CN112625391A

CN112625391A - Novel noctilucent marking agent, preparation method and marking warhead using same

Info

Publication number: CN112625391A
Application number: CN201910947696.1A
Authority: CN
Inventors: 徐华龙; 唐显博; 马小龙; 吴国超; 杨晓亮; 王状熙; 张林峰; 潘家明; 安寒刚; 马金浩
Original assignee: 69007 Troops Of People's Liberation Army Of China
Current assignee: 69007 Troops Of People's Liberation Army Of China
Priority date: 2019-10-08
Filing date: 2019-10-08
Publication date: 2021-04-09
Anticipated expiration: 2039-10-08
Also published as: CN112625391B

Abstract

The invention disclosesThe novel noctilucent marking agent is prepared from the following raw materials in percentage by mass: 0.95% of dihydrocapsaicin, 2% of absolute ethyl alcohol, 22% of fluorescent pigment, 0.2% of rhodamine, 0.85% of sodium hexametaphosphate and 74% of Wake EP707 emulsion; wherein the fluorescent pigment consists of SrCO₃、Al₂O₃、Eu₂O₃、Dy₂O₃、H₃BO₃The fluorescent pigment is prepared from the following components in a mass ratio of 1:1: 0.5: 1: 10, and a silicon dioxide coating film is coated on the surface of the fluorescent pigment, wherein the weight ratio of the silicon dioxide coating film to the fluorescent pigment is 1: 25. The novel noctilucent marking agent can realize three functions of day dyeing, night luminescence and cough stimulation, and meanwhile, the novel noctilucent marking agent has longer coloring time so as to improve the comprehensive efficiency of the fluorescent marking agent; the marking warhead applying the novel noctilucent marking agent is provided with a diffusion device, which is beneficial to increasing the explosive coloring area.

Description

Novel noctilucent marking agent, preparation method and marking warhead using same

Technical Field

The invention relates to a novel noctilucent marking agent, a preparation method and application thereof.

Background

The prior lacrimation shell and dyeing shell have single type and limited effect. The non-lethal bullet has low bullet shell strength, no invasion power and small killing effect on human body, and is widely applied to anti-terrorism and stability maintenance. However, the existing marking bullets are single in type and limited in effect. The dyeing elasticity for the marks has the defects of small coloring range, easy washing after dyeing and short dyeing duration, and the using effect of the dyeing elasticity is influenced by the defects.

Disclosure of Invention

Aiming at the technical defects, the invention aims to provide a novel luminous marking agent, a preparation method and a marking bullet applied by the luminous marking agent.

In order to solve the technical problems, the invention adopts the following technical scheme:

the invention provides a novel noctilucent marking agent which is prepared from the following raw materials in percentage by mass: 0.95% of dihydrocapsaicin, 2% of absolute ethyl alcohol, 22% of fluorescent pigment, 0.2% of rhodamine, 0.85% of sodium hexametaphosphate and 74% of Wake EP707 emulsion; wherein the fluorescent pigment consists of SrCO₃、Al₂O₃、Eu₂O₃、Dy₂O₃、H₃BO₃The fluorescent pigment is prepared from the following components in a mass ratio of 1:1: 0.5: 1: 10, a silicon dioxide coating film is coated on the surface of the fluorescent pigment, and the weight ratio of the silicon dioxide coating film to the fluorescent pigment is 1: 25.

The preparation method of the novel luminous marking agent is characterized by comprising the following steps:

1) preparing a fluorescent pigment: according to SrCO₃:Al₂O₃:Eu₂O₃:Dy₂O₃:H₃BO₃Accurately weighing SrCO according to the mass ratio of 1:1: 0.5: 1: 10%₃、Al₂O₃、Eu₂O₃、Dy₂O₃、H₃BO₃Adding appropriate amount of anhydrous ethanol into an agate mortar, grinding uniformly, mixing, drying, placing into a corundum crucible, placing the corundum crucible into a high-temperature furnace, calcining for 3h under 1300 ℃ weak reducing gas, cooling after the reaction is finished, taking out, grinding and crushing to obtain yellowish green light-emitting SrAl₂O₄:Eu²⁺,Dy³⁺Fluorescent pigment powder;

2) coating with fluorescent pigment: the fluorescent pigment of the alkaline earth metal aluminate system has poor water resistance and can generate hydrolysis reaction when contacting with water:

SrAl

₂0₄+4H ₂0→Sr²⁺+20H-+2Al(OH)₃

in order to prevent the fluorescent pigment from hydrolyzing in the emulsion, the surface of the fluorescent pigment is coated.

Weighing SrAl with formula amount₂O₄:Eu²⁺,Dy³⁺Placing the fluorescent pigment powder into a container, adding ethylene glycol, dispersing for 10 minutes by using ultrasonic waves, transferring into a water bath kettle, and dropwise adding Na with the mass fraction of 16% under the condition of keeping uniform stirring₂SiO₃Adjusting the pH value of the solution and 10% dilute sulfuric acid to 11, heating at the constant temperature of 90 ℃ for 2 hours, cooling the suspension to room temperature after the reaction is finished, and performing suction filtration, washing and drying to obtain the fluorescent pigment coated with the silicon dioxide coating;

3) weighing the following raw materials: 0.95% by mass: 2%: 22%: 0.2%: 0.85%: weighing 74% of dihydrocapsaicin, absolute ethyl alcohol, fluorescent pigment, rhodamine, sodium hexametaphosphate and Wake EP707 emulsion;

4) mixing and stirring: firstly, putting absolute ethyl alcohol with a formula amount into a stirring cylinder, then adding dihydrocapsaicin, stirring to uniformly mix the dihydrocapsaicin and the dihydrocapsaicin, then sequentially adding Wake EP707 emulsion, fluorescent pigment, rhodamine and sodium hexametaphosphate, stirring for 1 minute until the mixture is uniformly mixed, and obtaining a finished product of the novel noctilucent marking agent.

Preferably, the weak reducing gas in the step 1) is 5% H₂+95％N₂。

Use sign warhead of novel night light marking agent, it is stifled including warhead cap and warhead, novel night light marking agent set up in the space that warhead cap and warhead stifled formation, the fixed pivot that is provided with of the stifled inner wall of warhead, the wherein one end of pivot with the stifled fixed connection of warhead, the other end rotates and is provided with a circular slab, the preceding terminal surface of circular slab is equipped with a plurality of guide plate.

