CN105778564A - Pigment composition containing rosinamino-bisazo condensation compound and preparation method of pigment composition - Google Patents
Pigment composition containing rosinamino-bisazo condensation compound and preparation method of pigment composition Download PDFInfo
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- CN105778564A CN105778564A CN201610130721.3A CN201610130721A CN105778564A CN 105778564 A CN105778564 A CN 105778564A CN 201610130721 A CN201610130721 A CN 201610130721A CN 105778564 A CN105778564 A CN 105778564A
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- 239000000049 pigment Substances 0.000 title claims abstract description 63
- 150000001875 compounds Chemical class 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 238000009833 condensation Methods 0.000 title abstract description 21
- 230000005494 condensation Effects 0.000 title abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000001052 yellow pigment Substances 0.000 claims abstract description 8
- 150000001412 amines Chemical class 0.000 claims description 25
- 150000004982 aromatic amines Chemical class 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 150000002430 hydrocarbons Chemical group 0.000 claims description 12
- -1 anilino- Chemical class 0.000 claims description 9
- 150000004816 dichlorobenzenes Chemical class 0.000 claims description 7
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical group 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 238000006482 condensation reaction Methods 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000003368 amide group Chemical group 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims description 3
- RQRKMXABSUYQBV-UHFFFAOYSA-N 2-chloro-3-methylaniline Chemical compound CC1=CC=CC(N)=C1Cl RQRKMXABSUYQBV-UHFFFAOYSA-N 0.000 claims description 3
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 3
- 150000001448 anilines Chemical class 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 3
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 abstract description 18
- 125000001769 aryl amino group Chemical group 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000976 ink Substances 0.000 description 23
- 239000000047 product Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000004033 plastic Substances 0.000 description 12
- 229920003023 plastic Polymers 0.000 description 12
- 239000000460 chlorine Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 229920001684 low density polyethylene Polymers 0.000 description 7
- 239000004702 low-density polyethylene Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- ZUVPLKVDZNDZCM-UHFFFAOYSA-N 3-chloro-2-methylaniline Chemical compound CC1=C(N)C=CC=C1Cl ZUVPLKVDZNDZCM-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 5
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 5
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 5
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 4
- 229940117389 dichlorobenzene Drugs 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000009738 saturating Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
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- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000019612 pigmentation Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DMGFVJVLVZOSOE-UHFFFAOYSA-N 3-amino-4-chlorobenzoic acid Chemical compound NC1=CC(C(O)=O)=CC=C1Cl DMGFVJVLVZOSOE-UHFFFAOYSA-N 0.000 description 1
- 0 CC([C@](C(Nc(c(Cl)c1)cc(C)c1N(C)C([C@@](C(C)=O)N=*c(cc(cc1)C(*)=O)c1Cl)=O)=O)N=Nc1c(*)ccc(C(*)=O)c1)=N Chemical compound CC([C@](C(Nc(c(Cl)c1)cc(C)c1N(C)C([C@@](C(C)=O)N=*c(cc(cc1)C(*)=O)c1Cl)=O)=O)N=Nc1c(*)ccc(C(*)=O)c1)=N 0.000 description 1
- 229920002160 Celluloid Polymers 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 1
- 238000010218 electron microscopic analysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- WPPDXAHGCGPUPK-UHFFFAOYSA-N red 2 Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=2C=3C4=CC=C5C6=CC=C7C8=C(C=9C=CC=CC=9)C9=CC=CC=C9C(C=9C=CC=CC=9)=C8C8=CC=C(C6=C87)C(C=35)=CC=2)C4=C1C1=CC=CC=C1 WPPDXAHGCGPUPK-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000012795 verification Methods 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
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0046—Mixtures of two or more azo dyes
- C09B67/0055—Mixtures of two or more disazo dyes
-
- 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
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/23—Azo-compounds
- C08K5/235—Diazo and polyazo compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses a pigment composition containing a bisazo condensation compound and a preparation method of the pigment composition.The structure of the bisazo condensation compound is shown in the description, wherein X and Y indicate fatty amino or arylamino.The bisazo condensation compound with the specific structure is mixed into pigment yellow 93, and the yellow pigment composition is obtained; the intensity of green light of the yellow pigment composition is higher, the transparency is significantly increased, the heat resistance, solvent resistance, dispersity and rheological property on ink are comparable to those of existing pigment yellow 93, and the yellow pigment composition is suitable for high-transparency ink.
