WO2006062970A2 - Improved anthraquinone colorant compositions and methods for producing the same - Google Patents
Improved anthraquinone colorant compositions and methods for producing the same Download PDFInfo
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- WO2006062970A2 WO2006062970A2 PCT/US2005/044111 US2005044111W WO2006062970A2 WO 2006062970 A2 WO2006062970 A2 WO 2006062970A2 US 2005044111 W US2005044111 W US 2005044111W WO 2006062970 A2 WO2006062970 A2 WO 2006062970A2
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- colorant
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- polyalkyleneoxy
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Classifications
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- 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
- C09B69/00—Dyes not provided for by a single group of this subclass
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- 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
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
- C09B1/20—Preparation from starting materials already containing the anthracene nucleus
- C09B1/26—Dyes with amino groups substituted by hydrocarbon radicals
- C09B1/28—Dyes with amino groups substituted by hydrocarbon radicals substituted by alkyl, aralkyl or cyclo alkyl groups
- C09B1/285—Dyes with no other substituents than the amino groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T436/00—Chemistry: analytical and immunological testing
- Y10T436/13—Tracers or tags
Definitions
- This invention relates to compositions of N,N'-dialkyleneoxy-substituted 1 ,4-diaminoanthraquinone colorants which contain a low percentage of impurities, to a process to make the compositions, and also to the use of the compositions thus prepared for coloring consumer products.
- N,N'-dialkyleneoxy- substituted 1 ,4-diaminoanthraquinones are usually blue in shade, generally more brilliant than many other blue chromophores, and have good desirable stability properties, especially toward high alkaline environments, heat, and light.
- This invention relates to a colorant containing compounds having general formula (I):
- the colorant of the present invention contains very low levels of impurities, which are generated during the process to make the colorant.
- One impurity present in an amount that is less than about 1.0% by weight is a violet impurity.
- This impurity is represented by general formula (II): (II)
- Yet another impurity present in the colorant composition in an amount that is less than about 1.0% by weight is a water and methanol insoluble black material.
- N,N'-dialiphatic-substituted 1 ,4-diaminoanthraquinone colorants are generally synthesized from 1 ,4-dihydroxyanthraquinone (i.e. quinizarin) or 2,3- - ⁇ dihyxiroffil.OsdihydroxyjJr, ⁇ these two compounds with suitable amines.
- 1 ,4-dihydroxyanthraquinone i.e. quinizarin
- 2,3- - ⁇ dihyxiroffil.OsdihydroxyjJr 2,3- - ⁇ dihyxiroffil.OsdihydroxyjJr
- reaction routes also can be used to make the N,N'-dialkyleneoxy- substituted 1 ,4-diaminoanthraquinone colorants described in the present invention.
- 1 ,4-dihaloanthraquinone compounds may be treated with suitable amines and catalysts (such as, for example, copper chloride) to make 1 ,4-dialiphatic aminoanthraquinone colorants, as described in German Patent No. 125,698.
- the 1 ,4-disubstituted aminoanthraquinone compounds may also be made from 1 ,4-diaminoanthraquinones by reacting with organic halides, as described in German Patent No. 172,464.
- 1 ,4-ditosyloxy anthraquinone may be used to make both symmetrical and asymmetrical 1 ,4- ⁇ O ⁇ m ⁇ n ⁇ iWkq ⁇ m ⁇ ec ⁇ b ⁇ fhi ⁇ isci ⁇ ⁇ t ⁇ ⁇ S PatentfT ⁇ : 4,746,46I to' " Zielske.
- many of the raw materials necessary for these processes are generally not readily available. Additionally, many of these processes are not economical and also are not environmentally friendly due to the chemical waste produced.
- anthraquinone colorants such as 1 ,4-disubstituted aliphatic aminoanthraquinones
- anthraquinones are disclosed in US Patent No. 4,846,846 to Rekers et al. wherein anthraquinones were prepared from a mixture of quinizarin, leucoquinizarin, and amine in water followed by various purification procedures.
- the preferred amines are sec-alkyl primary amines with reactive groups, such as -OH, -NH 2 , or -SH, on the end of the molecules.
- These anthraquinone colorants are used to color polyurethane resins, particularly foams.
