CN101333357B - Luminous paint and method for preparing same - Google Patents

Abstract

Luminous paint and a preparation method thereof are disclosed, belonging to paint compound based on inorganic materials and particularly the technical filed of the preparation of luminous paint compound. The luminous paint is composed of long-afterglow phosphor powder coated with nano titanium dioxide and luminous paint compound. The invention has the advantages of being simple and novel, and under illumination, the luminous paint has long-afterglow irradiance effect and the stored luminance efficiency is greatly improved, so the luminous paint is particularly suitable for underwater signs and road signs in pluvial regions.

Description

A kind of luminous paint and preparation method thereof

technical field

The invention belongs to the technical field of preparation of paint compositions based on inorganic substances, especially luminescent paint compositions.

Background technique

At present, there are two main types of energy storage luminescent materials used in the coating industry, namely zinc sulfide ZnS-based luminescent materials and rare earth activated alkaline earth metal aluminate luminescent ^materialsi . A typical representative of zinc sulfide-based energy storage luminescent materials is zinc sulfide activated by copper and cobalt, which is light yellow powder. Zinc sulfide-based luminescent materials have always been considered as a long-lasting luminescent material and are used in many fields. However, the afterglow of this material can only last for 1 to 2 hours, and it does not have sufficient brightness in many applications, and it is easy to deteriorate after being exposed to ultraviolet rays or oxygen. Sometimes radioactive elements such as deuterium and promethium pm-147 are often added in order to prolong the afterglow time of luminescent coatings, causing radioactive pollution to the environment, so this material system has been gradually eliminated by the market. The rare earth activated alkaline earth aluminate luminescent material refers to a type of luminescent material that uses rare earths, especially europium Eu, as the active element and alkaline earth aluminate as the matrix. Among them, strontium aluminate co-activated by Eu and Dy is a typical representative, which is a new type of luminescent material developed in the early 1990s. It is characterized by high initial brightness, long afterglow time of more than 10 hours, no radioactivity, heat resistance, environmental erosion resistance, and good oxidation resistance. It is called a green energy-saving material. In alkaline earth metal aluminate luminescent materials, the wavelength and afterglow time of fluorescence are also different with the content ratio of strontium oxide and aluminum oxide. By changing the content of strontium oxide and aluminum oxide, the doping amount of europium Eu and dysprosium Dy and substituting part or all of strontium oxide SrO with calcium oxide CaO, magnesium oxide MgO, barium oxide BaO, etc., or adding them in combination, one can obtain a A series of rare earth activated alkaline earth metal aluminate luminescent materials with different initial luminous intensity and afterglow time. Because this type of luminescent material has advantages that other luminescent materials cannot match so far, the long-lasting energy-storage luminescent paint developed with this type of luminescent material has been promoted in the fields of solvent transportation, transportation and firefighting in recent yearsii ^{, iii} .

Long afterglow luminescent paint is one of the high-tech functional materials with rapid development in the world. This paint is made of luminescent pigments, organic resins or resins, organic solvents or solvents, inorganic pigments, fillers, additives, etc. in a certain proportion. , can absorb and store light energy under visible light such as sunlight or lamplight, and then slowly release the absorbed energy in the form of visible light in a dark place, and the luminous time can last for more than 10 hours. At present, long afterglow energy storage luminescent materials are developing in the direction of improving luminous intensity and afterglow time, being durable and environmentally friendly. The research on energy-storage luminescent coatings in my country is relatively late, but it develops rapidly, and the application of various aspects is in the exploratory stage. The research on the application of nano-materials in luminescent coatings is an important topic that the industry pays attention to. Nanoparticles have special properties such as surface effects, small size effects, and macroscopic quantum tunneling effects. After they are used in coatings, the optical properties, magnetic properties, electrical properties, and mechanical properties of the coatings can be greatly improved or new properties can be displayed. Function, can greatly improve the grade and market competitiveness of products such as automobiles, building materials, instruments, ships, aircrafts, etc., thus also aroused the strong interest of polymer materials and paint workers, nano-coating products have come out in domestic and foreign markets . The grade and market competitiveness of the product have also aroused the strong interest of polymer materials and coating workers ^iV .

CN1740242 provides "a nano-modified long-lasting energy-storage luminous paint", which once disclosed the technology of using nano-titanium dioxide doped in the luminous paint to improve the luminous performance of the paint. However, since nano-titanium dioxide is doped in the luminous coating, although the luminous intensity and afterglow time can be improved, its stability and luminous ability, especially when used in water, need to be further improved.