Description
Technical field
The invention belongs to chemical dye field, be specifically related to a kind of color compositions containing rosin amine disazo condensation compound and preparation method thereof.
Background technology
Biacetyl acetanilide azo condensation pigment couples a replacement aromatic ring again by amido link on biacetyl acetophenone amine pigment molecule basis at molecule two ends.This type of pigment, its molecular weight is big, and tinting strength, tinting power and fastness ability are stronger, especially more amide group is introduced, making compound be more likely formed in molecule and intermolecular hydrogen bonding, such molecular structure substantially improves every fastness ability, particularly thermostability and the solvent resistance of pigment.In coloring plastic, resistance to migration improves a lot.But owing to production cost is higher, therefore price is high, is mainly used in the occasion of top grade.Wherein pigment yellow 93 shows a kind of bright green light yellow, due to the thermostability of its brilliance, light resistance and good resistance to migration, has good application, be also widely used in plastic pvc, PP and LDPE in high-grade printing-ink, sedan car top coat.
Patent US3413279 discloses a kind of preparation method of yellow 93, the method by the diazol of diazo component 3-amino-4 chlorobenzoic acid and coupling component 2-chloro-5-methyl biacetyl acetyl-p-phenylenediamine at 105-110 DEG C in o-dichlorohenzene coupling prepare bisazo dicarboxylic acids intermediate, owing to the method is inhomogeneous reaction, causing that reaction is difficult to completely, productivity is relatively low.
The pigmentation method of pigment yellow 93 disclosed in patent US5194088.Crude pigment product, anhydrous sodium sulfate and steel ball are placed in ball grinder by the method, ball milling 48h under room temperature.Treat that ball milling is complete, under room temperature, ball milling crude product is processed in dimethyl sulfoxide 2h, through hot water making beating washing, dry can obtain pigment yellow 93 product.
According to market survey, although yellow 93 have high-fire resistance, good resistance to migration, the transparency of pigment yellow 93 needs the property improved, current Huang 93 adopts the preparation method disclosed in foregoing invention and pigmentation method, the product transparency obtained is still not satisfactory, for disazo condensation class pigment, it, by the particle adjustment of self, is difficult to there is breakthrough progress in the transparency.Present invention introduces the synthesis mode of mixed crystal, to obtain high transparent, thermostability has the excellent derivant being greatly improved simultaneously.
Summary of the invention
In order to overcome the problems referred to above, disazo pigment and preparation method thereof has been carried out studying with keen determination by the present inventor, obtain a kind of green glow disazo condensation compound significantly improved higher, transparent, and itself and pigment yellow 93 are mixed to get a kind of yellow pigment composition, on its thermostability, solvent resistance, dispersibility, ink, rheological characteristic is all suitable with existing pigment yellow 93, it is adaptable in the ink of the high grade of transparency.
