United States Patent [19J United States Patent [19]
`
`Weaver et ai.
`Weaver et al.
`
`[54] THERMOPLASTIC COMPOSITIONS
`[54] THERMOPLASTIC COMPOSITIONS
`CONTAINING ANTHRAQUINONE
`CONTAINING ANTHRAQUINONE
`POLYSULFONAMIDE COLORANTS
`POLYSULFONAMIDE COLORANTS
`
`[75]
`[75]
`
`Inventors: Max Allen Weaver; Wayne Payton
`Inventors: Max Allen Weaver; Wayne Payton
`Pruett, both of Kingsport; Kay Hunt
`Pruett, both of Kingsport; Kay Hunt
`Shackelford, Johnson City; Samuel
`Shackelford, Johnson City; Samuel
`David Hilbert, Jonesborough, all of
`David Hilbert, Jonesborough, all of
`Tenn.
`Tenn.
`
`[73] Assignee: Eastman Chemical Company,
`[73] Assignee: Eastman Chemical Company,
`Kingsport, Tenn.
`Kingsport, Tenn.
`
`
`
`[ *] Notice: [ *] Notice:
`
`This patent issued on a continued pros(cid:173)
`This patent issued on a continued pros(cid:173)
`ecution application filed under 37 CFR
`ecution application filed under 37 CFR
`1.53( d), and is subject to the twenty year
`1.53( d), and is subject to the twenty year
`patent term provisions of 35 U.S.C.
`patent term provisions of 35 U.S.c.
`154(a)(2).
`154(a)(2).
`
`[21] Appl. No.: 08/906,647
`[21] Appl. No.: 08/906,647
`
`[22] Filed:
`[22] Filed:
`
`Aug. 7, 1997
`Aug. 7, 1997
`
`[60]
`[60]
`
`[51]
`[51]
`[52]
`[52]
`
`[58]
`[58]
`
`[56]
`[56]
`
`Related U.S. Application Data
`Related U.S. Application Data
`
`Provisional application No. 60/025,367, Sep. 3, 1996. Provisional application No. 60/025,367, Sep. 3, 1996.
`
`Int. Cl? ................................ COSJ 5/10; COSL 81/10
`Int. CI? ................................ C08J 5/10; C08L 81/10
`U.S. Cl. ............................ 524/161; 524/89; 524/240;
`U.S. CI. ............................ 524/161; 524/89; 524/240;
`524/271; 525/437; 525/540; 528/289; 528/290;
`524/271; 525/437; 525/540; 528/289; 528/290;
`528/295; 523/507
`528/295; 523/507
`Field of Search .............................. 524/161, 89, 240,
`Field of Search .............................. 524/161, 89, 240,
`524/271; 525/437, 540; 528/289, 290, 295;
`524/271; 525/437, 540; 528/289, 290, 295;
`523/507
`523/507
`
`References Cited
`References Cited
`
`U.S. PATENT DOCUMENTS
`U.S. PATENT DOCUMENTS
`
`
`2,731,476 2,731,476
`
`3,299,103 3,299,103
`
`4,116,923 4,116,923
`
`4,403,092 4,403,092
`4,477,635
`4,477,635
`
`
`1!1956 Peter et a!. . 1/1956 Peter et al. .
`
`1!1967 Maier . 1/1967 Maier.
`9/1978 Gattner et a!. . 9/1978 Gattner et al. .
`
`
`9/1983 Davis et a!. . 9/1983 Davis et al. .
`10/1984 Mitra.
`10/1984 Mitra .
`
`
`
`111111 111111
`
`
`1111111111111111111111111111111111111111111111111111111111111 1111111111111111111111111111111111111111111111111111111111111
`
`US006121351A US006121351A
`[11] Patent Number:
`[11] Patent Number:
`[45] Date of Patent:
`[45] Date of Patent:
`
`6,121,351
`6,121,351
`*Sep.19,2000
`*Sep.19,2000
`
`
`5,032,670 5,032,670
`
`5,106,942 5,106,942
`
`5,194,463 5,194,463
`
`5,453,482 5,453,482
`
`5,650,481 5,650,481
`
`7/1991 Parham eta!. . 7/1991 Parham et al. .
`
`4/1992 Krutak et al. .
`4/1992 Krutak eta!. .
`3/1993 Krutak et al. .
`3/1993 Krutak et a!. .
`9/1995 Weaver et al. .
`9/1995 Weaver eta!. .
`7/1997 Yau et al.
`............................... 528/280
`7/1997 Yau eta!. ............................... 528/280
`
`FOREIGN PATENT DOCUMENTS
`FOREIGN PATENT DOCUMENTS
`
`
`92 07913A 9207913A
`92/07913
`92/07913
`92/13921
`92/13921
`
`
`5/1992 WIPO . 5/1992 WIPO.
