CA1196154A - Diester composition and textile processing compositions therefrom - Google Patents

Abstract

DIESTER COMPOSITION AND TEXTILE
PROCESSING COMPOSITIONS THEREFROM
Abstract A cycloaliphatic diester of the formula

Description

DIESTER COMPOSITION ~ND l~Xl~LE
PROCESSING COMPOSITIONS TH~REFROM

Technic:al Field This inven~ion relate~ ~o a combination of cyclo-aliphatic diester~ and high boiling aromatic estexs and their use in fiber treatin~ and textile processing compositions.

Background Art It has been proposed by Sturw~ld et al, in UO S.
Patent 3,925,589~ to use em~l~ions of ester~ derived from polyoxy-alkylene glycols of molecular weight 300~4000 and a dibasic acid mixture o a dimer acid of 32-54 car~on atoms and a short chain dibasic acid of 2-12 carbon atoms for lubricating polyamide fibexs.
Dumont~ in U. Sn Patent 3,694,257, has proposed . the ~e of polyesters prepared rom reaction of polyol~ with a di- or trib~lc acid a~ textile assistants ~or softening textile fabrics.
20 . It has been proposed by Crovatt, Jr~; in U. S.
Patent 3J329~633t to improve the lubricity of poly-h~. -thylene adipamide fiber~ by adding 0.1 - 5.0 by weight o olelc acid dimer to the polymer during the final polymerization ~tage thereo, Bi~hop et aly in U~ S. Patent 49135,871B~ has disclosed inclusion of up to 10% by weight ~f a . S dimer acid in an emulsifier-~olvent ~cour composition used for treating textile material~ undex alkaline conditions O
Preparatic:~n~ of adduc~s frQm conjugated octa-decadienoic acid and unsaturated ~cids and/or their 10 hydrogenation has been described by Teeter et al, J. ~L. ~hem.., vol~ 22 (1957) at 512-514, Ward in U. 5. Patent 3,899,476 and Ward et al in IJ. SO
Patent 3, 9 81~ 682 O
The preparation OI esters from the C21 diacid 15 adduct was reporte~l by Ward et al, J. Amer. . Oil Chemists ' Soc., volO 57 llg75~ at 219-224. Ethoxylat ted es~ers con~ g 4-llg ethylene oxide units are ~aid to 1~ particularly effective lime ~oap disper-san~sO The alkyl ester~ axe reportedl a5 being par-20 ticularly useful in lubricant applications, includinguses as textile lubricarlt~ and pla~ti~::izers ~Eor PVCJ
The use o~ l~wer aromatic e~ters in-t~stile trea~nent, particularly i~l8 dyeing as~istarlts i~ well kno~, a~ i~ disclo~ed in 13, S. Patent~:

2 ~ 880 ~ 050 Fortress et al 2 ~ 881, 045 Meccc) et al

3, 036, 876 5choellig et al 3 ,124; 412 Fidell et al 3, 92g, 4 07 Paxker 3, 932 ,128 Beaulie~l Reference~ whicll disclo~e t:he u~e of phthalate este~s in d~eing prl)ces~e~ lude U,, S., Pa~ents~
2 g 833 " 613 Halladla ~t al 2, 934, 3g7 ~and~rl ~ ~ 9B2 ~ 597 Salvin et al 3,667,899 HARNETT ET AL
3,973,907 FORSCHIRM

4,032,291 DELLIAN
Phthalate esters have been used as components of lubricants for textiles, for example, by Jaeger (U.S. patent 2,212,369~, Dickey et al (U.S. patent 2,2~1,246), Brennan et al (U.S. patent 2,882,231) and Iyengar et al (U.SO patent 3,853,607).
The use o hydroxyalkyl or alkoxyalkyl benzoates as dyeing assistants or fixatives is disclosed by Fuhr et al (U~S. patent 3~532,454), Baumann et al (U.S. pa~ent 3,950,419) and Lazar et al (U.S. patent 3,917,447).
Higher trialkyl trimellitates have been proposed by Hinton, Jr. et al as components of a soil release composition (U.S.
patent 3,824,125).
Disclosure of Invention The in~ention relates to a novel combination of cycloaliphatic and high boiling aromatic esters which, used as ingredients of textile-processing agents, particularly for polyester fibers, eliminates one or more otherwise conventi.onal processing steps without impairing the ultimate properties of the fiber treated therewith.
The invention in one aspect comprehends a fiber or textile treating composition which contains (a) a cycloaliphatic diester of For~ula I
A
n-C H - C ~ -(CH2)7COOR
OOR
wherein A is -CH2-CH2~; R is substituted or unsuhstituted straight or branched chain alkyl oE 4 - 20 carbon atoms, polyoxyalkylene of the formula HO(C~HyO)nCXHy~ or phosphated polyoxyalkylene of the formula O
~, (HO)2P ( x y )n x y or a salt thereo~ wherein lCXHyO)n is (CH2CH2O)n, (C3H6O)n or (CH2CH2O)p(C3H6O)q; x is 2 or 3; y is 4 or 6; n is 2 - 22;
and p + q = n and (b~(i) a high boiling aromatic ester of the ~ 3~

formula ArCOO-R1-OOCAr or ArCOOR2 wherein Ar is substituted or unsubstituted monocyclic aryl; Rl is alkylene of up to 8 carbon atoms or polyoxyalkylene of the formula ~CrH2r(O-CrH2r)S in which r is 2 or 3; s is up to 15 and R2 is alkyl or alkenyl of 8 to 30 carbon atoms; (b)(ii) an ester of a substituted or unsubstituted benzyl alcohol with a substituted or unsubstituted aromatic acid of at least 6 carbon atoms; or (b)~iii) an estex of a substituted or an unsubstituted benzyl alcohol with a substituted or unsubstituted aliphatic acid of at least 8 carbon atoms.
The invention provides a base for a multi-purpose fiber and textile-treating composition.
In another asp~ct, this invention relates to novel cycloaliphatic diester compounds (Formula II) wherein R is Ar'COO(CH2CH2O)nCH2CH2, Ar'COO(C3H6O)nC3H6, Ar'COO(C2H4O)p(C3H6O)qC3H6, or Ar'COO(C3H6O)p(C2H4O)qC2H4-Ar' is substituted or unsubstituted monocyclic aryl and n, p and q are as above.
This invention further relates to a synthetic fiber or fabric coated with a treating-agen-t containing one of the foregoing compositions.
This invention further relates in the conversion of synthetic fibers to piece goods and subsequent dyeing, to the improvement wherein a composition of this invention is the sole fiber-treating agent used.
This invention also relates to a method of making fabric or an article from a synthetic fiber or fabric comprising coating the fiber or fabric with 1 - 2% by weight of a knitting or weaving lubricant comprising

5 ~ 15 parts by weight of cycloaliphatic diester of Formula I, 30 - 50 parts by weight of high boiling aromatic ester, S - lS paxts by weight of dye-levelling agent and 10 - 30 parts by weight of emulsifiers, dispersing agents and/or anti~static agents; knitting or weaving the Eiber into fa~r:i c or a knitted c~r woven artic:l e and dyeing the fa~ric or knlt or woven article.
~en ~yclcsaliphatic die~ter~ of Formula II are use~ they will compri5~ 5-SS~ by weight of the S treatirlg ~ mposition.
Thl~ invention further re~ ate~ to a method for treating a syn~ie~lc ~iber compri~;ing applying ts:~
the- fiber to-a pick~up o~ 0.4-0.75% by weight a spin fini~h comprisins~ a cycloaliphatic di~ster~
10 (2) a high boiling aromatic die~ter and ~3) a dye-levelling agent; texturing the thus-coated synthetlc fiber at 180-23nC; knittiIIg or weaving the xesultin~
text~lre~ fiber into fabric or knittlng the textured fiber into a knit article and dyein~ the fabric or I5 knit article~, In another as~?ecty this invention r~olates to method for 1Owering the heat histo~y characteristics ana the degr~ o cryst~llin;ty of a synthetic fiber~
1Owering the temperature at which the fiber ca~ be texturized and 1Owering the temperature at which the fiber a~sorbs dye comprising app1ying to the fiber to a pick-up of 0O4 - 0.75% by weight of a composi-tion comprising a cyc1Oa1iphatic diester of Fonmu1a I and a high b~iling aromatic ester, wherein the weight ratio of cyc1Oa1iphatic die~ter to high boi1ing aromatic ester is 0.1 : 1 to 10 : 1 and wherein the combinat1on of cyclo-aliphatic ~iester and high boiling axomatic cons titutes 10-90~ by weight of the composition and texturing the thus-.coatea iber at 180-230~C. Moreo~ex~ aforesaid 30 composition can contain a dye levelling agent of the onnula R3COOR4. Cycloaliphatic diesters of Formula II
will comprise 10 90% by weight of the compositionO

Brief D~crip~io~ of ~r~wings In Fig. 1-4 are shown represeIltations o~ photo-.
microqraph~ of poïy~ster yarn treated w~th the com-po~ition of ~:xamp1e 15 and wi~h a c:onven~ na1 ~pin fini~h compo~itiorlD

. Best ~50de ~9f ~arrying ~ut th~ Inventiorl ~
The dilbasic a:id emp:loyed in making the c:om po~itions of lthi~ inventis~ is a Die1~-A1der adduct of acry1ic acid and 1ino1eic:-acid andl c2n 13e pre-parPd as described by Ward in IJ. S. Patent 3~753~9680 The aiacid has the formu1a lLO 6 13~ ~CH2~ 7~ OOH
0~
and therefore is a mixture of ~5 and 6~;carboxy-4~
hexyl-2-cyclohexene~ octanoic ac d~ The diacid is availabl~ commercially from Westvaco~ designat~d as "Diacid 1500l-~
The diacid can be esterified wi~h alcohols using, for example, a~idic cataly~t~ such as p-toluene-sulfonic acidd methane~ul~oni~ acid or sulfuric acida During the esterification r the react.ion mixture i~
preferably also treated with a decolorizing agent~
e.g~ carbo~ or clay~
The diacid is reduced following es~erification to a comp~und in which A i~ -CH~C~2~. A nickel ca~.alyst such a~ Raney Nickel, nick~l on kieselg~hr or nickel on ~lumina can be u~ed. The required amount varies up to 5 - 10~ by weight of ~he e~ter~
Hydxogenation is carried out ater esterification to prevent nickel from ~omplexing wi~h the free acid.
othex catalysts, eOg~, platin~m or rhodi~m, avoid ~his problem, but are prohi~itive in co~t~ The catalyst can be removea by filtration through a plat~ ~nd *rame filter pres~O ~he produc~ is the resu1ting fi1trate.