Preferably, the guide plates are radial with the axis of the circular plate as the center, the guide plates are perpendicular to the front end face of the circular plate, and the number of the guide plates is four.

The invention has the beneficial effects that: by preparing a light-storing luminescent material, selecting a coloring agent and a stimulating agent, developing a proper fluorescent agent and a releasing mode, three functions of day dyeing, night luminescence and cough stimulation are realized, so that the comprehensive efficiency of the fluorescent marking agent is improved; the marking warhead applying the novel luminous marking agent is provided with a diffusion device, which is beneficial to increasing the explosive coloring area.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without any creative effort.

FIG. 1 is a diagram of a fluorescent generation process by a luminous marking technique;

FIG. 2 is a schematic diagram of the mechanism of coating the surface of fluorescent pigment;

FIG. 3 is a schematic view of a fluorescent pigment surface coating;

FIG. 4 is a graph of gel time versus pH;

FIG. 5 is a graph of water resistance versus pH for samples;

FIG. 6 is a graph of water resistance versus temperature for the samples;

FIG. 7 is a graph of water resistance versus coating time for samples;

FIG. 8 is a graph showing the relationship between water resistance and coating amount of samples;

FIG. 9 is a graph of water resistance performance of samples versus different dispersion media;

FIG. 10 shows SrAl₂0₄：Eu²⁺，Dy³⁺Graph of the relationship between the soaking time and the pH value in water;

FIG. 11 is a graph showing the effect of various factors on the color fastness of reactive dyes;

FIG. 12 is a graph of fluorescence intensity versus fluorescent pigment content;

FIG. 13 is a graph of the effect of fluorescent dye content on the luminescence of fluorescent pigments;

FIG. 14 is a graph showing the effect of capsaicin content on the luminous intensity of a fluorescent pigment;

FIG. 15 is a schematic view of fluorescent pigment cycle luminescence;

FIG. 16 shows SrAl₂0₄：Eu²⁺,Dy³⁺A schematic diagram of a mechanoluminescence mechanism;

FIG. 17 is a plot of mechanoluminescence intensity versus pressure;

FIG. 18 is a schematic view of a garment dyeing principle;

FIG. 19 is a schematic view of the principle of skin staining;

FIG. 20 schematic of a Watt-gram (VAE) emulsion;

fig. 21 is a schematic structural view (a transparent shell) of a novel noctilucent identification bullet provided in the patent embodiment of the present invention;

fig. 22 is a schematic structural view of a circular plate.

Description of reference numerals:

1-bullet cap, 2-bullet block, 3-noctilucent marking agent, 4-rotating shaft, 5-circular plate and 6-guide plate.

Detailed Description

The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying 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.

The novel noctilucent marking agent is prepared from the following raw materials in percentage by mass: 0.95% of dihydrocapsaicin, 2% of absolute ethyl alcohol, 22% of fluorescent pigment, 0.2% of rhodamine, 0.85% of sodium hexametaphosphate and 74% of Wake EP707 emulsion; wherein the fluorescent pigment is formed by SrCO₃、Al₂O₃、Eu₂O₃、Dy₂O₃、H₃BO₃The fluorescent pigment is prepared from the following components in a mass ratio of 1:1: 0.5: 1: 10, and a silicon dioxide coating film is coated on the surface of the fluorescent pigment, wherein the weight ratio of the silicon dioxide coating film to the fluorescent pigment is 1: 25.

The preparation method of the novel luminous marking agent is partially referred to the following documents;

[1] trellier, king pavilion jie, jinyong, sun herd. The thermodynamics research on the surface of the titanium dioxide coated with the silicon oxide nano-film [ J ]. advanced college chemistry bulletin, 9(2001)1543-1545.

[2] Grand beautiful fruit, john bin, wei yu, research on the silicon coating process and formation mechanism of nano-scale titanium dioxide, university journal of north and river (natural science edition), 2002, 26: 298 to 291.

[3] Song dynasty is a well-known name, the color fastness of reactive dyes and their influencing factors, printing and dyeing 2006.11.

[4] The attritor brodifate (english), maryu stutzation, textile dyeing, chinese textile press, 2004.1.l to 14.352.

[5] Li Hongxia, Wu Zan Min, research on dyeing fastness of reactive dye [ J ]. Beijing textile, 2005(4): 35-38.

[6] He Jie Xin Main edition dye chemistry Beijing, Chinese textile Press, 2004(6): 143-144.

[7] The practice of increasing the dyeing fastness is (II) printing and dyeing, 2004(22) 15-20.

[8] Improving the dyeing fastness of the reactive dye of cotton fabrics [ J ] printing and dyeing, 2006(7):2123.

[9] Liu Zheng super, dye application manual, textile industry publication 1995.1

[10] Color index textile industry publication 1995.1

[11] Plum blossom, research on the fastness of the reactive dye to perspiration and light, printing and dyeing, 2007.3.

[12]Nakanishi J,Nakajima T,Ozawa T，et al.Imaging of Conformational Changes Proteins with a New Environment-Sensitive Fluorescent Probe Designed fo Site-Specific Labeling of Recombinant Proteins in Live Cells.Anal.Chem.,20073(13):2920～2928.

[13]Ho N,Weissleder R,Tung C H.Development of water-soluble far-re fluorogenic dyes for enzyme sensing.Tetrahedron,2006,62:578～585.

[14]Stavrianopoulos J G,Elazar R.Labeling reagents comprising aphenylic analog of rhodamine dyes.US.Patent,200424355,2004.

[15]Zhang Y Z,Haugland R P.Xanthylium dyes that are well retained in mitochondria.US.Patent,5686261,1997.

[16]Guilbault G.G.In Practical Fluorescence.Marcel Dekker Inc:New York,1990,Chapter 1.

[17]Aczel，Altila.Determination of Capsaicin content in Red Pepper by HPLC[J].Planar Chromatogr—Mod TLC，1989，2(2)：151～155.

[18] The research and development of the energy storage type luminous paint for the exterior wall of the building, the science and science of the university of teachers and universities in Hunan province.

[19] The Shouzhou light-storing luminescent material and the product chemical industry publisher 2002.10.

[20]YuanHua Lin,Zhimin Dang,Yuan Dang,et al,Studies on mechanoluminesconce from SrAl₂0₄：Eu,Dy phosphor[J].Materials Chemistry and Physics 80(2003)20-22.

