IE53002B1 - Diester composition and textile processing compositions therefrom - Google Patents

Abstract

A cycloaliphatic diester of the formula wherein R is substituted or unsubstituted straight or branched chain C4-C20 alkyl, polyoxyalkylene of the formula HO(CH2CH2O)nCH2CH2-, HO(C3H6O)nC3H6-, HO(CH2CH2O)p(C3H6O)qC3H6-,or HO(C3H6O)p(C2H4O)qC2H4- or phosphated polyoxyalkylene, wherein n is 2-22 and the sum of p+q is n, in combination with a high boiling aromatic ester of formula ArCOO- R1-OOCAr or ArCOOR2 where A is a monocyclic C6-10 aryl R1 is C2-8 alkylene or polyoxyalkylene of formula -CrH2r(O-CrH2r)s where r is 2 or 3 and r is 1-15, and R2 is C8-30 alkyl or alkenyl, is useful in fiber treating and textile processing compositions. Corresponding cycloaliphatic diesters wherein R is Ar'COO(CH2CH2O)nCH2CH2-, Ar'COO(C3H6O)nC3H6-, Ar'COO(C2H4O)pC3H6O)qC3H6-, or Ar'COO(C3H6O)p(C2H4O)qC2H4- and Ar' is substituted or unsubstituted monocyclic aryl can be used as the sole additive.

Description

This invention relates to a mixture of cycloaliphatic diesters and high boiling aromatic esters, and to their use In fibre-treating and textile processing compositions.

It has been proposed by Sturwold et al, in D.S. Patent No. 3,925,589, 5 to use emulsions of esters derived from polyoxyalkylene glycols of molecular weight 300-4000 and a dibasic acid mixture of a dimer acid of 32-54 carbon atoms and a short chain dibasic acid of 2-12 carbon atoms for lubricating polyamide fibres.

Dumont, in U.S. Patent No. 3,694,257, has proposed the use of Ί0 polyesters prepared from reaction of polyols with a di— or tribasic acid as textile assistants for softening textile fabrics.

It has been proposed by Crovatt, Jr. in U.S. Patent No. 3,329,633, to improve the lubricity of polyhexamethylene adipamide fibres by adding 0.1-5.0% by weight of oleic acid dimer to the polymer during the final polymerization stage thereof.

Bishop et al. in U.S. Patent No. 4,135,878, has disclosed Inclusion of up to 10% by weight of a dimer acid in an emulsifier-solvent scour composition used for treating textile materials under alkaline conditions.

Preparation of adducts from conjugated octadecadienoic acid and 20 unsaturated acids and/or their hydrogenation has been described by Teeter et al. J Org Chem vol 22 (1957) at 512-514: Ward in U.S. Patent No. 3,899,476; and Ward et al in U.S. Patent No. 3,981,682.

The preparation of esters from the diacid adduct was reported by Ward et al, J. Amer Chemists* Soc vol. 57 (1975) at 219-224.

Ethoxylated esters containing 4-119 ethylene oxide units are said to he particularly effective lime soap dispersants. The alkyl esters are reported as heing particularly useful in lubricant applications, including uses as textile lubricants and plasticizers for PVC. 2, S3002 The use of lower aromatic esters In textile treatment, particularly as dyeing assistants Is well known, as Is disclosed ln U.S. Patents: 2,880,050 (Fortress et al); 2,881,045 (Mecca et at); 3,036,876 (Schoelllg et al); 3,124,412 (Fidell et al); 3,929,407 (Parker), and 3,932,128 (Beaulieu).

References which disclose the use of phthalate esters In dyeing processes Include U.S. Patents: 2,833,613 (Hallada et al ; 2,934,397 (Landerl); 2,982,597 (Salvia et al); 3,667,899 (Harnett et al); 3,973,807 (Forschlrm), and 4,032,291 (Dellian).

Phthalate esters have been used as components of lubricants for textiles, for example, by Jaeger (U.S. Patent No. 2,212,369), Dickey et al (U.S. Patent 2,241,246), Brennan et al (U.S. Patent No. 2,882,231) and Iyengar et al (U.S, Patent No. 3,853,607).

The use of hydroxyalkyl or alkoxyalkyl benzoates as dyeing assistants or fixatives Is disclosed by Fuhr et al (U.S. Patent No. 3,532,454), Baumann et al (U.S. Patent No. 3,950,419) and Lazar et al (U.S. Patent No. 3,917,447).

Higher trialkyl trlmellltates have been proposed by Hinton, Jr. et al as components of a soil release composition (U.S. Patent No. 3,824,125).

It Is an object of the Invention to provide a novel mixture of cycloaliphatic and high boiling aromatic esters. Such mixtures can be ueed as ingredients of textile-processing agents, particularly for polyester fibres, and thereby eliminate one or more otherwise conventional processing steps without impairing the ultimate properties of the fibre treated therewith.

In one aspect of this Invention, there is provided a composition for treatment of fibres or textiles, the composition containing: (a) a cycloaliphatic diester of formula n-c6h13-< I (CH2)7C00R :oor 3. wherein R is substituted or unsubstituted straight or branched chain alkyl of 4 to 20 carbon atoms, polyoxyalkylene of the formula HO(CH2CH2O)nCH2CH2- , H0<C3H60)nC3H6-’ HO(CH2CH20)p(C3H60)qC3H6-, or HO(C3HgO)p(C2H4O)qC2H4-, or phosphated polyoxyalkylene or a salt thereof, wherein n Is 2 to 22 and £ + £ “ n]; and (b) a high boiling aromatic ester which is: (i) an ester of the formula ArC00-R^-00CAr [wherein Ar is substituted or unsubstituted monocyclic aryl and R^ Is alkylene of up to 8 carbon atoms or polyoxyalkylene of the formula -C H, (0-C H„ ) - in which r is 2 or 3 and s is up to 15]j r 2r r 2r s — — (ii) an ester of the formula ArC00R2 [wherein Ar is as defined above and R2 is alkyl or alkenyl of 8 to 30 carbon atoms]} (iii) an ester of a substituted or unsubstituted benzyl alcohol with a substituted or unsubstituted aromatic acid of 6 or more carbon atoms; (iv) an ester of a substituted or unsubstituted benzyl alcohol with a substituted or unsubstituted aliphatic acid of 8 or more carbon atoms; or (v) an amino-substituted alkyl ester of an aromatic acid.

