阅读说明：本技术 一种蓄能型发光涂料及其制备方法 (Energy storage type luminous paint and preparation method thereof ) 是由 唐念 周永言 孙东伟 于 2021-11-18 设计创作，主要内容包括：本发明公开了一种蓄能型发光涂料及其制备方法。涂料包括如下质量百分比计的组分：成膜物质30％～50％、夜光粉20％～40％、固化剂10％～15％、稀释剂8％～12％、分散剂0.5％～2％、消泡剂0.1％～0.5％、防沉剂0.2％～0.5％、增稠剂0.3％～0.7％。本发明的蓄能型发光涂料可以拥有多种光色,还同时具备较高的初始发光亮度、余辉持久、防水、耐高温、耐腐蚀、耐候和附着力强的性能。(The invention discloses an energy storage type luminous paint and a preparation method thereof. The coating comprises the following components in percentage by mass: 30 to 50 percent of film forming material, 20 to 40 percent of noctilucent powder, 10 to 15 percent of curing agent, 8 to 12 percent of diluent, 0.5 to 2 percent of dispersant, 0.1 to 0.5 percent of defoaming agent, 0.2 to 0.5 percent of anti-settling agent and 0.3 to 0.7 percent of thickening agent. The energy storage type luminous paint provided by the invention can have various light colors, and also has the performances of high initial luminous brightness, lasting afterglow, water resistance, high temperature resistance, corrosion resistance, weather resistance and strong adhesive force.)

1. The energy storage type luminescent coating is characterized by comprising the following components in percentage by mass: 30 to 50 percent of film forming material, 20 to 40 percent of noctilucent powder, 10 to 15 percent of curing agent, 8 to 12 percent of diluent, 0.5 to 2 percent of dispersant, 0.1 to 0.5 percent of defoaming agent, 0.2 to 0.5 percent of anti-settling agent and 0.3 to 0.7 percent of thickening agent.

2. The energy-storing luminous paint as claimed in claim 1, wherein the film-forming substance is fluorocarbon varnish.

3. Energy storing type luminescent paint according to claim 1,

the noctilucent powder is one or more of rare earth activated alkaline earth metal aluminate luminescent pigments;

the curing agent is aliphatic isocyanate.

4. Energy storing type luminescent paint according to claim 3,

the luminous powder is CaAl₂O₄∶Eu²⁺,Nd³⁺、Sr₄Al₁₄O₂₅∶Eu²⁺,Dy³⁺And SrAl₂O₄∶Eu²⁺,Dy³⁺At least one of (1);

the curing agent is at least one of dicyclohexyl methane diisocyanate and hexamethylene diisocyanate.

5. The energy storage type luminescent paint as claimed in claim 1, wherein the particle size of the luminescent powder is 5-70 μm.

6. The energy storage type luminescent coating as claimed in claim 1, wherein the diluent is at least one of butyl acetate and alcohol ether solvent.

7. Energy storing type luminescent paint according to claim 1,

the dispersing agent is polyether modified siloxane;

the defoaming agent is a non-silicon polyether modified copolymer.

8. Energy storing type luminescent paint according to claim 1,

the anti-settling agent is a modified polyurea anti-settling agent;

the thickening agent is nonionic associative polyurethane thickening agent.

9. The method for preparing energy storage type luminescent coating of any one of claims 1 to 8, characterized by comprising the following steps: stirring the film forming matter and the diluent, adding the dispersant, the defoamer, the anti-settling agent and the thickener, stirring for the second time, adding the noctilucent powder, stirring for the third time, adding the curing agent, and stirring for the fourth time to obtain the coating.

10. The method for preparing energy storage type luminescent paint according to claim 9,

stirring for 10-15min at 150-300 r/min;

the second stirring is carried out at 150-300 revolutions per minute for 5-10 min;

the third stirring is carried out at 500-700 rpm for 15-20 min;

the fourth stirring is carried out at 300-500 r/min for 10-30 min.

Technical Field

The invention relates to the technical field of coatings, in particular to an energy storage type luminous coating and a preparation method thereof.

