CA1243669A - Reactive colorants - Google Patents
Reactive colorantsInfo
- Publication number
- CA1243669A CA1243669A CA000483801A CA483801A CA1243669A CA 1243669 A CA1243669 A CA 1243669A CA 000483801 A CA000483801 A CA 000483801A CA 483801 A CA483801 A CA 483801A CA 1243669 A CA1243669 A CA 1243669A
- Authority
- CA
- Canada
- Prior art keywords
- coloring agent
- copolymers
- formula
- molecular weight
- average molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
-
- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
-
- 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
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
- C09B29/0059—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing only sulfur as heteroatom
-
- 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
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/106—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an azo dye
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/92—Synthetic fiber dyeing
- Y10S8/922—Polyester fiber
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/92—Synthetic fiber dyeing
- Y10S8/924—Polyamide fiber
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/92—Synthetic fiber dyeing
- Y10S8/926—Polyurethane fiber
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/92—Synthetic fiber dyeing
- Y10S8/927—Polyacrylonitrile fiber
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/92—Synthetic fiber dyeing
- Y10S8/928—Polyolefin fiber
Abstract
Abstract of the Disclosure Novel reactive colorants being the formula:
Description
~Z~366~
REACTIV~ COLOR~NTS
This invention relates to novel reactive colorants based on thiophene derivatives which have particular application in coloration of thermoset resins, exempliEied by polyurethanes.
It is known that polyurethane resins, produced by the reaction of polyol and an isocyanate may be colored by adding a pigment or dyestuff to the resin. When, however, certain thermoset materials such as polyurethanes are colored with a pigment, the resulting product may be only slightly tinted at normal pigment concentrations, and may thus require larger, undesirable amounts of pigment if a dark hue is to be attained. This phenomenon is particularly apparent in the case of polyurethane foams. On the other hand, if a conventional dyestuff is employed to color the thermos~t product, water resistance, oil reslstance, and/or resistance to migration of the dyestuff may often be disadvantageously inadequate. When such a dye is used as a coloring agent, it i5 difficult to prevent bleeding of the dye from the colored resin product. Thermosetting resin products, such as polyurethanes, however, which have been colored with a dyestuff, have certain advantages.
Particularly, such colored products may, for instance, possess a clearer hue, and improved ~transparency characteristics, both of which are important commercial attributes.
i ;; ~
- - ~
, . . .
' - !' 366~
Dyes rather than pigments are preferred for use in coloring polyurethane resins because each molecule of a dye imparts color to the product. Conversely, only the surface molecules of pigment particles impart color. From the standpoint of utilization, then, dyes are more ef~ective than pigments. Due to the above noted shortcomings oE dyes, however, pigments have historically been used extensively.
One definite improvement in prior art techniques is set forth in commonly assigned U.S. Patent 4,284,729 to Cross et al in which a liquid polymeric colorant is added to the reaction mixture during production of a thermoset resin.
Cross et al determined that a liquid, reactive, polymeric colorant could be added before or during the polyaddition reaction to achieve desired coloration of the thermoset resin. The specific polymeric colorant of Cross et al has the formula:
R (polymeric constituent-X)n wherein R is an organic dyestuff radical; the polymeric constituent is selected from polyalkylene oxides and copolymers of polyalkylene oxides in which the alkylene moiety of the polymeric constituent contains 2 or more carbon atoms and such polymeric constituent has a molecular weight of from about ~4 to about 1500; X is selected from -OH, -NH2 and -SH, and n i.s an integer of from about 1 to about 6. The liquid coloring agent is added to the reaction mixture in an amount sufficient to provide the intended degree of coloration of the thermoset resin.
, , .
,. . .. .
: ...........
- :. .
- : ' 36~9 Even though the Cross et al polymeric colorant represents vast improvement over prior art techniques, certain problems remain with regard to coloration of polyurethane resins, and foams, in particular. During the complex reactions experienced in producing thermosettiny resins, such as polyurethane foams, interactions may occur between certain substituents of the colorant and reactive components of the reaction mixture. In polyurethane foam production specifically, a careful balance must be maintained throughout the reaction to achieve the desired end product. If the proper balance is not maintained, a product may be produced that is outside the desired product specifications and/or the final product may exhibit poor stability under certain conditions.
Other approaches to coloration of polyurethanes specifically are set forth in U.S. Patent 3,994,835 to Wolf et al and 4,132,840 to Hugl et al. Wolf et al discloses the addition of dispersions of dyestuffs containing at least one free amino or hydroxyl group capable of reacting with the isocyanate under the conditions of polyaddition and liquids in which the dyes are soluble to an extent less than 2 percent. Hugl et al disclose the coloration of polyurethane resins with dyestuffs having the formula ., :
,: . , ,................ .... ~ .
, ~ ~ ... .
' ' ~ --. ~ ,, : , :. , -`` 3L;~9~3~69 NC ~ / A-OH
j =CH ~ N
\--/
NC ~ B-OH
Rl wherein Rl is hydrogen, halogen, optionally substikuted Cl-C4 alkyl, optionally substituted Cl C4 alkoxy and optionally substituted Cl-C4 alkylcarbonylamino and R2 denotes hydrogen, optionally substituted Cl-C~ alkyl and optionally substituted Cl-C~ alkoxy, while A and B denote optionally branched alkylene chains which can be identical or different and preferably have 2 to 6 carbon atoms.
Also as noted in "New Uses For Highly Miscible Liquid Polymeric Colorants In The Manufacture of Colored Urethane Systems", a paper presented by P. D. Moore, J. W.
Miley and S. Bates at the 27th Annual Technical/Marketing Conerence for SPI, many extra advantages are attendant to the use of polymeric colorants in polyurethanes beyond the mere aesthetic coloration of same. Specifically, such polymeric colorants can act as important process control indicators which enable one to more closely maintain quality control parameters by visual observation of product color.
While the polymeric colorants of Moore et al are of the type referred to in the aforementioned Cross et al patent, like advantages may also be realiæed from reactive colorants -according to the present invention. In fact, certain of the~ ;~
: :
~, . .
'; ..
:
~- :
: .. : :
. . :
Cross et al colorants encounter adverse interactions in the production of polyurethane foam which are not encountered by the novel colorants of the present invention. Particularly, it has been determined that while all of the Cross et al polymeric colorants may be successfully employed in the coloration of thermoset re~ins generally, certain of the colorants fail in the production of polyurethane foams where tin catalysts and Elame retardant chemicals are present.
Certain known prior art discloses dyestuffs that are somewhat related to certain of the colorants of the present invention, e.g. U.S. Patents 2,827,450; 4,301,068;
4,113,721; 4,282,144; 4,301,069; 4,255,326; British Patents 1,583,377; and 1,394,365; and German Offenlegungscrift
REACTIV~ COLOR~NTS
This invention relates to novel reactive colorants based on thiophene derivatives which have particular application in coloration of thermoset resins, exempliEied by polyurethanes.
It is known that polyurethane resins, produced by the reaction of polyol and an isocyanate may be colored by adding a pigment or dyestuff to the resin. When, however, certain thermoset materials such as polyurethanes are colored with a pigment, the resulting product may be only slightly tinted at normal pigment concentrations, and may thus require larger, undesirable amounts of pigment if a dark hue is to be attained. This phenomenon is particularly apparent in the case of polyurethane foams. On the other hand, if a conventional dyestuff is employed to color the thermos~t product, water resistance, oil reslstance, and/or resistance to migration of the dyestuff may often be disadvantageously inadequate. When such a dye is used as a coloring agent, it i5 difficult to prevent bleeding of the dye from the colored resin product. Thermosetting resin products, such as polyurethanes, however, which have been colored with a dyestuff, have certain advantages.
Particularly, such colored products may, for instance, possess a clearer hue, and improved ~transparency characteristics, both of which are important commercial attributes.
i ;; ~
- - ~
, . . .
' - !' 366~
Dyes rather than pigments are preferred for use in coloring polyurethane resins because each molecule of a dye imparts color to the product. Conversely, only the surface molecules of pigment particles impart color. From the standpoint of utilization, then, dyes are more ef~ective than pigments. Due to the above noted shortcomings oE dyes, however, pigments have historically been used extensively.
One definite improvement in prior art techniques is set forth in commonly assigned U.S. Patent 4,284,729 to Cross et al in which a liquid polymeric colorant is added to the reaction mixture during production of a thermoset resin.
Cross et al determined that a liquid, reactive, polymeric colorant could be added before or during the polyaddition reaction to achieve desired coloration of the thermoset resin. The specific polymeric colorant of Cross et al has the formula:
R (polymeric constituent-X)n wherein R is an organic dyestuff radical; the polymeric constituent is selected from polyalkylene oxides and copolymers of polyalkylene oxides in which the alkylene moiety of the polymeric constituent contains 2 or more carbon atoms and such polymeric constituent has a molecular weight of from about ~4 to about 1500; X is selected from -OH, -NH2 and -SH, and n i.s an integer of from about 1 to about 6. The liquid coloring agent is added to the reaction mixture in an amount sufficient to provide the intended degree of coloration of the thermoset resin.
, , .
,. . .. .
: ...........
- :. .
- : ' 36~9 Even though the Cross et al polymeric colorant represents vast improvement over prior art techniques, certain problems remain with regard to coloration of polyurethane resins, and foams, in particular. During the complex reactions experienced in producing thermosettiny resins, such as polyurethane foams, interactions may occur between certain substituents of the colorant and reactive components of the reaction mixture. In polyurethane foam production specifically, a careful balance must be maintained throughout the reaction to achieve the desired end product. If the proper balance is not maintained, a product may be produced that is outside the desired product specifications and/or the final product may exhibit poor stability under certain conditions.
Other approaches to coloration of polyurethanes specifically are set forth in U.S. Patent 3,994,835 to Wolf et al and 4,132,840 to Hugl et al. Wolf et al discloses the addition of dispersions of dyestuffs containing at least one free amino or hydroxyl group capable of reacting with the isocyanate under the conditions of polyaddition and liquids in which the dyes are soluble to an extent less than 2 percent. Hugl et al disclose the coloration of polyurethane resins with dyestuffs having the formula ., :
,: . , ,................ .... ~ .
, ~ ~ ... .
' ' ~ --. ~ ,, : , :. , -`` 3L;~9~3~69 NC ~ / A-OH
j =CH ~ N
\--/
NC ~ B-OH
Rl wherein Rl is hydrogen, halogen, optionally substikuted Cl-C4 alkyl, optionally substituted Cl C4 alkoxy and optionally substituted Cl-C4 alkylcarbonylamino and R2 denotes hydrogen, optionally substituted Cl-C~ alkyl and optionally substituted Cl-C~ alkoxy, while A and B denote optionally branched alkylene chains which can be identical or different and preferably have 2 to 6 carbon atoms.