Poly~xyalkylene die~ter~ are prepared by reac-tion of the diacid, in th~ pre~ence of an alkaline cataly~t, wi~h ethylene or propylene oxide. Reaction will occur at both acid ~ite~ and addition of ethylene .oxide is allowed to continue until the product be~
comes at lea~t di~persible or, preferably, s~luble in waterO Thi3 will corre~pond to addition of a total of 5-25 ethylene oxide unitsO The produc.
obtained using ethylene oxide ha~ a structure befoxe hydrogenation repre~ented by the formula-r=~
~ ( H2) ~ > ~CH~)7C~OCH2CH~
HO-~C~2CH20)y~C x + y--5 ~ 25 The phosphorylated product is readily obtained by reaction with phosphorus pentoxide. The ~aturated diester ~an be ob~; ne~ by nickel-catalyzed hydro-genation.
In the case of the phosphorylated derivativephydrogenation ~houla prec~de phosphorylation. The phosphorylated derivatives can b converted to sal~s thereof ~y reactîon wi~h a metal hydroxide. Sodium and potassium salts are preferred.
C~mp~nd~.o~Formu~a.II are obtained by treatin~
polyoxyalkylene intermediates with an aromati~ acid, e.g.~ benzoic, toluic or mellitic acidt usually with an açidic catalyst~ Hydrogenation of the double bond in the cycloaliphatic xing can be do~e before or after esteri~ication with ~he aromatic 2Ci~.
It will be understood that the diesters used in the composition~ of this invention have somewha~
varying propertiP~. ~owever~ the following general correlation between tr~cture ~nd properties of repre~en~ative preferred diester~ thydrogenated LO

can be made~ -dilauryl ester . liquid, good heat ~tablli~y~
good lubricant bis(2-ethylhexyl)ester liquid, g~od heat ~tability, good lubricant . distearyl ester solid, good heat ~tability~
good lubricant bi~eth~xyl~ted)ester ~olid, heat stable, cohe~ive (15 moles ethylene oxide~
bisgphosphated ethoxy- Solid, heat stable~ cohe~ive, lated)ester (15 mol~s antistatic ethylene oxide) Representative of substituted alkyl R which may be used in the products of thi3 invention are butoxybutyl, 10-hydroxystearyl, lO~hydxoxydecyl ~ 10-halostearyl, ~-alkanoyloxyalkyl or the like.
Preferred diesters for use in accordarlce wi th the principles o:E the invention are those wherein:
A is CH2CH2 and (a) R is straight or branched chain alkyl of 4-20 carbon atoms, ~b) R is 2-ethylhexyl, laur~rl or stearyl, (c) R is HO (CH2CH20) nCH2C112- r is ~0 ~C3H6~ ~lC3H6 ~e) R i~ H05C~ )p~c3H6~)q~3~6 ' (f)~ R is (HO)2Po~CH~CH20~nCH~cH2- or a salt ~thereof~
(g) R.is c6~5co~c2~o)~c2H4-~
~h1 R is CH3C6H4C~(C~40)nC2 4 g

6 5Co(~H6~)nc3H6-~ and (~) ~ is CH3C6H4c~c3~60~n 3 6 . ~1~ wil~.be:-under~tood that.~he textile~reating COmpOSitlOnS can contain more than o~e diester~ . r a mixture of bis(alkyl~ ester~ or a mix~ure cont~;ning a bisalkyl ester in combination with a bis(polyo~y-alkylene1 or bis(phosphate polyoxyalk~len~) ester of .5~

a corresponding salt.
Ester of the types disclo~ed by Dumont (U. S.
Pat~.nt 3,694,257), Sturwold et al ~U. S. Patent 3,925,589) or Bishop et al ~U~ S. Patent 4~135~878 can be used in~tead of the cycloaliphakic dies~ers ~f Formula I or used to replace part of t~e diester~
of Formula I or up to about 45% by weight of the di-estex~ of Formula II.

"High boiling axomatic ester~ as used in ~he specification and claim~ means an ester oE the fonmula ArCOO-Rl-OOCAr or ArCOOR2~ wher~in Ar is monocyclic aryl of up to 10 carbon atoms; Rl is alkylene of 2-8 carbon atoms or polyoxyalkylene of the formula -Cr~2r (O-Cr~I~r~ ~ in which r is 2 or 3 and s is up t3 15; and R2 îs substituted or un~t~stituted alkyl or AlXenyl of 8 30 carbon atoms.
Accoxaingly t aromatic e~ters used in the prac-tice of this invention include, bu~ are not limited to, esters of benzoic, toluic, aimethylben20ic 9 trimethylbenzoic~ butylbenzoic and 5im~ 1 ~r acidsO
In the case o~ aromatic diesters, alkylene (R~ b~ e~ ler~e, PxoPyle~e, h.oxyleI~e, 2 ~, 2-dimethyl-trimethylene, butylene, heptamethylene ~d octylene, including various isomers thereofO
Polyoxyalk~lene aiesters include those derived from polyethylene glycol or polypropyl~ne glycol.-In ~he case of monoaromatic esters~ alkyl can be ~ctyl, nonyl~ decyl~ dodecyl, tridecyl, hexadecyl, stearyl and ~lkenyl can be any corresponding mono-unsaturated function~ e.g. d Oleyla Preferred aromatic diesters are ~hose whexein:
(a) Ar i3 phenyl, (b) Ar is tolyl, (c~ ~ is ethylene or propylene, including each of (a) and (b~, ~d) Rl i~ ethyleneoxyethylerle or prop~rleneoxy-propylene, in~ludin~ each of ~a3 and ~b3 (e3 Rl i8 polyoxypropylene of molecu:Lar weigh~
200 5ûO , including each of (a) and (b~, and ( f ) R2 i~ decyl, dodec:yl, hexadecyl " tridecyl octadec~ L or oleyl, including each of ~a) and (b~, Contemplated equi~alents of the high boiling aroma~ic esters de~cribed above include e~ter~ of benzyl alcohol and substituted or lmsubstituted aroma~:ic acids of ~ or moxe carbon ~toms J or ~ub stituted or unsubstituted aïiphatic acids of 8 or more carbon atom~, including bu~ nc~ limit~d ~o ~
benzyl laurate, benzyl ~elargonate, benzyl octoat~, benzyl palmitat~, benzyl stearate, benzyl oleate O
benzyl hydroxylsteara~e or benzyl benzoate. I~
will be understoo~ that est~rs of substitu~ed benzyl alcohol~ can aîso be used.
It ha~ been found that aromatic esters fall ing outside of the foregoing definiltion, more particularly 2 0 methyl, ethyl, propyl, butyl ~ pentyl and hexyl ben-zoates, lack heat stability, low odor and lubricating propexties required for the plurality o~ functions fulfilled by the compo~itioll~ of this invel~tion.
E:thoxylated castor oil used i.n the composikions will contain 15-100 oxyethylene unit~, preflerably 40-85.
The hydrogenated castor oil deriva~ives wiïl contain S-200 oxyethylene units, preferably 20-300 These material~ can be purchased from ICI America and Whitest~sne Chemical.
. Ethoxylated alkyl phenols used in the composi-tions of this invention will c:ontain up to 12 carbo~
atoms in the alkyl function and from 1 25 ethylene oxide ~ulitsl. l?referred exa~nple~ are ethoxylated nonylpherlol having 10 15 ethyle~e oxide uni~s 3~ Ethoxylated Al k~nols include tho~;e derived ~rom 12-15 c~rb~n alkanol~ including 3miX~U:1:25 the~e-~1 ' e)f 9 or from secondary alcohol~ of 11-15 caxbon atoms, al~o including mix~ures ~ and c:ontaining 6-15 ethylene oxide Wli~3~. .
E~ho~phated ethoxylated a:lkanol c: r phenol~ employed 5 in the compo~itions of the inventiorl will generally have fewer ethyleneoxide units than the unphosphated com-pound~ " Exempla~ " ~ut not limit2tive " of the materials which can be used axe ~e pota~sium ~alt~ of POE ~103 nonylphenol phosphate, POE ( 3 ~ 5 ) lauryl alcc: hDl phos 10 pha~e, POE (7) lauryl zllcohol phosphate, ~OE ~9~
laur~yl alcohol phosphate, POE ( 6 ) decyl alcohol phGs-phate, and POE ( 9 ~ decyl alcohol phosE~hate ~ It will be understood th~t the fc~rrnula given for the phosphated ethoxstlated aerivatives includes various products, in-cluding phosphated mono- and diestersJ obtained by reac~
tion between the ethoxylated diacids and P205.
In many cases, ~he comp~sition of this inven~ion will be left o~ the fiber during dyeing and will there-fore function as dyeing a~si~tants~ in which case 10-25% ~y weight.of a dye-levelling agent will be in-cluded~ "Dye-levelling agent~ as used in the speci-fication and ~laim~ t will b~ of the fonmula R3COOR~, wherein R~ i~ an e~hoxylated alXylphenol resi~ue of the formula a 2a+1 ~ O~CH2CH2 ~ C~2C~
, a is 0-1~ and b is 1-~4 or an ethoxylated alkanol re sidue of the formula 3~ ~2)c (CH2cH~o)d-cH2c~2-c is 7~12 an~ d is 1-24 and wherein ~3 is linear or branched alkyl or alkenyl of 1-~1 carbon atomsO phe~yl or ~olyl~
Accor~ingly, exemplary dye-levelling agents in-clude lauratP, myristate~ pa~nitE~tey coconate, oleate~