Background

The energy-storage type environment-friendly luminous paint belongs to a modern high-tech functional material, can absorb and store the energy of sunlight or an artificial light source, and then slowly releases the absorbed energy in the form of visible light in a dark place, and the luminous time lasts for more than 10 hours. The luminescent paint has the advantages of super-long afterglow, high brightness, long luminescence time, no radiation, etc., and thus has wide application.

Although the energy storage type luminous paint has a plurality of excellent performances, the application of the energy storage type luminous paint is still limited at present, and the energy storage type luminous paint is difficult to popularize and use especially in places with large areas, such as building interior and exterior wall paint, terrace and the like. The main reasons are as follows: (1) on the economic aspect, the energy storage type luminous paint has higher cost and is difficult to popularize and use in a large area; (2) on the technical aspect, the comprehensive performance of the energy storage type luminous paint is difficult to meet the use requirements of variable environments, and particularly the weather resistance, the impact resistance and the scratch resistance are not strong; the luminescent pigment has larger size, poor compatibility with resin and unsatisfactory dispersion in the coating; the preparation and coating processes of the paint are complex, and most of the paint needs to be matched with primer or finish paint for use; the paint contains more organic solvents, and the environmental pollution is greater in the coating process. Therefore, in order to meet the requirements of coating and indexes in different occasions, more and more energy storage type luminescent coatings with high performance are expected to be developed.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provide an energy storage type luminous coating.

The invention also aims to provide a preparation method of the energy storage type luminous paint.

The purpose of the invention is realized by the following technical scheme: an energy storage type luminous paint comprises the following components in percentage by mass: 30 to 50 percent of film forming material, 20 to 40 percent of noctilucent powder, 10 to 15 percent of curing agent, 8 to 12 percent of diluent, 0.5 to 2 percent of dispersant, 0.1 to 0.5 percent of defoaming agent, 0.2 to 0.5 percent of anti-settling agent and 0.3 to 0.7 percent of thickening agent.

Preferably, the film-forming substance is a fluorocarbon varnish.

Preferably, the noctilucent powder is one or more of rare earth activated alkaline earth metal aluminate luminescent pigments; more preferably, CaAl₂O₄∶Eu²⁺,Nd³⁺、Sr₄Al₁₄O₂₅∶Eu²⁺,Dy³⁺And SrAl₂O₄∶Eu²⁺,Dy³⁺At least one of them.

Preferably, the particle size of the noctilucent powder is 5-70 μm.

Preferably, the curing agent is aliphatic isocyanate; more preferably, at least one of dicyclohexylmethane diisocyanate and hexamethylene diisocyanate.

Preferably, the diluent is at least one of butyl acetate and alcohol ether solvents.

Preferably, the dispersant is polyether modified siloxane.

Preferably, the defoamer is a non-silicon polyether modified copolymer.

Preferably, the anti-settling agent is a modified polyurea anti-settling agent.

Preferably, the thickener is a nonionic associative polyurethane thickener.

The preparation method of the energy storage type luminous paint comprises the following steps: stirring the film forming matter and the diluent, adding the dispersant, the defoamer, the anti-settling agent and the thickener, stirring for the second time, adding the noctilucent powder, stirring for the third time, adding the curing agent, and stirring for the fourth time to obtain the coating.

Preferably, the stirring is 150-300 r/min for 10-15 min.

Preferably, the second stirring is 150-.

Preferably, the third stirring is 500-700 rpm for 15-20 min.

Preferably, the fourth stirring is 300-500 rpm for 10-30 min.

Compared with the prior art, the invention has the following beneficial effects:

the energy storage type luminous paint provided by the invention can have various light colors, and has the advantages of high initial luminous brightness, lasting afterglow, good water resistance, excellent heat resistance, corrosion resistance, weather resistance and high hardness.

Drawings

FIG. 1 is a graph showing the results of measuring the initial luminance of afterglow of 15 kinds of luminescent coatings with different amounts of luminescent powder.

FIG. 2 is a graph showing the results of measuring the change in luminous intensity with time of the coatings of the luminescent paints of examples 1 to 4 in a dark environment.

