CA1323461C

CA1323461C - Water-dissipatable polyester and polyester-amides containing copolymerized colorants

Info

Publication number: CA1323461C
Application number: CA000590040A
Authority: CA
Inventors: Linda Jane Adams; Max Allen Weaver
Original assignee: Eastman Kodak Co
Current assignee: Eastman Chemical Co
Priority date: 1988-02-05
Filing date: 1989-02-03
Publication date: 1993-10-19
Anticipated expiration: 2010-10-19
Also published as: WO1989007118A1; US4804719A; EP0400038A1; JPH03502339A

Abstract

ABSTRACT OF DISCLOSURE

Water-dispersible polymeric material such as polyesters and poly(ester-amides) containing water-solublizing 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.

Description

3 ~

Water-Dissi~atable Polyester and Polvester-hmides Containinq Copolymerized Colorants This invention concerns certain water-dissipatable, water soluble, water dispersible, or water suspensible polymers, all hereinafter termed water-dispersible, containing colorants as an integral part o~ the polymer structures. The polymers which are thus colored are useful in adhesives, coating materials, films, pacXaging materials, and products which can be dissolved or otherwise dispersed in cold or hot water. Aqueous dispersions of the colored polymers have utility as inks, paints, and other coatings where it is advantageous to use aqueous as opposed to organic solvents.

The descriptions and manufacture of exemplary base polymer compositions useful herein are given in U.S.
Patents 3,734,874, 3,779,993, 3,828,010, 4,233,196, and 3,546,008. These base polymers are modi~ied according to the present invention which is defined in its broad sense as water-dispersible polymeric material having lir.king groups comprising at least about 20 mole % carbonyloxy and up to about 80 mole %
carbonylamido, said material containing water-solubili~ing 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, o~ colorant comprising one or more heat stable organic compounds initially having at least one condensable group. The aforementioned eguiva:Lents encompass the various condensable .~ ~
f ~ .

- 2 - j 3 ~ .3 ~

derivatiYes thereof includin~ c~rbalkoxy, carb~ryloxy, N-alkylcarbamyloxy, acyloxy, chlorocarbonyl, carbamyloxy, N-(alkyl)2carbamyloxy, alkylamino, N-phenylc~rb~myloxy, cyclohex~noyloxy, and carbocyclohexyloxy.
In a highly preferred embodiment o~ the present invention, the polymeric material contains carbonyloxy linking groups in the linear molecular structure wherein up to 80~ of ~aid linking groups may be.carbonylamido linking groups, the polymer hsving an inherent viscosity of from about 0.1 to about 1.0 measured in fl 60l40 parts by weight solution of phenol/te~rachloroethane ak 25C and at a concentration of 0.25 gram uf polymer in lO0 mL of the solvent, the polymer containing substantielly equimolar proportions of acid equivalents (100 mole percent) to hydroxy and amino equlvalents (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 ~ cld, hydro~yl and ~mino equivalents being equ~l to 200 mole percen~, of et least one di~unctional sulfomonomer contalning at ies~t one cationic ~ulfonate group st~teched to an ~romatic or cycloaliphatic nucleus ~herein the functional groups sre hydroxy, c~oxyl or amino;
(c) at least one difunctionsl react~nt 3elected from a glycol or a mixture o~ a glycol and diamine hav~ng two -NRH groups, the Klycol : 35 contalning two -CH2-OH group~ of which :
~ :' ~ . ' ' - 3 ~ r~ ~ ~

(1) ~t least 10 mole percent, b~sed on the totsl mole percent of hydroxy or hydroxy and amlno equivalents, is a poly(ethylene glycol) having the structur~l for~ula:
HtOCH2~H2tnOH, n bein2 ~n integer of from 2 to about 2Q, or (2) of which from about 0.1 to less than ~bout 15 mole percent, based on the total mole percent of hydroxy or hydroxy and amino equivalents t is a poly(ethylene glycol) having the structural formula:
HtocH2~H2tnoH, n being an integer o~ between 2 and about 500, and with the p~oviso that the mole percent of ~aid poly(eth~lene glycol) wi~hin said r~nge is inversely proportional to the quantity of n with said range;
td) from none to at least one difunctional react~nt selected from 8 hydroxycarboxylic ~cid having one -C(R)2-OH group, an amino-carboxylic acid having one -NRH
group, ~nd an amino-~lcohol~havin~ one -C(R)2-OH group and one -NRH group, or mixtures of s~id difunctional re~ctants;
wherein each R in the (c) or (d~ r~act~nts ~s a H ~tom or an ~lkyl group of 1 to 4 carbon atoms; and (e) from ~bout ~.1 mole ~ to about ~5 mole ~, based on A total 0~ cid, hydr~xyl ~nd : .

.
.: , - : ~ -- . .

.. ; ' .

~ ~ 32~ ' 31 amino equivalents being egual to 200 mole %
of colorant having at least one acid, hydroxy or amino group reacted onto or into the polymer chain.
In the above polymeric material it is preferred that very minor, e.g. 7 less than ahout 10 mol % based on all reactants, of reactant (d) is employed, that at least about 70 mol % of reactant (c) is glycol, and that at least about 70 mol % of all hydroxy equivalents is present in the glycol.
Colorants capable o~ withstanding the conditions of polymerization and which in varying degrees are useful in the present invention are disclosed, for example, in U.S. Patents: 4,2~7,306; 4,359,570; 4,403,092;
4,617,373; 4,617,374; 3,278,486; 3,359,230; ,401,192;
3,417,048; 3,42~,70~; 4,088,650; 4,116,9~3; 4,141,881~
4,477,635; 4,231,gl~; 3,104,233; 4,202,~14; 4,279,802;
4,2g2,232, 4~344,767; 2,571,319; 3,034,920; 3,48g,713, and 3,372,138. Particularly suitable of the above anthraquinone type colorants are those of U.S. Patents:
4,359,570; 4,267,306; and 4,403,092. ~hese colorants includa the carboxy, hydroxy, ester, acid halides, and amino derivatives of such types of compounds as anthraquinones; methines; bis-methines, 3H-dibens[f,ij]-isoquinoline 2,7-diones (anthrapyridones); triphenodi-oxzines; fluorindines; phthaloylpyrrocolines; coumarins;
phthaloylacridones; 4-amino-1,8-naphthalimidesi thioxan-thones; 2,5-arylaminoterephthalic acids (or esters);
benzanthrones; 3,6-diaminopyromellitic acid dimides;
quinophthalones; naphthalene 1:4:5:8-tetra carboxylio bis-imides; isothiazoloanthrones; anthrapyrimidines;
anthrapyrimidones; and indanthrones. A variety of ~ ~A

.

