LIGHT-ABSORBING POLYURETHANE COMPOSITIONS AND THERMOPLASTIC POLYMERS COLORED THEREWITH

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Field of the Invention

This invention belongs to the field of polymer chemistry. More particularly, this invention relates to 10 polyurethane compositions containing light— bsorbing compounds bearing two hydroxyal yl groups copolymerized therein.

Background of the Invention

15 It is well— nown that thermoplastic polymers may be colored by adding pigments or solvent dyes (e.g., see Thomas G. Weber, Editor, Coloring of Plastics. John Wiley & Sons, New York, 1979) . The use of pigments, however, is accompanied by undesirable

20 properties such as opacity, dullness of color, low tinctorial strength, etc. Also, difficulties in uniformly blending the insoluble pigments with the thermoplastic resin are often encountered. Also useful for coloring thermoplastic polymers are the solvent dyes

25 (K. Venkataraman, Editor, The Chemistry of Synthetic Dyes. Vol. 8, Academic Press, New York, 1978, pp. 81—131) , which provide compositions having improved clarity, brightness in hue and high tinctorial strength, but which may lead to dye migration, extraction, etc.

30 from the colored thermoplastic polymer. These problems are of particular concern when solvent dyes are used to color flexible polymers such as polyvinyl chloride, polyethylene and polypropylene which have low glass transition temperatures.

35 It is also known that one can prepare solvent soluble nonextractable polymeric aminotriaryl methane

dyes having polyester, polycarbonate, polyurethane, or polyethyleneimine backbones and incorporate them into polymers such as polyvinyl choride, polyvinylidene chloride and acrylic polymers such as poly(methyl ethacrylate) etc. by solvent blending techniques [U.S. Patent No. 4,477,635 (1984)]. Difficulties are encountered in preparing these polymeric colored compounds because a non—colored intermediate aromatic a ine containing polymer must be prepared and then the aromatic amine moiety in the polymer structure must be converted into an aminotriarylmethane moiety by further reaction with a diaryl ketone in the presence of a condensation catalyst such as phosphorous oxychloride, in an inert organic solvent. Attempts to make colored polyester compositions in one step by copolymerizing aminotriarylmethane colorants containing reactive groups generally fail, presumably because of the thermal instability of the triaryl ethane chromophore. These previously disclosed polymeric aminotriarylmethane compositions also have poor fastness to light and do not have the requisite thermal stability for use in coloring thermoplastic polymers via the more favorable method of high temperature melt blending.

It is further known that one may color plastics, in particular polyolefins, with low melting, cross—linked colored polyester compositions containing residues of terephthalic acid, isophthalic acid, or both, a low- molecular weight trimethylol alkane, i.e., 1,1,1— trimethylol propane and a copolymerizable colorant, said colorant being present at a level of 0.1—25% by weight (U.S. Patent No. 4,116,923). Difficulties are encountered, however, in preparing these highly cross- linked colored polymers as extreme care with regard to the temperature, amount of vacuum, the level of colorant present, and the reaction time, is necessary in order to

attempt to reproduce the same quality of cross—linked colored polyester composition. Further, these colored polyester compositions are brittle or low melting and may cause deterioration in physical properties of thermoplastic polymers when added in quantities sufficient to produce a high level of coloration. Critical in the preparation of these previously disclosed polymers is the achievement of a low degree of polymerization to give a low melting polymer which has adequate solubility characteristics in the polymer to be colored; however, to accomplish this the colorant may not be copolymerized, paricularly when added at high levels, thus leading to undesirable extractable colorants. It is also known to color thermoplastic polymeric materials using color concentrates consisting of physical admixtures of polymers and colorants. However, the use of such physical admixtures to color polymeric materials such as polyesters, e.g., poly(ethylene terephthalate) and blends thereof, present a number of problems:

(1) Colorant migration during drying of the colored polymer pellets.

(2) Colorant migration during extrusion and colorant accumulation on dies which can cause film rupture and shut-downs for clean— p, etc. Such colorant migration and accumulation result in time consuming and difficult clean¬ up when a polymer of another color is subsequently processed in the same equipment.

(3) Colorants may not mix well, for example, when using two or more color concentrates to obtain a particular shade.

(4) Colorants may diffuse or exude during storage of the colored polymeric material.

Furthermore, the presence of oligomeric material in the polymers, such as polyester, admixed with the colorants to produce the known color concentrates can cause problems of equipment contamination during processing.

As noted above, inorganic and low molecular weight organic compounds are widely used as colorants for polymeric materials. By proper combination of colors, nearly any color can be generated. However, there are problems with this coloration system, including chemical incompatibility between the colorant and polymer and the carcinogenic and/or toxic nature of many of the colorants. Of particular concern in the injection molding of polyesters and blends of polyester and polycarbonate is the appearance of a discolored, dark streak at weld lines. Weld lines are typically formed in an injection molded part whenever two advancing melt fronts meet. This problem is particularly severe when dark reds and greens are desired. Because these discolored weld lines are unacceptable in aesthetic applications, these materials often cannot be used in large parts which require multiple gates. Further, U.S. Patent Nos. 4,267,306; 4,359,570; 4,403,092; and 4,617,373; describe the preparation of colored polyester compositions by copolymerization of thermally stable colorants during the polyester prepara¬ tion. However, since the colorants are exposed to very high temperatures for prolonged periods of time

necessary for polyester formation, only very stable colorants are suitable, thus severely circumscribing the selection of efficacious colorants. For example, only the non azo type colorants have been shown to have the adequate thermal stability for copolymerization into polyesters; azo type compounds lack the requisite thermal stability for copolymerization into polyesters.

Further, Japanese Kokoku Patent No. Sho 48 [1973] 8562 describes polymeric urethane compositions derived from aliphatic and aromatic diisocyanates and colorants containing two hydroxy groups attached to aromatic rings. However, extreme reaction conditions are required to react the aromatic hydroxy groups completely and the colored polymers prepared from aromatic diols and diisocyanates have limited solubility in the preparative reaction solvents and in thermoplastic resins.

We have discovered novel light-absorbing poly¬ urethane compositions which have light absorbing moieties from various chromophore classes, including the broad range of easily—obtained and relatively inexpensive azo colorants copoly erized therein. These light—absorbing compounds can be copolymerized into polyurethane under sufficiently mild conditions, so as to not destroy the chromophoric moiety; the colored polyurethane compositions thus provided can then be used to impart color, ultraviolet and/or near infrared light absorbing properties to other thermoplastic polymers (e.g., polyesters) to provide colored thermoplastic polymer compositions in a wide ranged of colors either with or without UV or infrared light-absorbing properties.

Summary of the Invention

The present invention provides light—absorbing polyurethane compositions. The polyurethane composi— tions of the present invention are useful in applica¬ tions where color and/or ultraviolet light—absorbing properties are desired. The polyurethane compositions of this invention can be used alone as colorants or near ultraviolet light absorbers or blended with other thermoplastic polymers to impart coloration or near ultraviolet light absorption properties.

Detailed Description of the Invention

The present invention provides a light—absorbing polyurethane comprising repeating units of Formula (I)

{ GCNH-R-NHCC-R ¹ -n— (I)

wherein

R is a divalent radical selected from optionally substituted C_,—C _j0 —alkylene , C ₃ — C _t —cycloalkylene , arylene,

Cj-C^-alkylene—arylene-Cj—C_ _f -alkylene , C _t —C^-alkylene—C ₃ —C ₈ - cycloalkylene—C ₁ —C ₄ —alkylene or C _< —C ₄ —alkylene—

1,2,3,4,5,6,7—octahydronaphthalene-2,6-diyl—Cj—C ₄ - alkylene;

R ¹ is a divalent organic radical comprised of about

1 to 75 mole percent of the residue of a light—absorbing organic diol, wherein the hydroxyl groups of said diol are bonded via alkylene moieties to the remainder of the light—absorbing organic compound, with any remainder of

R ¹ comprised of the residue of organic diols of the formula HO- ² —OH; wherein

R ² is a divalent radical selected from C_,—C _lg alkylene, C ₃ -C ₈ —cycloalkylene, Cj—C ₄ alkylene— 1,2,3,4,5,6,7,8-octahydronaphthalen-2,6—diyl-C,-C ₄ alkylene , C _j -C^alkylene-C^-Cg-cycloalkylene—C _! -C ₄ - alkylene, C,—C alkylene—arylene—C ₁ -C ₄ —alkylene, C_,—C ₄ alkylene-O-Cj—C ₄ alkylene, C ₂ ~C ₄ alkylene—S—Cj—C alkylene or C_.-C ₄ alkylene-o-c_.-C ₄ alkylene-0-C ₂ -C ₄ alkylene; and n is equal to or greater than 2. In a preferred embodiment of the present invention, R ¹ is comprised of about 5 to 50 mole percent of the residues of a light—absorbing diol. Also as a preferred embodiment of the present invention, n is a range of greater than or equal to 2 and less than 100.

The light—absorbing organic diols used in preparing the polyurethane compositions of the invention are selected from a variety of chromophoric classes including azo, metallized azo, disazo, ethine, or arylidene, polymethine, azo—methine, anthraquinone, azamethine, anthrapyridone (3H—dibenz [f,ij] isoquinoline—2,7—dione, anthrapyridine (7H—dibenz [f,ij] isoquinoline—7—one) , phthaloylphenothiazine (14H—naphtho [2,3—a] phenothiazine—8,13—dione, benzanthrone (7H(de)anthracene—7—one) , anthrapyrimidine (7H—benzo [e] perimidine—7—one) , anthrapyrazole, anthraisothiazole, triphenodioxazine, thiaxanthene—9—one , flourindine (5, 12-dihydroquinoxaline [2,3-b] phenazine) , quinophtha- lone, phthalocyanine, naphthalocyanine, nickel dithiolenes, coumarin (2H—l—benzopyran—2—one) , coumarin i ine (2H—1—benzopyran—2—i ine) , indophenol, perinone, nitroarylamine, benzodifuran, phthaloylphenoxazine

(14H-naphtho[2,3—a]phenoxazine—8,13-dione) , phthaloyl- acridone (13H-naphtho[2,3-c] acridine 5,8,14-trione) , anthraquinonethioxanthone (8H—naphtho[2,3—c]— thioxanthene—5,8,13—trione) , anthrapyridazone,

naphtho[1' ,2' ,3' :4,5]quino[2 _r l—b] quinazoline—5,10— dione, 1H—anthra(2,l—b) (1, 4) thiazin-7,i2-dione, indigo, thioindigo, xanthene, acridine, azine, oxazine, 1,4— and 1 ,5-naphthoquinones , pyromellitic acid diimide, naphthalene—1,4,5,8—tetracarboxylic acid diimide, 3,4,9,10—perylenetetracarboxylie acid diimide, naphthotriazole, naphthoquinone, diminoisoindoline, naphthopyran (3H—naphtho[2,1—b]pyran—3—ones and 3—imineε) and aminonaphthalimide; with the proviso that two hydroxyl groups attached to one or two alkyl moieties be present in the colorant.