FIG. 3 is a graph showing the results of a water resistance test of the luminescent coating material of example 4.

FIG. 4 is a graph showing the results of a heat resistance test of the luminescent coating material of example 4.

FIG. 5 is a graph of the corrosion resistance test results for the luminescent coating of example 4.

FIG. 6 is a graph showing the results of the weather resistance test of the luminescent coating material of example 4.

FIG. 7 is a graph showing the results of hardness tests of the luminescent coating of example 4.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

An energy storage type luminous paint comprises the following raw materials in percentage by mass: 40% of fluorocarbon varnish, 12% of curing agent (dicyclohexylmethane diisocyanate), 10% of diluent (butyl acetate), and SrAl₂O₄∶Eu²⁺,Dy³⁺35% of yellow green luminous powder (particle size of 50 μm), 1.5% of dispersant (polyether modified siloxane F4250, olner polymer of Fushan City, Co., Ltd.), 0.5% of defoaming agent (polyether modified copolymer F291, olner polymer of Fushan City), 0.4% of anti-settling agent (modified polyurea compound F5705, olner polymer of Fushan City), and 0.6% of thickening agent (nonionic associated polyurethane F620, olner polymer of Fushan City).

The preparation method of the energy storage type luminescent coating comprises the following steps:

step 1: weighing the raw materials in proportion.

Step 2: sequentially adding fluorocarbon varnish and butyl acetate diluent into a container under the stirring condition, and mixing and stirring; the mixing speed was 150 rpm, and the mixing time was 15 minutes.

And step 3: adding a dispersing agent, a defoaming agent, an anti-settling agent and a thickening agent into a container, and uniformly mixing and stirring; the mixing speed was 200 rpm, and the mixing time was 10 minutes.

And 4, step 4: slowly adding SrAl₂O₄∶Eu²⁺,Dy³⁺And (3) adjusting the stirring speed to 500 r/min, and stirring and dispersing for 15 min.

And 5: and (3) regulating the stirring speed to 300 r/min, slowly adding the dicyclohexylmethane diisocyanate curing agent, and stirring and dispersing for 10min to obtain the energy storage type luminous coating.

Example 2

An energy storage type luminous paint comprises the following raw materials in percentage by mass: 45% of fluorocarbon varnish, 13% of curing agent (dicyclohexylmethane diisocyanate), 10% of diluent (ethylene glycol ethyl ether acetate) and Sr₄Al₁₄O₂₅∶Eu²⁺,Dy³⁺30% of blue-green luminous powder (particle size is 20 mu m), 1.2% of dispersing agent, 0.3% of defoaming agent, 0.2% of anti-settling agent and 0.3% of thickening agent (the dispersing agent, the defoaming agent, the anti-settling agent and the thickening agent are the same as those in the embodiment 1).

The preparation method of the energy storage type luminescent coating comprises the following steps:

step 1: weighing the raw materials in proportion.

Step 2: sequentially adding the fluorocarbon varnish and the diluent into a container under the stirring condition, and mixing and stirring; the mixing speed was 100 rpm, and the mixing time was 12 minutes.

And step 3: adding a dispersing agent, a defoaming agent, an anti-settling agent and a thickening agent into a container, and uniformly mixing and stirring; the mixing speed was 150 rpm, and the mixing time was 10 minutes.

And 4, step 4: slowly adding Sr₄Al₁₄O₂₅∶Eu²⁺,Dy³⁺Adjusting the stirring speed of the blue-green luminous powder to 600 revolutions per minute, and stirring and dispersing for 15 minutes.

And 5: and (3) regulating the stirring speed to 400 revolutions per minute, slowly adding the dicyclohexylmethane diisocyanate curing agent, and stirring and dispersing for 20 minutes to obtain the energy storage type luminous coating.