Also as noted in "New Uses For Highly Miscible Liquid Polymeric Colorants In The Manufacture of Colored Urethane Systems", a paper presented by P. D. Moore, J. W.
Miley and S. Bates at the 27th Annual Technical/Marketing Conerence for SPI, many extra advantages are attendant to the use of polymeric colorants in polyurethanes beyond the mere aesthetic coloration of same. Specifically, such polymeric colorants can act as important process control indicators which enable one to more closely maintain quality control parameters by visual observation of product color.
While the polymeric colorants of Moore et al are of the type referred to in the aforementioned Cross et al patent, like advantages may also be realiæed from reactive colorants -according to the present invention. In fact, certain of the~ ;~
: :
~, . .
'; ..
:
~- :
: .. : :
. . :
Cross et al colorants encounter adverse interactions in the production of polyurethane foam which are not encountered by the novel colorants of the present invention. Particularly, it has been determined that while all of the Cross et al polymeric colorants may be successfully employed in the coloration of thermoset re~ins generally, certain of the colorants fail in the production of polyurethane foams where tin catalysts and Elame retardant chemicals are present.
Certain known prior art discloses dyestuffs that are somewhat related to certain of the colorants of the present invention, e.g. U.S. Patents 2,827,450; 4,301,068;
4,113,721; 4,282,144; 4,301,069; 4,255,326; British Patents 1,583,377; and 1,394,365; and German Offenlegungscrift
2,334,169. Likewise the above prior art discloses techni~ues for coloration of polyurethane resinsO None of the known prior art, however, teaches or suggests the use of thiophene based, reactive colorants for in situ coloration as taught and claimed herein.
A need, therefore, continues to exist for a coloring agent which has excellent water resistance, Qil resistance and/or bleeding resistance, and which at the same time may be easily incorporated into the reaction mixture without adverse interaction with components of the reaction mixture. Accordingly, it would be highly desirable to provide a process for preparing colored thermosetting resin products in which the coloring agent has the foregoing . .. :
: :, : - :
. .
:
' ` -~
: .
~Z~6~g advantages. Briefly, the present invention is directed to reactive colorants which combine the very desirahle characteristics of high color yields of dyes with the non-migratory properties of pigments. The result is a product which is superior to both dyes and pigments in terms of cost effectiveness and properties of the cured polymer system.
According to the present invention novel reactive colorants are provided of the ormula:
R ~ ~ / R8 wherein Rl, R2 and R3 are selected from halogen, carboxylic acid, alkanoyl, aryloyl, carbocyclic forming polymethylene chains, alkyl, aryl, cyano, thioalkyl, dithioalkyl, thioaryl, dithioaryl, thiocyano, carboxyalkyl, carboxyaryl, amidoalkyl, amidodialkyl, amidoaryl, amidodiaryl, oxyalkyl, oxyaryl, thioamidoalkyl, thioamidodialkyl, or hydrogen when an adjacent group is isobutyryl; R4, Rs, R6 and R7 are selected from hydrogen, alkyl, oxyalkyl, oxyaryl, sulfonamidoalkyl, sulonamidoaryl, amidoalkyl, amidodialkyl, amidoaryl, amidodiaryl, halogen, thioalkyl and thioaryl; and R8 and Rg are selected from polyalkylene oxide, copolymers of polyalkylene oxides, and hydroxyalkylenes.
, .... , . - :, :
.
-,. ' ' ' ~L3~69 According to a preferred embodiment the R1, R2 andR3 groups in the above formula may be selected from cyano lower alkyl, a carbocyclic forming polymethylene chain, carboxyalkyl, alkanoyl, amidoaryl or hydrogen when an adjacent group is isobutyryl. In an even more preferred embodiment, the R4, Rs and R6 groups in the above formula may be selected from hydrogen, halogen or lower alkyl.
Colorants according to the present invention are generally liquid at ambient conditions of temperature and pressure, though if not, are generally soluble in reactants of processes in which they are employed.
In order to avoid adverse interactions during production of the polyurethane resin, the presence on the thiophene ring of certain substituents such as N02, ~0, NH2, NHR ~where R is alkyl or aryl), SH, 0~1, CONH2, S02NH2 as well as hydro~en except as specified above should be avoided .
The substituents provided in the R8 and Rg position for colorants of the present invention may be any suitable substituent having two or more carbon atoms and which will accomplish the objects of the present invention.
Typical of such substituents which may be attached to the dyestuff radical are the hydroxyalkylenesr polymeric epoxides, such as the polyalkylene oxides and copolymers thereof. Polymeric substituents are preferred. In this regard, polyalkylene oxides a~d copolymers of same which may J ~ ~
.
366~
be employed to provide the colorant of the present invention are, without limitation, polyethylene oxides, polypropylene oxides, polybutylene oxides, copolymers of polyethylene oxides, polypropylene oxides and polybutylene oxides, and other copolymers including block copolymers, in which a majority of the polymeric substituent is polyethylene oxide, polypropylene oxide and/or polybutylene oxide. Fuxther, such substituents generally have an average molecular weight in the range of from about 88 to about 1400, Examples of particularly preferred compounds within the scope of the present invention are set forth below ~in each instance R8 and Rg are selected from a copolymer of ethylene oxide and propylene oxide having a molecular weight of from about 88 ~o about 1400)o CH3~ ~CN
N=N ~~ \R9 (2) ~sN - ~N
Rg -8- :
, .. ... . . .
~L2~3~6~
CH3 C02C2H5 ~R
A need, therefore, continues to exist for a coloring agent which has excellent water resistance, Qil resistance and/or bleeding resistance, and which at the same time may be easily incorporated into the reaction mixture without adverse interaction with components of the reaction mixture. Accordingly, it would be highly desirable to provide a process for preparing colored thermosetting resin products in which the coloring agent has the foregoing . .. :
: :, : - :
. .
:
' ` -~
: .
~Z~6~g advantages. Briefly, the present invention is directed to reactive colorants which combine the very desirahle characteristics of high color yields of dyes with the non-migratory properties of pigments. The result is a product which is superior to both dyes and pigments in terms of cost effectiveness and properties of the cured polymer system.
According to the present invention novel reactive colorants are provided of the ormula:
R ~ ~ / R8 wherein Rl, R2 and R3 are selected from halogen, carboxylic acid, alkanoyl, aryloyl, carbocyclic forming polymethylene chains, alkyl, aryl, cyano, thioalkyl, dithioalkyl, thioaryl, dithioaryl, thiocyano, carboxyalkyl, carboxyaryl, amidoalkyl, amidodialkyl, amidoaryl, amidodiaryl, oxyalkyl, oxyaryl, thioamidoalkyl, thioamidodialkyl, or hydrogen when an adjacent group is isobutyryl; R4, Rs, R6 and R7 are selected from hydrogen, alkyl, oxyalkyl, oxyaryl, sulfonamidoalkyl, sulonamidoaryl, amidoalkyl, amidodialkyl, amidoaryl, amidodiaryl, halogen, thioalkyl and thioaryl; and R8 and Rg are selected from polyalkylene oxide, copolymers of polyalkylene oxides, and hydroxyalkylenes.
, .... , . - :, :
.
-,. ' ' ' ~L3~69 According to a preferred embodiment the R1, R2 andR3 groups in the above formula may be selected from cyano lower alkyl, a carbocyclic forming polymethylene chain, carboxyalkyl, alkanoyl, amidoaryl or hydrogen when an adjacent group is isobutyryl. In an even more preferred embodiment, the R4, Rs and R6 groups in the above formula may be selected from hydrogen, halogen or lower alkyl.
Colorants according to the present invention are generally liquid at ambient conditions of temperature and pressure, though if not, are generally soluble in reactants of processes in which they are employed.
In order to avoid adverse interactions during production of the polyurethane resin, the presence on the thiophene ring of certain substituents such as N02, ~0, NH2, NHR ~where R is alkyl or aryl), SH, 0~1, CONH2, S02NH2 as well as hydro~en except as specified above should be avoided .
The substituents provided in the R8 and Rg position for colorants of the present invention may be any suitable substituent having two or more carbon atoms and which will accomplish the objects of the present invention.
Typical of such substituents which may be attached to the dyestuff radical are the hydroxyalkylenesr polymeric epoxides, such as the polyalkylene oxides and copolymers thereof. Polymeric substituents are preferred. In this regard, polyalkylene oxides a~d copolymers of same which may J ~ ~
.
366~
be employed to provide the colorant of the present invention are, without limitation, polyethylene oxides, polypropylene oxides, polybutylene oxides, copolymers of polyethylene oxides, polypropylene oxides and polybutylene oxides, and other copolymers including block copolymers, in which a majority of the polymeric substituent is polyethylene oxide, polypropylene oxide and/or polybutylene oxide. Fuxther, such substituents generally have an average molecular weight in the range of from about 88 to about 1400, Examples of particularly preferred compounds within the scope of the present invention are set forth below ~in each instance R8 and Rg are selected from a copolymer of ethylene oxide and propylene oxide having a molecular weight of from about 88 ~o about 1400)o CH3~ ~CN
N=N ~~ \R9 (2) ~sN - ~N
Rg -8- :
, .. ... . . .
~L2~3~6~
CH3 C02C2H5 ~R
(3)~N=N ~ N~
CH3 C02CE~3 N-N--N=N~;3N /R8 ~C02CH3 (6) CH ~ Il=N ~ N ~Rg CH3 ~C02C2H5 C6HS-N ~ N=N~3 N /R8 ~_ ~
NC 5 ~--N=N _--~N ~ R ~ ~
:
:
.... .. . ~ ~ .. --. .
:. :.: ~ : , ",: "., ~ : :
~366~
g) CH3 CN
~--N=N--(~N ~ R8 ,. , . ,. - - :
, "~ ~
- -~, ' '`.. ' :
.
( 10 ) CH~3 C02C2H5 . . /
CH3~ ~S~ ~'--N=N ~3N ~
In formulas l through lO, R8 and Rg have the values given above. Any suitable procedure may be employed to produce the reactive colorants of the present invention whereby the reactive substituent, or substituents, are coupled to an organic dyestuff radical.~ ~or example, the procedure set forth in U.S. Patent 3,157,633, .
may be employed.
Further, it;may be desirable to use an organic solvent as the reaction medium since the reactive substituent is preferably in solution when coupled to the organic dyestuEf radicàl. Any 9ultable organic solution,~
even an aqueous organic~solution, may be employed. The partlcular shade of the colorant;~w1ll depend~primarily upon the~particular dye6tuff~radical selected.
