CN114479828A - Ultraviolet light curing fluorescent microsphere and preparation method thereof - Google Patents
Ultraviolet light curing fluorescent microsphere and preparation method thereof Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000001723 curing Methods 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 12
- 239000011159 matrix material Substances 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 239000002612 dispersion medium Substances 0.000 claims abstract description 7
- 239000003792 electrolyte Substances 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 238000005273 aeration Methods 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000012295 chemical reaction liquid Substances 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
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- 238000007599 discharging Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000007850 fluorescent dye Substances 0.000 abstract description 26
- 239000000049 pigment Substances 0.000 abstract description 12
- 239000000975 dye Substances 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000003973 paint Substances 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- MYIOYATURDILJN-UHFFFAOYSA-N rhodamine 110 Chemical compound [Cl-].C=12C=CC(N)=CC2=[O+]C2=CC(N)=CC=C2C=1C1=CC=CC=C1C(O)=O MYIOYATURDILJN-UHFFFAOYSA-N 0.000 description 9
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- 238000011895 specific detection Methods 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 206010051246 Photodermatosis Diseases 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers 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 aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers 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 a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses an ultraviolet curing fluorescent microsphere and a preparation method thereof, and relates to the technical field of fluorescent microspheres. The preparation method comprises the following steps: s1: adding a polymer monomer, an initiator, a dispersion medium and an electrolyte into a four-mouth bottle with a stirrer, a thermometer, a condenser pipe, a constant-pressure funnel and an aeration conduit in sequence, stirring, and uniformly stirring to obtain a mixed solution A. The invention adopts the ultraviolet light curing method to combine the fluorescent dye with the microsphere matrix, so that the fluorescent dye can be effectively fixed, the fluorescent dye is protected, and the preparation method only partially ensures the ultraviolet light curing process of the product, so that the pigment prepared by the preparation method can absorb ultraviolet light for further curing after contacting with the ultraviolet light in the using process, and the curing degree of the pigment is further increased due to the absorption of the ultraviolet light, so that the performance of the dye is more stable.
Description
Technical Field
The invention relates to the technical field of fluorescent microspheres, in particular to an ultraviolet curing fluorescent microsphere and a preparation method thereof.
Background
Fluorescent dyes are classified into inorganic fluorescent pigments (for example, fluorescent dyes used for fluorescent inks for fluorescent lamps and forgery prevention) and organic fluorescent dyes (also called fluorescent dyes), and substances having specific chemical structures have fluorescent characteristics. However, these fluorescent dyes themselves often have inherent deficiencies in light resistance and solvent resistance. However, the method for overcoming these inherent disadvantages is to fuse them into the framework of the polymer material by chemical or physical methods to form the fluorescent pigment, and the polymer material used for this purpose not only functions as a solvent for the fluorescent dye, but also provides protection for the fluorescent dye, thereby endowing the fluorescent dye with better light and solvent resistance.
In the process of manufacturing fluorescent pigment, a curing agent is often required to be added into the manufacturing raw materials to crosslink molecules in the bondable resin so as to achieve the purposes of uniformly dispersing the fluorescent dye and curing the fluorescent dye, but the fluorescent pigment manufactured by curing the fluorescent dye by using the curing agent has poor curing efficiency, when the fluorescent pigment is used for producing products, the light-color fastness performance of the products is easily low, a large amount of curing agent is often added into the formula in order to improve the curing efficiency of the fluorescent dye by the fluorescent pigment, and the use of excessive curing agent easily causes environmental pollution, so that the ultraviolet curing fluorescent microsphere and the preparation method thereof are provided.
Disclosure of Invention
The invention aims to provide an ultraviolet curing fluorescent microsphere and a preparation method thereof, and aims to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of ultraviolet curing fluorescent microspheres comprises the following steps:
s1: sequentially adding a polymer monomer, an initiator, a dispersion medium and an electrolyte into a four-mouth bottle with a stirrer, a thermometer, a condenser pipe, a constant-pressure funnel and an aeration conduit, stirring, and uniformly stirring to obtain a mixed solution A;
s2: continuously introducing protective gas into the mixed solution A through an air duct to continuously react for 20-60 minutes, then heating to 60-80 ℃, and reacting for 12-36 hours to obtain reaction solution B;
s3: cooling the reaction liquid B to below 35 ℃, discharging, filtering the reaction liquid B to remove condensate, centrifuging the reaction liquid B by a centrifuge, washing the reaction liquid B for three times by deionized water, and finally performing vacuum drying on the centrifuged product at 40-60 ℃ to obtain a microsphere matrix;
s4: respectively adding a microsphere matrix, a photoinitiator, a solvent and an organic dye into a four-mouth bottle with a stirrer, a thermometer, a condenser pipe, a constant-pressure funnel and an air duct, stirring, continuously introducing protective gas, performing an irradiation reaction by using ultraviolet light in the stirring process, and removing the solvent by adopting low-pressure distillation after the irradiation reaction is finished to obtain the ultraviolet light curing fluorescent microsphere.
