CN109627490A - A kind of red toner and preparation method thereof applied to coloring resin - Google Patents
A kind of red toner and preparation method thereof applied to coloring resin Download PDFInfo
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- CN109627490A CN109627490A CN201811484140.5A CN201811484140A CN109627490A CN 109627490 A CN109627490 A CN 109627490A CN 201811484140 A CN201811484140 A CN 201811484140A CN 109627490 A CN109627490 A CN 109627490A
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- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- 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
- 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
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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
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
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Abstract
The red toner and preparation method thereof that the present invention relates to a kind of applied to coloring resin, general structure is as shown in I:
Description
Technical field
The invention belongs to toner fields, and in particular to a kind of high-temperature resistant applied to coloring resin, resistance to migration, easily
Red toner of dispersion and preparation method thereof.
Background technique
The development of material science is higher and higher to the performance requirement of colorant, except excellent weatherability, light resistance and each
Except kind chemical resistance, there is higher requirement to the temperature tolerance of colorant, the resistance to migration in resin and dispersibility.It is organic
Colorant a part is all kinds of dyestuffs and solvent dye with certain water solubility or solvent soluble, and another part is insoluble in water
With the pigment of various applicating mediums.Coloring resin can only be solvent dye and pigment, and water-soluble dye cannot be applied.Although this kind of
Colorant commodity are various, but for coloring resin have the defects that it is certain.Such as: solvent dye has good coloring
Can, dispersion is dissolved in resin, but will appear in coloring process or in coloring object placement process color spilling, i.e., it is so-called resistance to
Migration is poor.And organic pigment is bright in luster, properties are good, do not migrate, but due to compact crystal structure, easily assemble, and answering
It is distributed in applicating medium with middle difficulty, especially when high-precision colours, such as in fiber original liquid coloring field, numerial code spray drawing field etc.
It will appear blockage problem, and color reducibility is poor, it is difficult to reach the coloring effect of dyestuff.
The existing disclosed colorant containing Anthrapyridone structure is more, and be directed to solvent dye has 4, is respectively
C.I. solvent red 52, C.I. solvent red 149, C.I. solvent red 150, C.I. solvent red 151；
Above structure colorant is bright in luster, and tinting strength, tinting power is high, and temperature tolerance is good (280 DEG C), can be coloured with thermoplastic resin.
But since molecule is small, solubility is big in a solvent, may not apply to high-quality product, especially apply the high PET of processing temperature,
In PA resin, it may occur that color transfer, i.e. resistance to migration are poor.
In recent years, many around Anthrapyridone mechanical development colorant research report, such as: being published within 2003 " dyestuff and dye
Color " on periodical, Jiangsu Aolunda Science and Technology Industry Co., Ltd Yin Yi et al. using halogenated Anthrapyridone as primary raw material, with
Ammonium hydroxide, monomethyl amine, monoethyl amine, n-propylamine, n-butylamine, ethanol amine, para-totuidine, 3,4- dimethylaniline, P-nethoxyaniline,
O-isopropyl aniline, isopropyl aniline, cumidine, to n-butyl aniline, p-tert-butyl-aniline, cyclohexylamine and benzyl
16 kinds of amine of amine carry out being condensed to yield corresponding dyestuff, and have carried out the measurement of solubility to the dyestuff of synthesis, it was therefore concluded that: it closes
At 16 kinds of compounds solubility in organic solvent increase instead with the reduction of solvent polarity；Solubility with carbochain increasing
Solubility is added to gradually increase.
Chinese patent CN 101535269A, which is disclosed, is related to the thermostable type colorant of Anthrapyridone compounds, can be used for
The coloring of polycarbonate article has excellent heat resistance, light resistance, bleeding resistance.Disclosed two new construction Anthrapyridones
Compound is as follows.
Dalian University of Technology's master thesis, Li Shiyu et al. have synthesized four novel anthrapyridone class magenta dyes
Material, such dyestuff have good light fastness stability energy.For water-soluble dye, four dye structures are as follows:
Around report of the research mainly from Japan for increasing molecular structure.