~ A large variety of colors and shades may be~
obtained by blending two or more colorants. Blendi~g` of~;the~
colorants of the present invention can be readily ~ ~`
~accomplished as~the colorants are~preferably 1iqu1d,;~though ;~
not, have~substantially ;ident1cal~601ubi~1ity charac~eristics.~ Therefore, the~reactive co10rants are~in~
~'h~3669 general soluble in one another, and are also in general completely compatible with each okher.
For example, the colorants according to the present invention may be prepared by converting a dyestufE
intermediate containing a primary amino group into the corresponding reactive compound, and employing the reactive compound to produce a colored product having a chromophoric group in the molecule~ In the case of azo dyestuffs, this may be accomplished by reacting a primary aromatic amine with an appropriate amount o an alkylene oxide or mixtures of alkylene oxides, such as ethylene oxide, propylene oxide, or even butylene oxide, according to procedures well known in the art.
Once the reactive coupler is produced along the lines described above, same can be reacted with the thiophene derivative as set forth in the Examples one through five hereinafter. As can be seen from the ~xamples, the colorant form includes liquids, oils, and powders, all of which may be successfully employed in a coloration process.
Reactive colorants of the invention may be incorporated into a resin for coloration of same by simply adding the colorant to the reaction mixture or to one of the components of the reaction mixture before or during the polyaddition reaction. For instance, for coloration of polyurethane resin, the colorant may be added to the polyol .... .. . .
.
~1 29~366~
or even in some instances to the polyisocyanate component o the reaction mixture either before or during polyurethane formation. The subsequent reaction may be carried out in the usual manner, i.e, in the same way as for polyurethane resins which are not colored.
The products of the present invention are advantageous for use in the production of polyurethane foams in which several reactions generally take place. First an isocyanate such as toluene diisocyanate is reacted with a polyol such as polypropylene glycol in the presence of heat and suitable catalyst. If both the isocyanate and the polyol are difunctional, a linear polyurethane results, whereas should either have functionalities greater than two, a cross linked polymer will result. If the hydroxylic compound available to react with the -NC0 group is water~
the initial reaction product is a carbamic acid which is unstable and breaks down into a primary amine and carbon dioxide. Since excess isocyanate is typically present, the reaction of the lsocyanate with the amine generated by decarboxylation of the carbamic acid occurs, and if controlled, the liberated carbon dioxide becomes the blowing agent for production of the foam. Further, the primary amine produced reacts with further isocyanate to yield a substituted urea which affords strength and increased firmness characteristics to the polymer.
:
,,, ~ ~ :
. :.:: ' : ' ~' ~:, 12436~
In general, amine and tin catalysts are used to delicately balance the reaction of isocyanate with water, the blowing reaction, and the reaction of isocyanate with polymer building substituents. If the carbon dioxide is released too early, the polymer has no strength and the foam collapses. If polymer formation advances to rapidly a closed cell foam results which will collapse on cooling. If the colorant or another component reacts to upset the catalyst balance poorly formed foam will result.
Additionally, the substituted urea may react with excess isocyanate, and the urethane itself reacts with further isocyanate to cross-link the polymer by both biruet and allophonate formation. Foams colored by the present colorants may be soft, semi-rigid, or rigid foams, including the so-called polyurethane integral skin and microcellular foams.
Coloring agents according to the present invention are reactive coloring agents, and may be added to the reaction mixture, or to one of the components thereof. When in liquid form, colorants of the present invention may be added as one or more of the components of the reaction mixture. Conversely when in oil or powder forms, the colorants are first added to one of the reactive components and are carried thereby, or conversely are dissolved in a solvent carrier and added as a separate component.
Obviously liquids have significant processing advantages .. ~
:
- : ' ~ :
: : . :
, ... . . ,:
~2~3669 over solids, and may, if desired, be added directly to the reaction mixture so that no extraneous nonreactive solvent or dispersing agent is present.
Polyurethane products which may be colored with reactive colorants of the present invention are useful for producing shaped produc~s by injection molding, extrusion or calendering and may be obtained by adding the ~oloring a~ent to the polyol or diol component of the reaction mixture, or to one of the other components r although addition to the polyol component is preferred. The polyols may be polyesters which contain hydroxyl groups, in particular reaction products of dihydric alcohols and dibasic carboxylic acids, or polyethers which contain hydroxyl groups, in particular products of the addition of ethylene oxide, propylene oxide, styrene oxide or epichlorohydrin to water, alcohols or amines, preferably dialcohols. The coloring agent may also be admixed with the so-called chain extending diols, eug., ethylene glycol, diethylene glycol and butane diol. In general, it is desirable not to use more than about 20 percent by weight of coloring agent based on the weight of poIyol. In most cases very strong colorations are produced with a small proportion of the coloring agent. For example, from about O.l to about 5 percent, preferably O.S to 2 percent by weight coloring agent may be utilized based on the weight of polyol.
.
. . .
: , . . . :
. . : , . , : ... , . - .
, . .
The preferred colorants of the invention may be soluble, for instance, in most polyols which would be used in polyurethanes, and in themselves. This property may be particularly valuable fox three reasons. First, this solubility may permit rapid mixing and homogenoeous distribution throughout the resin, thus eliminating shading differences and streaks when properly mixed. Second, the colorant may have no tendency to settle as would be the case with pigment dispersions. Third, it is possible to prepare a blend of two or more colors which provides a wide range of color availability.
Present reactive coloring agents may also be of considerable value in reaction injection molding (RIM) applications. The RIM process is a method of producing molded urethanes and other polymers wherein the two reactive streams are mixed while being poured into a mold. Upon reaction, the polymer is "blown" by chemicals to produce a foamed structure. This process may be hindered by the presence of solid particles, such as pigments. The present invention may not cause this hindrance because tbere are no particles in the system and the colorant becomes part of the polymer through reaction with one of the components.
The following examples illustrate the inventlon, and parts and percentage , unless otherwise noted are by weight:
, ~
, ~: , : : : ;
366~
Example 1 Ninety two and one half grams of phosphoric acid ~85% strength) was added along with 12.5 grams of sulfuric acid (98~ strength ) and 2 drops of 2-ethylhexanol defoamer to a 500 ml closed flask. The mixture was then cooled and 8.2 grams of 2-amino-3,5-dicyano-4-methyl thiophene was added followed by further cooling to below 0C. Eighteen grams of nitrosyl sulfuric acid (40%) was slowly added while maintaining temperature below 0C. After three hours, the mixture was tested for nitrite. A positive nitrite test was obtained and one gram of sulfamic acid was added and a vacuum was pulled. After one hour, a negative nitrite test was obtained. Ten and eight tenths grams of coupler ~M-toluidine - 2EO), 300 grams of ice and water, and 2 grams of urea were added to a 4 liter beaker and cooled to below 0C. The diazo solution from the flask was added dropwise to the beaker over 40 minutes, maintaining temperature below 0C. The reæuLting mixture was stirred for several hours and allowed to stand overnight, after which 122 grams of sodium hydroxide (50%) were added to neutralize excess acid to a pH o~ about 7. The resulting product was filtered~
washed several times with hot water. It was then dissolved in isopropyl alcohol, and precipitated again by adding water, filtered and dried to give a violet powder that melted at 208C.
, .. , ..... .. ~ ., , . . , . . .
,. , .
: :: ::
, . , :. .
- ,. .- - ~- ~
i2~3669 Example 2 The procedure of Example 1 was followed with the exception of amounts of reac~ants and the particular thiophene and coupler employed, all of which are specified below.
49 ml. acekic acid 19.5 ml. propionic acid 2.5 grams H2SO4 1 drop 2-ethylhexanol defoamer 5.7 grams 2-amino-3-carbomethoxy-5-isobutyryl thiophene 9 grams nitrosyl sufuric acid .5 grams Sulfamic acid
CH3 C02CE~3 N-N--N=N~;3N /R8 ~C02CH3 (6) CH ~ Il=N ~ N ~Rg CH3 ~C02C2H5 C6HS-N ~ N=N~3 N /R8 ~_ ~
NC 5 ~--N=N _--~N ~ R ~ ~
:
:
.... .. . ~ ~ .. --. .
:. :.: ~ : , ",: "., ~ : :
~366~
g) CH3 CN
~--N=N--(~N ~ R8 ,. , . ,. - - :
, "~ ~
- -~, ' '`.. ' :
.
( 10 ) CH~3 C02C2H5 . . /
CH3~ ~S~ ~'--N=N ~3N ~
In formulas l through lO, R8 and Rg have the values given above. Any suitable procedure may be employed to produce the reactive colorants of the present invention whereby the reactive substituent, or substituents, are coupled to an organic dyestuff radical.~ ~or example, the procedure set forth in U.S. Patent 3,157,633, .
may be employed.
Further, it;may be desirable to use an organic solvent as the reaction medium since the reactive substituent is preferably in solution when coupled to the organic dyestuEf radicàl. Any 9ultable organic solution,~
even an aqueous organic~solution, may be employed. The partlcular shade of the colorant;~w1ll depend~primarily upon the~particular dye6tuff~radical selected.
~ A large variety of colors and shades may be~
obtained by blending two or more colorants. Blendi~g` of~;the~
colorants of the present invention can be readily ~ ~`
~accomplished as~the colorants are~preferably 1iqu1d,;~though ;~
not, have~substantially ;ident1cal~601ubi~1ity charac~eristics.~ Therefore, the~reactive co10rants are~in~
~'h~3669 general soluble in one another, and are also in general completely compatible with each okher.
For example, the colorants according to the present invention may be prepared by converting a dyestufE
intermediate containing a primary amino group into the corresponding reactive compound, and employing the reactive compound to produce a colored product having a chromophoric group in the molecule~ In the case of azo dyestuffs, this may be accomplished by reacting a primary aromatic amine with an appropriate amount o an alkylene oxide or mixtures of alkylene oxides, such as ethylene oxide, propylene oxide, or even butylene oxide, according to procedures well known in the art.
Once the reactive coupler is produced along the lines described above, same can be reacted with the thiophene derivative as set forth in the Examples one through five hereinafter. As can be seen from the ~xamples, the colorant form includes liquids, oils, and powders, all of which may be successfully employed in a coloration process.
Reactive colorants of the invention may be incorporated into a resin for coloration of same by simply adding the colorant to the reaction mixture or to one of the components of the reaction mixture before or during the polyaddition reaction. For instance, for coloration of polyurethane resin, the colorant may be added to the polyol .... .. . .
.
~1 29~366~
or even in some instances to the polyisocyanate component o the reaction mixture either before or during polyurethane formation. The subsequent reaction may be carried out in the usual manner, i.e, in the same way as for polyurethane resins which are not colored.