Preferably, the polymer monomer in the S1 step is any one of methyl methacrylate or styrene.
Preferably, the initiator in the step S1 is potassium persulfate, the dispersion medium is a mixture of ethanol and toluene or a mixture of ethanol and water, and the electrolyte is sodium chloride.
Preferably, the protective gas in the steps S2 and S4 is any one of nitrogen gas and inert gas.
Preferably, the mass ratio of the polymer monomer, the initiator, the dispersion medium and the electrolyte in the S1 step is 1000-1500: 5-15: 4500-6000: 5-10.
Preferably, the mass ratio of the microsphere matrix, the photoinitiator, the solvent and the organic dye in the step S4 is 50-100: 15-30: 1000: 100-400 in sequence, wherein the photoinitiator is any one of 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone or 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, and the solvent is acetone.
Preferably, the ultraviolet irradiation reaction conditions are as follows: the wavelength of the ultraviolet light is 200-300nm, and the irradiation intensity is 8-10mW/cm2The irradiation time is 30-60 min.
Compared with the prior art, the invention has the beneficial effects that:
according to the ultraviolet curing fluorescent microsphere and the preparation method thereof, the fluorescent dye is combined with the microsphere substrate by adopting an ultraviolet curing method, so that the fluorescent dye can be effectively fixed, the protection effect on the fluorescent dye is achieved, the dispersity of the fluorescent dye can be improved, the uniformity of the coating can be ensured when the ultraviolet curing fluorescent microsphere is used for preparing the coating, and the covering power of the coating is improved.
Meanwhile, the ultraviolet curing fluorescent microspheres only need a small amount of curing agent or do not need curing agent during manufacturing, so that the environment is not polluted due to the use of a large amount of curing agent, and the preparation method of the invention only partially enables the ultraviolet curing process of the product of the invention, so that the pigment prepared by the preparation method of the invention can absorb ultraviolet rays for further curing after contacting with the ultraviolet rays during the using process, and the performance of the dye is more stable due to the absorption of the ultraviolet rays and the further increase of the curing degree of the pigment, thereby directly improving the light fastness performance of subsequent products.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
It should be noted that in the description of the present invention, the terms "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. indicate the orientation or positional relationship shown based on the embodiments, which are only for convenience of description and simplification of description, and do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation and operation, and thus, should not be construed as limiting the present invention.
Further, it should be understood that the dimensions of the various elements shown in the embodiments are not drawn to scale, for ease of description, and that, for example, the thickness or width of some layers may be exaggerated relative to other layers.
It should be noted that like reference numerals and letters refer to like items in the following embodiments, and thus, once an item is defined or described in one embodiment, further detailed discussion and description thereof will not be required in the description of the embodiments that follow.
The first embodiment is as follows:
the embodiment provides a technical scheme: an ultraviolet light curing fluorescent microsphere comprises the following preparation steps:
s1: 26g of methyl methacrylate, 0.24g of potassium persulfate, 100g of a mixture of ethanol and water (wherein the volume ratio of the ethanol to the water is 1: 1) and 0.1g of sodium chloride are sequentially added into a 200ml four-neck flask with a stirrer, a thermometer, a condenser, a constant pressure funnel and an aeration conduit and stirred uniformly to obtain 126.34g of mixed solution A;
s2: continuously introducing nitrogen into the mixed solution A through a ventilation conduit to continuously react for 30 minutes, then heating to 65 ℃, and reacting for 18 hours to obtain reaction solution B;
s3: cooling the reaction liquid B to below 35 ℃, discharging, filtering the reaction liquid B to remove condensate, centrifuging the reaction liquid B by using a centrifuge, washing the reaction liquid B for three times by using deionized water, and finally drying the centrifuged product in vacuum at the temperature of 45 ℃ to obtain 24.3g of a microsphere matrix;
s4: to a 200ml four-necked flask equipped with a stirrer, a thermometer, a condenser, a constant pressure funnel and an air-introducing tube were added 6.2g of the microsphere base and 2.1g of 2-dimethylamino-2-benzyl-1- [4- (4-morpholino) phenyl group]Stirring with-1-butanone, 100g of acetone and 23.5g of rhodamine 110 (fluorescent dye) and continuously introducing nitrogen, wherein the stirring process uses a wavelength of 253nm and the irradiation intensity is 9mW/cm2The irradiation reaction is carried out by the ultraviolet light, the irradiation time is 45min, and acetone is removed by low-pressure distillation after the irradiation reaction is finished, so that 29.3g of ultraviolet light curing fluorescent microspheres are obtained.
