CN112940431B - Laser-induced fluorescence emission composition and patterned fluorescence emission method - Google Patents

Laser-induced fluorescence emission composition and patterned fluorescence emission method Download PDF

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CN112940431B
CN112940431B CN202110154996.1A CN202110154996A CN112940431B CN 112940431 B CN112940431 B CN 112940431B CN 202110154996 A CN202110154996 A CN 202110154996A CN 112940431 B CN112940431 B CN 112940431B
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dichloroquinacridone
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CN112940431A (en
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周涛
彭小燕
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Sichuan University
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3437—Six-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J3/00—Processes of treating or compounding macromolecular substances
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C08K5/3447—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
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    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate
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    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates

Abstract

The invention relates to the technical field of fluorescent materials, in particular to a laser-induced fluorescence emission composition and a patterned fluorescence emission method. The composition provided by the invention comprises the following components in parts by weight: 0.01-10 parts of organic pigment; 90-99.99 parts of polymer resin. The polymer resin is a resin with a chain segment containing ester groups or hydroxyl groups. The invention adopts the following method to obtain the patterned fluorescence emission: irradiating the surface of the composition with laser light to form an irradiated area; the laser irradiated areas of the composition are then induced with ultraviolet light to cause the laser irradiated areas to produce fluorescent emissions. The method is simple and convenient to operate, safe, environment-friendly and low in energy consumption, is very suitable for industrial large-scale production, and has a good application prospect.

Description

Laser-induced fluorescence emission composition and patterned fluorescence emission method
Technical Field
The invention relates to the technical field of fluorescent materials, in particular to a laser-induced fluorescence emission composition and a patterned fluorescence emission method.
Background
The anti-counterfeiting mark can be pasted, printed by a national 315 product anti-counterfeiting inquiry center, pasted on the surface of an article or an accessory of a package (such as a commodity hang tag, a qualification certificate and an anti-counterfeiting certificate card) and has an anti-counterfeiting function. The existing anti-counterfeiting marks are mostly formed by adding various color-changeable masks on the surfaces of products.
At present, the anti-counterfeiting measures include traditional printing technologies such as water drop color change (or disappearance), high-temperature color change (or disappearance), ray burying, ultraviolet irradiation color change (or disappearance) and the like, and digital anti-counterfeiting technologies such as two-dimensional codes, inquiry codes and the like. The technique of ultraviolet radiation color change (or disappearance) is generally to use molecules with fluorescent properties that are one color in visible light and another fluorescent color due to the fluorescence emission that occurs in ultraviolet light.
However, the common anti-counterfeiting mark as a printed matter has a mature preparation technology and a too simple manufacturing technology, which results in that it is easily imitated and loses the anti-counterfeiting function. Therefore, there is a need to develop new anti-counterfeit mark manufacturing techniques.
Because the laser has both photo-thermal and thermal effects, generally speaking, after the polymer is irradiated by the laser with certain energy, the form, segment and crystallization degree of the polymer can be changed. In recent years, the interaction between laser and polymer has attracted much attention, and it has been applied to the fields of laser marking, laser writing technology, selective laser sintering, and the like. Since the appearance of a polymer after laser irradiation is related to various process conditions such as the composition and laser irradiation parameters, it is difficult to simulate the polymer. If the method of processing the polymer by laser is applied to the anti-counterfeiting mark, the difficulty of imitating the anti-counterfeiting mark can be greatly increased. However, the polymer parts produced by laser processing have no discoloration function and cannot be directly used as anti-counterfeiting marks.
Organic pigment molecules may be added to these polymers in order to impart a color-changing function to the polymer articles produced by laser processing. However, most organic pigment molecules can only show strong fluorescence emission in a very dilute solution, and the fluorescence emission is weakened or even completely disappeared in a high-concentration solution or solid state, which is called aggregation-induced quenching. It is very difficult to obtain a fluorescent emitting material in a solid state due to the problem of aggregation induced quenching.
For example, quinacridone molecules have five aromatic heterocyclic rings, and are conjugated in the molecules to form a large pi bond, so that the molecules have a planar rigid structure and cannot rotate, and meanwhile, continuous hydrogen bonds and pi-pi interactions exist among the quinacridone molecules, and the strong interactions cause the quinacridone molecules to be densely stacked, so that severe fluorescence quenching is caused, the luminous efficiency is low, and fluorescence emission cannot be realized in a solid state. This limits the application of quinacridone molecules. Similarly, pyrrolopyrroledione pigments and benzimidazolone pigments have a common problem.
Due to aggregation state induced quenching phenomenon, the mixture obtained after the organic pigment molecules and the polymer are simply selected and simply mixed and solidified cannot generate fluorescence emission phenomenon. Therefore, the polymer produced by laser processing at present cannot be applied to the manufacture of anti-counterfeiting marks.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a laser-induced fluorescence emission composition and a patterned fluorescence emission method, and aims to provide a laser-induced fluorescence emission composition and a patterned fluorescence emission method, which are characterized in that: the composition of the polymer and the organic pigment is irradiated by laser, and further induced by ultraviolet light, so that patterned fluorescence emission can be generated in a laser irradiation area. Therefore, the purpose that the polymer material generates fluorescence emission under laser irradiation is realized in a very simple and rapid mode.
The laser-induced fluorescence emission composition is characterized by comprising the following components in parts by weight: 0.01-10 parts of organic pigment; 90-99.99 parts of polymer resin;
the organic pigment is at least one selected from quinacridone pigments, pyrrolopyrroledione pigments and benzimidazolone pigments.
Preferably, the composition consists of the following components in parts by weight: 0.01-5 parts of organic pigment; 95-99.99 parts of polymer resin;
preferably: 0.01-1 part of organic pigment; 99-99.99 parts of polymer resin;
more preferably: 0.1-0.5 part of organic pigment; 99.5 to 99.9 portions of polymer resin.
Preferably, the molecular chain of the polymer resin contains ester groups and/or hydroxyl groups; preferably, the polymer resin having an ester group is at least one selected from the group consisting of polyvinyl acetate, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polyester elastomer, polybutylene succinate-terephthalate, polybutylene succinate-adipate, polymethacrylate-butadiene-styrene copolymer, styrene-acrylonitrile-acrylate copolymer, methacrylate-styrene copolymer, and methacrylate-butadiene-styrene copolymer.
Preferably, the quinacridone pigment is at least one of 5, 12-dihydro-quino [2,3-B ] acridine-7, 14-dione, 2, 9-dimethylquinacridone, 2, 9-dichloroquinacridone, 4, 11-dichloroquinacridone, 3, 10-dichloroquinacridone, 1, 8-dichloroquinacridone;
preferably, the pyrrolopyrroledione-based pigment is at least one of bis (m-acrylobenzene) 1, 4-pyrrolopyrroledione, 3, 6-bis (4-tert-butylphenyl) -2, 5-dihydropyrrolo [3,4-c ] pyrrole-1, 4-dione, bis (p-chlorophenyl) -1, 4-diketopyrrolopyrrole, 3, 6-diphenyl-2, 5-dihydropyrrolo [3,4-c ] pyrrole-1, 4-dione, 3, 6-bis (4-phenyl) -2, 5-dihydro-pyrrolo [3,4-c ] pyrrole-1, 4-dione, 3, 6-bis (4-methylphenyl) -2, 5-dihydro-pyrrolo [3,4-c ] pyrrole-1, 4-dione;
preferably, the benzimidazolone based pigment is 2- [ [1- [ [ (2, 3-dihydro-2-oxo-1H-benzimidazol-5-yl) amino ] formyl ] -2-oxopropyl ] azo ] benzoic acid, N- (2, 3-dihydro-2-oxo-1H-benzimidazol-5-yl) -3-oxo-2- [ [2- (trifluoromethyl) phenyl ] azo ] butanamide, dimethyl 2- [ [1- [ [ (2, 3-dihydro-2-oxo-1H-benzimidazol-5-yl) amino ] carbonyl ] -2-oxopropyl ] azo ] -1, 4-benzenedicarboxylate, dimethyl 2,2' - [1, 2-bis (oxy-2, 1-phenyleneazo) ] bis [ N- (2, 3-dihydro-2-oxo-1H-benzimidazol) -5-yl ] -3-oxo-butanamide, N- [4- (aminocarbonyl) phenyl ] -4- [ [1 (2, 3-dihydro-2-oxo-1H-benzimidazol-5-yl) -5-yl ] -3-oxo-butanamide, 4- (aminocarbonyl) phenyl ] -4- [ [1 (2, 3-dihydro-2-oxo-1H-benzimidazol-5-yl) -5-yl ] -1H-oxo-amino ] azo ] benzamide, N- [4- (4-amino ] carbonyl ] amide, 10-5-oxo-phenyl ] amide: 5,6] benzimidazolo [2,1-A ] isoquinoline-7, 11-dione, 2- [ (4-chloro-2-nitrophenyl) azo ] -N- (2, 3-dihydro-2-oxo-1H-benzimidazol-5-yl) -3-oxobutanamide, N- (2, 3-dihydro-2-oxo-5-benzimidazole) -3-hydroxy-4- [ [ 2-methoxy-5-methyl-4- [ (methylamino) sulfonyl ] phenyl ] diazo ] naphthalene-2-carboxamide.