- 5 - .L 3 ~

shades, e.g., ~rom yellow to blue can be obt~ined by either mixing the colorants during polymerization, or by mixing the polymeric compositions containing individual colorRnts.
5~ Preferred colorant types having excellent stability (good color yield snd llttle, i~ any, shlft in color) include the following: methines;
anthraquinones; 3H-dibenz[f,ij~isoquinoline-2,7-diones (Anthrapyridones); benzo[f~pyrido[l,2-a]
indole-6,11-diones; thioxanthene-9-ones; coum~rins;
2H-1,4-benzoxazine-2-ones, triphenodioxazines ?
5,12-dihydroquinoxalino[2,3 b3phenazine (fluorindines); 3,6-diaminopyromeliitic acid diimides; 2,5(3)diaryl~minoterephthalic acids (esters); 4-amino-1,8-naphthalimides; naphtho [1',2~3~:4,5]quino[2,1-b]quinazoline-5,10~diones;
7H benzo[de]snthracen-7-ones (benzanthrones);
7H-benzo[e]perimidin-7-ones;

6,15-dihydro-5,9,14,18-anthrazinetetrones (indanthrones); quinophthalones;
7H-benzimid~zo[2jl-~[de]isoquinolin-7-ones;
5H-benzo~]phenoxazine-5-ones; 6H,13H-pyrido[1,2-~:
3,4-b]diindole-~,13-diones; ~nd diindolo t3,2.1-~e-3',2',1'-i~][l,s~ naphthyridine-~,l 3-dibnes.
The anthr~pyridones (isoquinoline deriv~tives or subs~ituted 3H-dibenzo~ ]Isoquinoline-2,7-diones~
of the general formul~ (I), for examples, ~hown below, show excellent therm~l ~t~bility where R, :~
R2, R3, R4, Z snd Z' are selected from:hydrogen or, for example, a wide range~of substituents including those shown in TsbIe 18 ~elow, giving colors:including yellow, orange, red, and blue.

: : ` ~ ' : -`

:' ' ` :, : ~ ~
- ~, : . : .. . : -.
:
- ;

. .
.
.

- 6 - i~ 2~a~

Exemplary anthrapyridones have the formule \ ~ / \lp--R
.s~ \./ \./ ~---R

R4 B ~ - R -Z
(1) wherein: R is hydrogen, cyclo~lkyl or alkyl; X is -O-, -S-, or -NH-; -X-Rl-Z in combination is hydrogen or h~logen; Rl is selected from -slkylene-Z', -arylene-Z', -cyclo~lkylene-Z', -aralkylene-Z', -cycloalkylenealkylene-Z', -slkarylene-Z', -alXylenecycloalkylenealkylene-Z', -alkylenearalkylene-Z~, or alkylenecycloalkylene-Z', wherein -Z and Z' are independently selected from hydrogen, -SO2R , -SO2NR R , -NHSo2R5, -N(R5)So2R5,--N(R5)GoR5, -NHCoR5, -OH, -SR5, -oR5~ -NHR5. -NR5R5, -SO2N R , -CoNHR5,--~oNR5R5,--~02R5, -OCOR , -OC02R , --oOCNHR5 ~ _~H2 N/ ~ H2 ~ ~C _ il~ ~i CH2 H2 ~ H2 & :

r ~ wherein R5 l~ hydrogen, ~Ikyl, ~ : :
~llyi, ~ryl, cycloalkyl, hydroxyalkyl, alkoxyalkoxyalkyl, ~l~oxy~lkyl, hydroxy~lkoxy, hydroxyslkoxyalkoxy, ~lkoxyc~rbonylalkyl or : carboxyaryl, end when X is -O-, or -NH-, -~1-Z in comb~nst1on also cun be hydrogen, R2 ~s hydrogen, : ~ alkyl, ~ryl, cyano, ~lkoxyc~rbonyl~ aryIoxycvrbonyl, : nralkoxycarbonyl, cycloalkylalkoxycarbonyl, COCl, :

.' - 7 - ~ 3 ~ .3~

carboxy, carb~myl, N-alkylc~rb~myl, N, N-d i a 1 kylcarbamyl, N-alkyl-N-arylc~rba~yl, N-~rylcarbamyl, N-cyclo~lkylc~rb~myl, ~cyl, aroyl, amino, alkylamino, dialkylamino, Arylamino, cycloalkyl~mino, slkoxy, hydroxy, ~lkylthio or arylthio; each of R3 and R4 is hydrogen, alkyl, halogen or alkoxy; wherein each of the above alkyl, alkylene, aryl, arylene, cycloalkyl or cyclo~lkylene moieti~s or portions of a group or radical m~y be substi~uted where appropriate with 1-3 substituents selected from hydroxyl, acyloxy, alkyl, cyano, carboxy, al~oxycarbonyl, alkoxycarbonyloxy, halogen, alkoxy, hydroxyalkoxy, hydroxyalkyl~ aryl, aryloxy, or cycloalkyl; and wherein, when ~he above hydroxyl substituent ls absent or multicondens~ble groups are desired, at least one of R, R2, R3, or R4 carries one or more condensable groups.
In particularly preferred embodiments of the invention: X is -NH- snd -Rl-Z is combination is aryl, aryl substitueed with 1-3 of alkyl, alkoxy, halogen, hydroxyalkyl t hydroxyalkoxy or scylamido, alkyl or alkyl substituted with 1-3 of hydroxyl or acyloxy, cycloalkyl or cyclo~lkyl substituted with 1-3 of alkyl; -~ Rl-Z ln combination is H; R is alkyl; R~ is alkoxycarbonyl, hydroxyalkylamino, or cyano; and R3 ~nd R4 are each hydrogen.
In all of the above definitions the al~yl or alkylene moleties or portions o~ the various groups contain from 1-8 carbons 9 straight or br~nched chain, the aryl or arylene nuclei contPin from 4-10 carbons, ~nd the cycloalkyl or cycloalkylene nuclei contain from 4-6 carbons. The su~fix "ene," is used herein to designate a divslent radical or group, and the term "cycloalkyl" may be used interchangesbly wlth "cycloallphatic."