Japan Patent JP 2003-192930 A discloses the rosaniline dyes of a kind of Anthrapyridone structure within 2003, wherein R
Selected from hydrogen atom, alkyl or cyclohexyl, Y is selected from hydrogen atom, hydroxyl, amino, list or dialkyl amido, alkoxy, phenylamino, benzene
Oxygroup, aralkyl or cycloalkyl amino, naphthyl-amino etc., X group are selected from ethylenediamine, butanediamine, hexamethylene diamine etc., such compound exists
It is fast light, water-fast etc. that there is splendid fastness.
Patent JP 2012-126770 A disclosed in Japanese chemical drugs in 2012 discloses a new class of Anthrapyridone compounds,
Structure is as follows, and group X is ethylenediamine tetra-acetic acid dianhydride, which has the tone of high-resolution, in fast light, fastness to weathering side
Face is excellent.
But the studies above remains as water-soluble dye, and main application fields are numerial code spray drawing.And antimeric abutment is
Soft segment does not have rigid structural, therefore cannot form certain crystallinity, it is difficult to solve the problems, such as in coloring resin.
Summary of the invention
The object of the present invention is to provide the red toners and its system applied to coloring resin of a kind of structure novel
Preparation Method.
To achieve the above object, the invention adopts a technical scheme as:
A kind of red toner applied to coloring resin, colorant are compound shown in general formula I,
General formula I
In formula:
R is selected from hydrogen, C1-C4Alkyl, C1-C4Alkoxy or halogen.
It is preferred that in the general formula I R be selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl,
Methoxyl group, ethyoxyl, chlorine or bromine.
It is further preferred that R is selected from hydrogen, methyl or chlorine in the general formula I.
The preparation method of red toner applied to coloring resin,
Method one: reaction equation is
Wherein: X is selected from Cl, Br；
R is selected from-H, C1-C4Alkyl, C1-C4Alkoxy or halogen；
6-X-N- methyl-Anthrapyridone (6-X-3-methyl-3H-naphtho [1,2,3-de] quinoline-2,7-
Dione it) mixes with 2,4- diamino -6- substituted-phenyl -1,3,5-triazines, in high boiling organic solvent, in catalyst and ties up
In the presence of sour agent, by Ullmann condensation reaction, compound of Formula I is arrived.
Further, the 6-X-N- methyl-Anthrapyridone and 2,4- diamino -6- substituted-phenyl -1,3,5-triazines
Mixing, in high boiling organic solvent, in the presence of catalyst and acid binding agent, at 160-180 DEG C, is condensed by Ullmann
10-12h is reacted, compound of Formula I is obtained；Wherein, 6-X-N- methyl-Anthrapyridone and 2, substituted-phenyl -1 4- diamino -6-,
3,5- triazine molar ratios are 2:1, and high boiling organic solvent and 6-X-N- methyl-Anthrapyridone weight ratio are 10-13:1, acid binding agent
With 6-X-N- methyl-Anthrapyridone molar ratio 1:1, catalyst and 6-X-N- methyl-Anthrapyridone weight ratio are 1:14-16.
Method two, reaction equation are
6- Amino-N-methyl-Anthrapyridone and the chloro- 6- substituted-phenyl -1,3,5- triazine of 2,4- bis- are organic molten in higher boiling
In agent, Ullmann condensation reaction is carried out in the presence of acid binding agent and catalyst, arrives compound of Formula I.
Further, 6- Amino-N-methyl-Anthrapyridone and 2, the chloro- 6- substituted-phenyl -1,3,5-triazines of 4- bis- is in height
In boiling point organic solvent, in the presence of acid binding agent and catalyst, pass through Ullmann condensation reaction 10-12h at 160-170 DEG C,
To compound of Formula I；Wherein, 6- Amino-N-methyl-Anthrapyridone and 2, the chloro- 6- substituted-phenyl -1,3,5-triazines mole of 4- bis-
Than being 11-13:1, acid binding agent and 6- amino-for 2:1, high boiling organic solvent and 6- Amino-N-methyl-Anthrapyridone weight ratio
N- methyl-Anthrapyridone molar ratio 1:1, catalyst and 6- Amino-N-methyl-Anthrapyridone weight ratio are 1:14-16.