It is an object of the invention to provide following aspect:
(1) a kind of yellow pigment composition, it contains at least one compound and pigment yellow 93 as shown in formula I,
In formula I compound, X, Y are fat amido or aryl amine,
Containing aromatic hydrocarbons substituent group in described fatty amine based structures formula, it is preferable that containing C4～C20Aromatic hydrocarbons substituent group, and/or
Described aryl amine is substituted or unsubstituted anilino-, it is preferred to by one or more replaced anilino-of alkyl, alkoxyl or halogen atom；
(2) compositions as described in above-mentioned (1), it is characterised in that
Containing C in described fatty amine based structures formula8～C16Aromatic hydrocarbons substituent group, and/or
Described aryl amine is by the replaced anilino-of methyl and/or chlorine atom；
(3) compositions as described in above-mentioned (1) or (2), it is characterised in that
In formula I compound, X, Y are selected from group as shown in formula II or formula III,
(4) such as above-mentioned (1) to the compositions as described in one of (3), it is characterised in that
In formula I compound, X, Y can be identical or different, preferred X is group shown in formula II for such as group shown in formula III and Y, or, X is group shown in formula III for such as group shown in formula II and Y, the compound that more preferably formula I is as follows:
(5) such as above-mentioned (1) to the compositions as described in one of (4), it is characterised in that
Pigment yellow 93 can additionally add, it is also possible to acquisition is synthesized together with compound shown in formula I；
(6) one is prepared such as above-mentioned (1) to the method for compositions as described in one of (5), it is characterized in that, the such as compound shown in formula IV is carried out condensation reaction with fatty amine and arylamine, obtains compound shown in formula I
Optional interpolation pigment yellow 93；
Preferred the method comprises the following steps:
Step 1, the such as compound shown in formula IV is dissolved in solvent,
Step 2, it is added thereto to fatty amine and arylamine, the lower insulation reaction of heating,
Step 3, reaction are lowered the temperature after terminating, are filtered, and obtain compound shown in formula I；
(7) method as described in above-mentioned (6), it is characterised in that
In step 2, described reaction is condensation reaction, it is preferable that carry out 0.5～10h at 100～200 DEG C, carries out 1～6h at 120～180 DEG C, it is particularly preferred that carry out 2～4h at 140～160 DEG C；
(8) method as described in above-mentioned (6) or (7), it is characterised in that
Containing aromatic hydrocarbons substituent group in described fatty amine structural formula, it is preferable that containing C4～C20Aromatic hydrocarbons substituent group, more preferably contain C8～C16Aromatic hydrocarbons substituent group, and/or
Described arylamine is substituted or unsubstituted aniline, it is preferred to by one or more replaced aniline of alkyl, alkoxyl or halogen atom, more preferably by the aniline that methyl and/or chlorine atom are replaced, for instance 3-methyl-2-chloroaniline, and/or
The mole of described fatty amine is the 2～60% of arylamine mole, it is preferable that 4～40%, more preferably 5～20%；
(9) such as above-mentioned (6) to the method as described in one of (8), it is characterised in that
Described solvent is halogeno-benzene or alkylbenzene, it is preferred to dichloro-benzenes, trichloro-benzenes, dimethylbenzene or trimethylbenzene, and/or
Preferably it is initially charged fatty amine, adds arylamine.
(10) purposes of the compositions prepared such as above-mentioned (1) to one of (5) or (6) to method as described in one of (9), uses as yellow uitramarine.
The present invention is had the advantage that to include:
(1) present invention adds specific fatty amine in the pigment yellow 93 amidated process of condensation, a kind of disazo condensation compound of mixed crystal synthesis, its green glow is higher, the transparency significantly improves, on thermostability, solvent resistance, dispersibility, ink, rheological characteristic is all suitable with existing pigment yellow 93, it is adaptable in the ink of the high grade of transparency；
(2) preparation method of disazo condensation compound provided by the invention is simple, and easily-controlled reaction conditions, cheaper starting materials is easy to get, and is suitable to large-scale industrial production；
(3) color compositions provided by the invention mixes the above-mentioned disazo condensation compound of special ratios in pigment yellow 93, significantly improves the transparency of pigment, and its green glow is higher, can as coloring agent in multiple system.
Accompanying drawing explanation
Fig. 1 illustrates the testing electronic microscope figure of solid U.S.A yellow 3GNP thoroughly；
Fig. 2 illustrates the testing electronic microscope figure of the disazo condensation compound that embodiment 1 prepares；
Fig. 3 illustrates the X ray diffracting spectrum of solid U.S.A yellow 3GNP thoroughly；
Fig. 4 illustrates the X ray diffracting spectrum of the disazo condensation compound that embodiment 1 prepares；
Fig. 5 illustrates the infrared spectrogram of pigment yellow 93 that comparative example prepares；
Fig. 6 illustrates the infrared spectrogram of the disazo condensation compound that embodiment 1 prepares.
Detailed description of the invention
Below by accompanying drawing, experimental example and embodiment, the present invention is described in more detail.Being illustrated by these, the features and advantages of the invention will become more apparent from clearly.
According to the first aspect of the invention, it is provided that a kind of yellow pigment composition, it contains at least one compound and pigment yellow 93 as shown in formula I,
In formula I compound, X, Y are fat amido or aryl amine.