.

.
.' ~ . .
.

- 8 - ~ 3 2 ~

The present color~ntlpolymer compositions give stable aqueous dispersions, ~howing no settling or sludging-out of the colorant. Since the colorants ~re copolymerized, they cannot be removed from the polymer by ex~raction or by contact with the body thus minimizing toxicologicsl concerns as regards exposure to organic materi~ls. T~e inventlon ~llows the prepar~tion of squeous solutions of colored polymer having high tinctorial value ~nd good color stability to change in pH, temperature, concentration and the like Further preferred structure types given by exemplary formul~e below gener~lly exhlbit very acceptable thermal stability. These basic structures are modified as necessary by incorporation of known re~ctive groups such RS -COOH, -OH, ester, or the like. In these formulae, each available position on each ring may be unsubstituted or substituted with an R substituent as defined above.

.~ \

D sf , \, ~J\, ~
Rt 11 11~
B & ' ~ ' ,~-~ ,8, ~ , ,o,~
R I 11 1 - 11 R 111 1 1 li ~-~ \S~ -/ W \~!f W ~-~ 7 35~

.

.

, _ 9 _ ~ /3 i wherein X is , ~or ex~mple , --NHC6H5 ~ and Y is --N02 or NHCOCH3.

.~ \, ItR
IIJHCH3 ~ j CH2C~12 N~ ~N CH2cH2oH R ~ R

~H3 i1/ ~t~
15 Rt li l; tR Rt li Cl~ R
E~ R

_ ~R ~ -R~ C~

3 0 ~ b ~X\R

R~ ~ ~R

:

:

, . , ~ . . ` , . , R ~R

R;~

N li _-f ,~
,Q ~! :
~1 i T ti R~ R ~ R X\C=HC~

/CH~C~y A
,j f ~ $ ,CH=C~

CH{:H=C/X

, , .

'i3 ,~ ~,/ \,~ \
11 1 --ItR
R~'/ \ / ~'/

~R~ OH R~ ~,~ ~ ~X

R/~ . C~ i il R~/ \O/ ~O

./-~

Rf~' \/ ~O
x,R R
li X~ R
il i ! i I~
R/~ E~ ~5 ~R

I!JHR ~ :
R~. ,S .~"5 .~R ~ R~ R ~ ~R
il U: i U 1 1 ~ U !J~
~- a ~ ~ B

.

.

.

- 12~3~

' R
~ T
5 ~., ,8, ~ ~., ,'i, 4' ~

,~ / \S/ \ ~; R~ ~, ' 95 .

R~S? ~R ~ Bnd ~ ~ \/ ~' wherein the various R, X, and Y substitutents &re as 15 defined above.
~ xemplary specific colorants sre given below.
~H3 ~ \
. R ~
i1 i1~
\COOH

1~/\~ 2c2 If ~ OOCH, :

: : :
.

. . ..

~3~

~oNH~ 2 H4oH

i! i1 i1 ~'' `e,' \C02( 2H40H ,"

, ~ ~H \ ~ c2H4oH
,9~ \,~ \,/ ~, U U
s~ \ ~
~2 . _.
R ~H~
\ / \jj/ ~ \CH20H.

~HCOCH3 :~HCH

~ ! ~
HOCH2CH2-N~ ~ 2 : HCH3 :
:
, `:
~`' :: ~ : : : : :
:
-, ~ ; ' ' ' ~';

- : ~ . : .. . .
'. ~

. ` - ' ', - . , ' . . '.'., . . ' , ' ' ' . ' ,~ ' ' ' , , ' ' , , , ' ' ' - 14 - ~3~

iSSS \~
~IH ~

~, i~ \li r' H\~J/ \i/ :~i 3 C02C2H4 ) 2N--! ~ / !,o, ! ~

(HOC2H4 ~2N--!~ wi~o \-=-/ :
~1 HCH2CH2~ t il t i i li 1~1 ~CHzCH20H
~2H4H
i1 i: i i i1 . .
' . "' ~ '. " ,. ' . . ' : , .

' ~~

11 i I 1 11 ~ ~C02CH3 0--~ ~.

~OOH

~ ~ -NH-I Ij \ --/
~OOH
~OOC2~5 f ~---NH--i il \ -- /

~OOH

CH~O--~ ~ -NH-I I~ NH ~ OCH3 ~OOH
~OOC2H5 CH30-~f ~-~NH~ NH~ -OCH3 ~OOC2H

i! Ui O~C~H5 ~ :

: ~ ~ \ ~ \ H ~ ~ ~S~ ~S~ ~
~ I ~I N--CH2--C~ CH2--N j I j Q N Cu2~HcH2~H

: ~
. ` . . . , - ,: ::
... , . . - .
:, , -. , ' ~ : '' . .
.
~- ''.... ' ' ~
.

HOC H O--I \

,~ \,/
U
~H2 S02N ( C2H4H ) 2 i!

r~
i! 1 i!
~,/ \~/ ~./
~H3 / ~ ~OOH
. U, il U
~,/ \ / \.~

., ,-, ~
li iu I 2 5 1H~ C 1 O~Nt C2H40H ) }~r:

C~ ~i~ \
~ OOH

:: - - . . , . ..

.
, ~CH2CH20H C~ H2CH20H

\,= / \,=,/
0~ s f\N T \~

I! ! I ~i i ~-, HOOC~ ~ o T ~i I i HOOC~ ~ ~ / W \~

! li i, i i - .

~_,~ 2C2H5=

if-\Q~\~
` ' b R /C22~5 : : :
,b =.' b : ~ :
~ ::
:

- . .
', ,' . ' ~ ' .
.. . . . . .