Example two:
the operations of steps S1-S3 are the same as those of the first embodiment, and the operation of step S4 is as follows:
to a 200ml four-necked flask equipped with a stirrer, a thermometer, a condenser, a constant pressure funnel and an air-introducing tube were added 6.2g of the microsphere base and 2.1g of 2-dimethylamino-2-benzyl-1- [4- (4-morpholino) phenyl group]Stirring with-1-butanone, 100g of acetone and 15.5g of rhodamine 110 (fluorescent dye) and continuously introducing nitrogen, wherein the stirring process uses a wavelength of 253nm and the irradiation intensity is 8mW/cm2The irradiation reaction is carried out by the ultraviolet light, the irradiation time is 30min, and acetone is removed by low-pressure distillation after the irradiation reaction is finished, so that 23.7g of ultraviolet light curing fluorescent microspheres are obtained.
Example three:
the operations of steps S1-S3 are the same as those of the first embodiment, and the operation of step S4 is as follows:
to a 200ml four-necked flask equipped with a stirrer, a thermometer, a condenser, a constant pressure funnel and an air-introducing tube were added 6.2g of the microsphere base and 2.1g of 2-dimethylamino-2-benzyl-1- [4- (4-morpholino) phenyl group]Stirring with-1-butanone, 100g of acetone and 35.5g of rhodamine 110 (fluorescent dye) and continuously introducing nitrogen, wherein the stirring is carried out by using the material with the wavelength of 253nm and the irradiation intensity of 10mW/cm2The ultraviolet light carries out irradiation reaction on the mixture for 60min, and the irradiation reaction is finishedThen, acetone was removed by low pressure distillation to obtain 43.5g of UV-curable fluorescent microspheres.
Example four:
the embodiment provides a technical scheme: an ultraviolet light curing fluorescent microsphere comprises the following preparation steps:
s1: 25g of styrene, 0.30g of potassium persulfate, 100g of a mixture of ethanol and toluene (the volume ratio of ethanol to toluene is 2: 1) and 0.1g of sodium chloride are sequentially added into a 200ml four-neck flask with a stirrer, a thermometer, a condenser, a constant pressure funnel and an aeration conduit for stirring, and 125.40g of mixed solution A is obtained after uniform stirring;
s2: continuously introducing nitrogen into the mixed solution A through a ventilation conduit to continuously react for 30 minutes, then heating to 65 ℃, and reacting for 18 hours to obtain reaction solution B;
s3: cooling the reaction liquid B to below 35 ℃, discharging, filtering the reaction liquid B to remove condensate, centrifuging the reaction liquid B by using a centrifuge, washing the reaction liquid B for three times by using deionized water, and finally drying the centrifuged product in vacuum at the temperature of 45 ℃ to obtain 23.2g of a microsphere matrix;
s4: to a 200ml four-necked flask equipped with a stirrer, a thermometer, a condenser, a constant pressure funnel and an air introduction tube were added 6.0g of the microsphere base and 2.2g of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl group]Stirring (1-acetone) and 100g of rhodamine 110 (fluorescent dye) and stirring (acetone and 38.4g of rhodamine 110) with continuous nitrogen introduction, wherein the stirring process uses the material with the wavelength of 259nm and the irradiation intensity of 9mW/cm2The irradiation reaction is carried out by using the ultraviolet light, the irradiation time is 45min, and acetone is removed by adopting low-pressure distillation after the irradiation reaction is finished, so that 46.3g of ultraviolet light curing fluorescent microspheres are obtained.
Example five:
the operations of steps S1-S3 are the same as those of the fourth embodiment, and the operation of step S4 is as follows:
to a 200ml four-necked flask equipped with a stirrer, a thermometer, a condenser, a constant pressure funnel and an air introduction tube were added 6.0g of the microsphere base and 2.2g of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl group]Stirring (1-acetone) and 100g of rhodamine 110 (fluorescent dye) and stirring (acetone and 23.4g of rhodamine 110) with continuous nitrogen introduction, wherein the stirring process uses the material with the wavelength of 259nm and the irradiation intensity of 9mW/cm2The irradiation reaction is carried out by the ultraviolet light, the irradiation time is 30min, and acetone is removed by low-pressure distillation after the irradiation reaction is finished, so that 31.2g of ultraviolet light curing fluorescent microspheres are obtained.