The products of the present invention are advantageous for use in the production of polyurethane foams in which several reactions generally take place. First an isocyanate such as toluene diisocyanate is reacted with a polyol such as polypropylene glycol in the presence of heat and suitable catalyst. If both the isocyanate and the polyol are difunctional, a linear polyurethane results, whereas should either have functionalities greater than two, a cross linked polymer will result. If the hydroxylic compound available to react with the -NC0 group is water~
the initial reaction product is a carbamic acid which is unstable and breaks down into a primary amine and carbon dioxide. Since excess isocyanate is typically present, the reaction of the lsocyanate with the amine generated by decarboxylation of the carbamic acid occurs, and if controlled, the liberated carbon dioxide becomes the blowing agent for production of the foam. Further, the primary amine produced reacts with further isocyanate to yield a substituted urea which affords strength and increased firmness characteristics to the polymer.
:
,,, ~ ~ :
. :.:: ' : ' ~' ~:, 12436~
In general, amine and tin catalysts are used to delicately balance the reaction of isocyanate with water, the blowing reaction, and the reaction of isocyanate with polymer building substituents. If the carbon dioxide is released too early, the polymer has no strength and the foam collapses. If polymer formation advances to rapidly a closed cell foam results which will collapse on cooling. If the colorant or another component reacts to upset the catalyst balance poorly formed foam will result.
Additionally, the substituted urea may react with excess isocyanate, and the urethane itself reacts with further isocyanate to cross-link the polymer by both biruet and allophonate formation. Foams colored by the present colorants may be soft, semi-rigid, or rigid foams, including the so-called polyurethane integral skin and microcellular foams.
Coloring agents according to the present invention are reactive coloring agents, and may be added to the reaction mixture, or to one of the components thereof. When in liquid form, colorants of the present invention may be added as one or more of the components of the reaction mixture. Conversely when in oil or powder forms, the colorants are first added to one of the reactive components and are carried thereby, or conversely are dissolved in a solvent carrier and added as a separate component.
Obviously liquids have significant processing advantages .. ~
:
- : ' ~ :
: : . :
, ... . . ,:
~2~3669 over solids, and may, if desired, be added directly to the reaction mixture so that no extraneous nonreactive solvent or dispersing agent is present.
Polyurethane products which may be colored with reactive colorants of the present invention are useful for producing shaped produc~s by injection molding, extrusion or calendering and may be obtained by adding the ~oloring a~ent to the polyol or diol component of the reaction mixture, or to one of the other components r although addition to the polyol component is preferred. The polyols may be polyesters which contain hydroxyl groups, in particular reaction products of dihydric alcohols and dibasic carboxylic acids, or polyethers which contain hydroxyl groups, in particular products of the addition of ethylene oxide, propylene oxide, styrene oxide or epichlorohydrin to water, alcohols or amines, preferably dialcohols. The coloring agent may also be admixed with the so-called chain extending diols, eug., ethylene glycol, diethylene glycol and butane diol. In general, it is desirable not to use more than about 20 percent by weight of coloring agent based on the weight of poIyol. In most cases very strong colorations are produced with a small proportion of the coloring agent. For example, from about O.l to about 5 percent, preferably O.S to 2 percent by weight coloring agent may be utilized based on the weight of polyol.
.
. . .
: , . . . :
. . : , . , : ... , . - .
, . .
The preferred colorants of the invention may be soluble, for instance, in most polyols which would be used in polyurethanes, and in themselves. This property may be particularly valuable fox three reasons. First, this solubility may permit rapid mixing and homogenoeous distribution throughout the resin, thus eliminating shading differences and streaks when properly mixed. Second, the colorant may have no tendency to settle as would be the case with pigment dispersions. Third, it is possible to prepare a blend of two or more colors which provides a wide range of color availability.
Present reactive coloring agents may also be of considerable value in reaction injection molding (RIM) applications. The RIM process is a method of producing molded urethanes and other polymers wherein the two reactive streams are mixed while being poured into a mold. Upon reaction, the polymer is "blown" by chemicals to produce a foamed structure. This process may be hindered by the presence of solid particles, such as pigments. The present invention may not cause this hindrance because tbere are no particles in the system and the colorant becomes part of the polymer through reaction with one of the components.
The following examples illustrate the inventlon, and parts and percentage , unless otherwise noted are by weight:
, ~
, ~: , : : : ;
366~
Example 1 Ninety two and one half grams of phosphoric acid ~85% strength) was added along with 12.5 grams of sulfuric acid (98~ strength ) and 2 drops of 2-ethylhexanol defoamer to a 500 ml closed flask. The mixture was then cooled and 8.2 grams of 2-amino-3,5-dicyano-4-methyl thiophene was added followed by further cooling to below 0C. Eighteen grams of nitrosyl sulfuric acid (40%) was slowly added while maintaining temperature below 0C. After three hours, the mixture was tested for nitrite. A positive nitrite test was obtained and one gram of sulfamic acid was added and a vacuum was pulled. After one hour, a negative nitrite test was obtained. Ten and eight tenths grams of coupler ~M-toluidine - 2EO), 300 grams of ice and water, and 2 grams of urea were added to a 4 liter beaker and cooled to below 0C. The diazo solution from the flask was added dropwise to the beaker over 40 minutes, maintaining temperature below 0C. The reæuLting mixture was stirred for several hours and allowed to stand overnight, after which 122 grams of sodium hydroxide (50%) were added to neutralize excess acid to a pH o~ about 7. The resulting product was filtered~
washed several times with hot water. It was then dissolved in isopropyl alcohol, and precipitated again by adding water, filtered and dried to give a violet powder that melted at 208C.
, .. , ..... .. ~ ., , . . , . . .
,. , .
: :: ::
, . , :. .
- ,. .- - ~- ~
i2~3669 Example 2 The procedure of Example 1 was followed with the exception of amounts of reac~ants and the particular thiophene and coupler employed, all of which are specified below.
49 ml. acekic acid 19.5 ml. propionic acid 2.5 grams H2SO4 1 drop 2-ethylhexanol defoamer 5.7 grams 2-amino-3-carbomethoxy-5-isobutyryl thiophene 9 grams nitrosyl sufuric acid .5 grams Sulfamic acid
4.5 grams 2-methoxy-5-acetamido-aniline 2EO
100 grams ice 2 grams urea 50 grams ammonium acetate 300 grams water and ice The precipitated product (after neutralizing with sodium hydroxide) was collected and water washed several times. The product was oven dried at 75C and give a bluish violet solid.
Example 3 : The procedure of Example l~was followed except for amounts of reactants and the particular thiophene and coupler. Such are set for:th below as follows:
:
200:grams H3PO4 25 grams H2SO4 2 drops 2-ethylhexanol defoamer . :~
16.3 grams 2-amino-3,5-dicyano-4 : ~ ~ meth:yl thiophene~
35 gr;ms nLtrosyl sulfuric acld ~ 3669 3 grams sulfamic acid 121 grams m-toluidine-2EO/15PO/2EO
60.5 grams ice 4 grams urea The excess acid was neutralized with 272 grams o 50% sodium hydroxide, the bottom salt layer of the reaction mixture was removed hot and the product was dis~olved in methylene chloride, washed four times and then dried over magnesium sulfate. The methylene chloride solution was then filtered and stripped to yield a violet oil.
Example 4 The procedure of Example 3 was followed with the exception of amount of reactants and the particular thiophene and coupler employed, all of which are specified below:
183 Grams ~3PO4 25 grams H2SO4 2 drops 2-ethylhexanol defoamer 25.7 grams 2-amino 3,5-dicarboethoxy -4-methyl thiophene 35 grams nitrosyl sulfuric 1 gram sulfamic acid 121 grams m-toluidine 2EO/15PO/2EO
247 grams ice 2 grams urea A red oil resulted.
Example 5 The procedure of Example 3 was followed with the exception of amount of reactants and the particular thiophene and coupler employed, all of which are specified below: :
-18- ~ ~
: `
, :
, ~ :, -, .-.
~2436~
100 grams H3PO4 15 grams H2SO4 2 drops 2-ethylhexanol defoamer 8.9 grams 2-amino-3-cyano 4,5-tetramethylene thiophene 17.5 gxams nitrosyl sulfuric 1 gram sulfamic ~cid 60.5 grams m~toluidine 2EO/15PO/2EO
120 grams ice A red oil resulted.
Example 6 A masterbatch for the production of polyurethane foam was prepared by adding 3000 grams of Niax-16-S6 ~a 3000 molecular weight triol available from Union Carbide) 125.1 grams of water, and 7.8 grams of Dabco 33L~ ~amine catalyst available from Air Products) to a one qallon plastic jug, mixed wel~ and ~tored at 65F for further use.
Example 7 A polyether polyurethane foam (control) was produced as follows. One hundred and four grams of the masterbatch of Example 6 were added to a 400 milliliter disposable beaker, and:one gram of a reactive colorant as taught herein was added thereto along with one milliliter of Liquid Silicone L-520 (available from Union Carblde). The mixture was stirred in a blender for ~5-30 seconds, 0.20 milliliters of ~-9 (stannous octanoate catalyst) added thereto from a syringe, and stirred for an additional 5-8 ~
seconds. Thereafter, 46 milliliters of toluene diisocyanat were added to the beaker and the mixture stirred for six : * trade ~arks. ~
--lg~
:
~' - : , ~Z~3~9 seconds. A blended, homogenous mixture resulted and was poured into an 83 ounce paper bucket. The mixture foamed, and after the foam stopped rising, was cured in an oven at 130C for 15 minutes.
Example 8 Polyurethane foam samples containing a flame retardant were produced as described in Example 7 with the exception that 10 grams of Thermolin T-101 flame retardant (available from Olin) were added to the beaker with the other components, and the foam sample was cured at 130C for 30 minutes. The foam of this Example possessed flame retardant properties.
As discussed above, while a number of colorants have heretofore been utili~ed for in situ coloration of polymeric materials, polyurethane foams present somewhat special problems. 8pecifically, the colorant must be stable to tin catalysts utilized in the production of the urethane, and also stable to flame retardants that are normally included in the polymer.
InstabiIity as to the stannous tin catalysts, results in reduction of the dyestuff leading to significant, if not total, loss of color. Additionally, the foam producing process is also adversely affected. The foam does `
not rise at a proper rate and does not cure at a fast enou~h rate. A tacky polyurethane with poor polymer properties results. It is thus important~that coloranes for -20-~ * trade mark.
... . .. . .
~2~3~i6~
polyurethanes be stable to the tin catalysts. This is a desirable and qualifying characteristic of colorants of the present invention.
Also with instability to flame retardants, a color change or color shift will appear which renders an unstable colorant useless. Typically colorants unstable to 1ame retardants change color as Eollows: red to violet and orange to red. While a number oE commercially available dyestuffs are not stable in the presence of the flame retardants, colorants of the present invention do possess such stability.
In order to demonstrate stability to both the tin catalysts and flame retardants, Examples 7 and 8 were reproduced with a number of different specific colorànts, both according to the present invention and otherwise.
