particular, the frequency of purchasing and using solid wood furniture is increasing. Generally, the surface of the solid wood furniture is provided with a layer of light-cured coating or polyurethane coating, so that the dryness, collision resistance, scratch resistance, pollution resistance and the like of the solid wood furniture are ensured, and the solid wood furniture is inevitably scratched, collided, polluted and the like in some places along with the lapse of the using time. Resulting in visual unattractive appearance and also causing continued breakage of the furniture. Especially, the wooden floor generally generates obvious wear marks after 5 years, and European and American countries use wooden furniture in large quantities, so that the European and American countries can carry out minor repair in 5 years and major repair in 10 years, and the European and American countries are responsible for maintenance by special profitability organizations. However, the trend of the solid wood furniture is just beginning, and the market lacks such a maintenance and repair mechanism, so small-area spot repair and repair are needed.

Although the transparent light-cured coating is available in the market at present, the performance is good, and the coating can be used for repairing, but the coating is transparent, so that the coating is invisible to a user after being coated, and the user is easy to touch and step by mistake on the premise of no curing. Moreover, common household repairing equipment without ultraviolet irradiation can be cured only by the daytime environment, the reaction speed is not very high, and the equipment is easy to be touched by mistake and touched by mistake. Even if the warning strip is used for isolating the repairing area, the mistaken touch is avoided, the user still has the difficulty that the user cannot judge whether the coating is completely cured or not, and the coating can be touched by fingers possibly, so that the curing degree is tested, the coating is not completely cured frequently, and the attractiveness is influenced by one fingerprint.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a plant blue water-based photocureable coating and a preparation method thereof.

The purpose of the invention can be realized by the following technical scheme: a plant blue water-based photocureable coating is characterized by comprising the following components in parts by mass:

preferably, the modified blue waterborne polyurethane acrylate is prepared by mixing a plant series ceruleus went extract and a waterborne polyurethane acrylate according to a mass ratio of 1-2: 7-8, stirring at a low speed of 500-800r/min for 30min to obtain a blue aqueous dispersion solution, wherein the molecular weight of the dispersion solution is 5000-10000, the solid content is 25-30%, the pH value is 9-10, and the blue aqueous dispersion solution presents sky blue.

Preferably, the indigotin can be easily separated from the plant indigotin in an alcohol solution, and the indigotin can be quickly separated by the aid of high temperature of 40-50 ℃ and is compatible with the alkyl glycol. The plant indigo is weaker than the organic synthetic azo pigment in stability, and is more easily decomposed and faded particularly under the conditions of excessive amine and high temperature. Specifically, the plant series kalium japonicum extract is prepared by mixing the following components in a mass ratio of 45-50: mixing 50-55 alkyl glycol with folium Mali Asiaticae at 40-50 deg.C, shearing at high speed, filtering with 1-20 μm filter bag to obtain folium Mali Asiaticae extract.

Preferably, the aqueous polyurethane acrylate is prepared from unsaturated polyester, butanediol, acetone, 2-hydroxyethyl acrylate, isophorone diisocyanate, triethylamine and deionized water in a mass ratio of 20-25: 2-5: 5-10: 2-5: 10-15: 40-60, mixing and reacting under the action of a catalyst. Unsaturated polyester in the waterborne polyurethane acrylate, wherein neopentyl glycol is utilized for synthesis, and diol with a waterborne group endows water dispersibility of macromolecules. And the aqueous dispersion is prepared from diisocyanate-hydroxyethyl acrylate to obtain an aqueous oligomer containing a small amount of epoxy structures and urethane acrylate structures.

The catalyst is dibutyltin dilaurate, and the using amount of the catalyst is 0.1-1 wt% of the unsaturated polyester; the unsaturated polyester comprises herborist chemical BY3306 which is commercially available.

The active diluent is ethoxylated trimethylolpropane triacrylate selected from TMPTA (commercially available from Kyoho chemical). The reactive diluent has a relatively high reaction speed, and a relatively hard coating can be obtained due to a high crosslinking density of a paint film, so that the requirements on scratch resistance and scratch resistance are met.

The leveling agent is polydimethylsiloxane. The silicon leveling agent has silicon-oxygen bond, so that the coating has better wettability on a substrate and can obtain a smooth coating. The leveling agent is commercially available BYK 333.

The water-based photoinitiator is 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone. Such photoinitiators are capable of initiating free radicals for vinyl polymerization. The generation of free radicals can not only promote the reaction of the coating, but also the free radicals can degrade indigo in the extract of the horse blue in case of excess triethylamine.