- Purification of low melting or liquid water-soluble anthraquinone colorants usually involves time consuming extraction and washing procedures that often require organic solvents, which generally are not environmentally friendly. Additionally, these solvents are typically not suitable for use in many consumer product applications and complete removal is required. The organic solvents are often expensive and generate additional waste during production of the anthraquinone colorants. Furthermore, some of the impurities in these anthraquinone colorants are often difficult to filter and generally cause dull color, shade shift, and staining.
- me-c ⁇ object of this invention is to provide an N,N'-dialkyleneoxy-substituted 1 ,4- diaminoanthraquinone colorant with reduced amounts of impurities.
- Another object of this invention is to provide methods to make such anthraquinone colorants without the use of solvents.
- a further object of this invention is to use these inventive colorants for coloration of consumer products, such as liquid and solid laundry detergents and liquid fabric softeners.
- Figure 1 is a line graph showing effect of violet impurity on hue angle.
- polyalkyleneoxy generally refers to molecular structures containing the following repeating units: -CH 2 CH 2 O-, - CH 2 CH 2 CH 2 O-, - CH 2 CH 2 CH 2 CH 2 O-,
- anthraquinone generally refers to the following general chemical structure and numbering sequence:
- Ai and A 2 are, independently of each other, polyethyleneoxy-, polypropyleneoxy-, or polyethyleneoxy-/polypropyleneoxy-copolymers; wherein the number of repeating polyethyleneoxy-, and/or polypropyleneoxy- units is less than or equal to 25; or wherein A 1 and A 2 are, independently of each other, -
- a 1 and R 1 are as defined above in general formula (I), and wherein the colorant contains less than or equal to about 1.0 weight percent of a water and alcohol insoluble black impurity.
- the inventive N,N'-dialkyleneoxy-substituted 1 ,4-diaminoanthraquinone colorants aje p/jtfej ⁇ preferably water soluble at concentrations which provide sufficient coloration for a desired end-use application.
- the N,N'-dialkyleneoxy-substituted 1 ,4-diaminoanthraquinone colorants of the present invention are preferably water fugitive (i.e. washable from substrates with water) on all kinds of substrates, such as, for example, human skin, textile substrates, coated surfaces (such as, for example, painted surfaces), ceramic surfaces, etc.
- inventive N 1 N'- dialkyleneoxy-substituted 1 ,4-diaminoanthraquinone colorants are generally liquid or semi-solid at ambient conditions.
- "Semi-solid” generally means the colorant is a highly viscous liquid, or may even be paste-like, and its melting temperature, if it has any, is typically below about 6O 0 C.
- the N,N'-dialkyleneoxy-substituted 1 ,4-diaminoanthraquinone colorants may be synthesized from 1 ,4-dihydroxyanthraquinone (i.e. quinizarin), 2,3- dihydro-9,10-dihydroxy-1 ,4-anthracenedione (i.e. leucoquinizarin), or from a mixture of the two components with suitable amines as illustrated by the following reaction:
- this extra reduction reaction generally increases the impurities in the final product, and purification, such as by filtering out these impurities, is difficult. Accordingly, it is generally preferable to use a mixture of quinizarin and leucoquinizarin. More specifically, it is preferable that the molar ratio of quinizarin to leucoquinizarin in a mixture of leucoquinizarin and quinizarin is preferably from about 1 to about 5, and more preferably, the ratio is about 1 to 3.
- polyalkyleneoxy-substituted amines may be used to react with a mixture of leucoquinizarin and quinizarin to form the anthraquinone colorants of the present invention. It is desirable that the amines are primary amines. Preferably, the polyalkyleneoxy-substituted amine is predominantly comprised of a polyethyleneoxy-substituted amine, which tends to provide good water solubility. However, the amine may also be a polyethyleneoxy-polypropyleneoxy-substituted amine.
- the amount of polyalkyleneoxy-substituted amines added to the reaction mixture is between about 100% and about 120% of the required stoichiometric amount and, preferably, between about 100% and about 110% of the required stoichiometric amount.
- polyalkyleneoxy-substituted amines which can be used for this invention.
- the polyoxyalkylene amines include Jeffamine® amines (available from Huntsman Chemical Company of Austin, Texas) can be used, which include monoamines like M-600, M-100, M-2005 and M-2070; and diamines.
- Examples of amines having hydroxyl groups include diethylene glycol amine and 3-aminopropyl diethylene glycol (which is available from Dixie Chemical Company under the trade name DCA 163).
