CN116239895A - Preparation method of modified melamine resin type daylight fluorescent pigment - Google Patents
Preparation method of modified melamine resin type daylight fluorescent pigment Download PDFInfo
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- CN116239895A CN116239895A CN202310249880.5A CN202310249880A CN116239895A CN 116239895 A CN116239895 A CN 116239895A CN 202310249880 A CN202310249880 A CN 202310249880A CN 116239895 A CN116239895 A CN 116239895A
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- melamine resin
- modified melamine
- fluorescent pigment
- heat preservation
- mixture
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- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 64
- 239000004640 Melamine resin Substances 0.000 title claims abstract description 59
- 150000007974 melamines Chemical class 0.000 title claims abstract description 48
- 239000000049 pigment Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 15
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 12
- 239000007850 fluorescent dye Substances 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 238000004321 preservation Methods 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 13
- 229920002866 paraformaldehyde Polymers 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 2
- 238000010979 pH adjustment Methods 0.000 claims 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 25
- 229920005989 resin Polymers 0.000 abstract description 23
- 239000011347 resin Substances 0.000 abstract description 23
- 239000002904 solvent Substances 0.000 abstract description 21
- 238000013508 migration Methods 0.000 abstract description 20
- 230000005012 migration Effects 0.000 abstract description 20
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 24
- 238000001514 detection method Methods 0.000 description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000004744 fabric Substances 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical compound NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FXFIDVQMNRVEGQ-UHFFFAOYSA-N (7e)-3-(diethylamino)-7-imino-7h-chromeno[3',2':3,4]pyrido[1,2-a]benzimidazole-6-carbonitrile Chemical compound C1=CC=C2N(C(=N)C(C#N)=C3C4=CC5=CC=C(C=C5O3)N(CC)CC)C4=NC2=C1 FXFIDVQMNRVEGQ-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- JZGUXCXDBKBCDN-UHFFFAOYSA-N 21295-57-8 Chemical compound C12=C3C(=O)C4=CC=CC=C4C1=CC(=O)N(C)C2=CC=C3NC1CCCCC1 JZGUXCXDBKBCDN-UHFFFAOYSA-N 0.000 description 1
- DZNJMLVCIZGWSC-UHFFFAOYSA-N 3',6'-bis(diethylamino)spiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(N(CC)CC)C=C1OC1=CC(N(CC)CC)=CC=C21 DZNJMLVCIZGWSC-UHFFFAOYSA-N 0.000 description 1
- UTTFXJZCRVZYQF-UHFFFAOYSA-N 3-(diethylamino)-7-oxo-7h-(1)benzopyrano(3',2':3,4)pyrido(1,2-a)benzimidazole-6-carbonitrile Chemical compound C1=CC=C2N(C(=O)C(C#N)=C3C4=CC5=CC=C(C=C5O3)N(CC)CC)C4=NC2=C1 UTTFXJZCRVZYQF-UHFFFAOYSA-N 0.000 description 1
- SDUIURJVOCHJCO-UHFFFAOYSA-N 3-[5-(Aminosulfonyl)benzoxazol-2-yl]-7-(diethylamino)coumarin Chemical compound NS(=O)(=O)C1=CC=C2OC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 SDUIURJVOCHJCO-UHFFFAOYSA-N 0.000 description 1
- QPQKUYVSJWQSDY-UHFFFAOYSA-N 4-phenyldiazenylaniline Chemical compound C1=CC(N)=CC=C1N=NC1=CC=CC=C1 QPQKUYVSJWQSDY-UHFFFAOYSA-N 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 benzenesulfonamide-formaldehyde-melamine Chemical compound 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- MDIVCFDNUUVLFC-UHFFFAOYSA-N formaldehyde;4-methylbenzenesulfonamide;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1.CC1=CC=C(S(N)(=O)=O)C=C1 MDIVCFDNUUVLFC-UHFFFAOYSA-N 0.000 description 1
- MSYLJRIXVZCQHW-UHFFFAOYSA-N formaldehyde;6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound O=C.NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 MSYLJRIXVZCQHW-UHFFFAOYSA-N 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- QFVDKARCPMTZCS-UHFFFAOYSA-N methylrosaniline Chemical compound C1=CC(N(C)C)=CC=C1C(O)(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 QFVDKARCPMTZCS-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0092—Dyes in solid form
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
-
- 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
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a preparation method of a modified melamine resin type daylight fluorescent pigment, and relates to the technical field of fluorescent pigments. According to the invention, polyethylene glycol and urea are introduced into melamine resin for modification to prepare a modified melamine resin serving as carrier resin, and then the carrier resin, fluorescent dye and auxiliary agent are mixed to prepare the modified melamine resin type daylight fluorescent pigment. The fluorescent pigment prepared by the application has better heat resistance, solvent resistance, migration resistance and light resistance, higher softening point and better fluorescence; other melamine resin daylight type fluorescent pigments have lower formaldehyde content and are environment-friendly.