[21] Xiazhining, optical analytical chemistry, Chongqing: chongqing university Press, 2004: 112 to 128.

[22] Zhu Shilin Master edition, dyeing and finishing of cellulose fiber products [ M ], Beijing, China textile Press, 2002(8), 157-167.

[23]Stavrianopoulos J G,Elazar R.Labeling reagents comprising aphenylic analogs of rhodamine dyes.US.Patent,200424355,2004.

[24]Ghanadzadeh A,Zanjanchi M A.Self-association of rhodamine dyes in different host materials.Spectrochimica Acta Part A,2001,57(9):1865～1871.

[25]Ghanadzadeh A,Sariri R,Bahrpaima K.Aggregate formation of Rhodamine 6G in anisotropic solvents.Spectrochimica Acta Part A,2001,57(1):155～161.

The method comprises the following steps:

1 preparation of fluorescent pigments

1.1SrAl₂0₄：Eu²⁺，Dy³⁺Synthesis of fluorescent pigments

1.1.1 starting materials and Experimental conditions

The main reagents and drugs used in the experiment are shown in table 1.

TABLE 1 test reagents

Experimental reagent	Grade	Manufacturer of the product
			SrCO₃	Analytical purity	Tianjin chemical reagent three factories
Al₂O₃	Analytical purity	Tianjin chemical reagent three factories
			Eu₂O₃	Chemical purity	KUNMING INSTITUTE OF PRECIOUS METALS
Dy₂O₃	Chemical purity	KUNMING INSTITUTE OF PRECIOUS METALS
			H₃BO₃	Chemical purity	Tianjin chemical reagent three factories
Anhydrous ethanol	Analytical purity	Tianjin university Kewei Co Ltd

1.1.2 Experimental Equipment

The main instruments used in the experiments are shown in table 2.

TABLE 2 Experimental instruments

Device name	Model number	Place of origin and manufacturer
			Electronic balance	AY220	Shimadzu Japan Ltd
Tubular high-temperature furnace	SK-2-2-10	Electric furnace plant for growing sand
			Constant temperature automatic drying box	DL-101-2	TIANJIN ZHONGHUAN EXPERIMENT ELECTRIC STOVE Co.,Ltd.

1.1.3 sample preparation

According to SrCO₃:Al₂O₃:Eu₂O₃:Dy₂O₃:H₃BO₃Accurately weighing SrCO according to the chemical dose ratio of 1:1: 0.5% to 1% to 10%₃、Al₂O₃、Eu₂O₃、Dy₂O₃、H₃BO₃Adding a proper amount of absolute ethyl alcohol into an agate mortar, uniformly grinding, uniformly mixing, drying and placing the raw materials into a corundum crucible, placing the corundum crucible into a high-temperature furnace, and weakly reducing the corundum crucible at 1300 ℃ (5% H)₂+95％N₂) Calcining for 3h, cooling after the reaction is finished, taking out, grinding and crushing to obtain the SrAl emitting yellow green light₂O₄:Eu²⁺,Dy³⁺A fluorescent pigment;

1.2SrAl₂0₄：Eu²⁺，Dy³⁺coating film of fluorescent pigment

The fluorescent pigment of the alkaline earth metal aluminate system has poor water resistance and can generate hydrolysis reaction when contacting with water:

SrAl

₂0₄+4H ₂0→Sr²⁺+20H^-+2Al(OH)₃

1.2.1 Experimental drugs

The main reagents and drugs used in the experiment are shown in Table 3.

TABLE 3 test reagents

Name of article	Rank of	Manufacturer of the product
			Ethylene glycol	Analytical purity	Tianjin Shuiao chemical reagents Limited
Sodium silicate	Analytical purity	Tianjin Shisheng ao chemical reagent Co Ltd
			Sulfuric acid	Chemical purity	Tianjin chemical reagent three factories
Fluorescent pigments	300 mesh	Self-made

1.2.2 Main Instrument

The main equipment used in the experiment is shown in Table 4.

TABLE 4 Experimental instruments

Name of instrument	Model number	Manufacturer of the product
			Electronic balance	AL204	Mettler-Tollido instruments (Shanghai) Co., Ltd
Ultrasonic cleaner	3200H	Shanghai Kudos Ultrasonic Instrument Co.,Ltd.
			Constant temperature water bath kettle	HHS-4S	Shanghai optical and ground instruments & Equipment Ltd
High-power electric stirrer	JJ-1	Medical instrument factory in Jintan city, Jiangsu province
			PH meter	PHS-3C	Shanghai precision instruments science Co., Ltd
Infrared drying instrument	WS70-1	Wurime hardware factory, Shanghai City

1.2.3 silica coating

Silica has excellent properties of acid resistance, water resistance, ultraviolet resistance, organic solvent resistance and the like, is a common inorganic coating material, and is widely applied to the pigment industry. The subject is to use Na₂Si0₃The solution is a coating material. Na (Na)₂Si0₃The orthosilicic acid or low-polymerization-degree hydrated silicon dioxide generated in the presence of acid has small particle sizeThe polymer with high reactivity is adsorbed on the surface of the fluorescent pigment through hydroxyl groups, and is firmly bonded to the hydroxyl groups adsorbed on the surface of the fluorescent pigment, nucleation points are formed on the surface of silicon dioxide, the polymer for generating silicon is rapidly condensed and polymerized on the nucleation points, the dense silicon dioxide coating layer starts to grow along with the continuous polymerization, and finally a continuous silicon dioxide solid film is formed on the surface of the fluorescent pigment particles, as shown in fig. 2 and 3^[1]。

1.2.4 selection of coating conditions

The reaction of the alkaline earth aluminate long afterglow luminescent pigment and water can cause the pH of the solution to rise, so that the coating effect of the sample can be inferred from the change rate of the pH. Weighing a certain mass of SrAl₂0₄：Eu²⁺，Dy³⁺Fluorescent pigment, added into different dispersion media, dispersed for 10 minutes by ultrasonic wave, and then transferred into a water bath. Under the condition of keeping uniform stirring, water glass and 10 percent dilute sulfuric acid are added dropwise, the pH value is adjusted, and the mixture is heated at constant temperature. And after the reaction is finished, cooling the suspension, and performing the processes of suction filtration, washing, drying and the like to obtain the fluorescent pigment product modified by the silicon dioxide coating. The following studies and discussion of the various process parameters were performed, respectively:

(1) influence of the pH value

As shown in FIG. 4, the log gelation time of the silicic acid solution as a function of pH exhibited a complete "N" curve^[2]The highest speed is at the lowest point of the "N" curve (pH 6-8), and the lowest polymerization speed is at the 2 highest points of the "N" curve (pH 3 and pH 10).