5~

~tearata, isos teara~e, ~enzoate and toluate e~;terB of ethoxylated nonylphenol ~ octylphenol, dodecylphens~
decanol, n-dodecanol, ra-tetradecanol or rl-hexadecanol.
The extent of ethoxylation ~B ~rom 1-25 ethylene oxide 5 l~litB per alkylph~3n~1 c~r alk~nol, prefera}:)ly 6-15 ethylene o~sid~ unit~,, .
Preferre~ dye-levelling agents ar~ those wh~rein l~a) R3 i~3 of 11 17 carbon atoms~ including mixtures thereof;
(b~ R3 1~ n C17~33;
(c~ R3 i8 n C17}~35 7 (d) R3 ~ 7E~35 (e~ R3 is phenyl i ( f 3 R3 i5 n C11~23;
I5 (yj a i~ 9 ~ including eac~ of (a) - (f~;
(h) c: is 11-14, .including mixtures thereof and including each o~ ~a) ~
~ i) b is about g.~, including each of (a3 - (f3;
~j) d i8 6 10~ including each o (a) - [f) ~
~0 ~k~ b is 6 15, including each s:~f ~a3 - (f3; and (19 a i8 9, b is 8-10 and R3 i8 n-CllH23.
The compc~itions are especially ~;uited for trea~-ment of synthetic f ibers such a~ polyester, polyamide "
and polyac:rylic.. The polye~ter may be spun or textured polyester or filament ox warp yarn and may hP woven knitted, tufted, needle punc:hed or non-wt~ven. The polyester can be a polyalkylene terephthalate " sus::h as polyethylene tsrephtha3.ate ~ ox a polye~ter mad~ f rom . cyclohF~ ne-dimetha~ol~ The polyami 31e may be of ~ypes 6, 6, 6 or 6 ,10. The acrylic may ~e stxaight acrylic rylonitrile) or moaacry3 i c (m~diied with vinyl c}~ ride, vinyliaene chlor~de)O The compo~tian~
are 21190 adapted iEor ~pplica~ion ~s:3 blend~ of the abo~re fil:Pers with aaLch ~ther and wlth e:ellulosics ~ 3 (cotton, rayon, eltt o ~ or wool.
The composition~ can be applied at any o several stages of fiber processingO The fc: llowiny are exem-plary o:E applicatic~rl to polyester fiber:
5 . A., Spin Fir~ish Applic~ation:
The (~omposi~ion i~ applied to the yarrl froIo a 15-20Ps emulsion to give a finish level on the yar~ o O. 25 - 10%~ The trea~ed yarn can be built irlto yar~
packages which c~ be used in high speed texturizing 10 machines.
Composition~ used as spin finishes will pre-ferably have the following compo~itional range~
~arts by Weight Cycloaliphatic: diester of Fonnula I . - .~ 20-40 High Boiling Aromatic Ester 20-40 Dye Levelling Agent . 10-20 ~nulsifiers, aispersing agents and/or anti-static agents 20-30 Most preferably, the compo~itions will corltain 25-3~ parts by weight of the cycloaliphatic diester and 25-35 part~ by weight of high boiling axomaltic ester.
Spin finish compositions will preferably s~ontain a cycloaliphatic aiester in which R is alkyl o 4-20 car-bon atoms, most pr~ferably 6-12 carbon atoms, The high boiling aromatic ester w.ill preferably be of a glycol~ most pre~erably diesters from ethylene, propylene, or butylene glycol and benzoic or toluic ~acidD
The d~e-levelling agent is preferably an ethoxy~
lated nonylphenol ester, especially o nonylphenol.
~he emulsifier~; etc. will preferably compri~e ethoxylated castor oil r ethoxylated hydxogenated castor oil and phosphated ethoxylated alkylphenol i~ ratios of 1 : 2 :-2 to 1 : 3 : 3 by weigh~.

1~ . .
A most pxeferred ~pin finifih compositio~ will consist essentially of Paxts by Weight Cycloaliphatic bis(2-~thyl~
hexyl) e~ter 25 35 .Propylene glycol dibenzoate 25-35 Ethoxylated ~onylphenol laurate 10-20 Ethoxylated castvr oil 4-6 Ethoxylated hydrogenated ~astor oil 8-12 Ethoxylated nonylphenol-phosphate, K sal~ ~-12 The spin finish compositions can be diluted with water to form a stable ~mulsion or dispersion for appli-cation. The spin finish is preferably applied to pro-duce a pick-up o~ 0.4 - 0.75% by weight~
A representative polyester treated to 0.5 - 0.6%
pick-up wi~h the spin finish composition of this in-vention has lower heat history eharacteristics than yarn treated with a conventional spin finish. Yarns thus treated can theref~re be textuxized at lower tem-peratures than possible herekofore and dyed at lower temperatures than pxeviously used. In addition, the spin finish aoes n~t smoke or ~ume during texturizing at 200-240C~ In the case of spun yarns, the finish enhances the oohesive properties of ~he yar~ and pro-vides the desired lubricity during picking~ ~ardin~0 drawing~:~oving and sp; nn; ng O
It ;s recommendea that, once the spin finishing - compositions of this invention have been appliedp no conYentional lubxicant~ be used, so as to prevent adulteration of the finishes. Maximum bene~it is ob-tained by exclusive use o~ the compositions of ~h~
inve~tion through conversion of the $reated yarn to piece goods and dyeing, Spin fini~h composition~ u~ing the cyclt~aliphatic diester~ of ~ormula II will pre~erably ~e wi~l~in t~e following llmits: -Part3 by Weight 5 . Cycloaliphatic die~t-~r of F~xmula ~I 4û-~0 Dye-levelling agent 5-25 Emulsifier~ ,~ disper~ing agent~
and/or anti-sta~ic agents20-30 Mo~t preferably 7 the ~pin :Eini~;h compositions 10 will contain 50-70 parts by weight of a cycloaliphatic diester of Formula II and 1~-~5 parts 2: y weight of dy~ levelling agentO
B. Knitting Applicatîon The composition is applied ~ a Xnitting lubricant 15 a~d i left on the y~rn during subseguent yarn processin~.
That is, the lubricant need not be scoured off as are conventional lubxicant~. The capability o omitting a previously r~quire~ proces~ing step is an importarlt advantage in utilizing the teachings of thi~ invention.
During weaving or knitting, high temperatures are reached due to frictio.n an~ speed~, but the lubricants in accordanc~ with the invention remain functional and d~ not gum up or build up on equipment~ In the dyeing ~tage, the lubricant/dyeing asQiStant does no~ break down during the dyeing cycle 1250-270F~ and~Dr smoke du.ring drying and heat setting of the fiber. Elimina tion of ha~y blue smoke during drying and heat ~etting is impoxt~nt because of i.ncreasingly ~tringent stan~
dards against air pollutiGn~
The lubricant composition~ of ~hi~ inven~ion pre~
ferably will be of the following cc ~ition:
. ~Par~ by Weight Cycloaliphatic die~t~r of Fonmula ~- 10 30 ~igh boiling aroma~ic ester . ~-60 35 Dye-levelling agent . 10-30 Emulsifiex~ etc~ - . 10-30 ~L~

MoBt preferably, the composition will contain 15-30 par~s by weigh~ of cyc:loaliphall ic die~ter; 25-4~ ~art~
by weight of high ~olli~g aromatic ester and 15-25 part3 by we~ ght of dye-level ling agent~, S The preferred ~yc:loaliphatic slie~er arldl dye-levelling age~t- ar~3 a~ for the ~pin-fini~hing composi~
tion~ However, the high boiling aromatic is preferably a dibeIIzc~at~3 or ditoluate o~ di- or triethylene glyc~l or di~ ~r tripr~pylerAe glycolD .
The conventiorlal emul$iler and anti-s~atic agents prefexably are ethoxylated alkylphenol~ and the corres-ponding phosphate e~ters I mo~t pref~rably ethoxylated nonylpherlol .
Other matexial~ in the lubricant composition can inc:lude an anti-oxidant O such as butylatedl hydroxy-toluerle, in an amoun~ of up ~o 0,,5% by weigh~; an alkanol-ami~e s su~h as t:riethanola~ e, in an amount up to 5.0% by weight" and up to '~ ~)% by we~ght oiE water.
A most prefexred lubr~cant compositio~ comprises:
2 0 Parts by We ight Cycloaliphatic bi~; (2-ethylhexyl~ estex 25-35 Dipropylene glycol dibenzoate;~ 45 Ethoxylatea nonylphenol laurate 15-25 Ethoxylate~l nonylphenol : 5-15 ~5 Butylated hydroxytoluene O . 05-0 9 2 Ethoxylated nonylphenol phosphate 5-10 Tx.iethanolamine 1-5 l~ater . 1- 2 For satisfactory perf)xmance~ he take up, expressed 30 a~i r; n; percent eactrE~ctables, when the treated abric or fiber i5 loadea into the dyeing machine, s~ul d be at lea~t s ~ in:~-tn~.m ~ ex~rac:table ~yclo~liphatic die33ter o:E Fo~ul~ I 0.075 ~iyh boiling aro~a~:ic ester ~. ~ 0~075 Dye-levelling agerlt o 0 050 Add-on levels will vary depending on the point in the fiber processing at which the lubrican-t is applied, but will be from about 0.25 to about 5.0~ by weight of the fiber. During knitting, the add-on is pre-ferably 0.5 to 1.5% by weight.
In formulating knitting lubricants using aliphatic diesters of Formula 11, the preferred composition will be:
Parts by Weight Cycloaliphatic diester of Formula 11 10 60 Dye levelling agent 10-30 Emulsifiers, dispersing agents and/or anti-static agents 10-60 Most preferably, the lubricant compositions will contain 20-40 parts by weight of diester of Formula 11 and 15-25 parts by weight of dye-levelling agentO
For satisfactory per-formance, the take-up, expressed as minimum percent extractables, when the treated fiber or fabric is loaded into the dyeing machine, should be:
Minimum & Extractables Cycloaliphatic diester of Formula 11 0.45 Dye-levelling agent 0.05 ~dd-on levels will generally be adjusted as for the lubricant containing the diester of Formula 1.
Another type of knitting lubricant prepared in accord-ance with the invention will be of the composition:
Parts by Weight Cycloaliphatic diester of Formula 1 5-15 High boiling aromatic ester 30-50 Dye-levelling agent 5-15 30 Emulsifiers, etc. 10-20 Ethylene oxide-propylene oxide copolymer 10-30 .~,~,j .....
,~,.~,,1 3~ f~
lB

The ~nitking lubricant~ may also contain up to O. 25~ by weight o an anti-oxidant and up to 5% by weir~ht of an alkanolamine~. Og~ dibutylethanol~mine.
It i~ preferred that the knitting l~bricant~ contai~
a cycloallphatie diester in which R i~ al~yl of 4~20 ~arbon atom~, more preferably 6-12 carbon atom~.
The preferred high boîling aromatic e ter will be a dibenzoate or ditoluate of ethyl2ne or propylene glycol~
Propy~ene glycol dibenzoate is particularly preferred.
The ~ye-levelling agent used in the ~nitting lubricant compo~ition i~ preferably an ester of an ethoxylated alkanol~ more preferably the decanoate~
laurate, myristate or palmitate of ethoxylated decyl~
lauryl, myxistyl or hexadecyl alcohols~
Ethoxylated alkanols and corresponding phosphates are preferred emulsifiers in the knittin~ ~ubricant.
Ethylene oxide-propylene oxide copolymex of molecular weiyht 200U 5G00 is pre~erred, A most pxeferred knitting lubricant l~S
Parts ~y Weight Cycloallphatic bi~2-ethylhexyl~ester B-12 Pxopylene glycol dibenzoate 35~45 $thoxylated lauryl laurat~ 8-12 Ethoxylated lauryl alcohol 8-12 25 Butylated hydroxytoluene 0.5-2 Ethylene oxide-propylene oxide copolymex 20-25 E~hoxylated lauryl alcohol phosphate .:-3-6 Dibutylethanolamine 1-3 The lubrican~ is applied by drip~,~n~ or misting on to ~he needle~ to an uptake of 1-2~ ol~ the yarn. The thus-applied composit~on provides fib2r-metal and metal~
metal lubrication at te~peratures o 10~-150 ~Fo The comp~sition does not bre~k do~m or gum up the kn.itting m~h~n~

. .