, - 18 _ 1 3~3~

Other SUch useful colorflnts include those of the gener~ 1 f ormu 1 ~e, y~ 5~
COOH R( O_ 3; ¢ ~R( o_ r ) ANTHRAPYR I DONES
g~;3 ~ 5-3) HOOC~< X\R ( _ ~,/ \,~/ \.~ X~

ANTHRA I SOTH IAZOLES

_yl ~ ii ~i t~yl_~f ~
HOOC~ ~R ( ~ s ~OOH
ANTHRAPYR I M I D I NES

~ a ) ~ Y \ , and \ /~ COOH

HOOC
ANTHRAPYRIMIDONES
R ( O--a ~5 o--a ) 35 }~OOC~
~ O-~
PHTHALOYLACRIDONES

-. ' . : -' . , ' , ' - 19 ~

wherein each Y is -NH- or -S- and each R
represents 0-3 substituents RS defined ~bove. In these formul~e, the -COOH substituents include ~he various esters thereof.
Preferred general chemical ~tructures of colorants are given in formulas I, II, III, ~nd IV
below. See, for example, U.S. Patents: 4,403,092;
4,359,570; and 4,267,306.
(I) ~ +

~1 wherein: Rl and R2 each represents hydrogen or l-3 substituents, depending on the number of T
substituents present as defined below, sald Rl and R2 being independently selected from alkyl, alkoxy, alkyl~mino, ~lkylsulfonyl, alkylsulfonyIamino, alkanoylamino, aroylRmino, alkylthio, arylamino, amino, cycloalkylamino, alkanoyl, aroyl, arylsulfonyl, CF3, arylsulfamoyl, cyano~ halogen, hydroxyj nitro, sulfamoyl, al~ylsulfamoyl, dialkylsulfamoyl, carbamoyl, al~ylcarbamoyl and dialkylcarbamoyl; and T is l 4 independently selected substituents of the formuls ~ 4 S02~--R5--Q

in sny 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(SO2R)-, -ORO-, -OR-, -OROR-, -ORORO-, -ORSR-, ~nd -ORN(COR)RO-, wherein R is arAlkylene, alkylene, ~rylerle or cycloslkylene;

.

1 3 ~

23 represents h~drogen or 1-3 substituents independently selected from alkyl, alkoxy, cy~no, sl~noylamino, halogen, and a 1 ky 1 t h i o ;
each R~ is independently selected ~rom hydrogen, alkyl, cycloalkyl, and aryl;
each R5 is independently selected ~rom alkylene, arylene, cycloalkylene~
arylenealkylene, ~ryleneoxyalkylene, arylenethioalkylene, alkylenethioalkylene, ~lkyleneoxyalkylene, arylenedialkylene, and cyclohexylenedialkylene;
Q represents 1-3 groups independen~ly selected from acyloxy, -OCOO-alkyl, hydroxy, c~rboxy, -COO-alkyl, -COO-sryl, ~nd -COO-cyclo~lkyl;
~nd wherein the alkyl, ~lkylene, cycloalkyl, cycloalkylene, sryl and arylene moieties or segm~nts of the above Rl-R5 groups are unsubstituted or substituted with 1-3 of the following: hydroxy; h~logen; cyano;
amino; ~lkoxy; alkoxycarbonyl; Aroyloxy;
~lkoxyalkoxy; hydroxyalkoxy; succinimido;
glutarimido; phthalimido; phthalimidino;
~5 2-pyrolidono; cyclohexyl; phenoxy; phenyl;
phenyl substituted with Alkyl, ~lkoxy,:~
alkoxyc~rbonyl, h~lo~en, ~lkanoyl~mino or cy~no; ::
~crylamido; ~lkenyl; benzoylsulfonicimido;
groups of the formula 3 0 ~ Q ~ :

: ~ 2 : wherein Y is -NH~ hlkyl, -O-, -S-, >CHOH, or -CH2-0-; -S-R6 wherein R6 ~s selected from al~yl, ~lkyl ~ubstltuted with 1-3 ~:
of halogen, hydroxy, phenoxy, ~ryl, cyano, : ::
.
' ' : :, . .
, ' . ' ' . ' ` - ' `' ' . ' -~ 3 ~

cycloalkyl, ~lkylsulfonyl, alkylthio, alk~noyloxy, or ~lkoxy, phenyl, ph~nyl -substituted with one or more o~ halogen, alkyl, alkoxy, slk~noylamino, cy~no or ~lkoxycarbonyl, pyridyl, pyrimidinyl, 2-benzoxazolyl, 2-benzimidazolyl, 2-benzothiazolyl or ~ ~ -R

-SO2R ; -COOR8; -OXR8; -NH-X-R8;
-CoNR7R7; -So2NR7R7; wherein X is -CO-, COO-, or -SO2; R8 is selected from ~lkyl, aryl, c.ycloalkyl, and each of these groups unsubstitùted or substitu~ed with 1-3 substituPnts independently selected from halogen, hydroxy, phenoxy, aryl, alkyl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, ~nd alkoxy, and when X is -CO-, R8 i~ further selected from hydrogen, amino, alkenyl, alkylamino, dialkylamino, arylamino and furyl; R7 is selected from hydrogen, alkyl, aryl, ~lkoxy:~ubstituted sryi, cyclo~lkyl, amino, ~lkylamino, dialkylamino, arylamlno, furyl, and alkyl substituted with 1--3 o~ halo~en, hydroxy, phenoxy, aryI, cyano, cycloalkyl~ ~ :
alkylsulfonyl, ~lkylthio, alkanoylaxy, or alkoxy; alkoxy substitu~ed with 1-3 of hydroxy, cy~no or ~l~anoyloxy; ~lkoxyalkoxy ~ubstituted with 1--3 of hydroxy, cyano, alkanoyloxy or Alkoxy; and phenoxy substituted with 1 3 of ~lkyl, alkoxy Dr : halogen.

.

';

~ 3 ~ L

(II) COOR)n ¦

wherein either or both of rings A and B may contain in eny position thereon onP or two groups of the formula ~ (COOR )m ~ - ~R5 wherein:

R ~nd R e~ch is selected from hydro~en, lower ~lkyl or hydroxy substituked lower alXyl;
Rl, R , R and R each represents hydrogen or 1-3 substituents selected from lower alkyl, lower alkyl substituted with lower ~lkoxy, phenyl, Cl, Br, or lower alk~noylamino, lower slkoxy, lower alkoxy substituted with lower ~lkoxyt phenyl, Cl, Br, or lower ~lk~noylamino, chlorine, bromine, ~mino, lower ~lkylamino lower ~lkyl~mino substituted with lower~
~lkoxy, cyclohexyl, phenyl, Cl, Br, or lower al~ylsulfonyl,; lower ~lkylthio, lower ~:
alkanoylamino, or cyclohe~ylamino;
~nd whereln e~ch a~oresaid ~ryl moiety 30 is 6-10 carbons; ~ S- or -NH-;; n~

~: 35 :

.
: ~ : .