Preferred azo compounds correspond to the following Formula (II)

R ³ -N=N-Y (II)

wherein

R ³ is the residue of an aromatic amine which has been diazotized and coupled with a coupling component- (Y) and is preferably derived from the aromatic amine classes of aniline, 4—aminoazobenzene, 2-aminothiazole, 2—aminobenzothiazole, 3-amino-2,l—benzisothiazole, 2— aminothieno[2,3— ] thiazole, 5—aminoisothiazole, 5— aminopyrazole, 2—amino—1,3,4—thiadiazole, 5—amino—1,2,4— thiadiazole, 5—amino—1,2,3—triazole, 2(5) amino— imidazole, 3—a inopyridine , 2(3)aminothiophene, 3— a inobenzo [b] thiophene, 3-aminothieno [2,3-c] isothiazole, 3-amino-7—azabenz—2,1—isothiazole, 3- a inoisothiazole [3,4—d] pyrimidine, 3(4)—amino— phthalimides and such heterocyclic rings substituted with one or more groups selected from C _j —C ₄ alkyl, C _. *-^ cycloalkyl, halogen, C ₁ -C ₄ alkoxy, C _j —C ₄ alkylthio, C _j —C ₄ alkoxycarbonyl, Cj-C ₄ alkanoyl, trifluoroacety1, cyano, dicyanovinyl, carbamoyl, -C0NH-Cι-C ₄ alkyl, -C0N(C _j -C ₄

alkyl) ₂ , sulfamoyl, -S0 ₂ N(Cι-C ₄ -alkyl) ₂ , -S0 ₂ NHCj-C ₄ alkyl, alkanoyl, aroyl, aryl, arylazo, heteroaryl, hetero- arylazo, aryloxy, arylthio, heteroarylthio, aryl— sulfonyl, C _j —C ₄ alkylsulfony1, trifluoromethyl, fluorosulfonyl, trifluoro ethylsulfonyl, thiocyano, or nitro, and wherein the alkyl portions of the above groups are optionally substituted by one or more groups selected from Cι~C ₄ alkoxy, halogen, aryl, cyano, C^C ₄ alkanoyloxy, Cj—C ₄ alkoxycarbonyl, or hydroxy; Y is selected from the coupler classes of anilines, 1,2-dihydroquinolines, 1,2,3,4-tetrahydroquinolines, benzomorpholines, (3 ,4—dihydro—2H—1 ,4—benzoxazines) , 5— pyrazolones , 3—cyano—6-hydroxy-2—pyridones , 2 ,3-dihydro- indoles, indoles, 4—hydroxycoumarins, 4—hydroxy—2— quinolones, imidazo [2,1—b] thiazoles, julolidines (2,3,6,7—tetrahydro—1H,5H—benzo[ij]quinolizines) , 1—oxajulolidines, 1,2,5,6—tetrahydro—4H—pyrrolo]— 3,2,1-ij]quinolines, 2,6-diamino-3-cyanopyridines, 2— aminothiazoles, 2—aminothiophenes, naphthylamines, 5,5— dimethyl—1,3—cyclohexane dione (dimedohe) , phenols, naphthols, or acetoacetarylides; with the proviso that two aliphatic hydroxy groups are present in the colorant.

Further preferred disazo compounds correspond to Formula (III)

R ³ -N=N-R ⁴ -N=N-Y (III)

wherein R ³ and the coupling component (Y) are as defined above and R ⁴ is a divalent aromatic radical selected from 1,4—phenylene, naphthalene—1,4—diyl, thiazol—2,5- diyl, and thiophene—2,5—diy1:

_ _j _Q _

wherein X is hydrogen or 1—2 groups selected from halogen, C _f -q, alkyl, Cj-C ₄ alkoxy, -NHCOC ₁ -C ₄ alkyl, -NHC0 ₂ Cι~C ₄ alkyl, -NHCC—aryl, -NHCONH-aryl, or -NHCONHCj- alkyl; Y _x and Z are individually selected from hydrogen, C ₁ -C ₄ alkyl, halogen, heteroaryl or aryl; and Z ¹ is selected from hydrogen, C _j —C ₄ alkoxycarbonyl, cyano, carba oyl, aroyl, arylsulfonyl, —CONH-Cj—C ₄ alkyl, or C ₁ —C ₄ alkylsulfonyl; wherein the alkyl portion of the groups X, Y, and Z, are optionally substituted by one or more groups selected from Cj—C<-alkoxy, halogen, aryl, cyano, C _x —C ₄ -alkanoyloxy, C _j —C^-alkoxycarbonyl or hydroxy; provided that two aliphatic hydroxy groups are present.

Preferred azamethine and methine or arylidene compounds correspond to Formulae (IV) , (V) , (VI) , (VII) , (VIII) and (IX) :

R ⁵ is the residue of an aniline, 1—naphthylamine, 1,2-dihydroquinoline, 1,2,3,4-tetrahydroquinoline, 1,3,3—trimethyl—2—methyleneindoline, 1,3—dihydro—2— methylene—1,1,3—trimethyl—2H—benz[e]indole, benzo— orpholine (3,4-dihydro-2H-l,4-benzoxazine) , 2,3- dihydroindole, 2—aminothiazole, julolidine (2,3,6,7— tetrahydro-lH,5H— benz-ij]quinolizine) , 1—oxajulolidine, 4H-pyrrolo- [3,2,1-ij] quinoline, phenol, naphthol, thiophenol, pyrrole, pyrazole, furan, thiophene, carbazole, phenathiozine or phenoxazine;

R ⁶ is selected from hydrogen, C^-C ₄ alkyl, Cj—C ₈ cycloalkyl, aryl, or Cι~C ₄ alkylene- C ₃ —C ₈ cycloalkylene, wherein the Cj—C ₄ alkyl group is optionally substituted by one or more groups selected from hydroxy, halo, C _j —C ₄ alkoxy, C_—C ₄ alkanoyloxy, or C^-C ₄ alkoxycarbonyl;

A is the residue of an active methylene compound selected from malonitrile, a—cyanoacetic acid esters, malonic acid esters, alpha-cyanoacetic acid amides, a- C _! -C ₄ alkylsulfonylacetonitriles, α-arylsulfonyl- acetonitriles, α-Ci—C ₄ alkanoylacetonitrileff, α- aroylacetonitriles, α-heteroarylacetonitriles, 1,3- indandione, 2(5H)—furanones, 3—cyano—1,6-dihydro—4— methyl-2 ,6-dioxy (2H)-pyridines, benzo (b) thieno-3- ylidenepropanedinitrile-5,5-dioxides , 1 ,3—bis(dicyano— methylene)indanes, barbituric acid, 5—pyrazolones, dimedone, 3—oxo—2,3—dihydro—1—benzothiophene—1,1— dioxides, or aryl-C(CH ₃ )C=C(CN) ₂ .

Preferred azo-methine compounds correspond to Formula (X) :

A=HC-R ⁴ -N=N-Y (X)

wherein A, R ⁴ , and Y are as defined above.

. „ _.

Preferred anthraquinone and anthrapyridone compounds correspond to colored compounds of Formulae (XI) and (XII) , respectively:

(xi) (xn) wherein

L is a divalent linking moiety selected from —O—, -NH-, -S-, -S0 ₂ -, -S0 ₂ N(R ¹⁰ )-, or -C0 ₂ -;

R ⁷ is hydrogen or 1—4 groups selected from amino, — HCj—C ₄ —alkyl, —NHCj-Cj-cycloalkyl, —NH-aryl, halo, Cj—C ₄ alkoxy, aroyl, Cj—C ₄ alkanoyloxy, aryloxy, C^-C ₄ alkyl— thio, arylthio, heteroarylthio, cyano, nitro, trifluoro- ethyl, -CO^-C^alkyl, -SO _j l-JHC _j -^ alkyl, -S0 ₂ N(C ₁ -C ₄ alkyl) ₂ C ₁ -C ₄ alkyl, or hydroxy; R ⁸ is a hydrocarbyl radical selected from C ₂ — ₄ — alkylene—(OH) _m , C ₂ -C ₄ —alkylene—L-C^- _f -alkylene—(OH) _m , arylene—(Ci—C ₄ —alkylene-OH) _m , arylene—(L-C _j -C^-alkylene- OH) _m , arylene— -Cj—C—alkylene(OH) _m , C _∑ -C ₄ —alkylene—L- arylene—L-C ₂ -C ₄ —alkylene(OH) _m , or C _j -C^alkylene—cyclo—

R ⁹ is selected from hydrogen, cyano, C _x -C ₄ alkyl— amino, C _x -C ₄ alkoxy, halogen, —L-R ⁸ , Ci—C ₄ alkanoyl, aroyl, or arylsulfonyl;

R ¹⁰ is selected from hydrogen, C _x -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, C^-Cg cycloalkyl, aryl, or R ⁸ ; is one or two; _x is zero, one, or two; wherein the alkyl portion of the groups R ₇ , R _s , R and R ₁₀ are optionally

substituted by one or more groups selected from C _j —C ₄ —alkoxy, halogen, aryl, cyano, C _j —C—alkanoyloxy, C _! —C ₄ -alkoxycarbonyl or hydroxy; provided that two aliphatic hydroxy groups are present in the colorant and that when _j is zero, • L-R ⁸ )m ₁ equals hydrogen.