In a preferred embodiment in accordance with the present invention, containing aromatic hydrocarbons substituent group in described fatty amine based structures formula, it is preferable that containing C4～C20Aromatic hydrocarbons substituent group, more preferably contain C8～C16Aromatic hydrocarbons substituent group, and/or
Described aryl amine is substituted or unsubstituted anilino-, it is preferred to by one or more replaced anilino-of alkyl, alkoxyl or halogen atom, more preferably by the anilino-that methyl and/or chlorine atom are replaced.
Preferably, in formula I compound, X, Y are selected from group as shown in formula II or formula III,
In formula I compound, X, Y can be identical or different, preferred X is group shown in formula II for such as group shown in formula III and Y, or, X is group shown in formula III for such as group shown in formula II and Y, the compound that more preferably formula I is as follows:
In a preferred embodiment in accordance with the present invention, in described color compositions, the mole of compound as shown in formula I is the 1～50% of pigment yellow 93 mole, it is preferable that 3～30%, more preferably 5～20%.
Wherein, pigment yellow 93 can additionally add, it is also possible to acquisition is synthesized together with compound shown in formula I.
The green glow of above-mentioned disazo condensation compound provided by the invention is higher, the transparency significantly improves, on its thermostability, solvent resistance, dispersibility, ink, rheological characteristic is all suitable with existing pigment yellow 93, by its yellow pigment composition being mixed to get with special ratios and pigment yellow 93, its transparency significantly improves, can as coloring agent in multiple system, for instance be applied in the ink of the high grade of transparency.
According to the second aspect of the invention, a kind of method preparing color compositions described above is provided, the such as compound shown in formula IV is carried out condensation reaction with fatty amine and arylamine, obtains compound shown in formula I, optional interpolation pigment yellow 93
Wherein, containing aromatic hydrocarbons substituent group in described fatty amine structural formula, it is preferable that containing C4～C20Aromatic hydrocarbons substituent group, more preferably contain C8～C16Aromatic hydrocarbons substituent group, and/or
Described arylamine is substituted or unsubstituted aniline, it is preferred to by one or more replaced aniline of alkyl, alkoxyl or halogen atom, more preferably by the aniline that methyl and/or chlorine atom are replaced, for instance 3-methyl-2-chloroaniline, and/or
The mole of described fatty amine is the 2～60% of arylamine mole, it is preferable that 4～40%, more preferably 5～20%.
The method specifically includes following steps: be dissolved in solvent by the such as compound shown in formula IV, is added thereto to fatty amine and arylamine, and the lower insulation reaction of heating, reaction is lowered the temperature after terminating, filtered, and obtains compound shown in formula I.
Wherein, described solvent is halogeno-benzene or alkylbenzene, it is preferred to dichloro-benzenes, trichloro-benzenes, dimethylbenzene or trimethylbenzene, and/or
Preferably it is initially charged fatty amine, adds arylamine, and/or
Described condensation reaction carries out 0.5～10 hour at 100～200 DEG C, it is preferable that carry out at 120～180 DEG C 1～6 hour, carries out 2～4 hours at 140～160 DEG C.
In a preferred embodiment in accordance with the present invention, described method includes: the such as compound shown in formula IV is dissolved in dichloro-benzenes, sequentially drip the dichlorobenzene solution of fatty amine and arylamine wherein, dropwise post-heating to 140～160 DEG C, insulation reaction 2～4 hours, reaction is lowered the temperature after terminating, is filtered, dry after filter cake methanol and water washing, obtains compound shown in formula I.
Pigment yellow 93 can additionally add, it is also possible to acquisition is synthesized together with compound shown in formula I.Extra when adding pigment yellow so that the mole of pigment yellow 93 is as shown in formula I the 1～50% of compound mole, it is preferable that 3～30%, more preferably 5～20%.
According to the third aspect of the invention we, it is provided that the purposes of color compositions as mentioned above, it uses as yellow uitramarine.
Preferred above-mentioned color compositions provided by the invention is as coloring agent in ink, coating and plastic, and its green glow is higher, and transparency significantly improves.