FIG. 5 is a graph of pH versus water resistance of the samples, with the coated samples having a poorer water resistance at pH 8 and undergoing hydrolysis in water very rapidly, and the coated samples having an increased water resistance with increasing pH, best at pH l 1. This is because if the PH is too low, the polymerization rate of silicic acid is increased, and the hydrated silicic acid deposited on the surface of the powder particles has a high polymerization degree and a large particle diameter, so that the reactivity is reduced, and the formed coating layer is not dense enough and has poor adhesion. When the pH is high (>11), the polymerization rate of silicic acid is too slow, the settling rate of silica is too slow, and the coating layer is dense but takes too long.

(2) Influence of temperature of the coating

The temperature affects not only the polymerization rate of the hydrated silica but also the settling adsorption process of the hydrated silica on the surface of the fluorescent pigment particles.

FIG. 6 is a graph showing the relationship between temperature and water resistance of a sample, wherein the water resistance of the coated sample is poor at 30 ℃, hydrolysis occurs rapidly in water, the water resistance of the coated sample increases with the increase of temperature, and the coated sample shows good water resistance at a temperature higher than 80 ℃. When the temperature is too low, the reaction activity of the hydrated silicon dioxide is too low, the bonding probability of the hydrated silicon dioxide and metal ions on the surface of the fluorescent pigment body is small, and the hydrated silicon dioxide is mainly precipitated on the surface of powder particles by physical adsorption, so that the formed coating layer is loose.

(3) Effect of envelope time

FIG. 7 is a relation between the coating time and the water resistance of the sample, when the coating time is 0.5h, the water resistance of the coated sample is poor, hydrolysis occurs rapidly in water, the water resistance of the coated sample is enhanced along with the extension of the coating time, and when the coating time reaches 2h, the coated sample has good water resistance. Although the water resistance of the sample is improved by further prolonging the coating time, the efficiency is too low, so that the optimal coating time can be controlled to be 2 h.

(4) Influence of coating amount

The thickness of the silica coating layer is directly influenced by the coating amount, the coating amount is too high, the thickness of the coating layer is too large, the long afterglow luminescence performance of the fluorescent pigment can be influenced although the water resistance is good, and therefore the coating amount still needs to be controlled to be a certain optimal value. FIG. 8 is a graph showing the relationship between the water resistance of samples and the coating amount, and when the samples are not coated (the coating amount is zero), the samples show extremely poor water resistance, and the water resistance of the samples is improved as the coating amount is increased. When the coating amount reaches 4% of the weight of the fluorescent pigment, the sample has good water resistance, so the optimal coating amount is controlled to be about 4%.

(5) Influence of the dispersing Medium

Since fluorescent pigment particles react with water in water, it is important to select a suitable non-aqueous dispersion medium to ensure that both the fluorescent pigment is not attacked and the silica precipitation reaction can occur. FIG. 11 shows the relationship between the water resistance of different dispersion media and the water resistance of the sample, and it can be seen that the water resistance of the obtained fluorescent pigment sample is poor when water or ethanol is used as the dispersion medium. When water is used as a dispersion medium, the fluorescent pigment can react with the water to influence the precipitation of the silicon dioxide on the surface of the powder particles; when ethanol is adopted, due to poor intersolubility of the ethanol and the water glass, the water glass can be precipitated immediately after being added into water, and a compact coating layer cannot be obtained; the ethylene glycol is used as a dispersion medium, so that the side effect of water can be avoided, the intersolubility of the ethylene glycol and the water glass can be ensured, and the precipitation process of the silicon dioxide can be realized. Therefore, ethylene glycol is an ideal dispersion medium.

Through the experiments, the influence of the main coating conditions on the water resistance of the product is determined, and the optimization process conditions are obtained, and are shown in table 5.

TABLE 5 optimal coating conditions

PH	Temperature (. degree.C.)	Reaction time (h)	Coating amount (%)	Medium
					11	90	2	4	Ethylene glycol

(6) Coating effect

100g of fluorescent pigment and 80ml of ethylene glycol were added to a 500ml three-necked flask, 19g of Na₂SiO₃Adding 100ml deionized water to prepare a solution, adding a dropping funnel and connecting with a three-necked flask, adding 20ml 10% sulfuric acid into another dropping funnel and connecting with the three-necked flask, and mechanically stirring under the conditions shown in Table 6 to obtain the coated fluorescent pigment. And respectively placing the coated fluorescent pigment and the non-coated fluorescent pigment in deionized water, and measuring the change of the pH value. As can be seen in FIG. 9, the pH of the coated fluorescent pigment did not change significantly after prolonged immersion in water, but the pH of the uncoated fluorescent pigment changed significantly, indicating that most of the hydrolysis had occurred. FIG. 10 shows that the luminescence of the uncoated fluorescent pigment is significantly weak compared to the luminescence of the coated fluorescent pigment.

2 fluorescent dye selection

The dye matrix and its bonds to the fibres (covalent bonds and intermolecular forces) are of particular importance for dyeing reactive dyes. Relationship between typical influencing factors and color fastness^[3]See fig. 11. It can be seen that the factor causing the discoloration and fading of the color system, which is the dye precursor, is mainly the action of light, or the simultaneous action of light and sweat, and the discoloration and fading occurs by the change or destruction of the color system through a photochemical reaction. As a violence control agent, I pay more attention to the influence of chlorinated water on chromaticity. According to the standard of the color fastness to washing GB/T3921.3-1997 method for testing the color fastness to washing in textile color test and the like, the data of the dye index, the dye application manual and the like are searched^[4-11]The color fastness of the various dyes is shown in Table 6. It can be seen that the reactive dyes of azo structure have high color fastness, but low color fastness to chlorinated water, and are carcinogenic, and are banned in the European Union. Fluorescein appeared yellow but the color fastness was very low. Most of organic compounds having high fluorescence intensity contain aromatic rings or aromatic heterocycles, and the larger the number of aromatic rings, the larger the conjugated system, and fluorescenceThe stronger.