Example 3

An energy storage type luminous paint comprises the following raw materials in percentage by mass: 50% of fluorocarbon varnish, 15% of curing agent (hexamethylene diisocyanate), 12% of diluent (ethylene glycol monoethyl ether acetate), and SrAl₂O₄∶Eu²⁺,Dy³⁺20% of yellow-green luminous powder (particle size of 60 mu m), 1.4% of dispersing agent, 0.4% of defoaming agent, 0.5% of anti-settling agent and 0.7% of thickening agent (the dispersing agent, the defoaming agent, the anti-settling agent and the thickening agent are the same as those in example 1).

The preparation method of the energy storage type luminescent coating comprises the following steps:

step 1: weighing the raw materials in proportion.

Step 2: sequentially adding the fluorocarbon varnish and the diluent into a container under the stirring condition, and mixing and stirring; the mixing speed was 250 rpm, and the mixing time was 15 minutes.

And step 3: adding a dispersing agent, a defoaming agent, an anti-settling agent and a thickening agent into a container, and uniformly mixing and stirring; the mixing speed was 300 rpm, and the mixing time was 10 minutes.

And 4, step 4: slowly adding SrAl₂O₄∶Eu²⁺,Dy³⁺And (3) adjusting the stirring speed to 650 revolutions per minute, and stirring and dispersing for 16 minutes.

And 5: and (3) regulating the stirring speed to 550 revolutions per minute, slowly adding the hexamethylene diisocyanate curing agent, and stirring and dispersing for 25 minutes to obtain the energy storage type luminous coating.

Example 4

An energy storage type luminous paint comprises the following raw materials in percentage by mass: 36% of fluorocarbon varnish, 11% of curing agent (hexamethylene diisocyanate), 9.5% of diluent (butyl acetate), and CaAl₂O₄∶Eu²⁺,Nd³⁺40% of blue-violet luminous powder (particle size is 50 mu m), 1.8% of dispersing agent, 0.5% of defoaming agent, 0.5% of anti-settling agent and 0.7% of thickening agent (dispersing agent, defoaming agent and anti-settling agent)The thickener was the same as in example 1).

The preparation method of the energy storage type luminescent coating comprises the following steps:

step 1: weighing the raw materials in proportion.

Step 2: sequentially adding fluorocarbon varnish and butyl acetate diluent into a container under the stirring condition, and mixing and stirring; the mixing speed was 200 rpm, and the mixing time was 13 minutes.

And step 3: adding a dispersing agent, a defoaming agent, an anti-settling agent and a thickening agent into a container, and uniformly mixing and stirring; the mixing speed was 250 rpm, and the mixing time was 10 minutes.

And 4, step 4: slowly adding SrAl₂O₄∶Eu²⁺,Dy³⁺And (3) adjusting the stirring speed to 600 revolutions per minute, and stirring and dispersing for 12 minutes.

And 5: and (3) regulating the stirring speed to 500 revolutions per minute, slowly adding a hexamethylene diisocyanate curing agent, and stirring and dispersing for 30 minutes to obtain the energy storage type luminous coating.

Comparative example

TABLE 1

Table 1 shows the experiment for the mixing amount of noctilucent powder, where the samples ninu, r and r are the above examples 1-4, respectively, and the other 11 samples are obtained by adjusting the mixing amount of noctilucent powder in example 1. FIG. 1 shows the results of afterglow initial brightness detection of 15 luminescent coatings with different amounts of luminescent powder. The detection method comprises the following steps: and coating the luminous paint, exposing the obtained coating for 9 hours in the sun, and then placing the coating in a dark environment for detection.

Performance detection

FIG. 2 is a graph showing the results of measuring the change of luminous intensity with time of the coatings of the luminescent paints of examples 1 to 4 in a dark place, and showing that the coatings have an ultra-long afterglow of 12 hours or more in the dark place.

The coatings of the luminescent coatings of examples 1 to 4 were subjected to conventional water resistance and heat resistance tests, then excited for 30 minutes with a 48W fluorescent lamp light source, and then subjected to the test in a dark environment, and the test results are shown in Table 2.

TABLE 2

As can be seen from Table 2, the energy-storage luminescent coating provided by the invention has high afterglow brightness and long afterglow time.

