CA2048992C - Copolymerized methine colorant-polyester color concentrates - Google Patents

Abstract

Disclosed are polyester color concentrates, especially amorphous and partially-crystalline, polyester color concentrates, comprising a polyester having copolymerized therein colored residues of at least one polyester-reactive, thermally-stable methine colorant compound. The color concentrates may be used to impart yellow shades and colors to various polymeric materials, shaped articles fabricated of and coating formulated from such polymeric materials and, especially, personal, medical and home care products where non-extractability of the colorant material is esential. Also disclosed are colored semicrystalline powders de-rived from the color concentrates.

Description

91/106g3 ~ PCr/US9l/00019 - 1 - ` 2048992 COPOLY~lERIZED METi~INE COLORANT-POLYESTER COLOR CONCENTRATES
This invention pertains to polyester color concentrates comprising a polyester having copolymerized 5 therein colored residues of at least one polyester-reactive, thermally-stable methine colorant compound.
The color concentrates may be used to impart yellow shades and colors to various polymeric materials, shaped articles f2bricated of and coatings formulated 10 from such polymeric materials and, especially, personal, medic21 and home care products where non-extractnbility of the colorant m2terial is esse~tial. This inve:ltion also pertains to colored semicrystalline powders derived from the color concentrates.
Plastics, paints, printing inks, rubber, cosmetics nnd similar materinls typically are colored by organic pigments when superior brillinnce and tinctorinl strength are important. Toxicity considerations have been a chronic problem rel~tive to the use of organic 20 pigments since some have been shown to be potential c~rcinogens and to cause contact derm~titis. Plastics usually contain various ~dditives such as fillers, plasticizers, colorants, etc. The polymoric base of such plastics normally does not produce allergic or 25 other adverse reactions by themselves but leachnble or extractnble additives are known [Fregert, Manual of Contact Dermatitis, Munkaard Denmark (2nd Ed. 1981) ] to c~use contact dermatitis.
The color concentrates provided by this invention 30 h~ve the colorants incorporated into the polymer chain so that the colorant will not be leachable, ~iublimable or extrsctable and will not migrate or exude from compositions colored with the color concentrates. The colored semicrystalline powders of our invention may be 35 formulated into 2 wide variety of products such as WO 91/10693 ~ PCI/US91~00019 ~
~2~4~9~ - 2 -cosmetics, household care products a~d the like which do not pose nny risk or haz~rd to humans since eYposure to toxic molecules which m~y be absorbed by the body is essentinlly elimin~ted. The llmorphous and semi-5 crystalline color concentrates are preferred~ forcoloring thermoplastic polymeric m~teri~ls such as polyesters, polycarbonates, polyamides, cellulose esters, polyurethanes, polyolef ins, etc . by conventional melt or solution blending technigues.
It is known to color thermoplastic polymeric materi~ls using color concentrates consisting of physical ~Idmixtures of polymers and colorants. ~owever, the use of such physical ~dmixtures to color polymeric materinls such ~15 polyesters, e.g., poly(ethylene teIephthalate) and blends thereof, present a number of problems:
~1 ) Color~lnt migration during drying of the colored polymer pellets.
( 2 ~ Color~nt migration during extrusion nnd color~nt nccumul~tion on dies which c~n c~use film rupture and shut-downs for clean-up, etc.
Such colorant migration and accumulation result in time consuming and dif f icult clean-up when a polymer of another color is ~ubsequently processed in the same equipment.
(3) Colorants m~y not mix well, for example, when using two or more color concentrates to obt~in a pa~ticular shade.
(4 ) Color~nts mAy diffuse or exude during stor~ge of the colored polymeric m~terial.
~ . S . Patent 4, 617, 373 discloses polyester compositions having copolymerized therein low concentrntions, e.g., up to 5000 p~rts per million, of certnin methine colo~ants. The copolymeriz~tion of the 35 colornnt in ~ polyester requires the addition of the ~. .
. ~

~ 91/10693 PCr/US9~/00019 i1 ~04~992 colorant compound during the prep~ra~ion of the polyester, e.g., at the commencement of the preparation of the polyester or at the polycondensation stage. The disclosed colored polyesters are suitable for use in the 5 manuf~cture of various shaped articles, especinlly containers for bever~ges, foods, ph~rmaceutic~l prepar~tions and cosmetics. It ~lso is known to those skilled in the art that the susceptibility of organic polymer additives, including colorants, to thermal lO degr~dation increases dramatically as the concentration of the additives in the polymer increases. Thus, methiDe colorants which may be copolymerized with polyesters in moderate to high concentrations must possess outstanding stability at the high temperatures 15 commonly employed in the manufacture of high molecular weight polyesters.
The prior art, e . g ., U . S . Patent 4, 617, 373, also discloses polyesters containing methine compounds with one or three or more polyester-reactive groups. Such 20 methine compounds, which function as either polyester chnin termin~ting groups or cross-linking agents, provide polyester compositions which are useful in the manufacture of containers but are totally unsuitable for use in the preparation of the color concentrates of our 2 5 iDvention .
The color concentrates provided by this invention comprise a polyester having copolymerized therein at least l . 0 weight percent, b~sed on the weight of the polyester, of the residue of one or more methine 30 colorant compounds having the formula ÇN
A--CH~--B ( I ) wherein A is an aniline, 1,2,3,4-tetrahydroquinoline, 2, 3-dihydro-l, 4 -benzoxazine or 2, 3-dihydroindole residue 3 - PCr/US91/00019 ~
,9 2 4 _ of ~ methine colorant _ ~ bearing one polye5ter-resctive substituent; and B is ~In unsubstituted-or bubstituted alkoxycarbonyl radic~l or an aromatic, carbocyclic or heterocyclic 5 radical bearing one polyester-reactive substituent, i . e ., a group reactive with at least one of the functioDal groups of the monomers from which the polyester is prepared; provided that the methine colorant compound contains two polyester-reactive lO substituents.
The methine color~nt compounds of formula (I) and the reacted residues thereof possess the critical property of being sufficiently th~ lly stable to permit their copolymerization with polyesters by 2dding 15 them at the start or at an early stage of the polyester prepnration. Neither the colorant compounds nor their reacted residues sublime under polymerization conditions and the residues are not extract~ble from the polyesters. The thermal stability of the methine 20 colorant compounds is particularly important in the preparation of the color concentrates, i . e ., polyesters containing from l . 0, especially at least 5 . 0, to as hish as 50 weight percent of colorant residue. The color concentrates are advantageous in that the colorant 25 moiety ll) is stable to light, he~t and chemicals, (2) is resistant to sublimation, heat migration, bleeding and leaching by solvents, (3) possesses high color value or chroma and visible ligbt absorption characteristics which allows the color concentr~tes to be combined with 30 red (magenta) and/or blue (cyan) color concentrates to provide ~ range of colors, and (4) is safe to hum2ns and the environment.
The colored semicrystalline powders pro~ided by this invention may be derived from the color 35 concentrates by means of ~ dissolution-cryst2llization ~) 91/10693 PCr/US91/00019 ` ~0 4 8 ~92 precipitation technique described in detail hereinbelow.
Various processes for the manufacture of finely-divided forms of ~olyesters have been disclosed in the prioI ~rt - such as U.S. Patents 4,378,228, 4,254,207, 3,586,654, 3,931,082, 4,267,310, 4,305,864, 4,451,606, 3,674,736 and 3, 669, 922 . Some of these known processes include the presence of pigments such as carbon bl~ck during particle size reduction to produce colored polyester powders. The known procedures zlre summarized below.
10 1. Comminution, as by grinding, which is difficult ~nd expensive and results in highly irregul~r-shaped particle having a bro~d range of p~rticle size distribution .
2. Spray drying techniques which tend to produce ~hollow shells~ or porous particles aDd also are hazardous when organic solvents are used to dissolve the polyester.
3. DispersioD processes which involve melting the polymer in an inert solvent in the presence of a non-ionic dispersing agent. Polyester, in contrast to other thermoplastic polymers, tend to hydrolyze (de :~e) when melted in the presence of w~ter ~nd the p~rticles thus produced h~ve a strong tendency to agglomerate or coalesce.
25 4. ~ieating under shearing agitation conditions a condensation polymer in an aprotic liquid which is not a solvent for the polymer ~nd in the presence of ~ dispersing agent to form small liquid pz~rticles and cooling with ~git~tion. Color~nts 30 added during this process are still extract~ble, sublimable, and may exude from the polymer.
5. Solvent induced cryst~lliz~tion wherein an amorphous polymer is initially contacted with a crystal-inducing fluid under cert~in conditions while the polymer is subjected to physic~l ~nd/or WO 91/10693 PCI/US91/00019 ~
~` 2 ~ 2 - -- ultrasonic forces. Colorants àdded during this process ~ire not reacted with the polymer and therefore are subject to removal from the polymer.
6. Producing microcrystailine poiyesters by a hydrolytic removal of amorphous regions of synthetic, linear polyesters followed by ~
mechanical disintegration of the resulting ~ggregated miL:~u-ly~Lals.
7. Cryst~llizntion of polyesters in the presence of nuclenting agents.
The prior art does not disclose the preparation of colored microcrystàlline polyester powders wherein ~n nmorphou6 or partially-crystalline polyester, h~ving a thorr-lly-5t~lble~ methine colorant compound copolymerized therein, is converted to a colored, miu,o~,y~Lalline/ polyester powder by means of a dissolution-crystallization-precipitation procedure.
The prior nrt rlso fails to disclose microcrystalline, polyester powders containing high levèls of ~ colorant incorporated therein whIch cannot bè removed by ex-traction or sùblimation and which does not exude from the surface of the polymer.
Many of the methine colorant compounds useful in our invention nnd h~ving formuln tI j arè known compounds as shown by U . S . P~tents 2, 583, 6ii, 2, 811, 544, 2,850,520, 3,189,641, 3,247,ill, 3,326,960, 3,386,491, 3,453,270, 3, 553,245, 3,652!636, 3,787,476, 3,808, 256, 3,829,461, 3,879,434, 3,920,719, 3,927,063,~ 4,312,985 nnd 4, 316, 013 and the patents nnd other references disclosed therein. These references aiso provide a vast number: of ex~lmples of the aniïine, 1, 2, 3,4-tetrahydroquinoline, 2, 3-dihydro-1, 4 -benzoxazine or 2, 3 -dihydroindole residues reprgsented by A in f ormula ( I ~ .
Examples of such resi~ues include the following radic~ls: ~
, ' _ _ _ . _ _ __ _ _ _ _ ___ _ _ ____ _~ _ _ _ _, _ _ _ _ = _ .L_.