TABLE 6 color fastness of reactive dyes on cotton and viscose fabrics (unit: grade)

Rhodamine molecular structure

Rhodamine belongs to xanthene basic dyes, molecules contain conjugated large pi bond fluorophores, and the molecules have rigid coplanar structures due to the existence of an oxygen bridge between benzene rings, so that the molecular structure stability of the rhodamine is enhanced, strong fluorescence can be generated under the action of exciting light, and the maximum emission wavelength of the rhodamine is positioned in a red visible light region (500-700 nm). Can be used for treating-NH in active group, protein, nucleic acid and other biological macromolecules and monomer molecules₂OH, -SH, etc. form covalent bonds. Compared with other fluorescent dyes, the rhodamine fluorescent dye has the advantages of good photostability, insensitivity to pH, higher fluorescence quantum yield and the like^[12-16]. As a fluorescent probe, rhodamine is used for DNA sequence analysis and labeling of proteins and antibodies.

3 choice of irritant

The combined application of the fluorescent pigment, the fluorescent dye and the irritant can improve the anti-terrorism stability maintaining effect.

TABLE 7 comparison of capsaicin and chloroacetone Properties

Name (R)	Stability of	Irritation property	Physiological Effect	To the environment
					Capsaicine	Is more stable	Is very strong	Cough is the main cause	Friendly to the environment
Phenylchloroacetone	Is very stable	Is very strong	Mainly tear	Is not friendly to environment

At present, most of our army and the foreign army use phenylchloroacetone as a stimulant, but phenylchloroacetone has a stable structure, is not easy to naturally degrade and is not environment-friendly, the stimulation threshold is one 1000 times of that of capsaicin, and the performances of the phenylchloroacetone and the phenylchloroacetone are compared and shown in table 7.

Capsaicin is a generic name for capsaicin and its homologs, all having a common parent nucleus, 4-hydroxy-3-methoxybenzylamide, with the exception of a hydrocarbon radical containing predominantly 8-n carbon atoms. The structure is generally divided into 3 regions, a: an aromatic ring region; b: an amide linkage; c: unsaturated fatty chains. When the carbon atom number of the fatty side chain is 9 (namely capsaicin and dihydrocapsaicin), the pungency is strongest (100%); when the number of carbon atoms is 8, the pungency degree is 75 percent; when the number of carbon atoms is 10, the degree of pungency is 50%. Spicy flavor following itIncrease in the growth of the nonpolar tail chain, at C₉The left and right reach the highest peak and then rapidly decline, which is called C₉The most spicy rule. The piquancy degree is shown in Table 8^[17]。

Capsaicin (Capsaicin):

dihydrocapsaicin (Dihydrocapsaicin):

nordihydrocapsaicin (Dihydrocapsaicin):

high capsaicin (Homocapsaicin):

homodihydrocapsaicin (Homodihydrocapsaicin):

TABLE 8 relative peppery degree of various capsaicinoids^[17]

Capsaicine	Pungency degree (SHU)
		Capsaicin (Capsaicin)	16.1×10⁶
Dihydrocapsaicin (Dihydrocapsaicin)	16.1×10⁶
		Nordihydrocapsaicin (Nordihydrocapsaicin)	9.3×10⁶
High capsaicin (Homocapsaicin)	6.9×10⁶
		High dihydrocapsaicin (Homodihydrocapsaicin)	9.3×10⁶

Dihydrocapsaicin (DC) produced by Qingdao sea chemical industry Co., Ltd is selected as the stimulant.

4 formula of fluorescent marking agent

To ensure safe use, the fluorescent marking agent employs an aqueous solvent. Factors that affect the performance of the tag are: the dosage of the aqueous emulsion, the dosage of the fluorescent pigment and the dosage of the fluorescent dye.

4.1 emulsion selection and dosage

According to literature data and experiments, the film forming speed of the Wake emulsion is found to be high.

The drying time of the emulsion is measured by GB/T1728-79 (89), the emulsion film of 120um is dried in an infrared constant temperature box at 25 ℃, then the surface of the film is touched by fingers at regular intervals, if no emulsion sticks to the hand, the surface is dried, and the time is counted, as shown in Table 9.

TABLE 9 comparison of emulsion filming times

4.2 amount of fluorescent pigment

The fluorescent pigment dosage has great influence on the fluorescence intensity, and theoretically, the brightness of the coating increases with the increase of the fluorescent pigment dosage. The fixed amount of the emulsion was 7g, the content of the fluorescent pigment was increased, and the fluorescence intensity was measured, and the change curve of the emission luminance with the amount of the fluorescent pigment was shown in FIG. 12.

As can be seen from fig. 12, the fluorescence intensity increases as the fluorescent pigment increases. However, the fluorescent pigment is enhanced, so that the emulsion is thickened and is not easy to spray. If the dosage is too high, the viscosity is too high, the release is difficult, and the light transmittance is poor; if the amount is too small, the adhesion is poor. The amount of emissions of the Wake emulsion and the fluorescent pigment mixed in different proportions (pigment ratios) in the high pressure steel cylinder is shown in Table 10. It can be seen that when the face ratio is 22:74:4 (adjuvant), full ejection is possible, so the Wake emulsion dosage is determined to be 74%.

TABLE 10 relationship of fluorescent pigment content to spray amount

Ratio of the facial components	Discharge amount (%)
		0	99.6
12:88	99.6
		16:84	99.6
18:82	99.6
		20:80	99.4
22:78	98.3
		24:76	96.3
26:74	94.4
		28:72	93.2
30:70	90.0
		22:74:4 (auxiliary)	99.5

4.3 fluorescent dye dosage

The mass of the fluorescent pigment and the emulsion are respectively fixed to be 0.1 g, different contents of rhodamine are added, the excitation time is 15 minutes, the illumination is 1000lx, and a PR-305 fluorescent afterglow luminance tester is used for luminance test.

The influence of the content of the fluorescent dye on the brightness of the coating is shown in fig. 13, and the fluorescent dye (rhodamine) has a strong covering effect on the luminescence of the fluorescent pigment, so that the dosage of the fluorescent dye is not suitable to be large, and when the dosage is controlled to be less than 0.2%, the luminescent effects of the fluorescent dye and the fluorescent pigment can be better considered.