`5/1992 WIPO .
`5/1992 WIPO.
`8/1992 WIPO .
`8/1992 WIPO.
`
`OTHER PUBLICATIONS
`OTHER PUBLICATIONS
`
`
`K. Vendataraman, Editor, The Chemistry of Synthetic Dyes, K. Vendataraman, Editor, The Chemistry of Synthetic Dyes,
`vol. 8, Academic Press, New York, 1978, pp. 81-131 (no
`vol. 8, Academic Press, New York, 1978, pp. 81-131 (no
`month).
`month).
`R. Gachter and H. Muller, Editors, Plastics Additives Hand(cid:173)
`R. Gachter and H. Muller, Editors, Plastics Additives Hand(cid:173)
`book, Hansu Publishers, New York, 1985, pp 507-533;
`book, Hansu Publishers, New York, 1985, pp 507-533;
`729-741 (no month).
`729-741 (no month).
`N. Ohta, Photographic Science and Engineering, vol. 15,
`N. Ohta, Photographic Science and Engineering, vol. 15,
`No.5, Sep.-Oct. 1971, pp 395-415 (no month).
`No.5, Sep.-Oct. 1971, pp 395-415 (no month).
`
`
`Primary Examiner-Blaine Copenheaver Primary Examiner-Blaine Copenheaver
`
`Assistant Examiner-John J. Guarriello Assistant Examiner-John J. Guarriello
`
`Attorney, Agent, or Firm-Karen A Harding; Harry J. Attorney, Agent, or Firm~aren A. Harding; Harry J.
`Gwinn ell
`Gwinnell
`
`[57]
`[57]
`
`ABSTRACT
`ABSTRACT
`
`Thermoplastic compositiOns contammg certain
`Thermoplastic composItIOns contallllllg certain
`anthraquinone polysulfonamide colorants incorporated
`anthraquinone polysulfonamide colorants incorporated
`therein as toners or colorants. The anthraquinone colorant
`therein as toners or colorants. The anthraquinone colorant
`moieties which are incorporated into the polymer chain of
`moieties which are incorporated into the polymer chain of
`the polysulfonamide colorants are not leachable, sublimable
`the polysulfonamide colorants are not leachable, sublimable
`or extractable and do not exude from the thermoplastic
`or extractable and do not exude from the thermoplastic
`compositions. The anthraquinone polysulfonamide colo(cid:173)
`compositions. The anthraquinone polysulfonamide colo(cid:173)
`rants may be added to the thermoplastic polymers during
`rants may be added to the thermoplastic polymers during
`production or melt blended with the polymer by conven(cid:173)
`production or melt blended with the polymer by conven(cid:173)
`tional techniques to produce transparent thermoplastic com(cid:173)
`tional techniques to produce transparent thermoplastic com(cid:173)
`positions useful for a variety of end uses where nonmigrat(cid:173)
`positions useful for a variety of end uses where nonmigrat(cid:173)
`ing or nonextractable colorants are needed.
`ing or nonextractable colorants are needed.
`
`20 Claims, No Drawings
`20 Claims, No Drawings
`
`Page 1 of 19
`
`PETITIONERS' EXHIBIT 1005
`
`

`

`6,121,351
`6,121,351
`
`
`1 1
`
`THERMOPLASTIC COMPOSITIONS THERMOPLASTIC COMPOSITIONS
`
`CONTAINING ANTHRAQUINONE CONTAINING ANTHRAQUINONE
`
`POLYSULFONAMIDE COLORANTS POLYSULFONAMIDE COLORANTS
`
`This application claims benefit of Provisional application 5
`This application claims benefit of Provisional application 5
`Ser. No. 60/025,367 filed Sep. 3, 1996.
`Ser. No. 60/025,367 filed Sep. 3, 1996.
`
`BACKGROUND OF THE INVENTION
`BACKGROUND OF THE INVENTION
`
`1. Field of the Invention
`1. Field of the Invention
`This invention relates to thermoplastic compositions con(cid:173)
`This invention relates to thermoplastic compositions con(cid:173)
`taining certain anthraquinone polysulfonamide colorants
`taining certain anthraquinone polysulfonamide colorants
`incorporated therein as toners or colorants. Since the
`incorporated therein as toners or colorants. Since the
`anthraquinone colorant moieties are incorporated into the
`anthraquinone colorant moieties are incorporated into the
`polymer chain of the polysulfonamide colorants, they are
`polymer chain of the polysulfonamide colorants, they are
`not leachable, sublimable or extractable and do not exude
`not leachable, sublimable or extractable and do not exude
`from the thermoplastic compositions. The anthraquinone
`from the thermoplastic compositions. The anthraquinone
`polysulfonamide colorants may be added to the thermoplas(cid:173)
`polysulfonamide colorants may be added to the thermoplas(cid:173)
`tic polymers during production or melt blended with the
`tic polymers during production or melt blended with the
`polymer by conventional techniques to produce transparent
`polymer by conventional techniques to produce transparent
`thermoplastic compositions useful for a variety of end uses
`thermoplastic compositions useful for a variety of end uses
`where nonmigrating or nonextractable colorants are needed.