- polyalkyleneoxy-substituted diamines such as bis(hydroxyalkyl)diamines (including APDEA and APDIPA from Tomah Products, Inc.).
- glycol ether primary amines from Tomah include PA-EGM, PA-EGB, PA-EGH, PA-DEGM, PA-DEGB, PA-PGM, PA-PGB, include DPA-DEG, DPA-200E, DPA-400E, DPA-1000E, and NDPA-10.
- the inventive N,N'-dialkyleneoxy-substituted 1 ,4-diaminoanthraquinone colorants are generally synthesized according to the procedure described below.
- the rate of the reaction may be affected, for example, by the temperature, the amine, and the agitation rate employed.
- the progress of the reaction can be monitored by visible spectroscopy and/or High Performance Liquid Chromatography (HPLC).
- HPLC High Performance Liquid Chromatography
- a mixture of quinizarin and leucoquinizarin may be added to a polyalkyleneoxy-substituted amine in a reaction flask equipped with an agitator, temperature controller, and condenser under inert atmosphere.
- the reaction mixture is then heated to a temperature between about 65 0 C and about 12O 0 C, and preferably to a temperature between about 75 0 C and about 95 0 C 1 under an inert atmosphere. It is typically found that the reaction rate is too slow at lower temperatures. However, at higher temperatures, greater amounts of impurities are generally produced.
- the condensation reaction usually is completed at the reaction temperature between about one and about twenty hours. Once the condensation reaction is finished, several methods can be employed to oxidize the product in its leuco form to 1 ,4-diaminoanthraquinone.
- One method that may be used to oxidize the product is to bubble air through the reaction mixture at a temperature of between about 60 0 C and about 100 0 C and, preferably between about 75 0 C and about 95 0 C
- Other methods of oxidation may be used, such as oxidation by peroxides, heating in nitrobenzene, or oxidation by other weak organic oxidants. However, in most cases, these oxidation methods are not as clean and as economical as the air oxidation method.
- One of the impurities formed during this reaction is 1-aminoalkyleneoxy-substituted 4-hydroxy anthraquinone.
- This impurity is generally bright violet in shade and has visible absorption peaks at approximately 550 nm and 590 nm in methanol.
- ⁇ FtypicaTiy affects The brightness of the colorant and its washability from substrates, such as fabrics. It was discovered that this impurity may be controlled to a level of less than about 1.0% by controlling the reaction conditions used to make the anthraquinone colorants.
- the anthraquinone colorant may be synthesized using a process that does not require the use of solvents, such as water binding polar solvents, including glycerol, ethylene glycol, propylene glycol, polyols, etc. Under these anhydrous, or nearly anhydrous conditions, this violet impurity may be reduced to a minimum level (i.e. ⁇ 1.0%), which typically has no significant effect on the performance of the anthraquinone colorants.
- solvents such as water binding polar solvents, including glycerol, ethylene glycol, propylene glycol, polyols, etc.
- Another impurity present in the inventive anthraquinone colorants is a water and methanol insoluble black solid.
- the insoluble black solid is comprised of very fine particles, which can stain fabrics and is often difficult to remove by filtration, thereby causing process problems.
- some of the impurity tends to settle out in processing lines and in the bottom of drum containers forming an undesirable sludge-like build-up.
- the impurity also tends to plug filters using in purifying the colorant.
- the anthraquinone colorants of the present invention generally possess many other desirable and advantageous properties for use in various consumer products.
- the colorants generally have good alkali fastness. They can typically be used in high pH formulations, such as wherein the pH is between about 8 and about 13, without having stability problems. Such pH ranges are often found in powder detergents, heavy-duty liquid detergents, hard surface cleaners, etc.
- these anthraquinone colorants may exhibit desirable color brightness due to fluorescence of the anthraquinone chrornbphore.
- Xs sucrT'r these anthraqurr ⁇ ' ohe bd ⁇ raritSTfiay be used to color various personal care, home care, and fabric care products.
- the colorants may be used to color soap bars, liquid soaps, fabric softeners, car washing formulations, glass cleaners, toilet cleaners, shampoos, and the like.
- laundry detergent formulations both granular and liquid
- fabrics cleaners both granular and liquid
- fabric softener formulations which may be suitable for use with the anthraquinone of the present invention
- US Patent No. 5,770,557 examples of specific fabric softener formulations, which may be suitable for use with the anthraquinone of the present invention.