Raw material in two synthetic method of the method can be synthesized by existing literature to be obtained, such as 1016283 He of document SU
S.von Angerer.Product subclass 3:1,3,5-triazines and phosphorus analogues [J]
.Science of Synthesis, 2004,1 (7): 449-583. refers to the synthetic method of raw material.
In above two synthetic method, the catalyst is selected from copper powder, stannous chloride, cuprous iodide, copper acetate or sulfuric acid
Copper, preferably stannous chloride or cuprous iodide；Acid binding agent is alkali carbonate or alkali metal hydrogencarbonate；Preferred as alkali carbonic acid
Hydrogen salt.
High boiling organic solvent described in the above method one is usually dichloro-benzenes, nitrobenzene, dimethyl sulfoxide, N- methylpyrrole
Alkanone or alkylbenzene.
Inert organic solvents described in method two are dichloro-benzenes, nitrobenzene, dimethyl sulfoxide or alkylbenzene.
Described after Ullmann condensation reaction in above two synthetic method, product is heat-treated simultaneously through polar organic solvent
Partial size adjusts the compound of Formula I of the red powder to get fluffy configuration, disperses convenient for subsequent application, and can reduce
Recycling design cost.
The polar organic solvent is alcohols, N,N-dimethylformamide, dimethyl sulfoxide etc.；It is preferred that alcohols is organic molten
Agent.Wherein alcohols can be methanol, ethyl alcohol, n-butanol, isobutanol, amylalcohol, tert-pentyl alcohol, octanol etc..Further preferably butanol.
For above two synthetic method for the easy property processed of raw material and source, one synthetic method of method is more excellent.
A kind of application of the red toner applied to coloring resin, the compound of Formula I are used as resin
Application in colorant.
The resin can be PE, PP, PET, PC, PA ABS resin, PS resin, PMMA etc..Can be used for preparing Masterbatch,
The fields such as fiber original liquid coloring, plastic film, plastic cement printing or injection molding.Beneficial effects of the present invention protrusion is embodied in:
1. the present invention is suitable for the toner of coloring resin, which is that gorgeous yellow light is red, 320 DEG C of fusing point, XRD
Analysis shows that apparent crystallinity, electron microscope are shown as tiny rodlike crystallization out.The coloring agent particle is soft, using scraping
Plate fineness instrument detects the easily disperse energy of the colorant, and more traditional organic pigment easily disperse is obvious.
2. colorant of the present invention carries out temperature tolerance test, using PET resin injection moulding process, injecting condition is that this field is organic
Pigment limit testing conditions, i.e., 300 DEG C stop 5 minutes, the fine C.I. pigment of temperature tolerance generally acknowledged with fiber original liquid coloring field
Huang 147 does reference standard, its color change value of chromatism of colorant of the present invention has significant advantage, compared with C.I. pigment yellow
147 have better temperature tolerance.
3. carrying out patience test using national standard method, optimal rating scale is 5 grades, and worst is 1 grade, the present invention relates to
Colorant 5 grades of patience are illustrated as in opposed polarity organic solvent, while its resistance to acid and alkali is 5 grades, is shown excellent
Solvent resistance and chemical resistance.
To sum up, compound of Formula I of the present invention is toner structure novel, red for gorgeous yellow light, is had resistance to well
Hot, solvent resistance and easily disperse energy can satisfy the heatproof in the coloring resin of the high temperature process such as PET, resistance to migration is wanted
It asks, and particle is soft, there is fine easily disperse.As the purposes of resin colorant, it can be used for Masterbatch, fiber stoste
The fields such as color, plastic film, plastic cement printing or injection molding, meet PE, PP, PET, PC, PA ABS resin, PS resin, PMMA etc.
Using with potential commercial value.