`where nonmigrating or nonextractable colorants are needed.
`Thermoplastics are typically colored by organic pigments
`Thermoplastics are typically colored by organic pigments
`when superior brilliance and tinctorial strength are impor(cid:173)
`when superior brilliance and tinctorial strength are impor(cid:173)
`tant. Opacity, however, is introduced into the polymer com(cid:173)
`tant. Opacity, however, is introduced into the polymer com(cid:173)
`position as a result of the insoluble pigment. Also, toxicity
`position as a result of the insoluble pigment. Also, toxicity
`considerations have presented chronic problems relative to
`considerations have presented chronic problems relative to
`the use of organic pigments, since some have been shown to
`the use of organic pigments, since some have been shown to
`be potential carcinogens and to cause contact dermatitis.
`be potential carcinogens and to cause contact dermatitis.
`Plastics are also colored by using color concentrates
`Plastics are also colored by using color concentrates
`consisting of physical admixtures of polymers and colorants
`consisting of physical admixtures of polymers and colorants
`(usually solvent dyes). However, the use of such physical
`(usually solvent dyes). However, the use of such physical
`admixtures to color polymeric materials such as polyester,
`admixtures to color polymeric materials such as polyester,
`e.g., poly( ethylene terephthalate) and blends thereof, present
`e.g., poly( ethylene terephthalate) and blends thereof, present
`a number of problems:
`a number of problems:
`1. Colorant migration during drying of the colored poly(cid:173)
`1. Colorant migration during drying of the colored poly(cid:173)
`ester pellets.
`ester pellets.
`2. Colorant migration during extrusion and colorant accu(cid:173)
`2. Colorant migration during extrusion and colorant accu(cid:173)
`mulation on dies or plateout on rollers which can cause
`mulation on dies or plateout on rollers which can cause
`shutdowns for clean-up. Such colorant migration and
`shutdowns for clean-up. Such colorant migration and
`accumulation result in time consuming and difficult
`accumulation result in time consuming and difficult
`clean-up, particularly when a polymer of another color
`clean-up, particularly when a polymer of another color
`is subsequently processed on the same equipment.
`is subsequently processed on the same equipment.
`3. Colorants may not mix well, for example, when using
`3. Colorants may not mix well, for example, when using
`two or more color concentrates to obtain a particular
`two or more color concentrates to obtain a particular
`shade.
`shade.
`4. Colorants may diffuse or exude during storage and use
`4. Colorants may diffuse or exude during storage and use
`of the colored polymeric material.
`of the colored polymeric material.
`The use of polysulfonamide colorants eliminate or mini(cid:173)
`The use of polysulfonamide colorants eliminate or mini(cid:173)
`mize the aforementioned problems associated with the use
`mize the aforementioned problems associated with the use
`of conventional dyes and pigments.
`of conventional dyes and pigments.
`2. Description of the Prior Art
`2. Description of the Prior Art
`
`It is well-known in the art to color thermoplastic resins by It is well-known in the art to color thermoplastic resins by
`adding pigments or solvent dyes (e.g. see Thomas G. Weber,
`adding pigments or solvent dyes (e.g. see Thomas G. Weber,
`Editor, Coloring of Plastics, John Wiley and Sons, New
`Editor, Coloring of Plastics, John Wiley and Sons, New
`York, 1979). The use of pigments, however, is accompanied
`York, 1979). The use of pigments, however, is accompanied
`by undesirable properties such as opacity, dullness of color,
`by undesirable properties such as opacity, dullness of color,
`low tinctorial strength, etc. Also, difficulties in blending the
`low tinctorial strength, etc. Also, difficulties in blending the
`insoluble pigments uniformly with the thermoplastic resin
`insoluble pigments uniformly with the thermoplastic resin
`are encountered. Also, useful for coloring thermoplastic
`are encountered. Also, useful for coloring thermoplastic
`
`resins are solvent dyes (K. Vendataraman, Editor, The resins are solvent dyes (K. Vendataraman, Editor, The
`Chemistry of Synthetic Dyes, Vol. 8, Academic Press, New
`Chemistry of Synthetic Dyes, Vol. 8, Academic Press, New
`York, 1978, pp 81-131), which give compositions having
`York, 1978, pp 81-131), which give compositions having
`improved clarity, brightness in hue and high tinctorial
`improved clarity, brightness in hue and high tinctorial
`strength, but which may lead to dye migration, extraction,
`strength, but which may lead to dye migration, extraction,
`etc. from the colored thermoplastic resin. These problems
`etc. from the colored thermoplastic resin. These problems
`are of particular concern when solvent dyes are used to color 65
`are of particular concern when solvent dyes are used to color 65
`flexible resins such as polyvinyl chloride, polyethylene and
`flexible resins such as polyvinyl chloride, polyethylene and
`polypropylene which have low glass transition temperatures.
