Water-dissipatable polyester and polyester-amides containing copolymerized colorants

• US 4,804,719 A
• Filed: 02/05/1988
• Issued: 02/14/1989
• Est. Priority Date: 02/05/1988
• Status: Expired due to Term

• Current Assignee: Eastman Chemical Company
• Original Assignee: Eastman Kodak Company
• Inventors: Weaver, Max A., Adams, L. Jane
• Primary Examiner(s): NOT, DEFINED
• Assistant Examiner(s): NOT, DEFINED
• Application Number:
  US07/153,299
• Time in Patent Office: 375 Days
• Field of Search: 528/290, 528/293, 528/294, 528/295, 525/420, 525/421, 525/434, 525/437
• US Class Current: 525/420
• CPC Class Codes: C08G 63/68 Polyesters containing atoms other than carbon, hydrogen and oxygen C08G63/64 takes precedence
• CPC Class Codes: C08G 69/44 Polyester-amides

Abstract

Water-dispersible polymeric material such as polyesters and poly(ester-amides) containing water-solubilizing sulfonate groups and having reacted onto or into the polymer backbone from about 0.01 to about 40 mol % based on the total of all reactant hydroxy, carboxy or amino equivalents, of colorant comprising one or more heat stable organic compounds initially having one or more condensable groups, the polymeric material comprising the reaction residues of organic monomers and said colorant compounds containing one or more reactive groups condensable under polymerization conditions. This material is useful, for example, for printing inks or other coatings which are desireably applied from an aqueous system.

Claims

1. Composition of matter comprising water-dispersible polymeric material having linking groups comprising at least 20 mole % carbonyloxy and up to about 80 mole % carbonylamido, said material containing water-solubilizing sulfonate groups and having reacted onto or into the polymer backbone from about 0.01 to about 40 mole % based on the total of all reactant hydroxy, carboxy or amino equivalents, or the condensable derivative equivalents thereof, of colorant comprising one or more heat stable organic compounds initially having at least one condensable group.

2. The composition of claim 1, wherein the polymer has an inherent viscosity of from about 0.1 to about 1.0 measured in a 60/40 parts by weight solution of phenol/tetrachloroethane at 25°

C. and at a concentration of 0.25 gram of polymer in 100 mL of the solvent, the polymer containing substantially equimolar proportions of acid equivalents (100 mole percent) to hydroxy and amino equivalents (100 mole percent), the polymer comprising the reaction residues of the following reactants (a), (b), (c), (d), and (e) or the ester forming or esteramide forming derivatives thereof;

(a) at least one difunctional dicarboxylic acid;

(b) from about 4 to about 25 mole percent, based on a total of all acid, hydroxyl and amino equivalents being equal to 200 mole percent, or at least one difunctional sulfomonomer containing at least one cationic sulfonate group attached to an aromatic or cycloaliphatic nucleus wherein the functional groups are hydroxy, carboxyl or amino;

(c) at least one difunctional reactant selected from a glycol or a mixture of a glycol and diamine having two --NRH groups, the glycol containing two --CH₂ --OH groups of which

(1) at least 10 mole percent, based on the total mole percent of hydroxy or hydroxy and amino equivalents, is a poly(ethylene glycol) having the structural formula;

space="preserve" listing-type="equation">H--OCH.sub.2 --CH.sub.2 --.sub.n OH,

n being an integer of from 2 to about 20, or

(2) of which from about 0.1 to less than about 15 mole percent, based on the total mole percent of hydroxy or hydroxy and amino equivalents, is a poly(ethylene glycol) having the structural formula;

space="preserve" listing-type="equation">H--OCH.sub.2 --CH.sub.2 --.sub.n OH,

n being an integer of between 2 and about 500, and with the proviso that the mole percent of said poly(ethlene glycol) within said range is inversely proportional to the quantity of n with said range;

(d) from none to at least one difunctional reactant selected from a hydroxycarboxylic acid having one --C(R)₂ --OH group, an amino--carboxylic acid having one --NRH group, and an amino-alcohol having one --C(R)₂ --OH group and one --NRH group, or mixtures of said difunctional reactants;

wherein each R in the (c) or (d) reactants is a H atom or an alkyl group of 1 to 4 carbon atoms; and

(e) from about 0.1 mole % to about 15 mole %, based on a total of all acid, hydroxyl and amino equivalents being equal to 200 mole % of colorant having at least one acid, hydroxy or amino group reacted onto or into the polymer chain.