The diester (a) can be for example a compound of formula (I) wherein R is Ar' C00(CH2CH20)nCtT2CH2-, Ar'COO(C-H.O) C-H,-, jo n J o Ar'COO(C-H.O) (C,H,0) C-H,-, or 2 4 p Jo q j o Ar'C0O(C_H,O) (C-H.O) C-H.-, Ar* is substituted or JO p 2 4 q 2 4 unsubstituted monocyclic aryl and n, £ and £ are as above. Such compounds are referred to as diesters of formula (II).

This Invention further relates to fibres and textiles, for instance a synthetic fibre or fabric coated with a treating-agent containing a composition of this invention.

This invention further relates to a particular aspect to the conversion of synthetic fibres to piece goods and subsequent dyeing, to the improvement wherein a composition of this invention is the sole fibretreating agent used.

This invention also relates to a method of making fabric or an article from a synthetic fibre or fabric comprising coating the fibre or fabric with 1-22 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, 5-15 parts 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 fibre into fabric or a knitted or woven article and dyeing the fabric or knit or woven article. When cycloaliphatic diesters of Formula XI are used, they will comprise 5-65% by weight of the treating composition.

Thia invention further relates to a method for treating a synthetic fibre comprising applying to the fibre to a pick-up of 0.4-0.75% by weight a spin finish comprising (1) a cycloaliphatic diester, (2) a high boiling aromatic diester and (3) a dye-levelling agent; texturing the thus-coated synthetic fibre at 180-230°C; knitting or weaving the resulting textured fibre into fabric or knitting the textured fibre into a knit article and dyeing the fabric or knit article.

In another aspect, this invention relates to a method for lowering the heat history characteristics and the degree of crystallinity of a synthetic fibre, lowering the temperature at which the fibre can be texturized and lowering the temperature at which the fibre absorbs dye, comprising applying to the fibre to a pick-up of 0.4-0.75% by weight of a composition comprising a cycloaliphatic diester of Formula I and a high boiling aromatic ester, wherein the ratio of cycloaliphatic diester to high boiling aromatic ester is O.lsl to 10sl and wherein the combination of cycloaliphatic diester and high boiling aromatic constitutes 10-90% by weight of the composition and texturing the thus-coated fibre at 180-230°C. When cycloaliphatic diesters of Formula XI are used, they will comprise 10-90% by weight of the treating composition.

. Moreover, the aforesaid compositions can contain a dye-levelling agent of the formula C^COOR^ [wherein R^ is a linear or branched alkyl or alkenyl group of 1-21 carbon atoms, phenyl or tolyl, and R^ is an ethoxylated alkylphenol residue of the formula CaH2a+1 0(CH2CH20)bCH2CH2wherein a is 0-12 and b is 1-24, or R^ is an ethoxylated alkanol residue of the formula wherein c is 7-12 and d is 1-24]. ]0 As a further aspect of this invention, a cycloaliphatic diester of formula (ch2)7coor [wherein R Is substituted or unsubstituted straight or branched chain alkyl of 4 to 20 carbon atoms, polyoxyalkylene of the formula H0(CH2CH20)nCH2CH2-, ffiXC^O)^-, HO(CH2CH20)p(C3HgO)qC3H6-, or HO(C3HgO)p(C2H4O)qC2H4-, or phosphated polyoxyalkylene or a salt thereof, wherein n is 2 to 22 and £ + £ “ n] is admixed with a high boiling aromatic ester which Is: 6. (i) an eater of the formula ArC00-R^-00CAr [wherein Ar is substituted or unsubstituted monocyclic aryl and 8^ is alkylene of up to 8 carbon atoms or polyoxyalkylene of the formula -C H. (0-C H- ) - in which r is 2 or 3 and a is up to 15]; r 2r r 2r a — — (ii) an ester of the formula AXCOOOR2 [wherein Ar is as defined above and Rj ia alkyl or alkenyl of 8 to 30 10 carbon atoms]; (ill) an ester of a substituted or unsubstituted benzyl alcohol with a substituted or unsubstituted aromatic add of 6 or more carbon atoms; (iv) an ester of a substituted or unsubstituted benzyl alcohol with a substituted or unsubstituted aliphatic acid of 8 or more carbon atoms; or (v) an amino-substituted alkyl ester of an aromatic acid, in order to provide a base for a multi-purpose fibre and textile-treating composition.

Ihe dibasic add employed in this invention is a Diels-Alder adduct of acrylic add and linoleic add and can be prepared aa described by Ward in U.S. Patent No. 3,753,968. The dlacid has the formula n-C6H13~i (CH2)7- COOH COOH 7. and therefore is a mixture of (5 and 6)-carboxy-4-hexyl-2-eyclohexane1-octanoic acids. The diacid is available commercially from Westvaco, designated as Diacid 1500.

The diacid can be esterified with alcohols using, for example, acidic 5 catalysts such as p-toluenesulphonic acid, methanesulphonic acid or sulphuric acid. During the esterification, the reaction mixture is preferably also treated with a decolourizing agent, for example, carbon or clay.

The diacid is reduced following esterification to a compound of j q formula n-c6H13 (ch2)7coor COOR In which A is -C^CHj-. A nickel catalyst such as Raney Nickel, nickel or kieselguhr or nickel on alumina can he used. The required amount varies up to 5 to 10% hy weight of the ester.