`polypropylene which have low glass transition temperatures.
`
`2
`2
`
`It is known, also, to prepare solvent soluble nonextract(cid:173)It is known, also, to prepare solvent soluble nonextract(cid:173)
`able polymeric aminotriarylmethane dyes having polyester,
`able polymeric aminotriarylmethane dyes having polyester,
`polycarbonate, polyurethane, or polyethyleneimine back(cid:173)
`polycarbonate, polyurethane, or polyethyleneimine back(cid:173)
`bones and to incorporate them into resins such as polyvinyl
`bones and to incorporate them into resins such as polyvinyl
`chloride, polyvinylidene chloride and acrylic resins such as
`chloride, polyvinylidene chloride and acrylic resins such as
`poly(methyl methacrylate) etc. by solvent blending tech(cid:173)
`poly(methyl methacrylate) etc. by solvent blending tech(cid:173)
`niques [So Mitra (to 3M Corp.), U.S. Pat. No. 4,477,635
`niques [S. Mitra (to 3M Corp.), U.S. Pat. No. 4,477,635
`(1984)]. Difficulties are encountered in preparing these
`(1984)]. Difficulties are encountered in preparing these
`polymeric colored compounds because a non-colored inter-
`polymeric colored compounds because a non-colored inter-
`10 mediate aromatic amine containing polymer must be pre(cid:173)
`10 mediate aromatic amine containing polymer must be pre(cid:173)
`pared and then the aromatic amine moiety in the polymer
`pared and then the aromatic amine moiety in the polymer
`structure must be converted into the aminotriarylmethane
`structure must be converted into the aminotriarylmethane
`moiety by further reaction with a diaryl ketone in the
`moiety by further reaction with a diaryl ketone in the
`presence of condensation catalyst such as phosphorous
`presence of condensation catalyst such as phosphorous
`oxychloride in an inert organic solvent. These previously
`oxychloride in an inert organic solvent. These previously
`15 disclosed polymeric aminotriarylmethane compositions also
`15 disclosed polymeric aminotriarylmethane compositions also
`do not have the requisite thermal stability for use in coloring
`do not have the requisite thermal stability for use in coloring
`thermoplastic resins via the more favorable method of melt
`thermoplastic resins via the more favorable method of melt
`blending when high temperatures are encountered.
`blending when high temperatures are encountered.
`
`It is further known from U.S. Pat. No. 4,116,923 (1978) It is further known from U.S. Pat. No. 4,116,923 (1978)
`20 to color plastics, in particular polyolefins, with low melting,
`20 to color plastics, in particular polyolefins, with low melting,
`cross-linked colored polyester compositions containing resi(cid:173)
`cross-linked colored polyester compositions containing resi(cid:173)
`dues of terephthalic acid, isophthalic acid, or both, a low(cid:173)
`dues of terephthalic acid, isophthalic acid, or both, a low(cid:173)
`molecular weight trimethylol alkane, i.e. 1,1,1-triethylol
`molecular weight trimethylol alkane, i.e. 1,1,1-triethylol
`propane and a copolymerizable colorant, said colorant being
`propane and a copolymerizable colorant, said colorant being
`25 present at a level of 0.1-25% by weight. Difficulties are
`25 present at a level of 0.1-25% by weight. Difficulties are
`encountered, however, in preparing these highly cross(cid:173)
`encountered, however, in preparing these highly cross(cid:173)
`linked colored polymers as extreme care as regards to the
`linked colored polymers as extreme care as regards to the
`temperature, amount of vacuum, the level of colorant
`temperature, amount of vacuum, the level of colorant
`present and the reaction time is necessary to attempt to
`present and the reaction time is necessary to attempt to
`30 reproduce the same quality of cross-linked colored polyester
`reproduce the same quality of cross-linked colored polyester
`30
`composition. Furthermore, these colored polyester compo(cid:173)
`composition. Furthermore, these colored polyester compo(cid:173)
`sitions are brittle and low melting and may cause deterio(cid:173)
`sitions are brittle and low melting and may cause deterio(cid:173)
`ration in physical properties of thermoplastic resins when
`ration in physical properties of thermoplastic resins when
`added in quantities sufficient to produce a high level of
`added in quantities sufficient to produce a high level of
`coloration. Critical in the preparation of these previously
`coloration. Critical in the preparation of these previously
`35 disclosed polymers is the achievement of a low degree of
`35 disclosed polymers is the achievement of a low degree of
`polymerization to give a low melting polymer which has
`polymerization to give a low melting polymer which has
`adequate solubility characteristics in the resin to be colored;
`adequate solubility characteristics in the resin to be colored;
`however, to accomplish this the colorant may not be
`however, to accomplish this the colorant may not be
`copolymerized, particularly when added at high levels, thus
`copolymerized, particularly when added at high levels, thus
`40 leading to undesirable extractable colorant.