Example 7 ~without flame retardant) serves as a control for evaluation of stability to flame retardants. The tin stability test is set forth in Example 9.
Example 9 Tests were also conducted as to tin stabili~y according to the following procedure. First the color value for the colorants tested was determined by placing about 0.10 to 0.15 grams of colorant into a lOO milliliter volumetric flask and adding approximately 40 to 50 milliliters of methanol. The flask was swirled until the colorant dissolved in the methanol, after which excess ,. ,,, ~ .. . ~ - .
... . ..
, - , ' ' ~
~LZ43669 methanol was added to the 100 milliliter mark on the flask.
The flask was stoppered and the contents were mixed and shaken. Exactly 2.0 milliliters of the solution of the colorant in methanol was then added to a separate like flask and the flask was filled with methanol to the 100 milliliter mark, stoppered and shaken.
A Beckman DU~7 spectrometer was zeroed with methanol, filled with the test solution, and the solution was scanned from 300 to 750 mm. The maximum absorbance was recorded. Color value is obtained by multiplying the sample weight by 0.2 and dividing the product obtained into the maximum absorbance value.
In the case of liquid phase colorant, the colorant to be tested was then added to a 50 milliliter volumetric flask.
In order to correct for varying color strengths the amount of colorant added was determined by the following formula:
100 grams ice 2 grams urea 50 grams ammonium acetate 300 grams water and ice The precipitated product (after neutralizing with sodium hydroxide) was collected and water washed several times. The product was oven dried at 75C and give a bluish violet solid.
Example 3 : The procedure of Example l~was followed except for amounts of reactants and the particular thiophene and coupler. Such are set for:th below as follows:
:
200:grams H3PO4 25 grams H2SO4 2 drops 2-ethylhexanol defoamer . :~
16.3 grams 2-amino-3,5-dicyano-4 : ~ ~ meth:yl thiophene~
35 gr;ms nLtrosyl sulfuric acld ~ 3669 3 grams sulfamic acid 121 grams m-toluidine-2EO/15PO/2EO
60.5 grams ice 4 grams urea The excess acid was neutralized with 272 grams o 50% sodium hydroxide, the bottom salt layer of the reaction mixture was removed hot and the product was dis~olved in methylene chloride, washed four times and then dried over magnesium sulfate. The methylene chloride solution was then filtered and stripped to yield a violet oil.
Example 4 The procedure of Example 3 was followed with the exception of amount of reactants and the particular thiophene and coupler employed, all of which are specified below:
183 Grams ~3PO4 25 grams H2SO4 2 drops 2-ethylhexanol defoamer 25.7 grams 2-amino 3,5-dicarboethoxy -4-methyl thiophene 35 grams nitrosyl sulfuric 1 gram sulfamic acid 121 grams m-toluidine 2EO/15PO/2EO
247 grams ice 2 grams urea A red oil resulted.
Example 5 The procedure of Example 3 was followed with the exception of amount of reactants and the particular thiophene and coupler employed, all of which are specified below: :
-18- ~ ~
: `
, :
, ~ :, -, .-.
~2436~
100 grams H3PO4 15 grams H2SO4 2 drops 2-ethylhexanol defoamer 8.9 grams 2-amino-3-cyano 4,5-tetramethylene thiophene 17.5 gxams nitrosyl sulfuric 1 gram sulfamic ~cid 60.5 grams m~toluidine 2EO/15PO/2EO
120 grams ice A red oil resulted.
Example 6 A masterbatch for the production of polyurethane foam was prepared by adding 3000 grams of Niax-16-S6 ~a 3000 molecular weight triol available from Union Carbide) 125.1 grams of water, and 7.8 grams of Dabco 33L~ ~amine catalyst available from Air Products) to a one qallon plastic jug, mixed wel~ and ~tored at 65F for further use.
Example 7 A polyether polyurethane foam (control) was produced as follows. One hundred and four grams of the masterbatch of Example 6 were added to a 400 milliliter disposable beaker, and:one gram of a reactive colorant as taught herein was added thereto along with one milliliter of Liquid Silicone L-520 (available from Union Carblde). The mixture was stirred in a blender for ~5-30 seconds, 0.20 milliliters of ~-9 (stannous octanoate catalyst) added thereto from a syringe, and stirred for an additional 5-8 ~
seconds. Thereafter, 46 milliliters of toluene diisocyanat were added to the beaker and the mixture stirred for six : * trade ~arks. ~
--lg~
:
~' - : , ~Z~3~9 seconds. A blended, homogenous mixture resulted and was poured into an 83 ounce paper bucket. The mixture foamed, and after the foam stopped rising, was cured in an oven at 130C for 15 minutes.
Example 8 Polyurethane foam samples containing a flame retardant were produced as described in Example 7 with the exception that 10 grams of Thermolin T-101 flame retardant (available from Olin) were added to the beaker with the other components, and the foam sample was cured at 130C for 30 minutes. The foam of this Example possessed flame retardant properties.
As discussed above, while a number of colorants have heretofore been utili~ed for in situ coloration of polymeric materials, polyurethane foams present somewhat special problems. 8pecifically, the colorant must be stable to tin catalysts utilized in the production of the urethane, and also stable to flame retardants that are normally included in the polymer.
InstabiIity as to the stannous tin catalysts, results in reduction of the dyestuff leading to significant, if not total, loss of color. Additionally, the foam producing process is also adversely affected. The foam does `
not rise at a proper rate and does not cure at a fast enou~h rate. A tacky polyurethane with poor polymer properties results. It is thus important~that coloranes for -20-~ * trade mark.
... . .. . .
~2~3~i6~
polyurethanes be stable to the tin catalysts. This is a desirable and qualifying characteristic of colorants of the present invention.
Also with instability to flame retardants, a color change or color shift will appear which renders an unstable colorant useless. Typically colorants unstable to 1ame retardants change color as Eollows: red to violet and orange to red. While a number oE commercially available dyestuffs are not stable in the presence of the flame retardants, colorants of the present invention do possess such stability.
In order to demonstrate stability to both the tin catalysts and flame retardants, Examples 7 and 8 were reproduced with a number of different specific colorànts, both according to the present invention and otherwise.
Example 7 ~without flame retardant) serves as a control for evaluation of stability to flame retardants. The tin stability test is set forth in Example 9.
Example 9 Tests were also conducted as to tin stabili~y according to the following procedure. First the color value for the colorants tested was determined by placing about 0.10 to 0.15 grams of colorant into a lOO milliliter volumetric flask and adding approximately 40 to 50 milliliters of methanol. The flask was swirled until the colorant dissolved in the methanol, after which excess ,. ,,, ~ .. . ~ - .
... . ..
, - , ' ' ~
~LZ43669 methanol was added to the 100 milliliter mark on the flask.
The flask was stoppered and the contents were mixed and shaken. Exactly 2.0 milliliters of the solution of the colorant in methanol was then added to a separate like flask and the flask was filled with methanol to the 100 milliliter mark, stoppered and shaken.
A Beckman DU~7 spectrometer was zeroed with methanol, filled with the test solution, and the solution was scanned from 300 to 750 mm. The maximum absorbance was recorded. Color value is obtained by multiplying the sample weight by 0.2 and dividing the product obtained into the maximum absorbance value.
In the case of liquid phase colorant, the colorant to be tested was then added to a 50 milliliter volumetric flask.
In order to correct for varying color strengths the amount of colorant added was determined by the following formula:
5/(Color va~ue) = number of grams added.
Then 35 milliliters of 2-ethoxyethylether or 2-methoxylethylether were added to dissolve the colorant.
Further solvent was then added to bring the total contents to the 50 milliliter mark. The flask was stoppered and shaken. Exactly 2.0 milliliters of this solution were transferred to a further 50 milliliter flask and diluted to the 50 milliliter mark with one of the solvents.
, - .- ,, .
:
;' :
, 3L2~36~
In the case o solid colorant to be tested colorant to be tested was added to a 100 ml volumetric flask.
In order to correct for varying color strengths the amount of colorant added was determined as follows:
5/2 tcolor value) = number of grams added, Then 35 ml of 2-ethoxyethyl-either or 2-methoxyethylether solvent was added to dissolve the colorant. An additional amount of solvent was added to bring the level in the volumetric flask to the 100 ml mark; a stopper was inserted, and the contents of the flask were mixed well by shaking.
Exactly 4.0 ml of this solution were then transferred to another 100 ml volumetric flask and diluted to the 100 ml mark with solvent.
A solution of T-9 ~stannous octanoate) was prepared with minimum air exposure by dissolving 0.70 gram of stannous octanoate in seven milliliters of solvent in a vial which was kept sealed between runs. The Beckman spectrometer was set up for repetitive scanning. Two milliliters of colorant solution (either solid or liquid as described above) were placed into a vial with 2.0 milliliters of the tin catalyst solution and mixed well.
The mixture was then transferred to the cell of the spectrometer which was capped and qulckly placed into the spectrometer ~not more than 20 to 30 seconds elapsed time).
Five repetetive scans were then made for each colorant sample at three intervals. The percentage loss after :: `
. ,, , . - , ~ . .
.:
-. . .
:. , :
31~;2~a3f~6~
fifteen minutes (5 scans) was measured from initial absorbance and last absorbance.
A number of commercially useful benzothiazole colorants were investigated as to stability to flame retardants. In the control testl i.e., no flame retardant present, following the procedures of Example 7, all o the compounds tested passed, indicating no color change. When however, the same compounds were included in production o foam according to Example 8 where the flame retardant was included, all of the compounds failed.
Example 10 In like fashion to the benzothiazole investigations, a number of colorants according to the present invention were prepared according to the general procedures set orth in Examples 1 through 5. Thereafter, the colorants were utilized in the coloration of polyurethane foams as described in Examples 7 and ~ to determine stability of same to flame retardants~ All of the thiophene compounds passed both tests, indicating stability to flame retardants. Compounds tested are listed in Table I
below.
The following abbreviations are utilized in the following tables: Et-ethyl; EO=ethylene oxide; PO=propylene oxide; ME=methyl; Ac=acetate. Also where numbers are separated by diagonals, eg. 2/15/5, such refers to moles EO/moles PO/moles EO.
-2~-.., 13~
Table I
Effect of Flame Retardants on Thiophene Reactive Colorants ~ N=N ~N
EX .
No.Rl R~ R~R4- R7 Ra, Rq Colo~
11C02Et Me CNH H 2EO/lSPO/5EO Red 12 do do doMe do do Red 13 do do doOMe OMe 2/10/5 . Violet 14 do do COMe H H 2/15i5 Red CN do CO2Me do do do Red 16 C02Et do CONHC6Hs do do do Red 17 do do do Me do 2/15/5 Red 18 do do do H do do Red 19 do do C02Et do do do Red 2 0do do do Cl do 2/10/6 Red 21 do do do Me do 2/15/2 Red 22CO2Me doCO2Me H do 2/15/5 Red 23 do do do do do 2J10/6 Red 24CO2Et doCO2Et do do 2/15/5 Red 2 5do do do Cl do do Red ~
26 CO2Me do C02Me do do do Red ::
-, : ~ ; .