WO 91~l0693 _ -~ 7 -`-2048~:2 5_. ~.--,~R3 X i i1 7,R5 (l';)n ~ ~ ~R4 3~6 ~- ~-~~1 R5 ~ ~ ~ ~ \ ~R5 ~ 4 ;X ~ ~/ ~R4 3 5 ~--R9 ~ ~ .
~ ~.
i ~i1~ ~R7 (R )n X
wherein R1 is lower alkyl, lower alkoxy or hnlogen;
R2 is an unsubstituted or substituted alkyl, cycloalkyl or aryl radical devoid of polyester-re~ctive groupS;
R3 is a divalent organic group;
R4, R5 and R6 are the same or different and each represents hydrogen or lower alkyl;
R7 and R8 ~re the same or different and each represents lower alkyl or an unsubstituted or substituted aryl radical;
R9 nnd R10 are the same or different rnd each represents an unsubstituted or substituted ~lkyl, cyclo~lkyl or ~ryl r2dical;
n is 0, 1, 2 or 3; ~nd WO 91¢10693 PCr/US91/00019 ~.
2Q4~9,~2 X is a group reactive with at least one of the functional groups of the monomers from which the polyester is prepared.
Examples of the substituents represented by 5 include methyl, ethyl, propyl, butyl, 2-butyl, methoxy, ethoYy, propoxy, butoxy, chloro, bromo and the like. As used herein to describe an alkyl-containing or alkyl moiety-containing group, "lower" designates a carbon content of up to about 6 carbon atoms.
The unsubstituted and substituted alkyl radicals represeDted by R2 may contain a total of up to about 20 carbon atoms. Examples of the substituents which may be present on the substituted alkyl radicals include alkoxy; substituted ~lkoxy such as alkoxy-alkoxy, 15 haloalkoxy and cy~no~lkoYy; cyano; halogen; alkanoyl-amino; acrylamido; aryloxy such as phenoxy and phenoxy substituted with lower alkyl, lower alkoxy, halogen, alkanoylamino, cyano, nitro and/or alkylsulfonyl;
cycloalkyl such as cyclohexyl and cyclohexyl 20 substituted with lower ~lkyl, lower alkoxy and/or h~logen; alkylsulfonyl; vinylsulfonyl; groups having the f ormulas N~C~ and --S02CH2CH2--N~ ~Y
wherein Q is ~, --52-- or --CH2-- and Y is 1, 2- or 1,3-alkanediyl, 1,2-cyclohexylene, 1,2-phenylene or 1,2-~henylene su~stituted with lower alkyl, lower alkoxy, h~logen or nitro; or when Q is carbonyl Y also may be --OCH2--, --OCH2CH2--, --CH2OCH2--, --SCH2--, --CH25CH2, --NHCH2--, --NHCH2CH2--, --~ ~ alkyl ) CH2--, --~ ( alkyl ) CH2CH2-- or --NHC(C6H5)2--, groups having the formula ~O 91/10C93 ` i l?Cr/U~s1/ooms _ 9 ~0.~8~2 --S--R11 --SO CH CH 5_R11 - 10--S--.~ ~. and --S02CH2CH25--~ D' 2 --52--Rl3 --S02~R1 5 _C--~R15 --~--~c--R1 5 wherein R1l is lowel alkyl, cyclo~lkyl, aryl or 25 heteroaryl such as pyridyl, pyrimidinyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, 1,3,4-thiadiazolyl 2nd 1,3,4-oxadiazolyl; Rl2 is hydrogen, alkyl or ~lkyl substituted with aryl; R13 is alkyl, cycloalkyl, alkylcycloalkyl, phenyl or phenyl substituted with lower 30 alkyl, lower nlkoxy or halogeni R14 and R15 are independently selected from hydrogen and the substituents which R13 can represent.
The organic linking group represented by R3 is bonded to the ~djacent nitrogen ntom of residue A
35 through non-oxo carbon atoms, e . g ., unsubstituted or substituted methylene groups, a methylidene group and an unsubstituted methylene group or a nuclear carbon atom of a cnrbocyclic or heterocyclic aromatic group. Thus, linking group R3 may be selected from a wide variety of 40 nlkylene, alkenylene, alkynylene, cycloalkylene, carbocyclic and heterocyclic arylene and combinations of such divalent groups. The alkylene linking groups may contain within their main chain hetero atoms, e . g ., oxygen, sulfur, sulfonyl, nitrogen, substituted 45 nitrogen, and/or cyclic groups such AS cyclo!~lkylene, - carbocyclic arylene or divalent aromatic heterocyclic groups. Examples of alkylene linking groups containing a cyclic moiety in the linking chain include:

5 alkylene i ~alkylene, alkylene-O~ ~O--lkylene, alkylene I ~ I alkylene, alkylene~ alkylene, 25 Glkylene- ~ -alkylene, nlkylene~ -alkylene, C6~5 35 alkylene-~ -alkylene and alkylene-~ -alkyleDe.

4 0 ~ O
The carbocyclic groups may be cycloalkylene such ~L5 1,2-, 1,3- And 1,4-cyclohexylene, l,2-, l,3- and l, 4 -phenylene and 2, 6- ~nd 2, 7-naphthylene . Examples 4 5 of the divalent heterocyclic groups include unsubstituted an~ substituted trizlzines such as 1,3,5-triazin-2,4-diyl and 6-methoxy-1,3,5-tri~zin-2,4-diyl; diazines such ~s 2,4-pyr;m;~9intl;yl, 6-methyl-2,4-pyrimidindiyl, 6-phenyl-2,4-pyrimidin-diyl, 3,6-pyridazindiyl and 2-methyl-3-oxo-4,5-4,5-pyridazindiyl; dicyanopyridines such ~s 3, 5-dicyano-2, 6-pyridindiyl and 4 -pheDyl- 3, 5-cyano-2, 6-pyridindiyl; q--; nnl i n~S and isoquinolines such as 2,4-quinolindiyl and 2,8-i60quinolinediyl;
quinoxalines such as 2,3-ql~inrn~Al;ndiyl~ and azoles buch as 2,5-thiazoldiyl, 5-methylene-2-thiazolyl, 3,5-isothiazoldiyl, 5-methylene-3-isothiazolyl, 1,3,4-thiadiazol-2,5-diyl, 1,2,4-thiadi~zol-3,5-diyl, 2, 6-benzothiazoldiyl, 2, 5-benzoxazoldiyl, 2, 6-benzimid-azoldiyl, 6-methylene-2-benzothiazolyl snd the group havi n g the bt ~ UC ~ ure:

~0 1/10693 PCr~l)S91~00019 "20~9~92 - - ~S~ S~ ~ -10 and maleimides such ~s 1-methyl-3,4-maleimidediyl and l-phenyl-3,4-maleimidediyl. The _cyclic moieties of the linking group represented by R3 also may be fiubstituted, for ex_mple, with alkoxy, halogen, cyano, aryl, aryloxy, cycloalkyl, etc. The cyclic moieties of 15 linking group R3 may be substituted with alkyl as well as with the substituents already mentioned. In addition to the possible substitution described aboYe, the nitrogen atom of the nitrogen containing alkylene groups may be substituted, for example, with alkyl, aryl, 20 alkanoyl, aroyl, alkylsulfonyl, or cArhA- yl, e.g., CO-ary1 ~;O2-aryl alkylene-~-alkylene, alkylene-lb-alkylene IH- aryl alkylene-~-alkylene, alkylene- -alkylene ~-alkyl ~-cyclo~lkyl a lkyl ene - - a lkylene, a lkylene - N- a lkylene, or 4 0 alkyl alkylene-~l-alkylene .
Examples of the reactive groups which X may 45 represent include hydroxy, carboxy, an ester radic~l, amino, alkylamino, and the like. ~he ester radicals may be any radical h_ving the formula -O-~-R22, -O-~-O-R22, -O-~NH-R22 or _~_o_R22 wherein R22 is selected from the unsubstituted or substituted alkyl, cycloalkyl or aryl radicals set forth - in the above definition of R2. R22 prefer~bly is unsubstituted alXyl, e.g., alkyl of up to about 8 c~rbon atoms, or phenyl, and most preferably, lower alkyl, e.g., methyl and ethyl. Reactive group X preferably is WO 9l/10693 PCI`~US91/00019 ``2~48992 - 12 -hydroxy or Alkanoyloxy of up to about- 4 carbon ntoms, e . g ., a cetoxy .
The radicals represented by --R3--X ~lso include methine group- containing radic~ls having the structure --~ ~--CH--ÇC--B --R3--N-- ~ ~--CH--C--B
(Rl~n (Rl)n ~6 fN
R5 ~ ~ ~ ~ ~CH C B

wherein R1, R2, R3, R4, R5, R6, n and B ~re def ined ~bove. The methine colorant compounds wherein --R3--X
collectively represents one of the above methine group-containing radicals are referred to herein ~s bis-methine colorants.
For the methine colorant compounds of formula (I), divalent linking group R3 prefer~bly is alkylene, alkylene-O-alkylene, alkylene-S-alkylene, nlkylene-S02N(R14)-alkylene, alkylene-N(502R13)-alkylene, ~lkylene-arylene, alkylene-O-arylene, alkylene-S-arylene, alkylene-arylene-SO2N(R14 ) -nlkylene, alkylene-O-arylene-SO2N(R14)-alkylene, alkylene-SO2N(R14)-arylene, alkylene-N(SO2R13)-arylene, alkylene-CON~R14)-alkylene, alkylene-CON(R14)-arylene, alkylene-N(COR13)-alkylene, alkylene-N~COR13)-arylene, alkylene-5O2-nrylene, alkylene-cyclohexylene-alkylene, alkylene-arylene-alkylene, cyclohexylene, arylene, arylene-;~lkylene,arylene-O-alkylene, arylene-S02N(R14)-alkylene, and arylene-SO2N(R14)-arylene and X is hydroxyl or a group having the formula:

~ 91/10693 PCl`/US91/00019 - 13 - _ ~Q~4~9~2 --o~--Rl4 ~o--Rl4 --OCO--R
wherein each alkylene contains 2 to 8 c~rbon atoms, 5 each ar~lene i5 phenylene or phenylene substituted with lower alkyl, lower ~lkoxy or halogen, Rl3 is alkyl, cyclohexyl, phenyl or phenyl substituted with lower alkyl, lower alkoxy or halogen, and Rl4 i5 hydrogen or one of the groups which Rl3 c~n represent.
For the bis-methine compounds of formula (I) wherein the div~lent group R3 links two nniline or tetrahydroquinoline residues together, e.g., bis-methine compounds having the structures 2 0 B--C~CH~ R3--~ - ~ ~ ~H ~ C--B
(Rl~n (Rl)n 25CN ~ 6 N
7 ~ 5 ~ ~ HC--C--B
~X.~ ~ ~R4 R4~ y ~-~
R3 preferAbly is alkylene, arylene, alkylene-arylene-Alkylene, alkylene-cyclohexylene~alkYlene~ alkylene-O-alkylene, alkylene-S-Alkylene, alkylene-SO2-alkylene, alkylene-N(502Rl3)-alkylene, alkylene-N(Rl3)-alkylene,-slkylene-OC-alkylene, alkylene-O~O-alkylene, alkylene-O-55 C-alkylene-~O-alkylene, alkylene-OC-arylene-CO-alkylene, 60 ~lkylene-OC~--N--alkylene-N'~O---alkylene, alkylene-OC-65 N-arylene-N~O-alkylene or~ alkylene-o-arylene-alk~lene wherein each alkylene contains 2 to 8 carbon atoms, each arylene is phenylene or phenylene substituted with lower Wo91/10693 - PCI/US9l/00019 ~ 2~4gy9~ - 14 -~lkyl, lower alkoxy or halogen, R13 is ~lkyl, cyclohexyl, phenyl or phenyl substituted with lower alkyl, lower alkoxy or halogen, and R14 is hydrogen or one of the groups which R13 can represent.
EYamples of the alkyl groups represented by R4, R5 ~nd R6 are set forth in the preceding description of Rl. Representative examples of ~he alkyl, cycloalkyl and aryl radicals which each of R7, R8, R9 clnd R10 c~n represent are set forth in the above description of R2.
The alkoxycarbonyl rlldicals ~eprese-lted by B in formula (I ) include radic~ls having the formula ~G--R1 6 wherein R16 is an unsubstituted or substituted ~lkyl, cycloalkyl or aryl radical set forth hereinabove in the definition of R2. Examples of the heteroaromatic, i.e., heterocyclic aryl, radicals bearing one polyester-reactive substituent which B may represent include radicnls having the formula --Ar--~R17 )m~X
wherein Ar is a divalent, aromatic, carbocyclic or heterocyclic rl~dical, R17 is a divalent linking group ~s defined in the preceding definition of R3, X is defined hereinabove and m is 0 or 1. Examples of the carbocyclic arylene radicals repre~ented by Ar include 1,2- 1,3- and 1,4-phenylene, unsubstituted or substituted with lower alkyl, lower alkoxy or halogen.
Examples of the divalent heterocyclic groups include unsubstituted and substituted triazines such as 1,3,5-triazin-2,4-diyl and 6-methoxy-1,3,5- triazin-2,4-diyl; diazines such as 2,4-pyrimidindiyl, 6-methyl - 2, 4 -pyrimidindiyl, 6 -phenyl - 2, 4 -pyrimidin-diyl, 3,6-pyrid~zindiyl and 2-methyl-3-oxo-4,5-4, 5-pyrid~zindiyl; dicy~nopyridines such ~s _ _ _ _ _ _, ~ 91~10693 PCI/US91~00019 3, 5-dicyano- 2, 6 -pyridindiyl and 4 -phenyl -3, 5-cyano-2,6-pyridindiyl; quinolines nnd isoguinolines such as 2,4-quinolindiyl and 2,8-isoquinolinediyl;
qllin~r~lines such as 2,3-quinox~lindiyl; and azoles 5 fiuch as 2,5-thiazoldiyl, 5-methylene-2-thi~zolyl, 3,5-isothiazoldiyl, 5-methylene-3-isothiazolyl, 1,3,4-thiadiazol-2,5-diyl, 1,2,4-thiadiazol-3,5-diyl, 2, 6-benzothiazoldiyl, 2, 5-benzoxazoldiyl, 2, 6 -benzimid-azoldiyl, 6-methylene-2-benzothiazolyl and the like.
The methille colorant compounds which are especially preferred for use in our invention have the structures 20 R18--OC--C--CH---0 ~---~R3 X R --OC--C~CH~ O ~ ~ ~ R5 25 (II) R ~III) ~X ~ ~ ~CH