Embodiment
Embodiment 1
30g acyl chlorides compound (0.0144mol) is put in the 250ml four-hole boiling flask containing 100g dichloro-benzenes, oil bath is warming up to 130 DEG C, dropping 0.84g (0.00288mol) rosin amine, and the dichlorobenzene solution of 3.67g (0.02592mol) 3-chloro-2-methyl aniline, dropping 30min, is warming up to 150 DEG C and is incubated 3 hours after dropwising.Cooling is filtered, washing after methanol washing, and solvent recovery, filter cake is dried, and obtains described disazo condensation compound.
Its electron microscope observation result is as shown in Figure 2.
Its X-ray diffraction result is as shown in Figure 4.
Adopting infrared spectrometer to carry out examination of infrared spectrum, result is as shown in Figure 6.As seen from Figure 6, owing to introducing rosin amine so that having multiple methylene to exist in product, its infrared spectrogram is at vas≈2925cm-1And vs≈2850cm-1There is obvious methylene stretching vibration absworption peak at place, illustrates that embodiment 1 has prepared theoretical product, and preparation method provided by the invention is stable, reliable.
Its elementary analysis result is: C, 44.32；H, 37.15；Cl, 4.96；N, 8.09；O, 6.The molecular formula thereby determined that is C44.3H37.3N8.1O6Cl4.9.Being computed, in the product that embodiment 1 prepares, C, H element content increase, and Cl constituent content reduces, and meets the molecular composition of modified structure.
Embodiment 2
30g acyl chlorides compound (0.0144mol) is put in the 250ml four-hole boiling flask containing 100g dichloro-benzenes, oil bath is warming up to 130 DEG C, dropping 1.25g (0.00432mol) rosin amine, and the dichlorobenzene solution of 3.46g (0.02448mol) 3-chloro-2-methyl aniline, dropping 30min, is warming up to 150 DEG C and is incubated 3 hours after dropwising.Cooling is filtered, washing after methanol washing, and solvent recovery, filter cake is dried, and obtains described disazo condensation compound.
Its electron microscope observation result, X-ray diffractogram are similar with embodiment 1 products obtained therefrom with infrared spectrogram；
Its elementary analysis result is: C, 44.85；H, 38.56；Cl, 4.79；N, 8.21；O, 6.The molecular formula thereby determined that is C44.95H38.45N8.15O6Cl4.85.Being computed, in the product that embodiment 2 prepares, C, H element content increase, and Cl constituent content reduces, and also complies with the molecular composition of modified structure.
Comparative example
30g acyl chlorides compound (0.0144mol) is put in the 250ml four-hole boiling flask containing 100g dichloro-benzenes, oil bath is warming up to 130 DEG C, the dichlorobenzene solution of dropping 4.08g (0.0288mol) 3-chloro-2-methyl aniline, dropping 30min, is warming up to 150 DEG C and is incubated 3 hours after dropwising.Cooling is filtered, washing after methanol washing, and solvent recovery, filter cake is dried, and obtains compound as shown in formula (V), is pigment yellow 93.
By formula (V) structure it can be seen that only a small amount of methylene, methyl exist in the pigment yellow 93 for preparing of comparative example 1, its results of FT-IR is as it is shown in figure 5, at vas≈2925cm-1And vs≈2850cm-1Place is unconspicuous methylene stretching vibration absworption peak only.
Its elementary analysis result is: C, 42.71；H, 34.85；Cl, 5.07；N, 7.86；O, 6.The molecular formula thereby determined that is C43H35N8O6Cl5。
Experimental example
All verification test standards are the solid beautiful yellow 3GNP thoroughly of Ciba company.
Experimental example 1 electron-microscopic analysis
Adopting ultramicroscope, the disazo condensation compound respectively solid U.S.A yellow 3GNP thoroughly, embodiment 1 prepared is tested, and result is shown in Fig. 1～2.
As shown in Fig. 1～2, its particle crystallization state of the product that the present invention prepares clearly changes.
Experimental example 2X x ray diffraction analysis x
Adopting X-ray diffractometer, the disazo condensation compound respectively solid U.S.A yellow 3GNP thoroughly, embodiment 1 prepared is tested, and result is shown in Fig. 3～4.