4.4 adjuvant selection

4.4.1 antifreeze

The film-forming assistant can make the paint form film well at lower temperature, meet the requirements of freeze thawing stability, reducing film-forming temperature and preventing film cracking, and can be added with film-forming assistant such as ethanol and the like. The ethanol has the effects of preventing freezing and reducing the film forming temperature, can ensure that the fluorescent marking agent is not frozen at the temperature of minus 20 ℃, particularly can prevent a coating film from cracking and falling off at low temperature, and increases the adhesive force. Referring to the dosage of benzyl alcohol in the water-based paint, absolute ethyl alcohol with a lower melting point is selected as an antifreezing agent, and the dosage is 1.8%.

4.4.2 dispersing Agents

The dispersing agent mainly comprises sodium hexametaphosphate and sodium carboxymethyl cellulose, and the sodium carboxymethyl cellulose is easy to coagulate into clusters. The sodium hexametaphosphate can be adsorbed on the surface of the pigment, so that the pigment has the same charges and is mutually repelled, and the pigment particles are kept in an isolated state to achieve uniform dispersion without aggregation and precipitation. When the amount of the dispersant is too small, the dispersing effect is not obtained, and when the amount of the dispersant is too large, the compatibility is lowered. In water-based paints, the sodium hexametaphosphate is generally present in an amount of 0.54%.

4.5 capsaicin

The mass of the fluorescent pigment and the emulsion are respectively fixed to be 0.1 g, capsaicin with different contents is added, the excitation time is 15 minutes, the illumination is 1000lx, and the PR-305 fluorescent afterglow luminance tester is used for luminance test. As shown in fig. 14, capsaicin had little effect on the fluorescence intensity.

With reference to the FKB601 tear-gas charge (35g), the stimulation threshold for capsaicin is 1000 times that of chloroacetone, i.e. 1g capsaicin and 1000g chloroacetone are equally potent. The high pressure steel bottle used for applying can hold 2.5 kilograms of fluorescent marking agent, can be regarded as a FKB601 tear-gas shells charge (35g), and the capsaicin proportion is 1.4%. Because the capsaicine volatilizes along with the ethanol after the application, the influence on the luminescence of the fluorescent pigment is little. The content of capsaicin is 0.95%.

4.6 fluorescent marking agent formula

Through the above experiments, it was determined that the fluorescent marker formulation is shown in table 11. The preparation method comprises dissolving capsaicin in anhydrous ethanol, adding the emulsion, mixing the fluorescent pigment, rhodamine and sodium hexametaphosphate, adding the emulsion, and mechanically stirring for 1 min.

TABLE 11 fluorescent marker formulations

4.7 detection of luminescence Properties

The brightness and afterglow time of strontium europium dysprosium aluminate fluorescent pigment are related to the illumination time, and the strontium europium dysprosium aluminate fluorescent pigment is saturated at 20min under the general sunlight or lamplight and is saturated at 10min under the strong sunlight^[18]。

Crushed ice 100g and NaNO 50g₃And CaCl.6H₂And O is mixed to form a chilled salt bath at-20.3 ℃. 1000g of fluorescent marking agent is prepared according to the table 6, 6g is smeared on 4cm²After 20min of illumination, the cotton cloth is put into a-20.3 ℃ ice salt bath and observed in a dark room. 500g of the mixture was randomly sprayed on the surface of an adult cotton upper garment, and the surface was observed every 30min at night after 20min of irradiation with a fluorescent lamp, as shown in FIG. 20, and the results are shown in Table 12.

TABLE 12 luminescence time of different fluorescent pigments

It can be seen that the luminescence time of the non-coated fluorescent pigment is as short as 1.5 hours, because the non-coated fluorescent pigment has poor water resistance and is liable to undergo hydrolysis reaction to weaken the luminescence property. The luminescence time of the coated fluorescent pigment is about 33 hours, which is basically close to that of the pure fluorescent pigment, and the fluorescent pigment can emit light again after energy storage. The fluorescent marking agent can not freeze and can emit light normally under the condition of low temperature.

5 application mode

According to the principle of luminescence caused by the force of fluorescent pigment (under the action of external force such as pressure, friction and the like), in order to enhance the strength of the fluorescent marking agent and improve the marking performance, the application mode can adopt methods such as high-pressure injection, explosive explosion and the like. The fluorescent marking agent and the capsaicin are compatible for use, and the application method plays a role in marking, enables eyes of people to generate severe pain under the stimulation of the capsaicin, is difficult to endure and achieves the purpose of dispelling.

6 main tactical technical indexes and use requirements

6.1 the persistence of the fluorescent mark is more than or equal to 50 hours;

6.2 fluorescence display distance 50 meters range;

6.3, the environmental adaptability is-30-50 ℃;

6.4 fluorescence intensity > 0.32mcd/m²；

6.5 color fastness > grade 4.

7 discussion of results

7.1 luminescence properties of various long-afterglow fluorescent pigments

In recent years, research on long-afterglow luminescent materials has been rapidly developed, and various novel long-afterglow luminescent materials different in composition, structure, active ions and luminescent color are emerging continuously. There are several categories of sulfides, alkaline earth aluminate systems, alkaline earth silicate systems, titanate series, gallate series, and the like. Table 13 shows the luminescence properties of the various long-afterglow photoluminescent materials^[19]. The afterglow intensity in the table is expressed by the standard light source D specified in JIS (Japanese Industrial standards) Z8720 for a phosphor sample having a thickness of 3mm₆₅After irradiating 1000Lx light for 5min, the afterglow luminance measured 10min later and 60min later, respectively; and the afterglow time afterglow intensity is attenuated to 0.32mcd/m²The elapsed time.