Contents of the invention

The object of the present invention is to provide a simple and novel nano-titanium dioxide-coated light-storing material, which has a long afterglow luminescence effect and greatly improves the light-storage efficiency, and a nano-titanium dioxide-coated light-emitting material containing the above-mentioned nano-titanium dioxide-coated luminescent material A luminescent coating that can effectively improve the efficiency of storing luminescence and a preparation method thereof.

The technical solution of the present invention is to provide that the preparation of the luminous paint is carried out in two steps by the long-lasting luminous powder material coated with nano-titanium dioxide and the luminous paint composition.

(1) Preparation of nano-titanium dioxide-coated long-lasting luminous powder material: it is made of the following types of raw materials and their weight percentage ratios:

Fluorocarbon resin 5.00～20.00

Organic solvents 10.00～50.00

Dispersant 0.01～5.00

Nano titanium dioxide 0.20～6.00

Luminescent material powder 40.00～60.00

Wherein: the nano titanium dioxide is anatase type, rutile type or anatase and rutile mixed crystal type or a mixture of two;

The luminescent material is one or more mixtures of silicate luminescent material, aluminate luminescent material and aluminosilicate luminescent material, with an average particle size of 5-65 microns, preferably 25-60 microns;

The fluorocarbon resin is one of multiple chlorotrifluoroethylene copolymers and tetrafluoroethylene multiple copolymers;

The dispersant is an anionic surfactant, such as one or more of sodium hexametaphosphate, sodium dodecylbenzenesulfonate, etc.;

The organic solvent is one or more mixtures of xylene, isobutanol, propylene glycol, propylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol methyl ether acetate, and butyl acetate.

The method for preparing nano-titanium dioxide-coated luminescent material comprises the following steps:

(1) Disperse fluorocarbon resin, organic solvent, dispersant, nano-titanium dioxide, and luminescent material powder in a dispersion container at a medium speed (500-800 rpm) for 30-60 minutes;

(2) It is prepared by drying at 60-80°C and grinding.

(2) The preparation method of the luminescent coating composition containing the nano-titanium dioxide-coated luminescent material: it is made of the following types of raw materials and their weight percentage ratios:

Film-forming substances 25-50%:

Luminescent material coated with nano-titanium dioxide 5-50%;

Solvent 0～30%:

White filler 0～50%

Additives 0～30%

Wherein: the film-forming substance is one or more of fluorocarbon resin, fluoropropylene resin, epoxy resin, polyurethane resin, and acrylic resin, and the amount of each resin is 0-100% of the total film-forming substance;

The solvent is one or a mixture of two or more of xylene, isobutanol, propylene glycol, propylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol methyl ether acetate, butyl acetate, etc., and the amount of each solvent is 0-100% of the total amount;

The white filler is one or more of titanium dioxide, talcum powder, and calcium carbonate, and the amount of each filler is 0% to 100% of the total amount of filler;

The auxiliary agent is at least one of a dispersant, a defoamer, a leveling agent, and a film-forming auxiliary agent.

Among them, the optional additives are respectively:

Dispersant: 903, 904S, 926 (Deqian Company); BYK161 (Germany BYK Company), one or more of sodium hexametaphosphate, sodium dodecylbenzenesulfonate, etc., the amount of each dispersant is dispersant 0-100% of the total dose;

Defoamer: one or more of BYK066, 141 (Germany BYK Company), 2700, 5600 (Deqian Company), etc., the amount of each defoamer is 0-100% of the total amount of defoamer;

Leveling agent: one or more of BYK358, 390 (BYK Company of Germany); 433, 495 (Deqian Company), etc., the amount of each leveling agent is 0-100% of the total amount of leveling agent;

The preparation method of the luminous coating composition containing the nano-titanium dioxide-coated luminescent material comprises the following process steps:

(1) Add the solvent, film-forming resin, filler, other additives and nano-titanium oxide-coated luminescent pigments into the dispersing machine batching tank in sequence according to the preset ratio, stir and disperse at a medium speed (500-800 rpm) 30-60 minutes;

(2) After filtering, the finished luminous paint can be obtained.

The beneficial effects and benefits achieved by the present invention are that, by adopting the above-mentioned technical scheme, the nano-titanium dioxide-coated luminous paint proposed by the present invention can be applied by brushing, spraying or rolling, and can be stirred before use, and the viscosity can be adjusted with a solvent. A uniform and luminous coating can be formed when the paint film thickness reaches more than 80 μm. Paint the same thickness of luminous paint on different color primers, the luminous coating on the white paint has the best effect, so in order to reduce the cost and reduce the amount of luminous paint, it is best to pre-coat the white primer. Compared with the prior art, the beneficial effect of the present invention is that the luminescent paint prepared by the technology of the present invention can significantly improve the luminous intensity of the luminous paint, which is better than the luminous storage capacity of the luminescent paint prepared by using the luminescent material not coated with nano-titanium dioxide. It can be increased by 3 times, especially after being illuminated in a certain depth of water and seawater, its stored luminous intensity reaches 8 to 10 times that of the stored luminous intensity after being illuminated in the air.