In the above preferred azo, disazo and azo—methine compounds it is further preferred that Y be selected from the following formulae:

_ ^ ^_

wherein R _u is hydrogen or 1—2 groups selected from Cj—C ₄ alkyl, Ci—C ₄ alkoxy, 0-C ₁ -C ₄ alkylene-OH, Cj-C ₄ alkylene-OH, C _! -C ₄ alkylene-Cι-C ₄ alkanoyloxy, halogen, C*_-C ₄ alkanoylamino, ( -C, cycloalkylcarbonylamino, Cj-C ₄ alkylεulfonylamino, arylsulfonyla ino or arylcarbonyl— amino;

R _I2 and R ₁₃ are independently selected from unsubstituted or substituted Cj—C ₁₀ alkyl; unsubstituted or substituted C _j -Cg cycloalkyl; C^-Cg alkenyl; Cj—C ₈ alkynyl; aryl; or R _J2 and R _J3 may be combined with the nitrogen to which they are attached to form a Y radical having the formula

wherein Xi is selected from a covalent bond, —CH ₂ —, -0-, -S-. -S0 ₂ -, -C(O)-, -C0 ₂ -, -N(C _! -C ₄ alkyl), -N(C0C ₁ -C ₄ alkyl)-, -N(S0 ₂ C _! -C ₄ alkyl)-, -N(CC-aryl)- or —N(S0 ₂ —aryl)—;

R _H , _JJ , and R ₁₆ are hydrogen or Cj—C ₄ alkyl; and

R _π is selected from hydrogen, unsubstituted or substituted Cy—C ₁₀ alkyl, Ca-C _T -c c ⁰²¹ !^ ¹ » hetero- aryl or aryl; with the provision that two aliphatic hydroxy groups are present in the light absorbing compound.

In the above preferred, aza ethine, methine or arylidene compounds corresponding to Formula IV, V, VI, VII, VIII and IX it is further preferred that Rj be selected from the following formulae:

wherein R _n , R ₁₂ , R ₁₃ , R ₁ , R _1S , _w and R _π are as defined above in the definition of Y; with the provision that two aliphatic hydroxyls be present.

The preferred polymethine light absorbing compounds correspond to the following formulae:

or Y-(CH=CH) -CH=A ;

wherein A, R _u and R _J2 are as defined above; Y is as defined above for the preferred azo, diazo and azo— methine compounds; X _} is selected from cyano, aryl, heteroaryl, C _x —C ₄ —alkoxycarbony1, arylsulfonyl or Cι—C ₄ —alkoxycarbonyl; X ₂ is selected from -C0 ₂ —, S0 ₂ ,

C0N(R ₁₇ ) or arylene; Lj is selected from a covalent bond; unsubstituted or substituted phenylene; C^-Cg cyclo¬ alkylene; —O—; —S—; —S0 ₂ —; —CO—; —C0 ₂ —; -OC0 ₂ —; -0 ₂ C—alkylene-C0 ₂ —; —0 ₂ C—arylene-C0 ₂ ; —0 ₂ C-C ₃ —Cg-cyclo— alkylene-C0 ₂ —; -0 ₂ CNH-alkylene-NHC0 ₂ -; -0 ₂ CNH- arylene-NHC0 ₂ —; —S0 ₂ N(R _π )—; —S0 ₂ -alkylene-S0 ₂ —; —S0 ₂ —arylene—S0 ₂ -; —S0 ₂ N(R ₁₇ )—alkylene-N(R _r7 )S0 ₂ ; -S0 ₂ N(R ₁₇ )-arylene-N(R ₁₇ )S0 ₂ ; -NfSO^-Q, alkyl)-; -N-(S0 ₂ aryl)—; —O-alkylene-O— or -O-arylene-O-; I^ is selected from unsubstituted or substituted alkylene, C ₃ -C ₈ cycloalkylene, arylene, alkylene-arylene-alkylene, alkylene—(C _j —C ₈ )cycloalkylene—alkylene,

alkylene-O-alkylene, alkylene-S—alkylene, alkylene- S0 ₂ —alkylene, alkylene-O—arylene- -alkylene, alkylene- N(S0 ₂ Cι-C-alkyl) or alkylene-arylene; B _t and B ₂ are selected independently from the following formula:

wherein R _12f R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ are as defined above; p is an integer of 1—3; with the proviso that two aliphatic hydroxy groups be present in the light absorbing compound.

Preferred coumarin compounds correspond to the following formulae:

., _Q

- I o -

wherein R _u , R ₁₂ and R _J3 are as defined above; X ₃ is selected from cyano, C ₁ -C ₄ alkylsulfonyl, aryl, arylsulfonyl, heteroaryl, for yl, aroyl, C _r —C ₄ —alkanoyl or —CH=A, wherein A is the residue of an active methylene compound as defined above; with the proviso that two aliphatic groups be present.

Typical diazotizable amines R ₃ -NH ₂ useful in the preparation of azo, bisazo and azo—methine compounds are adequately disclosed in the literature, e.g.:

M. Weaver and L. Shuttleworth, Dyes and Pigments, 3 (1982) 81-121;

L. Shuttleworth and M. Weaver, Chem. Appl. Dyes, 1990, 107—63, edited by D. Waring and G. Hallas, Plenum, New York, N.Y.;

U.S. Patents 3,438,961; 3,707,532; 3,816,388; 3,980,634; 4,049,643; 4,083,844; 4,105,655; 4,140,683; 4,180,503; 4,189,428; 4,207,233; 4,283,332; 4,400,318; 4,431,585; 4,621,136;

4,734,490; 4,751,288; and 4,760,133, incorporated herein by reference.

Typical coupling components Y useful in the preparation of azo, bisazo and azo—methine compounds are disclosed in the literature, e.g.:

H. R. Schwander, Dyes and Pigments, 3 (1982) 133-160; L. Shuttleworth and M. Weaver, Chem. Appl. Dyes, 1990, 107—63, edited by D. Waring and G. Hallas, Plenum, New York, N.Y. ;

U. S. Patents 3,639,384; 3,657,215; 3,673,169; 3,829,410; 3,919,188; 3,980,634; 4,097,475;

4,119,621; 4,283,332; 4,341,700; 4,400,318; 4,431,585; 4,619,992; and 4,764,600, incorporated herein by reference.

Typical active ethylenes used in the preparation of the methine, polymethine and azo-methine compounds are disclosed in the literature, e.g.:

U.S. Patents 4,338,247; 4,617,373; 4,617,374; 4,707,537; 4,749,774; 4,826,903; 4,845,187;

4,950,732; and 4,981,516, incorporated herein by reference.

The reactive hydroxyalkyl groups are normally attached to the light absorbing chromogens by virtue of a covalent bond or one or more of the following linking groups: —0-, —S-, —SO-, —S0 ₂ -, —C0 ₂ —, —CON(R )—, aryl)— or —N=. In the above definitions the unsubstituted and substituted Cj—C ₁₀ alkyl groups mentioned refer to fully saturated hydrocarbon radicals containing one to ten carbons, either straight or branched chain, and such alkyl radicals substituted with one or more of the following:

C^-Cg cycloalkyl or C^-Cg cycloalkyl substituted with one or two of Cj—C ₄ alkyl, Cj—C ₄ alkylene—OH, lower alkoxy or halogen; phenyl and phenyl substituted with one or two of lower alkyl, lower alkoxy, halogen, lower alkanoylamino, cyano, nitro or lower alkylsulfonyl;

C _j —C ₄ —alkylene-OH; 0—Cj—Qr-alkylene-OH; cyano; halogen; 2—pyrrolidino; phthalimidino; vinylsulfonyl; acrylamido; o—benzoic εulfimido; lower alkoxyalkoxy; cyanoalkoxy; phenoxy; phenoxy substituted with lower alkyl, lower alkoxy, or halogen; groups of the formulae:

^" <- 2 ' -° ^CH 2 ^CH 2< 2 ° ^r -°2 ^SCH 2 ^CH 2< 2

wherein Y ₂ is selected from o— phenylene; o— phenylene substituted with lower alkyl, lower alkoxy, halogen or nitro; Cj-Cj alkylene; vinylene; -C—CH ₂ -; -0CH ₂ CH ₂ -; -CH ₂ 0CH ₂ ; -S-CH ₂ -; -CH ₂ SCH ₂ -; NHCH ₂ -; -NHCH ₂ CH ₂ -; -N (alkyl ) CH ₂ -; -N (alkyl) CH ₂ CH ₂ - or NHCfCeHj ; groups of the formulae:

-S-R 18 -S0 ₂ C ₂ H ₄ SR ₁₈ - -ss--ccrf ^{' "s} CH or

wherein R _u is selected from lower alkyl; C^-Cg cycloalkyl; phenyl; phenyl substituted with one or more groups selected from lower alkyl, lower alkoxy or halogen; a heterocyclic radical selected from pyridyl; pyrimidinyl; benzoxazolyl; benzothiazolyl; benzimidazolyl; 1,3,4—thiadiazolyl, 1,3,4-oxadiazolyl; said heterocyclic radicals further substituted with one or more groups selected from lower alkyl, lower alkoxy carbamoyl, carboxy, lower alkoxy or halogen;

R ₁₉ is selected from hydrogen, C^C^-alkylene-OH, lower alkyl or benzyl; groups of the formulae:

- ^S0 2 ^R 20 ^? -S0 ₂ N(R ₂₁ )R ₂₂ ; -CON(R ₂₁ )R ₂₂ ; -N R ₁₂ )CO ₂₂ -N(R ₂₁ )S0 ₂ R ₂₂ ; -C0 ₂ R ₂₁ ; -OCO ₂ R ₂₀ ; -0 ₂ C-R ₂₁ ; and -0 ₂ CN(R ₂₁ )R ₂₂ ;

wherein R _JQ is selected from C ₃ -C ₈ cycloalkyl; C ₃ —C ₈ cycloalkyl substituted with Cj-C ₄ alkyl; allyl; phenyl; phenyl substituted with one or two groups selected from lower alkyl, lower alkoxy or halogen; lower alkyl; lower alkyl substituted with one or more groups selected from lower alkoxy, halogen, hydroxy, lower carbalkoxy, lower alkanoyloxy, cyano, C ₃ —C ₈ cycloalkyl, aryl, aryloxy, arylthio, lower alkylthio or lower alkylsulfonyl; and R _2I and R- ₂₂ are each independently selected from hydrogen or those groups represented by R^.