Preferably, the composition is a powder, sheet, plate, bar or film material.
The invention also provides a preparation method of the composition, which comprises the following steps: mixing organic pigment with polymer resin, blending, extruding, granulating and injection molding to obtain the pigment; preferably, the temperature in the blending and extrusion process is 180-270 ℃; the injection temperature is 180-270 ℃.
The invention also provides a preparation method of the composition, which comprises the following steps: sequentially dissolving polymer resin and organic pigment in a solvent to prepare a membrane material, and volatilizing the solvent to obtain the composite pigment; preferably, the weight ratio of the organic pigment to the solvent is 0.00001:1 to 1:1.
the invention also provides a laser-induced patterned fluorescence emission method, which is characterized by comprising the following steps of:
(1) Taking the composition, and irradiating the surface of the composition by using laser to form an irradiation area;
(2) And irradiating the irradiation area by using ultraviolet light, so that the laser irradiation area can generate fluorescence emission.
Preferably, the laser is selected from the group consisting of near-infrared laser, green laser, ultraviolet laser, CO 2 One or a combination of two or more of laser and excimer laser; preferably, the laser is CO 2 Laser; further preferably, the CO is 2 The wavelength of the laser is 9.3-10.6 μm;
and/or the laser is continuous laser or pulse laser;
and/or the power of the laser is 1.8-80W, and the scanning speed of the laser is 1-10000 mm/s; preferably, the power of the laser is 5-70W, and the scanning speed of the laser is 1000mm/s; more preferably, the power of the laser is 5 to 50W, the scanning speed of the laser is 1000mm/s, and the frequency of the laser is 20kHz.
And/or the wavelength of the ultraviolet light is 365-395 nm; preferably, the ultraviolet light wavelength is 365nm.
The present invention also provides a solid fluorescent emission material prepared by irradiating the composition according to any one of claims 1 to 6 with laser light;
preferably, the laser is selected from near infrared laser, green laser, ultraviolet laser, CO 2 One or a combination of two or more of laser and excimer laser; preferably, the laser is CO 2 Laser; further preferably, said CO 2 The wavelength of the laser is 9.3-10.6 μm;
preferably, the laser is a continuous laser or a pulse laser;
preferably, the power of the laser is 1.8-80W, and the scanning speed of the laser is 1-10000 mm/s; preferably, the power of the laser is 5-70W, and the scanning speed of the laser is 1000mm/s; more preferably, the power of the laser is 5 to 50W, the scanning speed of the laser is 1000mm/s, and the frequency of the laser is 20kHz.
The invention also provides the use of the above composition or emissive material in the manufacture of a security marking.
The invention disperses organic pigment which is originally aggregation state induced quenching (ACQ) in a solid state in a solid composition to ensure that the solid composition has the characteristic of strong fluorescence emission. The method breaks the conventional that plane rigid organic pigment molecules cannot emit fluorescence in a solid state, and widens the application range of the organic pigment. On the other hand, the invention realizes the generation of fluorescence emission on the polymer resin and also expands the application range of the polymer resin. Therefore, the invention has very good industrial application prospect. In addition, the method of the present invention is a method of producing strong patterned fluorescent emission by irradiating a polymer resin and organic pigment composition with a laser and then exciting with an ultraviolet lamp. Has application potential in the anti-counterfeiting field.
In a preferred technical scheme, the invention optimizes the types and the dosage ratios of the polymer resin and the organic pigment molecules, and optimizes parameters such as wavelength, power, scanning speed and the like of a laser. Experiments have shown that the compositions of the present invention are capable of producing a strong patterned fluorescence emission in the preferred embodiment, whereas the compositions have a weak or no fluorescence emission intensity outside the scope of the preferred embodiment.
Definitions of terms used in connection with the present invention: the initial definitions provided herein for a group or term apply to that group or term throughout the specification unless otherwise indicated; for terms not specifically defined herein, the meanings that would be afforded to them by a person skilled in the art, in light of the disclosure and context, should be given.
Fluorescence emission is the process by which a fluorescent molecule fluoresces. The process specifically comprises the following steps: after the fluorescent molecule absorbs energy, the ground state electrons are excited to a singlet excited state and then return from the first singlet excited state to the ground state, releasing energy in the form of a photon.
Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Drawings
FIG. 1 is a scheme for passing CO 2 A photograph in visible light of the composition of example 39 after laser irradiation;
FIG. 2 is a photograph of the composition of example 39 after irradiation with laser light under a 365nm ultraviolet lamp.
Wherein the laser emitter is pulsed CO 2 Laser device(ii) a The wavelength is 9.3 μm; marking speed (scanning speed of laser) 1000mm/s; the laser power was 10W and the laser pulse frequency was 20kHz.
Detailed Description
The raw materials and equipment used in the embodiment of the present invention are known products and commercially available products.
(1) The device information used by the present invention is as follows:
injection molding machine, model K-TEC 40, manufactured by Miracolon International Inc.; an adjustable film applicator, model KTQ-II, manufactured by Shanghai Liangyan Intelligent science and technology Limited; CO 2 2 The laser marking machine has a model BK-C30, the maximum power of a laser is 100W, the laser wavelength is 9.3 mu m, and the variable range of the laser pulse frequency is 1-200kHz. Manufactured by mark laser technology (Hangzhou) Inc.; a 365nm ultraviolet lamp with power of 3-5W.
(2) The raw materials used to prepare the composition of the present invention have the following specific information:
2, 9-dichloroquinacridone: guangzhou Yulong chemical Co., ltd; dichloromethane: chengdu Kolon Chemicals Co., ltd, AR, the content is not less than 99.5%; polymethyl methacrylate (PMMA): win Chuangdegusai, 8N; polymethyl methacrylate (PMMA): taiwan, qimei, CM-211; polymethyl methacrylate (PMMA): mitsubishi yang, mf001; polymethyl methacrylate (PMMA): acalma, france, V020; polycarbonate (PC): kesichuang, makrolon 6557; polycarbonate (PC): taiwan Chimei, wonderlitf PC-175; polyethylene terephthalate (PET): teleweaving industry, CB-602; polybutylene terephthalate (PBT): basf, germany, PBT B41000; polyvinyl alcohol (PVA-1788): exploration platform, AR; and (3) water.
Example 1
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin (b): polymethyl methacrylate (PMMA) win sandUGETASHIC, 8N;
putting 99.9 weight parts of polymethyl methacrylate and 0.1 weight part of 2, 9-dichloroquinacridone into a high-speed mixer to be uniformly mixed; adding the mixed materials into a double-screw extruder for blending and extrusion, granulating the extruded materials, and then performing injection molding to obtain a plate, wherein the temperature in the blending and extrusion processing process is controlled to be 180-230 ℃; the injection temperature is controlled between 180 ℃ and 230 ℃.
Carrying out laser irradiation on the composite board by adopting the following conditions: the wavelength of the carbon dioxide laser is 9.3 mu m, the marking speed is 1000mm/s, the laser power is 10W, and the laser frequency is 20kHz.
After laser irradiation, a 365nm ultraviolet lamp is used for irradiating the whole plate, and whether fluorescence is generated in the irradiated area of the laser is visually observed. The fluorescence intensity was visually classified as:
Figure SMS_1
in the evaluation of fluorescence intensity, "it" means no fluorescence emission, and the larger the "-" number, the stronger the fluorescence intensity.