3 5 R - oc - c - c~ - . ~ ~. _~_ . 4 ~---CH~ ~o_Rl 8 ( IV ) R R
45 R18_c_c CH--.0 ~._~_Rl~--.~ ~---CH~--CO--R18 (V) ~1 fl R R
wherein R1 is hydrogen, methyl, methoxy, ethoxy or chloro;
R2 is lower alkyl; lower alkyl substituted with cyclohexyl, phenyl, phenoxy, lower rlkoxy, halogen or cyano; nllyl; cyclohexyl; or phenyl;
R3-X is ~lkylene-OH, alkylene-O-alkylene-OH, alkylene-OC-alkyl, alkylene -OCO-alk~l, alkylene-WO 91/10693 PCI/US91/000l9 ' 20~8~92 - 16 -O, ' O
phenylene-CO-alkyl, alkylene-O-phenylene-CO-alkyl or alkylene-O-alkylene-OC-alkyl wherein each alkylene contains 2 to about 4 carbon atoms nnd each alkyl contains up to about 4 carbon atoms;
R5 and R6 each is hydrogen or methyl;
Rl8 is lower alkyl; and Rl9 is alkylene, alkylene-O-alkylene, alkylene-SO2-alkylene, alkylene-phenylene-alkylene, alkylene-O-phenylene-O-alkylene, alkylene-OC-alkylene-CO-alkylene or alkylene-O~-phenylene-CO-alkylene .
The methine colorant ~ ~u-.ds ~hich m~y be used in the preparation of the compositions provided by this inveDtion are f urther described in the following eYamples. 3~:xamples of colorant _ 'c not suitable for use in our invention are described in Comparati~re Examples 1 through 3. The identity of the colorant compounds prepared in the examples is confirmed by mass spectrometry analysis.

N-~2-Acetyloxyethyl)-N-ethyl-m-toluidine (66.3 g, 0.30 mol~ i5 added to N,N-aimethylfo~--mid~ 1150 mL).
With stirring and cooling, phosphorous oxychloride (46.5 g, 0.304 mol) is added dropwise at 30-45C. After addition is completed, heating is continued at 85-90C
for 1. 5 hours . The reaction miYture is then added dropwise to a stirred mixture of methyl cyanoacetate (34.6 g, 0.35 mol), sodium acetate (93.8 g) and isopropyl alcohol ~300 mL~ at 50-60C. ~ieating is continued at 60-65C for 1.5 hours and then water (500 mL) is added dropwise to precipitate the yello~
product. After being cooled to about 25C, the product is collected by filtration, washed well with warm ~-ater, ~O 9l/10693 PCI'~US91/00019 - 17 - '2048~,92 and dried in air. The yield is 87.0 g (87.9o of theory) of methyl 3- [4- L [2- (acetyloxy)ethyl]ethyl2mino]-2-methylphenyl]-2-cyano-2-propenoate, which melts at 101-102C, 2S evidenced by mass spectrometry.
- 5 An absorption maximum (~ max) is observed nt 428 nm (Em2X = 43,340) in the visible spectrum in acetone. The colorant may be further purified by recrystallization from methanol in presence of activated charcoal if needed .
EXAMPLE 2 ~ ~
To a solution of N-(2-acetyloxy)ethyl-1,2,3,4-tetrahydro-2,2,4,7-tetrAmethyl~uinoline (55.0 g, 0.20 mol) in N,N-dimethylformamide (150 mL) is ~dded phosphorous oxychloride (20 mL) at 15-20C with good stirring. The reaction mixture is heated for 1 hour at 90-95C, cooled to 25C, ~nd added dropwise to n stirred mixture of methyl cyanoacetate (19.8 g, 0.20 mol) and sodium ~cetate (80.0 g) in isopropanol (350 mL) at nbout 50C. Heating is continued at 90-95C for 1 hour, the reaction mixture cooled, and water (3 L) is ndded to precipitzte the yellow product. The cake is pressed as dry as possible, recrystallized from ethanol (1150 mL) nnd dried to yield 67.6 g (87.9~ of theory), m.p.
134-5C) of methyl 3-l1-[2-(acetyloxy)ethyl]-1,2,3,4-tetrahydro-2,2,4,7-tetramethyl-6-quinolyl]-2-cyano-2-propenoate .
The yellow colorant has an absorption maximum ~' max) at 437 nm in the visible absorption spectrum in acetone .

- Bi s [ 2 - [ ( 3 - methylphenyl ) ethyl ami n o ] ethyl ] hexane -dioate (93.6 g, 0.20 mol) and N,N-dimethylformamide (200 mL) zre mixed znd heated with stirring until complete solution is obtained. Phosphorous oxychloride 35 (42 mL) is added at 15-25C. The reaction mixture is WO 91/106g3 PCI`/US91/00019 ~;~4 ~:g~ 2 - 1 8 heated at 90-95C for 1.5 hours and then cooled to about 50C. A mixture of methyl cyzno~cetate (41.0 g, 0.41 mol), sodium acetate (120 g) and isopropanol (500 mL) i5 added gradually to the Vilsmeier reaction 5 mixture and heating continued at 65-75C for 2 hours.
After cooling to about 25-30C, the reaction mixture is treated dropwise with 1000 mL of water to precipitate the yellow product, which is collected by filtration, w2shed with water, 2nd dried in air. The yield is 120 g (88.496 of the theory) of bis[2-[~4(2-cyano-3-methoxy-3-oxy -1- propenyl ) 3 -methylphenyl ] ethylamino] ethyl ] hexane -dioate which is consistent with mass spectrometry. The product is purified by recrystallization from 2-ethoxyethanol ~500 mL). A visible absorption maximum (~ max) is observed in the visible absorption spectrum in methylene chloride ( ~ 80, 789 ) .

N, N ' - (Sulfonyldiethylene ) -bis- ( N-ethyl-m-toluidine ) (77.6 g, 0.20 mol) is treated aceording to the procedure described in Example 3 to~obtain 117.4 g (97.0~ of the theory) of product having the strueture:
CH30-~ ~ C2H4502C2H4 - \ ,C,OCH3 Recrystallization of the product from 2-ethoxyethanol (500 mL) in presence of eharcoal (5.0 g) gave the pure yellow eolorant (81.0 g), which has a A max at 417 nm in the ~risible absorption speetrum ( = 68,757) in methylene ehloride solvent.

Malononitrile ~16.5 g, 0.25 mol), ethanol (23.8 9, 0.52 mol), ethyl ~cetate (90.0 g) are mixed together 2nd stirred. Acetyl chloride (21.0 9, 0.25 mol) is added ~ 91/10693 - - PCr/US91/O00l9 - 19 - ~4~2 dropwise at 25-30C and the reaction mixture is stirred ~,t room temperature for about 4 hours. To the immedi~te solution is added methyl 3-amino-4-llydL.~yLen2Oate (35.8 g, 0.25 mol). The reaction mixture is he~ted ~t - 5 reflux for 2 hours and then treated with 2-ethoxyeth~nol (193 g). As refluxing is continued, distillate is removed (approximately 150 mL) using ~ distillation head. After cooling to room temper~ture, the reaction mixture is treated with sodium acetate (68.5 9), followed by a solution of Vilsmeier reaction complex prepared by adding phosphorous oxychloride (42.4 9) to a solution of N- (2-acetyloxy)ethyl-N-ethyl-m-toluidine (55.3 g, 0.25 mol) dissolved in N,N-dimethylfo~^m;~e (100 mL) and heating for 2 hours at gO-95DC and cooling.
The condensation reaction is then completed by heating the mixture at 95C for 0 . 5 hours . After bei~g cooled to about 50C, the yellow colorant is precipitated by the addition of water, collected by f iltration, washed with water and air dried. Purification is accomplished by reslurrying the yellow 601id in hot methanol, cooling, f iltering, and washing with methanol . The yield is 60.5 g of pure methyl 2-12-cyano-[4-[[2-acetyloxyethyl)ethyl]amino] -2-methylphenyl]ethylidene] -5-benzoxazole carboxylate.
In the visible absorption spectrum in methylene chloride, nn absorption maximum (~max) is observed at 447 nm ~ - 43,976).
EXAMPL~ 6 _ ~
A solution of N-methyldiphenylamine ( 91. 5 g, 0.50 mol) and N,N-dimethylformamide (200 mL) is cooled and stirred. Phosphorous oxychloride (100 mL) is added dropwise at 25-30C and the reaction mixture is then heated and stirred at about 90C for 21 hours followed by drowning into water-ice mixture (1.5 L). A stic3~y mixture results which is basified by adding 50~ sodium WO 91/10693 PCr/US91/00019 S?Q~8~2 - 20 -hydroxide. The aqueous l~yer is decanted ~md the stic}~y product washed once with water by decantation and then tre~ted with 300 m~ methanol. Crystallization occurs and the product is collected by filtration and w~shed with methanol. The wet product is reslurried in methanol, filtered, w~shed with methanol, and dried in air (yield - 52.5 g, 43.9~ of the theory). Mass spectrometry indicates that the product consists mostly of 4,4'-(methylimino)-bis-benzaldehyde with a small amount of the mono-aldehyde present.
A mixture of 4,4'-(methylimiDo)-bis-be~z21dehyde (35.9 g, 0.1~ mol) methyl cyanoacet~te (30.0 g, 0.30 mol~, methanol (200 mL~) and piperidine acetate (2.0 g) is heated at reflux. After about 5 minutes at reflux, the yellow product begins to crystnllize and the re~ction mixture becomes very thick. Additional methaDol (400 mL) is added to keep the mixture stirr~ble and refluxiDg is continued for 0 . 5 hours . The yellow product is collected by f iltration, washed with meth~Dol, and dried in air.= The yield is 48.0 g ~79.8 of theory) of the yellow methine colorant dimethyl 3,3' [(methylimino)di-4,1-phenylene]bis[2-cyano-2-propeDoate] which has an absorption maximum (Amax ) at 449 nm in methylene chloride (~ - 49,319).
CO~PARATIVE EXAMPLE 1 - To a solution of N,N-bis[2-(acetyloxy)ethyl]-m-toluidine (139.5 g, 0.50 mol) in N,N-dimethylformamide (200 mL) is added phosphorous oxychloride (50 mL) at less than 25C. After being he~ted for 2 hours nt 90-95C, the reaction mixture is drowned on ice-water mixture and neutralized with 50~ sodium hydroxide solution. Extraction with 2-100 mL portions of methylene chloride, followed by removal of the solvent OD rot~ry evaporator affords the aldehyde as a dark 35 viscous oil (139.0 g, 90.5~ of theory).
-~0 91/10693 - 2~ - ~ 2048992 A portion of the aldehyde (4- [bis [2-(acetyloxyethyl]amino]-2-methylbenzyldehyde) thus prepared (92.1 g, 0.30 mol) malononitrile (20.5 g, 0.31 mol), methanol (200 mL) and piperidine (12 drops are mixed and heated with stirring at reflux for 3 hours. The reaction mixture is cooled and the yellow product collected by filtration, washed with methanol, nnd dried in ~ir. A yield of 76.2 g (71.5~ of theory) of the yellow color~nt is obtained. Recrystallization from methanol (300 mL) in the presence of ch~rcoal (5 g gives 66.5 g of the pure product, [[4-[bis[2-(acetyloxy)ethyl]amino] -2-methylphenyl]methylene] -propanedinitrile, which has a visible absorption maximum at 431 nm ( - 52,440) in the visible absorption spectrum in methylene chloride.