Hydrogenation is carried out after esterification to prevent nickel from complexing with free acid. Other catalysts, for example, platinum or rhodium, avoid this problem, hut are prohibitive in cost. The catalyst can be removed by filtration through a plate and frame filter press. The product is the resulting filtrate. 8.

Polyoxyalkylene diesters are prepared by reaction of the diacid, in the presence of an alkaline catalyst, with ethylene or propylene oxide. Reaction will occur at both acid sites and addition of ethylene oxide is allowed to continue until the product becomes at least dispersible or, preferably, soluble in water. This will correspond to addition of a total of 5-25 ethylene oxide units. The product obtained using ethylene oxide has a structure before hydrogenation represented by the formula: HO-(CH2CH20)yOC (CH2)?CH-(OCH2CH2)χ-ΟΗ x + y = 5 - 25 The phosphorylated product is readily obtained by reaction with phosphorus pentoxide. The saturated diester can be obtained by nickel-catalyzed hydrogenation.

In the case of the phosphorylated derivative, hydrogenation should precede phosphorylation. The phosphorylated derivatives can be converted to salts thereof by reaction with a metal hydroxide. Sodium and potassium salts are preferred.

Compounds of Formula II are obtained by treating polyoxyalkylene intermediates with an aromatic acid, e.g., benzoic, toluic or mellitic acid, usually with an acidic catalyst. Hydrogenation of the double bond in the cycloaliphatic ring can be done before or after esterification with the aromatic acid.

It will be understood that the diesters used in the compositions of this invention have somewhat varying properties. However, the following general correlation between structure and properties of representative preferred diesters (hydrogenated form) can be made: dilauryl ester liquid, good heat stability, good lubricant bis(2-ethylhexyl)ester liquid, good heat stability, good lubricant distearyl ester solid, good heat stability, good lubricant bis(ethoxylated)ester solid, heat stable, cohesive (15 moles ethylene oxide, bis(phosphated ethoxy- Solid, heat stable, cohesive, lated)ester (15 moles antistatic ethylene oxide) Representative of substituted alkyl R which may be used in the products of this invention are butoxybutyl, -hydroxystearyl, 10-hydroxydecyl, 10-halostearyl, ω-alkanoyloxyalkyl or the like.

Preferred diesters of formula' (I) for use in accordance with the principles of the invention are those wherein: (a) R xs straight or branched chain alkyl of 4-20 carbon atoms, (b) R is 2-ethylhexyl, lauryl or stearyl, (C) R is HO(CH2CH2O)nCH2CH2-, (d) R is HO(C3H6O)nC3Hg-, (e) R is HO(C2H4O)p(C3HgO)gC3H6-, (f) R is (HO,2PO(CH2CH2O)nCH2CH2- or a salt thereof, (g) .R. is C^H5CO(C2H4O)nC2H4-, (h) R is CH3CgH4CO(C2H4O)nC2H4-, (i) R is C-H_CO(C_HrO) C-,Η,-, and b □ Jo n J o (j, R is CH3CgH4CO(C3HgO)nC3Hg-.

Tt will .be understood that the textile-ireating compositions can contain more than one diester, e.g., a mixture of bis(alkyl, esters or a mixture containing a bisalkyl ester in combination with a bis(polyoxyalkylene, or bis(phosphate polyoxyalkylene) ester of a corresponding salt. 1.0 Esters of the types disclosed by Dumont (U.S. Patent 3,964,257), SLurwold et al (U.S. Patent 3,925,589) or Bishop et al (U.S. Patent No. 4,135,878) can be used to replace part of the (Hesters of Formula I.

The high boiling aromatic ester Is preferably an ester of the formula 5 ArC00-Rj-00CAr or ArCOOR^, wherein Ar Is monocyclic aryl of up to 10 carbon atoms; Is alkylene of 2-8 carbon atoms or polyoxyalkylene of the formula -C H„ (0-C H. ) In which r Is 2 or 3 and s Is up to r zr f zr 8 — “ ; and R£ Is substituted or unsubstituted alkyl or alkenyl of 8-30 carbon atoms.

Accordingly, aromatic esters used in the practice of this Invention include, but are not limited to esters of benzoic, toluic, dimethylbenzoic, trimethylbenzoic, butylbenzoic and similar acids.

In the ease of aromatic esters, alkylene (R^) can be ethylene, propylene, hexylene, 2,2-dimethyl-trimethylene, butylene, heptamethylene and octylene, including various isomers thereof.

Polyoxyalkylene diesters include those derived from polyethylene glycol or polypropylene glycol.

In the case of monoaromatic esters, alkyl can be octyl, nonyl, decyl, dodecyl, tridecyl, hexadecyl, stearyl and alkenyl can be any corresponding mono-unsaturated function, for example, oleyl.

Preferred aromatic diesters are those wherein: (a) Ar is phenyl, (b) Ar is tolyl, (c) R^ Is ethylene or propylene, including each of (a) and (b), (d) is ethyleneoxyethylene or propyleneoxypropylene, including each of (a) and (b), (e) R^ is polyoxypropylene of molecular weight 200-500, including each of (a) and (b), and if) R2 <3ecylf dodecyl, hexadecyl, tridecyl, octadecyl or oleyl, including each of (a) and (b).

Contemplated equivalents of the high boiling aromatic esters ArCOO-R-j-OOCAr or ArC00R2 include esters of benzyl alcohol and substituted or unsubstituted 10 aliphatic acids of 6 or more carbon atoms, including but not limited to, benzyl laurate, benzyl pelargonate, benzyl octoate, benzyl palmitate, benzyl stearate, benzyl oleate, benzyl hydroxylstearate or benzyl benzoate. It will be understood that esters of substituted benzyl alcohols can also be used.

It has been found that aromatic esters falling outside of the foregoing definition, more particularly methyl, ethyl, propyl, butyl, pentyl and hexyl ben20 zoates, lack heat stability, low odour and lubricating properties required for the plurality of functions fulfilled by the compositions of this invention.