Comparison diagram 3 and Fig. 4 are known, its crystal habit of product that the embodiment of the present invention 1 prepares is different from the solid beautiful yellow 3GNP thoroughly of standard substance, its be distinguished by X-ray diffraction Fig. 2 θ angle be 44.5 °, 64.8 °, 78.2 ° places have 3 relatively weak absorbing peak become multiple to weaken, simultaneously, 2 θ angles are that 7.1 ° of place's absworption peaks become 4.8 ° and 9.0 ° of two absworption peaks, as can be seen here, its microstructure of product that the present invention prepares clearly changes.
Experimental example 3 ink system compares coloured light, tinctorial strength and transparency
Coloured light comparative approach: pigment sample 0.200g embodiment 1～2 prepared is dispersed to 0.600 oleum lini, 5 the totally 250 circle dispersions of plain grinding instrument, ink dispersion scraper plate identical with the pigment yellow 93 that comparative example prepares compares pigment difference.
Tinctorial strength comparative approach: the pigment sample 0.050g that embodiment 1～2 is prepared, and 1.000g titanium dioxide (R902) is dispersed to 1.000g oleum lini, 5 the totally 250 circle dispersions of plain grinding instrument, ink dispersion scraper plate identical with the pigment yellow 93 that comparative example prepares compares pigment difference.
Transparency comparative approach: to be printed on the paper of black ribbon line as a setting, the method that naked eyes judge compares.
Coloured light, tinctorial strength and transparency comparative result in table 1. ink system
| Gu beautiful yellow 3GNP thoroughly | Comparative example | Embodiment 1 | Embodiment 2 | |
| Form and aspect | Standard | Slightly red | Slightly green | Greener |
| Covering power | Standard | Micro-high | More saturating | More saturating |
| Intensity | Standard | 100 | 97 | 95 |
As shown in Table 1, the product that the embodiment of the present invention 1～2 prepares compares with standard substance, and its coloured light is substantially partially green, and transparency is greatly improved, and the pigment yellow 93 that comparative example prepares compares then substantially slightly red with standard substance, hides higher, and transparency is relatively low.
Experimental example 4 ink fluidity compares
By the dispersion ink 0.100g of the coloured light containing pigment sample carrying out in experimental example 3 preparing when coloured light the compares Circular glass sheet center being placed in metal fixed disk, upper Circular glass sheet is placed on the Circular glass sheet in metal fixed disk, centre is made to have ink to partly overlap, press 200g counterweight (noticing that metal fixed disk keeps level) immediately, start timing；
Removing counterweight after 15min, measure maximum and the minima of ink cylinder diameter with transparent gage, if the difference of maximum and minima is be more than or equal to 2mm, then experiment re-starts.
The arithmetic mean of instantaneous value of measurement result is the numerical value of fluidity, and result is in Table 2.
Table 2. ink fluidity measurement result
| Gu beautiful yellow 3GNP thoroughly | Comparative example | Embodiment 1 | Embodiment 2 | |
| Fluidity/mm | 23.2 | 18.9 | 21.0 | 22.8 |
As shown in table 2, its ink fluidity of product that embodiment 1～2 prepares has clear improvement.
Experimental example 5 plastics (LDPE) system compares coloured light, tinctorial strength and covering power
True qualities: weigh pigment sample that embodiment 1～2 prepares and each 0.1500g of pigment yellow 93 that comparative example prepares, after LDPE resin is placed on two roller machines (120 DEG C), open motor, preplasticizing about 1 minute is (when two roller machines roll, resin should stick on preliminary roller, must again refund between two rollers from the material dropped between two rollers), after resin plastifies completely, the above-mentioned pigment sample weighed up slowly is homogeneously added in the plastics plastified, two roller machines carry out mixing, after resin and pigment are thoroughly mixed, start timing, and carry out upset 6 minutes with bamboo chip scraper is continual, close motor, adjusting roller spacing is 5mm, open motor, continue mixing 0.5 minute (color chips should stick on preliminary roller) membrane afterwards, comparing embodiment and comparative example gained tabletting.