A solution of N,N-bis[2-(ethoxycarbonyl)ethyl]-m-toluidine (92.1 g, 0.30 mol) in N,N-dimethylformamide (150 mL) is treated dropwise with phosphorous oxychloride (0.30 mol) at 10-25C. After being heated zt about 90C for 1.5 hours, the solution is cooled to room temperature and added to a stirred mixture of malononitrile (20.5 g, 0.31 mol), sodium acetate (94.0 9) and isopropanol (300 mL) below 50C. The renction mixture is heated at 60-65C for 1.5 hours, diluted by addition of water (750 mL), and filtered.
The product, [[4-bis[2-(ethoxycarbonyl)ethyl]]amino]-2-methylphenyl]methylene]-propanedinitrile, is washed wit3:
w2ter znd then ethanol (200 mL) followed by drying in air (yield-98 . 6 g-85. 8~ of the theoretical yield) .
Pure product is obtained by recrystallization from ethanol (700 mL) in the presence of charcoal (5 g).
In the visible absorption spectrum in methylene chloride, an absorption maximum (~ax) is observed at 431 nm ( ~ 53,072).

PCI~/US91/00019 ~ 2`~4899~

A mixture of 4 - ~is (phenylmethyl ~ amino] benzaldehyde (60.2 g, 0.20 mol), methyl cyanoacetate (21.8 g, 0.22 mol), meth~nol (300 mL), and piperidine (10 drops 5 is heated at reflux for 1.5 hours. After cooling, the yellow product is collected by f iltration, washed with methanol, and dried in air. The yello~ colorant, methyl 3- [4- Ibis(phenylmethyl)amino]phenyl]-2-cyano-propeno~te~
is obtained in n yield of 53.5 g (70.0~ of theory).
In methylene chloride solvent, the colorant h~s an rbsorption maximum (~max) at 417 nm (E - 49,815) in the visible absorption spectrum.
Additionàl examples of methine colorant compounds useful in the preparation of the color concentrate 15 compositions of this invention are set forth in the following tables. These colorant compounds may be prepared according to the procedures described in the preceding examples and conform to the formulas set forth in each table.

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Pcr/ussl/aools ~4~9'~ - 38 -The color concentr~tes of the present invention comprise crystalline, semi-crystalline and amorphous polyesters having copolymerized therein at least 1. 0, normally at least 5 . 0, weight percent of the residues of 5 at least one methine colorant compound of formula (I ) .
The concentration of the methine colorant residue in the polyester is dependent on such factors as the end use for which a p2rticular concentrate is designed, the polyester being used and the physical characteristics 10 required of the color concentrate. Normally, the color concentrates will not contain more than 55 weight percent of methine colorant residues with a concentration in the range of about 10 to 40 weight percent being more common. Typically, the polyester 15 color concentrates have an inherent viscosity of at least 0.20 and are comprised of ~i) a diacid component consisting of the residues of one or more dicarboxylic acids, (ii) a diol component consistiDg of the residues of one or more diols and ~iii) ~ colorant component 20 consisting of the residues of one or more methine compounds of f ormula ( I ) . The concentration of colorant component (iii) and inherent viscosity are interrel~ted to the extent that the degree of polymerization and the inherent viscosity should be sufficiently high to ensure 25 that substantially all of the colorant compound is reacted into the polymer and, preferably, into polymer chains which are not extractable. Thus, for example, when the concentr~tion of colorant component (iii) is 20 weight percent or higher, the inherent ~iscosity of the 30 polyester rormally will be about 0 . 25 or higher .
~ he diacid residues may be derived from aliphatic, alicyclic, or aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 1,4-cyclohexane-dicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, 35 succinic acid, glutaric acid, adipic 2cid, sebacic acid, 9l/10693 PCr/US9l/000l9 _ 39 ~0~ 2 1,12-dodecanedioic acid, 2, 6-naphthalenedicarboxylic acid and the like. In the polymer preparation, it is often preferable to derive the diacid residues from an ester-forming derivative of the dicarboxylic acid such 5 as the dimethyl, diethyl, or dipropyl esters. The nnhydrides or acid halides of these acids also may be employed where practical.
The diol components of the described polyesters may be selected from ethylene glycol, 1,2-prop~nediol, 1,3-propanediol, i-methyl-1,3-propanediol, 1,4-butane-diol, 2, 2-dimethyl- 1, 3-propanediol, 1, 6-hexanediol, 1,10-decanediol, 1,12-dodecanediol, 1, 2-cycloheYanediol, 1,4-cycloh~Y~ne-l;ol, 1,2-cyclohexanedimethanol, 1, 3 - cyclohexanedimethanol, 1, 4 - cyclohexanedimethanol, X,8-bis(hydroxymethyl)-tricyclo-[5.2.1.0]-decane wherein X represents 3, 4, or 5; and diols containing one or more oxygen atoms in the chain, e.g., diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, 1,3- and 1,4-bis(2-hydroxyethyl)benzene And the 20 like. In general, these diols contain 2 to 18, preferably 2 to 12 carbon atoms. Cycloaliphatic diols c~n be employed in their cis or trans conf iguration or as mixtures of both forms.
The amorphous color concentrates of our invention 25 exhibit ~ glass transition temperature (Tg) and no, or only a trace of, crystalliz~tion or melting point by differenti~l scanning cnlorimetry (DSC). Examples of such amorphous polyesters include those obtained by the polymerization of a methine colorant compound of formula 30 (I), terephthalic and/or 2,6-naphthalenedicarboxylic ~cid ~nd ~ branched-chain diol having the formula - 3~20 3 5 . = HO CH2 ~2CH2 OH