, 36~3 27 do doCO2Et H do 2/10/6 Red 28 CN doCN OMeOMe 2/10/5Violet 29 do dodo Me H 2/15/5Violet do dodo dodo 2/15/2Violet 31 do do. do dodo 2/10/8Violet 32 do dodo dodo 2/7/6Violet 33 do dodo dodo 2/10/6Violet 34 do dodo H do 2/15/5Violet CN doCN Me H 2EOViolet 36 do dodo OMeOMe do Blue 3 7 do dodo NHAc OMe do Blue 38 do -(cH2)4- H H do Red 39 CO2EtMe CO2Et do do do Red 40 CO2Me H COCHMe2 NHAc OMe do Violet 41 CO2Et-(CH2)4- Me H 2/15/2 Red 42 do -(cH2)4- H do 2/15/5 Red 43 do do Me do 2/15/8 Red 44 do do H do 2/10/6 Red do do Me do 2/15/ 8 Red 46 CO2Et do H H 2/15/5 Red 47 CO2Me H COCXMe2 Me H 2/lS/2Violet 48 CONHC2H40H do do do do do Blue 49 C02Me do do OMe do 2/10/5Violet 50 CONHC2H40H do do do OMe do Blue 51 do do do NHAc do do Blue :
. ...
' - . ' ':
:.
~Z~3669 Benzothiazoles of the type tested as to flame retardant stability were also tested as to stability as to the stannous octanoate catalyst according to the test procedures set forth in Example 9. Compounds and results are set forth in Table II.
Table II
Effect of Stannous Octonate Catalyst on Colorants For Polymeric Resins R2~r~ ~n / R8 ENxo R1 R2 R~ R4 R~ R' 9 % LOSB Color 52 H H OMe Me 10E0 56.S Red 53 Cl do H H 2/15/5 91.5 Red 54 OMe do do OMe 12E0 66.7 Red Me do Cl H 2/10/5 85.9 Red 56 Cl do H Cl 2/15/5 97.8 Red~ :
-~7- :
.
. . . .
~Z~3~9 57 do do C1 H do 87.9 Red 58 H Cl do do do 100.0 Red Like tests were performed as to colorants according to the present invention, results of which may be compared to the benzothiazole results of Examples 52 through 58~ Compounds tested and results are set forth in Table III.
Table III
Effect of Stannous Octoate on Thiophene Based Colorants R2 /Rl R7 ~=I~/R8 Ex.
No. Rl ~? R3 R4 _ R7 RR, R4 % Loss Color 59 CO2Et Me CO2Et Me H 2/15/2 5.3Red CN do CN H do 2/15/5 0.0Violet 61 CO2Et do do do do do 3.3Red 62 CN do CO2Et do do 2/15/8 2.9Red 63 CO2Et do do Cl do 2/10/6 2.7Red ~ ' :
., . :, . , - -: ~ .. . , ::, : ~ '': ; - .
"
. . ;
64 CN do CN OMe OMe do 6.2Blue 65 CO2Et do do CN H 2/15/2 4.0Red 66 CN do CO2Et H do2/15/5 5.9Violet 67 CO2Et do COMe do do do 4.8Red 68 do doCONHC6Hs Me do2/15/2 3.0Red 69 CN do CN OMe do 12E0 7.0Violek CN -(cH2)4- H H do 3.2Red 71 do do Me do2/15/8 2.3~ed 72 do do H do2/15/5 0.9Red 73 CN Me CN Me H 2E0 3.9Violet 74 do do do OMe OMe do 4.2Blue do do do NHAc do do 4.4Blue 76 do -(cH2)4- H H do 2.1Red 77 CO2Et Me CO2Et do do do 5.6Red 78 do H COCHMe2 NHAc OMe do 4.8Blue As can be seen from a comparison of the benzothiazoles of Examples 52 to 58 and the thiophenes of Examples 59 to 78, only the thiophenes are stable to the effects o the tin catalyst.
Moreover, as defined herein, all of the thiophenes exhibit similar stability.
Having described the present invention in detail it is obvious that one skilled in the art will be able to make variations and modifications thereto without departin~ from the scope of the present invention. Accordingly, the scope of~ the ~ :
~,.... , .. ~...... ~
` . : ' , ~LZ~366~
present invention should be determined only by the claims appended hereto.
--" . :
'~ :-.. ~ - ' , ~:
~, ~
- : -: -, - -
Then 35 milliliters of 2-ethoxyethylether or 2-methoxylethylether were added to dissolve the colorant.
Further solvent was then added to bring the total contents to the 50 milliliter mark. The flask was stoppered and shaken. Exactly 2.0 milliliters of this solution were transferred to a further 50 milliliter flask and diluted to the 50 milliliter mark with one of the solvents.
, - .- ,, .
:
;' :
, 3L2~36~
In the case o solid colorant to be tested colorant to be tested was added to a 100 ml volumetric flask.
In order to correct for varying color strengths the amount of colorant added was determined as follows:
5/2 tcolor value) = number of grams added, Then 35 ml of 2-ethoxyethyl-either or 2-methoxyethylether solvent was added to dissolve the colorant. An additional amount of solvent was added to bring the level in the volumetric flask to the 100 ml mark; a stopper was inserted, and the contents of the flask were mixed well by shaking.
Exactly 4.0 ml of this solution were then transferred to another 100 ml volumetric flask and diluted to the 100 ml mark with solvent.
A solution of T-9 ~stannous octanoate) was prepared with minimum air exposure by dissolving 0.70 gram of stannous octanoate in seven milliliters of solvent in a vial which was kept sealed between runs. The Beckman spectrometer was set up for repetitive scanning. Two milliliters of colorant solution (either solid or liquid as described above) were placed into a vial with 2.0 milliliters of the tin catalyst solution and mixed well.
The mixture was then transferred to the cell of the spectrometer which was capped and qulckly placed into the spectrometer ~not more than 20 to 30 seconds elapsed time).
Five repetetive scans were then made for each colorant sample at three intervals. The percentage loss after :: `
. ,, , . - , ~ . .
.:
-. . .
:. , :
31~;2~a3f~6~
fifteen minutes (5 scans) was measured from initial absorbance and last absorbance.
A number of commercially useful benzothiazole colorants were investigated as to stability to flame retardants. In the control testl i.e., no flame retardant present, following the procedures of Example 7, all o the compounds tested passed, indicating no color change. When however, the same compounds were included in production o foam according to Example 8 where the flame retardant was included, all of the compounds failed.
Example 10 In like fashion to the benzothiazole investigations, a number of colorants according to the present invention were prepared according to the general procedures set orth in Examples 1 through 5. Thereafter, the colorants were utilized in the coloration of polyurethane foams as described in Examples 7 and ~ to determine stability of same to flame retardants~ All of the thiophene compounds passed both tests, indicating stability to flame retardants. Compounds tested are listed in Table I
below.
The following abbreviations are utilized in the following tables: Et-ethyl; EO=ethylene oxide; PO=propylene oxide; ME=methyl; Ac=acetate. Also where numbers are separated by diagonals, eg. 2/15/5, such refers to moles EO/moles PO/moles EO.
-2~-.., 13~
Table I
Effect of Flame Retardants on Thiophene Reactive Colorants ~ N=N ~N
EX .
No.Rl R~ R~R4- R7 Ra, Rq Colo~
11C02Et Me CNH H 2EO/lSPO/5EO Red 12 do do doMe do do Red 13 do do doOMe OMe 2/10/5 . Violet 14 do do COMe H H 2/15i5 Red CN do CO2Me do do do Red 16 C02Et do CONHC6Hs do do do Red 17 do do do Me do 2/15/5 Red 18 do do do H do do Red 19 do do C02Et do do do Red 2 0do do do Cl do 2/10/6 Red 21 do do do Me do 2/15/2 Red 22CO2Me doCO2Me H do 2/15/5 Red 23 do do do do do 2J10/6 Red 24CO2Et doCO2Et do do 2/15/5 Red 2 5do do do Cl do do Red ~
26 CO2Me do C02Me do do do Red ::
-, : ~ ; .
, 36~3 27 do doCO2Et H do 2/10/6 Red 28 CN doCN OMeOMe 2/10/5Violet 29 do dodo Me H 2/15/5Violet do dodo dodo 2/15/2Violet 31 do do. do dodo 2/10/8Violet 32 do dodo dodo 2/7/6Violet 33 do dodo dodo 2/10/6Violet 34 do dodo H do 2/15/5Violet CN doCN Me H 2EOViolet 36 do dodo OMeOMe do Blue 3 7 do dodo NHAc OMe do Blue 38 do -(cH2)4- H H do Red 39 CO2EtMe CO2Et do do do Red 40 CO2Me H COCHMe2 NHAc OMe do Violet 41 CO2Et-(CH2)4- Me H 2/15/2 Red 42 do -(cH2)4- H do 2/15/5 Red 43 do do Me do 2/15/8 Red 44 do do H do 2/10/6 Red do do Me do 2/15/ 8 Red 46 CO2Et do H H 2/15/5 Red 47 CO2Me H COCXMe2 Me H 2/lS/2Violet 48 CONHC2H40H do do do do do Blue 49 C02Me do do OMe do 2/10/5Violet 50 CONHC2H40H do do do OMe do Blue 51 do do do NHAc do do Blue :
. ...
' - . ' ':
:.
~Z~3669 Benzothiazoles of the type tested as to flame retardant stability were also tested as to stability as to the stannous octanoate catalyst according to the test procedures set forth in Example 9. Compounds and results are set forth in Table II.
Table II
Effect of Stannous Octonate Catalyst on Colorants For Polymeric Resins R2~r~ ~n / R8 ENxo R1 R2 R~ R4 R~ R' 9 % LOSB Color 52 H H OMe Me 10E0 56.S Red 53 Cl do H H 2/15/5 91.5 Red 54 OMe do do OMe 12E0 66.7 Red Me do Cl H 2/10/5 85.9 Red 56 Cl do H Cl 2/15/5 97.8 Red~ :
-~7- :
.
. . . .
~Z~3~9 57 do do C1 H do 87.9 Red 58 H Cl do do do 100.0 Red Like tests were performed as to colorants according to the present invention, results of which may be compared to the benzothiazole results of Examples 52 through 58~ Compounds tested and results are set forth in Table III.
Table III
Effect of Stannous Octoate on Thiophene Based Colorants R2 /Rl R7 ~=I~/R8 Ex.