Description
Technical Field
The invention relates to the technical field of fluorescent pigments, in particular to a preparation method of a modified melamine resin type daylight type fluorescent pigment.
Background
The daylight fluorescent pigment is a special organic pigment, can emit fluorescence under the irradiation of sunlight or ultraviolet light, has very bright color, and is widely used for coloring plastics, paint ink, candles and textiles. The daylight type fluorescent pigment consists of carrier resin, fluorescent dye and auxiliary agent, wherein the fluorescent dye gives fluorescent effect to the pigment, and the carrier resin determines the performances of solvent resistance, migration resistance, heat resistance and the like of the pigment. Fluorescent pigments, which are relatively common in the market at present, are classified into polyesters, polyamides, polyureas, melamine, styrene-acrylic emulsions, and the like according to carrier resins.
The polyester, polyamide and styrene-acrylic emulsion has poor solvent resistance due to the poor solvent resistance of the resin, and the resin softening point (less than 150 ℃) and poor solvent resistance, so that the resin can only be used in the plastic coloring field. The fluorescent pigment resistant to common solvents (such as common organic solvents) takes a p-toluenesulfonamide-formaldehyde-melamine resin system as a raw material, and the resin is crosslinked by adding melamine so as to have solvent resistance. In general, the greater the amount of melamine added, the better the solvent resistance. However, with the increase of melamine, the viscosity of the resin is increased, the dyeing is uneven, and the reaction operation time is greatly shortened, so that the method cannot obtain the fluorescent pigment with high solvent resistance.
The Japanese catalyst chemical company developed an emulsion curing method using benzoguanamine-formaldehyde resin as a carrier. Firstly synthesizing low-condensation-degree benzomelamine-formaldehyde resin, then carrying out high-shear emulsification, and finally curing under an acidic condition to obtain the microsphere type solvent-resistant sunlight-type fluorescent pigment with the thickness of 1.5-3 mu m. But also has the following disadvantages: 1. the free formaldehyde content in the production process is high; 2. there is also a slight bleeding when resistant to strong solvents.
In 1998, day-Glo company released solvent-resistant ionic polymer fluorescent pigment, organic-inorganic composite particle polymer was prepared by using polyamine, polybasic acid anhydride, metal compound and epoxy resin, and the solvent resistance of the product was greatly improved by fully crosslinking with ionic bonds. However, the ionic bond has poor water resistance, is easy to agglomerate in the storage process, and is easy to cause bleeding phenomenon due to water in use.
Therefore, aiming at the technical problems of the fluorescent pigment of the benzenesulfonamide-formaldehyde-melamine resin system, the invention provides the fluorescent pigment of the modified melamine resin, which has obviously improved heat resistance, solvent resistance, migration resistance and light resistance, higher softening point and better fluorescence.
Disclosure of Invention
The invention aims to provide a preparation method of a modified melamine resin daylight type fluorescent pigment, which solves the following technical problems:
the existing fluorescent pigment has poor solvent resistance and is easy to bleed; poor storage property and easy caking.