The effect of fluorescent labeling is shown in Table 1.
Example 2
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin (b): polymethylmethacrylate (PMMA) win engenderdiose, 8N;
putting 99.5 parts by weight of polymethyl methacrylate and 0.5 part by weight of 2, 9-dichloroquinacridone into a high-speed mixer to be uniformly mixed; adding the mixed materials into a double-screw extruder for blending and extruding, granulating the extruded materials and then injecting the granulated materials into a plate, wherein the temperature in the blending and extruding process is controlled to be 180-230 ℃; the injection temperature is controlled between 180 ℃ and 230 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 3
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polymethyl methacrylate (PMMA) win sandUGETASHIC, 8N;
putting 95 parts by weight of polymethyl methacrylate and 5 parts by weight of 2, 9-dichloroquinacridone into a high-speed mixer and uniformly mixing; adding the mixed materials into a double-screw extruder for blending and extruding, granulating the extruded materials and then injecting the granulated materials into a plate, wherein the temperature in the blending and extruding process is controlled to be 180-230 ℃; the injection temperature is controlled between 180 ℃ and 230 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 4
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin (b): polymethyl methacrylate (PMMA) win sandUGETASHIC, 8N;
putting 90 parts by weight of polymethyl methacrylate and 10 parts by weight of 2, 9-dichloroquinacridone into a high-speed mixer to be uniformly mixed; adding the mixed materials into a double-screw extruder for blending and extrusion, granulating the extruded materials, and then performing injection molding to obtain a plate, wherein the temperature in the blending and extrusion processing process is controlled to be 180-230 ℃; the injection temperature is controlled between 180 ℃ and 230 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 5
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin (b): polymethyl methacrylate (PMMA) win sandUGETASHIC, 8N;
putting 85 parts by weight of polymethyl methacrylate and 15 parts by weight of 2, 9-dichloroquinacridone into a high-speed mixer, and uniformly mixing; adding the mixed materials into a double-screw extruder for blending and extruding, granulating the extruded materials and then injecting the granulated materials into a plate, wherein the temperature in the blending and extruding process is controlled to be 180-230 ℃; the injection temperature is controlled between 180 ℃ and 230 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 6
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polymethylmethacrylate (PMMA) win engenderdiose, 8N;
putting 80 parts by weight of polymethyl methacrylate and 20 parts by weight of 2, 9-dichloroquinacridone into a high-speed mixer, and uniformly mixing; adding the mixed materials into a double-screw extruder for blending and extruding, granulating the extruded materials and then injecting the granulated materials into a plate, wherein the temperature in the blending and extruding process is controlled to be 180-230 ℃; the injection temperature is controlled between 180 ℃ and 230 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 7
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin (b): polymethyl methacrylate (PMMA) Chinesemei, taiwan, CM-211;
putting 99.9 weight parts of polymethyl methacrylate and 0.1 weight part of 2, 9-dichloroquinacridone into a high-speed mixer to be uniformly mixed; adding the mixed materials into a double-screw extruder for blending and extrusion, granulating the extruded materials, and then performing injection molding to obtain a plate, wherein the temperature in the blending and extrusion processing process is controlled to be 180-230 ℃; the injection temperature is controlled between 180 ℃ and 230 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 8
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polymethyl methacrylate (PMMA), taiwan, curio, CM-211;
putting 99.5 parts by weight of polymethyl methacrylate and 0.5 part by weight of 2, 9-dichloroquinacridone into a high-speed mixer to be uniformly mixed; adding the mixed materials into a double-screw extruder for blending and extruding, granulating the extruded materials and then injecting the granulated materials into a plate, wherein the temperature in the blending and extruding process is controlled to be 180-230 ℃; the injection temperature is controlled between 180 ℃ and 230 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 9
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polymethyl methacrylate (PMMA), taiwan, curio, CM-211;
putting 95 parts by weight of polymethyl methacrylate and 5 parts by weight of 2, 9-dichloroquinacridone into a high-speed mixer and uniformly mixing; adding the mixed materials into a double-screw extruder for blending and extrusion, granulating the extruded materials, and then performing injection molding to obtain a plate, wherein the temperature in the blending and extrusion processing process is controlled to be 180-230 ℃; the injection temperature is controlled between 180 ℃ and 230 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 10
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polymethyl methacrylate (PMMA), taiwan, curio, CM-211;
putting 90 parts by weight of polymethyl methacrylate and 10 parts by weight of 2, 9-dichloroquinacridone into a high-speed mixer to be uniformly mixed; adding the mixed materials into a double-screw extruder for blending and extrusion, granulating the extruded materials, and then performing injection molding to obtain a plate, wherein the temperature in the blending and extrusion processing process is controlled to be 180-230 ℃; the injection temperature is controlled between 180 ℃ and 230 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 11
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polymethyl methacrylate (PMMA) Chinesemei, taiwan, CM-211;
putting 85 parts by weight of polymethyl methacrylate and 15 parts by weight of 2, 9-dichloroquinacridone into a high-speed mixer, and uniformly mixing; adding the mixed materials into a double-screw extruder for blending and extruding, granulating the extruded materials and then injecting the granulated materials into a plate, wherein the temperature in the blending and extruding process is controlled to be 180-230 ℃; the injection temperature is controlled between 180 ℃ and 230 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 12
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin (b): polymethyl methacrylate (PMMA), taiwan, curio, CM-211;
putting 80 parts by weight of polymethyl methacrylate and 20 parts by weight of 2, 9-dichloroquinacridone into a high-speed mixer to be uniformly mixed; adding the mixed materials into a double-screw extruder for blending and extrusion, granulating the extruded materials, and then performing injection molding to obtain a plate, wherein the temperature in the blending and extrusion processing process is controlled to be 180-230 ℃; the injection temperature is controlled between 180 ℃ and 230 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 13
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polymethyl methacrylate (PMMA) santong mitsubishi yang, MF001;
putting 99.9 weight parts of polymethyl methacrylate and 0.1 weight part of 2, 9-dichloroquinacridone into a high-speed mixer to be uniformly mixed; adding the mixed materials into a double-screw extruder for blending and extruding, granulating the extruded materials and then injecting the granulated materials into a plate, wherein the temperature in the blending and extruding process is controlled to be 180-230 ℃; the injection temperature is controlled between 180 ℃ and 230 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 14
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polymethyl methacrylate (PMMA) santoprene mitsubishi, MF001;
putting 99.5 parts by weight of polymethyl methacrylate and 0.5 part by weight of 2, 9-dichloroquinacridone into a high-speed mixer, and uniformly mixing; adding the mixed materials into a double-screw extruder for blending and extrusion, granulating the extruded materials, and then performing injection molding to obtain a plate, wherein the temperature in the blending and extrusion processing process is controlled to be 180-230 ℃; the injection temperature is controlled between 180 ℃ and 230 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 15
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin (b): polymethyl methacrylate (PMMA) santong mitsubishi yang, MF001;
95 parts by weight of polymethyl methacrylate and 5 parts by weight of 2, 9-dichloroquinacridone are placed in a high-speed mixer and uniformly mixed; adding the mixed materials into a double-screw extruder for blending and extruding, granulating the extruded materials and then injecting the granulated materials into a plate, wherein the temperature in the blending and extruding process is controlled to be 180-230 ℃; the injection temperature is controlled between 180 ℃ and 230 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 16
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin (b): polymethyl methacrylate (PMMA) santoprene mitsubishi, MF001;
putting 90 parts by weight of polymethyl methacrylate and 10 parts by weight of 2, 9-dichloroquinacridone into a high-speed mixer, and uniformly mixing; adding the mixed materials into a double-screw extruder for blending and extrusion, granulating the extruded materials, and then performing injection molding to obtain a plate, wherein the temperature in the blending and extrusion processing process is controlled to be 180-230 ℃; the injection temperature is controlled between 180 ℃ and 230 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 17