3. The composition of claim 2 wherein the polymeric material contains less than about 10 mol %, based on all reactants, of reactant (d), at least about 70 mol % of reactant (c) is glycol, and at least about 70 mol % of all hydroxy equivalents is present in the glycol.

4. The composition of claim 3 wherein the colorant is selected from:

anthraquinones;

methines;

bis-methines;

3H-dibenz[f,ij]isoquinoline 2,7-diones (anthrapyridones);

triphenodioxzines;

fluoridines;

phthaloylpyrrocolines;

coumarins;

4-amino-1,8-naphthalimides;

thioxanthones;

2,5-arylaminoterephthalic acids (or esters);

benzanthrones; and

indanthrones;

said colorants containing at least one condensable group.

5. The composition of claim 3 wherein the colorant is selected from 3H-dibenz[f,ij]isoquinoline-2,7-diones (anthrapyridones);

benzo[f]pyrido[1,2-a]indole-6,11-diones;

thioxanthene-9-ones;

coumarins;

2H-1,4-benzoxazine-2-ones;

triphenodioxazines;

5,12-dihydroquinoxalino[2,3-b]phenazine (fluorindines);

3,6-diaminopyromellitic acid diimides;

2,5(3)diarylaminoterephthalic acids (esters);

4-amino-1,8-naphthalimides;

naphtho [1'"'"',2'"'"',3'"'"';

4,5]quino[2,1-b]quinazoline-5,10-diones;

7H benzo[de]anthracen-7-ones (benzanthrones);

7H-benzo[e]perimidin-7-ones;

6,15-dihydro-5,9,14,18-anthrazinetetrones (indanthrones);

quinophthalones;

7H-benzimidazo[2,1-a][de]isoquinolin-7-ones;

5H-benzo[a]phenoxazine-5-ones;

6H,13H-pyrido[1,2-a;

3,4-b]diindole-6,13-diones; and

diindolo[3,2,1-de-3'"'"',2'"'"',1'"'"'-ij][1,5]naphthyridine-6,13-dione.

6. The composition of claim 3 wherein the colorant is selected from those of the formula:

##STR128## wherein;

R is hydrogen, cycloalkyl or alkyl;

X is --O--, --S--, or --NH--;

--X--R₁ --Z in combination is hydrogen or halogen;

R₁ is selected from -alkylene-Z'"'"', -arylene-Z'"'"', -cycloalkylene-Z'"'"', -aralkylene-Z'"'"', -cycloalkylenealkylene-Z'"'"', -alkarylene-Z'"'"', -alkylenecycloalkylenealkylene-Z'"'"', -alkylenearalkylene-Z'"'"', or alkylenecycloalkylene-Z'"'"', wherein -Z and Z'"'"' are independently selected from hydrogen, --SO₂ R⁵, --SO₂ NR⁵ R⁵, --NHSO₂ R⁵, --N(R⁵)SO₂ R⁵, --N(R⁵)COR⁵, --NHCOR⁵, --OH, --SR⁵, --OR⁵, --NHR⁵, --NR⁵ R⁵, --SO₂ NHR⁵, --CONHR⁵, --CONR⁵ R⁵, --CO₂ R⁵, --OCOR⁵, --OCO₂ R⁵, --OOCNHR⁵, ##STR129## wherein R⁵ is hydrogen, alkyl, allyl, aryl, cycloalkyl, hydroxyalkyl, alkoxyalkoxyalkyl, alkoxyalkyl, hydroxyalkoxy, hydroxyalkoxyalkoxy, alkoxycarbonylalkyl or carboxyaryl, and when X is --O--, or --NH--, --R₁ --Z in combination also can be hydrogen;