The aim of the invention can be achieved by the following technical scheme:
a preparation method of a modified melamine resin daylight type fluorescent pigment comprises the following steps:
s1: adding benzomelamine and paraformaldehyde into a reaction kettle, heating and stirring, adjusting pH to be alkaline, and carrying out heat preservation reaction to obtain a mixture A;
s2: adding polyethylene glycol into the mixture A, and carrying out heat preservation reaction to obtain a mixture B;
s3: adding methanol into the mixture B, adjusting pH to be acidic, and carrying out heat preservation reaction to obtain a mixture C;
s4: adding urea into the mixture C, heating, preserving heat and stirring to obtain modified melamine resin;
s5: adding fluorescent dye and auxiliary agent into modified melamine resin, stirring uniformly, discharging, cooling, drying and crushing to obtain the modified melamine resin daylight type fluorescent pigment.
As a further aspect of the invention: benzomelamine: paraformaldehyde: polyethylene glycol: methanol: the mass ratio of urea is 90-100:40-110:6-10:40-110:4-7.
As a further aspect of the invention: modified melamine resin: fluorescent dye: the mass ratio of the auxiliary agent is 100:3-7:1-2.
As a further aspect of the invention: in S1, the pH is adjusted to be alkaline, specifically, the pH is adjusted to 8.5-9 by adding 10% sodium hydroxide aqueous solution.
As a further aspect of the invention: in the step S3, the pH is regulated to be acidic, specifically, the pH is regulated to be 5-5.5 by adding a citric acid aqueous solution with the mass concentration of 10%.
As a further aspect of the invention: the heat preservation reaction in S1 is specifically to heat up to 80-90 ℃ and keep the temperature for 10-20min.
As a further aspect of the invention: the heat preservation reaction in S2 is specifically to heat up to 80-90 ℃ and the heat preservation reaction is carried out for 20-40min.
As a further aspect of the invention: and S3, carrying out heat preservation reaction, namely, cooling to 40-60 ℃ and carrying out heat preservation reaction for 60-70min.
As a further aspect of the invention: and S4, heating, heat-preserving stirring, namely heating to 75-95 ℃, and heat-preserving stirring for 20-40min.
As a further aspect of the invention: the molecular weight of the modified melamine resin is 7000-9000.
As a further aspect of the invention: the particle size of the modified melamine resin type daylight fluorescent pigment is 2-4um.
As a further aspect of the invention: the fluorescent dye is one or more of solvent red 196, solvent red 197, solvent red 49, solvent red 149, alkaline red 1, alkaline red 1:1, alkaline violet 10, alkaline violet 11, alkaline violet 11:1, alkaline yellow 40, solvent violet 9, solvent yellow 172 and solvent yellow 145 in any ratio.
As a further aspect of the invention: the auxiliary agent is one or more of an antioxidant, an ultraviolet-infrared absorber, a dispersing agent and an antistatic agent which are mixed according to any ratio.
The invention has the beneficial effects that:
(1) According to the invention, the melamine resin is prepared by using benzomelamine and paraformaldehyde as raw materials and performing hydroxylation reaction on amino groups on the benzomelamine and formaldehyde after depolymerization of the paraformaldehyde and then performing polycondensation, polyethylene glycol is also introduced into a melamine resin reaction system for modification, and is a linear triol which can connect triazine rings in the melamine resin, so that a connecting chain between molecules is prolonged, residual hydroxymethyl is removed, the crosslinking degree between resins is high, and compared with the common amino resin, the melamine resin has better heat resistance, solvent resistance, migration resistance, light resistance, higher softening point and better fluorescence.
(2) According to the invention, urea is introduced into melamine resin for modification, cyclization reaction is carried out on urea, amine groups in the urea react with formaldehyde to generate methylol urea, and when the addition reaction of benzomelamine and formaldehyde reaches a certain degree, free formaldehyde can react with amine groups in the urea in a dispersing way to generate methylol urea, so that the release amount of formaldehyde is reduced, and the formaldehyde content of the product is greatly reduced.