WO 91/10693 ~ PCI/US91tO0019 ~
:~204899~ 40 wherein R20 is hydrogen or an unsubstituted or substituted ~lkyl, cycloalkyl or nryl radical, e.g., the r~dic~ls which R2 m~y represent, and R2l is an unsubstituted or substituted alkyl, cyclo~lkyl or ~ryl radical . Pref erred amorphous polyester color concentrates have an inherellt viscosity of about O . 2 to O . B and are comprised of: `
~i) diacid residues comprised of at least 50, preferably at l~ st 80, mole percent terephth~lic and/or 2,6-naphthalenedicarboxylic acid residues;
(ii) diol residues comprised of at least 50, preferably at least 80, mole percent of residues of a diol having the formuls ~20 HO - CH2 - f - CH2 - OH
~ R2l wherein R20 is hydrogen or lower alkyl and R2l is lower alkyi; and (iii) residues of methine colorant compound (I).
The p~rticularly preferre morphous polyester color concentrates are com~rised of (i) diacid residues consisting essentia~ ~ y of terephthalic and/or 2,6-naphthalenedicarboxyiic acid residues; (ii) diol residues consisting essentially of 2,2-dimethyl-l,3-propanediol residues; ~nd (iii) residues of one or more methine colorant _ ;_ d (I ), especinlly a methine compound of formula (II), (III), (IV) or (v).
Other amorphous pol yesters, as def ined ~bove, suitable for preparing the colored semicrystalline powders may be obt~ined by employing (l) two dicarboxylic acids ~nd one or morè diols or (2) two diols and one or more dicarboxylic acids ~ccording to kno~-n procedures for obtaining amorphous polyesters.
The polyester comprising a diacid component consisting of 75 mole percent terephth~lic ncid residue~ and 25 _ _ , ~ 91/10693 ~ ~ PCl/US9l/000l9 " 2~48992 mole percent 1l4-cyclohexanedicarboxylic acid residues, ~ diol component consisting of 1,4-butanediol residues and residues of methine compound ~ I ) is an example of such a polyester.
~he partially-crystalline color concentrates of this invention U5UDlly exhibit n glass transition temperature, a crystallization temperature and a melting temperature by DSC. These partially-crystalline, poly-ester concentrates are comprised of (i) diacid residues consisting of` at least 80 mole percent terephthalic acid residues, 2, 6-n~phthalenedicarboxylic acid residues, 1, 3-cycloheYanedicarboxylic acid residues, l, 4 -cyclo-hexanedicarboxylic acid residues or a mixture thereof, (ii) diol residues consisting of at least 50 mole percent of residues having the formula (}(C~2 )p~
wherein p is 2, preferably 4, to 12 and (iii) residues of colorant compound (I). A preferred partially-crystalline color concentrate has a melting temperature ~f at least 110C and is comprised of ( i ) diacid res:idues comprised of at least 80 mole percent terephthalic acid residues, (ii) diol residues comprised of at least 80 mole percent of residues of 1,4-butanediol ~nd (iii) residues of colorant compound (I). An especially preferred partially-crystalline color concentrate has n melting temperature of at least 110C and consists essentially of (i) terephthalic acid residues, (ii) 1,4-butanediol residues and (iii) residues of one of the colorant compounds of formula (II), (III), (IV) or (V).
Ihe colored semicryst~lline powders provided by our invention may be obtained by means of a dissolution-crystalliz~tion-precipitation procedure wherein the amorphous or partially- crystalline polyester color concentrates described above are dissolved in an organic solvent from which the polymeric color concentrate is WO 9l/10693 ~ _ PCI/US9l/00019 -` 20~8~92 - ~2 -recovered in n f inely divided form consisting of particles of rel2tively uniorm size, e.g., from about 10 to 30 microns. If desired, the particle ~ize of the colored semicryst~lline powders m~y be reduced further 5 by conventional grinding processes. Examples of solvents in which the ~morphous and/or partially-crystalline concentrhtes m~y be dissolved include halogenated hydrocarbons such ~5 aliphatic chlorides, e . g ~, methylene chloride , esters such as alkyl esters of 10 carboxylic acids, e . g ., ethyl ~cetate and methyl benzoate, hydroc~rbons such as toluene and ethers such ns tetrahydrof ur~ n . We have f ound methylene chloride to be a particularly effective solvent.
The particular dissolution-crystalliz~tion-15 precipitation procedure utilized is Dot critic&l. The amorphous or partially-crystalline concentrate may be dissolved in a suitable solvent at elevated temperatures ~nd then crystallized in a f inely-divided state by cooling, with or without a reduction in the volume of 20 solvent, i.e., either with or without a solution concentration step. Another useful technique involves dissolving the amorphous concentrate in ~n organic solvent, either ~t ambient or elevated temperature, and then adding to the solution another miscible solvent 2~ which causes crystallization of the colored ~emicrystalline powder. The use of methylene chloride as the primary solvent and an alkyl àcet~te such as ethyl acetate ~s the "crystallization-inducing" solvent has been found to be p~rticularly efficacious.
30 Depending on their intended utility, the colored ~emicrystalline powders may be extracted with ~
suitable org~nic solYent to remove relatively low molecular weight polyester oligomers. Examples of oligomer-extracting solvents include ketones such ~s acetone, 2-pent~none, 3-methyl-2-butanone, 4-methyl-2-~o 9l/10693 2 0 ~ g 9 9 2 pCI/US9l~0l9 pent~none, 2-hexanone and 5-methyl-2-hexanone;
hyarocarbons such as hexane, heptane and toluene; 2nd ethers such as tetrahydrofuran. Another, but not preferred, dissolution-precipitation procedure involves dissolving the amorphous color concentrates in cert~in solvents, e.g., ethyl acetate, from which the polymeric color concentr te, after undergoing a change in morphology, precipitates.
Some of the more crystalline polyesters such as poly(ethylene terephthalate) and poly(tetramethylene terephthalate) reguire the use of a high-boiling solvent in the dissolution-precipitation procedure.
Examples of such high-boiling solvents include alkyl esters of ~romatic carboxylic acids, e.g. alXyl benzoates, aromatic ketones, e.g., acetophenone, and aromatic oxides, e . g . diphenyl oxide. Methyl benzoate is a particularly preferred high-boiling solvent since it is readily avail2ble, hns a pleasant odor and does not cause color problems during crystallizntion which sometimes is a problem uith acetophenone.
In one variation of the process, crude polyester color concentrate is prepared and granulated to a very course powder which is heated with a high-boiling solvent (methyl benzoate) to facilitate solution. Upon cooling, crystallization-precipitation occurs and a diluent such as acetone usually is needed to permit stirring . Filtration gives the f inely-divided powder which may require washing or reslurrying to remove the cryst~lliz2tion solvent.
In another variation of the dissolution-crystalliz~tion-precipitation process, crystallization can occur as an integral p~rt of the polyester color concentrate manufacturing process wherein the crystallization solvent is added to a melt of the concentrate to obtain a solution of the color WO 91/10693 : ` PCI/US91/00019 concentrate which then may be obtained as ~I powder by precipitation. The polyester color concentrate powder is thus obtained in a purified form without the need of granul~ting by a means which m~y be used in conjunction with batch processing.
The dissolution-cryst~llization-precipitation procedure alters the morphology of the amorphous and partially-crystalline polyester color concentrates in a number of respects. X-Ray diffraction analysis of the 10 colored semicryst~lline powders shows a marked incre~se in the crystallinity of the polyester and, while the amorphous polyester concentr~tes do not exhibit ~
melting temperature, the microcrystalline concentrates usually (almost ~lways) exhibit a melting temperature by 15 DSC. Although the weight average molecular weight (Mw may increase, decrease or not be cha ged by the aissolution-crystallization-precipitation procedure, the number Jlverage molecular weight (Mn ) always increases, the magnitude of the increase depending on the degree to 20 which oligomeric materi~l has been removed from the colored semlcrystalline polyester powder. The polydispersity ratio (Mw:Mn) of the colored semi-crystalline polyester is Always less than that of the polyester concentrate from which it is prep~red due to 25 the increase in Mn (even when Mw increases, ~n inc~eases more~. Finally, the inherent viscosity of the colored semicrystalline powders normally is slightly higher th~n that of the color concentrate.
The nmorphous and partially-crystalline polyester 30 color concentr~tes may be used in coloring various thermoplastic polymeric materi~ls when non-extractability or non-vol~tility of the colorant is critical because of toxicity considerations, e.g., in rigid and f~exible pac}~aging materials for food. The 35 concentr~tes ~nd powders ~ay be used in formul~ting ~ 91/10693 - PCI~US91~00019 _ 45 _ -2~4~9~2 inks, co~tings, toners for imp~ctless printing, and similar products.
The polyester color concentrates-m~y be prepared according to conventional esterification or transesterification and melt polycondensation procedures using (i) a dicarboxylic acid or, preferably, a lower alkyl ester thereof, (ii) a diol and (iii) a nethine colorant compound bearing two reactive groups.
Normally, at a 50 mole percent excess of the diol is used. The methine colorant compound prefer~bly is added with the other monomers at the commencement of the color concentrate manuf~cture although it may be added subsequently, e . g ., at the beginning or during the polycondensation step. The concentration (weight percent ) of the colorant residue is determined by summing up the weights of all the --Ants charged to the reactor and subtracting the sum of the weights of the components removed during transesterif ication and polycondensation , e . g ., methanol and excess diol . The difference represents the theoretical yield of the color concentrate. The weight of the methine colorant charged to the reactor is divided by the theoretical weight and m,ultiplied by 100 to give the weight percent of colorant res idue .
Our novel color concentrates and their preparation ~re further illustrated by the follo~ing examples. The inherent viscosities specified herein are determined ~t - 25C using 0 . 5 g of polymer (polyester color concentrate) per 100 mL of a solvent consisting of 60 weight percent phenol and 40 weight percent tetrachloroethane. The weight average molecular weight (M~ ) and number average molecular weight values referred to herein are determined by gel permeation chromatography. The melting temperatures are determined by differential scanning calorimetry on the first ~nd/or WO 9l/10693 ~ ~ ~ PCI/US9l/00019 Eieco~d heating cycle ~t a sc~nning rate of 20C per minute ~nd are reported as the peaks of the transitions.
E~AMPLF` 170 The follo~ing materlals ~re placed in a 500-mL
three-necked, round-bottom flask:
155.2 g (0.80 mol) aimethyl terephthal~te 99.2 g (1.60 mol) ethylene glycol 0 . 0175 g Ti from n n-butanol solution of titanium tetraisopropoxide 18.0 g (0.545 mol) methyl 3-[4-[[2-(acetyloxy)-- ethyl ] ethyl~mi no ] - 2 -methylphenyl ] - 2 -cyAno-2-propeno~te (from Ex~mple 1) The flnsk is equipped with a nitrogen inlet, stirrer, vncuum outlet, and condensing fl~sk. The flask and contents ~re heated in a ~3elmont met~l bath with n itrogen sweep over the reaction mixture ~s the temper~ture is increased to 200C and then to 220C over 75 minutes. Over the next 30 minutes the temper~ture is increased to about 240CC and then to about 260C over the next 30 minutes. The temperature is quickly r~ised (over about 10 minutes ) to 275C ~nd a vacuum is ~pplied until the pressure is reduced to 0 . 5 mm Hg . The polycondensation is completed by heating the fl~sk ~nd contents ~t ~bout 275C for ~bout 45 to 60 minutes under ~ pressure of 0 .1 to 0 . 5 mm Hg . The ~lask is removed from the met~l b~th ~nd is Rllowed to cool while the polymer solidifies. The resulting d rk yellow polyester, containing 10.3 weight percent of the methine color~nt residue, has an inherent viscosity of 0.52, a melting temper~ture (Tm) of 237C, a weight ~ver~ge molecular weight of 44, 379, a number average molecular weight of 20, 843 ~nd a polydispersity v~lue of 2 . 1 3 ~ 91110693 PCr/US91/00019 - 47 - 20489~2 EXA~PLE 17 1 The procedure described in Example 170 i5 repeated USiDg the following materirls:
119 . 3 g ~ 0 . 615 mol ) dimethyl terephthalate 85.5 g (1.39 mol) ethylene glycol O . 0156 9 Ti from Zl n-butanol solution of titanium tetraisopropoxide 52.0 g (0.158 mol) methyl 3-[4-[l2-(acetyloxy)-ethyl ] ethyl~mino ] - 2 -methylphenyl ] - 2 -cyano-2-propenoate (from Example 1) The d~rk yellow polyester obtained contains 33.4 weight percent of the methine color~nt residue, has ~In inherent viscosity of 0 . 54, a weight average molecular weight of 68,105, a number average molecular weight of 17 ,174 and a polydispersity value of 3 . 97 .

The following materials are placed in a 500-mL
three-necked, round-bottom flask:
125.1 g (0.645 mol) dimethyl terephth~late 94.6 9 (0.91 mol) 2,2-dimethyl-1,3-propanediol 0 . 01864 g Ti from a n-butanol solution of titanium tetraisopropoxide 36.3 g (0.11 mol) methyl 3-[4-[~2-(acetyloxy)-ethyl3ethylamino] -2-methylphenyl] -2-cyano-2-propenoate (from ~xample 1) The flask is e~uipped with ~ nitrogen inlet, stirrer, vacuum outlet, ~nd condeDsing flask. The flask and contents are he2ted in a Belmont metal bath with a nit~ogen sweep over the reaction mixture ~s the temperature is increased to 200C and then to 220C over 90 minutes. Over the next 30 minutes the temperature is increased to about 240C and then to about 260C over the next 30 minutes. The temperature is quickly raised (over about 10 minutes ) to 275C with a stream of nitrogen bleeding into the s~stem ~nd a vacuum is .

-WO 91/10693 PCI`/US91/000l9 2(~4~9r~ - - 48 -applied until the pressure i5 reduced to 0 . 5 mm Hg . The polycondens~tion i5 completed by heating the flask and contents at about 275C for about 1. 25 hours under a pressure of 0 .1 to 0 . 5 mm Hg . The f lask is remc>ved ~rom the metal b~th and i5 ~llowed to cool while the polymer solidifies. The resulting high molecular weight yellow polyester, containing 19.76 weight percent of the methine colorant residue, has an inherent viscosity of 0.30, no melting temperature, a weight average molecular weight of 21,691, n number average molecular weight of 13,366 and a polydispersity value of 1.63.
EXAMPLE 173 _-The procedure described in Example lio lS repeated using the following materials:
97.0 g (0.50 mol) dimethyl terephthalate 62 . 0 9 ~1. 0 mol ) ethylene glycol 0 . 0120 g Ti from a n-butanol solution of titanium tetraisopropoxide 36.0 g (0.109 mol) methyl 3-[4-1[2-~acetyloxy)-ethyl]ethylamino]-2-methylphenyl]-2-cyano-2-propenoate (from Example 1) Upon completion of polycondensation, the Yacuum is relieved with nitrogen ~nd methyl benzoate (160 mL) is added 510wly. The mixture is stirred to solution over ~bout 10 minutes with the flask still in the metal bath.
The heat iS then removed and stirring continued.
Cryst&llization begins to occur at about 115C. At 50C, acetone (150 mL) is added to facilitate stirring.
The diluted slurry is stirred for about 30 minutes, filtered and the cake washed three times with acetone and dried. The resulting dark yellow polyester contains 29 . 9 weight percent of the methine colorant residue, h~s an inherent viscosity of 0 . 29, a weight average molecular weight of 30,518, a number average molecul~r 35 weight of 16,889 and a polydispersity valu~ of 1.80.

/~
0693 2 ~ 9 2 PCr/US91/00019 The weight of polyester color concentrate powder recovered is 104.7 g, 86.9~ of theory.