The preparation method of the plant series blue water-based photocureable coating is characterized by comprising the following steps:

(1) mixing the cut kale leaves with alkyl diol, carrying out high-speed shearing, filtering leaf residues by using a filter bag with the diameter of 1-20 microns, and extracting a plant kale extract;

(2) introducing nitrogen into a reaction kettle to replace air, adding unsaturated polyester and butanediol, dehydrating for 1h at 100 ℃, cooling to 80 ℃, slowly adding acetone, dropwise adding isophorone diisocyanate and a catalyst within 1h, continuously reacting for 2h, reducing the reaction temperature to 60 ℃, adding a capping agent of 2-hydroxyethyl acrylate, adding triethylamine for neutralization after testing that the content of NCO is less than or equal to 0.05%, stirring for 0.5h to enable the pH value to be between 9 and 10, and adding deionized water under high-speed stirring to obtain a 25-30% aqueous dispersion solution;

(3) adding the kale extract prepared in the step (1) and the aqueous dispersion solution prepared in the step (2), and stirring the kale extract and the aqueous dispersion solution at a low speed at normal temperature to obtain modified blue waterborne polyurethane acrylate with the mass fraction of 25-30%;

(4) and (4) mixing the blue waterborne polyurethane acrylate prepared in the step (3), a reactive diluent, a waterborne photoinitiator, a leveling agent and deionized water, and dispersing at a low speed to obtain the plant series blue waterborne photocuring coating.

Extracting a kale extract by using a sleeve type stirring device, and stirring at a constant temperature and a high speed for 20-60 min at a stirring speed of 1500-;

the high-speed stirring speed in the step (2) is 1500-2500 r/min;

the low-speed stirring speed in the step (3) is 500-800r/min, and the stirring time is 20-60 min;

and (the speed of the low-speed dispersion is 500-800 r/min).

The invention adopts the technical idea of cold splicing and mixing the ceruleus went extract and the water-based polyurethane acrylate, and the dosage of triethylamine is deliberately increased in the synthesis process of the water-based polyurethane acrylate, so that the pH value of the aqueous dispersion is between 9 and 10. It is specified here that, using a bimolecular photoinitiator, benzophenone, in the photoexcited state, is capable of abstracting a hydrogen atom from the vinyl group to generate a radical, a portion of which promotes the curing of the coating and another portion of which participates in the decomposition of indigo in the extract of horse blue, in the presence of excess amine. During the free radical polymerization of the coating, heat is released, and the indigo can be promoted to decompose under the condition of excessive amine and excessive free radicals. The coating slowly becomes transparent color along with the slowly ultraviolet excitation solidification of sky blue coating in the environment, the decomposition of indigo to this reminds the user, and the coating solidification can touch.

Compared with the prior art, the beneficial effects of the invention are embodied in the following aspects:

(1) the kalanchoe extract plant indigo can endow the aqueous photocuring product with sky blue color;

(2) the sky blue can prompt a user that the coating is just repaired and is carefully and mistakenly touched;

(3) the sky blue color can indicate to the user that the coating is uncured and should not be touched.

Detailed Description

The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.

Example 1

A plant blue water-based photocureable coating comprises the following components in parts by mass:

the preparation method of the coating comprises the following steps:

(1) stirring with a sleeve type stirring device in water bath of 40-50 deg.C at constant temperature. Mixing the cut and crushed herba kalanchoes Palmatae with alkyl diol, stirring at high speed of 1500-; adding the two into the Chinese Bihornia leaf: alkyl glycol 50: 50;

(2) introducing nitrogen into a reaction kettle to replace air, adding unsaturated polyester and butanediol, dehydrating for 1h at 100 ℃, cooling to 80 ℃, slowly adding acetone, dropwise adding isophorone diisocyanate and a proper amount of catalyst within 1h, and continuously reacting for 2 h. Reducing the reaction temperature to 60 ℃, adding an end-capping reagent of 2-hydroxyethyl acrylate, adding triethylamine for neutralization after testing that the NCO content is less than or equal to 0.05 percent, and stirring for 0.5h to ensure that the PH is between 9 and 10. Adding deionized water under stirring at high speed of 1500-: butanediol: acetone: 2-hydroxyethyl acrylate: isophorone diisocyanate: deionized water 20: 2: 5: 3: 10: 60, adding a solvent to the mixture;

(3) and (3) stirring the kalium extract prepared in the step (1) and the aqueous dispersion solution prepared in the step (2) at normal temperature and low speed of 500-: 85 parts by weight;

(4) mixing the blue waterborne polyurethane acrylate prepared in the step (3), a reactive diluent, a waterborne photoinitiator, a leveling agent and deionized water according to a mass ratio of 70: 20: 2: 0.2: 7.8 mixing and dispersing at a low speed of 500 and 800r/min for 30min to obtain a plant blue water-based photocureable coating;

the paint films obtained in this example were subjected to the relevant performance tests, the results of which are shown in the following table:

the paint is coated on an automobile, shows sky blue, and can be dried and cured for 1-2 hours under the sunshine to become colorless.