Reduced shade: weigh pigment sample that embodiment 1～2 prepares and each 0.0250g of pigment yellow 93 that comparative example prepares, 0.2500g titanium dioxide, LDPE resin is placed on two roller machines after hot 20 seconds, open motor, preplasticizing about 1 minute is (when two roller machines roll, resin should stick on preliminary roller, must again refund between two rollers from the material dropped between two rollers), after resin plastifies completely, load weighted pigment and titanium dioxide are slowly homogeneously added in the plastics plastified, two roller machines carry out mixing, after resin and pigment are thoroughly mixed, start timing, and carry out upset 6 minutes with bamboo chip scraper is continual, close motor, adjusting roller spacing is 5mm, open motor, continue mixing 0.5 minute (color chips should stick on preliminary roller) membrane afterwards；The solid beautiful independent tabletting according to the method described above of yellow 3GNP thoroughly of standard substance.
For reference, the tinctorial strength of sample is evaluated by Computer color testing instrument with the solid beautiful yellow 3GNP thoroughly of standard substance.
Coloured light and covering power comparative result in table 3. plastics (LDPE) system
| Title | Gu beautiful yellow 3GNP thoroughly | Comparative example | Embodiment 1 | Embodiment 2 |
| Form and aspect | Standard | 2 grades red | 2 grades green | 3 grades green |
| Covering power | Standard | 1 grade high | 2 grades thoroughly | 3 grades thoroughly |
Tinctorial strength comparative result in table 4. plastics (LDPE) system
| Gu beautiful yellow 3GNP thoroughly | Comparative example | Embodiment 1 | Embodiment 2 | |
| Relative intensity | 100.000 | 98.962 | 95.719 | 94.698 |
Thermostability test result in table 5. plastics (LDPE) system
The above results shows, it is partially green that the modified pigment prepared by embodiment 1～2 applies coloured light in plastics system, but does not have ink system medium green obvious mutually, and covering power is partially saturating, and also without obvious in ink system, intensity slightly declines.
The experimental example 6 application in NC ink
In vial, it is sequentially added into 28.8g celluloid lacquer, 32.0g dehydrated alcohol, 120g bead, 19.2g pigment, vibrates 50 minutes with vibration case after sealing, shake after well and take off standing 15 minutes, obtain dispersion.
True qualities: take the above-mentioned dispersion of 12.0g in plastic cup, add 18.0gLetdownVarnish glue head to stir evenly, pigment sample embodiment 1～2, comparative example prepared with disposable dropper is a little with standard sample dropping on PP film, scrape uniformly film with silk rod (12 μm), be drying and forming-film (evaluating the transparency) after placing 10 minutes.
The pigment sample prepared by disposable dropper just embodiment 1～2, comparative example is a little with standard sample dropping in being with on black thick stick art paper, put 75 μm of wet film preparing devices, scrape coating agent which has to be dissolved in alcohol before use with automatic spray device, be drying and forming-film (evaluating coloured light and glossiness) after placing 10 minutes.
Reduced shade: take the above-mentioned dispersion of 1.50g in plastic cup, add 13.5g chalk, stir evenly with glue head, the pigment sample prepared by disposable dropper just embodiment 1～2, comparative example is a little with standard sample dropping in being with on black thick stick art paper, put 75 μm of wet film preparing devices, scrape coating agent which has to be dissolved in alcohol before use with automatic spray device, be drying and forming-film after placing 10 minutes, use colour photometer colour examining.
Coloured light and covering power test result in table 6.NC ink system
Tinctorial strength test result in table 7.NC ink system
| Title | Gu beautiful yellow 3GNP thoroughly | Comparative example | Embodiment 1 | Embodiment 2 |
| Relative intensity | 100.000 | 99.321 | 98.568 | 95.486 |
The above results shows, under N/C system, the pigment sample coloured light that embodiment 1～2 prepares is substantially partially green, and micro-Huang, covering power significantly becomes, and intensity slightly declines.
Above in association with preferred implementation and exemplary example, the present invention is described in detail.But it is to be understood that, these detailed description of the invention are only the illustrative explanations to the present invention, not to protection scope of the present invention constitute any restriction.When without departing from spirit and scope of the present invention, it is possible to the technology of the present invention content and embodiment thereof are carried out various improvement, equivalencing or modification, and these each fall within protection scope of the present invention.Protection scope of the present invention is as the criterion with claims.