The procedure described in Example 173 is repeated except that upon completion of the polycondensation, the vacuum is relieved with nitrogen and diphenyl oxide (200 mL) is added dropwise and the mixture is 5tirred to solution. He~ting is discontinued and crystallization begins to occur ~t about 130C. At about 100C, acetone (100 mL) is ~dded to facilitate stirring. The diluted slurry is f iltered and the cake washed well with acetone and dried in ~ir (yield - 100.5 9). ~he resulting d~lrk yellow polyester contains 29 . 9 weight percent of the methine colorant residue, has ~n inherent viscosity of 0.67, a melting temperature of 176C, a glass tr~nsition temperature of 80C, ~ weight average molecular weight of 46,040, a number average molecular weight of 22, 502 and a polydispersity value of 2 . 05 .

The following materi~ls are pl~ced in a 500-mL
three-necked, round-bottom flasX:
97.0 g (0.50 mol) dimethyl terephthalate 67.5 g (0.75 mol) 1,4-butanediol 0.0142 g Ti from a n-but~nol solution of titanium tetraisopropoxide 4 5 . 0 g ( 0 . 54 5 mol ) methyl 3 - [ 4 - [ l 2 - ( acetyloxy ) -ethyl]ethylamino] -2-methylphenyl] -2-cyano-2-propenoate (from Example 1) The f lask is equipped with a nitrogen inlet, stirrer, vacuum outlet, and condensing flask. ~he flask and contents are heated in a Belmont met~l bath with a nitrogen sweep over the reaction mixture as the temperature is increased to 200C and then to 220C over 2 hours. Over the next 30 minutes the temperature is 35 increased to about 240C and then to about 260C over -eU,~
WO 91/10693 ~ PCI/US91/00019 the next 30 minutes. The temper~ture is 9uickly raised (over about 10 minutes~ to 275C and a vacuum is applied until the pressure is reduced to 0 . 5 mm Hg . The polycondensation i5 completed by heating the flask and contents at about 275C for &bout 45 minutes under D
pressure of 0.1 to 0.5 mm Hg. The flask is removed from the metal bath and is ~llowed to cool while the polymer solidifies. The resulting dl-rk yellow polyester, cont~ining 31.5 weight percent of the methine colorant residue, has an inherent viscosity of 0.49, a weight ~verage molecular weight of 28,909, number average molecular weight of 15, 4 31, polydispersity value of 1. 87 and a melting temperature of 185~C.

The procedure described in Example 175 is repeated except that upon completion of the polycondens~tion, the vacuum is relieved with nitrogen and methyl benzoate (125 mL) is added slowly ~nd the mixture is stirred to ~olution with the fl~sk still in the metal b~th. The resulting solution is transferred to ~ 2 L beaker and stirred until cryst~llization occurs. Acetone (500 mL) is added slowly with stirring to dilute the slurry and keep it stirrable. The diluted slurry is stirred for 30 minutes, f iltered and the cake washed with acetone . The cake is twice leslurried in ~cetone and the dried in air. The resulting dark yellow semicryst~lline -polyester powder contains 31. 5 weight percent of the methine colorant residue, has an inherent viscosity of 0.359, a melting temper~ture of 185C, a weight averz~ge molecul~r weight of 29,385, a number aver~ge molecular weight of 17,655 and a polydispersity value of 1.66.
The weight of the powder recovered is 129.4 g, 90.8~ of theory .

~p 91/10693 PCI/US91/00019 - 51 - 2 0 ~ 2 EXAMPLE 17 7 _ _ The following materials are pl~ced in a 500-mL
three-necked, round-bottom flask: ~
- 155.2 g ~0.80 mol) dimethyl terephthalate 108.0 g ~0.75 mol) 1,4-butanediol 0 . 0226 9 Ti from a n-butanol solution of titanium tetraisopropoxide 70 0 g ~0.212 mol) methyl 3-~4-[[2-~acetyloxy)-ethyl ] ethylamino] - 2 -methylphenyl ] - 2 -cyano-2-propenoate ~from Example 1) The flask is equipped with a nitrogen inlet, ~tirrer, vacuum outlet, and condensing flask. The flask and contents are heated in ~ Belmont met~l bath with a nitrogen sweep over the reaction mixture as the temperPture is increased to 200C and then to 220C over 2 hours. Over the next 90 minutes the temperature is increased to about 230C and a vacuum is applied until the pressure is reduced to 0 . 5 mm Hg . The poly~ on~ncation is completed by heating the flask and 20 contents at about 230C for about 8 hours under a pressure of 0 .1 to 0 . 5 mm Hg . The vacuum is relieved with nitrogen and methyl benzoate ~200 mL) is added slowly and the mixture is stirred to solution over about 10 minutes with the flask still in the metal bath. The 25 resulting solution is transferred to a 2 L beaker and stirred until crystallization occurs. Hexane (800 mL) is added slowly with stirring to dilute the slurry and keep it stirrable. The diluted slurry is stirred for 30 minutes, f iltered and the cake is washed with acetone .
30 The cake is twice reslurried in acetone and the dried in air. The resulting dark yellow semicrystalline polyester powder contains 30 . 87 weight percent of the methine colorant residue, has an inherent viscosity of 0.550, a melting temperature of 179C, a weight average 35 molecular wei~ht of 33,707, a number ~verage molecular WO 9l/10693 PCI/US91/00019 2~899~ - 52 - -weight of 19,956 and n polydispersity value of 1.69.
The weight of the powder recovered is 213 . 4 g .
EXA14PLE 178 ~ ..
The procedure described in Ex~mple 172 is repeated 5 using the following m~teriAls:
126 . 5 g ~ 0 . 652 mol ) dimethyl terephthalate 94.6 g (0.91 mol) 2,2-dimethyl-l,3-prop~nediol 0 . 01864 g Ti from a n-butanol solution of titanium tetraisopropoxide 37.0 g (0.096 mol) methyl 3-[1-12-(acetyloxy) ethyl]-1,2,3,4-tetr~hydro-2,2,4,7-tetramethyl-6-~auinolyl] 2-cyano-2-propenoate tfrom Example 2) The resulting dark yellow polyester cont~ins 19 . 8 weight 15 percent of the methine colorant residue, has an inherent viscosity of 0.38, no melting temper ture, a weight ~verage molecular weight of; 27,625, a number zlverage molecular weight of 13, 770 ~nd a polydispersity value of 1.78 .
20 EXA~IPLE 179 _ _ -The procedure described in Example 172 is repeatedusing the following materials:106.7 g (0.549 mol) dimethyl terephthalate 81. 2 g ~ 0 . 78 mol ) 2, 2-dimethyl-1, 3 -propanediol 0 . 0165 g Ti from a n-butanol solution of tit~nium tetr~isopropoxide 34.3 g ~0.050 mol) bisl2-[[4~?-cyano-3-methoxy-3-oxy-1-propenyl)3-methyl-phenyl]ethyl-amino~ ethyl ] hexanedio~te ~ f rom : ~ Example 3 ) The dark yellow polyester obtained has an inherent viscosity of 0.55, no melting temperature, ~ weight a~erage moleculAr weight of 40,515, a number aYerage molecular weight of 17,991 and a polydispersity v~lue of 2.25.

~) 91/10693 PCI/US91/000l9 - 53 ~ `.~ 8992 The procedure described in EYample 172 is repeated ~ising the following m2terizls:
106.25 g ~0.548 mol) dimethyl terephthalzte 81.76 g (0.786 mol) 2,2-dimethyl-1,3-propznediol 0 . 016;5 9 Ti from z n-butanol solution of titanium tetr~isopropoxide 34.56 g (0.057 mol) methine colorznt of Ex~mple 4 The dark yellow polyester color concentrzte obtzined h2s 2n inherent viscosity of 0 . 25, no melting temperature, z weight zverzge moleculzr weight of 17,935, a number zverzge molecular weight of 8, 922 and ~ polydispersity value of 2 . 0 .
EXA~5PLE 181 The procedure described in Example 172 i8 repe~ted using the following mzterizls:
127.8 g (0.659 mol) dimethyl terephthalate 94 . 64 g ( 0 . 91 mol ) 2, 2 -dimethyl - l, 3 -propanediol 0.0183 g Ti from z n-butanol solution of titanium tetraisopropoxide 37.0 9 (0.083 mol) methyl 2-[2-cyzno-[4-1[2-acetyloxyethyl ) ethyl ] zmino~ - 2 -methylphenyl ~ ethylideDe] - 5 -benzoxzzole carboxylate (from Ex2mple 5) 25 The dark yellow polyester color concentrzte obtained has an inherent viscosity of 0 . 50 and no melting temperature .
EXA~5PLE 18 2 The procedure described in Example 172 is repeated 30 using the following mzterials:
90.62 g (0.467 mol) dimethyl terephthalate 77.83 g (0.748 mol) 2,2-dimethyl-1,3-propznediol 0 . 0161 g Ti from z n-butznol solution of titznium tetraisopropoxide 35 47.4 g (0.108 mol) methine color2nt of Exzmple 34 WO 9l/10693 ~ PCr/US9l/00019 4; c, 9 9 2 - ~4 -The resulting color concentr2te cont~ins 29.4 weight percent of colorant residue, has ~n inherent viscoSity of 0 . 53, no melting temper~ture, a weisht nverage molecular weight of 33 ,120, z number aver~ge molecul~r weight of 15,830 and a po~ydispersity value of 2.09 EXAMPL~ 18 3 The procedure described in Example 172 is repeated using the following m~teri~ls:
75 . 97 g ( 0 . 392 mol ) dimethyl terephthal~te 66.41 g (0.639 mol) 2,2-dimethyl-1,3-prop~nediol 0 . 0135 g Ti from z n-butznol solution of tit~nium tetraisopropoYide 3 9 . 9 6 g ( 0 . 0 9 9 6 mol ) d ime thyl 3, 3 ' - [ ( me thy l im i no ) -di-4, l-phenylene]bis [2-cyano-2-propenoate] (from Example 6 ) The resulting color concentrate contains 29 . 5 weight percent of colorant residue, has ~n inherent viscosity of 0.636, no melting temper2ture, A weight average molecular weight of 71,052, a number Aver~ge molecular weight of 18, 019 and ~ polydispersity v~lue of 3 . 94 A portion (25.0 g) of the amorphous polyester color concentrate prepared in Ex~lmple 172 is gr~nulated using a Wiley mill and dissolved i~ methylene chloride (200 mL) nt about 25C with stirring. Ethyl acetate (200 mL) is added and the methylene chloride is removed by distillation. The mixture is stirred for about 12 to 15 hours (usuzlly overnight) at zbout 25C during which time the colored semicryst~lline powder separates. The solid is collected by filtration ~nd reslurried in ~cetone (200 mL e~ch time) and filtered four times to remove oligomers from the product which after drying weighs 20 . C g . The colored semicryst~lline powder thus prepared h~s 2n inherent viscosity of 0.35, a~melting temperature of 134C, a weight ~verage molecul~r weight ~) 91~10693 - PCI/US9l/00019 - 55 ~ ?048992 of 23,793, a number average molecular weight of 17,323 and a polydispersity value of 1.37. The total accountability of the methine colorant compound is 93~
zs determined by visuzll spectroscopy and a compzrison of 5 the absorbance of a methylene chloride solution of the starting methine colorant reactant with the absorbance of a methylene chloride solution of the color concentrate . The comparison shows no shif t iD
absorbance indicating that the color~nt is not 10 decomposed during the synthesis of the polyester.