Ethoxylated castor oil when used in. the compositions will contain 15-100 oxyethylene units, preferably 40-85 The hydrogenated castor oil derivatives will contain 5-200 oxyethylene units, preferably 20-30. These materials can be purchased from ICI America and Whitestone Chemical.

Ethoxylated alkyl phenols when used in the composi30 tions of this invention will contain up to 12 carbon atoms in the alkyl function and from 1-25 ethylene oxide units. Preferred examples are ethoxylated nonylphenol having 10-15 ethylene oxide units.

Ethoxylated alkanols include those derived from 12-15. carbon alkanols, including mixtures there12. of, or from secondary alcohols of 11-15 carbon atoms, also including mixtures, and containing 6-15 ethylene oxide units.

Phosphated ethoxylated alkanols or phenols employed 5 in the compositions of the invention will generally have fewer ethyleneoxide units than the unphosphated compounds. Exemplary, but not limitative, of the materials which can be used are the potassium salts of POE (10) nonylphenol phosphate, POE (3.5) lauryl alcohol phos10 phate, POE (7) lauryl alcohol phosphate, POE (9) .lauryl alcohol phosphate, POE -(6) decyl alcohol phosphate, and POE (9) decyl alcohol phosphate. It will be understood that the formula given for the phosphated ethoxylated derivatives includes various products, in15 eluding phosphated mono- and diesters, obtained bv reaction between the ethoxylated diacids and P^O^.

In many cases, the composition of this invention will be left on the fibre during dyeing and will therefore function as dyeing assistants, in which case -25% by weight of a dye-levelling agent will be included. As mentioned above, the dye-levelling agent can be of the given formula RgCOOR^.

Accordingly, exemplary dye-levelling agents include laurate, myristate, palmitate, coconate, oleate, stearate, isostearate, benzoate and toluate esters of ethoxylated nonylphenol, octylphenol, dodecylphenol, ndecanol, n-dodecanol, n-tetradecanol or n-hexade decanol.

The extent of ethoxylation is from 1-25 ethylene oxide units per alkylphenol or alkanol, preferably b-15 ethylene oxide units.

Preferred dye'levelling agents R^COOR^ are those wherein: (a) R_ Is of 11-17 carbon atoms, including mixtures thereof; 10 (b) R3 is n-C17H33; (c) R3 is n-C17H35, (d) R3 is iso-C17H35, (e) R3 is phenyl; ff)R3 1S n_CllH23; 15 (g) a is 9, including each of (a) — (f); (h) c is 11-14, including mixtures thereof and including each of (a) — (f); (i) b is about 9.5, including each of (a) - (f); ii) d is 6—10, including each of (a) - (f); 20 (k) b is 6—15, including each of (a) — (f) ; and (1) a is 9, b is 8-10 and R3 is n-cnH23 The compositions are especially suited for treat— ment of synthetic fibres such as polyester, polyamide, and polyacrylic. The polyester may be spun or textured polyester or filament or vazp yarn and may be woven, knitted, tufted, needle punched or non-woven. The polyester can be a polyalkylene terephthalate, such as polyethylene terephthalate, or a polyester made from cyclohexane-dimethanol. The polyamide may be of types δ; 6,6 or 6,10. The acrylic may be straight acrylic (acrylonitrile) or modacrylic (modified with vinyl chloride, vinylidene chloride). The compositions are also adapted for application to blends of the above fibres with each Other and with cellulosics (cotton, rayon, etc.) or wool.

The compositions can be applied at any of several stages of fibre processing. The following are exemplary of application to polyester fibre: .A. Spin Finish Applications The composition is applied to the yarn from a 10-20% emulsion to give a finish level on the yam of 0.25 - 10%. The treated yarn can be built into yam packages which can be used in high speed texturizing machines.

Compositions used as spin finishes will preferably have the following compositional range: Parts by Weight Cycloaliphatic diester of Formula X 20-40 High Boiling Aromatic Ester 20-40 Dye Levelling Agent 10-20 Emulsifiers, dispersing agents and/or anti-static agents 20-30 Most preferably, the compositions will contain 25-30 parts by weight of the cycloaliphatic diester and 25-35 parts by weight of high boiling aromatic ester.

Spin finish compositions will preferably contain a cycloaliphatic diester in which R is alkyl of 4-20 ca·'bon atoms, most preferably 6-12 carbon atoms.

The high boiling aromatic ester will preferably be of a glycol, most preferably diesters from ethylene, propylene, or butylene glycol and benzoic or toluic acid.

The dye-levelling agent is preferably an ethoxylated nonylphenol ester, especially of nonylphenol.

The emulsifiers, etc. will preferably comprise ethoxylated castor oil, ethoxylated hydrogenated castor oil and phosphated ethoxylated alkylphenol in ratios of 1 : 2 : 2 to 1 ; 3 : 3 by weight.

A most preferred spin finish composition will consist essentially of: Parts by Weight Cycloaliphatic bis(2-ethylhexyl) ester 25-35 .Propylene glycol dibenzoate · 25-35 Ethoxylated nonylphenol laurate 10-20 Ethoxylated castor oil 4-6 Ethoxylated.Jiydrogenated-castor oil 8-12 Ethoxylated nonylphenolphosphate, X salt 8-12 The spin finish compositions can ne diluted with water to form a stable emulsion or dispersion for application. The spin finish is preferably applied to produce a pick-up of 0.4 — 0.75% by weight.

A representative polyester treated to 0.5 — 0.6% pick-up with the spin finish composition of this invention has lower heat history characteristics than yam treated with a conventional spin finish. Yams thus treated can therefore be texturized at lower temperatures than possible heretofore and dyed at lower temperatures than previously used. In addition, the spin finish does not smoke or fume during texturizing at 200-240°C. In the case of spun yarns, the finish enhances the cohesive properties of the yam and provides the desired lubricity during picking, carding, drawing, roving and spinning.