In the terms "lower alkyl", "lower alkoxy", "lower alkoxycarbonyl", "lower alkylthio", "lower alkyl¬ sulfonyl", "lower alkanoylamino" and "lower alkanoyl¬ oxy", the alkyl portion of the group contains one to four carbons and may contain as substituents one or two groups selected from C _j —C ₄ -alkoxy, halogen, hydroxy, cyano or phenyl and may denote a straight or branched chain.

The term "lower alkylene" denotes a straight or branched chain divalent hydrocarbon moiety containing one to four carbon atoms.

The term "alkylene" denotes a straight or branched chain divalent hydrocarbon moiety containing one to ten carbons. The term "carbamoyl" is used to represent —C0NH ₂ , —CONHR ₁₂ or CON(R ₁₂ ) , wherein R _n is as defined herein above.

The term "cycloalkylene" is used to represent a fully saturated divalent hydrocarbon radical containing three to eight carbons, e.g., 1,4-cyclohexylene.

The unsubstituted and substituted C ₃ —C ₈ cycloalkyl groups mentioned above refer to cycloaliphatic hydro¬ carbon groups which contain 3 to 8 carbons in the ring, preferably 5 or 6 carbons, and these cycloalkyl groups

substituted with one or two of C _x -C ₄ alkyl, Cι~C ₄ alkoxy, hydroxy or C _x —C alkanoyloxy.

The term "aryl" is used to include carbocyclic aryl groups containing up to fourteen carbons, e.g., phenyl and naphthyl, and those substituted with one or two groups selected from C _j —C ₄ —alkyl, C ₁ —C ₄ alkoxy, Cj—C ₄ — alkoxycarbonyl, Cj—C ₄ —alkanoyloxy, halogen, cyano, nitro, C^-C ₄ —alkylsulfonyl, Cj—C ₄ — alkylene-(OH) _n , 0-C ₁ -C ₄ -alkylene-(OH) _n , -S-Cj-Q, -alkylene-(OH) _n , -SOj-Ci-C _f - lkylene-JOH),,, -C0 ₂ -Cι*-C ₄ - alkylene-(OH) _n , S0 ₂ N(R )Cι-C ₄ -alkylene-(OH) _n , -S0 ₂ N(C ₁ -C ₄ - alkylene-OH) ₂ , -CON(R )C ₁ -C ₄ -alkylene-(OH) _n , --CON(C _l --C ₄ - alkylene-OH) ₂ , -N(S0 ₂ Cj-C ₄ -alkyl)-alkylene-(OH)„ or -N(S0 ₂ phenyl)—C ₁ —C ₄ —alkylene—(OH) _n ; wherein n is one or two. The term "heteroaryl" is used to describe a 5 or 6—membered heterocyclic aromatic ring containing one oxygen atom, and/or one sulfur atom, and/or up to three nitrogen atoms, said heterocyclic aryl ring optionally fused to one or two phenyl rings or another 5 or 6—membered heteroaryl ring. Examples of such ring systems include thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, thiadiazolyl, oxadiazolyl, tetrazolyl, thiatriazolyl, oxatriazolyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, thiazinyl, oxazinyl, triazinyl, thiadiazinyl, oxadiazinyl, dithiazinyl, dioxazinyl, oxathiazinyl, tetrazinyl, thiatriazinyl, oxatriazinyl, dithiadiazinyl, imidazolinyl, dihydro- pyri idy1, tetrahydropyrimidy1 , tetrazoio—[l ,5-b]- pyridazinyl and purinyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, indolyl, and the like and those rings substituted with one or more substituents listed above in the definition of the term "aryl".

— ___ o —

The term "arylene" is used to represent a divalent carbocylic aryl hydrocarbon moiety containing up to fourteen carbons, e.g., o-, m- and p-phenylene, and those substituted with one or two groups selected from C _! -C ₄ -alkyl, C _j -C^-alkoxy or halogen.

The C ₃ —C ₈ alkenyl and C^—C ₈ alkynyl groups represent straight or branched chain hydrocarbon radicals contain¬ ing 3 to 8 carbons in the chain and which contain a carbon—carbon double bond or a carbon—carbon triple bond, respectively.

The term "light absorbing compound" is used to describe an organic compound which absorbs light in the regions of the electromagnetic spectrum usually referred to as the near infrared, near ultraviolet and visible, more particularly between the wavelengths of 300—1200 nm.

The light absorbing polyurethane compositions of the invention may be prepared by reacting one or more of the light absorbing compounds described above, which contains reactive aliphatic hydroxy1 groups, with a diisocyanate and additional diol component if desired, such as a C_.—C ₁₂ glycol, under solution polymerization procedures known to be useful for preparing poly- urethanes in general (see, for example, D. J. Ly an, Journal of Polymer Science, Vol. XLV, pp. 49-59 (I960)). Typical useful diisocyanates include 2,4—tolylene diiso¬ cyanate, 2,6-tolylene diisocyanate, mixtures of 2,4 and 2,6-tolylene diisocyanate, 4,4'—biphenylene diiso¬ cyanate, p-xylylene diisocyanate, methylenedi—p-phenyl diisocyanate, m—phenylene diisocyanate, p—phenylene diisocanate, hexa ethylene diisocyanate, isophorone diisocyanate, 4,4'-diisocyanatodiphenyl ether, bis(4- isocyanatopheny1)sulfone, isopropylidene bis(4-pheny1 isocyanate) , naphthalene-1,5-diisocyanate, l—chloro—2,4- phenylene diisocyanate, 3,3'-bitolylene-4,4'-diiso-

cyanate, 3,3'-dimethoxy-4 ,4'-biphenylene diisocyanate , 3 ,3'-dichloro-4 ,4'-biphenylene diisocyanate, 2,2',5,5'- tetramethy1—4,4'—biphenylene diisocyanate, dipheny1— ethane— , '—diisocyanate, dicyclohexylmethane— ,4'— diisocyanate, and the like.

The diol components are preferably selected from ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2- ethy1—1,3—propanediol, 1,4—butanediol, 2,2-dimethy1— 1,3—propanediol, 1,6—hexanediol, 1,lO-decanediol, 1,12— dodecanediol, 1,2—cyclohexanediol, 1,3—cyclobutanediol, 2,2,4,4—tetramethylcyclobutane—1,3-diol, 1,4—cyclo¬ hexanediol , 1 ,2-cyclohexanedimethanol , 1,3-cyclohexane- di ethanol, 1 ,4—cyclohexanedimethanol, x,8—bis(hydroxy— methyl)—tricyclo—[5.2.1.0]-decane, wherein x represents 3, 4, or 5; and diols containing one or more oxygen or sulfur atoms in the chain, e.g., diethylene glycol, 2,2'—thiodiethanol, triethylene glycol, dipropylene glycol, tripropylene glycol, 1,3- and l,4-bis(2-hydroxy— ethyl)benzene and the like. In general, these diols contain 2 to 18, preferably 2 to 12 carbon atoms.

Cycloaliphatic diols can be employed in their cis or trans configuration or as mixtures of both forms. A particularly preferred diol is 1,4-butanediol.

Although it is within the scope of the invention that all of the diol component consists of a light absorbing compound, normally no more than 75 mole percent of the diol component consists of the light absorbing compound, with the range of 5—50 mole percent being more typical. In the preparation of the colored polyurethanes, it may be desirable to react the terminal isocyanate groups with water to give carbamic acid groups which lose carbon dioxide with the formation of amine groups or to react the terminal isocyanate groups with amines to produce ureas or with alcohols to give urethane groups.

(J. M. Buist and H. Gudgeon, editors. Advances in Poly¬ urethane Technology. Elsevier Publishing Co., London, 1970, p. 5).

As a further aspect of the present invention, there is provided a light-absorbing thermoplastic polymer composition, which comprises one or more thermoplastic polymers having blended therein one or more light- absorbing polyurethane(s) of Formula (I) above.

A wide range of thermoplastic polymers useful for blending with the light—absorbing polyurethanes in the practice of the present invention are known in the art and includes the homopolymers and copolymers of poly¬ esters, e.g. , poly(ethylene terephthalate) ; poly— olefins, e.g., polypropylene, polyethylene, linear low density polyethylene, polybutylene, and copolymers made from ethylene, propylene and/or butylene; copolymers from acrylonitrile, butadiene, and styrene; copolymers from styrene and acrylonitrile; polyamides, e.g.. Nylon 6 and Nylon 66; polyvinyl chloride; (other) poly- urethanes; polyvinylidene chloride; polycarbonates; cellulose esters, e.g., cellulose acetate, propionate, butyrate, or mixed esters; polyacrylates, e.g., poly- (methyl methacrylate) ; polyimides; polyester-amides; polystyrene; etc. According to the present invention the light- absorbing polyurethanes are incorporated into the thermoplastic polymers using conventional techniques, e.g., solution or melt—blending, such as those employed to incorporate other additives in such polymers (see R. Gachter and H. Muller, Editors, Plastics Additives

Handbook. Hansu Publishers, New York, 1985, pp. 507-533; 729-741) . For example, the colored polyurethanes may be dry blended in the form of pellets or ground powders with or without an adhesion promoter or a dispersing agent. This premix can be subsequently processed on

extruders or injection molding machines. Other conventional additives such as plasticizerε, antioxidants, stabilizers, nucleating agents, flame retardants, lubricants, etc. may also be present in the polymer compositions of the present invention.