The procedure of Example 184 is repeated using 25 . 0 g of the amorphous color concentrate of Example 178 to obtain an essentially theoretical yield of colored semi-crystalline powder having an inherent viscosity of 0 . 37, a weight 2verage molecular weight of 27, 625, a number ~verage molecular weight of 19 ,130, &
polydispersity value of 1.4 and a melting temperature of 2~bout 130C.
COMPARAIIVE EXA~PLE 4 ~he procedure described in Example 172 is repe~ted in part using the following materi~ls:
106.2 g (0.548 mol~ dimethyl terephthalate 79.97 g ~0.769 mol) 2,2-dimethyl-1,3-prop~nediol 2 5 0 . 014 5 g ~i f rom a n -butanol solution of titanium tetr~isopropoxide 32.0 g (0.085 mol) [[4-[bis[2-(acetyloxy)ethyl]
- amino] -2 -methylphenyl ] methylene ] -propanedinitrile (from Compar2tive 3 0 Example 1 ) ~fter 5 minutes at a temperature of 275C, stirring becomes difficult because of extreme thickening of the polymer melt, an indication that cross-linking has occurred, further indicating decomposition of the 35 methine compound of Comparative Example 1. ~hen `~2b~8~2 - 56 -crystalliz~tion of 25 9 of the granulated polymer is attempted according to the procedure of Example 184, the polymer is found to be insoluble which further establishes the occurrence of cross-linking.
5 COMPA~ATIVE EXAMPLE S
The procedure described in Example~ 172 is repeated in part using the following materials:
I06.2 g (0.548 mol) dimethyl terephthnlate 79.97 g (0.769 mol) 2,2-dimethyl-1,3-propanediol 0 . 0163 g Ti from a n-butanol solution of titanium tetraisopropoxide 33.8 g (0.088 mol) [l4-bis[2-(ethoxycarbonyl)-ethyl~ ]amino] -2-methylphenyl] -methylene]-propanedinitrile (from Comparative Exnmple 2) ~hen a temperature of 275C is renched, the polycondensation reaction occurs very rapidly and has to be stopped after about 10 minutes because of difficulty in stirring. The polymer is bro~-nish-black in color, as opposed to yellow, which is further evidence of the thermal instability of the methine compound of Comparntive Example 2.
COMPA~ATIVE EXAMPLE 6 The procedure described in Example 172 is repented in part using the following materials:
76.7 g (0.395 mol) dimethyl terephthalate 63.64 g (0.769 mol) 2,2-dimethyl-1,3-propanediol 0 . 0118 g Ti from a n-butanol solution of tit~nium tetraisopropoxide 39.0 9 (0.142 mol) 2-cyano-3- [4- ~ethyl-2-(hydroxyethyl)amino] -2-methylphenyl] -2-propenoic acid After polycondensation at 275C for 1 hour, the viscosity of the polymer melt is abnormally low. The polymer solidifies upon cooling and has n low inherent ~) 91/10693 = PCltU591/000l9 ~ ~04~992 viscosity of 0.122, indicating that the methine color~nt is functioning as r chain terminator,` presumably as result of decomposition of the carboxyl group via - decarboxylation.

The procedure described in Example 172 is repe~ted in part using the following m~terials:
- 101.85 g (0.525 mol) dimethyl terephthal~te 70.98 g ~0.683 mol) 2,2-dimethyl-1,3-propanediol O . 0146 g Ti from a n-butanol solution of titanium tetraisopropoYide 44.98 g (0.110 mol) 3-[4-[bis(2-acetyloYyethyl)-amino] -2-methylphenyl] -2-methyl-sulfonyl-2-propenenitrile After heating the polycondensation reaction mixture at 2 temperature of 275C for nbout 10 minutes, a rapid increase in viscosity occurs ~nd stirring cannot be continued, which indicates that polymer cross-linking has occurred. The polymer color is brownish-black and a strong sulfur odor is present, both of which indicate colorant decomposition and thermal instability. The inherent viscosity of the polymer is 0 . 536, the weight average molecular weight is 58, 898, the number average molecular weight is 9,745 and the polydispersity value is 6Ø
COMPARATIVE EXA~PLE B
The procedure described in Example 172 is repeated using the following m~terials:
89.05 g (0.459 mol~ dimethyl terephthalate 62.06 g (0.597 mol) 2,2-dimethyl-1,3-propanediol 0 . 012g 9 Ti fIom ~ n-but~nol solution of titanium tetraisopropoxide 39.94 g ~0.0944 mol) of the methine colorant having the str~cture WO 91/10693 __ - PCr/US9l/00019 ~
f Z ~ 2 -- 5 8 NC C CH~1 ~.~ ~3 CH
1 0 CH3 ~- ~ ~C~ ;?
20~CC~j~OCCH3 20 The polyester thus preparèd is black in color instead of yellow, indicating therm~l inst2bility and colorant decompos it ion .
CO~PARATIVE EXAMPLE 9 The procedure described in Example 173 is repe~ted 25 in part using the following materials:
76.96 g (0.397 mol) dimethyl terephthalate 54.28 9 (0.875 mol) ethylene glycol 0 . 00957 9 Ti from n n-butanol solution of titan i um tetra i S-~l .,pc,xide 29.0 g (0.081 mol) [[4-[bis[2-(~cetyloxy)ethyl]
amino] -2-methylphenyl]methylene] -propanedinitrile (from Comparative Example 1) After heating for about 5 minutes at r temperature of 275C, the reaction mixture becomes eYtremely thick ~nd stirring has to be discontinued and the polymer has turned dark brownish-blnck, all of which indicates instability of the colorant. The vacuum is relieved with nitrogen and methyl benzoate 1220 mL) is added with rapid stirriDg. The mixture is heated at reflux for 45 minutes ~nd the polymer appears to be in solution. ~pon cooling, the polymer separates ~s ~ hard black ball. It h~s an inherent viscosity of 0 . 244, a melting temperature of 156C, a weight average molecular weight of 43,992, a number average molecular weight of 6,512 and ~ polyd~spersity Yalue of 6.75.
.

~ 9l/10693 - PCr/Us9i/00019 ~Q4 ~92 The procedure described in Example 170 is repeated in p~rt using the following materiAls:
136.04 g (0.701 mol) dimethyl terephthal~te 86.95 g (1.40 mol) ethylene glycol 0 . 01655 9 Ti from a n-butanol solution of titanium tetraisopropoxide 33.23 g (0.088 mol) 114-bisl2-(ethoxyc~rbonyl)-ethyl] ]amino] -2-methylphenyl] -methylene]-propAnedinitrile (from Compnr2tive Ex~mple 2 ) The reaction has to be stopped after about 10 minutes ~t 275C because of stirring difficulties. The polymer turns dark brownish-bl~ck indicating thermal inst~bility of the methine colorant. A strong odor of ethyl ~cryl~te is present which further indicates decomposition of the colorant.
CO~PARATIVE EXAMPLE 11 The procedure described in Example 170 is repe~ted in part using the following materi~ls:
147.6 g (0.759 mol) dimethyl terephthalate 9 9 . 2 g ( 1. 6 0 mol ) ethylene glycol 0 . 01536 g Ti from a n-butanol solution of titanium tetraisoplopoxide 16.0 g (0.041 mol) methyl 2-cyano-3-[4-[bis(2-acetyloxyethyl ) amino ] - 2 -methylphenyl ] -2 -propenoate After heating the reaction mixture at 275C for about 5 minutes, stirring is discontinued because of a r~pid increase in viscosity which indic~tes th~t cross-linking h~s occurred. The resulting polymer has a low inherent viscosity of 0 . 061, a weight 2Iver~ge molecular weight of 26,270, a number average molecular weight of 4,947, a polydispersity v~lue of 5 . 31 and a melting temperature of 230C.

`
WO 91/10693 - - -- PCI/US91/000l9 0-~8~2 CO~PARATIVE EXAMPLE 12 The crystalline, cross-linked polymer from Compz,r~,tive Example 11 ~20.0 g~ does~not dissolve in methyl benzoate ~150 mL) at 150C and at 180C it forms soft gel, but does not dissolve. ~eating is discontinued and the gel appe~rs to solidify at about 115C with stirring. At 90C, acetone (100 mL) addition is started, z-llowing the temperature to decrease. A
smooth slurry is obt~ined upon further cooling ~nd stirring . The slurry f ilter5 very slowly and the solid collected is reslurried four times in 200 mL of acetone and the polymer then is dried. It has an inherent viscosity of 0 . 298, ~ weight average molecular weight of 42,465, a number average molecul~r weight of 13,493 and a polydispersity value of 3.15.
CO~PARATIVE EI~MPLE 13 The procedure described in Example 172 is repeated using the following materials:
106.22 g (0.548 mol) dimethyl terephthalAte 79.97 g (0.769 mol) 2,2-dimethyl-1,3-propanediol 0 . 0164 g Ti from a n-butanol solution of titanium tetraisopropoxide 33.8 g (0 .088 mol) methyl 3-14- [bis(phenyl-methyl ) amino] phenyl ] - 2 - cyanopropenoate ~from Comp~,r~tive Example 3) After polycondensation at 275CC for 1 hour, the viscosity of the polymer melt remains abnormally low.
The polymer solidifies upon cooling and has a low inherent viscosity of 0.105, indicating th~t the methine colorant is functioning as a chain terminator. A
portion (25 g) of the polyester is cryst~llized from ethyl acet~,te accor~ing to ~the procedure described in Example 184. The amount of the cryst~,llized yellow polyester powder obtained is only 68 . 0~ of theory . The crystallized polyester has an inherent viscosity of ~ 91/10693 PCI/US9l/00019 0 .156, a weight averzge molecul~r weight of 110, 819, a number aver~ge molecular weight of 8,426, a polydispersity value of 1.28 aDd a melting~temperature of 144C.
CO~PAR~TIVE EXA.~PLr 14 l`he procedure described in Ex~mple 172 is repeated using the followinq m~terials:
75.88 g (0.391 mol) dimethyl terephthalate 60.09 g (0.577 mol~ 2,2-dimethyl-1,3-prop~nediol 0 . 0124 g Ii from a n-butanol solution of titanium tetraisopropoxide 40.0 g (0.106 mol) of the methine colorant having the structure:

!i ~
.~ ~, ~ S C~ CCOCH3 After polycondensation at 275C for 1 hour, the degree of polymerization ~ppears low as evidenced by the low 35 ~iscosity of the polymer melt. The polymer solidifies upon cooling and has a low inherent viscosity of 0.118, indicating that the methine colorant is functioning as a ch~ in termin~tor .
The invention has been described in detail with 40 particular reference to preferred C~mhQ~ nts thereof, but it will be understood th~t ~rariations and modifications can be efIected within the spirit and scope of the int~ention.
.