Detailed Description
The following description will clearly and fully describe the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A preparation method of modified melamine resin comprises the following steps:
(1) Adding 95g of benzomelamine and 43g of paraformaldehyde into a reaction kettle, starting stirring, heating to 85 ℃, adding 10g of 10% sodium hydroxide aqueous solution, and reacting at 85 ℃ for 10min under heat preservation to obtain a mixture A;
(2) Adding 9g of polyethylene glycol into the mixture A, and reacting at 85 ℃ for 30min to obtain a mixture B;
(3) Reducing the temperature to 50 ℃, adding 42g of methanol into the mixture B, adding 62g of 10% citric acid aqueous solution by mass fraction, and carrying out heat preservation reaction for 60min at 50 ℃ to obtain a mixture C;
(4) 4.5g of urea is added into the mixture C, the temperature is raised to 85 ℃, and the reaction is carried out for 30min under the heat preservation, thus obtaining the modified melamine resin.
Example 2
A preparation method of modified melamine resin comprises the following steps:
(1) Adding 96g of benzomelamine and 62g of paraformaldehyde into a reaction kettle, starting stirring, heating to 85 ℃, adding 9g of 10% sodium hydroxide aqueous solution, and reacting at 85 ℃ for 10min under heat preservation to obtain a mixture A;
(2) Adding 6.5g of polyethylene glycol into the mixture A, and reacting at 85 ℃ for 30min to obtain a mixture B;
(3) Reducing the temperature to 50 ℃, adding 63g of methanol into the mixture B, adding 62g of 10% citric acid aqueous solution by mass fraction, and carrying out heat preservation reaction for 60min at 50 ℃ to obtain a mixture C;
(4) 4.2g of urea is added into the mixture C, the temperature is raised to 85 ℃, and the reaction is carried out for 30min under the heat preservation, thus obtaining the modified melamine resin.
Example 3
A preparation method of modified melamine resin comprises the following steps:
(1) Adding 96g of benzomelamine and 83g of paraformaldehyde into a reaction kettle, starting stirring, heating to 85 ℃, adding 7.5g of 10% sodium hydroxide aqueous solution, and reacting at 85 ℃ for 10min under heat preservation to obtain a mixture A;
(2) Adding 7.5g of polyethylene glycol into the mixture A, and reacting at 85 ℃ for 30min to obtain a mixture B;
(3) Reducing the temperature to 50 ℃, adding 82g of methanol into the mixture B, adding 56g of 10% citric acid aqueous solution by mass fraction, and carrying out heat preservation reaction for 60min at 50 ℃ to obtain a mixture C;
(4) 5.5g of urea is added into the mixture C, the temperature is raised to 85 ℃, and the reaction is carried out for 30min under the heat preservation, thus obtaining the modified melamine resin.
Example 4
A preparation method of modified melamine resin comprises the following steps:
(1) Adding 96g of benzomelamine and 106g of paraformaldehyde into a reaction kettle, starting stirring, heating to 85 ℃, adding 6g of 10% sodium hydroxide aqueous solution, and reacting at 85 ℃ for 10min under heat preservation to obtain a mixture A;
(2) Adding 9.6g of polyethylene glycol into the mixture A, and reacting at 85 ℃ for 30min to obtain a mixture B;
(3) Reducing the temperature to 50 ℃, adding 104g of methanol into the mixture B, adding 62g of 10% citric acid aqueous solution by mass fraction, and carrying out heat preservation reaction for 60min at 50 ℃ to obtain a mixture C;
(4) 6.6g of urea is added into the mixture C, the temperature is raised to 85 ℃, and the reaction is carried out for 30min under the heat preservation, thus obtaining the modified melamine resin.
Example 5
A preparation method of a modified melamine resin daylight type fluorescent pigment comprises the following steps:
adding 1.8g of fluorescent dye, 0.7g of auxiliary agent and 60g of modified melamine resin prepared in example 1 into a reaction kettle, stirring at a high speed, discharging, rapidly cooling, and performing filter pressing and drying; and coarsely crushing the dried material, and further carrying out jet milling to obtain the modified melamine resin daylight type fluorescent pigment.
Example 6
Compared with example 5, the modified melamine resin prepared in example 1 added in example 5 was replaced with the modified melamine resin prepared in example 2 in equal amounts, and the other component proportions and the preparation method were the same as those in example 5.