No. Rl ~? R3 R4 _ R7 RR, R4 % Loss Color 59 CO2Et Me CO2Et Me H 2/15/2 5.3Red CN do CN H do 2/15/5 0.0Violet 61 CO2Et do do do do do 3.3Red 62 CN do CO2Et do do 2/15/8 2.9Red 63 CO2Et do do Cl do 2/10/6 2.7Red ~ ' :
., . :, . , - -: ~ .. . , ::, : ~ '': ; - .
"
. . ;
64 CN do CN OMe OMe do 6.2Blue 65 CO2Et do do CN H 2/15/2 4.0Red 66 CN do CO2Et H do2/15/5 5.9Violet 67 CO2Et do COMe do do do 4.8Red 68 do doCONHC6Hs Me do2/15/2 3.0Red 69 CN do CN OMe do 12E0 7.0Violek CN -(cH2)4- H H do 3.2Red 71 do do Me do2/15/8 2.3~ed 72 do do H do2/15/5 0.9Red 73 CN Me CN Me H 2E0 3.9Violet 74 do do do OMe OMe do 4.2Blue do do do NHAc do do 4.4Blue 76 do -(cH2)4- H H do 2.1Red 77 CO2Et Me CO2Et do do do 5.6Red 78 do H COCHMe2 NHAc OMe do 4.8Blue As can be seen from a comparison of the benzothiazoles of Examples 52 to 58 and the thiophenes of Examples 59 to 78, only the thiophenes are stable to the effects o the tin catalyst.
Moreover, as defined herein, all of the thiophenes exhibit similar stability.
Having described the present invention in detail it is obvious that one skilled in the art will be able to make variations and modifications thereto without departin~ from the scope of the present invention. Accordingly, the scope of~ the ~ :
~,.... , .. ~...... ~
` . : ' , ~LZ~366~
present invention should be determined only by the claims appended hereto.
--" . :
'~ :-.. ~ - ' , ~:
~, ~
- : -: -, - -
Claims (13)
1. A reactive coloring agent, having the general formula:
wherein R1, R2 and R3 are selected from halogen, carboxylic acid, alkanoyl, aryloyl, carbocyclic forming polymethylene chains, alkyl, aryl, cyano, thioalkyl, dithioalkyl, thioaryl, dithioaryl, thiocyano, carboxyalkyl, carboxyaryl, amidoalkyl, amidodialkyl, amidoaryl, amidodiaryl, oxyalkyl, thioamidoalkyl, thioamidodialkyl, or hydrogen when an adjacent group is isobutyryl; R4, Rs, R6 and R7 are selected from hydrogen, alkyl, oxyalkyl, oxyaryl, sulfonamidoalkyl, sulfonamidoaryl, amidoalkyl, amidodialkyl, amidoaryl, amidodiaryl, halogen, thioalkyl and thioaryl; and R8 and R9 are selected from polyalkylene oxide and copolymers of polyalkylene oxides having an average molecular weight of from about 88 to about 1400.
wherein R1, R2 and R3 are selected from halogen, carboxylic acid, alkanoyl, aryloyl, carbocyclic forming polymethylene chains, alkyl, aryl, cyano, thioalkyl, dithioalkyl, thioaryl, dithioaryl, thiocyano, carboxyalkyl, carboxyaryl, amidoalkyl, amidodialkyl, amidoaryl, amidodiaryl, oxyalkyl, thioamidoalkyl, thioamidodialkyl, or hydrogen when an adjacent group is isobutyryl; R4, Rs, R6 and R7 are selected from hydrogen, alkyl, oxyalkyl, oxyaryl, sulfonamidoalkyl, sulfonamidoaryl, amidoalkyl, amidodialkyl, amidoaryl, amidodiaryl, halogen, thioalkyl and thioaryl; and R8 and R9 are selected from polyalkylene oxide and copolymers of polyalkylene oxides having an average molecular weight of from about 88 to about 1400.
2. The reactive coloring agent of claim 1, wherein R1, R2, and R3 are selected from cyano, lower alkyl, a carbocyclic forming polymethylene chain, carboxyalkyl, alkanoyl, amidoaryl or hydrogen when an adjacent group is isobutyxyl.
3. The reactive coloring agent of claim 2 wherein R4, R5, R6 and R7 are selected from hydrogen, halogen or lower alkyl.
4. A reactive coloring agent of the formula:
wherein R8 and R9 are selected from polyalkylene oxide and copolymers of polyalkylene oxides having an average molecular weight of from about 88 to about 1400.
wherein R8 and R9 are selected from polyalkylene oxide and copolymers of polyalkylene oxides having an average molecular weight of from about 88 to about 1400.
5. A reactive coloring agent of the formula:
wherein R8 and R9 are selected from polyalkylene oxide and copolymers of polyalkylene oxides having an average molecular weight of from about 88 to about 1400.
wherein R8 and R9 are selected from polyalkylene oxide and copolymers of polyalkylene oxides having an average molecular weight of from about 88 to about 1400.
6. A reactive coloring agent of the formula:
wherein R8 and R9 are selected from polyalkylene oxide and copolymers of polyalkylene oxides having an average molecular weight of from about 88 to about 1400.
wherein R8 and R9 are selected from polyalkylene oxide and copolymers of polyalkylene oxides having an average molecular weight of from about 88 to about 1400.
7. A reactive coloring agent of the formula:
wherein R8 and R9 are selected from polyalkylene oxide and copolymers of polyalkylene oxides having an average molecular weight of from about 88 to about 1400.
wherein R8 and R9 are selected from polyalkylene oxide and copolymers of polyalkylene oxides having an average molecular weight of from about 88 to about 1400.
8. A reactive coloring agent of the formula:
wherein R8 and R9 are selected from polyalkylene oxide and copolymers of polyalkylene oxides having an average molecular weight of from about 88 to about 1400.
wherein R8 and R9 are selected from polyalkylene oxide and copolymers of polyalkylene oxides having an average molecular weight of from about 88 to about 1400.
9. A reactive coloring agent of the formula:
wherein R8 and R9 are selected from polyalkylene oxide and copolymers of polyalkylene oxides having an average molecular weight of from about 88 to about 1400.
wherein R8 and R9 are selected from polyalkylene oxide and copolymers of polyalkylene oxides having an average molecular weight of from about 88 to about 1400.
10. A reactive coloring agent of the formula:
wherein R8 and R9 are selected from polyalkylene oxide and copolymers of polyalkylene oxides having an average molecular weight of from about 88 to about 1400.
wherein R8 and R9 are selected from polyalkylene oxide and copolymers of polyalkylene oxides having an average molecular weight of from about 88 to about 1400.
11. A reactive coloring agent of the formula:
wherein R8 and R9 are selected from polyalkylene oxide and copolymers of polyalkylene oxides having an average molecular weight of from about 88 to about 1400.
wherein R8 and R9 are selected from polyalkylene oxide and copolymers of polyalkylene oxides having an average molecular weight of from about 88 to about 1400.
12. A reactive coloring agent of the formula:
wherein R8 and R9 are selected from polyalkylene oxide and copolymers of polyalkylene oxides having an average molecular weight of from about 88 to about 1400.
wherein R8 and R9 are selected from polyalkylene oxide and copolymers of polyalkylene oxides having an average molecular weight of from about 88 to about 1400.
13. A reactive coloring agent of the formula:
wherein R8 and R9 are selected from polyalkylene oxide and copolymers of polyalkylene oxides having an average molecular weight of from about 88 to about 1400.
wherein R8 and R9 are selected from polyalkylene oxide and copolymers of polyalkylene oxides having an average molecular weight of from about 88 to about 1400.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US62437984A | 1984-06-25 | 1984-06-25 | |
| US624,379 | 1984-06-25 |
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| CA1243669A true CA1243669A (en) | 1988-10-25 |
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| CA000483801A Expired CA1243669A (en) | 1984-06-25 | 1985-06-12 | Reactive colorants |
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Families Citing this family (70)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1243669A (en) * | 1984-06-25 | 1988-10-25 | Edward W. Kluger | Reactive colorants |
| US4923903A (en) * | 1989-01-24 | 1990-05-08 | Minnesota Mining And Manufacturing Company | Dyed aqueous air foams |
| DE3902005A1 (en) * | 1989-01-25 | 1990-07-26 | Basf Ag | THIOPHENAZO DYES WITH A CLUTCH COMPONENT BASED ON M-PHENYLENE DIAMINE |
| DE3911949A1 (en) * | 1989-04-12 | 1990-10-18 | Basf Ag | NEW NAVY BLUE AND BLACK DYE BLENDS |
| US5052380A (en) * | 1989-07-07 | 1991-10-01 | Minnesota Mining And Manufacturing Company | Colored orthopedic resins and orthopedic casting materials incorporating same |
| US5731398A (en) * | 1996-05-31 | 1998-03-24 | Milliken Research Corporation | Black colorant composition exhibiting low flairing |
| US5780528A (en) * | 1996-06-28 | 1998-07-14 | Tektronix, Inc. | Isocyanate-derived colored resins for use in phase change ink jet inks |
| US5958584A (en) * | 1996-07-22 | 1999-09-28 | Dsm Nv | Radiation-curable, optical glass fiber coating composition and optical glass fiber drawing method |
| US5933559A (en) * | 1996-07-22 | 1999-08-03 | Dsm N.V. | Radiation-curable cross-linked ribbon matrix material for bonding an array of coated optical glass fibers |
| US5864002A (en) * | 1996-10-18 | 1999-01-26 | Milliken Research Corporation | Process for coloring polymer resins and products thereof |
| US6706218B2 (en) | 2000-01-11 | 2004-03-16 | The Board Of Governors For Higher Education, State Of Rhode Island And Providence Plantations | Thermochromic polymers for rapid visual assessment of temperature |
| US6479561B1 (en) | 2000-08-30 | 2002-11-12 | Milliken & Company | Colored polyurethane surface coatings |
| KR100571631B1 (en) * | 2002-04-04 | 2006-04-17 | 니혼 메타루 가스켓토 가부시키가이샤 | Metallic gasket |
| US7134718B2 (en) * | 2002-04-26 | 2006-11-14 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Vehicle seat |