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polymethyl methacrylate (PMMA) santong mitsubishi yang, MF001;
putting 85 parts by weight of polymethyl methacrylate and 15 parts by weight of 2, 9-dichloroquinacridone into a high-speed mixer, and uniformly mixing; adding the mixed materials into a double-screw extruder for blending and extrusion, granulating the extruded materials, and then performing injection molding to obtain a plate, wherein the temperature in the blending and extrusion processing process is controlled to be 180-230 ℃; the injection temperature is controlled between 180 ℃ and 230 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 18
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin (b): polymethyl methacrylate (PMMA) santong mitsubishi yang, MF001;
putting 80 parts by weight of polymethyl methacrylate and 20 parts by weight of 2, 9-dichloroquinacridone into a high-speed mixer to be uniformly mixed; adding the mixed materials into a double-screw extruder for blending and extrusion, granulating the extruded materials, and then performing injection molding to obtain a plate, wherein the temperature in the blending and extrusion processing process is controlled to be 180-230 ℃; the injection temperature is controlled between 180 ℃ and 230 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 19
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin (b): polymethyl methacrylate (PMMA) french arkema, V020;
putting 99.9 weight parts of polymethyl methacrylate and 0.1 weight part of 2, 9-dichloroquinacridone into a high-speed mixer to be uniformly mixed; adding the mixed materials into a double-screw extruder for blending and extrusion, granulating the extruded materials, and then performing injection molding to obtain a plate, wherein the temperature in the blending and extrusion processing process is controlled to be 180-230 ℃; the injection temperature is controlled between 180 ℃ and 230 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 20
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin (b): polymethyl methacrylate (PMMA) french arkema, V020;
putting 99.5 parts by weight of polymethyl methacrylate and 0.5 part by weight of 2, 9-dichloroquinacridone into a high-speed mixer to be uniformly mixed; adding the mixed materials into a double-screw extruder for blending and extruding, granulating the extruded materials and then injecting the granulated materials into a plate, wherein the temperature in the blending and extruding process is controlled to be 180-230 ℃; the injection temperature is controlled between 180 ℃ and 230 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 21
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polymethyl methacrylate (PMMA) french arkema, V020;
uniformly mixing 95 parts by weight of polymethyl methacrylate and 15 parts by weight of 2, 9-dichloroquinacridone in a high-speed mixer; adding the mixed materials into a double-screw extruder for blending and extruding, granulating the extruded materials and then injecting the granulated materials into a plate, wherein the temperature in the blending and extruding process is controlled to be 180-230 ℃; the injection temperature is controlled between 180 ℃ and 230 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 22
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polymethyl methacrylate (PMMA) french arkema, V020;
putting 90 parts by weight of polymethyl methacrylate and 10 parts by weight of 2, 9-dichloroquinacridone into a high-speed mixer to be uniformly mixed; adding the mixed materials into a double-screw extruder for blending and extrusion, granulating the extruded materials, and then performing injection molding to obtain a plate, wherein the temperature in the blending and extrusion processing process is controlled to be 180-230 ℃; the injection temperature is controlled between 180 ℃ and 230 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 23
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polymethyl methacrylate (PMMA) french arkema, V020;
putting 85 parts by weight of polymethyl methacrylate and 15 parts by weight of 2, 9-dichloroquinacridone into a high-speed mixer, and uniformly mixing; adding the mixed materials into a double-screw extruder for blending and extrusion, granulating the extruded materials, and then performing injection molding to obtain a plate, wherein the temperature in the blending and extrusion processing process is controlled to be 180-230 ℃; the injection temperature is controlled between 180 ℃ and 230 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 24
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polymethyl methacrylate (PMMA) french arkema, V020;
putting 80 parts by weight of polymethyl methacrylate and 20 parts by weight of 2, 9-dichloroquinacridone into a high-speed mixer, and uniformly mixing; adding the mixed materials into a double-screw extruder for blending and extrusion, granulating the extruded materials, and then performing injection molding to obtain a plate, wherein the temperature in the blending and extrusion processing process is controlled to be 180-230 ℃; the injection temperature is controlled between 180 ℃ and 230 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 25
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polycarbonate (PC) kesichuang, makrolon 6557;
putting 99.9 parts by weight of polycarbonate and 0.1 part by weight of 2, 9-dichloroquinacridone into a high-speed mixer and uniformly mixing; adding the mixed materials into a double-screw extruder for blending and extrusion, granulating the extruded materials, and then performing injection molding to obtain a plate, wherein the temperature in the blending and extrusion processing process is controlled to be 180-270 ℃; the injection temperature is controlled between 180 ℃ and 270 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 26
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin (b): polycarbonate (PC) kesichuang, makrolon 6557;
putting 99.5 parts by weight of polycarbonate and 0.5 part by weight of 2, 9-dichloroquinacridone into a high-speed mixer and uniformly mixing; adding the mixed materials into a double-screw extruder for blending and extruding, granulating the extruded materials and then injecting the granulated materials into a plate, wherein the temperature in the blending and extruding process is controlled to be 180-270 ℃; the injection temperature is controlled between 180 ℃ and 270 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 27
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin (b): polycarbonate (PC) kesichuang, makrolon 6557;
95 parts by weight of polycarbonate and 0.5 part by weight of 2, 9-dichloroquinacridone are placed in a high-speed mixer and uniformly mixed; adding the mixed materials into a double-screw extruder for blending and extruding, granulating the extruded materials and then injecting the granulated materials into a plate, wherein the temperature in the blending and extruding process is controlled to be 180-270 ℃; the injection temperature is controlled between 180 ℃ and 270 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 28
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polycarbonate (PC) kesichuang, makrolon 6557;
putting 90 parts by weight of polycarbonate and 10 parts by weight of 2, 9-dichloroquinacridone into a high-speed mixer and uniformly mixing; adding the mixed materials into a double-screw extruder for blending and extruding, granulating the extruded materials and then injecting the granulated materials into a plate, wherein the temperature in the blending and extruding process is controlled to be 180-270 ℃; the injection temperature is controlled between 180 ℃ and 270 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 29
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polycarbonate (PC) kesichuang, makrolon 6557;
putting 85 parts by weight of polycarbonate and 15 parts by weight of 2, 9-dichloroquinacridone into a high-speed mixer and uniformly mixing; adding the mixed materials into a double-screw extruder for blending and extruding, granulating the extruded materials and then injecting the granulated materials into a plate, wherein the temperature in the blending and extruding process is controlled to be 180-270 ℃; the injection temperature is controlled between 180 ℃ and 270 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 30
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polycarbonate (PC) kesichu, makrolon 6557;
putting 80 parts by weight of polycarbonate and 20 parts by weight of 2, 9-dichloroquinacridone into a high-speed mixer and uniformly mixing; adding the mixed materials into a double-screw extruder for blending and extruding, granulating the extruded materials and then injecting the granulated materials into a plate, wherein the temperature in the blending and extruding process is controlled to be 180-270 ℃; the injection temperature is controlled between 180 ℃ and 270 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 31
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polycarbonate (PC) Chi Mei, taiwan, WONDERLITF PC-175;
putting 99.9 parts by weight of polycarbonate and 0.1 part by weight of 2, 9-dichloroquinacridone into a high-speed mixer and uniformly mixing; adding the mixed materials into a double-screw extruder for blending and extrusion, granulating the extruded materials, and then performing injection molding to obtain a plate, wherein the temperature in the blending and extrusion processing process is controlled to be 180-270 ℃; the injection temperature is controlled between 180 ℃ and 270 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 32