`40 leading to undesirable extractable colorant.
`Additionally, it is known to produce polyester color
`Additionally, it is known to produce polyester color
`concentrates having colorants copolymerized therein and to
`concentrates having colorants copolymerized therein and to
`use these for coloring thermoplastics (See U.S. Pat. No.
`use these for coloring thermoplastics (See U.S. Pat. No.
`5,032,670; U.S. Pat. No. 5,106,942; WO 92/07913; WO
`5,032,670; U.S. Pat. No. 5,106,942; WO 92/07913; WO
`45 92113921). The polycondensation reactions required to pre(cid:173)
`45 92113921). The polycondensation reactions required to pre(cid:173)
`pare these polymeric colorants require high temperature
`pare these polymeric colorants require high temperature
`conditions (>250° C.) and continuous large scale processing
`conditions (>250° C.) and continuous large scale processing
`to be cost effective, in contrast to the polysulfonamide
`to be cost effective, in contrast to the polysulfonamide
`colorants of this invention which can be prepared at rela(cid:173)
`colorants of this invention which can be prepared at rela(cid:173)
`tively low temperatures (e.g. usually 100° c., or less) in
`tively low temperatures (e.g. usually 100° C., or less) in
`50 batch processing equipment.
`50 batch processing equipment.
`Finally, it is known (U.S. Pat. No. 5,194,463) to color
`Finally, it is known (U.S. Pat. No. 5,194,463) to color
`thermoplastics using polyurethane color concentrates;
`thermoplastics using polyurethane color concentrates;
`however, these colorants have the inherent disadvantage of
`however, these colorants have the inherent disadvantage of
`being derived from diisocyanate compounds as one of the
`being derived from diisocyanate compounds as one of the
`55 reactants, which are known to be toxic and difficult to handle
`55 reactants, which are known to be toxic and difficult to handle
`safely on a large scale.
`safely on a large scale.
`This invention provides thermoplastic compositions com(cid:173)
`This invention provides thermoplastic compositions com(cid:173)
`prising one or more thermoplastic materials and one or more
`prising one or more thermoplastic materials and one or more
`anthraquinone polysulfonamide colorants. The colorant may
`anthraquinone polysulfonamide colorants. The colorant may
`60 be added during the preparation of the thermoplastic or
`60 be added during the preparation of the thermoplastic or
`afterwards via melt blending techniques.
`afterwards via melt blending techniques.