1~

The foregoing lubricants, ~f left on tha cloth or yarn during the dyeing ~tepr pro~ote ~niform dye uptake.
In fact, their presence ~i~s dye exhau~tion at 240 270~F.
The lubricant~ do not. cau~e exce~ive foaming or affPct 5 . fastnes~ properties of the dyed fabric.
Lubricant cont~;n;n~ a diestex of Fonnula II will contain 20 50 parts by weight of this material5 Other proportions of in~redient~ will be as above.
Use of ~hese compositions substan~ially reduces or eliminates carrier odor and smoke inside an~ out~ide processing plants. In addition to reducing air pollu-tion, use of the l~bricant compositions of thi~ invPn-tion reduces water pollution. Generally, plant sur charges for high BOD/COD or separable oils become unnPcessary.
C. Application as Coning Oil:
For use as a coning oil, int~nded for application after texturing or during windi~g of the yaxn; the -^
compositions o this invention will al~o contain a major amount, up to 70~ by weightJ of ethylene oxide-propylene oxi~e copolymers of molecular weight 2000-5000.
Exemplary of an appropriate material are Ucon ~ LB and.
HB (U on Carbide Corp~), the Pluronics ~ ~BASF) o~
. Jeffox fluids (Texaco, Inc.~.
Coning oil compositions in accordance with the in~ention will ~clude:.
- Parts by Wei~ht - Cycloaliphatic diester of Formula I 5-10 High boiling aromatic ester5-10 30 Dye~levelling agent 2-5 Emulsifiers, dispersing agents an~/or anti-sta~ic agents 10-20 ~thylene oxide-propylene oxide : copolymer 60 70 ~referred cycloaliphatic die~ers fox coning oil composition~ include tho~e in whlch R i~ alkyl of 4-20 carbon atoms~ mo~ preferably 6-12 carbon atoms~
The high boiling aromatic ester will preferably be of an alkanol of 8-30 carbon atom~ m~re pre-ferably ~ecyl, iau.ryl or myristyl benzoate or toluate~
The dye-level1ing agent will preferably be an ester of ethoxylated alkylphenol, mo~e preferably of nonylphenol.
The emul~ifier~ will preferably be ethoxylated alkanols~ the corresponding phosph~te~ and ethoxy~
lated hydrogenated castor oilO
Other ingxedients in the coning oil composi-tions can include up to about 0.5~ by weight of ~n antioxiaant, such a~ butyl~ted hydroxytoluene, up to about 2.5% by weight of an alkanolamine, such as triethanolamine and up to 2.5~ by weight of water.
A most preferx d coning oil formulation i~o Parts by Wei~ht Cycl~aliphatic ~ 2-ethyl-hexyl~ester 6-B
Lauryl benzoate 6-8 Ethoxylated nonylphenol coconate 2-4 25 Ethoxylated lauryl al~ohol 8-12 Ethoxylated hydrogenated castor oil ' 2-~
Ethoxylated nonylphenol phosphate 2-4 30 Ethylene oxide-propylene oxide copolymer ~0-70 Butylated hydroxyltoluene 0.05~0~2 Triethanol~mine 0.5-2 Water o 5-~
., .:

Coning oil in accordance with the invention penetrate~ the fiber rapi~ly, but does not ~ling off the fiber or feeder roll during application~
The treated yarn ~ 8 lubricated ~llfficiently for the 5 yarn to be rapidly con~d~ ~nitted or woven~ The composition i8 ~table and doe~ not smoke, yellow or discolor at temperatures up to about 150~F.
D. Dyeing:
Dyeing assistant compositions in aceordance with the invention will consi~t of:
. Parts b~ Weight Cycloaliphatic diester of Formula 1 is ~
~igh boiling aromatic ester 20 55 3ye-levelling agent 10-25 15 Emul~ifiers~ etc~ . 10-30 The cycloaliphatic die3ters utilized for this aspect of the invention will pxefer~hly be those wherein R is alkyl of 4-2Q carbon atoms, preferably 6-12 carbon atoms.
2G ~referred high boiling aromatic esters for this utility are dibenzoates and ditoluates of mono- and diethylene or propylene glycols~
Dye-levelliny agents preferred for~this aspect of the invention will ~e ester~ of the ethoxylated alky~phe~ols, particularly ethoxylated nonylphenol.
-It is preferred that dyeing assist~nt composi-tion~ also contain ethoxylated castor oîl and ethoxy-lated hydrogenated castor oil; as well as the phosphate (potassium salt) of an ethoxylated cycloaliphati.c diestex, that is, R is pho~phat~d polyoxyethylene.
Prefexabl~8 thb dyeing assistant compositions will contain 15-35 parts by weight of cycloaliphatic diester, of Formula I, 3~ parts ~y weight of high boi~ing aromatic ester and 1'0 ~ parts by weight of dye-~evelling age~t~ .

:D ~ .?~

.
A mc)st pref~rre~i dyeing assi~tant composltion will contain:
P~rts by Weight - (:ycloaliphatic: bi~ ~-2-et~yl-hexyli e~tex 1S-25' . Dipropylene glycol ~iben~oate 35-5~-POE nonylpheno~ laurate 13-20 POE castor oil 4-6 POE hydrogenated castor oil8- 12 lQ POE ~ycloaliphatic diester pho~phate, ~ 8alt 8-12 Cycloaliphatic diester3 of Formula II are used in dyeing assistant composition~3 containing:
Parts by Weight Cycloaliphatic diester of Fonnula II 4 0- 9 0 Dye-levelling agents 10-25 Emulsii~rs, e c. 10-30 More preferably, these composi~ions will contain 20 55~80 parts by weight of cycloaliphatic diester of }~on[lula II .
A most preferred dyeing assistant composiiion will contain:
Parts by Weight 25 Cycloaliphatic diester o:
Formula II, R is 6H5C (C3H60) 1~C3~i6_ 55~65 POE (9 . 5) nonylphenol laurate 15 25 POE (80j casto:r oil 5-15 POE ~25) hydrogenated castox oil 5-15 The s:ompositions ' are ap3?1ied toj!th~ dyebath at a level s:~f 00 25 - 1. 0~ " based oll the weight ~f ~he goods ,, The dye ba~ i~ acidic: (p~ - 5 ~ O. 5) an~ :on~ains dye as the only additional ingredient~ ~'hi~3 i5 35 unl i ke co~ventiollal proce~ g requiring a dyeing as~ tant o:E 2~4% ana other a~11iary 1eve11ing agents. Furthermore, the dyeing cycle is ]ess sensitive to rate of temperature change than in conventional systems.
The dyeing temperature in both systems is usually 265F
in jet dyeing equipment.
Dyed yarns obtained using the compositions of the invention compare favorably with conventionally dyed yarn in properties s~lch as light-fastness, crocking, shade depth and levelness.
Accordingly, the compositions of this invention, applied to a synthetic fiber when manufactured, or used as a processing aid for texturizing instead of prior art lubricants, both improve the dye affinity of the fiber and generally eliminate the need for further downstream pro-cessing and consumption of chemicals associated therewith.
Typical processes or treating agents eliminated include:
(1) Lubrication during knitting or weaving (2) Scour and removal of lubricant (3) Dye carrier during dyeing (~) Dye dispersant during dyeing (5) Dye leveller during dyeing (6) Fiber lubricant during dyeing

(7) Defoamer during dyeing

(8) Afterclean and scour after dyeing

(9) Winding lubricant for dyed yarn A most preferred general purpose textile-treating composition consists essentially of:
Percent by Weight Bis(2-ethylhexyl) cycloaliphatic ester 15-25 Propylene glycol dibenzoate 30-50 Polyoxyethylenenonylphenol laurate 15-20 Polyoxyethylene hydrogenated castor oil 5-15 Polyoxyethylene castor oil 5-15 i,, !

3~

Without urther elaboratior~ belleved that one ~killed in the art can, using the preceding de scription 9 util~ze the pre~ent inventiGn ~o it~ fulle~t extent. The folls:wing ~pecific embodiments are 1, 5-. thexefore, tv be construe~l as merely illu~tra~ive and n~t limitatilJ~ of the remainder of the disc:losure in any way wha~soe~7er.: i ~n-~he ollowing examples, the ~
temperatures are ~et orth uncorrected in degree~ elsius.
Unles~ otherwi~e indicated, all part~ and percen~agPs are by

10 weight.

Example 1 Praparatio~ o~ Dialky~ Ester ~A is -CH2CH2-, R i~ 2-e~h~lhexyl)O
To three-necked flask ~itted with ~tirrer~ ther-mometer, nitrogen purge, condenser, side-arm receiver and heating mantle were charged 352 ~ ~1 mole) of Diacid 1550, 273 g (201 moles) o~ 2-ethylhexanol, 1~5 g of p-toluenesulfonic acid and 2 g of decolorizing carbon.
Air wa6 purged rom ~he flask wi~h nitroge~ and the 2C reaction mixture wa~ ~tirred and heated to 160-173~C
for 4-6 hours. Water formed during the re~tion was collected in the ~ide arm receive.r~ The reaction was continued until the acid value was below 5 mg KOH/g.
- The catalyst and carbon were removed by filtration.
~5 ~he ester product and 2S gx~ms of nickel on kies21-guhr wer~ charged to a stirredt heated pressure ve~selO The mixture wa~ heated to 160-170C and pre~urized to 4Q0 p~ig with hydrogen. A sample was taken after 6-8 hour~ and the iodine value was determined. . The reactio~ was continued un~il the iodine ~alue wa~ below 0~5 ~ o iodine/100 g of sample~
The product was cooled to 50DC and the catalyst r ~l..... ...oved ~y filtra ion~
Esters ar2 prepared ~ larly from (1~ Diac.id 1550 ~nd decyl alcoholg 1 ~ 2 molar .