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polycarbonate (PC) Chi Mei, taiwan, WONDERLITF PC-175;
putting 99.5 parts by weight of polycarbonate and 0.5 part by weight of 2, 9-dichloroquinacridone into a high-speed mixer and uniformly mixing; adding the mixed materials into a double-screw extruder for blending and extrusion, granulating the extruded materials, and then performing injection molding to obtain a plate, wherein the temperature in the blending and extrusion processing process is controlled to be 180-270 ℃; the injection temperature is controlled between 180 ℃ and 270 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 33
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polycarbonate (PC) Chi Mei, taiwan, WONDERLITF PC-175;
putting 95 parts by weight of polycarbonate and 5 parts by weight of 2, 9-dichloroquinacridone into a high-speed mixer and uniformly mixing; adding the mixed materials into a double-screw extruder for blending and extruding, granulating the extruded materials and then injecting the granulated materials into a plate, wherein the temperature in the blending and extruding process is controlled to be 180-270 ℃; the injection temperature is controlled between 180 ℃ and 270 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 34
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin (b): polycarbonate (PC) Chi Mei, taiwan, WONDERLITF PC-175;
putting 90 parts by weight of polycarbonate and 10 parts by weight of 2, 9-dichloroquinacridone into a high-speed mixer and uniformly mixing; adding the mixed materials into a double-screw extruder for blending and extrusion, granulating the extruded materials, and then performing injection molding to obtain a plate, wherein the temperature in the blending and extrusion processing process is controlled to be 180-270 ℃; the injection temperature is controlled between 180 ℃ and 270 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 35
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin (b): polycarbonate (PC) Chi Mei, taiwan, WONDERLITF PC-175;
putting 85 parts by weight of polycarbonate and 15 parts by weight of 2, 9-dichloroquinacridone into a high-speed mixer and uniformly mixing; adding the mixed materials into a double-screw extruder for blending and extruding, granulating the extruded materials and then injecting the granulated materials into a plate, wherein the temperature in the blending and extruding process is controlled to be 180-270 ℃; the injection temperature is controlled between 180 ℃ and 270 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 36
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polycarbonate (PC) Chi Mei, taiwan, WONDERLITF PC-175;
putting 80 parts by weight of polycarbonate and 20 parts by weight of 2, 9-dichloroquinacridone into a high-speed mixer and uniformly mixing; adding the mixed materials into a double-screw extruder for blending and extruding, granulating the extruded materials and then injecting the granulated materials into a plate, wherein the temperature in the blending and extruding process is controlled to be 180-270 ℃; the injection temperature is controlled between 180 ℃ and 270 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 37
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polyethylene terephthalate (PET) spunlace industry, CB-602;
95 parts by weight of polyethylene terephthalate and 5 parts by weight of 2, 9-dichloroquinacridone are placed in a high-speed mixer and uniformly mixed; adding the mixed materials into a double-screw extruder for blending and extruding, granulating the extruded materials and then injecting the granulated materials into a plate, wherein the temperature in the blending and extruding process is controlled to be 180-230 ℃; the injection temperature is controlled between 180 ℃ and 230 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 38
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin (b): polybutylene terephthalate (PBT), basf, germany, PBT B41000;
95 parts by weight of polybutylene terephthalate and 5 parts by weight of 2, 9-dichloroquinacridone are placed in a high-speed mixer and uniformly mixed; adding the mixed materials into a double-screw extruder for blending and extruding, granulating the extruded materials and then injecting the granulated materials into a plate, wherein the temperature in the blending and extruding process is controlled to be 180-230 ℃; the injection temperature is controlled between 180 ℃ and 230 ℃.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 39
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polymethyl methacrylate (PMMA) win sandUGETASHIC, 8N;
dichloromethane: gemini Colone chemical Co., ltd, the content of AR is more than or equal to 99.5%;
dissolving 99 parts by weight of polymethyl methacrylate in 500 parts by weight of dichloromethane solution, weighing 1 part by weight of 2, 9-dichloroquinacridone after the polymethyl methacrylate is completely dissolved, adding the 2, 9-dichloroquinacridone into the dichloromethane solution, stirring the mixture at room temperature for 1 hour, and preparing the mixture into a film material by using an adjustable film coating machine. After the solvent is volatilized, the film is subjected to laser irradiation under the following conditions: the wavelength of the carbon dioxide laser is 9.3 mu m, the marking speed is 1000mm/s, the laser power is 10W, and the laser frequency is 20kHz.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 40
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polymethyl methacrylate (PMMA) Chinesemei, taiwan, CM-211;
dichloromethane: chengdu Kolon Chemicals Co., ltd, AR, the content is not less than 99.5%;
dissolving 99 parts by weight of polymethyl methacrylate in 500 parts by weight of dichloromethane solution, weighing 1 part by weight of 2, 9-dichloroquinacridone after the polymethyl methacrylate is completely dissolved, adding the 2, 9-dichloroquinacridone into the dichloromethane solution, stirring the mixture at room temperature for 1 hour, and preparing the mixture into a film material by using an adjustable film coating machine. After the solvent is volatilized
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
EXAMPLE 41
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polymethyl methacrylate (PMMA) santoprene mitsubishi, MF001;
dichloromethane: gemini Colone chemical Co., ltd, the content of AR is more than or equal to 99.5%;
dissolving 99 parts by weight of polymethyl methacrylate in 500 parts by weight of dichloromethane solution, weighing 1 part by weight of 2, 9-dichloroquinacridone after the polymethyl methacrylate is completely dissolved, adding the 2, 9-dichloroquinacridone into the dichloromethane solution, stirring the mixture at room temperature for 1 hour, and preparing the mixture into a film material by using an adjustable film coating machine. After the solvent is volatilized
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 42
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin (b): polymethyl methacrylate (PMMA) french arkema, V020;
dichloromethane: chengdu Kolon Chemicals Co., ltd, AR, the content is not less than 99.5%;
99 parts by weight of polymethyl methacrylate is dissolved in 500 parts by weight of dichloromethane solution, after the dissolution is completed, 1 part by weight of 2, 9-dichloroquinacridone is weighed and added, the mixture is stirred for 1 hour at room temperature, and then the mixture is made into a film material by an adjustable film coating device. After the solvent is volatilized
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 43
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polycarbonate (PC): kosi wound Makrolon 6557;
dichloromethane: chengdu Kolon Chemicals Co., ltd, AR, the content is not less than 99.5%;
dissolving 99 parts by weight of polycarbonate in 500 parts by weight of dichloromethane solution, weighing 1 part by weight of 2, 9-dichloroquinacridone after the polycarbonate is completely dissolved, stirring for 1 hour at room temperature, and preparing the mixture into a film material by using an adjustable film coating device. After the solvent is volatilized
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 44
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin (b): polycarbonate (PC) Qimei, taiwan, WONDERLITF PC-175;
dichloromethane: gemini Colone chemical Co., ltd, the content of AR is more than or equal to 99.5%;
dissolving 99 parts by weight of polycarbonate in 500 parts by weight of dichloromethane solution, weighing 1 part by weight of 2, 9-dichloroquinacridone after the polycarbonate is completely dissolved, stirring for 1 hour at room temperature, and preparing the mixture into a film material by using an adjustable film coating device. After the solvent is volatilized
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 45
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polyvinyl alcohol (PVA-1788);
dissolving 99 parts by weight of polyvinyl alcohol in 400 parts by weight of aqueous solution, weighing 1 part by weight of 2, 9-dichloroquinacridone after the polyvinyl alcohol is completely dissolved, stirring for 1 hour at room temperature, and preparing the mixture into a film material by using an adjustable film coating device. After the solvent is volatilized
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 46
Pyrrolopyrrole-dione-based pigment: bis (p-chlorophenyl) -1, 4-diketopyrrolopyrroles;
polymer resin (b): polyvinyl alcohol (PVA-1788);