Claims (13)

- 62 -

1. A color concentrate comprising a polyester having copolymerized therein at least 1.0 weight percent, based on the weight of the concentrate, of the residue of one or more methine colorant compounds having the formula wherein A is selected from ;
;
;
;
;

; and ;
wherein B is a radical having the formula:
or -Ar-(R17)m-X
wherein R16 is C1-C20 alkyl, cyclohexyl or phenyl optionally substituted by C1-C20 alkoxy, C1-C20-alkoxy-C1-C20 alkoxy, cyano-C1-C20 alkoxy, cyano, halo, C1-C20 alkanoylamino, phenylamido, and phenoxy;
Ar is a divalent, aromatic, carbocyclic or heterocyclic radical selected from 1,3,5-triazin-2,4-diyl;
6-methoxy-1,3,5-triazin-2,4-diyl; 2,4-pyrimidindiyl; 6-methyl-2,4-pyrimidindiyl; 6-phenyl-2,4-pyrimidindiyl;
3,6-pyridazindiyl; 2-methyl-3-oxo-4,5-4, 5-pyridazindiyl;
3,5-dicyano-2,6-pyridindiyl; 4-phenyl-3,5-cyano-2,6-pyridindiyl; 2,4-quinolindiyl; 2,8-isoquinolinediyl;
2,3-quinoxalindiyl; 2,5-thiazoldiyl; 5-methylene-2-thiazolyl; 3,5-isothiazoldiyl; 5-methylene-3-isothiazolyl; 1,3,4-thiadiazol-2,5-diyl; 1;2,4-thiadiazol-3,5-diyl; 2,6-benzothiazoldiyl; 2,5-benzoxazoldiyl; 2,6-benzimidazoldiyl; 6-methylene-2-benzothiazolyl; and phenyl;
R17 is a divalent linking group; and X is defined below;
R1 is C1-C6 alkyl, C1-C6 alkoxy or halogen;
R2 is C1-C20 alkyl, cyclohexyl or phenyl radical devoid of polyester-reactive groups, said radical optionally substituted by C1-C20 alkoxy, C1-C20- alkoxy-C1-C20 alkoxy, cyano-C1-C20 alkoxy, cyano, halo, C1-C20 alkanoylamino, arylamido, and phenoxy;
R3 is a divalent organic group;
n is 0, 1, 2 or 3; and X is hydroxy, carboxy or an ester radical having the formula:
, , , or wherein R22 is C1-C20 alkyl, cyclohexyl or phenyl radical, said radical optionally substituted by C1-C20 alkoxy, C1-C20- alkoxy-C1-C20 alkoxy, cyano-C1-C20 alkoxy, cyano, halo, C1-C20 alkanoylamino, arylamido, and phenoxy;
and wherein said divalent group is , , , , and , wherein each alkylene group contains 2 to 4 carbon atoms;
1,2-, 1,3- and 1,4-cyclohexylene ; 1,2-, 1,3- and 1,4-phenylene; 2,6- and 2,7-naphthylene;
1,3,5-triazin-2,4-diyl; 6-methoxy-1,3,5-triazin-2,4-diyl; 2,4-pyrimidindiyl; 6-methyl-2,4-pyrimidindiyl;
6-phenyl-2,4-pyrimidindiyl; 3,6-pyridazindiyl; 2-methyl-3-oxo-4, 5-4, 5-pyridazindiyl; 3,5-dicyano-2,6-pyridin-diyl; 4-phenyl-3,5-cyano-2,6-pyridindiyl;
2,4-quinolindiyl; 2,8-isoquinolinediyl;
2,3-quinoxalindiyl; 2,5-thiazoldiyl, 5-methylene-2-thiazolyl; 3,5-isothiazoldiyl;
5-methylene-3-isothiazolyl; 1,3,4-thiadiazol-2,5-diyl;
1,2,4-thiadiazol-3,5-diyl; 2,6-benzothiazoldiyl;
2,5-benzoxazoldiyl; 2,6-benzimidazoldiyl;
6-methylene-2-benzothiazolyl; and the group having the structure:
;
1-methyl-3,4-maleimidediyl; and 1-phenyl-3,4-maleimidediyl;
R4, R5, and R6 are the same or different and each represents hydrogen or C1-C6 alkyl;
R7 and R8 are the same or different and each represents C1-C6 alkyl or a phenyl radical;

R9 and R10 are the same or different and each represent a C1-C20 alkyl, cyclohexyl, or phenyl radical, R18 is C1-C6 alkyl; and R19 is alkylene, alkylene-O-alkylene, alkylene-SO2-alkylene, alkylene-phenylene-alkylene, alkylene-O-phenylene-alkylene, or , wherein each alkylene group contains 2 to 8 carbon atoms.

2. A color concentrate according to Claim 1 comprising a polyester having an inherent viscosity of at least 0.20 having copolymerized therein at least 5.0 weight percent based on the weight of the concentrate, of the residue of one or more methine colorant compounds having the formula:
.

3. A color concentrate according to Claim 1 comprising a polyester having an inherent viscosity of at least 0.20 having copolymerized therein about 10 to 40 weight percent, based on the weight of the polyester, of the residue of one or more methine colorant compounds having the formula:
wherein R1 is hydrogen, methyl, methoxy, ethoxy, or chloro;

R is C1-C6 alkyl; C1-C6 alkyl substituted with cyclohexyl, phenyl, phenoxy, C1-C6 alkoxy, halogen or cyano; allyl; cyclohexyl; or phenyl;
R3-X is alkylene-OH, alkylene-O-alkylene-OH, , alkylene , alkylene-, or wherein each alkylene contains 2 to about 4 carbon atoms and each alkyl contains up to about 4 carbon atoms; and R18 is C1-C6 lower alkyl.

4. A color concentrate according to Claim 1 comprising a polyester having an inherent viscosity of at least 0.20 having copolymerized therein at least 5.0 weight percent, based on the weight of the concentrate, of the residue of one or more methine colorant compounds having the formula:
wherein R1 is hydrogen, methyl, methoxy, ethoxy, or chloro;
R is C1-C6 alkyl; C1-C6 alkyl substituted with cyclohexyl, phenyl, phenoxy, C1-C6 alkoxy, halogen or cyano; allyl; cyclohexyl; or phenyl;
R18 is C1-C6 alkyl.

5. A color concentrate according to Claim 1 comprising polyester having an inherent viscosity of at least 0.20 having copolymerized therein at least 5.0 weight percent, based on the weight of the concentrate, of the residue of one or more methine colorant compounds having the formula:

wherein R1 is hydrogen, methyl, methoxy, ethoxy, or chloro;
R2 is C1-C6 alkyl; C1-C6 alkyl substituted with cyclohexyl, phenyl, phenoxy, C1-C6 alkoxy, halogen or cyano; allyl; cyclohexyl; or phenyl;
R18 is C1-C6 alkyl.
R19 is alkylene, alkylene-O-alkylene, alkylene-SO2-alkylene, alkylene-phenylene-alkylene, alkylene-O-phenylene-alkylene, or ; wherein each alkylene group is of from 2 to 8 carbon atoms.

6. A color concentrate according to Claim 1 comprising a polyester having an inherent viscosity of at least 0.20 having copolymerized therein at least 5.0 weight percent, based on the weight of the concentrate, of the residue of one or more methine colorant compounds having the formula:
wherein B is a radical having the formula:
or -Ar-(R17)m-X

wherein R16 is alkyl, cyclohexyl or phenyl radical optionally substituted by C1-C20 alkoxy, C1-C20-alkoxy-C1-C20 alkoxy, cyano-C1-C20 alkoxy, cyano, halo, C1-C20 alkanoylamino, arylamido, and phenoxy; Ar is as defined in claim 1;
R17 is a divalent group wherein said divalent group is as defined in Claim 1; and X is defined below;
R1 is C1-C6 alkyl, C1-C6 alkoxy or halogen;
R3 is a divalent organic group;
R4, R5, and R6 are the same or different and each represents hydrogen or C1-C6 alkyl;
n is 0, 1, 2 or 3; and X is hydroxy, carboxy or an ester radical having the formula:
, , , or wherein R22 is a C1-C20 alkyl, cyclohexyl or phenyl radical.

7. A color concentrate according to Claim 1 comprising a polyester having an inherent viscosity of at least 0.20 having copolymerized therein about 10 to 40 weight percent, based on the weight of the polyester, of the residue of one or more methine colorant compounds having the formula:
wherein R1 is hydrogen, methyl, methoxy, ethoxy, or chloro;

R3-X is alkylene-OH, alkylene-O-alkylene-OH, , , alkylene- , or wherein each alkylene contains 2 to about 4 carbon atoms and each alkyl contains up to about 4 carbon atoms; and R5 and R6 each is hydrogen or methyl; and R18 is C1-C6 alkyl

8. A color concentrate according to Claim 1 comprising a polyester having an inherent viscosity of at least 0.20 having copolymerized therein at least 5.0 weight percent, based on the weight of the concentrate, of the residue of one or more methine colorant compounds having the formula:
wherein B is a radical having the formula:
or -Ar-(R17)m-X
wherein R16 is C1-C20 alkyl, cyclohexyl or phenyl radical; Ar is as defined in claim 1; radical; R17 is as defined in Claim 1;
R1 is C1-C6 alkyl, C1-C6 alkoxy or halogen;
R3 is a divalent group as defined in claim 1;
R4 and R5 are the same or different and each represents hydrogen or C1-C6 alkyl;
n is 0, 1, 2, or 3; and X is hydroxy, carboxy or an ester radical having the formula:
, , , or wherein R22 is C1-C20 alkyl, cyclohexyl or phenyl radical.

9. A color concentrate according to Claim 8 wherein the polyester has copolymerized therein about 10 to 40 weight percent of the residue of one or more of the methine colorant and wherein:
B is a radical having the formula R18 wherein R18 is C1-C6 alkyl;
R1 is methyl, methoxy, ethoxy, or chloro; and n is 0 or 1;
R3-X is alkylene-OH, alkylene-O-alkylene-OH, , , alkylene-, or wherein each alkylene contains 2 to about 4 carbon atoms and each alkyl contains up to about 4 carbon atoms.

10. A color concentrate according to Claim 1 comprising a polyester having an inherent viscosity of at least 0.20 having copolymerized therein at least 5.0 weight percent, based on the weight of the concentrate, of the residue of one or more methine colorant compounds having the formula:

wherein B is a radical having the formula:
or -Ar-(R17)m-X
wherein R16 is C1-C20 alkyl, cyclohexyl or phenyl radical; Ar is as defined in Claim 1; R17 is as defined in Claim 1;
R1 is C1-C6 alkyl, C1-C6 alkoxy or halogen;
R3 is as defined in Claim 1;
R6 is hydrogen or C1-C6 alkyl;
R4 and R5 are the same or different and each represents C1-C6 alkyl or a phenyl radical; and n is 0, 1, 2, or 3;
X is hydroxy, carboxy or an ester radical having the formula:
, , . , or wherein R22 is a C1-C20 alkyl, cyclohexyl or phenyl radical.

11. A color concentrate according to Claim 10 wherein the polyester has copolymerized therein about 10 to 40 weight percent of the residue of one or more of the methine colorant and wherein:

B is a radical having the formula R18 wherein R18 is C1-C6 alkyl;
R1 is methyl, methoxy, ethoxy, or chloro; and n is 0 or 1;
R3-X is alkylene-OH, alkylene-O-alkylene-OH, , , alkylene- , or wherein each alkylene contains 2 to about 4 carbon atoms and each alkyl contains up to about 4 carbon atoms.

12. A color concentrate according to Claim 1 comprising a polyester having an inherent viscosity of at least 0.20 having copolymerized therein at least 5.0 weight percent, based on the weight of the concentrate, of the residue of one or more methine colorant compounds having the formula:
wherein B is a radical having the formula:
or -Ar-(R17)m-X

wherein R16 is a C1-C20 alkyl, cyclohexyl or phenyl radical; Ar is as defined in Claim 1; R17 is as defined in Claim 1;
R1 is C1-C6 alkyl, C1-C6 alkoxy or halogen;
R3 is as defined in Claim 1;
R7 and R8 are the same or different and each represents C1-C6 alkyl or a phenyl radical; and n is 0, 1, 2, or 3; and X is hydroxy, carboxy or an ester radical having the formula:
, , , or wherein R22 is C1-C20 alkyl, cyclohexyl or phenyl radical.

13. The color concentrate of Claim 1, wherein said polyester is in the form of a semicrystalline powder having an average particle size of less than 30 microns comprising a normally-amorphous polyester which has been modified by dissolution-crystallization-precipitation to impart crystallinity thereto, having an inherent viscosity of at least 0.20 comprised of:
(i) diacid residues comprised of at least 50 mole percent terephthalic and/or 2,6-naphthalene-dicarboxylic acid residues;
(ii) diol residues comprised of at least 50 mole percent of the residue of a diol having the formula:
and wherein R20 is hydrogen or C1-C6 alkyl and R21 is C1-C6 alkyl; and (iii) residues of one or more methine colorant compounds as defined in Claim 1.