R₂ is hydrogen, alkyl, aryl, cyano, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, cycloalkylalkoxycarbonyl, COCl, carboxy, carbamyl, N-alkylcarbamyl, N,N-dialkylcarbamyl, N-alkyl-N-arylcarbamyl, N-arylcarbamyl, N-cycloalkylcarbamyl, acyl, aroyl, amino, alkylamino, dialkylamino, arylamino, cycloalkylamino, alkoxy, hydroxy, alkylthio or arylthio; and

each of R₃ and R₄ is hydrogen, alkyl, halogen or alkoxy;

wherein each of the above alkyl, alkylene, aryl, arylene, cycloalkyl or cycloalkylene moieties or portions of a group or radical may be substituted with 1-3 substituents selected from hydroxyl, carboxyl, carboxy ester, acyloxy, alkyl, cyano, alkoxycarbonyl, alkoxycarbonyloxy, halogen, alkoxy, hydroxyalkoxy, hydroxyalkyl, aryl, aryloxy, or cycloalkyl.

7. The composition of claim 6 wherein X is --NH-- and --R₁ --Z in combination is selected from:

aryl;

aryl substituted with 1-3 of alkyl, alkoxy, halogen, hydroxyalkyl, hydroxyalkoxy or acylamido;

alkyl;

alkyl substituted with 1-3 of hydroxyl or acyloxy;

cycloalkyl;

or cycloalkyl substituted with 1-3 of alkyl;

--X--R₁ --Z in combination is H;

R is alkyl;

R₂ is alkoxycarbonyl, hydroxyalkylamino, or cyano; and

R₃ and R₄ are each hydrogen.

8. The composition of claim 3 wherein the colorant is selected from those of the formulae ##STR130## wherein Y¹ is --NH or --S--, and each R, when present, is selected from Cl, Br, alkyl of 1-10 carbons, aryl, aroyl, cycloalkyl, CN, alkoxy of 1-6 carbons, hydroxyalkyl of 1-6 carbons, alkanoyl of 1-6 carbons, alkoxycarbonyl of 1-6 carbons, alkanoyloxy of 1-6 carbons, alkylamino of 1-6 carbons, alkanoylamino of 1-6 carbons, or mono- or dialkylcarbamyl of 1-6 carbons.

9. The composition of claim 3 wherein the water-dispersible polymeric material comprises (a) an acid component of from about 75 to about 84 mole % isophthalic acid and conversely from about 25 to about 16 mole % 5-sodio-sulfoisophthalic acid, (c) a glycol component of from about 45 to about 60 mole % diethylene glycol and conversely from about 55 to about 40 mole % 1,4-cyclohexanedimethanol or ethylene glycol or mixtures thereof, and (e) from about 0.5 to about 10 mole % of mono- or difunctional colorant.

10. The composition of claim 3 wherein the inherent viscosity of the water-dispersible polymeric material is from about 0.28 to about 0.38, the said acid component comprises from about 80 to about 83 mole % isophthalic acid and conversely from about 20 to about 17 mole % 5-sodiosulfoisophthalic acid, and the said glycol component comprises from about 52 to about 56 mole % diethylene glycol and conversely from about 48 to about 44 mole % 1,4-cyclohexanedimethanol.

11. The composition of claim 8 wherein the polymeric material has an inherent viscosity of from about 0.20 to about 0.38.