Water resistance test (GB 1733-93):

deionized water was added to the glass tank, the water temperature was adjusted to 25 ℃ and maintained throughout the experiment. The coating of examples 1-4 was applied to test panels, and after the coating was allowed to dry, the panels were placed in a glass sink such that 2/3, the length of each panel, was immersed in water. After soaking for 5 days, the test panel was taken out of the bath, blotted dry with filter paper, immediately visually inspected, and recorded whether there was loss of gloss, discoloration, blistering, wrinkling, peeling, rusting, etc. The water resistance test was carried out using the epoxy resin in place of the fluorocarbon varnish of example 1, and the resulting paint was used as a control. The results show that the panels coated with the coatings of examples 1-4 show no change, whereas the coatings made with epoxy resins show a large amount of milky films on the surface with slightly curled edges (see FIG. 3 for the test results for the control and the coating of example 4), indicating that the luminescent coatings obtained with fluorocarbon varnish can be used in air, even in humid environments, for a long period of time with good water resistance.

Heat resistance test (GB/T1735-2009):

the test panels were coated with the coating materials of examples 1 to 4, and after the coating materials were completely dried, the test panels were placed in a forced air oven at a predetermined temperature, the distance between the test panels and each surface of the oven was 100mm, and the test panels were spaced apart from each other at 20mm intervals, and the test panels were left at the predetermined temperature for 5 days. After 5 days the test panels were removed from the oven and allowed to cool to room temperature. The coatings obtained were tested for heat resistance as a control using an epoxy resin instead of the fluorocarbon varnish of example 1. The test panel was inspected to see if there was a change in the color of the coating and if the coating was damaged. The results show that the coatings prepared from the coatings of examples 1-4 have no significant change in surface, color and edge, whereas the coatings prepared from epoxy resin have started to yellow in color on the surface and gum run-out on the edges (see fig. 4 for test results for control and example 4 coatings). The result shows that compared with epoxy resin paint, the paint prepared by adopting the fluorocarbon varnish has more excellent heat resistance and can be used in extreme external environment.

Corrosion resistance test (GB 1763-79):

coatings from examples 1 to 4 were prepared on substrates according to GB1763-79 and were put into the experiment after drying for 48 hours at constant temperature and humidity. Sulfuric acid and sodium hydroxide were separately prepared into 5 wt% solutions with distilled water. Two thirds of the area of the test plate is respectively immersed in an acid solution and an alkali solution at the temperature of 25 ℃, the test plate is taken out after the immersion time specified by the product standard is reached, the tap water is used for washing acid and alkali stains, and the filter paper is used for sucking and drying. The coating was observed for flaking, wrinkling, blistering, rusting, discoloration, and loss of gloss. The results show that the test panels after immersion in both the acid and base solutions showed no flaking, wrinkling, blistering, rusting, discoloration, and loss of gloss (the test results for the example 4 coating are shown in fig. 5).

Weather resistance test (GB/T9276 + 1996):

coating the paint of the embodiment 1-4 on a test panel, soaking the test panel in hot water at 80 ℃ for 1h after the paint is completely dried, washing with cold water to reduce the temperature, then placing the test panel in a freezer at-20 ℃ for low-temperature freezing for 1h, and observing the appearance and the luminescence condition of the sample after circulating three times.

The experimental result shows that the surface and the edge of the test plate have no obvious change after three cold and hot cycles. After being irradiated by a 48W lamp box for 30min, the test panel still shines well, which indicates that the appearance is unchanged, and indicates that the coatings of examples 1-4 still have weather resistance after being aged at high and low temperatures artificially (the test result of the coating of example 4 is shown in FIG. 6).

Hardness test (GB 6739-2006):

the coatings of examples 1 to 4 were applied to test panels and four hardness tests were carried out on the panels after the coatings had dried, using pencils with hardness of 6H, 4H and 3H, 2H. The results show that the panels tested with 6H, 4H, and 3H all exhibited dents, while the panels tested with the 2H pencil did not leave dents, so that the coating hardness of examples 1-4 was 2H (the test results for the coating of example 4 are shown in FIG. 7).

While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.