According to the analysis, the reason for the greatly improved long-lasting luminescent performance of the luminescent material and the luminescent coating in the technical solution of the present invention is that there are trap levels of different depths in the luminescent material. When excited by ultraviolet light, the trap level with a certain energy depth captures a sufficient number of electrons from the excited state and stores them. After the ultraviolet light stops the excitation, the electrons stored in the trap energy level are gradually released under the thermal disturbance at room temperature, and the released electrons then jump to the excited state, and the electrons return to the ground state from the excited state to produce long afterglow luminescence. Nano-titanium dioxide belongs to nano-semiconductor compound particles. Due to its semiconductor properties, electrons are excited under the irradiation of ultraviolet light and transition from the valence band to the conduction band, thereby producing a broad-band strong absorption of ultraviolet light. Nanoparticles are small enough in size to emit light when excited by light of a certain wavelength. The nano-titanium dioxide particles modified by fluorocarbon resin and dispersant coat the luminescent material particles, the electron-hole Coulomb interaction is enhanced, the exciton binding energy and oscillator strength are increased, and the dielectric effect is increased, resulting in the luminescent material and nano-titanium dioxide. The electronic transition process of each promotes each other, so that the long-lasting light storage performance is greatly improved.

The fluorocarbon resin has a stable chemical structure and has excellent resistance to light radiation and aging. Therefore, the nano-titanium dioxide-coated luminescent material of the present invention has good solvent stability and can obtain a luminescent paint with stable storage. The luminescent coating has good adhesion on the surface of cement, iron, aluminum alloy, wood, glass, PVC plastic and other substrates. The paint film has good water resistance, alkali resistance and weather resistance, high luminous brightness and long afterglow time, which can be widely used. In safety passages, mine tunnels, traffic signs, fire-fighting equipment, electrical switches, etc., as emergency signs in the absence of electric lighting, it can also be used in luminous crafts. Especially suitable for underwater signs and traffic road signs in rainy areas.

Detailed ways

The present invention will be further described below in combination with specific embodiments.

Example 1:

(1) Add 200g of fluorocarbon resin, 250g of organic solvent, 2g of sodium hexametaphosphate, 8g of P25 nano-titanium dioxide, and 540g of PLO-7C-B luminescent material according to the preset ratio, stir and disperse at medium speed (650 rpm) for 30 Minutes, the luminescent pigment pre-dispersion of nano-titanium oxide coating treatment is obtained;

(2) drying the pre-dispersion of the luminescent pigment coated with nano-titanium oxide at 60° C., and grinding to obtain the luminescent pigment coated with nano-titanium oxide;

(3) Add the solvent, film-forming resin, filler, other additives and nano-titanium oxide-coated luminescent pigments into the dispersing machine batching tank in sequence according to the preset ratio, stir and disperse at a medium speed (650 rpm) for 45 minutes . After filtering through an 80-mesh filter, the finished luminous paint can be obtained.

ZB2002 Fluorocarbon Resin (Dalian Zhenbang) 50g

Nano titanium dioxide coated luminescent material 30g

Titanium dioxide (pigment and filler) 18g

BYK161 (dispersant) 1g

Deqian 903 (dispersant) 0.3g

BYK066 (defoamer) 0.3g

BYK358 (leveling agent) 0.4g

HR-969 titanium dioxide (pigment and filler) 25.5g

BYK141 (defoamer) 0.2g

BYK390 (leveling agent) 0.3g

Example 2:

(1) Add 190g of fluorocarbon resin, 200g of organic solvent, 2g of sodium hexametaphosphate, 8g of domestic anatase nano-titanium dioxide, and 600g of SB-8C luminescent material according to the preset ratio, stir and disperse at medium speed (800 rpm) for 20 Minutes, the luminescent pigment pre-dispersion of nano-titanium oxide coating treatment is obtained;

(2) drying the pre-dispersion of the luminescent pigment coated with nano-titanium oxide at 80° C., and grinding to obtain the luminescent pigment coated with nano-titanium oxide;

(3) Add the solvent, film-forming resin, filler, other additives and nano-titanium oxide-coated luminescent pigments into the dispersing machine batching tank in sequence according to the preset ratio, stir and disperse at a medium speed (500 rpm) for 30 minutes . After filtering through a 100-mesh filter, the finished luminescent paint can be obtained.