dissolving 99 parts by weight of polyvinyl alcohol in 400 parts by weight of aqueous solution, weighing 1 part by weight of bis (p-chlorophenyl) -1, 4-diketopyrrolopyrrole and adding the solution after the solution is completely dissolved, stirring for 1 hour at room temperature, and preparing the mixture into a membrane material by using an adjustable membrane coater. After the solvent is volatilized
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 47
Benzimidazolone pigment: n- (2, 3-dihydro-2-oxo-1H-benzimidazol-5-yl) -3-oxo-2- [ [2- (trifluoromethyl) phenyl ] azo ] butanamide;
polymer resin: polyvinyl alcohol (PVA-1788);
dissolving 99 parts by weight of polyvinyl alcohol in 400 parts by weight of aqueous solution, weighing 1 part by weight of N- (2, 3-dihydro-2-oxo-1H-benzimidazol-5-yl) -3-oxo-2- [ [2- (trifluoromethyl) phenyl ] azo ] butanamide, adding the mixture into the aqueous solution after the polyvinyl alcohol is completely dissolved, stirring the mixture at room temperature for 1 hour, and preparing the mixture into a membrane material by using an adjustable coating device. After the solvent is volatilized
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 48
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin (b): polymethylmethacrylate (PMMA) win engenderdiose, 8N;
dichloromethane: chengdu Kolon Chemicals Co., ltd, AR, the content is not less than 99.5%;
99.90 parts by weight of polymethyl methacrylate is dissolved in 500 parts by weight of methylene chloride solution, after the methyl methacrylate is completely dissolved, 0.10 part by weight of 2, 9-dichloroquinacridone is weighed and added, stirred for 1 hour at room temperature, and then the mixture is made into a film material by an adjustable film coater. After the solvent is volatilized, the film is subjected to laser irradiation under the following conditions: the wavelength of the carbon dioxide laser is 9.3 mu m, the marking speed is 1000mm/s, the laser power is 10W, and the laser frequency is 20kHz.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 49
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polymethylmethacrylate (PMMA) win engenderdiose, 8N;
dichloromethane: chengdu Kolon Chemicals Co., ltd, AR, the content is not less than 99.5%;
99.95 parts by weight of polymethyl methacrylate is dissolved in 500 parts by weight of methylene chloride solution, after the methyl methacrylate is completely dissolved, 0.05 part by weight of 2, 9-dichloroquinacridone is weighed and added, stirred for 1 hour at room temperature, and then the mixture is made into a film material by an adjustable film coater. After the solvent is volatilized, the film is subjected to laser irradiation under the following conditions: the wavelength of the carbon dioxide laser is 9.3 mu m, the marking speed is 1000mm/s, the laser power is 10W, and the laser frequency is 20kHz.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 50
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin (b): polymethylmethacrylate (PMMA) win engenderdiose, 8N;
dichloromethane: gemini Colone chemical Co., ltd, the content of AR is more than or equal to 99.5%;
dissolving 99.96 weight parts of polymethyl methacrylate in 500 weight parts of dichloromethane solution, weighing 0.04 weight part of 2, 9-dichloroquinacridone after the polymethyl methacrylate is completely dissolved, adding the 2, 9-dichloroquinacridone into the dichloromethane solution, stirring the mixture at room temperature for 1 hour, and preparing the mixture into a film material by using an adjustable film coater. After the solvent is volatilized, the film is subjected to laser irradiation under the following conditions: the wavelength of the carbon dioxide laser is 9.3 mu m, the marking speed is 1000mm/s, the laser power is 10W, and the laser frequency is 20kHz.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 51
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polymethylmethacrylate (PMMA) win engenderdiose, 8N;
dichloromethane: gemini Colone chemical Co., ltd, the content of AR is more than or equal to 99.5%;
99.97 parts by weight of polymethyl methacrylate is dissolved in 500 parts by weight of methylene chloride solution, after the methyl methacrylate is completely dissolved, 0.03 part by weight of 2, 9-dichloroquinacridone is weighed and added, stirred for 1 hour at room temperature, and then the mixture is made into a film material by an adjustable film coater. After the solvent is volatilized, the film is subjected to laser irradiation under the following conditions: the wavelength of the carbon dioxide laser is 9.3 mu m, the marking speed is 1000mm/s, the laser power is 10W, and the laser frequency is 20kHz.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 52
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polymethylmethacrylate (PMMA) win engenderdiose, 8N;
dichloromethane: chengdu Kolon Chemicals Co., ltd, AR, the content is not less than 99.5%;
99.98 parts by weight of polymethyl methacrylate is dissolved in 500 parts by weight of dichloromethane solution, 0.02 part by weight of 2, 9-dichloroquinacridone is weighed and added after the polymethyl methacrylate is completely dissolved, the mixture is stirred for 1 hour at room temperature, and then the mixture is made into a membrane material by an adjustable membrane coater. After the solvent is volatilized, the film is subjected to laser irradiation under the following conditions: the wavelength of the carbon dioxide laser is 9.3 mu m, the marking speed is 1000mm/s, the laser power is 10W, and the laser frequency is 20kHz.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 53
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polymethylmethacrylate (PMMA) win engenderdiose, 8N;
dichloromethane: gemini Colone chemical Co., ltd, the content of AR is more than or equal to 99.5%;
99.99 parts by weight of polymethyl methacrylate is dissolved in 500 parts by weight of methylene chloride solution, after the complete dissolution, 0.01 part by weight of 2, 9-dichloroquinacridone is weighed and added, stirred for 1 hour at room temperature, and then the mixture is made into a film material by an adjustable film coater. After the solvent is volatilized, the film is subjected to laser irradiation under the following conditions: the wavelength of the carbon dioxide laser is 9.3 mu m, the marking speed is 1000mm/s, the laser power is 10W, and the laser frequency is 20kHz.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Example 54
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polymethylmethacrylate (PMMA) win engenderdiose, 8N;
dichloromethane: gemini Colone chemical Co., ltd, the content of AR is more than or equal to 99.5%;
99.999 weight portions of polymethyl methacrylate is dissolved in 500 weight portions of dichloromethane solution, after the methyl methacrylate is completely dissolved, 0.001 weight portion of 2, 9-dichloroquinacridone is weighed and added, the mixture is stirred for 1 hour at room temperature, and then the mixture is made into a film material by an adjustable film coater. After the solvent is volatilized, the film is subjected to laser irradiation under the following conditions: the wavelength of the carbon dioxide laser is 9.3 mu m, the marking speed is 1000mm/s, the laser power is 10W, and the laser frequency is 20kHz.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Comparative example 1
Perylene-based pigments: 3,4,9,10-perylenetetracarboxylic dianhydride;
polymer resin (b): polymethylmethacrylate (PMMA) win engenderdiose, 8N;
dichloromethane: gemini Colone chemical Co., ltd, the content of AR is more than or equal to 99.5%;
dissolving 99 parts by weight of polymethyl methacrylate in 500 parts by weight of dichloromethane solution, weighing 1 part by weight of 3,4,9, 10-perylenetetracarboxylic dianhydride after the polymethyl methacrylate is completely dissolved, adding the weighed mixture into the dichloromethane solution, stirring the mixture at room temperature for 1 hour, and preparing the mixture into a membrane material by using an adjustable membrane coater. After the solvent is volatilized, the film is subjected to laser irradiation under the following conditions: the wavelength of the carbon dioxide laser is 9.3 mu m, the marking speed is 1000mm/s, the laser power is 10W, and the laser frequency is 20kHz.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Comparative example 2
Indanthrone-based pigment: 6, 15-dihydrodianthrapyridazine-5, 9,14, 18-tetraone;
polymer resin (b): polymethylmethacrylate (PMMA) win engenderdiose, 8N;
dichloromethane: gemini Colone chemical Co., ltd, the content of AR is more than or equal to 99.5%;
99 parts by weight of polymethyl methacrylate is dissolved in 500 parts by weight of dichloromethane solution, after the complete dissolution, 1 part by weight of 6, 15-dihydrodianthrapyridazine-5, 9,14, 18-tetraone is weighed and added, the mixture is stirred for 1 hour at room temperature, and then the mixture is made into a membrane material by an adjustable membrane coater. After the solvent is volatilized, the film is subjected to laser irradiation under the following conditions: the wavelength of the carbon dioxide laser is 9.3 mu m, the marking speed is 1000mm/s, the laser power is 10W, and the laser frequency is 20kHz.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Comparative example 3
Azo pigments: n- (4-chloro-2-methylphenyl) -2- [ (4-chloro-2-nitrophenyl) azo ] -3-oxobutanamide;
polymer resin (b): polymethylmethacrylate (PMMA) win engenderdiose, 8N;
dichloromethane: gemini Colone chemical Co., ltd, the content of AR is more than or equal to 99.5%;