Example 7
Compared with example 5, the modified melamine resin prepared in example 1 added in example 5 was replaced with the modified melamine resin prepared in example 3 in equal amounts, and the other component proportions and the preparation method were the same as those in example 5.
Example 8
Compared with example 5, the modified melamine resin prepared in example 1 added in example 5 was replaced with the modified melamine resin prepared in example 4 in equal amounts, and the other component proportions and the preparation method were the same as those in example 5.
Comparative example 1
A method for preparing a carrier resin comprising the steps of:
(1) Adding 62g of melamine, 76g of paraformaldehyde and 195g of p-toluenesulfonamide into a reaction kettle, starting stirring, heating to 110 ℃, and carrying out heat preservation reaction for 10min;
(2) Continuously heating to 130 ℃, adding 36g of 10% citric acid aqueous solution by mass percent, and reacting for 10min to obtain the carrier resin.
Comparative example 2
A method for preparing a carrier resin comprising the steps of:
(1) Adding 95g of benzomelamine and 43g of paraformaldehyde into a reaction kettle, starting stirring, heating to 85 ℃, adding 10g of 10% sodium hydroxide aqueous solution, and reacting at 85 ℃ for 10min under heat preservation to obtain a mixture A;
(2) Reducing the temperature to 50 ℃, adding 42g of methanol into the mixture B, adding 62g of 10% citric acid aqueous solution by mass fraction, and carrying out heat preservation reaction for 60min at 50 ℃ to obtain a mixture C;
(3) 4.5g of urea is added into the mixture C, the temperature is raised to 85 ℃, and the reaction is carried out for 30min under the heat preservation, thus obtaining the carrier resin.
Comparative example 3
A method for preparing a carrier resin comprising the steps of:
(1) Adding 95g of benzomelamine and 43g of paraformaldehyde into a reaction kettle, starting stirring, heating to 85 ℃, adding 10g of 10% sodium hydroxide aqueous solution, and reacting at 85 ℃ for 10min under heat preservation to obtain a mixture A;
(2) Adding 9g of polyethylene glycol into the mixture A, and reacting at 85 ℃ for 30min to obtain a mixture B;
(3) The temperature is reduced to 50 ℃, 42g of methanol is added into the mixture B, 62g of 10% citric acid aqueous solution with mass fraction is added, and the temperature is kept at 50 ℃ for reaction for 60min, thus obtaining the carrier resin.
Comparative example 4
In comparison with example 5, only the modified melamine resin prepared in example 1 added in example 5 was replaced by the carrier resin prepared in comparative example 1 in equal amounts, and the remaining component proportions and the preparation method were the same as in example 5.
Comparative example 5
In comparison with example 5, only the modified melamine resin prepared in example 1 added in example 5 was replaced by the carrier resin prepared in comparative example 2 in equal amounts, and the remaining component proportions and the preparation method were the same as in example 5.
Comparative example 6
In comparison with example 5, only the modified melamine resin prepared in example 1 added in example 5 was replaced by the carrier resin prepared in comparative example 3 in equal amounts, and the remaining component proportions and the preparation method were the same as in example 5.
Performance detection
(1) Solvent resistance test: 1g of the pigment prepared in examples 5 to 8 and comparative examples 4 to 6 was added to 15g of the solvent and shaken well. After 24 hours, the state of the pigment in the solvent was observed, and the detection results are shown in Table 1.
Table 1: solvent resistance test of examples 5 to 8 and comparative examples 4 to 6
(2) Migration test: 0.36g of the pigments prepared in examples 5 to 8 and comparative examples 4 to 6 were added to 150g of PVC resin particles, respectively, to prepare injection molded plaques at 170℃and press-fit the above injection molded plaques with blank injection molded plaques (without adding pigments) in an oven at 60 ℃. And (3) attaching the colorless transparent plate which is not used for resisting migration and the two colorless transparent plates which are used for resisting migration to A4 paper side by side, attaching the colorless transparent plate which is not used for resisting migration to the middle, attaching the two colorless transparent plates which are used for resisting migration to two sides, visually observing the colors of the two colorless transparent plates which are used for resisting migration, and judging the migration resistance of the product. If no color is seen on the two colorless transparent plates with migration resistance, the product can be judged to have good migration resistance. On the color measuring instrument, the colorless transparent sample plate which is not used for resisting migration is set as a reference, the color difference of the two colorless transparent sample plates which are used for resisting migration is measured respectively, if the color difference of the two sample plates is less than or equal to 0.5, the product can be judged to have good migration resistance, and the detection results are shown in tables 2-3.