It is recommended that, once the spin finishing compositions of this invention have been applied, no conventional lubricants be used, so as to prevent adulteration of the finishes. Maximum benefit is obtained by exclusive use of the compositions of the invention through conversion of the treated yam to piece goods and dyeing. 53003 B. Knitting Application: The composition is applied as a knitting lubricant and is left on the yarn during subsequent yarn processing. That is, the lubricant need not be scoured off as are 5 conventional lubricants. The capability of omitting a previously required processing step is an important advantage in utilizing the compositions of this invention. During weaving or knitting, high temperatures are reached due to friction and speeds, but the lubricants 10 in accordance with the invention remain functional and do not gum up or build up on equipment. In the dyeing stage, the lubricant/dyeing assistant does not break down during the dyeing cycle (250-270°F) and/or smoke during drying and heat setting of the fibre. Elimina15 tion of hazy blue smoke during drying and heat setting is important because of increasingly stringent standards against air pollution.

The lubricant compositions of this invention preferably will be of the following' composition: Parts by Weight Cycloaliphatic diester of Formula I 10-30 25-60 10-30 10-30 High boiling aromatic ester Dye-levelling agent Emulsifiers, etc.

Moot preferably, the composition will contain 15-30 parts by weight of cycloaliphatic diester, 25-45 parts by weight of high boiling aromatic ester and 15-25 parts by weight of dye-levelling agent.

The preferred cycloaliphatic diester and dyelevelling agent are as for the spin-finishing composition. However, the high boiling aromatic is preferably a dibenzoate or-ditoluate of di- or triethylene glycol or di- or trxpropylene glycol.

The conventional emulsifier and anti-static agents preferably are ethoxylated alkylphenols and the corresponding phosphate esters, most preferably ethoxylated nonylphenol.

Other materials in the lubricant composition can include an anti-oxidant, such as butylated hydroxy- toluene, in an amount of up to 0.5% by weight; an alkanol-amine, such as triethanolamine, in an amount up to 5.0% by weight, and up to 5 .(5% by weight of water. A most preferred lubricant composition comprises: Parts by Weight Cycloaliphatic bis(2-ethylhexyl)ester 25-35 Dipropylene glycol dibenzoate 25--45 Ethoxylated nonylphenol laurate 15-25 Ethoxylated nonylphenol 5-15 Butylated hydroxytoluene 0.05-0.2 Ethoxylated nonylphenol phosphate 5-10 Triethanolamine 1-5 Water 1-2 For satisfactory.performance, the take up, expressed as minimum percent extractables, when the treated fabric or fibre is loaded into the dyeing machine. should be at least: Minimum % extractable Cycloaliphatic diester of Formula I 0.075 High boiling aromatic ester 0.075 Dye-levelling agent 0.050 Add-on levels will vary depending on the point in the fibre processing at which the lubricant is applied, but will be from about 0.25 to about 5.0% by weight of the fibre. During knitting, the add-on is preferably 0.5 to 1.5% by weight.

Another type of knitting lubricant prepared in accordance with the invention will be of the compositions: Parts hy Weight.

Cycloaliphatic diester of Formula I 5-15 High boiling aromatic ester 30-50 Dye-levelling agent 5-15 Emulsifiers, etc. 10-20 Ethylene oxide-propylene oxide copolymer 10-30 2 The knitting lubricants may also contain up to 0.25% by weight of an anti-oxidant and up to 5% by weight of an alkanolamine, e.g., dibutylethanolamine.

It is preferred that the knitting lubricants contain a cycloaliphatic diester in which R is alkyl of- 4-20 carbon atoms, more preferably 6-12 carbon atoms.

The preferred high boiling aromatic ester will be a dibenzoate or ditoluate of ethylene or.propylene glycol. Propylene glycol dibenzoate is particularly preferred.

The dye-levelling agent used in the knitting lubricant composition is preferably an ester of an ethoxylated alkanol, more preferably the decanoate, laurate, myristate or palmitate of ethoxylated decyl, lauryl, myristyl or hexadecyl alcohols.

Ethoxylated alkanols and corresponding phosphates are preferred emulsifiers in the knitting lubricant.

Ethylene oxide-propylene oxide copolymer of molecular weight 2000 — 5000 is preferred.

A most preferred knitting lubricant is: Parts by Weight Cycloaliphatic bis(2-ethylhexyl)ester 8-12 Propylene glycol dibenzoate 25-45 Ethoxylated lauryl laurate 8-12 Ethoxylated lauryl alcohol 8-12 Butylated hydroxytoluene 0.5-2 Ethylene oxide-propylene oxide copolymer 20-25 Ethoxylated lauryl alcohol phosphate 3-6 Dibutylethanolamine 1-3 The lubricant is applied by dripping or misting on to the needles to an uptake of 1-2% on the yam. The thus-applied composition provides fibre-metal and metalmetal lubrication at temperatures of 100-150°F (say 38-66°C). The composition does not break down or gum up the knitting machine.

The foregoing lubricants, if left on the cloth or yarn during the dyeing step, promote uniform dye uptake.

In fact, their presence aids dye exhaustion at 240-270°F (say H6-132°C). The lubricants do not cause excessive foaming or fastness properties of· the dyed fabric.

Lubricant containing a diester of Formula II will contain 20-50 parts by weight of this material. Other proportions of ingredients will be as above.

Use of these compositions substantially reduces or eliminates carrier odour and smoke inside and outside processing plants. In addition to reducing air pollution, use of the lubricant compositions of this invention reduces water pollution. Generally, plant surcharges for high BOD/COD or separable oils become unnecessary.