Example 2

A plant blue water-based photocureable coating comprises the following components in parts by mass:

the preparation method of the coating comprises the following steps:

(1) stirring with a sleeve type stirring device in water bath of 40-50 deg.C at constant temperature. Mixing the cut and crushed herba kalanchoes Palmatae with alkyl diol, stirring at high speed of 1500-; adding the two into the Chinese Bihornia leaf: alkyl glycol 48: 52;

(2) introducing nitrogen into a reaction kettle to replace air, adding unsaturated polyester and butanediol, dehydrating for 1h at 100 ℃, cooling to 80 ℃, slowly adding acetone, dropwise adding isophorone diisocyanate and a proper amount of catalyst within 1h, and continuously reacting for 2 h. Reducing the reaction temperature to 60 ℃, adding an end-capping reagent of 2-hydroxyethyl acrylate, adding triethylamine for neutralization after testing that the NCO content is less than or equal to 0.05 percent, and stirring for 0.5h to ensure that the PH is between 9 and 10. Adding deionized water under stirring at high speed of 1500-: butanediol: acetone: 2-hydroxyethyl acrylate: isophorone diisocyanate: deionized water 25: 3: 7: 5: 15: 45, a first step of;

(3) and (3) stirring the kalium extract prepared in the step (1) and the aqueous dispersion solution prepared in the step (2) at normal temperature and low speed of 500-: 90, respectively;

(4) mixing the blue waterborne polyurethane acrylate prepared in the step (3), a reactive diluent, a waterborne photoinitiator, a leveling agent and deionized water according to a mass ratio of 77: 15: 2: 0.2: 5.8 mixing and dispersing at a low speed of 500 and 800r/min for 30min to obtain a plant blue water-based photocureable coating;

the paint films obtained in this example were subjected to the relevant performance tests, the results of which are shown in the following table:

the paint is coated on an automobile, shows sky blue, and can be dried and cured for 1-2 hours under the sunshine to become colorless.

Example 3

A plant blue water-based photocureable coating comprises the following components in parts by mass:

the preparation method of the coating comprises the following steps:

(1) stirring with a sleeve type stirring device in water bath of 40-50 deg.C at constant temperature. Mixing the cut and crushed herba kalanchoes Palmatae with alkyl diol, stirring at high speed of 1500-; adding the two into the Chinese Bihornia leaf: alkyl glycol 45: 55;

(2) introducing nitrogen into a reaction kettle to replace air, adding unsaturated polyester and butanediol, dehydrating for 1h at 100 ℃, cooling to 80 ℃, slowly adding acetone, dropwise adding isophorone diisocyanate and a proper amount of catalyst within 1h, and continuously reacting for 2 h. Reducing the reaction temperature to 60 ℃, adding an end-capping reagent of 2-hydroxyethyl acrylate, adding triethylamine for neutralization after testing that the NCO content is less than or equal to 0.05 percent, and stirring for 0.5h to ensure that the pH value is between 9 and 10. Adding deionized water under stirring at high speed of 1500-: butanediol: acetone: 2-hydroxyethyl acrylate: isophorone diisocyanate: deionized water 20: 2: 5: 2: 10: 40; the catalyst is dibutyltin dilaurate, and the dosage of the catalyst is 0.1 wt% of the unsaturated polyester;

(3) and (3) stirring the kalium extract prepared in the step (1) and the waterborne polyurethane acrylate prepared in the step (2) at normal temperature and low speed of 500-: 8;

(4) mixing the blue waterborne polyurethane acrylate prepared in the step (3) with an active diluent, a waterborne photoinitiator, a leveling agent and deionized water according to the mass ratio, and dispersing at a low speed of 500-800r/min for 30min to obtain a plant blue waterborne photocuring coating;

the paint films obtained in this example were subjected to the relevant performance tests, the results of which are shown in the following table:

the paint is coated on an automobile, shows sky blue, and can be dried and cured for 1-2 hours under the sunshine to become colorless.

Example 4

A plant blue water-based photocureable coating comprises the following components in parts by mass:

the preparation method of the coating comprises the following steps:

(1) stirring with a sleeve type stirring device in water bath of 40-50 deg.C at constant temperature. Mixing the cut and crushed herba kalanchoes Palmatae with alkyl diol, stirring at high speed of 1500-; adding the two into the Chinese Bihornia leaf: alkyl glycol 50: 50;