TABLE 13 luminescence properties of various long-afterglow fluorescent pigments^[19]

As can be seen from the table, SrAl₂0₄：Eu²⁺，Dy³⁺The long afterglow luminescent material has the highest luminous brightness and afterglow time. Generally, the wavelength of light to which the human visual nerve is most sensitive is 510nm in a dark place and 550nm in a bright place, and yellowish green light having a peak of 520nm in a light emission spectrum is the brightest color light seen with the naked eye. Strontium europium dysprosium aluminate (SrAl)₂0₄：Eu² ⁺，Dy³⁺) Has a peak at 520nm, is a "green" fluorescent pigment with high quantum conversion, excitation emission spectrum, long afterglow, stability and durability, and no radioactive elements, and can allow the cycle of absorption-storage-emission-absorption-re-absorption to proceed indefinitely (FIG. 15). Therefore, the subject selects strontium europium dysprosium aluminate as the fluorescent pigment. 7.2 luminescent mechanism of rare earth activated aluminate long afterglow fluorescent pigment

Luminescence is the process by which energy absorbed in some way is converted into light radiation inside a substance. The rare earth excited long afterglow luminescent material is a kind of long afterglow luminescent material developed in the last decade. Scholars at home and abroad have carried out a great deal of research work on the light-emitting machine, put forward various models and make a lot of explanations^[19]. However, due to the complexity of the problems involved, various explanations have some drawbacks and deficiencies, and no completely consistent conclusion has been reached so far. The luminescence mechanism model with a large influence is as follows: hole transfer model and configuration coordinate model, etc. But at least the following consensus has been achieved: eu-doped²⁺Is a luminescent center; the addition of co-doped trivalent rare earth ions has important influence on the long afterglow performance; electrons and holes generated during excitation are respectively captured by the electron trap and the hole trap; the recombination of electrons and holes trapped by the thermally perturbed sag trap results in long persistence light emission.

7.2.1 photoluminescence mechanism

Under the excitation of light, the matrix ions absorb energy and transmit the energy to the luminescence center Eu²⁺Or the light-emitting central ions directly absorb energy and then generate photoionization to generate electron-hole pairs. Under the action of electrostatic attraction, electrons and holes generated in the photoionization process enter a potential electron trap and a potential hole trap respectively, so that electron capture and hole capture are formed, when the electron trap and the hole trap are far away, electrons are released from the electron trap and jump to a conduction band under thermal excitation, then jump to the hole trap from the conduction band, are compounded with the holes, and simultaneously, energy is transferred to a light-emitting center to enable the light-emitting center to be excited by light.

7.2.2 mechanoluminescence mechanism

The fluorescent pigment can emit visible light with certain intensity under the action of external force such as friction, pressure and the like, and the phenomenon is mechanoluminescence. The long afterglow luminescence mechanism is the same as that of aluminate-based luminescent material^[20]When external force such as pressure and friction is applied to the luminescent material, mechanical energy is converted into heat energy, the holes trapped by the hole trap are excited by heat and released, and then the luminescent material is in a metastable state (Eu)⁺¹) Recombine and convert to another metastable state (Eu)²⁺) Finally, the Eu returns to Eu again after relaxation²⁺While accompanying the emission of light (fig. 16).

The larger the applied force, the more heat energy is generated, the more probability that the trapped electrons or holes are excited and released from the trap is increased, the higher the thermal excitation rate of the electrons and holes, the faster the recombination rate of the electrons and holes, and the stronger the intensity of the force luminescence (fig. 17). Therefore, this subject is to employ high-pressure jet discharge.

7.3 fluorescent dye luminescence and dyeing principle

7.3.1 fluorescent dye luminescence principle

When ultraviolet or visible light is irradiated on some substances, the substances emit light with a wavelength and intensity different from those of the irradiated light, and when the irradiation of the irradiated light is stopped, the light is immediately or gradually disappeared, and the fluorescence is obtained.

The process of fluorescence generation is shown in FIG. 1^[21]. In general, the fluorescent dye molecule is inThe ground state, after absorbing light, the molecule is in an electronic excited state, the ground state and the excited state are both singlet state and triplet state, and the ground state of most organic molecules is in the singlet state. With S₀、S₁、S₂Respectively representing the ground state, the first excited singlet state and the second excited singlet state of the molecule, and the energy is from low to high. By T₁、T₂Representing a first excited state and a second excited state of the triplet state, respectively. Electrons in the molecule from the ground state singlet S₀Transition to excited singlet state S₁、 S₂… … occurs relatively easily and proceeds very quickly (about 10)^-4Second) while from the ground state singlet state to the excited state triplet state does not readily occur. High energy singlet excited state molecules (S)₂) Can collide with other molecules of the same type or solvent molecules and return to the lowest energy level S of the excited state by internal transition (radiationless transition)₁This process is 10^-12Second, the lifetime of the molecule at the lowest energy level of the excited state is generally 10^-4～10^-8They emit photons back to the ground state, and the light produced is fluorescence.

7.3.2 principle of staining with fluorescent dyes

The clothes are dyed by van der Waals force, hydrogen bond, ionic bond, covalent bond and dative bond between fiber and dye molecule^[22]As shown in fig. 18. The skin is stained by active groups penetrating cell membrane and-NH in biological macromolecules such as protein and nucleic acid and monomer molecules₂Form covalent bonds with-OH, -SH, etc^[23-25]As shown in fig. 19.

7.4 fluorescent pigments and fluorescent dyes

When there is light, the two pigments are excited simultaneously, and the fluorescent dye is mainly red because the luminous intensity is much higher than that of the fluorescent pigment; when there is no light at night, the fluorescent pigment releases its stored light, and a part of it is absorbed by a red fluorescent dye (rhodamine) and converted into orange-red light, thereby exhibiting composite light. The weaker the yellow-green light of rhodamine is due to the coverage of rhodamine on fluorescent pigments, the stronger the yellow-green fluorescence is when the rhodamine content is low. The fluorescent pigment to fluorescent dye ratio is shown in table 14.

TABLE 14 comparison of fluorescent pigments with fluorescent dyes

7.5 use of the emulsions

The fluorescent pigment must be attached to the human body to enable identification. The Tile emulsion has good matching performance with the fluorescent pigment, the fluorescent pigment can be uniformly dispersed in the tile emulsion, the transparency is good, the impurity content is low, no other color tones exist, the transparent tile emulsion can better display the luminous effect, and the tile emulsion is quick to dry, difficult to wash off, and difficult to burn and explode. The Wake emulsion belongs to an oil-in-water (O/W) VAE emulsion, is mainly prepared by copolymerizing vinyl acetate (VAc) and ethylene monomers serving as basic raw materials by an emulsion polymerization method (figure 20), is nontoxic and tasteless, green and environment-friendly, and has excellent adhesive force on a plurality of materials. Since the fluorescent pigment is insoluble in water and the fluorescent dye is soluble in water, the Wake emulsion can disperse and dissolve both. The surface drying time can also be shortened by adding alcohol and reducing the moisture content.