dissolving 99 parts by weight of polymethyl methacrylate in 500 parts by weight of dichloromethane solution, weighing 1 part by weight of N- (4-chloro-2-methylphenyl) -2- [ (4-chloro-2-nitrophenyl) azo ] -3-oxobutanamide after the polymethyl methacrylate is completely dissolved, adding the mixture into the dichloromethane solution, stirring the mixture at room temperature for 1 hour, and preparing the mixture into a membrane material by using an adjustable membrane coater. After the solvent is volatilized, the film is subjected to laser irradiation under the following conditions: the wavelength of the carbon dioxide laser is 9.3 mu m, the marking speed is 1000mm/s, the laser power is 10W, and the laser frequency is 20kHz.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Comparative example 4
Isoindole pigment: 3,3' - [ (2-methyl-1, 3-phenylene) diimino ] bis [4,5,6, 7-tetrachloro-1H-isoindol-1-one ];
polymer resin (b): polymethylmethacrylate (PMMA) win engenderdiose, 8N;
dichloromethane: gemini Colone chemical Co., ltd, the content of AR is more than or equal to 99.5%;
99 parts by weight of polymethyl methacrylate is dissolved in 500 parts by weight of dichloromethane solution, after the dissolution is completed, 1 part by weight of 3,3' - [ (2-methyl-1, 3-phenylene) diimino ] bis [4,5,6, 7-tetrachloro-1H-isoindol-1-one ] is weighed and added, the mixture is stirred for 1 hour at room temperature, and then the mixture is made into a membrane material by an adjustable membrane coater. After the solvent is volatilized, the film is subjected to laser irradiation under the following conditions: the wavelength of the carbon dioxide laser is 9.3 mu m, the marking speed is 1000mm/s, the laser power is 10W, and the laser frequency is 20kHz.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Comparative example 5
Phthalocyanine pigment: 4316 pigment phthalocyanine blue B4G;
polymer resin: polymethylmethacrylate (PMMA) win engenderdiose, 8N;
dichloromethane: chengdu Kolon Chemicals Co., ltd, AR, the content is not less than 99.5%;
dissolving 99 parts by weight of polymethyl methacrylate in 500 parts by weight of dichloromethane solution, weighing 1 part by weight of 4316 pigment phthalocyanine blue B4G after the polymethyl methacrylate is completely dissolved, adding the mixture into the dichloromethane solution, stirring the mixture for 1 hour at room temperature, and preparing the mixture into a membrane material by using an adjustable membrane coater. After the solvent is volatilized, the film is subjected to laser irradiation under the following conditions: the wavelength of the carbon dioxide laser is 9.3 mu m, the marking speed is 1000mm/s, the laser power is 10W, and the laser frequency is 20kHz.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Comparative example 6
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin (b): polymethylmethacrylate (PMMA) win engenderdiose, 8N;
dichloromethane: gemini Colone chemical Co., ltd, the content of AR is more than or equal to 99.5%;
dissolving 99 parts by weight of polymethyl methacrylate in 500 parts by weight of dichloromethane solution, weighing 1 part by weight of 2, 9-dichloroquinacridone after the polymethyl methacrylate is completely dissolved, adding the 2, 9-dichloroquinacridone into the dichloromethane solution, stirring the mixture at room temperature for 1 hour, and preparing the mixture into a film material by using an adjustable film coating machine. After the solvent is volatilized, the film is subjected to laser irradiation under the following conditions: the wavelength of the carbon dioxide laser is 9.3 mu m, the marking speed is 1000mm/s, the laser power is 1.8W, and the laser frequency is 20kHz.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Comparative example 7
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin (b): polymethylmethacrylate (PMMA) win engenderdiose, 8N;
dichloromethane: chengdu Kolon Chemicals Co., ltd, AR, the content is not less than 99.5%;
99 parts by weight of polymethyl methacrylate is dissolved in 500 parts by weight of dichloromethane solution, after the dissolution is completed, 1 part by weight of 2, 9-dichloroquinacridone is weighed and added, the mixture is stirred for 1 hour at room temperature, and then the mixture is made into a film material by an adjustable film coating device. After the solvent is volatilized, the film is subjected to laser irradiation under the following conditions: the wavelength of the carbon dioxide laser is 9.3 mu m, the marking speed is 1000mm/s, the laser power is 1.7W, and the laser frequency is 20kHz.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Comparative example 8
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polymethylmethacrylate (PMMA) win engenderdiose, 8N;
dichloromethane: chengdu Kolon Chemicals Co., ltd, AR, the content is not less than 99.5%;
99 parts by weight of polymethyl methacrylate is dissolved in 500 parts by weight of dichloromethane solution, after the dissolution is completed, 1 part by weight of 2, 9-dichloroquinacridone is weighed and added, the mixture is stirred for 1 hour at room temperature, and then the mixture is made into a film material by an adjustable film coating device. After the solvent is volatilized, the film is subjected to laser irradiation under the following conditions: the wavelength of the carbon dioxide laser is 9.3 mu m, the marking speed is 1000mm/s, the laser power is 1.5W, and the laser frequency is 20kHz.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Comparative example 9
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polymethylmethacrylate (PMMA) win engenderdiose, 8N;
dichloromethane: chengdu Kolon Chemicals Co., ltd, AR, the content is not less than 99.5%;
dissolving 99 parts by weight of polymethyl methacrylate in 500 parts by weight of dichloromethane solution, weighing 1 part by weight of 2, 9-dichloroquinacridone after the polymethyl methacrylate is completely dissolved, adding the 2, 9-dichloroquinacridone into the dichloromethane solution, stirring the mixture at room temperature for 1 hour, and preparing the mixture into a film material by using an adjustable film coating machine. After the solvent is volatilized, the film is subjected to laser irradiation under the following conditions: the wavelength of the carbon dioxide laser is 9.3 mu m, the marking speed is 1000mm/s, the laser power is 75W, and the laser frequency is 20kHz.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Comparative example 10
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polymethylmethacrylate (PMMA) win engenderdiose, 8N;
dichloromethane: gemini Colone chemical Co., ltd, the content of AR is more than or equal to 99.5%;
99 parts by weight of polymethyl methacrylate is dissolved in 500 parts by weight of dichloromethane solution, after the dissolution is completed, 1 part by weight of 2, 9-dichloroquinacridone is weighed and added, the mixture is stirred for 1 hour at room temperature, and then the mixture is made into a film material by an adjustable film coating device. After the solvent is volatilized, the film is subjected to laser irradiation under the following conditions: the wavelength of the carbon dioxide laser is 9.3 mu m, the marking speed is 1000mm/s, the laser power is 80W, and the laser frequency is 20kHz.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Comparative example 11
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polymethylmethacrylate (PMMA) win engenderdiose, 8N;
dichloromethane: gemini Colone chemical Co., ltd, the content of AR is more than or equal to 99.5%;
dissolving 99 parts by weight of polymethyl methacrylate in 500 parts by weight of dichloromethane solution, weighing 1 part by weight of 2, 9-dichloroquinacridone after the polymethyl methacrylate is completely dissolved, adding the 2, 9-dichloroquinacridone into the dichloromethane solution, stirring the mixture at room temperature for 1 hour, and preparing the mixture into a film material by using an adjustable film coating machine. After the solvent is volatilized, the film is subjected to laser irradiation under the following conditions: the wavelength of the carbon dioxide laser is 9.3 mu m, the marking speed is 1000mm/s, the laser power is 81W, and the laser frequency is 20kHz.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
Comparative example 12
Quinacridone pigment: 2, 9-dichloroquinacridone;
polymer resin: polymethylmethacrylate (PMMA) win engenderdiose, 8N;
dichloromethane: chengdu Kolon Chemicals Co., ltd, AR, the content is not less than 99.5%;
dissolving 99 parts by weight of polymethyl methacrylate in 500 parts by weight of dichloromethane solution, weighing 1 part by weight of 2, 9-dichloroquinacridone after the polymethyl methacrylate is completely dissolved, adding the 2, 9-dichloroquinacridone into the dichloromethane solution, stirring the mixture at room temperature for 1 hour, and preparing the mixture into a film material by using an adjustable film coating machine. After the solvent is volatilized, the film is subjected to laser irradiation under the following conditions: the wavelength of the carbon dioxide laser is 9.3 mu m, the marking speed is 1000mm/s, the laser power is 85W, and the laser frequency is 20kHz.
The laser irradiation conditions were the same as in example 1. The UV irradiation conditions and manner were the same as in example 1. The laser-irradiated area was visually observed for the generation of fluorescence, and the results are shown in Table 1.
The fluorescence intensity generation after irradiating the compositions of examples 1 to 54 and comparative examples 1 to 12 with a laser and then with a 365nm ultraviolet lamp is shown in Table 1.