Table 2: migration Performance test of examples 5-8, comparative examples 4-6
| 1d | 3d | 7d | 15d | 30d | |
| Example 5 | No color | Light color | Deeper | Dark color | Dark color |
| Example 6 | No color | Light color | Deeper | Dark color | Dark color |
| Example 7 | No color | No color | Light color | Light color | Light color |
| Example 8 | No color | No color | Light color | Deeper | Dark color |
| Comparative example 4 | Light color | Deeper | Dark color | Dark color | Dark color |
| Comparative example 5 | No color | Light color | Deeper | Dark color | Dark color |
| Comparative example 6 | No color | Light color | Deeper | Dark color | Dark color |
Table 3: color difference data in migration performance test of examples 5 to 8 and comparative examples 4 to 6
As is clear from tables 2 to 3, the pigment prepared in example 7 was found to have the best migration resistance and can withstand more than 30 days by visual observation and instrumental color difference measurement.
(3) Light fastness test: 6g of the pigments prepared in examples 5 to 8 and comparative examples 4 to 6 were weighed and placed in 50mL stainless steel cups, respectively, and 14g of transparent ink was added to the mixture and stirred uniformly on a stirrer. And (3) uniformly coating the uniformly stirred sample on a white cloth strip by using a scraper, wherein the effective coating area is not smaller than 5cm multiplied by 3cm, and pulling out 10 white cloth strip samples by using the same method.
The sample cloth is simultaneously placed in a sunning field with sufficient sun rays for solarization (or an ultraviolet aging box with the temperature set at 40 ℃), and the solarization time is analyzed as follows: 4. 8, 16, 32, 64 and 72 hours, and taking non-exposed sample cloth as a standard, testing chromatic aberration, wherein the smaller chromatic aberration is the better the light resistance, and the detection result is shown in table 4.
Table 4: light fastness detection data for examples 5-8, comparative examples 4-6
| 2h | 4h | 8h | 16h | 32h | 72h | |
| Example 5 | 0.35 | 0.86 | 1.21 | 1.56 | 2.81 | 3.62 |
| Example 6 | 0.28 | 0.69 | 0.95 | 1.29 | 2.65 | 4.15 |
| Example 7 | 0.08 | 0.15 | 0.26 | 0.32 | 0.47 | 0.68 |
| Example 8 | 0.24 | 0.23 | 0.45 | 0.86 | 1.65 | 2.59 |
| Comparative example 4 | 1.25 | 2.93 | 4.65 | 5.33 | 6.41 | 7.25 |
| Comparative example 5 | 0.43 | 1.45 | 2.21 | 3.77 | 5.11 | 5.99 |
| Comparative example 6 | 0.39 | 1.37 | 2.08 | 3.41 | 4.78 | 5.67 |
As is clear from Table 4, the pigment prepared in example 7 of the present application has the best effect of light resistance.
(4) The detection result is shown in Table 5 according to the detection of the industry standard HG/T5188-2017 fluorescent pigment.
Table 5: examples 5 to 8 and comparative examples 4 to 6 were related to the detection data
Compared with the existing fluorescent pigment of a tosylamide-formaldehyde-melamine resin system and the pigment prepared in comparative examples 4-5, the melamine resin daylight type fluorescent pigment modified by adding polyethylene glycol and urea prepared in the invention has the advantages of obviously improved solvent resistance, migration resistance, heat resistance and light resistance, high softening point and better fluorescence degree of products.
The foregoing describes one embodiment of the present invention in detail, but the description is only a preferred embodiment of the present invention and should not be construed as limiting the scope of the invention. All equivalent changes and modifications within the scope of the present invention are intended to be covered by the present invention.