Detailed description of the invention
Fig. 1 is the transmission microscopic appearance figure of the colorant that provides of the embodiment of the present invention 1 under an optical microscope.
Fig. 2 is the scanning microscopic appearance figure of the colorant that provides of the embodiment of the present invention 1 under an electron microscope.
Fig. 3 is the XRD analysis figure of colorant of the present invention.
Specific embodiment
The following example is for present invention be described in more detail.In embodiment unless otherwise stated, the number and
Percentage is by weight.
The migration difference of colorant known to those skilled in the art be typically due to colorant have in applicating medium it is certain
There is supersaturation precipitation as application conditions change in dissolubility；Either colorant temperature tolerance is poor, divides in high temperature application
Solution, distillation, overflow color.Therefore temperature tolerance and solvent resistance are the essential conditions of evaluation coloring resistance to migration.Dispersibility is
Since the molecular polarity of compound, flatness and symmetry influence the growth and aggregation of its nascent state structure, to influence
The crystal form of colorant and the size of aggregation and hardness.The compound of structure novel is provided based on this present invention, it will
Molecular polarity is moderate, it is larger that there is fine durothermic Anthrapyridone structure to be connected by triazine structure compound as abutment
The compound of molecular weight.The compound maintains the excellent temperature tolerance feature of Anthrapyridone structure, and due to the increasing of molecular weight
It ensure that its solvent resistance feature greatly, to guarantee its resistance to migration；Abutment triazine structure connects the molecule knot so that big simultaneously
Structure rigidity enhances but does not have flatness, although overall molecule structure has symmetry and rigidity, since flatness is poor, still
It influences whether the growth of crystalline solid and the growth and aggregation of nascent state particle, therefore compound particle is soft, is easy to be situated between in application
Disperse in matter, to have preferable easily disperse.
Anthrapyridone compounds shown in general formula I of the present invention are characterized in that gorgeous yellow light is red, have excellent heat resistance, lead to
Cross the injection molded test and resistance to ethyl alcohol, ethyl acetate, n,N-Dimethylformamide, diformazan that 5min is stopped at 300 DEG C of PET resin
The bleed test of base sulfoxide equal solvent and the experiment of acidproof alkali process, it was demonstrated that compound of Formula I can be used under hot conditions
The coloring of resin, will not because of the injecting condition and resin of high temperature and plasticizer etc. polarity and lead to the migration of color.Together
When compound of Formula I particle it is soft, be easily dispersed, be the colorant with potential commercial value, can be used for PE PP
The coloring of the resins such as PET, PA ABS can be used for the original liquid coloring of the fibers such as terylene, polypropylene fibre, acrylic fibers, spandex.
Prepare embodiment
Embodiment 1
Reaction equation are as follows:
Wherein: X is selected from Br；R is selected from-H.
In 250mL four-hole boiling flask, be added the bromo- N- methyl-Anthrapyridone of 7.1 parts of 6-, 1.87 parts of benzoguanamines,
0.42 part of cuprous iodide and 90 milliliters of alkylbenzenes.170 DEG C are warming up to, insulation reaction 30 minutes, 2.1 are then gradually added by several times
Part sodium bicarbonate, adjusts the pH of reaction, reacts 12 hours at a temperature of 165 DEG C~170 DEG C.It is complete by liquid chromatogram tracking reactant
It totally disappeared mistake, cool to 90-95 DEG C.Alkylbenzene mother liquor is recycled in filtering.Colourless to filtrate with a small amount of ethanol washing filter cake, recycling is washed
Liquid.Filter cake is washed with water and is shown as neutral to pH, moves into lower step processing.
Take filter cake be added 100 milliliters of butanol solutions, be sufficiently stirred 2 hours, after be warming up to reflux, maintain the reflux for 3 hours, drop
For temperature to 50 DEG C, heat filtering recycles mother liquor.A small amount of washing, drying, obtain about 6.1 grams of dry powder.Appearance: deep red powder, yield
86.5%.