`
`SUMMARY OF THE INVENTION
`SUMMARY OF THE INVENTION
`
`The invention provides a colored thermoplastic compo(cid:173)
`The invention provides a colored thermoplastic compo(cid:173)
`sition which comprises at least one thermoplastic polymer
`sition which comprises at least one thermoplastic polymer
`having combined therewith at least one colorant having the
`having combined therewith at least one colorant having the
`formula I:
`formula I:
`
`Page 2 of 19
`
`

`

`
`
`3 3
`
`
`
`4 4
`
`
`
`6,121,351 6,121,351
`
`--+N(R)02S-Ar-X-AQ-X'-Ar'-S02N(R')-R]»-
`--+N(R)02S-Ar-X-AQ-X'-Ar'-S02N(R')-Rjl>-
`
`
`
`5 5
`
`
`
`wherein: wherein:
`
`Ar and Ar' each independently represent a divalent radical
`Ar and Ar' each independently represent a divalent radical
`
`of the benzene or naphthalene series; X and X' are of the benzene or naphthalene series; X and X' are
`
`independently selected from Y, - Y -alkylene, independently selected from Y, - Y -alkylene,
`
`- Y -alkylene-Y'm, - Y -alkylene-C 3 -C 8 -- Y -alkyl ene-Y'm' - Y -alkylene-C 3 -C g -
`
`cycloalkylene, Y -C 3 -C 8 -cycloalkylene-Y', cycloalkylene, Y -C 3 -C g -cycloalkylene-Y',
`
`Y -alkylene-C3 -C8 -cycloalkylene-alkylene-Y', Y -alkylene-C3 -C g -cycloalkylene-alkylene-Y',
`wherein m is 1-3, Y and Y' are independently selected
`wherein m is 1-3, Y andY' are independently selected
`from -0-, -S-, -N(R)CO-, -N(R)S02- , and
`from -0-, -S-, -N(R)CO-, -N(R)S02-' and
`-N(R2) - , AQ is a divalent anthraquinone radical; R -N(R2)-' AQ is a divalent anthraquinone radical; R
`
`
`and R' are independently selected from hydrogen, and R' are independently selected from hydrogen,
`
`C1-C8 alkyl, C3-C8 cycloalkyl, heteroaryl and aryl; R1 C1-Cg alkyl, C3-Cg cycloalkyl, heteroaryl and aryl; Rl
`
`is a divalent organic radical, with the proviso that when is a divalent organic radical, with the proviso that when
`R1 is ethylene, R and R' may be combined to represent Rl is ethylene, Rand R' may be combined to represent
`
`an ethylene radical; and R2 is selected from hydrogen, an ethylene radical; and R2 is selected from hydrogen,
`
`
`C1-C8 alkyl, C3-C8 cycloalkyl, CcC8 alkanoyl, aroyl, C1-Cg alkyl, C3-Cg cycloalkyl, CCCg alkanoyl, aroyl,
`
`C1-C8 alkylsulfonyl, arylsulfonyl, carbamoyl, and sul(cid:173)C1-Cg alkylsulfonyl, arylsulfonyl, carbamoyl, and sul(cid:173)
`
`famoyl; n is an integer of from about 3 to about 30, famoyl; n is an integer of from about 3 to about 30,
`
`preferably an integer from about 5 to about 20. preferably an integer from about 5 to about 20.
`Each divalent radical represented by Ar and Ar' may be
`Each divalent radical represented by Ar and Ar' may be
`further substituted with 1-4 groups which may be the same
`further substituted with 1-4 groups which may be the same
`30 or different and are selected from CcC8 alkyl, CcC8 30 or different and are selected from CCCg alkyl, CCCg
`
`
`alkoxy, C1-C8 alkanolyamino, aroylamino, CcC8 alkylthio alkoxy, C1-Cg alkanolyamino, aroylamino, CCCg alkylthio
`
`and halogen. and halogen.
`
`The divalent anthraquinone radical (AQ) may be further The divalent anthraquinone radical (AQ) may be further
`substituted with 1-6 groups which may be the same or
`substituted with 1-6 groups which may be the same or
`
`different and are selected from C1-C8 alkyl, CcC8 alkoxy, different and are selected from C1-Cg alkyl, CCCg alkoxy,
`CcC 8 alkanolyamino, aroylamino, CcC 8 alkylthio, CCCg alkanolyamino, aroylamino, CCCg alkylthio,
`
`
`halogen, amino, nitro, C 1 -C 8 alkylamino, C 3 -C 8 halogen, amino, nitro, C1-C g alkylamino, C 3 -C g
`
`cycloalkylamino, C1-C8 alkanoyl, CcC8 alkoxycarbonyl, cycloalkylamino, C1-Cg alkanoyl, CCCg alkoxycarbonyl,
`40 trifiuoromethyl, cyano, C 3 -C 8 cycloalkoxy, C 3 -C 8 40 trifiuoromethyl, cyano, C 3 -C g cycloalkoxy, C 3 -C g
`
`cycloalkylthio, heteroarylthio, CcC 8 alkylsulfonyl, cycloalkylthio, heteroarylthio, CCCg alkylsulfonyl,
`
`
`arylsulfonyl, aroyl, carbamoyl, sulfamoyl, C 1 -C 8 arylsulfonyl, aroyl, carbamoyl, sulfamoyl, C1-C g
`alkanoylamino, aroylamino, CcC 8 alkylsulfonamido, alkanoylamino, aroyl amino, CCC g alkylsulfonamido,
`
`
`arylsulfonamido, arylthio, aryloxy, arylamino, and hydroxy. arylsulfonamido, arylthio, aryloxy, arylamino, and hydroxy.