618 epoxy resin 50g

Encapsulated luminescent pigment 30g

Talc powder (800#, Dalian Keli) 10g

Xylene 7g

Deqian 495 (leveling agent) 1.4g

Deqian 926 (dispersant) 1.2g

Deqian 2700 (defoamer) 0.2g

Example 3:

(1) Add 190g of fluorocarbon resin, 200g of organic solvent, 4g of sodium dodecylbenzenesulfonate, 6g of domestic anatase nano-titanium dioxide, and 600g of SP-4 luminescent material according to the preset ratio, and medium speed (600 rpm ) Stirring and dispersing for 40 minutes to prepare a luminous pigment predispersion coated with nano-titanium oxide;

(2) drying the pre-dispersion of the luminescent pigment coated with nano-titanium oxide at 70° C., and grinding to obtain the luminescent pigment coated with nano-titanium oxide;

(3) Add the solvent, film-forming resin, filler, other additives and nano-titanium oxide-coated luminescent pigments into the dispersing machine batching tank in sequence according to the preset ratio, stir and disperse at a medium speed (600 rpm) for 30 minutes . After filtering through a 150-mesh filter, the finished luminescent paint can be obtained.

Acrylic resin M-133 42g

Solvent 26g

Luminous Powder 30g

Sodium hexametaphosphate (dispersant) 2g

Example 4:

(1) Add 190g of fluorocarbon resin, 200g of organic solvent, 4g of sodium hexametaphosphate, 6g of P25 type nano-titanium dioxide, 300g of SP-4 type luminescent material, 300g of PLO-7C-B type luminescent material according to the preset ratio, medium speed ( 800 rpm) stirring and dispersing for 40 minutes to obtain a pre-dispersion of luminous pigment coated with nano-titanium oxide;

(2) drying the pre-dispersion of the luminescent pigment coated with nano-titanium oxide at 65° C., and grinding to obtain the luminescent pigment coated with nano-titanium oxide;

(3) Add the solvent, film-forming resin, filler, other additives and nano-titanium oxide-coated luminescent pigments into the dispersing machine batching tank in sequence according to the preset ratio, and stir and disperse at a medium speed (800 rpm) for 30 minutes . After being filtered through a 120-mesh filter, the finished luminous paint can be obtained.

Polyurethane resin 25g

Luminous Powder 25g

R-501 rutile titanium 14g

Heavy calcium (800#) 10g

Xylene 24.6g

Deqian 904S (wetting and dispersing agent) 0.8g

Deqian 5600 (defoamer) 0.2g

Deqian 433 (leveling agent) 0.4g

Comparative examples 1 to 4:

The formulation of the luminescent paint of the comparative example is the same as that of the above-mentioned Examples 1-4, the difference is that the luminescent material is a commercial luminescent material not coated with nano-titanium dioxide.

Experiment 1: paint storage and luminescence test: each example and comparative example luminescent paint is evenly coated on 5 pieces of 50mm×50mm×1.5mm glass plates coated with white primer, and after natural drying for 7 days, it is carried out in a well-closed dark room test. During the test, the coating sample was placed flat in the light incubator, and the light source was turned off after a certain period of light. Use a photometer to measure the stored luminance of the test luminescent coating at regular intervals, and the unit is lux.

Test Results:

Table 1 Relative storage luminous illuminance in air

example Example 1/Comparative Example 1 Example 2/Comparative Example 2 Example 3/Comparative Example 3 Embodiment 4/comparative example 4 Relative storage luminance 2.76 1.92 2.46 2.22

Experiment 2: paint storage and luminescence test: each example and comparative example luminescent paint is evenly coated on 5 pieces of 50mm×50mm×1.5mm glass plates coated with white primer, and after natural drying for 7 days, it is carried out in a well-sealed dark room test. During the test, the sample submerged in a 1000ml beaker filled with 200ml deionized solvent was placed flat in the light incubator, and the light source was turned off after a certain period of light. Use a photometer to measure the stored luminance of the test luminescent coating at regular intervals, and the unit is lux.