.

ratio.
~ 2) Diacid 1550 and tridecyl alcohol, 1 :
molar rati~
(3~ ~iacid 15SO and Neodol 25, a mixtuxe o~
C12-C15 linear alcohol~ 2 molar ratio (4) Diacid 1550 and butanol, 1 o 2 molar ratio.

Example 2 Preparation o~ Polyoxyethylene Diester ~ C~~C~-, R is HO (C~2cH2o) n 2 2 1~ l`o a stirred autocïave fitted with heating and cc)oling coils was chaxged 352 g (1 mole) of Diacid 1550 Catalyst ~1, 0 g of potassium hydroxide) wa~ charged to the reactor. The temperature was rai~ed to 110 C
and the reactor wa~ vacuum strippetl for 30-60 mi~ute~
to remove any residual water from previous wa~hing of the reactor or from one or more o~ the charged reacl:ants or catalyst. The reactor was purged with nitrogen to remo~e air, evacuated again and purged again with nitrogen~ It was stirred and heated to 140C and 100 g ~3 moles~ of ethylene oxide was added to the reactor4 ~he pressure inside the reactor ; ^~iately bu.ilt up to 30-50 psig, After 30-60 minutes' induction t~ne~ an exothenmi~ polymerization reaction (to 150-16GC) beyan with an accompanyi2lg pre~sure drop to zero (0 psig) as ethylene oxide was consumed. ~thylene oxlde wa~ added to the reactor to a t~tal of 660 gram~ (15 mole~). The tempera~ure was main~;ne~ at 150-160C ~y cooling. Addi~ion of ethyle~e oxide was ~topped and the reaction wa~
allowed to continue for an additional 30 mlnutes.
Thb re~ctor was cooled to 90-100C and purged ~wice with nitrog~n.
A sample of the product had a hydroxyl ~lue of 110 mg of RO~g ~15 mole~ of e~hylene oxide added to ~he dia~îd). The dies~e~ wa3 acidified with aceti~

2~ .

acid to neutralize the pot~ium hydroxlde cataly~t and 3 g of hyd~ogen peroxide was added to bleach and lighten the color of the product~ The reactor wa~
cooled to 30~C and the product wa~ filtered through 5 filter paper u~ing a porcelain filtex.
B. Reduction to the Polyoxyethylene Die~ter C~2C~2-~ 8 . ~he product of Example 2A and 25 g of nickel o~
kieselguhr were charged to a stirred t heated pressure vessel. The mixture was heated to 160-170C and pre~surized with hydrogen to 400 psig~ After 6-8 hours, s~mples were remove~ at intervals for deter-mination of the iodine value~ The reaction wa~ con-ti~ued until the iodine value wa~ le~s than 0 b 5 g~100 g o sample.

Example 3 Preparation of Phosphated Polyoxyethylene Diester (~ ls -CH2CH~-, R is (Ho)2~tcH2c~2o)nc~2c~2 ~
Polyethoxylated ~15 mole~) diacid, obtained as in Example 2B wa5 heated to 50-60C~ stirred and purged thoroughly with nitrogen to remove air. To abou~ 1015 g (1.0 mole) of ~hi~ material was added 24 g (0.17 molel of P2O~ An immediate exothermic reaction occurred ~exotherm to 85-95C~ The reaction mixture was mainta$ned at ~hi~ temperature by cooling and an ~dditional 24 g (OO17 mole) of P2C5 was addedu ~he reaction wa~ continued for 3 hour~ after all the P205 was adde~. The reactor wa~ cooled to 50C prior to rem~val Qf a ~ample, Th~ product had an acid value of 32 m~ R0~/g (indicate~ the re~cl:ion i~
: complete~O Tbe batch wa~ bleached at B5-95C wit~
! 5 g of hydrogen peroxide~ cooled to 30C and filtgEedO

. . ~7 .

Example 4 Preparation of Pxopylene Glycol Dibenzoate~
To a 3-~ecked 1ask fitted with stirrer, con denser~ receivar, ~hermomet~r, nitrogen purge and hea$ing mantle were charged B4 g (lo 1 mole) of propylene glycolt 2~4 g ~2 moles~ ~f benzoic acid ~nd 0.8 g of p-toluene~ulf~nic acid, Air was purge~
from the flask with nitrogen and the contents of the flask were heated ~o 1600170~C~ Water formed by the reaction wa~ remo~ed continuou~ly~ The reaction was continued until the product had an ~cid value below 5 mg KO~Jg~ The sample wa~ cooled and filtered.
Other e~er~ axe prepared using the following reactant~: -(1~ dipropylene glycol and benzoic acid, 1 ~ 2 molar ratio - .
(23 PPG 200 and benzoic acid, 1 : 2 mol~r ratio (3) PPG 500 and benzoic acid, 1 : 2 molar xatio~

Example 5 Preparation ~f Polyoxye~hylene Nonylphenyl Laurate~
To a three-necked fla~k fitted out as in Example 4 was char~ed 750 g (1. 1 mole) of polyoxyethylated nonylpherlol (9D 5 mole~ o oxyethylesle, NP 9D~ 208 g (1 mole~ of lauric i3cid and 2.4 g of p-toluellesulfonic acid. Aix wa~ purged from the fla~k with nitrogen and the mixtuxe was heated to 160-170C until an :acid value below lû mg KOHJg wa~ ob~ainedO l~e product wa3 cooled and filteredO
Other polyoxyethyl~ne nonylphenyl ester~ are made in a s~nilar -fa~his:)n from- -(1~ NP 9D 5 and c3~oonut fatty ~cid~ 1 : 1 molar ratio (2 ) NP 9 ,. 5 and oleic: ~cid ~ 1 ~ 1 molar ratis~

~.~.$~ f~

(3) N~ 9O5 and stearic acidp 1 : 1- molar ratio ~4) NP 9.5 and benzoic acid, 1 : 1 molar ratio.

Example 6 ~thoxylated ca~tor and hydrogenated castor oils were prepared a~ in Example ~6 ~thylene oxide adds to the hydroxyl`group of castor oil~

Example 7 A textile treating composition was made by com-bini~g materials prepared a~ above in the following amounts by weight . % by wei~ht Bis-2-ethylhexyl diester ~Ex~mple 1) 20 Propylene glycol dibenzoate 40 Polyethoxyethylene nonylphenol laurate (9.5 moles ethylene o~ide~ 20 Polyethoxyethylen~ hydrogenated c~stor 125 moles ethylene oxide~ 10 Polyethoxyethyle~e castor (80 moles ethylene oxide~ 10 ... .
~xampl~ 8 The textile-treating composition o~ ~xample 7 wa~
applied during the dyeing cycle to a 10 g swatch of T56 textured polyester test abric by the follnwing tech-ni~ue:
.The 5ample swatch was placed in a stainles~ steel .. beaker: cont~;n;ng 150 ml of water, 0.067 g of disperse yellow 67, 0~091 g of disperse red 91t o.a26 g of dis-perse blue 56, 0.1 ~ acetic acid ~56%) and 0,03 g of the textile-treating COmpQSitiOn. The beaker was sealed and pl~ced in a launderometer s~t at 38DC. The tempexa-ture was raised at 4-~C per minute to 130~C and held for 30 mirutes. Thd beaker wa9 cooled at 4 5C per .

.

minllte to 5~ C and removed f rom the launderometerO
The polye~tex s~atch wa~ removed from the beaker~ It wa~ lmifoxmly dyQd in a medium brown ~hade. Nearly all of the dye wa~ exhausted rom the a~sueou~ solut:LonO
The ~watch was rin3ed with c~ool water and dried in an oYen at 121 oc.

Example 9 Texturized polyester doubleknit ~1500 pounds~ were loaded into a 6 por~ Gastoll Cous~ty j t machirae. r~he machine wa~ filled with water ~d the goods given an ovexflow wa~h. The machine wa~ refilled and ramped to 60C. Fifteen pounds of acetic acid ~56%3 and 4.5 pounds of tlle compo~ition~ of Example 7 were dropped into the jet from th~ drug rosm. Aft~r 5 minute~ ~ 18 pourlds of Samaron Yellow 6 GSL ~disperse yellow 114), 15 pounds of Bucron Rubine 2BNS (disperse xed) and 13 pounds of Foron Blue 5BGI, ~aisp~rse blue 73~ were added to the j et machine f rom ~he drug xoom~ ~Jrhe j et was sealed off and ramp~d t;~ 130~C~, The tel[lperature was held for 30 minutes at 1309~ and ramped back to 56C,, The ~abric wa~ patched for ~hade, the ~hade matched standaxd~ The tempeLatur~ wa~ dropped to 38~C. The spen~ ~e liquor wa~ dropped and the machine re-illed with waterO The goodLs we~e rinsed thoYoughly and removed from the jet. The goods were f3lit, .
dried and inspect:ad. Final inspection indicated goods of excellen~ ~uali !ty ,, During the dyeing c:ycle IlSiIlg the compos ition of Example 7, the odor level in the dye house was much low~r tharl observed with conYerltic>nal systems.
Little smoking from ~he ovens wa~ observed during drying and.heat setting at ~he end o:iE the dyein~
cycle ~ ~plalyee comfcart was therefore si gnifican~ly .i...~Lov~2d.

The dyeing assistant undergoe~ Eacile degradation upon being fed to the plant effluent. The following values were obtained.
ConventionalDye Assistant System As Above COD mg/kg 2,~40,0002,210,000 ~OD mg/kg ~ 2,000 750,000 Ratio, COD:BOD~1300:12.95:1 Because little of the dyeing assistant remains on the fabric after dyeing, use of the product of Example 7 does not affect fastness propexties of the dyed goods.
The foregoing is typical of production-scale appli-cation of the composition.