C. Application as Coning Oil: For use as a coning oil, intended for application after texturing or during winding of the yarn, the compositions of this invention will also contain a major amount, up to 70% by weight, of ethylene oxidepropylene oxide copolymers of molecular weight 2000-5000. Exemplary of an appropriate material are_ *Ucon LB and HB (Union Carbide Corp.), the *Pluronics (BASF) or tjeffox fluids (Texaco, Inc.).

Coning oil compositions in accordance with the invention will include: Farts by Weight Cycloaliphatic diester of Formula I High boiling aromatic ester Dye-levelling agent Emulsifiers, dispersing agents and/or anti-static agents Ethylene oxide-propylene oxide copolymer *Ucon, *Pluronics and *Jeffox are Trade Marks -10 -10 2-5 -20 60-70 Preferred cycloaliphatic diesters for coning oil compositions include those In which R is alkyl of 4-20 carbon atoms, most preferably 6-12 carbon atoms.

The high boiling aromatic ester will preferably be of an alkanol of 8-30 carbon atoms, more preferably decyl, lauryl or myristyl benzoate or toluate The dye-levelling agent will preferably be an ester of ethoxylated aikylphenol, more preferably of nonylphenol.

The emulsifiers will preferably be ethoxylated alkanols, the corresponding phosphates and ethoxylated hydrogenated castor oil.

Other ingredients in the coning oil compositions can include up to about 0.5% by weight of an antioxidant, such as butylated hydroxy toluene; up to about 2.5% by weight of an alkanolamine, such as triethanolamine and up to 2.5% by weight of water.

A most preferred coning oil formulation is; Parts by Weight Cycloaliphatic bis(2-ethyl- hexyl)ester 6-8 Lauryl benzoate 6-8 Ethoxylated nonylphenol coconate 2-4 Ethoxylated lauryl alcohol 8-12 Ethoxylated hydrogenated castor oil 2-4 Ethoxylated nonylphenol phosphate 2-4 Ethylene oxide-propylene oxide copolymer 60-70 Butylated hydroxyltoluene 0 .05-0.2 Triethanolamine 0.5-2 Water 0.5-2 Coning oil in accordance with the invention penetrates the fibre rapidly, but does not sling off the fibre or feeder roll during application.

The treated yam is lubricated sufficiently for the yam to be rapidly coned, knitted or woven. The composition is stable and does not smoke, yellow or discolor at temperatures up to about 150®F (say 66°C) D. Dyeing: Dyeing assistant compositions in accordance with the invention will consist of: Pgrts by Weight Cycloaliphatic diester of Formula 1 15-40 High boiling aromatic ester 20-55 Dye-levelling agent 10-25 Emulsifiers, etc. 10-30 The cycloaliphatic diesters utilized for this aspect of the invention will preferably be those wherein R is alkyl of 4-20 carbon atoms, preferably 6-12 carbon atoms.

Preferred high boiling aromatic esters for this utility are dibenzoates and ditoluates of mono- and diethylene or propylene glycols.

Dye-levelling agents preferred for this aspect of the invention will be esters of the ethoxylated alkylphenols, particularly ethoxylated nonylphenol.

It is preferred that dyeing assistant compositions also contain ethoxylated castor oil and ethoxylated hydrogenated castor oil, as well as the phosphate (potassium salt) of an ethoxylated cycloaliphatic diester, that is, R is phosphated polyoxyethylene.

Preferably, the dyeing assistant compositions will contain .15-35 parts by weight of. cycloaliphatic diester, of Formula I. 35-55 carts by weight of high boiling aromatic ester and 10-20 parts by weight of dye-levelling agent.

A most preferred dyeing assistant composition will contain: Parts by weight Cycloaliphatic bis (2-ethylhexyl) ester 15-25 Dipropylene glycol dibenzoate 35-55 POE nonylphenol laurate 10-20 POE castor oil 4-6 POE hydrogenated castor oil 8-12 POE cycloaliphatic diester phosphate, K Salt 8-12 Such compositions are applied to the dye bath at a level of 0.25-1.0%, based on the weight of the goods. The dye hath is acidic (pH = 5 + 0.5) and contains dye as the only additional ingredient. This is unlike conventional processing requiring a dyeing assistant of 2-4% and other auxiliary levelling agents. Furthermore, the dyeing cycle is less sensitive to rate of temperature change than in conventional systems. The dyeing temperature in both systems is usually 265°F (say 129°C) in jet dyeing equipment.

Dyed yarns obtained using the compositions of the invention compare favourably with conventionally dyed yarn in properties such as light-fastness, crocking, shade depth and levelness. 24.

Accordingly, the compositions of this Invention, applied to a synthetic fibre when manufactured, or used as a processing aid for texturizing Instead of prior art lubricants, both Improve the dye affinity of the fibre and generally eliminate the need for further downstream processing 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 (4) Dye dispersant during dyeing (5) Dye leveller during dyeing (6) Fibre 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 The present invention is illustrated by the following non-limiting examples which describe the preparation of components for the present . compositions aa well as the use of euch compositions In treating fibres and fabrics. Comparison treatments are also given. The temperatures are set forth uncorrected in degrees Celsius. Unless otherwise indicated, all parts and percentages are by weight. Reference is made to the accompanying drawings: In Figures 1-4 are shown representations of photomicrographs of polyester yarn treated with the composition of Example 15 and with a conventional spin finish composition.

Example 1 Preparation of Dialkyl Ester (A Is -CH^CHj-, R is 2-ethylhexyl).

To three-necked flask fitted with stirrer, thermometer, nitrogen purge, condenser, side-arm receiver and heating mantle were charged 352 g (1 mole) of Diacid 1550, 273 g (2.1 moles) of 2-ethylhexanol, 1.5 g of p-toluenesulphonic acid and 2 g of decolourizing carbon. Air was purged from the flask with nitrogen and the reaction mixture was stirred and heated to 160-170°C for 4-6 hours. Water formed during the reaction was collected in the side arm receiver. The reaction was continued until the acid value was below 5 mg KOH/g. The catalyst and carbon were removed by filtration. The ester product and 25 grams of nickel on kieselguhr were charged to a stirred, heated pressure vessel. The mixture was heated to 160-170°C and pressurized to 400 psig (say 2.7 MPag) with hydrogen. A sample was taken after 6-8 hours and the iodine value was determined. The reaction was continued until the Iodine value was below 0.5 g of iodine/lOOg of sample.