: ' ' - . :

:

~ 3 ~

or 2; m is 0, 1, or 2.
(III) o RH4 C 2~ ~1~2H4R
H ~N~ --St B l! li A~tS \N~

wherein R is -OH, -COORl or -COX wherein R is -H or lower alkyl, and X is lQ halogen, either of rings A or B may cont~in one or more groups of the formula ,_,~ (CH2R)1 or 2 -NHCH --/ S

wherein R is ~s deflned above, and each of rings A snd B m~y be ~urther substituted with 1-3 substituents selected from: lower ~lkyl which m~y be su~s~ituted with lower alkoxy, aryl, Cl, Br, or lower alkanoylemino; lower alkoxy which msy be substituted with lower slkoxy, phenyl, Cl, Brs or lower~alkanoylamino; chlorine;
bromine; amino; lower:alkyl ~mino:which msy be substituted with lower alkoxy, cyclohexyl, phenyl; Cl, Br, or lower alkanoylamino; ~ryl:amino; arylthio; or aroyl~mino; lower alkylsulfonyl; lower lkylthio; lower alkanoyl~mino; or cyclohexyl~mino; wherein e~ch ~ryl ls 6-10 carbons.
~lV
C=CH--A, A~H=~ =CH--A, : ~ ( ' )n ' :

, '-' ~' :
, ~ 3~ L

\C=HC--~ ~H=C/P
Q/ ~; \R 3--Z--R 3 ~; \Q

and \C=CH-- ~ ~-- f ~--CH=C

wherein e~ch A is selected from the following r~dicals:

\, ,/
~U--Rl o (R)nt [I [I t~R)n' (R)nt 11 11 ~ R~n~

~6 (l~)n ~ 1 (R)~/ \R
~ ' (R) \ ,~;~\ /O\ n~
i~ tR4 ~
~ R~ \R10 :
, ~ :

: ~ :
- : . -: , :
, - , '- : - ' - :
, .- , ~ :
: , ' , ' ~ 3 ~

$n Rlo h~R8 \~ \S/ \R

,~12 \. ;~ /X\(R )n ÇH

I ~H
R/~ CH--1~ 3 R1~ ~H=CH--( )n 4, ~R5 ~ ~ a li ~- R and wherein:
: R and R ' sre selected from hydrogen, ~
30 $1uorine, chlorine, bromine 9 ~lkyl 3 ~lkoxy, phenyl, phenoxy, alkylthio, or ~rylthio; n i~ O, 1 or 2;
~ Rl and R2 ~re each selected from hydrogen; cyclo~lkyl; cyclo~lltyl ~ubstituted with one or two o~ ~lkyl, ~H, ~lkoxy, halogen, or hydroxy substituted slkyl; phenyl; phenyl substltuted with alkyl, alkoxy, halogen, alkanoyl~mino, c~rboxy 3 :

' ~ 3 ~

cyano, or ~lkoxycarbonyl; ~tr~ight or br~nched lower alkenyl; straight or br~nched alkyl of 1-8 carbons and such ~lkyl substitu~ed wi~h the following:
hydroxy; hAlogen; cyano; succinimido;
hydroxysuccinimido; acyloxysuccinimido; glut~rimidoi phenylcarbamoyloxy; phthalimido;
4-carboxyphthalimido; phthalimidino; 2-pyrrolidono;
cyclohexyl; phenyl; phenyl substituted with ~lkyl, alkoxy, halogen, hydroxy alkanoyl~mino, c~rboxy, cyano, or alkoxycarbonyl; alkylsulfamoyl;
vinylsulfonyl; acrylamido; sulfamyl; benzoyl-sulfonicimido; alkylsulfonamido; phPnylsulfonamido;
alkoxycarbonyl~mino; alkylcarb~moyloxy; alkoxy-carbonyl; alkoxyoarbonyloxy; alkenylcarbonylamino;
groups of the formula .
wherein Y is -NH~ slkyl, -O-, -S-, or -CH20-;
14i S2~H2CH2SR14; wherein R14 is slkyl, phenyl. phenyl substituted with halogen, slkyl, ~lkoxy, alk~noylamino, cyuno, or ~lkoxycarbonyl; pyridyl; pyrim~dinyl; benzoxazolyl;
benzimidszolyl; benzothi~zolyl; r~dicals o~ the formula ~ ~R15;

-XRl6; -~HXRl6; -X-R16; -CONR15 15 -SO2NR15R15; wherein RlS i~ ~elected from H, ~ryl, alkyl, ~nd ~lkyl sub~tituted with h~lo~en, -OH, phenoxy~ aryl, -CN, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, or alkoxy; X is -CO-, -COO-, or -SO2-; Rl~ is selected from ~lkyl ~nd ~lkyl . .
, .
, ~ 3~ 1 'J~

substituted with halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, ~lXylthio, alkanoyloxy, and slkoxy; and when X is -CO-, R16 also can be hydrogen, amino, al~enyl, alkylamino, dialkylamino, arylamino, sryl, or furyl; alkoxy;
alkoxy substituted with hydroxy, cyano, alkanoyloxy, or ~lkoxy; phenoxy; phenoxy substituted with one or more of alkyl, carboxy, alkoxy, carbslkoxy, or halogen; Rl snd R2 can be a single combined group such as pentsmethylene, tetramethylene, ethyleneoxyethylene, ethylene sulfonylethylene, or _~R17 ethylene -ethylene which, with ~he nitrogen to which it is attached, forms a ring and wherein R17 is alkyl, aryl, or cycloalkyl;
R3 is alkylene, arylene, aralkylene, or alkyleneoxyalkylene;
Z is selected from a direct single bond, -OCO-, O Q
' ~ 2 ~ 17S02N , - Oe alkylene~ O-, -0~-arylene ~ O-, -S-S-, -O~Nff-alkylene-NH~O-, -OC~H-arylene-NHC~-, -O~O-, arylene, or alkylene;
R4, R5, and R~ are each selected from hydrogen or alkyl;
R7 is carboxy, carbalkoxy, or (R)n;
Rlo is hydrogen, ~lkyl 9 or ~ryl;
R8 and Rg are each selected from hydrogen and ~ubstituted or unsubstituted ~lkyl, aryl, or cycloslkyl Rll ~nd R12 are each selected from hydrogen, alkyl, hydroxyl, or acyloxy;