Embodiment 2
Difference from Example 1 is, cuprous iodide will be replaced as catalysis using stannous chloride in above-mentioned preparation process
Agent repeats the operating procedure of embodiment 1, obtains about 5.9 grams of dry powder.Appearance: deep red powder, yield 83.7%.
Embodiment 3
Difference from Example 1 is, replaces alkylbenzene as solvent using o-dichlorohenzene, in 250mL four-hole boiling flask,
The bromo- N- methyl-Anthrapyridone of 6.8 parts of 6-, 1.87 parts of benzoguanamines, 0.42 part of catalyst cuprous iodide is added, is added 80
Milliliter o-dichlorobenzene solution is warming up to 170 DEG C, and during which 2.1 parts of acid binding agent sodium bicarbonates are added in insulation reaction by several times, adjustment is anti-
The pH answered reacts 12 hours, and liquid chromatogram shows that the material consumption of system Central Plains is completed, and reaction terminates.90-95 DEG C is cooled to, is filtered,
It is washed with o-dichlorohenzene substantially colorless to filtrate, then obtains wet cake with pure and mild be washed to after neutrality, filtrate recycling.
It takes filter cake that 100 milliliters of butanol solutions are added, is sufficiently stirred 2 hours, be warming up to reflux, heat preservation reflux 3 hours, cooling
Filtering, washing, drying.Obtain about 6.12 grams of dry powder.Appearance: red yield 86.8%.
By dry powder sample obtained by the various embodiments described above, the viewed in transmittance under 400 times of optical microscopies, sample are tiny respectively
Rodlike crystallization, particle is tiny, and size distribution is uniform, there is (referring to Fig. 1) without apparent big aggregation, ensure that colorant
Apply the coloring in resin that there is good color characteristics and easily disperse.Observing sample by electron-microscope scanning again simultaneously has
Apparent rodlike crystallization shape (referring to fig. 2).
Then above-mentioned acquisition sample is done further XRD analysis (referring to Fig. 3), the dry powder sample compound of preparation has
Apparent crystalline state and crystallinity, have organic pigment feature.
It can be seen that above-mentioned gained colorant has the crystallization shape of complete rule, have organic pigment characteristics.Compound tool
There are more perfect crystal structure and crystallinity, so that it is with good temperature tolerance, solvent resistance and chemical resistance, and aobvious
Show preferable color effects.
Embodiment 4
2,4- diamino -6- benzene -1,3,5-triazines is replaced with into 2.01 parts of 2,4- diaminos with 1 preparation method of above-described embodiment
Base -6- methylbenzene -1,3,5-triazines obtains about 5.96 grams of dry powder.Appearance: kermesinus, yield 82.9%.
Embodiment 5
2,4- diamino -6- benzene -1,3,5-triazines is replaced with into 2.21 parts of 2,4- diaminos with 1 preparation method of above-described embodiment
Base -6- chlorobenzene -1,3,5-triazines obtains about 6.15 grams of dry powder.Appearance: dark red powder, yield 83.2%.
R=alkane proposed by the present invention can also be prepared by being simultaneously replaced raw material according to above-mentioned preparation method
Other compounds when base, alkoxy or halogen similarly have the characteristics that said effect in addition to form and aspect shift.
Application Example
The application performance and application effect of the following example the present invention will be described in detail colorant, with the acquisition of above-described embodiment 1
For sample, while other compounds that the present invention limits also have the characteristics that corresponding effect.
Embodiment 6: color characteristic test
1 gained sample of embodiment is uniformly mixed with the additive amount of 1wt% with polyester PET powder, in 280 DEG C of injection molding systems
At PET injection-molded plaques, electronics colour photometer is used with Lab system, to carry out color detection, the color characteristic of sample is such as under d 65 illuminant
Table 1:
Table 1: the PET injection-molded plaques chromatic value of sample
Table 1 shows that compound of the present invention is that gorgeous yellow light is red, has good vividness, can be used as colorant makes
With.