12. The composition of matter of claim 1, wherein the colorant comprises one or more compounds of the formula ##STR131## wherein:

R₁ and R₂ each represents hydrogen or 1-3 substituents, depending on the number of T substituents present, and are independently selected from alkyl, alkoxy, alkylamino, alkylsulfonyl, alkylsulfonylamino, alkanoylamino, aroylamino, alkylthio, arylamino, amino, cycloalkylamino, alkanoyl, aroyl, arylsulfonyl, CF₃, arylsulfamoyl, cyano, halogen, hydroxy, nitro, sulfamoyl, alkylsulfamoyl, dialkylsulfamoyl, carbamoyl, alkylcarbamoyl and dialkylcarbamoyl; and

T is 1-4 independently selected substituents of the formula ##STR132## in any positions on rings A and/or B, wherein;

each Z is a divalent linking group independently selected from --NH--, --S--, --O--, --NHR--, --SR--, --SRS--, --SRO--, --SRSR--, --NHRO--, --NHRORO--, --NHRS--, --NHRSR--, --NHRN(COR)--, --NHRN(SO₂ R)--, --ORO--, --OR--, --OROR--, --ORORO--, --ORSR--, and --ORN(COR)RO--, wherein R is aralkylene, alkylene, arylene or cycloalkylene;

R₃ represents hydrogen or 1-3 substituents independently selected from alkyl, alkoxy, cyano, alkanoylamino, halogen, and alkylthio;

each R₄ is independently selected from hydrogen, alkyl, cycloalkyl, and aryl;

each R₅ is independently selected from alkylene, arylene, cycloalkylene, arylenealkylene, aryleneoxyalkylene, arylenethioalkylene, alkylenethioalkylene, alkyleneoxyalkylene, arylenedialkylene, and cyclohexylenedialkylene;

each Q represents 1-3 groups independently selected from acyloxy;

--OCOO-alkyl, hydroxy, carboxy, --COO-alkyl, --COO-aryl, and --COO-cycloalkyl;

and wherein the alkyl, alkylene, cycloalkyl, cycloalkylene, aryl and arylene moieties or portions of the above R₁ -R₅ groups are unsubstituted or substituted with 1-3 of the following;

hydroxy, halogen;

cyano;

amino;

alkoxy;

alkoxycarbonyl;

aroyloxy;

alkoxyalkoxy;

hydroxyalkoxy;

succinimido;

glutarimido;

phthalimido;

phthalimidino;

2-pyrolidono;

cyclohexyl;

phenoxy;

phenyl;

phenyl substituted with alkyl, alkoxy, alkoxycarbonyl, halogen, alkanoylamino or cyano;

acrylamido;

alkenyl;

benzoylsulfonicimido;

groups of the formula ##STR133## wherein Y is --NH--, ##STR134## --O--, --S--, >

CHOH, or --CH₂ --O--;

--S--R⁶ wherein R⁶ is selected from alkyl, alkyl substituted with 1-3 of halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, or alkoxy, phenyl, phenyl substituted with one or more of halogen, alkyl, alkoxy, alkanoylamino, cyano or alkoxycarbonyl, pyridyl, pyrimidinyl, 2-benzoxazolyl, 2-benzimidazolyl, 2-benzothiazolyl or groups of the formula ##STR135## --SO₂ R⁸ ;

--COOR⁸ ;

--OXR⁸ ;

--NH--X--R⁸ ;

--CONR⁷ R⁷ ;

--SO₂ NR⁷ R⁷ ;

wherein X is --CO--, COO--, or --SO₂ ;

R⁸ is selected from alkyl, aryl, cycloalkyl, and each of these groups substituted with 1-3 substituents independently selected from halogen, hydroxy, phenoxy, aryl, alkyl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, or alkoxy, and when X is --CO--, R⁸ is further selected from hydrogen, amino, alkenyl, alkylamino, dialkylamino, arylamino or furyl;

R⁷ is selected from hydrogen, alkyl, aryl, alkoxysubstituted aryl, cycloalkyl, amino, alkylamino, dialkylamino, arylamino, furyl, or alkyl substituted with 1-3 of halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, or alkoxy;

alkoxy substituted with 1-3 of hydroxy, cyano or alkanoyloxy;

alkoxyalkoxy substituted with 1-3 of hydroxy, cyano, alkanoyloxy or alkoxy;

or phenoxy substituted with 1-3 of alkyl, alkoxy or halogen.