| US7094812B2 (en) | 2003-04-24 | 2006-08-22 | Xerox Corporations | Colorant compositions |
| US6790267B1 (en) | 2003-04-24 | 2004-09-14 | Xerox Corporation | Colorant compositions |
| US6764541B1 (en) | 2003-04-24 | 2004-07-20 | Xerox Corporation | Colorant compositions |
| US7034185B2 (en) * | 2003-04-24 | 2006-04-25 | Xerox Corporation | Colorant precursor compositions |
| US7018768B2 (en) * | 2003-06-30 | 2006-03-28 | Samsung Electronics Company | Organosols comprising a chromophore, methods and uses |
| US20060063861A1 (en) * | 2004-09-17 | 2006-03-23 | Milliken & Company | Method for employing colorants as indicators in polymer blending |
| US7572325B2 (en) * | 2005-11-30 | 2009-08-11 | Xerox Corporation | Ink carriers, phase change inks including same and methods for making same |
| US7758268B2 (en) * | 2005-12-20 | 2010-07-20 | Xerox Corporation | Hand held photochromic marking implement |
| CN101370925B (en) | 2006-01-23 | 2014-03-26 | 美利肯公司 | Laundry care compositions with thiazolium dye |
| PL2192169T3 (en) * | 2007-01-19 | 2012-10-31 | Procter & Gamble | Laundry care composition comprising a whitening agents for cellulosic substrates |
| US20080177089A1 (en) | 2007-01-19 | 2008-07-24 | Eugene Steven Sadlowski | Novel whitening agents for cellulosic substrates |
| US7642282B2 (en) * | 2007-01-19 | 2010-01-05 | Milliken & Company | Whitening agents for cellulosic substrates |
| US8728373B2 (en) * | 2007-03-20 | 2014-05-20 | Albany International Corp. | Industrial fabric having a thermochromic sensor |
| PL2133410T3 (en) * | 2008-06-13 | 2012-05-31 | Procter & Gamble | Multi-compartment pouch |
| EP2163608A1 (en) | 2008-09-12 | 2010-03-17 | The Procter & Gamble Company | Laundry particle made by extrusion comprising a hueing dye and fatty acid soap |
| EP2166077A1 (en) | 2008-09-12 | 2010-03-24 | The Procter and Gamble Company | Particles comprising a hueing dye |
| EP2166078B1 (en) | 2008-09-12 | 2018-11-21 | The Procter & Gamble Company | Laundry particle made by extrusion comprising a hueing dye |
| US8449626B2 (en) | 2009-11-11 | 2013-05-28 | The Procter & Gamble Company | Cleaning method |
| US20110257065A1 (en) | 2010-04-19 | 2011-10-20 | Alan Thomas Brooker | Detergent Composition |
| US9011966B2 (en) | 2010-06-18 | 2015-04-21 | Basf Se | Polyurethane foam article and method of forming same |
| US9068081B2 (en) | 2010-11-12 | 2015-06-30 | Milliken & Company | Thiophene azo dyes and laundry care compositions containing the same |
| US8715368B2 (en) | 2010-11-12 | 2014-05-06 | The Procter & Gamble Company | Thiophene azo dyes and laundry care compositions containing the same |
| BR112013030993B1 (en) * | 2011-06-01 | 2021-04-20 | Unilever Ip Holdings B.V | liquid laundry detergent composition and domestic method of treating a textile article |
| US9163146B2 (en) | 2011-06-03 | 2015-10-20 | Milliken & Company | Thiophene azo carboxylate dyes and laundry care compositions containing the same |
| US20140371435A9 (en) | 2011-06-03 | 2014-12-18 | Eduardo Torres | Laundry Care Compositions Containing Thiophene Azo Dyes |
| US9670373B2 (en) | 2011-08-24 | 2017-06-06 | Lambson Limited | Polymers comprising photoinitiator moieties and dye moieties |
| US9796952B2 (en) | 2012-09-25 | 2017-10-24 | The Procter & Gamble Company | Laundry care compositions with thiazolium dye |
| EP2757118A1 (en) | 2013-01-17 | 2014-07-23 | Allnex Belgium, S.A. | Radiation curable aqueous compositions with reversible drying. |
| EP2806018A1 (en) | 2013-05-20 | 2014-11-26 | The Procter & Gamble Company | Encapsulates |
| US20140338134A1 (en) | 2013-05-20 | 2014-11-20 | The Procter & Gamble Company | Encapsulates |
| US20150080560A1 (en) * | 2013-09-18 | 2015-03-19 | Milliken & Company | Laundry Care Compositions Containing Dyes |
| RU2645331C1 (en) | 2015-03-30 | 2018-02-21 | Дзе Проктер Энд Гэмбл Компани | Solid detergent composition for laundry made of free-flowing particles |
| EP3075828B1 (en) | 2015-03-30 | 2018-02-07 | The Procter and Gamble Company | Solid free-flowing particulate laundry detergent composition |
| EP3075825B1 (en) | 2015-03-30 | 2018-02-07 | The Procter and Gamble Company | Solid free-flowing particulate laundry detergent composition |
| EP3075824B1 (en) | 2015-03-30 | 2018-02-21 | The Procter and Gamble Company | Solid free-flowing particulate laundry detergent composition |
| WO2016161219A1 (en) | 2015-04-02 | 2016-10-06 | The Procter & Gamble Company | Solid free-flowing particulate laundry detergent composition |
| WO2016161217A1 (en) | 2015-04-02 | 2016-10-06 | The Procter & Gamble Company | Solid free-flowing particulate laundry detergent composition |
| ES2672395T3 (en) | 2015-04-02 | 2018-06-14 | The Procter & Gamble Company | Solid laundry detergent composition in the form of free-flowing particles |
| EP3115446A1 (en) | 2015-07-09 | 2017-01-11 | The Procter and Gamble Company | Compacted liquid laundry treatment composition |
| EP3115447A1 (en) | 2015-07-09 | 2017-01-11 | The Procter and Gamble Company | Method of pretreating fabrics |
| US20170015949A1 (en) | 2015-07-16 | 2017-01-19 | The Procter & Gamble Company | Cleaning compositions containing a cyclic amine and an encapsulated perfume |
| US20170015951A1 (en) | 2015-07-16 | 2017-01-19 | The Procter & Gamble Company | Cleaning compositions containing a cyclic amine and a fabric shading agent and/or a brightener |
| US20170015948A1 (en) | 2015-07-16 | 2017-01-19 | The Procter & Gamble Company | Cleaning compositions containing a cyclic amine and a silicone |
| JP6141369B2 (en) * | 2015-08-28 | 2017-06-07 | ミリケン・アンド・カンパニーＭｉｌｌｉｋｅｎ ＆ Ｃｏｍｐａｎｙ | Thiopheneazo dye and laundry care composition containing the same |
| US10155868B2 (en) * | 2015-10-13 | 2018-12-18 | Milliken & Company | Whitening agents for cellulosic substrates |
| US9976035B2 (en) * | 2015-10-13 | 2018-05-22 | Milliken & Company | Whitening agents for cellulosic substrates |
| US9777250B2 (en) * | 2015-10-13 | 2017-10-03 | Milliken & Company | Whitening agents for cellulosic substrates |
| US10597614B2 (en) * | 2015-10-13 | 2020-03-24 | The Procter & Gamble Company | Whitening agents for cellulosic substrates |
| US10377975B2 (en) | 2015-10-23 | 2019-08-13 | The Procter & Gamble Company | Packaged composition |
| US10731112B2 (en) | 2017-10-12 | 2020-08-04 | The Procter & Gamble Company | Leuco colorants in combination with a second whitening agent as bluing agents in laundry care compositions |
| US20220098520A1 (en) | 2019-01-22 | 2022-03-31 | Conopco, Inc., D/B/A Unilever | Laundry detergent |
| US20220098525A1 (en) | 2019-01-22 | 2022-03-31 | Conopco, Inc., D/B/A Unilever | Laundry detergent |
| US20210277335A1 (en) * | 2020-03-02 | 2021-09-09 | Milliken & Company | Composition Comprising Hueing Agent |
| US11718814B2 (en) | 2020-03-02 | 2023-08-08 | Milliken & Company | Composition comprising hueing agent |
| US20210269747A1 (en) | 2020-03-02 | 2021-09-02 | Milliken & Company | Composition Comprising Hueing Agent |
| US20230392018A1 (en) | 2020-10-27 | 2023-12-07 | Milliken & Company | Compositions comprising leuco compounds and colorants |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2827450A (en) * | 1955-08-12 | 1958-03-18 | Eastman Kodak Co | 2-aminothiophene azo compounds |
| GB1394365A (en) * | 1972-01-28 | 1975-05-14 | Impperial Chemical Ind Ltd | Disperse azo dyestuffs |
| US4264495A (en) * | 1972-05-15 | 1981-04-28 | Eastman Kodak Company | 2-Thienyl azo dyestuff compounds |
| CH554395A (en) * | 1972-07-11 | 1974-09-30 | Sandoz Ag | PROCESS FOR THE PRODUCTION OF PERSISTENTLY SOLUBLE AZO COMPOUNDS IN WATER. |
| GB1429484A (en) * | 1972-08-25 | 1976-03-24 | Ici Ltd | Azo dyestuffs derived from carbocyclic-fused 2-aminothiophene diazo components |
| CH438674A4 (en) * | 1974-03-29 | 1975-10-31 | ||
| JPS5276933A (en) * | 1975-12-23 | 1977-06-28 | Olympus Optical Co Ltd | Light sensitive screen drum for electrophotographic copying machine |
| US4132284A (en) * | 1977-02-22 | 1979-01-02 | Tomecek Jerry J | Electronic cruise control |
| GB1583377A (en) * | 1977-04-25 | 1981-01-28 | Ici Ltd | Disperse azo dyestuffs derived from a 2-aminothiophene-5-aldehyde |
| US4284729A (en) * | 1980-03-31 | 1981-08-18 | Milliken Research Corporation | Process for coloring thermosetting resins |
| JPS58101155A (en) * | 1981-12-09 | 1983-06-16 | Gosei Senriyou Gijutsu Kenkyu Kumiai | Monoazo dye for synthetic fiber |
| JPS60226556A (en) * | 1984-04-24 | 1985-11-11 | Nippon Kayaku Co Ltd | Water-insoluble monoazo dye and dyeing therewith |
| CA1243669A (en) * | 1984-06-25 | 1988-10-25 | Edward W. Kluger | Reactive colorants |
| US4601725A (en) * | 1984-08-27 | 1986-07-22 | Milliken Research Corporation | Thiophene based fugitive colorants |
| JP2834088B2 (en) * | 1996-04-16 | 1998-12-09 | 株式会社日本システムアカデミー | Cooking rice control method |
-
1985
- 1985-06-12 CA CA000483801A patent/CA1243669A/en not_active Expired
- 1985-06-25 JP JP60137099A patent/JPH0635551B2/en not_active Expired - Fee Related
-
1987
- 1987-06-01 US US07/058,696 patent/US4775748A/en not_active Expired - Lifetime
-
1988
- 1988-05-17 US US07/194,761 patent/US4912203A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0635551B2 (en) | 1994-05-11 |
| US4912203A (en) | 1990-03-27 |
| US4775748A (en) | 1988-10-04 |
| JPS6157649A (en) | 1986-03-24 |
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