As a general proposition, it is known that attempts to blend thermoplastic polymers often results in a blend with inferior physical properties. (See for example. Encyclopedia of Polymer Science and Engineering. Vol. 12, p. 399, Ed. by H. F. Mack et al.. John Wiley and Sons, Inc., New York (1988).)

However, the present invention provides light- absorbing polymeric thermoplastic blends wherein the blends do not appreciably differ in physical properties from the discrete polymers.

It should also be appreciated that a multiplicity of colors of colored polyurethanes may be obtained by combining individual colors, e.g., εubtractive colors such as yellow, magenta and cyan according to known color technology (see N. Ohta, Photographic Science and Engineering. Volume 15, No. 5, Sept. — Oct. 1971, pp. 395-415) .

The particular chromophore groups present will, of course, determine the color (hue + value + chroma) of the polyurethane composition and finally the color (hue + value + chroma) of the thermoplastic polymer blends of the present invention. A large gamut of colors may be obtained, as noted above.

The actual amount of the colored polyurethane used to color the thermoplastic polymer will depend on the inherent tinctorial strength of the copolymerized colorant, the weight percent of the colorant in the colored polyurethane composition and the desired depth of shade. Typically, the amount of colored polyurethane added to the thermoplastic polymer is such that the

total amount of colorant residue present by weight in the final thermoplastic blend is from about 0.001% to about 10%, preferably from about 0.01% to about 5%. The colored thermoplastic polymer blends thus provided by the present invention are useful as thick and thin plastic films, plastic sheeting, molded plastic articles, containers, and fibers.

The present invention thus provides a solution to the problems associated with the toxicity of organic pigments and solvent dyes routinely used to impart color and/or UV—absorbing properties to thermoplastic materials; because the light-absorbing moiety (Formula (I)) of the present invention is copolymerized, the danger of human skin exposure to potentially toxic colorants is alleviated, since the colorants will not be leachable, sublimable, extract ble, igratable, or be exuded from the thermoplastic blend. Another consequence of the present invention is the obtainment of nonhazardous light—absorbing thermoplastic composi- tions having good brilliance, clarity and fastness to sunlight, high heat stability, excellent homogeneity of light—absorber, and which normally maintain the desir¬ able physical properties of the uncolored thermoplastic materials. The polymers of this invention are easily ground to very fine powder forms by conventional dry grinding processes or liquid milling processes using grinding agents. Using air attrition grinding technology, average particle sizes of 1—4 microns are easily obtained. At average particle sizes < 4 microns, these polymers have excellent light absorption properties and are useful as colorants or near ultraviolet absorbers when dispersed in ink or coating compositions. For example, in various aqueous formulations these polymeric pigments can be substituted for conventional pigments

,_. _ft

- 28-

with the following new performance advantages: permanence (non-extractable, non-diffusing, non- bleeding, non-chalking) , safety (non-toxic, non-staining and non—penetrating on human skin, less problems with waste disposal) , stability (no aggregation, agglomeration, flocculation, settling on storage) , and economics (greater strength than inorganic pigments and many organic pigments, easier, clean—up, less variability in mixtures due to pigment interactions, speed and reproducibility of production batches of a given pigment mixture.)

Our novel compounds and their preparation are further illustrated by the following examples. The inherent viscosities specified herein are determined at 25°C using 0.5 g of polymer (polyester light— bsorbing concentrate) per 100 mL of a solvent consisting of 60 weight percent phenol and 40 weight percent tetra— chloroethane. The weight average molecular weight (Mw) and number average molecular weight (Mn) values referred to herein are determined by gel permeation chroma¬ tography. The melting temperatures are determined by differential scanning calori etry on the first and/or second heating cycle at a scanning rate of 20°C per minute and are reported as the peaks of the transitions.

Experimental Section

Example 1

To a solution of l,5-bis[(2,2-dimethyl—3-hydroxy- propyl) amino] 9,10—anthraquinone (5.13g, 0.0125 mole) and 1,4—butanediol (3.38g, 0.0375 mole) dissolved in N,N-dimethylformamide (lOOmL) was added dropwise tolylene 2,4-diisocyanate (8.70g, 0.05 mole) with good stirring. The exothermic reaction which followed raised

the temperature from about 23 ^β C to about 35°C. The reaction temperature was increased to about 80°C and stirring continued at this temperature for 0.5 h and the temperature then allowed to come to room temperature. With stirring, the reaction mixture was added dropwise to 400mL of water. The red polymeric solid thus produced was collected by filtration, washed with water and dried in air (yield=17.2g, 99.9% of theoretical yield). Thin—layer chromatography (1:1 tetrahydro— furan : cyclohexane) showed only a very slight amount of unreacted starting material (colorant) left. The polyurethane colorant composition had an inherent viscosity of 0.127, a weight average molecular weight of 10,969, a number average molecular weight of 5,224 and a polydispersity value of 2.1 and contained about 29.8 weight percent of the anthraquinone colorant residue.

Example 2

To a solution of l,4-bis[(2-hydroxyethyl)amino]- 9,10—anthraquinone (4.08g, 0.0125 moles) and 1,4— butanediol (3.38g, 0.0375 moles) dissolved in N,N- dimethylformamide (lOOmL) was added with good stirring tolylene 1,4-diisocyanate (3.38g, 0.0525 moles). The temperature then rose to about 35°C without any external heat source. The temperature was then increased to about 80 ^β C and maintained at 80—85°C for 0.5h with stirring. After being cooled, the reaction mixture was added dropwise to water (600mL) and stirring was continued for 0.5h. The resulting dark blue polymeric solid was collected by filtration, reslurried in water, refiltered, washed with water, and dried in air (yield = 16.0g, 99.1% of the theoretical yield) and had an inherent viscosity of 0.159, a weight average molecular weight of 13,214, a number average molecular

weight of 6,249, and a polydispersity value of 2.1, and contained approximately 25.2 weight percent of anthra¬ quinone colorant residue.

Example 3

To a solution of [[4—[bis[2-hydroxyethyl]amino]2— methylphenyl]methylene propanedinitrile (3.39g, 0.0125 mole) and 1,4—butanediol (3.38g, 0.0375 mole) in N,N— dimethylformamide (lOOmL) was added dropwise tolylene 2,4—diisocyanate (9.14g, 0.0525 mole) with stirring. The temperature then rose to about 35 ^β C. External heat was then applied and the temperature of the reaction mixture was kept at 80—85°C for 0.5h. After cooling, the reaction mixture was added dropwise to water (600 mL) and stirring was continued for 0.5h. The methine yellow polymeric colorant composition thus obtained was collected by filtration and washed with water. The filter cake was reslurried once in water containing a few drops of cone. HC1, refiltered, washed with water and dried at 50°C in a vacuum oven under nitrogen. The yield of the yellow colorant composition thus obtained was 15.36g, 99.3% of the theoretical yield. When tested, the polymer composition had an inherent viscosity of 0.168, a melting temperature of 114°C, a weight average molecular weight of 22,795, a number average molecular weight of 8,977 and a polydispersity of 2.54 and contained about 21.9 weight percent of the methine colorant residue.

Example 4

To a solution of 1,4-bis[(2-hydroxyethyl)amino]— 5,8-di—hydroxy—9,10— nthraquinone (4.48g, 0.0125 mole) and 1,4—butanediol (3.38g, 0.0375 mole) dissolved in

N,N—dimethylformamide (lOOmL) was added dropwise tolylene 2,4—diisocyanate (9.14g, 0.0525 mole) and the temperature rose to about 36 ^β C. Stirring was continued for about 15 minutes and the reaction mixture heated at 80—85°C for about 0.5h. Heating was discontinued and the reaction mixture stirred for two hours longer and then added dropwise to water (600mL) with stirring. After being stirred for 30 minutes longer, the reaction mixture was filtered and the anthraquinone polymeric colorant composition washed with water, reslurried in water, refiltered and washed with water and dried at 50°C in a vacuum oven under nitrogen. The yield of greenish—blue polymeric colorant composition was essentially quantitative. When tested, the polymer compoistion had an inherent viscosity of 0.112, a weight average molecular weight of 10,616, a number average molecular weight of 6,233, and a polydispersity value of 1.70. A melting temperature of 93,4°C was observed by Differential Scanning Calorimetry. The colored polyurethane composition contained approximately 27.1 weight percent of the anthraquinone colorant residue.

Example 5

A solution of N,N-bis(2-hydroxyethyl)—4-[ (6-methyl- εulfonylbenzothiazol—2—yl)azo] aniline (5.25g, 0.0125 mole) and 1,4— utanediol (3.38g, 0.0375 mole) was dissolved in N,N—dimethylformamide (lOOmL) and treated dropwise with tolylene 2 , —diisocyanate (9.l4g, 0.0525 mole) . The temperature rose to about 35°C. External heat was applied and the temperature kept at 80—85°C for 30 minutes with εtirring continued. Heating waε discontinued and the reaction mixture allowed to cool to room temperature and drowned gradually into water (600mL) with stirring. The polymeric product was

_{m ≥} _

collected by filtration, washed with water, reslurried in water, refiltered, washed further with water and dried in air. The red azo polymeric colorant composi¬ tion was obtained in 91% of the theoretical yield (15.8g) and had a melting temperature of 93°C, an inherent viscosity of 0.112, a weight average molecular weight of 10,616, a number average molecular weight of 6,233 and a polydispersity value of 1.70 and contained about 30 weight percent of azo colorant residue.