(2) introducing nitrogen into a reaction kettle to replace air, adding unsaturated polyester and butanediol, dehydrating for 1h at 100 ℃, cooling to 80 ℃, slowly adding acetone, dropwise adding isophorone diisocyanate and a proper amount of catalyst within 1h, and continuously reacting for 2 h. Reducing the reaction temperature to 60 ℃, adding an end-capping reagent of 2-hydroxyethyl acrylate, adding triethylamine for neutralization after testing that the NCO content is less than or equal to 0.05 percent, and stirring for 0.5h to ensure that the pH value is between 9 and 10. Adding deionized water under stirring at high speed of 1500-: butanediol: acetone: 2-hydroxyethyl acrylate: isophorone diisocyanate: deionized water 25: 5: 10: 5: 15: 60, adding a solvent to the mixture; the catalyst is dibutyltin dilaurate, and the dosage of the catalyst is 1 wt% of the unsaturated polyester;

(3) and (2) stirring the cervus chinensis extract prepared in the step (1) and the waterborne polyurethane acrylate prepared in the step (2) at normal temperature and low speed of 500-: 7;

(4) mixing the blue waterborne polyurethane acrylate prepared in the step (3) with an active diluent, a waterborne photoinitiator, a leveling agent and deionized water according to the mass ratio, and dispersing at a low speed of 500-800r/min for 30min to obtain a plant blue waterborne photocuring coating;

the paint films obtained in this example were subjected to the relevant performance tests, the results of which are shown in the following table:

the paint is coated on an automobile, shows sky blue, and can be dried and cured for 1-2 hours under the sunshine to become colorless.

Claims (7)

1. A plant blue water-based photocureable coating is characterized in that the coating comprises the following raw materials in parts by mass:

the modified blue waterborne polyurethane acrylate is prepared by mixing a plant series kalium extract and waterborne polyurethane acrylate according to the mass ratio of 1-2: 7-8, stirring at low speed of 500-;

the waterborne polyurethane acrylate is prepared from unsaturated polyester, butanediol, acetone, 2-hydroxyethyl acrylate, isophorone diisocyanate and deionized water in a mass ratio of 20-25: 2-5: 5-10: 2-5: 10-15: 40-60, mixing, and reacting under the action of a catalyst to obtain the catalyst; the water-based photoinitiator is 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone.

2. The plant-based blue aqueous photocurable coating according to claim 1, wherein the plant-based kalium extract is prepared by mixing together, in a mass ratio of 45-50: mixing 50-55 alkyl glycol with folium Mali Asiaticae at 40-50 deg.C, shearing at high speed, filtering with 1-20 μm filter bag to obtain folium Mali Asiaticae extract.

3. The botanical blue waterborne photocurable coating according to claim 1, wherein the catalyst is dibutyltin dilaurate, and the amount of the catalyst is 0.1-1 wt% of the unsaturated polyester.

4. The botanical blue aqueous photocurable coating of claim 1 wherein the reactive diluent is ethoxylated trimethylolpropane triacrylate.

5. The plant-based blue aqueous photocurable coating according to claim 1, wherein said leveling agent is polydimethylsiloxane.

6. A method for preparing the plant-based blue water-based light-cured paint according to any one of claims 1 to 5, comprising the following steps:

(1) mixing the cut kale leaves with alkyl diol, carrying out high-speed shearing, filtering leaf residues by using a filter bag with the diameter of 1-20 microns, and extracting a plant kale extract;

(2) introducing nitrogen into a reaction kettle to replace air, adding unsaturated polyester and butanediol, dehydrating for 1h at 100 ℃, cooling to 80 ℃, slowly adding acetone, dropwise adding isophorone diisocyanate and a catalyst within 1h, continuously reacting for 2h, reducing the reaction temperature to 60 ℃, adding a capping agent of 2-hydroxyethyl acrylate, adding triethylamine for neutralization after testing that the content of NCO is less than or equal to 0.05%, stirring for 0.5h to enable the pH to be 9-10, and adding deionized water under high-speed stirring to obtain a 25-30% aqueous dispersion solution;

(3) adding the kale extract prepared in the step (1) and the aqueous dispersion solution prepared in the step (2), and stirring the kale extract and the aqueous dispersion solution at a low speed at normal temperature to obtain modified blue waterborne polyurethane acrylate with the mass fraction of 25-30%;

(4) and (4) mixing the blue waterborne polyurethane acrylate prepared in the step (3), a reactive diluent, a waterborne photoinitiator, a leveling agent and deionized water, and dispersing at a low speed to obtain the plant series blue waterborne photocuring coating.

7. The method for preparing the plant series blue water-based photocureable coating according to the claim 6, wherein the step (1) is to extract the kale extract by using a sleeve type stirring device, and to stir the kale extract at a constant temperature and a high speed by using a water bath at the temperature of 40-50 ℃, wherein the stirring speed is 1500-;

the high-speed stirring speed in the step (2) is 1500-2500 r/min;

the low-speed stirring speed in the step (3) is 500-800r/min, and the stirring time is 20-60 min;

the speed of the low-speed dispersion in the step (4) is 500-800 r/min.