Example 10 The procedure of Example 9 was repeated, except that no composition of Example 7 was used~ Upon patching at the end of the dyeing cycle, the shade is sligh-tly off due to incomplete dye exhaustion. The bath temperature was taken back up to 132C and held an additional 30 minutes.
The next patch indicated the shade matched the standard, whereupon the goods were rinsed, removed, slit and dried.
Upon inspection, the goods were found to have dye streaks, rope marks, bad barre coverage and a generally unlevel dyeing from end to end and piece to piece. The goods had to be reworked by being loaded back into a dyeing machine and treated with additional dye and levelling agents. The goods were kept in the machine for 3-~ hours until a level dyeing was achieved, but the fabric had a poor appearance as a result of prolonged processing.
This comparative example shows that omission of the composition of the invention produces an unaceeptable dyeing.

"~
i ~

Example 11 A textile-treating composition is prepared from the following ingredients:
Percent by Weight bislauryl diester IExample l~ 20 dipropylene glycol dibenzoate 40 POE (9.5) nonylphenol coconate 20 POE (80) castor oil 10 POE (25) hydrogenated castor oil 10 This composition is comparable in properties with the composition of Example 7.

Example 12 A textile-treating composition is prepared as in Example 7, except that 22% by weigh~ of polyoxyethylene diester (Example 2B) and 28% by weight of propylene glycol dibenzoate were used. The composition enhances processing of polyester fabric as described in Example 9.

Example 13 A textile-processing composition is prepared as in Example 7, except that 18% by weight of phosphated poly-oxyethylene diester (Example 3) and 42% by weight of dipropylene glycol dibenzoate are used. The composition improves the processing of polyester fabric and acts as an anti-static agent.

Example 14 (a) A textile-treating composition was prepared as in Example 7 from the following:
Percent by Weight Cycloaliphatic bis(2-ethylhexyl)ester 30.0 5~
3~ ` :
Part~ by Weight Dipropylene glycol dibenzoate 30 7 0 POE ~ 9 ~ 5) nonylphenol laurate 15 . O
POE ~B0) ca~tor oil PC~E ~25~ ~drogenat~d castor oil 10 . O
POE (15~ die~ter ph~sphate poltassium salt (Example 3) ln. 3 (b) The composition thu~ obtained wa~ appl ied from a 20%- aqueou~ solutio:n as a spin finish t:o l~i0 10 denier polye~ter fiber, which was then spun and tex~
~ured. The finish of the yarn ( foy~ prior to tex-turizing was 0.29%; after texturizirlg foy was 0025%~
The textured yarn built a satis:fa~tory package,.
Spin finish ~ applied ~ above, did not smoke, 15 dxip, build uE~ on heater plate~ or cauFte other undesirable rl~nrli ng conditis~rls 1, The texturized yarn was knitted on an Invoit 18 Gauge ~ch; ne into a double knit fabric,. The yarn krlitted well ~ with a minimum hPat huild up on the 20 knittiIl~ machine. No haze, m~st ox odor was ob-se~ved i~ the knitting plantO
Tha fabric wa~ taken to the dyehou~e arad loaded into a 6-port Gaston Cou2lty j et machine . l~he goods were neithex over10w wa~hed nor scoured. Foaming 2~ during loading of the fabric was significantly lower than that nf fabrics treated with conventional lubricants. The fab.ri~ wa~ dyed a~ in :~:xa3nple 9 to yield a produs~t judged of ~uperior qualityO
Both dye yield and barré coverage were improved 30 as~d ~he fabric had a better overall appearance than mtreated fabrics~

~ a3 A spin finishing compo~ition was prepared f~o~:
' ~3 ~3 Part~ by Weight Cycloaliphatic bi~ (2-ethylhexyl) e~tex 30 Propylene glyrol dibenzoate 30 POE (9~ nonylphenol ~aurate 15 l?OE ~81) ca~tor oil 5 . POE (253 hydrogenated ca~tor oil 10 POl~ ( 10 ~ nonylphenol phosphate, ~ salt lû
~ b) The compo~ition of part (a~ was applied, a1 a 20~ ~nulsion, to polyester yarn (505 denier/34 fila-10 ment~ fxom a si ngle merge ~o as to as::hieve 0. 5 ~ O 0 6%dry pick~upD The treated yaxn and yaxn treated with conventional lubricant (Diamond Shamrock FT 504, con-t~ininy a fa~ty ester lubric::an1:, noniorli~ ethcixylate emulsifiers and anti~tat at û. 5 -- ûO 6% picX-up~ we:re textured at 20S-220 C on a sample Scragg X-2 tex~turing machineO After texturing, the tx2ated yarns were tested fc~r the:rmal and other propertiesD The fol-lowi~g results were obtained.

St~ne~d Spin Fi~ish o Spin Finish Example 15 ~a) Tube ~:olorViolet~Sreen Stripea Or~ge nii~r ~hor~ denier me~hod)~164 -167 1 A-ri&rt~ Co~,t Density (D~n~ity gr dient ~ube methc3d), gfcc 1. 3883 1~, 3856 ,",, (rang~ of 10 sam (range of 10 sam~
ples, 0.001~ ples, ûoOOC3) TMA ~Therrnomechan~ cal Analysis~ 165aC 145C C recheck, 168C reche~k, 148C
DSC ~Di~ferential SCAnni ~g CAlcsrimetry), C 15~C 1 52C
Lubricant (~3ther Soxhl et Extract~ on) O ~ 31 0 ~ ~1 .
TMA is a measure of softening or melting tendency of yarn heated under a con~tant tensionO l'he decxease in TMA and DSC of the tes~ yar~ indicate~ that the degree of crystallinity i8 lower than t~at of yarn 5 txeated with a conventional spin fini~h. Accor-dingly, treated fibers could be texturized and would absorb dyes at low~3r temp~ratures than customary, resulting in decreased energy experlditure.
(c) Photomicrograp~ic studie~ of yarn cross sections indicated that both yarns maintained th~ir co~figurationsO Accordingly,-it is thought that o~served change~ in heat history were caused by changes in crystallinity inauced by the spin finish applied. Dye penetration of both yarn lot~ was essentially e~uivalent~ but dye absorption of the fibers treated with the compositions of this Example are higher. The photomicrographs (Figs. 1-4) also show that ~he crystallinity o the test specimPns has been changed.
(d~ Lubricating properties of the yarns was evaluated on ~ha Scragg X-2 machine under varying conditions " The yarn was textured at 34 0 meters~min at 205-220C.
The following results were obtairledo Package Disc/ Draw . Center ~ea~ed - Break No. Yar?l Ratio Spindle T T Den. Shrinkage Shrinkage - ~peeds - Tension 1 2 _ % Elongation Conventi onal Spin Fin-ish :- (Average) - 1 lc~l 3,.~55 3~.û 44 ~7 1~8 1~ 535~18, Fiber Fini-~h of Example 15 la) 1 . gl 3~, 20~ 3~ . 0 4~ ~7 170 16 515~18~ 5 ~"
1. 91 3. 25-5 36. ~ ~S 5~ 1 6~ 13 5~9/1~ 3 3~ O gl 3. ~6 3~ u ~ ~7 54 1~ 13 524 41~ 91 3. 25~ 35 . 0 Sl 3~ 1~8 1~ 538~
5~ . gl 3. 255 3~ . 5 4~ 48 166 ~5 526~1 g 6 3GG m/m 36 O 0 45 49 168 15 535~18 71 ~ 91 3 a 25~; 3~i o 5 4 0 ~;5 165 1~1 534~17 c~ 7 8. D ~ ~ ~ 5 3 7 ~ 3 8 8 0 1 6 9 ~ ;~ 4 9 4 ~
g~ ~ 7~ 3 ~ 255 3~; ~ 0 4~ 57 ~ 6~ 1 4 501~16 ~/ 6 101. 96 3c 2/i5 36 ~ 0 45 ~7 168 1~ 5:~!5~7 7 99 3. 255 36. 0 ~6 ~6 16~ lS 537/1 7 .
The rictional propertie-q, breaking ~trength, elongation and heated shrinka~e were judged equi-valent~
(e) mhe eff~ct of textuxing tempera~ure on dye uptake of yarn kni~ted into a sock and dyed.was studied from 180 230C. Dye ab~orpti.on by the fibex was mea~ured usin~ a Macbeth Color Ey2 instrumentO
The test lot was texkurized using the composition of Example 15(a) and contained no other additivesO
The control lot contained ~ipochem TA-3, a commercial dye carrier co~t~; ni ~g chlorinated solvents~ methyl~
naphthalene and emul~ifier~.
The K/S value~ (Kubelk-Munk/Scattering) were calculated as follow~:
~ _ (1 reflectance~2 /S 2Xreflectance The K/S value is dlrectly propoxtional to the c~mount of dye on the fabric~
The following result~ were obtained:
Temperatuxe K/S with R/S with Fini3h % Color C ~arrier~f ~xample 15~a~Increase 180 5.~9~ 6.58~ 9~7 1~5 ~.g~7 6.510 1~
190 5O8~ 6.556 12.8 195 50 814~ 6 . 432 1~ ., 6 2Q0 5.721 6~4~6 12,3 205 5.719 ~ 6.4~4 ~3.~
210 5.715 ~49~ 13.6 215 5.81~ 6.542 12~
~20 5.~7g 6.614 12~5 225 5.~93 6.73~ ~2~4 23~ 6.151 6~ 12.~
These re~ults show tha~ th~ tesk fabrics had K~S
values about 10% higher than a fabric dyed using a convenkional carrier r In additon, dye uptake was relatively unifonm over a wid~ temperature range for . 38 texturing. The~e data further indicate that spin fini~h application i~ relatlv21y more un~form than heretofore~
~f~ Large scale q~antitie~ of polye~ter tex 5 turized f~llowing use of the pin ~ini~h of Example 15(a) were knitted i~to fabric and dyed in Gaston Cou~ty Jet Machine~ without addition of lubricarlt, leveller, dyeing a~s~stant or dye carriPr. The treated polye~ter consistently gave 7 12~ higher color yields than usual. Heat history barré seconds dropped 3 30%, deRending on the style and shadeO