Example 6

To a solution of 1,5—biε[(2,2—dimethyl—3—hydroxy— propyl)amino]—9,10—anthraquinone (5.13g, 0.0125 mole) and 1,4—butanediol (3.38g, 0.0375 mole) diεsolved in

N,N—dimethylformamide (lOOmL) was added methylenedi—p— phenyl diisocyanate (13.13g, 0.0525 mole) portionwise with stirring. The temperature rose to about 32°C. Reaction temperature was then increased and held at 80— 85°C for 0.5h and then heat was removed and εtirring continued overnight at room temperature. The reaction mixture was added dropwise with stirring to water (600mL) and the product collected by filtration, washed with water, reslurried in 600mL of water, refiltered, washed with additional water, reslurried in acetone

(600mL) , refiltered, washed with acetone, and dried in air. When teεted, the red polymeric colorant composi¬ tion had an inherent viscosity of 0.189, a melting temperature of 147°C, a weight average molecular weight of 18,792, a number average molecular weight of 10,454, a polydispersity value of 1.80 and contained about 24.4 mole percent of the anthraquinone colorant residue.

Example 7

Poly(ethylene terephthalate) (400g) having an inherent viscosity of about 0.71, which had been ground using a Wiley mill to a particle size of about 2mm, was dry blended with 0.4g of polymeric red colorant composi¬ tion of Example 1 and ethylene glycol (0.5g) . This blend waε dried in a vacuum oven at 110°C for 16h. A 15mil film was prepared using a C. w. Brabender 3/4 in. extruder at 280°C. A transparent red film was produced thereby—indicating the solubility of the polymeric red colorant. No sublimation of the colorant was observed and good color development was the result.

Example 8

Example 7 is repeated using 0.20g of the yellow methine polymeric colorant composition of Example 3 to produce a bright yellow transparent film having good color development.

Example 9

Example 7 is repeated using 0.12g of the blue anthraquinone polymeric colorant composition of Example 2 to produce a transparent blue film having good color development.

Example 10

TENITE ^® 423—S polypropylene (Eaεtman Kodak Company) (300g) , which had been granulated on a Wiley mill using a 2mm screen was dry blended with 0.30g of polymeric red colorant of Example 1 and the blend extruded on a C. W. Brabender 3/4 in. extruder at 240°C to produce a red

15 mil film having good color development. No loss of colorant by volatilization or sublimation was observed.

Example 11

Example 10 is repeated using 0.30g of the yellow methine colorant composition of Example 3.

Example 12

Example 10 is repeated using 0.30g of the blue anthraquinone colorant composition of Example 2 to provide a blue film.

Example 13

To a solution of 3—acetamido—N,N—bis(2—hydroxy— ethyl)—4[(4—cyano—3— ethylisothiazol—5—yl)azo]aniline (31.8g, 0.0819 mol) and 1,4—butanediol (19.6g, 0.218 mol) disssolved in N,N-dimethylformamide (400 mL) was added with good stirring tolylene 2,4—diisocyanate (52. g, 0.30 mol) , allowing the temperature to rise. The reaction mixture was then heated and stirred at 85—90°C for about 0.5h and allowed to cool to room temperature. Additional N,N—dimethylformamide (300 mL) and methanol (150 mL) were added with stirring. Upon drowning the solution in water (2.5 L), a dark red solid resulted which was collected by filtration, waεhed with water (2.0 L) and dried in air. The yield was 100.Og (96.5% of theoretical yield) of a red polymeric colorant which has an inherent viscosity of 0.174, a weight average molecular weight of 12,126, a number average molecular weight average of 7,631, a polydispersity of 1.59 and contains approximately 30.7 weight percent of azo colorant residue. An absorption mamimum (lambda max) at

552 n is observed in the visible spectrum in N,N— dimethylformamide.

Example 14

To a solution of 1,5-biε[(2-hydroxyethyl)thio]— 9,10—anthraquinone (15.Og, 0.0416 mol) and 1,4—butane¬ diol (9.30g, 0.1034 mol) dissolved in N,N-dimethyl— formamide (300 mL) was added with good stirring tolylene 2,4—diisocyanate (25.23g, 0.145 mol), while allowing the temperature to rise. The temperature was increased to about 80°C and maintained at 80-85°C for 0.5h. After cooling, the reaction mixture was added dropwise to an ice/water mixture (2.0 L) and stirring continued for 0.5h. The polymeric colorant thus produced was collected by filtration, reslurried in water (1.0 L) , refiltered, washed with water and dried in air in esεentially quantitative yield. The reddiεh—yellow polymeric colorant haε an inherent viεcosity of 0.202, a melting temperature of about 115 ^β C, a weight average molecular weight of 12,675, a number average molecular weight of 6,787, a polydispersity value of 1.87 and contained approximately 30.3 weight percent of the anthraquinone colorant residue. An absorption maximum (lambda max) at 448 nm iε observed in the visible spectrum in N,N-dimethylformamide.

Example 15

A greenish-blue polyurethane colorant waε prepared by reacting l,4-bis[4-(2-hydroxyetho__y)anilino]-9,10- anthraquinone (5.3g, 0.0104 mol), i,4-butanediol (3.56g, 0.0396 mol) and tolylene 2,4-diiεocyanate (8.70g) in N,N-dimethylformamide (100 mL) aε described in Example 14 and the product isolated in a εimilar manner. The

colorant was obtained in 92.8% of the theoretical yield and has an inherent viscoεity of 0.198, a melting temperature of about 100°C, a weight average molecular weight of 11,021, a number average molecular weight of 6,551, a polydiεpersity of 1.68 and contained approximately 30.2 weight percent of the anthraquinone colorant residue. Absorption maxima are observed at 420 nm and 642 nm in the viεible spectrum in N,N—dimethyl¬ formamide.

Example 16

A polyurethane colorant containing about 30.7 weight percent of an anthrapyridone red colorant residue was prepared by reacting 18.Og (0.0338 mol) of the compound having the structure

1,4—butanediol (11.8g, 0.131 mol), tolylene 2,4- diiεocyanate (28.7lg, 0.165 mol) disεolved in N,N— dimethylformamide (300 mL) and the resulting product isolated in a manner analogous to Example 14.

The bright red polymeric colorant (56.Og, 95.7% of the theoretical yield) has an inherent viscosity of 0.161, a melting temperature of 112 ^β C, a weight average molecular weight of 5,712, a number average molecular weight of 3,864 and a polydispersity value of 1.48. An absorption

maximum iε observed at 535 nm in the visible spectrum in N,N-dimethylformamide.

Example 17

A polyurethane colorant containing about 1.1 weight percent of a triphenodioxazime colorant reεidue waε prepared by reacting 0.15g (0.00032 mol) of a compound having the formula

1, -butanediol (4.47g, 0.0497 mol), tolylene 2,4— diiεocyanate (8.7g, 0.05 mol) diεsolved in N,N- dimethylformamide (100 mL) and the product isolated in a manner analogous to that of Example 14. The pink polymeric colorant (11.5g, 86.3 % of the theoretical yield) haε an inherent viscosity of 0.128, a melting temperature of 88.5°C, a weight average molecular weight of 8,314, a number average molecular weight of 5,952, and a polydispersity value of 1.40. Absorption maxima are observed at 505 nm and 539 nm in the visible spectrum in N,N-dimethylformamide.

Example 18

A polyurethane colorant containing about 30.3 weight percent of a copper phthalocyanine colorant residue was prepared by reacting 5.5g of a copper phthalocyanine colorant repreεented largely by the formula CuPc[S0 ₂ NHCH ₂ C(CH ₃ ) ₂ CH ₂ OH] ₂ . ₅ , wherein CuPc repreεents the copper phthalocyanine portion of the structure, 1,4-

butanediol (3.95g, 0.0439 mol), tolylene 2,4—diiso¬ cyanate (8.7g, 0.05 mol) dissolved in N,N-dimethyl- formamide (100 mL) and the product isolated in a manner analogous to that of Example 14. The bright cyan polymeric colorant (16.9g, 87.6% of the theoretical yield) has an inherent viscosity of 0.129, a melting temperature of about 99 ^β c, a weight average molecular weight of 9,162, a number average molecular weight of 5,848, and a polydispersity value of 1.57. In the visible absorption spectrum in N,N-dimethylformamide, an absorption mamimum is observed at 676 nm.

Example 19

A polyurethane colorant containing about 1.1 weight percent of a blue azo colorant was prepared by reacting 3—acetamido—N,N—bis(2—hydroxyethyl)—4—[(5— itrothiazol— 2—yl)azo] aniline (0.15 mol, 0.000381g), 1,4—butanediol (4.47g, 0.0496 mol) , tolylene 2,4—diisocyanate (8.70g, 0.05 mol) disεolved in N,N-dimethylformamide (lOOmL) and the product isolated in a manner analogous to that of Example 14. The blue polymeric colorant (12.7g, 95.3% of the theoretical yield) has an inherent viscosity of 0.245, a melting temperature of 89°c, a weight average molecular weight of 16,558, a number average molecular weight of 9,376, and a polydispersity value of 1.76. An absorption maximum is observed at 599 nm in the visible spectrum in N,N— imethylformamide.

Example 20

A polyurethane colorant containing about 1.1 weight percent of a blue azo colorant was prepared by reacting 3-acetamido-4-[(2,6-dicyano—4-nitrophenyl)azo]-N—(2,3- dihydroxypropyl)—N-ethylaniline (0.15g, 0.00033 mol).

1,4—butanediol (4.47g, 0.0497m), tolylene 2,4-diiso— cyanate (8.7g, 0.05 mol) dissolved in N,N—dimethyl¬ formamide (100 mL) in a manner analogous to that of Example 14. The resulting blue polymeric colorant (9.60g, 72% of the theoretical yield) has an inherent viscosity of 0.206, a melting temperature of 88°C, a weight average molecular weight of 13,780, a number average molecular weight of 9,596, and a polydispersity value of 1.44. An absorption maximum is observed at 6l8nm in the viεible εpectrum in N,N-dimethylformamide.