Claims (9)
1. The preparation method of the modified melamine resin daylight type fluorescent pigment is characterized by comprising the following steps of:
s1: adding benzomelamine and paraformaldehyde into a reaction kettle, heating and stirring, adjusting pH to be alkaline, and carrying out heat preservation reaction to obtain a mixture A;
s2: adding polyethylene glycol into the mixture A, and carrying out heat preservation reaction to obtain a mixture B;
s3: adding methanol into the mixture B, adjusting pH to be acidic, and carrying out heat preservation reaction to obtain a mixture C;
s4: adding urea into the mixture C, heating, preserving heat and stirring to obtain modified melamine resin;
s5: adding fluorescent dye and auxiliary agent into modified melamine resin, stirring uniformly, discharging, cooling, drying and crushing to obtain the modified melamine resin daylight type fluorescent pigment.
2. The method for preparing a modified melamine resin type daylight type fluorescent pigment according to claim 1, wherein the benzomelamine: paraformaldehyde: polyethylene glycol: methanol: the mass ratio of urea is 90-100:40-110:6-10:40-110:4-7.
3. The method for producing a modified melamine resin-based daylight type fluorescent pigment according to claim 1, wherein the modified melamine resin: fluorescent dye: the mass ratio of the auxiliary agent is 100:3-7:1-2.
4. The method for producing a modified melamine resin type daylight type fluorescent pigment according to claim 1, wherein the step of adjusting the pH to be alkaline in S1 is specifically adding a 10% by mass aqueous sodium hydroxide solution to adjust the pH to 8.5 to 9.
5. The method for producing a modified melamine resin based daylight type fluorescent pigment according to claim 1, wherein the pH adjustment in S3 is carried out to be acidic, specifically, the pH adjustment is carried out to be 5 to 5.5 by adding an aqueous solution of citric acid having a mass concentration of 10%.
6. The method for preparing a modified melamine resin daylight type fluorescent pigment according to claim 1, wherein the heat preservation reaction in S1 is specifically carried out by heating to 80-90 ℃ and then carrying out the heat preservation reaction for 10-20min.
7. The method for preparing a modified melamine resin daylight type fluorescent pigment according to claim 1, wherein the heat preservation reaction in S2 is specifically heating to 80-90 ℃, and the heat preservation reaction is carried out for 20-40min.
8. The method for preparing a modified melamine resin daylight type fluorescent pigment according to claim 1, wherein the heat preservation reaction in S3 is specifically carried out by cooling to 40-60 ℃ and then carrying out the heat preservation reaction for 60-70min.
9. The method for preparing a modified melamine resin daylight type fluorescent pigment according to claim 1, wherein the temperature rise in S4 is specifically 75-95 ℃, and the temperature keeping stirring is performed for 20-40min.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3795628A (en) * | 1970-11-11 | 1974-03-05 | Hoechst Ag | Daylight fluorescent pigments and process for preparing them |
| CN1053626A (en) * | 1990-01-25 | 1991-08-07 | 北京工业大学特种颜料厂 | Water soluble tri-idiochromatic fluorescent printing ink and preparation method thereof |
| US5439971A (en) * | 1991-11-12 | 1995-08-08 | Eastman Chemical Company | Fluorescent pigment concentrates |
| CN111848917A (en) * | 2020-08-12 | 2020-10-30 | 黄山加佳荧光材料有限公司 | Preparation method and application of polyurea fluorescent microsphere pigment |
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- 2023-03-15 CN CN202310249880.5A patent/CN116239895A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3795628A (en) * | 1970-11-11 | 1974-03-05 | Hoechst Ag | Daylight fluorescent pigments and process for preparing them |
| CN1053626A (en) * | 1990-01-25 | 1991-08-07 | 北京工业大学特种颜料厂 | Water soluble tri-idiochromatic fluorescent printing ink and preparation method thereof |
| US5439971A (en) * | 1991-11-12 | 1995-08-08 | Eastman Chemical Company | Fluorescent pigment concentrates |
| CN111848917A (en) * | 2020-08-12 | 2020-10-30 | 黄山加佳荧光材料有限公司 | Preparation method and application of polyurea fluorescent microsphere pigment |
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