- the anthraquinone colorants can also be used in industrial formulations, such as heavy-duty industrial cleaners and detergents and fertilizers. Additionally, it is contemplated that the colorants of the current invention may be ideal for use in coloring thermoplastic materials (such as, for example, polyolefin and polyester) and thermoset materials (such as, for example, polyurethane foam). Examples of specific thermoplastic formulations, which may be suitable for use with the anthraquinone of the present invention, are disclosed in US Patent Nos. 4,640,690; 4,732,570; and 4,812,141 to Baumgartner et al.
- thermoset formulations which may be suitable for use with the anthraquinone of the present invention, are disclosed in commonly assigned US Patent Nos. 4,284,729 to Cross et al. and 4,846,846 to Rekers et al.
- polyurethane foam is produced through the catalyzed polymerization of the reaction products of polyols and isocyanates. Blowing agents present within the polymerization step typically provide the necessary foam-making capability. Such a reaction is well known throughout the polyurethane industry and has been practiced for many years.
- a large variety of colors and shades may be obtained by blending the inventive anthraquinone colorant with one or more additional water soluble colorants.
- One exemplary class of colorants includes the Reactint ® colorants (available from Milliken Chemical of Spartanburg, South Carolina).
- the Reactint ® colorants are generally water soluble, or dispersible, at room temperature and may be suitably blended with the anthraquinone colorant of the present invention to achieve improved colors and shades. Examples
- the water and methanol insoluble black impurity was measured using the following method: Approximately 10 grams of blue colorant was diluted to about 5% by weight with water. The mixture was then stirred for about 15 minutes, and the pH was adjusted to about ⁇ 5.0 with concentrated hydrochloric acid. The mixture was stirred for another 15 minutes and filtered through a pre-weighed one-micron size filter. The solid black impurity was washed with methanol until the liquid passing through the filter was substantially colorless. The solid impurity and filter were allowed to air dry for about 15 minutes and then were dried in a 100 0 C oven for about 30 minutes. The dried filter and impurity were weighed and the percentage of insoluble impurity was calculated.
- the colorant contained 0.2% 1-(3-(2-(2- hydroxyethoxy)ethoxy)propylamino-4-hydroxyanthraquinone (i.e. violet impurity) and 0.7% of water and methanol insoluble black impurity.
- the structure of the io anthraquinone colorant is shown below:
- the colorant contained 1.67% of 1-(3-(2-(2- hydroxyethoxy)ethoxy)propylamino-4-hydroxyanthraquinone (i.e. violet impurity) and 1.73% of water and methanol insoluble black impurity.
- the colorant had a color value of 22.07 (abs/g/L in methanol) and a maximum absorbance at 639 nm.
- the colorant contained 0.2% of 1-(3-(2-(2- methoxyethoxy)ethoxy)propylamino)-4-hydroxyanthraquinone (i.e. violet impurity) and 0.32% of water and methanol insoluble black impurity.
- the structure of ihe anthraquinone colorant ' is ' s ' h ⁇ w ⁇ b ' el ⁇ w:
- the colorant had a maximum absorbance at 639 nm and a color value of 14.29 (abs/L/g in methanol) with a solid content of 46.32%.
- the colorant contained 7.81 % 1-(3-(2-(2- methoxyethoxy)ethoxy)propylamino)-4-hydroxyanthraquinone (i.e. violet impurity) and 4.68% of water and methanol insoluble black impurity.
- the colorant contained 0.74% of 1-(3-(bis(2- hydroxyethyl)amino)propylamino-4-hydroxyanthraquinone (i.e. violet impurity) and 0.35% of water and methanol insoluble black impurity.
- the structure of the anthraquinone colorant is shown below:
- the reaction mixture was oxidized by bubbling air through the reaction mixture at 8O 0 C for 2 hours to give 160 g of a blue liquid with a color value of 20.4 (abs/g/L in methanol) and a maximum absorbance at 640 nm.
- the colorant contained 4.34% of 1-(3-(bis(2- hydroxyethyl)amino)propylamino-4-hydroxyanthraquinone (i.e. violet impurity) and 2.91 % of water and methanol insoluble black impurity.
- Colorant formulations used for consumer products such as liquid and solid laundry detergents and fabric softeners, often employ an anthraquinone colorant in the formulation.
- anthraquinone colorant in the formulation.