Comparative example one:
fluorescent pigments using curing agents to cure rhodamine 110 (a fluorescent dye) are commercially available for comparison.
Comparative experiment:
the ultraviolet curing fluorescent microspheres in the first to fifth embodiments are respectively adopted to produce the paint according to the paint production process, the paint produced by the comparative example product in the same proportion according to the paint production process is used as a comparative experiment, and the rhodamine 110 (fluorescent dye) is directly used as the pigment to produce the fluorescent paint according to the paint production process is used as a blank experiment.
1) Paint hiding power (dye dispersibility)
One end of a 100mm by 250mm glass plate was covered by 100mm by 50mm (left for hand-held use in the test), and then the remaining 100mm by 200mm area was sprayed with a layer of black nitro-lacquer. After drying, squares with the size of 25mm multiplied by 25mm are carefully scratched out by a knife at intervals, the glass plate is put into water to be soaked for a moment, taken out to be dried, the paint film of the squares is stripped at intervals, a layer of white nitrolacquer is sprayed to obtain the glass plate with the interval of 32 squares, then a piece of smooth kraft paper is pasted, and a layer of epoxy glue is knife-coated (to prevent solvent from permeating and damaging the black and white check paint film), so that the firm black and white grating plate is prepared.
A wooden dark box with the volume of 600mm multiplied by 500mm multiplied by 400mm is manufactured, the box is divided into an upper part and a lower part by ground glass with the thickness of 3mm in the dark box, the ground surface of the ground glass is downward, and a light source is uniform. The upper part of the dark box is uniformly provided with 2 parallel devices of 15-watt fluorescent lamps, the front surface of the dark box is provided with a light barrier, the front surface of the lower part of the dark box is opened for inspection, and the inner wall of the dark box is coated with matt black paint.
The cup with the coating and brush were weighed on a 0.01g scale according to the viscosity specified by the product standards (if the viscosity was thick and could not be brushed, the sample was adjusted to the brushing viscosity, but the amount of diluent was subtracted when calculating the hiding power). The paint is uniformly coated on a glass black-white grid plate by a brush, the glass black-white grid plate is placed in a dark box, the distance between the glass black-white grid plate and a ground glass sheet is 15-20 cm, the intersection angle of one end with a black grid and a white grid and a plane is inclined to form a 30-45-degree intersection angle, and observation is carried out under 1 and 2 fluorescent lamps, and the end point is that the black grid and the white grid can not be seen immediately. And weighing the cup and the brush filled with the residual paint to obtain the weight of the coating on the black and white grid plate. The coating should be fast and uniform and should not be applied to the edges of the panel.
The covering power calculation method is as follows:
X＝(W1-W2)×104/S＝50×(W1-W2)；
wherein W1The total weight in grams of the cup and paint brush containing paint before painting
W2The total weight of the cup filled with the residual paint and the paint brush after painting is unit gram;
and S is the area of the black-white grid plate painted in square centimeter.
The results are measured in parallel twice, the error of the results is not more than 5%, the average value is taken as the experimental result, and the experimental results of the paint hiding power of the examples I to fifth, the comparative experiment and the blank experiment are shown in the table 1:
TABLE 1
2) Test of natural light resistance of paint
The detection method is based on the principle that the capability of the paint for resisting the damage of sunlight and maintaining the original performance is called the natural light resistance of the paint. The process of gradual change in properties of a coating under the influence of environmental conditions of natural light irradiation is called photoaging of the coating. Exposing the sample plate coated with the coating under a certain condition, inspecting the aging phenomenon according to a specified inspection period, and grading according to a specified coating gray card color fastness grading method, wherein the specific detection method comprises the following steps:
the method is characterized in that steel plates, heat-treatment-strengthened aluminum alloy plates, magnesium alloy plates and other practical plates such as wood plates, plastic plates, cement plates and other alloy plates are used for manufacturing an exposure sample plate and a standard sample plate, wherein the size of the exposure sample plate is 150mm multiplied by 250mm, and the size of the standard sample plate is 70mm multiplied by 150 mm. The method specified prepares the exposure and standard panels and coats the coating products of examples one through five, comparative experiments, and blank experiments on the surfaces of the exposure and standard panels. The method comprises the steps of preparing two exposure sample plates and a standard sample plate by using the same operation method for each experimental coating variety, placing the exposure sample plates in an area with the same irradiance in the open air, covering the upper half parts of the exposure sample plates by using opaque products, placing the standard sample plates in a sealed mode in a shady and lightless place indoors, storing and testing the exposure sample plates within half a year, checking the exposure sample plates once every month, detecting the exposure sample plates once every three months after the test is carried out for half a year, cleaning and drying the lower half parts of the exposure sample plates in clear water before the exposure sample plates are checked, and not carrying out any treatment on the upper half parts of the exposure sample plates. In the test, a standard sample is used as a standard sample, a covered part and an uncovered part of the exposure sample are used as test samples, the color fastness to light of the coating on the exposure sample is evaluated by a method for evaluating the color fastness by using a gray sample card, when the color difference is less than 2 grades, the test is stopped, and the specific detection result is shown in table 2:
TABLE 2
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A preparation method of ultraviolet curing fluorescent microspheres is characterized by comprising the following preparation steps:
s1: sequentially adding a polymer monomer, an initiator, a dispersion medium and an electrolyte into a four-mouth bottle with a stirrer, a thermometer, a condenser pipe, a constant-pressure funnel and an aeration conduit, stirring, and uniformly stirring to obtain a mixed solution A;
s2: continuously introducing protective gas into the mixed solution A through an air duct to continuously react for 20-60 minutes, then heating to 60-80 ℃, and reacting for 12-36 hours to obtain reaction solution B;
s3: cooling the reaction liquid B to below 35 ℃, discharging, filtering the reaction liquid B to remove condensate, centrifuging the reaction liquid B by a centrifuge, washing the reaction liquid B for three times by deionized water, and finally performing vacuum drying on the centrifuged product at 40-60 ℃ to obtain a microsphere matrix;
s4: respectively adding a microsphere matrix, a photoinitiator, a solvent and an organic dye into a four-mouth bottle with a stirrer, a thermometer, a condenser pipe, a constant-pressure funnel and an air duct, stirring, continuously introducing protective gas, performing an irradiation reaction by using ultraviolet light in the stirring process, and removing the solvent by adopting low-pressure distillation after the irradiation reaction is finished to obtain the ultraviolet light curing fluorescent microsphere.
2. The method for preparing ultraviolet curing fluorescent microspheres of claim 1, wherein the polymer monomer in the step S1 is any one of methyl methacrylate or styrene.
3. The method of claim 1, wherein the initiator in step S1 is potassium persulfate, the dispersion medium is a mixture of ethanol and toluene or a mixture of ethanol and water, and the electrolyte is sodium chloride.
4. The method of claim 1, wherein the protective gas in the steps S2 and S4 is nitrogen or inert gas.
5. The method for preparing UV-curable fluorescent microsphere according to claim 1, wherein the mass ratio of the polymer monomer, the initiator, the dispersion medium and the electrolyte in the step S1 is 1000-1500: 5-15: 4500-6000: 5-10 in sequence.
6. The method for preparing ultraviolet curing fluorescent microsphere as claimed in claim 1, wherein the mass ratio of the microsphere matrix, the photoinitiator, the solvent and the organic dye in the step S4 is 50-100: 15-30: 1000: 100-400 in sequence, wherein the photoinitiator is any one of 2-dimethylamino-2-benzyl-1- [4- (4-morpholino) phenyl ] -1-butanone or 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, and the solvent is acetone.
7. The method for preparing ultraviolet curing fluorescent microspheres according to claim 1, wherein the ultraviolet irradiation reaction conditions in the step S4 are as follows: the wavelength of the ultraviolet light is 200-300nm, and the irradiation intensity is 8-10mW/cm2The irradiation time is 30-60 min.
8. An ultraviolet light curing fluorescent microsphere, which is characterized by being prepared according to the preparation method of the ultraviolet light curing fluorescent microsphere in any one of claims 1 to 7.
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| CN101481556A (en) * | 2008-01-11 | 2009-07-15 | 上海广电电子股份有限公司 | UV cured fluorescent color conversion film for electroluminescence display device and preparation |
| CN110042673A (en) * | 2019-04-28 | 2019-07-23 | 浙江理工大学 | A kind of large area fast preparation method of textile substrate surface photon crystal structure color coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101481556A (en) * | 2008-01-11 | 2009-07-15 | 上海广电电子股份有限公司 | UV cured fluorescent color conversion film for electroluminescence display device and preparation |
| CN110042673A (en) * | 2019-04-28 | 2019-07-23 | 浙江理工大学 | A kind of large area fast preparation method of textile substrate surface photon crystal structure color coating |
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