13. The composition of matter of claim 1, wherein the colorant comprises one or more compounds of the formula ##STR136## wherein either or both of rings A and B may contain in any position thereon one or two groups of the formula ##STR137## wherein:

R and R³ each is selected from hydrogen, lower alkyl or hydroxy substituted lower alky;

R¹, R², R⁴ and R⁵ each represents hydrogen or 1-3 substituents selected from lower alkyl, lower alkyl substituted with lower alkoxy, phenyl, Cl, Br, or lower alkanoylamino, lower alkoxy, lower alkoxy substituted with lower alkoxy, phenyl, Cl, Br, or lower alkanoylamino, chlorine, bromine, amino, lower alkylamino, lower alkylamino substituted with lower alkoxy, cyclohexyl, phenyl, Cl, Br, or lower alkylsulfonyl, lower alkylthio, lower alkanoylamino, or cyclohexylamino;

wherein each aforesaid aryl moiety is 6-10 carbons;

X is --S-- or --NH--;

n is 1 or 2; and

m is 0, 1, or 2.

14. The composition of claim 1, wherein the colorant comprises one or more compounds of the formula ##STR138## wherein:

R is --OH, --COOR¹ or --COX wherein R¹ is --H or lower alkyl and X is halogen;

either or both of A and B may contain at least one additional group of the formula ##STR139## wherein n is 1 or 2; and

wherein each of rings A and B may be further substituted with 1-3 radicals selected from the following;

lower alkyl which may be substituted with lower alkoxy, aryl, Cl, Br, or lower alkanoylamino;

lower alkoxy which may be substituted with lower alkoxy, phenyl, Cl, Br, or lower alkanoylamino;

chlorine;

bromine;

amino;

lower alkyl amino which may be substituted with lower alkoxy, cyclohexyl, phenyl, Cl, Br, or lower alkanoylamino;

arylamino, arylthio, or aroylamino, wherein each aryl is 6-10 carbons;

lower alkylsulfonyl;

lower alkylthio;

lower alkanoylamino;

or cyclohexylamino.

15. The composition of claim 1, wherein the colorant comprises one or more compounds of the formulae ##STR140## wherein each A is selected from the following radicals:

##STR141## wherein;

R and R'"'"' are selected from hydrogen, fluorine, chlorine, bromine, alkyl, alkoxy, phenyl, phenoxy, alkylthio, or arylthio;

n is 0, 1 or 2;

R₁ and R₂ are each selected from hydrogen;

cycloalkyl;

cycloalkyl substituted with one or two of alkyl;

--OH, alkoxy, halogen, or hydroxy substituted alkyl;

phenyl;

phenyl substituted with alkyl, alkoxy, halogen, alkanoylamino, carboxy, cyano, or alkoxycarbonyl;

straight or branched lower alkenyl;

straight or branched alkyl of 1-8 carbons and such alkyl substituted with the following;

hydroxy;

halogen;

cyano;

succinimido;

hydroxysuccinimido;

acyloxysuccinimido;

glutarimido;

phenylcarbamoyloxy;

phthalimido;

4-carboxyphthalimido;

phthalimidino;

2-pyrrolidino;

cyclohexyl;

phenyl;

phenyl substituted with alkyl, alkoxy, halogen, hydroxy alkanoylamino, carboxy, cyano, or alkoxycarbonyl;

alkylsulfamoyl, vinylsulfonyl;

acrylamido;

sulfamyl;

benzoyl-sulfonicimido;

alkylsulfonamido;

phenylsulfonamido;

alkoxycarbonylamino;

alkylcarbamoyloxy;

alkoxycarbonyl;

alkoxycarbonyloxy;

alkenylcarbonylamino;

groups of the formula ##STR142## wherein Y is --NH--, ##STR143## --O--, --S--, or --CH₂ O--;

--S--R₁₄ ;