`The organic radical R1 can be selected from a wide variety The organic radical Rl can be selected from a wide variety
`
`
`of divalent linking groups including, C2-C12 alkylene, of divalent linking groups including, C2-C12 alkylene,
`
`C3-C8 cycloalkylene, -CH2-C3-C8 cycloalkylene-CH2 -, C3-Cg cycloalkylene, -CH2-C3-Cg cycloalkylene-CH2-,
`carbocyclic and heterocyclic arylene and these in combina(cid:173)
`carbocyclic and heterocyclic arylene and these in combina(cid:173)
`tion. The alkylene linking groups may contain within or
`tion. The alkylene linking groups may contain within or
`50 attached to their main chain one or more hetero atoms, e.g., 50 attached to their main chain one or more hetero atoms, e.g.,
`
`
`oxygen, sulfur, nitrogen, substituted nitrogen, and/or cyclic oxygen, sulfur, nitrogen, substituted nitrogen, and/or cyclic
`
`groups such as C3-C8 cycloalkylene, carbocyclic arylene, groups such as C3-Cg cycloalkylene, carbocyclic arylene,
`
`divalent aromatic heterocyclic groups or ester/amide groups divalent aromatic heterocyclic groups or ester/amide groups
`
`such as such as
`
`
`
`35 35
`
`45
`45
`
`o
`o
`0
`0
`II
`II
`II
`II
`-oco-, -oc-,
`-o cO - , -oC - ,
`o
`o
`0
`0
`0
`0
`II
`II
`II
`II
`II
`II
`II
`II
`
`-OC-C1-C12alkylene-CO-, -OC-arylene-CO-, - oC -CJ-C12alkylene-CO-, -OC-arylene-CO-,
`o
`0
`
`0 0
`II
`II
`II
`II
`
`
`
`-OCNH-C1-C12alkylene-NHCO-, -OCNH-CJ-CJ2a1kylene-NHCO- ,
`
`0
`0
`
`
`wherein: wherein:
`
`AQ is a divalent anthraquinone radical which may be AQ is a divalent anthraquinone radical which may be
`
`substituted with from 1 to 6 substituents which may be substituted with from 1 to 6 substituents which may be
`the same or different and are selected from C1-C8 alkyl,
`the same or different and are selected from C1-Cg alkyl, 10
`10
`CcC 8 alkoxy, CcC8 alkanolyamino, aroylamino, CCC g alkoxy, CCCg alkanolyamino, aroylamino,
`
`CcC 8 alkylthio, halogen, amino, nitro, CcC 8 CCC g alkylthio, halogen, amino, nitro, CCCg
`
`
`alkylamino, C3-C8 cycloalkylamino, CcC8 alkanoyl, alkylamino, C3-Cg cycloalkylamino, CCCg alkanoyl,
`
`C1-C8 alkoxy-carbonyl, trifiuoromethyl, cyano, C3-C8 C1-Cg alkoxy-carbonyl, trifiuoromethyl, cyano, C3-Cg
`
`cycloalkoxy, C3-C8 cycloalkylthio, heteroarylthio, cycloalkoxy, C3-Cg cycloalkylthio, heteroarylthio, 15
`15
`
`C1-C8 alkylsulfonyl, arylsulfonyl, aroyl, carbamoyl, C1-Cg alkylsulfonyl, arylsulfonyl, aroyl, carbamoyl,
`sulfamoyl, CcC8 alkanoylamino, aroylamino, CcC8 sulfamoyl, CCCg alkanoylamino, aroylamino, CCCg
`
`
`alkylsulfonamido, arylsulfonamido, arylthio, aryloxy, alkylsulfonamido, arylsulfonamido, arylthio, aryloxy,
`
`arylamino, and hydroxy groups; arylamino, and hydroxy groups;
`X and X' are independently Y, -Y-alkylene, 20
`X and X' are independently Y, -Y-alkylene, 20
`
`-Y-alkylene-Y'-)m, -Y- alkylene-C3-C8 --Y-alkylene-Y'-)m, -Y- alkylene-C3-Cg -
`
`cycloalkylene, Y -C 3 -C 8 -cycloalkylene-Y', or cycloalkylene, Y -C 3 -C g -cycloalkylene-Y', or
`
`Y -alkylene-C3-C8 -cycloalkylene-alkylene-Y', Y -alkylene-C3-C g -cycloalkylene-alkylene-Y',
`wherein m is 1-3, and Y and Y' are independently
`wherein m is 1-3, and Y and Y' are independently
`-0-, -S-, -N(R)CO-, -N(R)S0 2- , or-N 25
`-0-, -S-, -N(R)CO-, -N(R)S02-' or-N 25
`(R2 ) - ;
`(R2)-;
`Ar and Ar' are independently a divalent benzene or
`Ar and Ar' are independently a divalent benzene or
`
`naphthalene radical which may be substituted with naphthalene radical which may be substituted with
`
`from 1 to 4 substituents which may be the same or from 1 to 4 substituents which may be the same or
`
`different and are selected from CcC8 alkyl, C1-C8 different and are selected from CCCg alkyl, C1-Cg
`alkoxy, CcC8 alkanolyamino, aroylamino, CcC8 alkoxy, CCCg alkanolyamino, aroylamino, CCCg
`
`
`alkylthio and halogen groups; alkylthio and halogen groups;
`
`Rand R' are independently hydrogen, C1-e8 alkyl, C3-C8 Rand R' are independently hydrogen, C1-Cg alkyl, C3-Cg