The product was cooled to 50°C and the catalyst removed by filtration.

Esters are prepared similarly from: (1) Diacid 1550 and decyl alcohol, 1 ; 2 molar ratio (2) Diacid 1550 and tridecyl alcohol, 1:2 molar ratio (3) Diacid 1550 and Neodol 25, a mixture of Cj^2“C^5 linear alcohols, 1:2 molar ratio (4) Diacid 1550 and butanol, 1 : 2 molar ratio.

Example 2 A. Preparation of Polyoxyethylene Diester (A is —CH=CH—, R is HO(CH2CH2O)nCH2CH2-).

To a stirred autoclave fitted with heating and cooling coils was charged 352 g (1 mqle) of Diacid 1550. Catalyst (1.0 g of potassium hydroxide, was charged to the reactor. The temperature was raised to 110°C and the reactor was vacuum stripped for 30-60 minutes to remove any residual water from previous washing of the reactor or from one or more of the charged reactants or catalyst; The reactor was purged with nitrogen to remove air, evacuate! again and purged again with nitrogen. It was stirred and heated to 140°C and 100 g (2.3 moles) of ethylene oxide was added to the reactor. The pressure inside the reactor immediately built up to 30-50 psig (say 0.2 to 0.3 MPag). After 30-60 minutes’ induction time, an exothermic polymerization reaction (to 150-160°C, began with an accompanying pressure drop to zero (0 psig 0 MPag) as ethylene oxide was consumed. Ethylene oxide was added to the reactor to a total of 660 grams (15 moles). The temperature was maintained at 150-160°C by cooling. Addition of ethylene Oxide was stopped and the reaction was allowed to continue for an additional 30 minutes.

The reactor was cooled to 90-100°C and purged twice with nitrogen.

A sample of the product had a hydroxyl value of 11 mg of KOH/g (15 moles of ethylene oxide added to the diacid). The diester was acidified with acetic acid to neutralize the potassium hydroxide catalyst and 3 g of hydrogen peroxide was added to bleach and lighten the colour of the product. The reactor was cooled to 30 °C and the product was filtered through filter paper using a porcelain filter.

B. Reduction to the Polyoxyethylene Diester (A is -CH2CH2-)..

The product of Example 2A and 25 g of nickel on kieselguhr were charged to a stirred, heated pressure TO vessel. The mixture was heated to 160-170°C and pressurized with hydrogen to 400 psig (say 2.7 MPag). After 6-8 hours, samples were removed at intervals for determination of the iodine value. The reaction was continued until the iodine value was less than 0.5 g/100 g of sample.

Example 3 Preparation of Phosphated Polyoxyethylene Diester (A is -CH2CH2-, R is Polyethoxylated (15 moles) diacid, obtained as in Example 2B was heated to 50-60 °C, stirred and purged thoroughly with nitrogen to remove air. To about 1015 g (1.0 mole) of this material was added 24 g (0.17 mole) of PjOg. immediate exothermic reaction occurred (exotherm to 85-95°C). The reaction mixture was maintained at this temperature by cooling and an additional 24 g (0.17 mole) of Ρ2Ο^ was added. The reaction was continued for 3 hours after all the F2°5 was a<^3e^· T^e reactor was cooled to 50 “C prior to removal of a sample. The product had an acid value of 32 mg KOH/g (indicates the reaction is complete) . The batch was bleached at 85-95 °C with 5 g of hydrogen peroxide,' cooled to 30“C and filtered.

Example 4 Preparation of Propylene Glycol Dibenzoate.

To a 3-necked flask fitted with stirrer, condenser, receiver, thermometer, nitrogen purge and heating mantle were charged 84 g (1.1 mole) of propylene glycol, 244 g (2 moles) of benzoic acid and 0.8 g of p-toluenesulfonic acid. Air was from the flask with nitrogen and the contents of the flask were heated to 160-170°C. Water formed by the reaction was removed continuously. The reaction was continued until the product had an acid value below 5 mg KOH/g. The sample was cooled and filtered.

Other esters are prepared using the following reactants : (1) dipropylene glycol and benzoic acid, 1 : 2 molar ratio (2) PPG 200 and benzoic acid, 1:2 molar ratio (3) PPG 500 and benzoic acid, 1:2 molar ratio.

Example 5 Preparation of Polyoxyethylene Nonylphenyl Laurate. To a three-necked flask fitted out as in Example was charged 750 g (1.1 mole) of polyoxyethylated nonylphenol (9.5 moles of oxyethylene, NP 9.5), 208 g (1 mole) of lauric acid and 2.4 g of p-toluenesulfonic acid. Air was purged from the flask with nit ;ogen and the mixture was heated to 160-170eC until an acid value below 10 mg KOH/g was obtained. The product was cooled and filtered.

Other polyoxyethylene nonylphenyl esters are made in a similar fashion from: (1) NP 9.5 and coconut fatty acid, 1:1 molar ratio (2) NP 9.5 and oleic acid, 1:1 molar ratio (3) NP 9.5 and stearic acid, 1:1 molar ratio (4) NP 9.5 and benzoic acid, 1 : 1 molar ratio.

Example 6 Ethoxylated castor and hydrogenated castor oils 5 were prepared as in Example 2. Ethylene oxide adds to the hydroxyl group of castor oil.