Embodiment 7: easily disperse can be tested
It takes above-described embodiment 1 not plus pre-dispersed and pulverization process colorant dry powder 6# varnish is raised in plain grinding instrument
It is even.It is ground in the case where counterweight is not added, is changed with the fineness of grind of Hegman fineness grind instrument tracing detection colorant.
Table 2: the easily disperse of sample
Usually there is the organic pigment for improving crystallization to be easy to that particle aggregation occurs during the drying process, form hard
Grain, it is difficult to be distributed in applicating medium, it is necessary to carry out pre-dispersed processing and efficient pulverization process, and to pass through certain mesh
Several screen such as 100 mesh, 300 mesh etc. just can be carried out application.Certain pressure is used when being detected with plain grinding instrument, it is usually flat
Grinding instrument and carrying counterweight pressure is 47 kilograms.This application embodiment sample used is without at any pre-dispersed processing and crushing
Reason, directly progress plain grinding instrument detection.And remove the counterweight of plain grinding instrument when detecting.The test result of table 2 shows do not divided in advance
In the case where dissipating with pulverization process, colorant of the invention can be completely dispersed under lesser grinding condition, the present invention relates to
Colorant have preferable easily disperse.
Embodiment 8: solvent resistance detection
Water resistance, solvent resistance, resistance to acid and alkali according to GB/T 5211.5-2008 " pigment tolerance determination method " etc. are to this
The sample of inventive embodiments 1 carries out fastness ability detection.It the results are shown in Table 3:
Table: 3: the part fastness ability of sample
Compound of the present invention meets the solvent resistant of high-performance colorant and the requirement of chemical resistance, in resin application
In can be to avoid by solubility bring migration problem.
Embodiment 9: heat resistance test
It is that 1wt% and PET resin mix to obtain mixture by the resulting color additive of embodiment 1, is infused at 300 DEG C
Modeling.Residence time is respectively 15 seconds and stops 5 minutes, and injection-molded plaques are made, and carries out acetes chinensis.It simultaneously can with art-recognized
The C.I. pigment yellow 147 for meeting PET fiber original liquid coloring temperature tolerance requirement be molded with condition, compares its discoloration.Color
Using electronics colour photometer, Lab system carries out DE comparison under d 65 illuminant for difference detection, judges the sample of embodiment 1 in PET tree with this
Heat resistance in rouge.Testing result such as table 4
Table 4: the heat resistance in sample P ET resin
Test result shows that colorant of the present invention has good temperature tolerance, resistance to compared with the height that industry generally uses
Warm nature C.I. pigment yellow 147 has better temperature tolerance.The high temperature process coloring that can satisfy the resins such as PET requires, while also keeping away
The migration of color caused by exempting from because of temperature tolerance difference.
Embodiment 10: resistance to migration can be tested
The measuring method of resistance to migration energy: 1 gained sample of embodiment is mixed with the additive amount of 2wt% with polyester PET powder
Uniformly, PET injection-molded plaques are made in 275 DEG C of injection moldings, take one piece of (3.2 × 2.0) cm colour PET sheet, be placed on one piece it is white
Above the PET looped fabric of color, it is subject to after placing 3min in the pressure of 7MPa and the inside heat-circulation oven of 180 DEG C of temperature, removing has
Color PET sheet is observed on white PET looped fabric by contamination degree (by electronics colour photometer under d 65 illuminant with the progress of Lab system
The measurement of DE value), according to ISO 105-A03 Standard Judgement.5 grades of expressions are non-migratory, and 1 grade of expression migration is serious, and resistance to migration is surveyed
Test result such as table 5:
Table 5: sample resistance to migration test
Test result shows that colorant of the present invention has good resistance to migration, is detected according to ISO105-A03
Standard Judgement is 4-5 grades.
Claims (10)
1. a kind of red toner applied to coloring resin, it is characterised in that: colorant is compound shown in general formula I,
In formula:
R is selected from hydrogen, C1-C4Alkyl, C1-C4Alkoxy or halogen.
2. the red toner according to claim 1 applied to coloring resin, it is characterised in that: R in the general formula I
Selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, methoxyl group, ethyoxyl, chlorine or bromine.