TABLE 1 fluorescence intensity Generation in examples
Figure SMS_2
Figure SMS_3
Figure SMS_4
The results show that the composition can generate patterned fluorescence emission under the action of laser after the organic pigment is added into the plate material or the membrane material and is excited by an ultraviolet lamp. Compared with the prior art that fluorescent molecules and polymers need to react, the composition can be prepared only by blending and extruding twin screws or mixing and dissolving and then volatilizing the solvent, has simple and efficient process, simple and convenient operation, safety, environmental protection and low energy consumption, and is very suitable for industrial large-scale production.
In addition, the invention combines fluorescence and laser irradiation, utilizes the laser irradiation composition, induces fluorescence by ultraviolet light, and can generate patterned fluorescence emission on the surface of the polymer. Provides a new method for the field of polymer anti-counterfeiting.

Claims (22)

1. The laser-induced fluorescence emission composition is characterized by comprising the following components in parts by weight:
0.01-10 parts of organic pigment;
90-99.99 parts of polymer resin;
the organic pigment is at least one selected from a pyrrolopyrroledione pigment and a benzimidazolone pigment, and the molecular chain of the polymer resin contains an ester group and/or a hydroxyl group.
2. The laser-induced fluorescence emission composition is characterized by comprising the following components in parts by weight:
0.01-10 parts of organic pigment;
90-99.99 parts of polymer resin;
the organic pigment is selected from quinacridone pigment, and the polymer resin is selected from at least one of styrene-acrylonitrile-acrylate copolymer, methacrylate-styrene copolymer, methacrylate-butadiene-styrene copolymer, polyvinyl alcohol, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polycarbonate and polyvinyl acetate.
3. The composition according to claim 1 or 2, characterized by consisting of the following components in parts by weight:
0.01-5 parts of organic pigment;
95-99.99 parts of polymer resin.
4. The composition according to claim 3, which consists of the following components in parts by weight:
0.01-1 part of organic pigment;
99 to 99.99 parts of polymer resin.
5. The composition according to claim 4, which consists of the following components in parts by weight:
0.1-0.5 part of organic pigment;
99.5-99.9 parts of polymer resin.
6. The composition of claim 1, wherein: the polymer resin containing an ester group is at least one selected from polyvinyl acetate, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, a polyester elastomer, polybutylene succinate-terephthalate-butylene succinate, polybutylene succinate-adipate-butylene succinate, styrene-acrylonitrile-acrylate copolymer, methacrylate-styrene copolymer, or methacrylate-butadiene-styrene copolymer; the polymer resin containing hydroxyl groups is selected from polyvinyl alcohol.
7. The composition of claim 1, wherein:
the pyrrolopyrrole-dione-based pigment is at least one of bis (m-acrylobenzene) 1, 4-pyrrolopyrroledione, 3, 6-bis (4-tert-butylphenyl) -2, 5-dihydropyrrolo [3,4-c ] pyrrole-1, 4-dione, bis (p-chlorophenyl) -1, 4-diketopyrrolopyrrole, 3, 6-diphenyl-2, 5-dihydropyrrolo [3,4-c ] pyrrole-1, 4-dione, 3, 6-bis (4-phenyl) -2, 5-dihydropyrrolo [3,4-c ] pyrrole-1, 4-dione, 3, 6-bis (4-methylphenyl) -2, 5-dihydropyrrolo [3,4-c ] pyrrole-1, 4-dione;
the benzimidazolone-based pigments are 2- [ [1- [ [ (2, 3-dihydro-2-oxo-1H-benzimidazol-5-yl) amino ] formyl ] -2-oxopropyl ] azo ] benzoic acid, N- (2, 3-dihydro-2-oxo-1H-benzimidazol-5-yl) -3-oxo-2- [ [2- (trifluoromethyl) phenyl ] azo ] butanamide, 2- [ [1- [ [ (2, 3-dihydro-2-oxo-1H-benzimidazol-5-yl) amino ] carbonyl ] -2-oxopropyl ] azo ] -1, 4-dimethyl phthalate, 2' - [1, 2-ethylenebis (oxy-2, 1-phenyleneazo) ] bis [ N- (2, 3-dihydro-2-oxo-1H-benzimidazol) -5-yl ] -3-oxo-butanamide, N- [4- (aminocarbonyl) phenyl ] -4- [ [1- [ [ (2, 3-dihydro-2-oxo-1H-benzimidazol-5-yl ] -1, 4-oxo-1H-benzimidazol-5-yl ] benzamido [ 7, 6-oxo-1H-benzimidazol-5-yl ] benzamido [ 7,11, 7, 2- [ (4-chloro-2-nitrophenyl) azo ] -N- (2, 3-dihydro-2-oxo-1H-benzimidazol-5-yl) -3-oxobutanamide, N- (2, 3-dihydro-2-oxo-5-benzimidazole) -3-hydroxy-4- [ [ 2-methoxy-5-methyl-4- [ (methylamino) sulfonyl ] phenyl ] diazo ] naphthalene-2-carboxamide.
8. The composition of claim 2, wherein:
the quinacridone pigment is at least one of 5, 12-dihydro-quinoline [2,3-B ] acridine-7, 14-diketone, 2, 9-dimethylquinacridone, 2, 9-dichloroquinacridone, 4, 11-dichloroquinacridone, 3, 10-dichloroquinacridone and 1, 8-dichloroquinacridone.
9. The composition according to any one of claims 1 or 2, characterized in that: the composition is a coating, powder, sheet, plate, bar, or film material.
10. A process for the preparation of a composition according to any one of claims 1 to 9, characterized in that it comprises the following steps: mixing the organic pigment with polymer resin, blending, extruding, granulating and injection molding.
11. A process for preparing a composition according to claim 10, characterized in that:
the temperature in the blending and extrusion process is 180-270 ℃; the injection molding temperature is 180-270 ℃.
12. A method for preparing a composition as claimed in any one of claims 1 to 9, comprising the steps of: sequentially dissolving polymer resin and organic pigment in a solvent to prepare a membrane material, and volatilizing the solvent to obtain the composite pigment.
13. A process for preparing a composition according to claim 12, characterized in that:
the weight ratio of the organic pigment to the solvent is 0.00001:1 to 1:1.
14. a laser-induced patterned fluorescence emission method, comprising the steps of:
(1) Taking the composition of any one of claims 1-9, irradiating the surface of the composition with a laser to form an irradiated area;
(2) And irradiating the irradiation area by using ultraviolet light, so that the laser irradiation area can generate fluorescence emission.
15. The method of emission according to claim 14, wherein said laser is selected from the group consisting of near infrared laser, green laser, ultraviolet laser, CO 2 One or a combination of two or more of laser and excimer laser;
and/or the power of the laser is 1.8 to 80W, and the scanning speed of the laser is 1 to 10000mm/s;
and/or the wavelength of the ultraviolet light is 365 to 395nm.
16. The firing method of claim 15, wherein said laser is CO 2 Laser;
and/or the power of the laser is 5 to 70W, and the scanning speed of the laser is 1000mm/s;
and/or the wavelength of the ultraviolet light is 365nm.
17. The transmitting method of claim 16, wherein the CO is 2 The wavelength of the laser is 9.3 to 10.6 mu m;
and/or the power of the laser is 5 to 50W, the scanning speed of the laser is 1000mm/s, and the frequency of the laser is 20kHz.
18. A solid state fluorescent emissive material, characterized by: which is prepared by irradiating a composition according to any one of claims 1 to 9 with laser light.
19. A solid state fluorescent emissive material according to claim 18, wherein:
the laser is selected from near infrared laser, green laser, ultraviolet laser, and CO 2 One or a combination of two or more of laser and excimer laser;
or, the laser is continuous laser or pulse laser;
or the power of the laser is 1.8 to 80W, and the scanning speed of the laser is 1 to 10000mm/s.
20. A solid state fluorescent emissive material according to claim 19, wherein:
the laser is CO 2 Laser;
or the power of the laser is 5-70W, and the scanning speed of the laser is 1000mm/s.
21. A solid state fluorescent emissive material according to claim 20, wherein:
the CO is 2 The wavelength of the laser is 9.3 to 10.6 mu m;
or the power of the laser is 5 to 50W, the scanning speed of the laser is 1000mm/s, and the frequency of the laser is 20kHz.
22. Use of a composition according to any one of claims 1 to 9 or an emissive material according to any one of claims 18 to 21 in the manufacture of a security marking.
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