- Colorant Formulation 1 was prepared with the inventive anthraquinone colorant made according to the process described in Example 1.
- Colorant Formulation 2 was prepared with a prior art anthraquinone made according to the process described in Comparative Example 1. Their tendency to stain cotton terry cloth fabric was evaluated as described below.
- Colored zeolite adjunct containing 6% of the respective colorant formulation was incorporated onto white powder detergent at 2.5%. Each colorant formulation contained about 36% of the respective anthraquinone.
- the colored detergent 2.5 g was sprinkled on three swatches of white terry cloth fabric on a plate. Fifty milliliters of water was slowly poured onto the plate and allowed to stand for 16 hours. The swatches were then rinsed in water and dried. The staining of the two formulations was compared to an unstained fabric sample and evaluated using the American Association of Textile Chemists and Colorists Gray Scale for Evaluating Staining. This Scale evaluates staining using a rating scale from 1 to 5, with higher numbers denoting less staining. The test results are shown in Table 1 below.
- Colorant Formulation 1 4.0 • , :. . - . ; -. :: ⁇ . . - Goi ⁇ ' raritTorrnu]atiofi " 2 ' ' ' ⁇ -- " * >- ' ⁇ ' * ⁇ ' ⁇ ' ' - - " - " " 3.O - ' ' - " ' ⁇ ⁇ : " - ⁇ '' ' ⁇ " ⁇ ' - : -
- test results indicate that there is less staining of the fabric when the inventive anthraquinone colorant, which is made by the inventive process described herein, is added to the colorant formulation.
- inventive anthraquinone is water fugitive, i.e. the colorant can be washed from the fabric with water.
- the novel process for synthesizing the anthraquinone colorant of the present invention results in the production of less violet impurity.
- This reduction in violet impurity results in a colorant having brighter color, typically, brighter blue color.
- blue colorants having higher levels of the violet impurity appear to have more redness in the colorant. This is undesirable because the redness tends to dull the colorant, and the colorant appears less chromatic.
- a batch of the inventive anthraquinone colorant was synthesized as described in Example 1 above.
- a batch of prior art anthraquinone colorant was synthesized as described in Comparative Example 1 above.
- the hue angle of the colorants was determined using a Gretag-MacBethTM Color-Eye 7000A. Hue angle is typically a measure of the shade of a color.
- the test results show that the inventive anthraquinone colorant exhibited a hue angle of about 241.5°, while the prior art colorant exhibited a hue angle of about 244.3°.
- the prior art colorant exhibited more of a red shade, which is less desirable, when compared to the colorant of the present invention.
- a standard colored polyurethane foam article was made similar to the process disclosed in U.S. Patent No. 4,846,846 to Rekers et al.
- the Colorant Blend consisted of 0.2 php of the inventive anthraquinone colorant (made according to the procedure described in Example 1 ) and 0.8 php of a yellow colorant (Reactint® Yellow X15, available from Milliken Chemical of Spartanburg, South Carolina).
- reaction vessel The components above were combined and mixed together within a reaction vessel, the reaction created a "health" bubble (indicating gelation and blowing balance), and the vessel was then exposed to 185°C (generated within a microwave oven to simulate actual heat history encountered on an industrial 15 production level) for about 10 minutes. A polyurethane foam article was thus produced.
- the foam article was then sliced in half and evaluated for color using a Hunter Ultrascan XE Spectrophotometer The foam article exhibited a C * (chroma) of 45.54.
- the Colorant Blend consisted of 0.2 php of blue colorant (made according to the procedure described in Comparative Example 1 ) and 0 8 php of yellow colorant (Reactint® Yellow X15, available from Milliken Chemical of Spartanburg, South Carolina).
- the resultant foam article was sliced in half and evaluated for color using 30 a Hunter Ultrascan XE Spectrophotometer.
- the foam article exhibited a C * (chroma) of 43.96.
- the foam article of Example 6 exhibited a higher C * value than the foam article of Comparative Example 6.
- C * values are characteristic of brighter colors
- the test results illustrate that a brighter green color can be achieved by using the anthraquinone colorant of the present invention.
- the inventive anthraquinone colorant made without the use of solvents or purification results in lower levels of impurities.
- reduced impurity levels are desirable because they exhibit less staining on substrates, such as fabric substrates.
- the reduced impurity levels are also advantageous since it has been shown that high impurity levels result in a colorant having a red cast, which makes the blue anthraquinone colorant dull and less chromatic.