Example 21

A εtirred εolution of 4—(2,6-dichloro—4-nitro- phenylazo)—N,N—di—(2—hydroxyethyl)aniline (4.0 g, 0.0100 m) , 5—acetamido—4—(2— romo—4,6—dinitro— phenylazo)—N,N-di—(2—hydroxyethyl)—2—methoxyanilin e (6.0 g, 0.0111 m) , 1,4—butanediol (12.4 g, 0.138 m) and N,N-dimethylformamide (200 ml) waε treated with tolylene 2,4-diisocyanate (27.7 g, 0.159 m) at room temperature and then heated at 85—90°C for 0.5 hour. Methanol (15 ml) waε added to the solution after cooling to room temperature. The black polyurethane powder waε obtained by drowning the reaction mixture into water with stirring. A small amount of saturated sodium chloride solution was added to facilitate filtration and the product waε then collected by filtration, washed with water (2.0 L) and dried in air (yield - 50.6 g) . The resulting black polymeric powder has an inherent viscoεity of 0.128, a melting temperature of 112°C, a weight average molecular weight of 8,955, a number average molecular weight of 5,693 and a polydisperεity value of 1.57.

Example 22

A polymethine ultra—violet light—absorbing compound (0.15 g, 0.0003 ) having the structure

waε diεεolved in N,N-dimethylformamide (100 mL) containing 1,4-butanediol (4.47 g, 0.0497 m) with εtirring. The solution was treated with tolylene 2,4-diisocyanate (8.7g, 0.050m) at room temperature and then heated at 80-85°C for 0.5 hour. Methanol (5.0 ml) was added and the solution drowned into water (800 mL) . Saturated salt solution (5.0 ml) was added with stirring and esεentially white polymeric powder waε collected by filtration, waεhed with water and dried in air (yield — 12.1 g) . The polymer haε an inherent viεcoεity of 0.146, or melting temperature of 93 ^β C, a weight average molecular weight of 10,154, a number average molecular weight of 7,336, a polydiεperεity value of 1.38 and an absorption maximum at 354 nm in the UV absorption spectrum in N, -dimethylformamide.

Example 23

A polymethine ultra—violet light absorbing compound (0.15 g (0.00029 m)) having the structure

HOC ₂ H ₄ 0- -CH >"SHC- >-OC _A OH

CH ₃ 0 ^/ ^^3

and 1,4-butanediol (4.47 g, 0.0497 ) were reacted with tolylene diiεocyanate (8.7 g, 0.05 m) in N,N-dimethyl— formamide (100 ml) and the product isolated in a manner analogouε to that of Example 22. The ultra—violet light absorbing polyurethane powder (12.4 g) has an inherent viεcosity of 0.133, a melting temperature of 95 ^β C, a weight average molecular weight of 7,276, a number average molecular weight of 5,351, a polydisperεity of 1.36, an absorption maximum at 377 nm in the UV abεorption εpectrum in N,N—dimethylformamide and contains about 1.0 percent by weight of the residue of the starting UV absorbing compound.

Additional colorants containing aliphatic hydroxy groups and which are uεeful in the practice of the present invention are disclosed in the following tables. The compounds below are either known in the art or are syntheεized by known methodology.

TABLE 1

R ³ -N=N-Y (PHENYL AZO COMPOUNDS)

EX.

No. R ³ Y (Coupling Component)

^{24 "} < • -___:• >- ^N < ^C 2 ^H 4 ^OH >2

²⁵ °2 ^N -< ^*

26 0 ₂ N- X / X / — (CH ₂ CH(CH ₃ )OH) ₂

• -_r=•

Cl'

^" < /- ^N < ^C 2 ^H 4 ^OH >2 flCOC ₂ H ₅

x I f a

TABLE 1 - (Cont'd.)

R ³ -N=N-Y (PHENYL AZO COMPOUNDS)

TABLE 1 - (Cont'd.)

R ³ -N=N-Y (PHENYL AZO COMPOUNDS)

Ex. No. Y (Coupling Component)

^{0 CH} 3

40 -4 X /

/ X.

CH.

EX. No. R ³ Y (Coupling Component)

_/ CONHC ₂ H ₄ OH

43 ^y X /

TABLE 1 - (Cont'd.)

R ³ -N=N-Y (PHENYL AZO COMPOUNDS)

Y Cou lin Com onent

47

48 (HOCH ₂ CH ₂ OCH ₂ CH ₂ ) ₂ NS0 ₂ -

-48-

CM

- -

CM

x I

I I a

I ai

Y (Coupling Component)

•

\ / -N(C ₂ H ₄ OH) ₂

-52-

x a _ i a

TABLE 2 - (Cont'd.) R ³ -N=N-Y (HETEROARYL AZO COMPOUNDS)

Y (Coupling Component)

N(C '2,H 4.O —H) ' 2

-NHCH ₂ CH (OH) CH ₂ OH

TABLE 2 - (Cont'd.)

Ex.

No. E ³ Y (Coupling Component)

TABLE 2 - (Cont'd.)

R ³ -N=N-Y (HETEROARYL AZO COMPOUNDS)

Ex. No. Y (Coupling Component)

79 HOC-H . S—

TABLE 2 - (Cont'd.)

R ³ _N=N-Y (HETEROARYL AZO COMPOUNDS)

EX.

No. E ³ Y (Coupling Component)

CH ₂ OH

r-- co

TABLE 2 - (Cont'd.)

R ³ -N=N-Y (HETEROARYL AZO COMPOUNDS)

Ex .

No . B ³ Y (Coupling Component)

CH(OH)CH ₂ OH

- ^C0 2 ^C 2 ^H 4 ^OH > 2

-60-

X a I

II f a

o •H CM o O O •H •H

- -

X o o o fa a H

TABLE 2 - (Cont'd.)

R ³ -N=N-Y (HETEROARYL AZO COMPOUNDS)

EX.

No. R ³ Y (Coupling Component)

- -

a

VO CO

X o H

H a

-66-

TABLE 3 - (Cont'd.)

R ³ -N=N-Y PHTHALIMIDYL AZO COMPOUNDS

Y (Coupling Component)

TABLE 4

R ₃ _N^N-R ₄ -N=N-Y DISAZO COMPOUNDS

B _. Y (Coupling Component)

/ ^CH 3 y X / \ / -N(C ₂ H ₄ OH) ₂ cύ,

127 _{N /} -

12 ⁹ <~ -

TABLE 4 - (Cont'd.)

R ₃ -N=N-R ₄ -N=N-Y DISAZO COMPOUNDS

Ex. No. B4 Y (Coupling Component)

TABLE 4 - (Cont'd.)

R ₃ -N=N-R ₄ -N-_-N-Y DISAZO COMPOUNDS

TABLE 4 - (Cont'd.)

TABLE 4 - (Cont'd.)

R ₃ -N=N-R ₍ ,-N=N-Y DISAZO COMPOUNDS

EX.

No. B _. B» Y (Coupling Component)

TABLE 4 - (Cont'd.)

R ₃ -N=N-R ₄ -N=N-Y DISAZO COMPOUNDS

Ex. No. B. Y (Coupling Component)

TABLE 5 - (Cont'd.)

AZAMETHINE; METHINE OR ARYLIDENE COMPOUNDS

EX.

No. Structure of Compound

⁰

154 (HOC ₂ H ₄ ) ₂ N-y eft-. ^ ^/,

X.

CH, ^So 2-\

- 6-

TABLE 5 - (Cont'd.)

AZAMETHINE; METHINE OR ARYLIDENE COMPOUNDS

Ex.

No. Structure of Compound

TABLE 5 - (Cont'd.)

AZAMETHINE; METHINE OR ARYLIDENE COMPOUNDS

Ex.

No. Structure of Compound

•—• y v

164 (HOC ₂ H ₄ ) ₂ N-y ^'", >-CH -y ^,"'

TABLE 5 - (Cont'd.)

AZAMETHINE; METHINE OR ARYLIDENE COMPOUNDS

Ex.

No. Structure of Compound

171 (HOC ₂ H ₄ )

-80

to

Q a o ε oJ

TABLE 5 - (Cont'd.)

AZAMETHINE; METHINE OR ARYLIDENE COMPOUNDS

Ex.

No. Structure of Compound

-82-

CM O

CO O ω •H rH

TABLE 5 - (Cont'd.)

AZAMETHINE, METHINE OR ARYLIDENE COMPOUNDS

Ex.

No. Structure of Compound

TABLE 6

AZO-METHINE COMPOUNDS A=HC-R ₄ -N=N-Y

Ex. No. A= B Y (Coupling Component)

/ CN

NC,

185 :c= X /

NC -X • -as* >- ^N ( ^C 2 ^H 4 ^OH ) ₂

X

CN NllCOCH.,

NC CN

Y CN

187 A i ^A I \ y I X 2 ^H 4 ^OH ) ₂ ^' A^ ₀ » / -X • as • - ^N < ^C

X,

CN Nf_COC ₂ H ₅

TABLE 6 - (Cont'd.)

AZO-METHINE COMPOUNDS A=HC-R ₄ -N=N-Y

Ex. No. A= B Y (Coupling Component)

190 y \ — •

^ / \ y X / -N (C ₂ H ₄ OH) , B ^*

NC^ CN

191 C ₂ H ₄ OH)

TABLE 6 - (Cont'd.)

AZO-METHINE COMPOUNDS A=HC-R-N=N-Y

Ex. No. A= B« Y (Coupling Component)

TABLE 6 - (Cont'd.)

AZO-METHINE COMPOUNDS A=HC-R ₄ -N=N-Y

Ex.

No. A= B. Y (Coupling Component)

TABLE 6 - (Cont'd.)

AZO-METHINE COMPOUNDS A=HC-R-N=N-Y

Y (Coupling Component)

TABLE 6 - (Cont'd.)

Ex. No.

205

- -

CM CM

TABLE 7

ANTHRAQUINONE COMPOUNDS

Ex. No. E, ^• fL-RO^

210 H 1 ,5-di-NHCH ₂ CH ₂ OH

211 H l,8-di-NHCH ₂ C(CH ₃ ) ₂ CH ₂ OH

212 H l,4-di-NHCH ₂ CH ₂ OH

₂ 13 H l,4-di-NHCH ₂ C(CH ₃ ) ₂ CH ₂ OH

₂ 14 H l,5-di-NHCH ₂ -y S _/ —CH ₂ OH

_• —•

•_•*-_-•

215 H l,4-di-NHCH ₂ -y S _/ —CH ₂ OH

216 H l,5-di-NHCH ₂ CH ₂ OCH ₂ CH ₂ OH

217 H l, 8-di-NHCH ₂ CH ₂ CH ₂ OH

TABLE 7 - (Cont'd.)