SO₂ CH₂ CH₂ SR₁₄ ;

wherein R₁₄ is alkyl, phenyl, phenyl substituted with halogen, alkyl, alkoxy, alkanoylamino, cyano, or alkoxycarbonyl;

pyridyl;

pyrimidinyl;

benzoxazolyl;

benzimidazolyl;

benzothiazolyl;

radicals of the formula ##STR144## --OXR₁₆ ;

--NHXR₁₆ ;

--X--R₁₆ ;

--CONR₁₅ R₁₅ ; and

--SO₂ NR₁₅ R₁₅ ;

wherein R₁₅ is selected from H, aryl, alkyl, and alkyl substituted with halogen;

--OH, phenoxy, aryl, --CN, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, or alkoxy;

X is --CO--, --COO--, or --SO₂ --;

R₁₆ is selected from alkyl and alkyl substituted with halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, and alkoxy; and

when X is --CO--, R₁₆ also can be hydrogen, amino, alkenyl, alkylamino, dialkylamino, arylamino, aryl, or furyl;

alkoxy;

alkoxy substituted with hydroxy, cyano, alkanoyloxy, or alkoxy;

phenoxy;

phenoxy substituted with one or more of alkyl, carboxy, alkoxy, carbalkoxy, or halogen;

R₁ and R₂ can be a single combined group such as pentamethylene, tetramethylene, ethyleneoxyethylene, ethylene sulfonylethylene, or ##STR145## which, with the nitrogen to which it is attached, forms a ring;

R₁₇ is alkyl, aryl, or cycloalkyl;

R₃ is alkylene, arylene, aralkylene, alkyleneoxy, or alkyleneoxyalkylene;

Z is a direct single bond, OCO, O, S, SO₂, R₁₇ SO₂ N═

, ##STR146## arylene, or alkylene;

R₄, R₅, and R₆ are each selected from hydrogen or alkyl;

R₇ is carboxy, carbalkoxy, or (R)_n ;

R₁₀ is hydrogen, alkyl, and aryl;

R₈ and R₉ are each selected from hydrogen and substituted or unsubstituted alkyl, aryl, or cycloalkyl

R₁₁ and R₁₂ are each selected from hydrogen, alkyl, hydroxyl, or acyloxy;

B represents the atoms necessary to complete a five- or six-membered ring and is selected from ##STR147## each P and Q is selected from cyano, carbalkenyloxy, carbcycloalkyloxy, carbalkoxy, carbaryloxy, carbaralkyloxy, carbamyl, carboxy, N-alkylcarbamyl, N-alkyl-N-arylcarbamyl, N,N-dialkylcarbamyl, N-arylcarbamyl, N-cyclohexylcarbamyl, aryl, 2-benzoxazolyl, 2-benzothiazolyl, 2-benzimidazolyl, naphthyl, pyridyl, pyrimidinyl, 1,3,4-thiadiazol-2-yl, 1,3,4-oxadiazol-2-yl, SO₂ alkyl, SO₂ aryl, and acyl, or P and Q may be combined as ##STR148## wherein R₁₇ is defined above and R₁₈ is CN, COOH, CO₂ alkyl, carbamyl, or N-alkylcarbamyl;

wherein at least one of A, P, and Q for each dye molecule must be or bear a condensable group selected from carboxy, carbalkoxy, carbaryloxy, N-alkylcarbamyloxy, acyloxy, chlorocarbonyl, carbamyloxy, N-(alkyl)₂ carbamyloxy, amino, alkylamino, hydroxyl, N-phenylcarbamyloxy, cyclohexanoyloxy, and carbocyclohexyloxy;

wherein when an (R) substituent is present, n is an integer up to the available substitution sites on the ring; and

wherein in the above definitions, each alkyl, aryl, or cycloalkyl moiety or portion of a group or radical may be substituted with hydroxyl, acyloxy, alkyl, cyano, alkoxycarbonyl, halogen, alkoxy, or aryl, aryloxy, or cycloalkyl.