Example 16 Lubricant of the following compo~ition was prepared:
Parts by Weight Cycloaliphatic bis(2~ethyl-hexyl)ester 20.0 Dipropylene glycol dibenzQat~ 39O3 POE (9.53 nonylphenol laurate 20 D O
POE (10) nonylphenol 10.0 Butylated hydroxy~oluene 0Ol POE (9.5) nonylphenol phosphate 6,3 Triethanolamine, 98~ 2.5 Water 1.8 Example 17 Coning oil, ~or application at a level o~ 2-4 ater texturizing, wa~ prepared from:
Wei~ht Percent Cycloaliphatic bis (2~ethyl-3û hexyl) este~ 7. 5D
Lauryl benzoate 7.50 POE ~9.5~ nonylphenol coconatP 3.75 PO~ ~3.5) lauryl aloohol10.00 3tj;~

Weight Perce~t POE ~25~ Hydrogenated castor oil 2. 50 POE: ~10) nonylphenol pho~phate 2.5û
Ucor~ 65 64~1 5 Butylated hydroxytoluene 0.,10 Triethanolamine 1, 00 Water - ~ O 00 This coning oil provided necessary lubrication to allow the yarn to be rapidly coned, knitted or lû woven. It did not smoke, yellc~w or discolor during processing temperature~ of up to 65C.
. . .
- Example 18 Knitting lubricant in accordance with the inventiorl wa~ prepared from:
- Wei~ht Perc:erlt:
Cycloaliphatic bis (2-ethyl-h~?xyl~ ester 10 ~ 0 Propylene glyc:ol dibealzoate 41~ 0 Lauryl (POE; 9~ laurate 10. 0 POE ~9) lauryl alcohol 10, 0 But:ylated hydroxyto:Luerle0.1 Vcon I~-65 ~1. 9 POE 19 ) lauryl acid phosphate 5 . O
Dibutylethanc)lamine ~.O
a5 The lubric:ant was applied to the kni kting needles at a level c~ 2% by ~Iripping or misting and wa~
effective as a lubrica~st at 38-65C.

Ex anlpl~ 19 Into a three-neck 1000 ml gla5E; flask fitted with stirrer, thermometerl, nitrogen puxge and Dean~
Stark trap were charged:
122. 0 g ~enzoic acid 191. 0 g di-n~butylaminoethano:L

, .

1. 3 g methanesulfonic ~cid (70P~
0" 3 g hypopho~phoxou~ acid ~5096i 20ûo 0 ml ~ toluene The re~ulting mix~ure wa~ heated to 70-85~C and 5 held at refïux until the theoretical amount ~18 g) of water was removed. Th~ sample was cooled and wa~hed in a separato~y funnel. Toluene was removed in a rotary evaporator. Approximately 260 grams of di~
butylaminoethyl benzoate were recovered.
Amino-substi~uted alkyl ester~ of aromatic acids as prepared above ~ can be used in the composition~
of thi~ invention ~o replace all or part of the unsubstituted aromatis~ e~ters w~ich would s: therwise be used.

15 Example 20 A xepresentative benzyï ester was prepared as in ;Example 19 f rom:
227~ 0 ~ ben~yl alcohol 400O 0 g lauric acid 202 . 4 g methanesulfonic acid (709 0. 6 g hypopho3phorous acid (S0%~
l~he resulting mixture was heated and hel~ at 165-175C until the theor . tical amount ~37 g3 of water was removed., Approximal:ely 580 grams benzyl laurate were recovexed.
The benzyl esters of pelargorlic ~, octanoic O
palmitic, stearic, oleic and hydroxy~tearic acids were prepared in a similar fashion.

~Exa~pl~ 21 A diester of Formula II wa3 synthesize~ in a .two-liter au~.ocla~e fitted with nit:rogerl purge~, con~
denser an~l receiver ~c)r water removal. Charge weights wereo 510.0 g diacid 1550 2,0 g flake caustic 636.0 g ethylene oxide After purging with nitrogen, Diacid 1550 and caustic were heated to 130C. Ethylene oxide was added over a four hour period, during which the temperature was kept at 150-165C. The resulting ethoxylate was cooled to 90C, sampled and the molecular weight determined by hydroxyl value. A value of 139 was found. The Eollowing were added:
3.5 g acetic acid (glacial) 7.5 g methanesulfonic acid (70~) 340.0 g benzoic acid After purging thoroughly with nitrogen, the temperature was raised to and held at 165-170C until the acid value was less than 5 mg KOH per gramO The theoritical amount of water was removed during the reaction and collected in the receiver. The sample was cooled and filtered.
The above composition was hydrogenated in the two-liter autoclave:
1000.0 g example above 50.0 g Raney nickel QS hydrogen The reduction was run at 100-125C and 200-250 psig until hydrogen consumption ceased~ The product was cooled and filtered.
A propoxylated dibenzoate ester was prepared in a similar fashion.

Example 22 A textile-treating composition was prepared from:
Percent by Weight dibenzoate ester of bis-propoxylated cycl.oaliphatic ester (above sample) 60.0 , :
.

D~

POE (9.5) nonylphenol laurate 20.0 POE (80) cas-tor oil 10.0 POE (25) hydrogenated castor oil 10.0 The composition was used to treat woven polyester in a launderometer a-t 130C. Sodyecron Navy A~ (disperse blue 281) and acetic acid in appropriate amounts were used.
A ten gram swatch of polyester was treated with 0.05 grams of the textile treating compositionO Dye yield, migration and levelness were excellent. The fabric also had a pleasing handle.

Examp]e 23 To a three-necked flask fitted out as above was charged:
750.0 g polyoxyethylated nonylphenol (NP 9.5) 15317.0 g hydroxstearic acid 4.0 g methanesulfonic acid (70%) 1.0 g hypophosphorous acid (50%) The mixture was heated to 160-170C under nitrogen purge until the acid value was below 10 mg XOH/gm. The product was cooled and filtered. Approximately 1035 grams of polyoxyethylene nonylphenyl hydroxystearate were re-covered. This material can be substituted for the dye levelling agent of the previous example, i.e., POE (9.5) nonylphenol laurate.

Claims (61)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A fiber or textile treating composition which contains a) a cycloaliphatic diester of formula I

I

wherein A is -CH2-CH2-R is substituted or unsubstituted straight or branch-ed chain alkyl of 4-20 carbon atoms, polyoxyalkylene of the formula HO(CXHyO)nCxHy- or phosphated poly-oxyalkylene of the formula or a salt thereof wherein (CXHyO)n is (CH2CH2O)n, (C3H6O)n or (CH2CH2O)p(C3H6O)q x is 2 or 3 y is 4 or 6 n is 2-22; and p + q = n and b) a high boiling aromatic ester of the formula ArCOO-R1-OOCAr or ArCOOR2 wherein Ar is substituted or unsubstituted monocyclic aryl;
R1 is alkylene of up to 8 carbon atoms or polyoxyalkylene of the formula -CrH2r(O-CrH2r)s in which r is 2 or 3 s is up to 15;
and R2 is alkyl or alkenyl of 8 to 30 carbon atoms.

2. The composition of claim 1 wherein the weight ratio of cycloaliphatic diester to high boiling aromatic ester is 0.1:1 to 10:1.

3. A composition according to claim 1 in which the combination of cycloaliphatic diester and high boiling aromatic ester constitutes 10 - 90% by weight of the composition.

4. A composition according to claim 1 which additionally contains one or more emulsifiers, dispersing agents, or antistatic agents.

5. A composition according to claim 1 which additionally contains a dye-levelling agent.

6. A composition according to claim 5 in which the dye-levelling agent has the formula wherein R4 is an ethoxylated alkylphenol residue of the formula where a is 0 - 12 b is 1 - 24 or an ethoxylated alkanol residue of the formula CH3(CH2)c-O-(CH2CH2O)d-CH2CH2-where c is 7 - 12 and d is 1 - 24; and wherein R3 is linear or branched alkyl or alkenyl of 1 - 21 carbon atoms, phenyl or tolyl.

7. A composition according to claim 6 in which R3 is all of 11 to 17 carbon atoms.

8. A composition according to claim 4 which additionally contains a dye-levelling agent.

9. A composition according to claim 8 in which the dye-levelling agent has the formula wherein R4 is an ethoxylated alkylphenol residue of the formula where a is 0 - 12 b is 1 - 24 or an ethoxylated alkanol residue of the formula CH3(CH2)c-O-(CH2CH2O)d-CH2CH2-c is 7 - 12 and d is 1 -24 and wherein R3 is linear or branched alkyl or alkenyl of 1 - 21 carbon atoms, phenyl or tolyl.

10. A composition according to claim 9 in which R3 is of 11 to 17 carbon atoms.

11. A composition according to claim 1 which contains 20-40 parts by weight of cycloaliphatic diester, 20-40 parts by weight of high boiling aromatic ester, 10-20 parts by weight of dye levelling agent and 20-30 parts by weight of emulsifiers, dispersing agents and/or anti-static agents.

12. A composition according to claim 1 or 11 in which the cycloaliphatic diester is cycloaliphatic bis(2-ethyl-hexyl)ester and the high boiling aromatic ester is propylene glycol dibenzoate.

13. A composition according to claim 1 which contains 10-30 parts by weight of cycloaliphatic diester and 25-60 parts by weight of high boiling aromatic ester.

14. A composition according to claim 1 which contains 5-15 parts by weight of cycloaliphatic diester and 30-50 parts by weight of high boiling aromatic ester.

15. A composition according to claim 14 in which the cy-cloaliphatic ester is cycloaliphatic bis(2-ethylhexyl) ester and the high boiling aromatic ester is propylene glycol dibenzoate.

16. A composition according to claim 1 which contains 5 -10 parts by weight of cycloaliphatic diester and 5 - 10 parts by weight of high boiling aromatic ester.

17. A composition according to claim 16 in which the cycloaliphatic diester is cycloaliphatic bis(2-ethylhexyl) ester and the high boiling aromatic ester is lauryl benzoate.

18. A composition according to claim 1 which contains 15 -40 parts by weight of cycloaliphatic diester and 20 -55 parts by weight of high boiling aromatic ester.

19. A composition according to claim 1 which additionally contains a dye.

20. A composition according to claim 18 in which the cycloaliphatic diester is bis(2-ethylhexyl) cycloaliphatic ester and the high boiling aromatic ester is propylene glycol dibenzoate.

21. A method of making a fabric which comprises treating a synthetic fiber with a composition of claim 1 and converting the fiber to a fabric.

22. A method according to claim 21 in which the fabric is subsequently dyed.

23. A method of making a knit or woven fabric which comprises coating a synthetic fiber with 1 - 2% of weight of a composition of claim 1 and knitting or weaving the fiber into a knit or woven fabric.