7.6 application of Anhydrous ethanol

The application of absolute ethyl alcohol has four functions of diluting the emulsion, quickly drying the emulsion, dissolving capsaicin and preventing freezing. When the spraying amount of the emulsion and the fluorescent pigment is 78:22, the spraying amount is 98 percent, and the spraying amount is 99 percent at most after the addition of the auxiliary agent such as absolute ethyl alcohol and the like; according to the report of foreign patents, the proportion of water in the emulsion is reduced and the surface drying speed of the emulsion is improved by adding alcohols which have high volatilization speed and are mutually soluble with water to replace water. The emulsion with high solid content is added with ethanol, so that the surface drying speed is improved; the capsaicin is not easy to dissolve in the aqueous emulsion, and the solubility of the capsaicin is improved by adding the absolute ethyl alcohol; the melting point of the absolute ethyl alcohol is-114 ℃, and the absolute ethyl alcohol can be prevented from freezing under the low-temperature condition after being added. In contrast, benzyl alcohol and ethylene glycol can also be used as antifreeze, but both have poor solubility for capsaicin.

8 conclusion

1. The fluorescent marking agent is composed of fluorescent pigment, fluorescent dye, capsaicin, emulsion and the like, integrates three functions of day dyeing, night luminescence and cough stimulation, shows red color in the day and yellow light in the night, can repeatedly and circularly emit light, and realizes all-weather fluorescent dyeing and marking.

2. The strontium aluminate fluorescent pigment is synthesized by taking the rare earth element europium ion as a luminescence center and taking the rare earth element dysprosium as an auxiliary activator, and is subjected to coating treatment, so that the fluorescent pigment has better water resistance, stronger luminous bright background and longer afterglow time, and the night marking effect is enhanced.

3. The developed fluorescent dye taking rhodamine as a main agent has strong ability of penetrating cell membranes, high color fastness, high dyeing speed, no fading after washing and obvious daytime marking effect.

4. The German Wake VAE emulsion is used as a film forming agent, so that the film forming time is shortened, the fluorescent pigment is firmly attached to clothes and skin, and the film is not easy to peel off, safe and environment-friendly.

5. The anhydrous ethanol is used as an auxiliary agent, so that the problems of low solubility of capsaicin and easiness in freezing of the emulsion under the low-temperature condition are solved, the rapid drying of the emulsion is further promoted, and the method is environment-friendly.

6. The fluorescence intensity is enhanced by applying the mechanoluminescence principle and adopting high-pressure injection application, and the operation is simple.

As shown in fig. 21 to 22, use sign warhead of novel night light marking agent, including warhead cap 1 and warhead stifled 2, night light marking agent 3 sets up in the space that warhead cap 1 and warhead stifled 2 formed, the fixed pivot 4 that is provided with of warhead stifled 2 inner walls, one of them one end and the stifled 2 fixed connection of warhead of pivot 4, the other end rotates and is provided with a plectane 5, the preceding terminal surface of plectane 5 is equipped with four guide plates 6, guide plate 6 is radially taking the axis of plectane 5 as the center, guide plate 6 perpendicular to plectane 5.

The working principle of the marking warhead is as follows: when the bullet cap collides with clothes, the luminous marking agent splashes to the clothes, and simultaneously, due to the inertia effect, the circular plate starts to rotate at the moment that the bullet cap bursts, and the guide plate drives the luminous marking agent to diffuse around by taking the axis of the rotating shaft as the center, so that the coloring area is enlarged.

It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is intended to include such modifications and variations.

Claims

1. The novel luminous marking agent is characterized by being prepared from the following raw materials in percentage by mass: 0.95% of dihydrocapsaicin, 2% of absolute ethyl alcohol, 22% of fluorescent pigment, 0.2% of rhodamine, 0.85% of sodium hexametaphosphate and 74% of Wake EP707 emulsion; wherein the fluorescent pigment consists of SrCO₃、Al₂O₃、Eu₂O₃、Dy₂O₃、H₃BO₃The fluorescent pigment is prepared from the following components in a mass ratio of 1:1: 0.5: 1: 10, and a silicon dioxide coating film is coated on the surface of the fluorescent pigment, wherein the weight ratio of the silicon dioxide coating film to the fluorescent pigment is 1: 25.

2. The preparation method of the novel luminous marking agent is characterized by comprising the following steps:

1) preparing a fluorescent pigment: according to SrCO₃:Al₂O₃:Eu₂O₃:Dy₂O₃:H₃BO₃Accurately weighing SrCO according to the mass ratio of 1:1: 0.5: 1: 10%₃、Al₂O₃、Eu₂O₃、Dy₂O₃、H₃BO₃Adding a proper amount of absolute ethyl alcohol into an agate mortar, uniformly grinding, uniformly mixing, drying and placing the raw materials into a corundum crucible, placing the corundum crucible into a high-temperature furnace, calcining for 3 hours at 1300 ℃ under weak reducing gas, taking out after the reaction is finished and cooling, grinding and crushing to obtain the SrAl emitting yellow green light₂O₄:Eu²⁺,Dy³⁺Fluorescent pigment powder;

2) coating with fluorescent pigment: weighing SrAl with formula amount₂O₄:Eu²⁺,Dy³⁺Placing the fluorescent pigment powder into a container, adding ethylene glycol,dispersing for 10 minutes by ultrasonic waves, then transferring the mixture into a water bath kettle, and dropwise adding Na with the mass fraction of 16% under the condition of keeping uniform stirring₂SiO₃Adjusting the pH value of the solution and 10% dilute sulfuric acid to 11, heating at the constant temperature of 90 ℃ for 2 hours, cooling the suspension to room temperature after the reaction is finished, and performing suction filtration, washing and drying to obtain the fluorescent pigment coated with the silicon dioxide coating;

3. The method for preparing a novel luminous marking agent as claimed in claim 2, characterized in that the weak reducing gas in step 1) is 5% H₂+95％N₂。

4. Use sign warhead of novel night light marking agent, including warhead cap and warhead stifled, its characterized in that, novel night light marking agent set up in the space that warhead cap and warhead stifled formation, the fixed pivot that is provided with of the stifled inner wall of warhead, the wherein one end of pivot with the stifled fixed connection of warhead, other end rotate and are provided with a plectane, the preceding terminal surface of plectane is equipped with a plurality of guide plate.

5. The identification warhead of claim 4, wherein said baffles are radial about the axis of said circular plate, perpendicular to the front face of said circular plate and the number of baffles is four.