`
`cycloalkyl, heteroaryl or aryl; cycloalkyl, heteroaryl or aryl;
`R1 is a divalent organic radical, with the proviso that when Rl is a divalent organic radical, with the proviso that when
`
`R1 is ethylene, R and R' may be combined to represent
`Rl is ethylene, Rand R' may be combined to represent
`
`an ethylene radical; an ethylene radical;
`R2 is hydrogen, C1-C8 alkyl, C3-C8 cycloalkyl, CcC8
`R2 is hydrogen, C1-Cg alkyl, C3-Cg cycloalkyl, CCCg
`alkanoyl, aroyl, CcC8 alkylsulfonyl, arylsulfonyl, alkanoyl, aroyl, CCCg alkylsulfonyl, arylsulfonyl,
`
`
`carbamoyl, or sulfamoyl; and n is an integer of from carbamoyl, or sulfamoyl; and n is an integer of from
`
`about 3 to about 30. about 3 to about 30.
`
`The invention also provides a method of forming a The invention also provides a method of forming a
`
`thermoplastic composition which comprises melting a ther(cid:173)thermoplastic composition which comprises melting a ther(cid:173)
`
`moplastic polymer and blending therewith a colorant having moplastic polymer and blending therewith a colorant having
`
`the above formula I. the above formula I.
`The invention further provides a colored thermoplastic
`The invention further provides a colored thermoplastic
`composition which comprises, at least one thermoplastic
`composition which comprises, at least one thermoplastic
`polymer having combined therewith at least one colorant
`polymer having combined therewith at least one colorant
`
`having a unit of the above formula I. having a unit of the above formula I.
`
`The toned and colored thermoplastic compositions into The toned and colored thermoplastic compositions into
`
`which the colorants of the present invention are incorporated which the colorants of the present invention are incorporated
`
`have a high enough molecular weight so that the resultant have a high enough molecular weight so that the resultant
`
`colored polymer will not be leachable, extractable, colored polymer will not be leachable, extractable,
`
`sublimable, migratable, etc. from the thermoplastic compo(cid:173)sublimable, migratable, etc. from the thermoplastic compo(cid:173)
`sition thus minimizing toxicity concerns with human expo- 55 sition thus minimizing toxicity concerns with human expo- 55
`
`
`sure. The colored compositions are nonhazardous, have sure. The colored compositions are nonhazardous, have
`
`good brilliance, clarity, fastness to light, high heat stability, good brilliance, clarity, fastness to light, high heat stability,
`
`excellent homogeneity of colorant, and which normally excellent homogeneity of colorant, and which normally
`
`maintain the desirable physical properties of the uncolored maintain the desirable physical properties of the uncolored
`
`thermoplastic materials. thermoplastic materials.
`
`
`
`60 60
`
`
`DETAILED DESCRIPTION OF 1HE DETAILED DESCRIPTION OF IRE
`
`PREFERRED EMBODIMENT PREFERRED EMBODIMENT
`
`In accordance with the present invention thermoplastic In accordance with the present invention thermoplastic
`
`compositions are produced by adding, during the prepara(cid:173)compositions are produced by adding, during the prepara(cid:173)
`
`tion of the thermoplastics or by melt blending the 65 tion of the thermoplastics or by melt blending the 65
`
`thermoplastic, anthraquinone polysulfonamide colorants of thermoplastic, anthraquinone polysulfonamide colorants of
`
`the Formula I the Formula I
`
`0
`0
`0
`000
`
`
`
`-OCNH-arylene-NHCQ--, --NHCNH--, -OCNH-arylene-NHCo--, --NHCNH--,
`
`II
`II
`
`II
`II
`
`II
`II
`
`Page 3 of 19
`
`

`

`6,121,351
`6,121,351
`
`5
`5
`
`-continued -continued
`o
`
`0 0
`0
`
`
`II II
`II II
`-NHC-C1-C12alkylene-CNH-. -NHC-C1-C12alkylene-CNH- .
`
`
`o
`
`0 II II
`
`
`
`-NHC-,and -NHC-,and
`
`
`Examples of C2-C12 alkylene radicals containing cyclic Examples of C2-C12 alkylene radicals containing cyclic
`
`moieties in the alkylene chain includ