28 - 1 3 ~

B represents the atoms necessary to comple~e a five- or six-membered ring and is selected from S\ / ~ ~S\ " ~
7 \ f 7 \ ~ 7 ~ \ -R / ~ R7 ~
R7 ,S~ ~R, ,N~
~. R 7 , ii .tR 7 ~ 7 il ~T R7 and / \-N-~ i each P and Q is selected from cyano, carbalkenyloxy, carbcycloalkyloxy, carbalkoxy, c~rbaryloxy, carbsralkyloxy, carbamyl, carboxy, N-alkylcarbamyl, N-alkyl-N-arylc~rbamyl, N,N-dialkylcarbamyl,N-arylcarbamyl, N-cyclohexylcarbamyl, aryl, 2-benzoxazolyl, 2-benzothiazolyl, 2-benzimidazolyl, napthyl, pyridyl, pyrimidinyl, 1,3,4-thiadiazol-2 yl, 1,3,4-oxadiazol-2-yl, S02 slkyl, S02 ~ryl, ~nd ucyl, or P and Q m~y be combined as , 17\ ~13 wherein R17 is defined above ~nd R18 is CN, COOH, C02 ~lkyl, carbamyl, or ~-alkylcarbamyl;
wherein at le~st one of A, P, ~nd Q for each dye molecule:must be or bear a conden~abl.e group ~elected , ..
- . ' ' . , , ' - 29 - 1 ~ 2~

from carboxy, carbalkoxy, carbaryloxy, N-alkylc~rbamyloxy, acyloxy, chlorocarbonyl, carbsmyloxy~ lkyl~2carbsmyloxy, amino, alkylamino, hydroxyl, N-phenylcarbamyloXY, cyclohexanoyloxy, or carbocyclohexyloxY;
wherein when an (R) substituent is present, n is any integer up to the ~vailable substitut~on sites on the ring; ~nd wherein in the above definitions, each alkyl, aryl, or cycloalkyl moiety or portion of a group or radical may be substituted where flppropriate with hydroxyl, acyloxy, alkyl, cyano, alkoxycarbonyl, halogen, alkoxy, or aryl, aryloxy, or cycloalkyl.
In further preferred embodiments of the invention:
(A? the water-dispersible polymeric material comprises (A) an acid component (moiety) of ~rom about 75 to ~bout 84 mole ~ isophthalic acid snd conversely from ~bout 25 to about 16 mole ~ 5-sodio-sulfo-isophthalic acid, (5) a glycol component ~moiety) o~from about 45 to about 60 mole ~ diethylene glycol ~nd conversely from about 55 to ~bout 40 mole ~
1,4-cyclohexanedimethanol or ethylene glycol or mixtures ~hereof 9 ~nd (e) from nbout 0.5 to about 10 mole ~ of mono- or difunct~on~l colorant m~terial;
wi~h regHrd to the polymer, the ~erm "moiety" as used h~rein designates the re~idual portion, for example, of the reactan~ scid or glycol or condens~ble deriv~tive thereof which ~ctu~lly enters into or onto the polymer chain during the~ ondens~tion or polycondensatlon r~sction;
(B~ the inherent vi3cosity of the w~ter-dispersible pol~meric materi~l is from about 0.20 to about 0.38, the s~id acid component ~mo~ety) comprises ~rom ~bout 80 to About 83 mole % i~oph~halic acid ~nd conver~ely from ~bout Z0 to about 17 mole ~

: .

-, ~ 3 ~
~o 5-sodiosulfoisophth~lic ~cid, and the s~id glycol component (moiety) comprises from about 52 to about 56 mole ~ diethylene glycol and conversely from about 4~ to about 44 mole ~ 1,4-cyclohexanedimethanol;
~C) the polyester materials h~Ye ~n inherent viscosity of from ~bout 0.28 to ~bout 0.~8, an ~cid moiety of from about 75 to ~bout 84 mole ~ isophth~lic ~cid snd conversely from about 25 to about 16 mole S
5-sodiosulfoisophthalic acid, ~nd ~ glycol moiety of from about 45 to about 60 mole ~ diethylene glycol ~nd conversely from about 55 to ~bout 44 mole ~
1,4-cyclohexsnedimethanol or ethylene glycol or mixtures thereof; and (D) the acid moiety comprises from About 80 to about 83 mole ~ isophthalic ~cid and conversely from about 20 to about 17 mole ~ 5-sodiosulfoisophth~lic acid, ~nd said glycol moiety comprises from about 52 to ~bout 56 mole ~ diethylene glycol and conversely from about 48 to about 44 mole ~ -1,4-cyclohexanedimethanol.
The inherent viscosities (I.V.) of the particul~r polyester materials useful herein r~nge from ~bout 0.1 to ~bout 1.0 determined sccording to ASTM D2857-70 procedure, in A Wagner Viscometer of Lab Glass, Inc. of Vinel~nd, New Jersey, h~ving ~ 1/2 mL
caplllary bulb, using ~ polymer concentr~tion about Q.25~ by weight ln 60/40 by weight of phenolttetrachloroethane. The procedure is carried out by h~ting the polymerlsolvent ~ystem st 120~ for 15 minutes, cooling the solution to 25C ~nd me~suring the time of flow ~t 25C. The I.V. is c~lcul~ted from the eguation:

35 ~ ~n) 0 50~ c , .
.
, .` ~ '" ' ' ' ' . . ' ' - ' ' :

wherein:
(n) = inherent viscosity at 25C ~t R polymer concentration of 0.25 g/lO0 mL of solvent;
ln = natur~l logarithm;
ts = s~mple flow time;
to = solvent-blank flow time; and C = concentr~tion of polymer in grams per lO0 mL of _olvent = 0.25.
The units of the inherent viscosity throughout this application are in deciliters/gram. It ic noted th~t higher concentr~tions of polymer, e.g., 0.50 g of polymer/lO0 mL ~olvent may be employPd for more precise I.V. determinations.
In general, for one particul~r utility of the present invention, the present colored water-dispersible polyester materisls are excellent film for~ers for water-based printing inks. The polymers form stable solutions or dispersions in water and produce tough, flexible films ~n drying.
Films will form at temper~tures down to ~ust above the freezing point of water. The polymers in dispersion form may ~e plasticized if necessary, for example, with cert~in water i~miscible ph~halate esters to high degree~ of flexibility. Printing lnks prepared from the present concentr~tes ~re readily ~urther wa~er reducible (dilution) ~nd t~e fini~hed or press-ready inks typlc~lly compri~e in S by : :
weight, from about 55~ to ~bout 90~ water, preferably from about 65% to about 75~, ~nd from about 4~ to ~bout 30~ colored, ~ater-di~persible polymeric :
m~teri~l, preferably from ~bout 10~ to ab~ut 25S, from ~bout l~ to about 20~ pi~ment, prefer~bly from : ~bout 8~ to ~bout 15~. V~rious types of modiflers may be used 3UC~ as up to About 10.0~ polyvinyl alcohol or the ~ike. The lnks dry r~pidly upon printlng, wet surf~ces exceptionally well and have :
:

excellent adhesion to many plastic films and metal foil as well as to paper, glass, polyethylene and many o~her substrates. Both the 100% solids, water-dissipatable polymers and the corresponding aqueous dispersions thereof may be further pigmented by conventional techniques.
The aforedescribed colored polyester material is prepared according to the polyester preparation technoloyy described in U.S. Patents 3,734,874;
3,779,993; and 4,233,196, and the use of the term "acid"
in the above description and in the appended claims includes the various ester forming or condensable derivatives of the acid reactants such as the acid halides and dimethyl esters as employed in the prepara-tions set out in these patents. Among the preferred sulfo-monomers are those wherein the sulfonate group is attached to an aromatic nucleus such as benzene, naphthalene, diphenyl, or the like, or wherein the nucleus is cycloaliphatic such as in 1,4-cyclohexanedicarboxylic acid.
Dispersal of the present polyester material in water may be done, for example, at preheated water temperature of about a 180 to about 200~F and the polymer added as pellets to the vortex under high shear stirring. A Cowles Dissolver, Waring Blender, or similar equipment may be used. Once water is heated to temperature, additional heat input is not required. Depending upon the volume prepared, dispersal of the pellets by stirring should be complete within 15 to 30 minutes. Continued agitation with cooling may be desirable to prevent thickening at the surface due to water evapora~ion~
Viscosities of the dispersions remain low up to nonvolatile levels of about 25%-30%, but generally increase sharply above these levels. Viscosities of A

.

:~ 3 ~

the dispersions will be influenced by the degree of polymer dispersion (fineness) obtained which is affected by ~he dispersing temperature, shear1 and time.

Practice of the Inven_ion - IncorPorstion of DYe Into the Pol~mer Ex~mple 1 Components (a)-(g) comprising (a) 79.54 ~ (0.41 m) dimethyl ~erephthslate, (b) 26 . 64 g (O . 09 m) dimethyl-5-sodiosulfoisophthalste, ~c) 54.06 g ~0.51 m) diethylene glycol~
(d) 37.44 g (0.26 m) 1,4-cyclohexane dlmethsnol, (e) 0.74 g (0.009 m) anhydrous sodium acetate, (f) 100 ppm Ti catalyst as titanium-tetralsopropoxide, and (g) 0.68 g ~1.42 x 10 3 m) red colorant ~1,5-biscarboxyanilinoanthr~quinone) OOH
~,/'\./'\,9~' g~ ' '~ ~ H
~ OOH :
were added to a 500-mL round bot~om fl~sk that ~as fit~ed with ~ stirrer, condens te take o~f, snd nitrogen inlet he~d. The flask ~nd conten~s were immersed into a Belmont met~l b~th ~nd heflted for two hours at ~bout 200~-220C, while ester interchsnge ~nd re~ction of the colorant with ethylene ~lycol occurred. To carry out the polycondens~tion re~ction, the temperature wa~ incre~sed to -250C
~nd the fl~sk w~s held under vacuum of ~0.5 mm HB
for about 45 minutes. The regulting polymer w~s dark -~ ' , red and had an I.V. of 0.323 and Tg = 60.0C. This polymer cont~ins ~bou~ 0.5% (wtJwt) red coloran~, and is readily soluble in hot w~er producing ~ dark red Mqueous solution.

ExamPle 2 The procedure o~ Exsmple l was repeated using 2.77 g (4.7B9 x lO 3 m) of colorant (g), thus producing a polymer cont~ining about 2.0~ (wtlwt) of red color~nt and having ~n I.V. of 0.270 ~nd Tg =
58.6C.

ExamPle 3 The procedure of Ex~mple l was repeated using 15 2.77 g (5.653 x lO m) of the blue colorant (h) below to produoe a dark blue polymer having an I.V.
of 0.274 and Tg = 62.9C.
R ~HCH2--' s ,-~H20H
.~
I! I! !
a ~H~H2--' S ` ~H20H
(h) The polymer contains ~bout 2.0~ (wt/wt) of colorant ~nd gives a dark blue solution in w~ter at room tempera~ure.

: ExAmPle 4 The procedure of Ex~mple l was repe&ted us~ng l3.59 g (0.028 m) o~ the blue co~or~nt (h) to ~ive a polymer containing ~bout 10~ (wt/wt) of color~nt ~nd h~ving ~n~I.V. of 0.286 and Tg - 64.6C.
All four of the ~bove exempl~ry polymers were easily di~solved in hot woter ~t the ~5~ ~olids level to produce st~ble solutlonsO

:

: ' ', ' ' ' .
-:
.

.

- 35 - ~3~

Example 5 Polyesters designated (a), (b), (c) and (d) may be prepared essentially in accordance with Example 1 of the aforementioned U.S. Patent 4,233,196 from the following materials and including the condensable colorant of choice in molar proportions such as employed in any of Examples l-4 above.
(a) q. moles Dimethyl Isophthalate (IPA) 0.415 Dimethyl-5-Sodiosul~oisophthalate (SIP) 0.085 l,4-Cyclohexanedimethanol (CHDM) 0.520 Carbowax (trademark~ 1000 (CW 1000) 0.0237 Sodium Acetate 0.0085 Irganox (trademark) 1010 0.0085 The Carbowax 1000 has the structure HtOCH2-CH2~nOH wherein n is about 22. The polymer should analyze by NMR to contain (in reacted form) about 83 mole % IPA, about 17 Mole % SIP, about 94.5 mole %
CHDM, and about 5.5 mole % of CW lO00, and have an I.V.
of about 0.39.