Test Results:

Table 2 Relative storage luminescence illuminance in water

example Example 1/Comparative Example 1 Example 2/Comparative Example 2 Example 3/Comparative Example 3 Example 4/ratio 4 Relative storage luminance 7.61 5.37 7.28 6.72

Experiment 3: paint storage and luminescence test: each example and comparative example luminescent paint is evenly coated on 5 pieces of 50mm×50mm×1.5mm glass plates coated with white primer, and after natural drying for 7 days, it is carried out in a well-sealed dark room test. During the test, the sample submerged in a 1000ml beaker filled with 400ml of natural seawater was placed flat in the light incubator, and the light source was turned off after a certain period of light. Use a photometer to measure the stored luminance of the test luminescent coating at regular intervals, and the unit is lux.

Test Results:

Table 3 Relative storage luminescence illuminance in seawater

example Example 1/Comparative Example 1 Example 2/Comparative Example 2 Example 3/Comparative Example 3 Embodiment 4/comparative example 4 Relative storage luminance 22.66 15.36 20.13 17.05

Table 4 The relative storage luminescence illuminance of comparative examples after light in seawater and air

example Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Relative storage luminance 0.61 0.43 0.55 0.47

The relative storage luminescence illuminance of table 5 embodiment after light in seawater and air

example Example 1 Example 2 Example 3 Example 4 Relative storage luminance 8.16 9.74 7.85 8.49

Claims (9)

1. a luminous paint is characterized in that, the luminescent material 5～50%, solvent 0～30%, white filler 0～50% and the auxiliary agent 0～30% that are coated processing by filmogen 25～50%, nano titanium oxide are formulated according to weight percent.

2. a kind of luminous paint according to claim 1, it is characterized in that it is formulated according to weight percent by fluorocarbon resin 5～20%, solvent 10～50%, dispersion agent 0.01～5%, nano titanium oxide 0.2～6% and luminescent material powder 40～60% that described nano titanium oxide coats the luminescent material of handling;

Wherein, described fluorocarbon resin is a kind of in trifluorochloroethylene multiple copolymer, the tetrafluoroethylene multiple copolymer;

Described dispersion agent is an aniorfic surfactant, and this promoting agent is one or more in Sodium hexametaphosphate 99, the Sodium dodecylbenzene sulfonate;

Described nano titanium oxide is one or both the mixture in anatase titanium dioxide, rutile-type or anatase titanium dioxide and the rutile mixed crystal type;

Described luminescent material powder is one or more mixtures in silicate luminescent material, aluminate luminescent material or the aluminosilicate luminescent material, and median size is the 5-65 micron.

3. a kind of luminous paint according to claim 2 is characterized in that, the particle diameter of described luminescent material powder is the 25-60 micron.

4. a kind of luminous paint according to claim 1 and 2, it is characterized in that described solvent is one or more the mixture in dimethylbenzene, isopropylcarbinol, propylene glycol, propylene glycol monomethyl ether, butyl glycol ether, 1-Methoxy-2-propyl acetate or the N-BUTYL ACETATE.

5. a kind of luminous paint according to claim 1 is characterized in that, described filmogen is one or more in fluorocarbon resin, fluorine third resin, Resins, epoxy, urethane resin or the acrylic resin.

6. a kind of luminous paint according to claim 1 is characterized in that, described white filler is one or more in titanium dioxide, talcum powder or the lime carbonate.

7. a kind of luminous paint according to claim 1 is characterized in that, described auxiliary agent is one or more in dispersion agent, defoamer, flow agent or the film coalescence aid.

8. a kind of luminous paint according to claim 7 is characterized in that, described dispersion agent is one or more in the modest company 903 of moral, the modest 904S of company of moral, the modest company 926 of moral, BYK161, Sodium hexametaphosphate 99, the Sodium dodecylbenzene sulfonate;

Described defoamer is one or more in BYK066, BYK141, BYK2700, the modest company 5600 of moral;

Described flow agent is one or more in the modest company 433 of BYK358, BYK390, moral, the modest company 495 of moral;

9. prepare the method for the described a kind of luminous paint of claim 1, it is characterized in that, this method may further comprise the steps:

A. prepare nano titanium oxide and coat the luminescent material of handling:

The first step: in proportion fluorocarbon resin, solvent, dispersion agent, nano titanium oxide and luminescent material powder are put into the dispersion cup middling speed and disperseed 30～60 minutes, its rotating speed is 500～800 rev/mins;

Second step:, grind and make the luminescent material that the nano titanium oxide coating is handled 60～80 ℃ of oven dry down;

B. prepare the finished product luminous paint:

The first step: by preset ratio solvent, film-forming resin, white filler, auxiliary agent and nano titanium oxide are coated the luminescent material of handling and join successively in the dispersion machine material-compound tank, middling speed dispersed with stirring 30～60 minutes, its rotating speed is 500～800 rev/mins;

Second step: luminous paint gets product after 80～150 mesh filter screens filter.