24. A method for making a woven or knit fabric which comprises applying to a synthetic fiber, to a pick-up of 0.4 - 0.75%
by weight, a composition according to claim 5 or 6, texturing the coated fiber at a temperature of 180 - 230°C
and knitting or weaving the textured fiber into a fabric.

25. A method for making a woven or knit fabric which comprises applying to a synthetic fiber, to a pick-up of 0.4 - 0.75%
by weight, a composition according to claim 8 or 9, texturing the coated fiber at a temperature of 180 - 230°C
and knitting or weaving the textured fiber into a fabric.

26. A method for lowering the heat history characteristics and degree of crystallinity of a synthetic fiber, lowering the temperature at which the fiber can be texturized and lowering the temperature at which the fiber absorbs dye which comprises applying to the fiber to a pick-up of 0.4 - 0.75% by weight of a composition of claim 2 where the cycloaliphatic diester and high boiling aromatic ester constitutes 10 - 90% by weight of the composition, and texturing the coated fiber at a temperature of 180 - 230°C.

27. A method according to claim 26 in which the composition additionally contains a dye-levelling agent according to claim 6.

28. A method according to claim 26 in which the composition additionally contains a dye-levelling agent according to claim 9.

29. A composition according to claim 1 in which the high boiling aromatic ester has the formula ArCOO R1-OOCAr where Ar is phenyl or tolyl R1 is ethylene, propylene, ethyleneoxyethylene, propyleneoxypropylene or polyoxypropylene of molecular weight 200-500.

30. A composition according to claim 1 in which the high boiling aromatic ester has the formula ArCOOR2 where Ar is phenyl or tolyl R2 is decyl, dodecyl, hexadecyl, tridecyl, octadecyl or oleyl.

31. A fiber or textile which has been treated with a com-position of claim 1, 2 or 3.

32. A fiber or textile which has been treated with a composition of claim 4, 5 or 6.

33. A fiber or textile containing one or more of polyester, polyamide, polyacrylic or polymodacrylic which has been treated with a composition of claim 1, 2 or 3.

34. A fiber or textile containing one or more of polyester, polyamide, polyacrylic or polymodacrylic which has been treated with a composition of claim 4, 5 or 6.

35. A fiber or textile containing one or more of polyester, polyamide, polyacrylic or polymodacrylic and further containing a cellulosic or wool, which fiber or textile has been treated with a composition of claim 1, 2 or 3.

36. A fiber or textile containing one or more of polyester, polyamide, polyacrylic or polymodacrylic and further containing a cellulosic or wool, which fiber or textile has been treated with a composition of claim 4, 5 or 6.

37. A fiber or textile treating composition which contains a) a cycloaliphatic diester of formula I

I

wherein A is -CH2-CH2-R is substituted or unsubstituted straight or branched chain alkyl of 4-20 carbon atoms, poly-oxyalkylene of the formula HO(CXHyO)nCxHy-or phosphated polyoxyalkylene of the formula or a salt thereof wherein (CXHyO)n is (CH2CH2O)n, (C3H6O)n or (CH2CH2O)p(C3H6O)q x is 2 or 3 y is 4 or 6 n is 2-22; and p + q = n and b) i) a high boiling aromatic ester of the formula ArCOO-R1-OOCAr or ArCOOR2 wherein Ar is substituted or unsubstituted monocyclic aryl;
R1 is alkylene of up to 8 carbon atoms or polyoxyalkylene of the formula -CrH2r(O-CrH2r)s in which r is 2 or 3;

(claim 37 cont'd) s is up to 15;
and R2 is alkyl or alkenyl of 8 to 30 carbon atoms;
b)(ii) an ester of a substituted or unsubstituted benzyl alcohol with a substituted or unsubstituted aromatic acid of at least 6 carbon atoms; or b)(iii) an ester of a substituted or unsubstituted benzyl alcohol with a substituted or unsubstituted aliphatic acid of at least 8 carbon atoms.

38. The method according to claim 26, wherein the fiber is coated with a minimum extractable of 0.075% by weight of cycloaliphatic diester, 0.075% by weight of high boiling aromatic ester and 0.050% by weight of a dye-levelling agent according to claim 6.

39. The method according to claim 26 wherein the composition includes a dye-levelling agent according to claim 6 and the synthetic fiber is polyester.

40. The composition of claim 1 further containing one or more emulsifiers, dispersing agents and/or antistatic agents comprising one or more of ethoxylated castor oil, ethoxylated hydrogenated castor oil, ethoxylated alkylphenol, ethoxylated primary or secondary alkanol or a salt of a phosphated ethoxylated primary alkanol or alkylphenol, and wherein the ratio or cycloaliphatic diester to high boiling aromatic ester is 0.1:1 and 10:1 and wherein the combination of cycloaliphatic diester and high boiling aromatic ester constitutes 10 - 90% by weight of the textile-treating composition.

41. The composition of claim 40 which composition is a dyeing assistant containing 10 - 25% by weight of the dye-levelling agent. according to claim 6.

42. The composition of claim 40, comprising a dyeing assistant composition consisting essentially of 15 - 40 parts by weight of cycloaliphatic diester, 20 - 55 parts by weight of high boiling aromatic ester, 10 - 25 parts by weight of dye-levelling agent and 10 - 30 parts by weight of emulsifiers, dispersing agents and/or anti-static agents.

43. The composition of claim 42, wherein the cycloaliphatic diester is one wherein R is substituted or unsubstituted alkyl of 4 - 20 carbon atoms, the high boiling aromatic ester is a dibenzoate or ditoluate of mono or diethylene or propylene glycol, the dye-levelling agent is an ester of an ethoxylated alkylphenol and the emulsifiers, dispersing agents and/or anti-static agents are ethoxylated castor oil, ethoxylated hydrogenated castor oil and potassium salt of a phosphated ethoxylated cycloaliphatic diester.

44. The composition of claim 40, which composition is a spin finish consisting essentially of 20 - 40 parts by weight of cycloaliphatic diester, 20 - 40 parts by weight of high boiling aromatic ester, 10 - 20 parts by weight of a dye-levelling agent and 20 - 30 parts by weight of emulsifiers, dispersing agents and/or anti-static agents.

45. The composition of claim 40 which composition is a spin finish consisting essentially of 25 - 35 parts by weight of cycloaliphatic ester in which R is alkyl of 4 - 20 carbon atoms; 25 - 35 parts by weight of a high boiling aromatic ester selected from ethylene, propylene or butylene dibenzoate or ditoluate, 10 - 20 parts by weight of ethoxylated castor oil, ethoxylated hydrogenated castor oil, and phosphated ethoxylated alkylphenol in ratios of 1:2:2 to 1:3:3 by weight.

46. The composition of claim 40, which composition is a lubricant consisting essentially of 10 - 30 parts by weight of cycloaliphatic diester, 25 - 60 parts by weight of high boiling aromatic ester, 10 - 30 parts by weight of dye-levelling agent and 10 - 30 parts by weight of emulsifiers, dispersing agents and/or antistatic agents.

47. The composition of claim 40, which composition is a knitting lubricant comprising 5 - 15 parts by weight of cycloaliphatic diester, 30 - 50 parts by weight of high boiling aromatic ester, 5 - 15 parts by weight of dye-levelling agent, 10 - 30 parts by weight of an ethylene-propylene oxide copolymer and 10 - 20 parts by weight of emulsifiers, dispersing agents and/or antistatic agents.

48. The composition of claim 40 which composition is a lubricant composition consisting essentially of 15 - 25 parts by weight of a cycloaliphatic diester in which R
is alkyl of 4 - 20 carbon atoms; 35 - 45 parts by weight of a high boiling aromatic ester selected from a dibenzoate or ditoluate of di- or triethylene glycol or di- or tripropylene glycol; 15 - 25 parts by weight of an ethoxylated alkylphenol ester and 10 - 30 parts by weight of emulsifiers, dispersing agents and/or anti static agents.

49. The composition of claim 40, consisting essentially of:
Percent By Weight Cycloaliphatic bis(2-ethyl-hexyl)ester 15 - 25 Propylene glycol dibenzoate 30 - 50 Ethoxylated nonylphenol laurate 15 - 20 Ethoxylated hydrogenated castor oil 5 - 15 Ethoxylated castor oil 5 - 15

50. A method according to claim 26 wherein the ratio of cycloaliphatic diester to high boiling aromatic ester is 0.1:1 to 10:1, provided that, when R is unsubstituted straight or branched chain alkyl, the ratio of cycloaliphatic diester to high boiling aromatic ester is 2:1 to 10:1.

51. A method according to claim 26 in which the composition additionally contains a dye-levelling agent.

52. The method of claim 51 wherein the fiber is coated with a minimum extractable of 0.075% by weight of cycloaliphatic diester, 0.075% by weight of high boiling aromatic ester and 0.050% by weight of dye-levelling agent.

53. The method of claim 51 wherein the synthetic fiber is polyester.

54. A method according to claim 51 or 52 in which the dye-levelling agent is according to claim 9.

55. A fiber or textile treated by the method of claim 51.

56. A method of treating a synthetic fiber comprising the steps of (a) applying to the fiber to a pick up of 0.4 - 0.75%
by weight a spin finish composition according to claim 44 or 45;
(b) texturing the thus-coated synthetic fiber at 180°
- 230°C;
(c) knitting or weaving the resulting textured fiber into fabric or a knit article;
(d) dyeing the fabric or knit article.

57. A method of making fabric or an article from a synthetic fiber or textile comprising the steps of (a) coating the fiber or textile with 1 - 2% by weight.
of a knitting lubricant according to claim 46 or 47;
(b) knitting or weaving the fiber or textile into fabric or an article; and (c) dyeing the fabric or article.

58. A fiber or textile containing one or more of polyester, polyamide, polyacrylic or polymodacrylic which has been treated with a composition of claim 40, 41 or 42.

59. A fiber or textile containing one or more of polyester, polyamide, polyacrylic or polymodacrylic which has been treated with a composition of claim 43, 44 or 45.

60. A fiber or textile containing one or more of polyester, polyamide, polyacrylic or polymodacrylic which has been treated with a composition of claim 46, 47 or 48.

61. A fiber or textile coated with a composition of claim 1 or 40 to an add on 0.25 - 5.0% by weight of fabric or textile.