(b) q. moles Dimethyl Isophthalate 0.328 Dimethyl-5-Sodiosulfoisophthalate 0.072 1,4-Cyclohexanedimethanol 0.442 Carbowax 400 tn=10) 0.058 Sodium Acetate 0.0072 The polymer should analyze by NMR to contain (in reacted form) about 82 mole % IPA, about 18 mole % SIP, about 85.5 mole % CHDM and about 14.5 mole % CW 400, and have an I.V. of about 0.46.

~ 3 ~

(c) ~. moles Dimethyl Isophthal~te 0.41 Dimethyl-5-Sodiosulfoisophth~l~te 0.09 l,4-Cyclohexanedimethanol 0.55 Carbowax 4000 (n-90) 0.0005 Sodium Aceta~e 0.009 The polymer should ~nalyze by NMR to cont~in (in reacted from~ about 82 mole ~ IPA, about 18 mole ~ SIP, about 99.9 mole ~ CHDM and about 0.1 mole CW 4000, and have ~n I.V. of about 0,16.

~ . moles Dimethyl Isophthalate 0.205 Dimethyl-5-Sodiosulfoisophth~lste 0.045 Ethylene Glycol (EG) 0.9638 Carbowax 2000 (n=45) 0.03625 Sodium Acetate 0.0045 The polymer should analyze by NMR to contain (in re~cted from) about 82 mole ~ IPA, ~bout 18 mole SIP, about 85.5 mole ~ EG and about 14.5 mole CW 2000, and have an I.V. of about 0.34.
` In such polymers containing the C~rbowax material 9 the n v~lue is preferably between about 6 and 150.

In ~ccordance with the pre~ent ~nvention, inks prepared from the present colored polymers, with or without v~rious property modifiers such as polyYinyl ~lcohol, Pluronic~0 or the like would have unexpectedly superior properties such as flow-out or pr~ntability, pigment wetting (where pigment is employed as co-eolorant), temperflture stability (heat and freeze-th~w), nonsettling for extended periods of time, nonpolluting with respect to odor ~nd volatile .

, .. . . . .

. . .~ , , .. . : , ' , ' . ' ,:.

1 ~ 2 ~

organics, nonflocculating, wide viscosity range inks, adhesion to a variety of substrates, h~rdness, gloss, drying rate on substrates, resistance to greese, water and scuff, compa~ibility with other water-based inks, wet rub resistance, ink mileage char~cteristics (considerable water dilution Allowable at the press), ink press stability in general, print~bili~y (clean, sharp transfer without "stringing or misting"), trapping, easy clean up, nonplugging of printing plates, flexibility, redispersibility or rewetting, crinkle resistance, solvent resist~nce, ulkali, chemical and detergent resistance, blocking resistance, lightfastness, toughness, subs~rate wetting, hold-out, dry-rate, and no offset on the printing press ~coating, e.g., on tension rollers).
The following tables give exemplsry color~nt reactants useful in the present invention.

:

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The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that vari&tions and modific~tions can be effected within the ~pirit and scope of the invention.

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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, of 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:
H?OCH2-CH2?nOH, 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:
H?OCH2-CH2?nOH, n being an integer of between 2 and about 500 9 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;
fluorindines; 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[l,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:

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', -alkylenear&lkylene-Z', or alkylenecycloalkylene-Z', wherein -Z and Z' are independently selected from hydrogen, -SO2R5, -SO2NR5R5, -NHSO2R5, -N(R5)SO2R5, -N(R5)COR5, NHCOR5, -OH, -SR5, -OR5, -NHR5, -NR5R5, -SO2NHR5, -CONHR5, -CONR5R5, -CO2R5,-OCOR5, -OCO2R5, -OOCNHR5, , , , or , 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 -Rl-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 , , , , and , 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 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 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(SO2R)-, -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, -OCOD-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 wherein Y is -NH-, -N-alkyl, -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 ;

-SO2R8; -COOR8; -OXR8; -NH-X-R8;
-CONR7R7; -SO2NR7R7; 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 l-3 of hydroxy, cyano or alkanoyloxy; alkoxyelkoxy substituted with l-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 l, wherein the colorant comprises one or more compounds of the formula 1 or 2 wherein either or both of rings A and B may contain in any position thereon one or two groups of the formula wherein:

R and R3 each is selected from hydrogen, lower alkyl or hydroxy substituted lower alkyl; R1, R2, R4 and R5 each represents hydrogen or 1-3 substituents selected from lower alkyl, lower alkyl substituted with lower alkoxy, phenyl, C1, Br, or lower alkanoylamino, 1ower alkoxy, lower alkoxy substituted with lower alkoxy, phenyl, Cl, Br, or lower alkanoylamino, chlorine, bromine, amino, lower alkylamino, lower alkylamino subtituted 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 matter of Claim 1, wherein the colorant comprises one or more compounds of the formula wherein:

R is -OH, -COORl 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 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 , , and wherein each A is selected from the following radicals:

, , , , , , , ' , , and wherein:
R and R1 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-pyrrolidono; cyclohexyl; phenyl; phenyl substituted with alkyl, alkoxy, halogen, hydroxy alkanoylamino, carboxy, cyano, or alkoxycarbonyl; alkylsulfamoyl; vinylsulfonyl;
acrylsmido; sulfamyl; benzoyl- sulfonicimidoi;
alkylsulfonamido; phenylsulfonamido;
alkoxycarbonylamino; alkylcarbamoyloxy; alkoxy-carbonyl; alkoxycarbonyloxy;
alkenylcsrbonylamlno; groups of the formula wherein Y is -NH-, N-alkyl, -O-, -S-, or -CH2O-; -S-R-14; SO2CH2CH2SR14;
wherein R14 is alkyl, phenyl, phenyl substituted with halogen, alkyl, alkoxy, alkanoylamino, cyano, or alkoxycarbonyl;
pyridyl; pyrimidinyl; benzoxazolyl;
benzimidazolyl; benzothiazolyl; radicals of the formula ;

-OXR16; -NHXR16; -X-R16; -CONR15R15; and -SO2NR15R15; 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, alkyl-thio, 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 selected from the group consisting of pentamethylene, tetramethylene, ethyleneoxyethylene, ethylene sulfonylethylene, or 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, S02, R17SO2N=, , , -S-S-, , , , 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 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 , , , , , , , , and ;
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-benzothiszolyl, 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 , or 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)2carbamyloxy,amino, alkylemino, hydroxyl, N-phenylcarbamyloxy, cyclohexanoyloxy, and carbocyclohexyloxy;
wherein when an (R) substituent is present, n is any 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.