- anthraquinone colorant of the present invention may be incorporated into various personal care, home care, and fabric care products (such as, for example, liquid and solid laundry detergents and liquid fabric softeners) as well as into thermoplastic materials and thermoset materials (such as polyurethane foam articles).
- various personal care, home care, and fabric care products such as, for example, liquid and solid laundry detergents and liquid fabric softeners
- thermoplastic materials and thermoset materials such as polyurethane foam articles.
Abstract
Description
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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CN2005800461045A CN101098938B (en) | 2004-12-08 | 2005-12-02 | Improved anthraquinone colorant compositions and methods for producing the same |
EP05853122.9A EP1828314B1 (en) | 2004-12-08 | 2005-12-02 | Improved anthraquinone colorant compositions and methods for producing the same |
JP2007545563A JP5219517B2 (en) | 2004-12-08 | 2005-12-02 | Improved anthraquinone colorant composition and process for its production |
BRPI0518892-0A BRPI0518892A2 (en) | 2004-12-08 | 2005-12-02 | perfected anthraquinone dye compositions and methods for their production |
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US11/007,453 US7632682B2 (en) | 2004-12-08 | 2004-12-08 | Anthraquinone colorant compositions and methods for producing the same |
US11/007,453 | 2004-12-08 |
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WO2006062970A2 true WO2006062970A2 (en) | 2006-06-15 |
WO2006062970A3 WO2006062970A3 (en) | 2006-09-14 |
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US (1) | US7632682B2 (en) |
EP (1) | EP1828314B1 (en) |
JP (1) | JP5219517B2 (en) |
CN (1) | CN101098938B (en) |
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WO2011063332A2 (en) | 2009-11-23 | 2011-05-26 | 3M Innovative Properties Company | Microwell array articles and methods of use |
CN108395381B (en) * | 2018-04-10 | 2020-09-22 | 大连傲视化学有限公司 | Synthesis method of 1, 4-diamino anthraquinone leuco body |
WO2022197295A1 (en) | 2021-03-17 | 2022-09-22 | Milliken & Company | Polymeric colorants with reduced staining |
WO2023233026A1 (en) | 2022-06-03 | 2023-12-07 | Unilever Ip Holdings B.V. | Laundry detergent product |
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US6528564B1 (en) * | 2001-10-12 | 2003-03-04 | Milliken & Company | Articles comprising novel polymeric blue anthraquinone-derivative colorants |
US6635350B2 (en) * | 2001-10-16 | 2003-10-21 | Milliken & Company | Polymeric 1,5- or 1,8-disubstituted anthraquinone-derivative colorants and articles comprising such colorants |
US6642283B2 (en) * | 2001-10-26 | 2003-11-04 | Milliken & Company | Stable novel black polyurethane article colorants |
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2004
- 2004-12-08 US US11/007,453 patent/US7632682B2/en active Active
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2005
- 2005-12-02 WO PCT/US2005/044111 patent/WO2006062970A2/en active Application Filing
- 2005-12-02 JP JP2007545563A patent/JP5219517B2/en active Active
- 2005-12-02 BR BRPI0518892-0A patent/BRPI0518892A2/en active IP Right Grant
- 2005-12-02 CN CN2005800461045A patent/CN101098938B/en active Active
- 2005-12-02 EP EP05853122.9A patent/EP1828314B1/en not_active Revoked
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US5770557A (en) * | 1997-03-13 | 1998-06-23 | Milliken Research Corporation | Fabric softener composition containing poly(oxyalkylene)-substituted colorant |
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WO2002016464A2 (en) * | 2000-08-24 | 2002-02-28 | Milliken & Company | Method of producing colored polyester thermoplastic materials through specific solid-state procedures |
Also Published As
Publication number | Publication date |
---|---|
WO2006062970A3 (en) | 2006-09-14 |
CN101098938B (en) | 2012-01-11 |
EP1828314A2 (en) | 2007-09-05 |
CN101098938A (en) | 2008-01-02 |
JP2008523215A (en) | 2008-07-03 |
JP5219517B2 (en) | 2013-06-26 |
US7632682B2 (en) | 2009-12-15 |
BRPI0518892A2 (en) | 2008-12-16 |
US20060117499A1 (en) | 2006-06-08 |
EP1828314B1 (en) | 2016-07-13 |
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