ANTHRAQUINONE COMPOUNDS

218 H l,4-di-NH(CH ₂ ) ₆ OH

219 H l,5-di-NHC(CH ₃ ) ₂ CH ₂ OH

220 H -NHCH ₂ CH (OH) CH ₂ OH

221 2-CH, 1-NHCH ₂ CH (OH) CH ₂ 0H

222 H 1 , 4-di-NHCH ₂ CH (CH ₃ ) OH

223 H 1 , 5-di-NHCH ₂ CH (CgHg) OH

224 H l,4-di-NH~y X- CH ₂ CH ₂ OH

._.

225 H l,4-di-NH~y ^— OCH_CH_OH

X / _S _5

^• =•

aι a

0. CM CM

TABLE 7 - (Cont'd.)

ANTHRAQUINONE COMPOUNDS

231 -NH ₂ , 4-OH 2-OCH ₂ CH(OH)CH ₂ OH

232 1-NH ₂ , 2-OCH ₃ 4-NHCH ₂ CH(OH)CH _j OH

233 l,4-di-NH_ 2,3-di-SC ₂ H ₄ OH

234 1,4-di-NH, 2,3-di-O— — SO-NHC-H.OH ' X / 2 2 4

235 1,8-di-OH 4 , 5-di-NHCH ₂ CH ₂ OH

TABLE 7 - (Cont'd.)

ANTHRAQUINONE COMPOUNDS

Ex. No. s -έL-rE-i,

236 1,5-di-OH 4 ,8- i-NH~y y-CH ₂ CH ₂ OH

237 l-NH ₂ -4-NHC ₆ H ₅ 2-S0 ₂ N(C ₂ H ₄ OH) ₂

238 l-NH ₂ -4-NHC ₆ H _1;L 2-SCH ₂ CH(OH)CH ₂ OH

239 l-NH ₂ -2-CN 4-NHCH ₂ CH(OH)CH ₂ OH

240 l-NH ₂ -2-CF ₃ 4-NHCH ₂ CH(OH)CH ₂ OH

241 ₁ _ _N H ₂ -2-C0 ₂ C ₂ H ₅ 4-NHCH ₂ CH(OH)CH ₂ OH

242 1,8-di-OH, 5-NO, 4-NH-A j.-OCH ₂ CH(OH)CH ₂ OH

243 1-NH-, 4-SC-H,. 2-S0 ₂ N(C ₂ H ₄ OH) ₂ 6 5

TABLE 7 - (Cont'd.)

ANTHRAQUINONE COMPOUNDS

Ex. No. ^• fl-R-JU

244 1-NH, 4-NHC ₂ H ₄ OH 2-S0 ₂ NHC ₂ H ₄ OH

245 1-NH ₂ , 2-OC ₆ H ₅ 4-NHCH ₂ CH(OH)CH ₂ OH

246 l-NH„-2-Br 4-NHCH ₂ CH(OH)CH ₂ OH

247 l-NH2_-4-NHC6-H5 _π -S0 ₂ CH ₂ CH(OH)CH ₂ OH

248 1,5,8-Tri-OH 4-NH— X /

249 H 1,4-di-NHCH ₂ CH ₂ S0 ₂ NHC ₂ H ₄ 0H

250 H 1,4-di-NHCH ₂ CH ₂ C0 ₂ C ₂ H ₄ OH 251 1,5-di- H, 4,8-di-NH ₂ 3-SCH ₂ CH (OH) CH ₂ OH

TABLE 7 - (Cont'd.)

ANTHRAQUINONE COMPOUNDS

Ex.

____>__. B; i-t-rSnim

252 H l,4-di-NHC ₂ H ₄ N(CH ₃ )CH ₂ CH ₂ OH

253 1

254 ¹ ~ ^NH ₂ 2,4-di-SC ₂ H ₄ OH

4-NHC ₆ H ₄ -p-C ₂ H ₄ OH

TABLE 7 - (Cont'd.)

ANTHRAQUINONE COMPOUNDS

TABLE 8

ANTHRAPYRIDONE COMPOUNDS

S7 -ffiirSβ i B9 Bio

6-NHC ₂ H ₄ OH H C ₂ H ₄ OH

6-NHCH ₂ C(CH ₃ ) ₂ CH ₂ OH H CH ₂ C(CH ₃ ) ₂ CH ₂ OH

6,8-di-NHC ₂ H ₄ 0H COCH. H

/ ^CH 2 ^OH

262 4-CH, 6-NH— ^• -CH ₃ CN CH,

X

X.

CH ₂ OH

263 4-Br 6-NHCH ₂ CH(OH)CH ₂ OH CN C ₄ H _g -n

264 6 , 8-di-NHCgH ₅ H CN CH ₂ CH (OH) CH ₂ OH

265 H H NHCH ₂ CH ₂ 0H CH ₂ CH ₂ OH

TABLE 8 - (Cont'd.)

ANTHRAPYRIDONE COMPOUNDS

266 H H SCH ₂ CH ₂ OH CH ₂ CH ₂ OH

267 H H NH— y ^-C^OH (CH ₂ ) ₆ OH

• 53 ft

268 5-Br, 6-NH ₂ H CN CH ₂ CH(OH)CH ₂ OH

• — •

269 6-NH ₂ 5-0~y ^— OC^OH CN CH ₂ CH ₂ OH

.—..'

270 H 6-NH~y ^—OC ₂ H ₄ OH CN CH ₂ CH ₂ OH

• — ♦.

271 H 6-NH-A -C^OH ^C0 2 ^C 2 ^H 5 CH ₂ CH(CH ₃ )OH

• ___ ^■ •

TABLE 8 - (Cont'd.)

ANTHRAPYRIDONE COMPOUNDS

EX. No. :£-_..:_ __- _* ._ E, SlO

272 H -SCH ₂ CH(OH)CH ₂ OH CH,

^C0 2 ^C 2 ^H 5

273 H CH.

274 H ^CH 2 ^" < ^S - ^CH 2 ^0H

TABLE 8 - (Cont'd.)

ANTHRAPYRIDONE COMPOUNDS

Ex. No. E ₇ ϋil RuL _n i E. sio

277 6-SC ₆ H ₅ H COCH. CH ₂ C(CH ₃ ) ₂ CH ₂ 0H

278 6-NH, 5-S0 ₂ (CH ₂ ) ₄ OH

279 H 6-NH-y ^--OCH ₂ CH(OH)CH ₂ OH

280 H 6-NH-

X j— SCH ₂ CH ₂ 0H

TABLE 8 - (Cont'd.)

ANTHRAPYRIDONE COMPOUNDS

Ex. No. E ₇ __ϊ_ι___R _& l_ _ιrιl E. Bio

283 6 , 8-di-SC ₄ H _g -n H H CH ₂ CH(OH)CH ₂ OH

284 H 6-NHC ₂ H ₄ S0 ₂ N(C ₂ H ₄ OH) ₂ H CH.

285 H 6,8- i-NH-y ^— C ₂ H ₄ OH H CH,

286 H 6-NHCH ₂ -y S _/ •-CH ₂ OH C0 ₂ C ₂ H ₄ OH C ₅ H _g

TABLE 9

COUMARIN AND IMINOCOUMARIN COMPOUNDS

EX.

No. Structure of Colorant

2 ^C 6 ^H 5

289

TABLE 9 - (Cont'd.)

COUMARIN AND IMINOCOUMARIN COMPOUNDS

EX.

No. Structure of Colorant

TABLE 9 - (Cont'd.)

COUMARIN AND IMINOCOUMARIN COMPOUNDS

Ex.

No. Structure of Colorant

TABLE 9 - (Cont'd.)

COUMARIN AND IMINOCOUMARIN COMPOUNDS

Ex.

No. Structure of Colorant

- -

O

TABLE 10 - (Cont'd.)

MISCELLANEOUS LIGHT ABSORBER TYPES

Ex.

No. Structure of Light Absorber

TABLE 10 - (Cont'd.)

MISCELLANEOUS LIGHT ABSORBER TYPES

EX.

No. Structure of Light Absorber

CO •H O

TABLE 10 - (Cont'd.)

MISCELLANEOUS LIGHT ABSORBER TYPES

Ex.

No. Structure of Light Absorber

TABLE 10 - (Cont'd.)

MISCELLANEOUS LIGHT ABSORBER TYPES

Ex.

No. Structure of Light Absorber

328 [Copper Phthalocyanine^-(Sθ ₂ NHC ₂ H ₄ θH) ₂

329 [Copper Phthalocyanine^—(S0 ₂ NHCH ₂ CH ₂ OCH ₂ CH ₂ OH) ₂

TABLE 10 - (Cont'd.)

MISCELLANEOUS LIGHT ABSORBER TYPES

Ex.

No. Structure of Light Absorber

331 -S0 ₂ N(C ₂ H ₄ OH) ₂

• — • • — •

333 H0C 2-H 4.— X ^ /— NH— \ *_ - CONHC.H.OH

.*___« • *___•/ 2 4

Λo ₂

334

TABLE 10 - (Cont'd.)

MISCELLANEOUS LIGHT ABSORBER TYPES

Ex.

No. Structure of Light Absorber

337 y _X - _/ _? ^C _ _X ^~ v _/ •-OCH ₂ CH(OH)CH ₂ OH

_* ____ • • rr_= • off

TABLE 10 - (Cont'd.)

MISCELLANEOUS LIGHT ABSORBER TYPES

EX.

No. Structure of Light Absorber

TABLE 10 - (Cont'd.)

MISCELLANEOUS LIGHT ABSORBER TYPES

Ex.

No. Structure of Light Absorber

TABLE 10 - (Cont'd.)

MISCELLANEOUS LIGHT ABSORBER TYPES

Ex.

No. Structure of Light Absorber