Claims (10)
1. a yellow pigment composition, it is characterised in that it contains at least one compound and pigment yellow 93 as shown in formula I,
In formula I compound, X, Y are fat amido or aryl amine,
Containing aromatic hydrocarbons substituent group in described fatty amine based structures formula, it is preferable that containing C4～C20Aromatic hydrocarbons substituent group, and/or
Described aryl amine is substituted or unsubstituted anilino-, it is preferred to by one or more replaced anilino-of alkyl, alkoxyl or halogen atom.
2. compositions according to claim 1, it is characterised in that
Containing C in described fatty amine based structures formula8～C16Aromatic hydrocarbons substituent group, and/or
Preferred described aryl amine is by the replaced anilino-of methyl and/or chlorine atom.
3. compositions according to claim 1 and 2, it is characterised in that
In formula I compound, X, Y are selected from group as shown in formula II or formula III,
4. according to the compositions one of claims 1 to 3 Suo Shu, it is characterised in that
In formula I compound, X, Y can be identical or different, preferred X is group shown in formula II for such as group shown in formula III and Y, or, X is group shown in formula III for such as group shown in formula II and Y, the compound that more preferably formula I is as follows:
5. according to the compositions one of Claims 1-4 Suo Shu, wherein,
Pigment yellow 93 can additionally add, it is also possible to acquisition is synthesized together with compound shown in formula I.
6. prepare the method for compositions as described in one of claim 1 to 5 for one kind, it is characterised in that
Compound as shown in formula IV carries out condensation reaction with fatty amine and arylamine, obtains compound shown in formula I,
Optional interpolation pigment yellow 93,
Preferred the method comprises the following steps:
Step 1, the such as compound shown in formula IV is dissolved in solvent,
Step 2, it is added thereto to fatty amine and arylamine, the lower insulation reaction of heating,
Step 3, reaction are lowered the temperature after terminating, are filtered, and obtain compound shown in formula I.
7. method according to claim 6, it is characterised in that
In step 2, described reaction is condensation reaction, it is preferable that carry out 0.5～10h at 100～200 DEG C, carries out 1～6h at 120～180 DEG C, it is particularly preferred that carry out 2～4h at 140～160 DEG C.
8. the method according to claim 6 or 7, it is characterised in that
Containing aromatic hydrocarbons substituent group in described fatty amine structural formula, it is preferable that containing C4～C20Aromatic hydrocarbons substituent group, more preferably contain C8～C16Aromatic hydrocarbons substituent group, and/or
Described arylamine is substituted or unsubstituted aniline, it is preferred to by one or more replaced aniline of alkyl, alkoxyl or halogen atom, more preferably by the aniline that methyl and/or chlorine atom are replaced, for instance 3-methyl-2-chloroaniline, and/or
The mole of described fatty amine is the 2～60% of arylamine mole, it is preferable that 4～40%, more preferably 5～20%.
9. according to the method one of claim 6 to 8 Suo Shu, it is characterised in that
Described solvent is halogeno-benzene or alkylbenzene, it is preferred to dichloro-benzenes, trichloro-benzenes, dimethylbenzene or trimethylbenzene, and/or
Preferably it is initially charged fatty amine, adds arylamine.
10., according to one of claim 1 to 5 or the purposes of compositions for preparing according to the described method of one of claim 6 to 9, use as yellow uitramarine.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3413279A (en) * | 1965-01-25 | 1968-11-26 | Ciba Ltd | Disazo pigments |
| US5559216A (en) * | 1992-09-02 | 1996-09-24 | Hoechst Ag | Single-step process for the preparation of bis-(acetoacetylamino) benzene disazo pigments |
| CN103048900A (en) * | 2011-10-12 | 2013-04-17 | 佳能株式会社 | Toner including compound having bisazo skeleton |
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2016
- 2016-03-08 CN CN201610130721.3A patent/CN105778564B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3413279A (en) * | 1965-01-25 | 1968-11-26 | Ciba Ltd | Disazo pigments |
| US5559216A (en) * | 1992-09-02 | 1996-09-24 | Hoechst Ag | Single-step process for the preparation of bis-(acetoacetylamino) benzene disazo pigments |
| CN103048900A (en) * | 2011-10-12 | 2013-04-17 | 佳能株式会社 | Toner including compound having bisazo skeleton |
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