3. the red toner as described in claim 2 applied to coloring resin, it is characterised in that: R in the general formula I
Selected from hydrogen, methyl or chlorine.
4. a kind of preparation method of the red toner described in claim 1 applied to coloring resin, it is characterised in that:
Wherein: X is selected from Cl, Br；
R is selected from-H, C1-C4Alkyl, C1-C4Alkoxy or halogen；
6-X-N- methyl-Anthrapyridone and 2,4- diamino -6- substituted-phenyl -1,3,5-triazines mixing are organic molten in higher boiling
In agent, in the presence of catalyst and acid binding agent, by Ullmann condensation reaction, compound of Formula I is obtained.
5. the preparation method of the red toner according to claim 4 applied to coloring resin, it is characterised in that: institute
State 6-X-N- methyl-Anthrapyridone and 2,4- diamino -6- substituted-phenyl -1,3,5-triazines mixing, in high boiling organic solvent
In, in the presence of catalyst and acid binding agent, at 160-180 DEG C, by Ullmann condensation reaction 10-12h, obtain general formula Iization
Close object；Wherein, 6-X-N- methyl-Anthrapyridone and 2,4- diamino -6- substituted-phenyl -1,3,5-triazines molar ratio is 2:1, high
Boiling point organic solvent and 6-X-N- methyl-Anthrapyridone weight ratio are 10-13:1, acid binding agent and 6-X-N- methyl-Anthrapyridone
Molar ratio 1:1, catalyst and 6-X-N- methyl-Anthrapyridone weight ratio are 1:14-16.
6. a kind of preparation method of the red toner described in claim 1 applied to coloring resin, it is characterised in that:
Reaction equation is
6- Amino-N-methyl-Anthrapyridone and 2, the chloro- 6- substituted-phenyl -1,3,5-triazines of 4- bis- in high boiling organic solvent,
Ullmann condensation reaction is carried out in the presence of acid binding agent and catalyst, arrives compound of Formula I.
7. the preparation method of the red toner according to claim 6 applied to coloring resin, it is characterised in that: 6-
Amino-N-methyl-Anthrapyridone and 2, the chloro- 6- substituted-phenyl -1,3,5-triazines of 4- bis- are tiing up acid in high boiling organic solvent
In the presence of agent and catalyst, passes through Ullmann condensation reaction 10-12h at 160-170 DEG C, arrive compound of Formula I；Wherein, 6-
Amino-N-methyl-Anthrapyridone and 2, the chloro- 6- substituted-phenyl -1,3,5-triazines molar ratio of 4- bis- are 2:1, and higher boiling is organic molten
Agent and 6- Amino-N-methyl-Anthrapyridone weight ratio are 11-13:1, acid binding agent and 6- Amino-N-methyl-Anthrapyridone mole
Than 1:1, catalyst and 6- Amino-N-methyl-Anthrapyridone weight ratio are 1:14-16.
8. by the preparation method for the red toner for being applied to coloring resin described in claim 4,5,6 or 7, feature
Be: the catalyst is selected from copper powder, stannous chloride, cuprous iodide, copper acetate or copper sulphate；Acid binding agent is alkali carbonate
Or alkali metal hydrogencarbonate；The high boiling organic solvent is alkylbenzene, dichloro-benzenes, nitrobenzene, dimethyl sulfoxide or N- methyl
Pyrrolidones.
9. by the preparation method for the red toner for being applied to coloring resin described in claim 4,5,6 or 7, feature
It is: described after Ullmann condensation reaction, the red powder that product is heat-treated to get fluffy configuration through polar organic solvent
The compound of Formula I of shape.
10. a kind of application of red toner described in claim 1, it is characterised in that: the compound of Formula I is being made
For the application in resin colorant.
Priority Applications (1)
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| CN113024889A (en) * | 2021-04-30 | 2021-06-25 | 鞍山辉虹颜料科技有限公司 | Organic colorant for coloring resin and preparation method thereof |
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| CN109627490B (en) | 2021-02-05 |
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