Example 7 A textile treating composition was made by combining materials prepared as above in the follow.'ng amounts by weight % by weight Bis-2-ethylhexyl diester (Example 1) 20 Propylene glycol dibenzoate 40 Polyethoxyethylene nonylphenol laurate (9.5 moles ethylene oxide) 20 Polyethoxyethylene hydrogenated castor (25 moles ethylene oxide) 10 Polyethoxyethylene castor (80 moles ethylene oxide) 10 Example' 8 The textile-treating composition of Example 7 was applied during the dyeing cycle to a 10 g swatch of T56 textured polyester test fabric by the following technique: .The sample swatch was placed in a stainless steel beaker containing 150 ml of water, 0.067 g of disperse yellow 67, 0.091 g of disperse red 91, 0.026 g of disperse blue 56, 0.1 g acetic acid (56%) and 0.03 g of the textile-treating composition. The beaker was sealed and placed in a launderometer set at 38eC. The temperature was raised at 4-5°C per minute to 130°C and held for 30-minutes. The beaker was cooled at 4-5eC per minute to 52 °C and removed from the launderometer.

The polyester swatch was removed from the beaker. It was uniformly dyed in a medium brown shade. Nearly all of the dye was exhausted from the aqueous solution. The swatch was rinsed with cool water and dried in an oven at 121°CExample 5 Texturized polyester doubleknit (1500 pounds) were loaded into a 6 port Gaston County jet machine. The machine was filled with water and the goods given an overflow wash. The machine was refilled and ramped to 60“C. Fifteen pounds (say 7 kg) of acetic acid (56%) and 4.5 pounds (say 2 kg) of the compositions of Example 7 were dropped into the jet from the drug room. After 5 minutes, 18 pounds (say 8 kg) of Samaron Yellow 6 GSL (disperse yellow 114), pounds (say 7 kg) of Bucron Rubine 2 BNS (disperse red) and 13 pounds (say 6 kg)ofForon Blue SBGL (disperse blue 73) were added to the jet machine from the drug room. Thejet was sealed off and ramped to 130°C. The temperature was held for 30 minutes at 130“C and ramped back to 66°C.

The fabric was patched for shade, the shade matched standard. The temperature was dropped to 38°C. The spent dye liquor was dropped and the machine refilled with water. The goods were rinsed thoroughly and removed from the jet. The goods were slit, dried and inspected. Final inspection indicated goods of excellent quality.

During the dyeing cycle using the composition of Example 7, the odour level in the dye house was much lower than observed with conventional systems.

Little smoking from the ovens was observed during drying and heat setting at the end of the dyeing cycle. Employee comfort was therefore significantly improved.

The dyeing assistant undergoes facile degradation upon being fed to the plant effluent. The following values were obtained: Conventional Dye Assistant System As Above COD mg/kg BOD mg/kg Ratio, COD;BOD 2,640,000 2,210,000 < 2,000 750,000 >1300:1 2.95:1 Because little of the dyeing assistant remains 10 on the fabric after dyeing, use of the product of Example 7 does not affect fastness properties of the dyed goods.

The foregoing is typical of production-scale application of the composition.

Example 10 The procedure of Example 9 was repeated, except that no composition of Example 7 was used. Opon patching at the end of the dyeing cycle, the shade is slightly off due to incomplete dye exhaustion.

The bath temperature was taken back up to 132 °C 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 3-4 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 unac32 ceptable dyeing.

Example 11 A textile-treating composition is prepared from the following ingredients: % by weight bislauryl diester (Example 1) 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 weight 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 polyoxyethylene 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 ' 53002 Parts by Weight Dipropylene glycol dibenzoate 30.0 POE (9.5) nonylphenol laurate 15.0 POE (80) castor oil 5.0 POE (25) hydrogenated castor oil 10.0 POE (15) diester phosphate potassium salt (Example 3) 10.0 (b) The composition thus obtained was applied from a 20% aqueous solution as a spin finish to 150 denier polyester fiber, which was then spun and textured. The finish of the yarn (foy) prior to texturizing was 0.29%; after texturizing foy was 0.25%. The textured yam built a satisfactory package.

Spin finish, applied as above, did not smoke, drip, build up on heater plates or cause other undesirable running conditions.

The texturized yam was knitted on an Invoit 18 Gauge machine into a double knit fabric. The yarn knitted well, with a minimum heat build Up on the knitting machine. No haze, mist or odour was observed in the knitting plant.

The fabric was taken to the dyehouse and loaded into a 6-port Gaston County jet machine. The goods were neither overflow washed nor scoured. Foaming during loading of the fabric was significantly lower than that of fabrics treated with conventional lubricants. The fabric was dyed as in Example 9 to yield a product judged of superior quality.

Both dye yield and barre coverage were improved and the fabric had a better overall appearance than untreated fabrics.

Example 15 (a) A spin finishing composition was prepared from: PartB by Weight Cycloaliphatic bis(2-ethylhexyl)ester Propylene glycol dibenzoate POE (9) nonylphenol laurate 5 POE (81) castor oil .POE (25) hydrogenated castor oil POE (10) nonylphenol phosphate, X salt (b) The composition of part (a) was applied, as a 20% emulsion, to polyester yam (505 denier/34 fila10 ment) from a single merge so as to achieve 0.5 - 0.6% dry pick-up. The treated yam and yam treated with conventional lubricant (*Diamond Shamrocx FT 504, containing a fatty ester lubricant, nonionic ethoxylate emulsifiers and antistat at 0.5 — 0.6% pick-up) were textured at 205-220°C on a sample Scragg X-2 texturing machine. After texturing, the treated yams were tested for thermal and other properties. The following results were obtained: *Diamond Shamrock is a Trade Mark. <Η s—·* 0 Φ Λ ιη 03 τί β «Η -Η Φ fe β -»4 |“4 & X ω W Χί ο Ί3 «τ4 J4 η φ •Η Ό β p4 α β 43 -Η C0 Ct co] ο tp r* <· §kd η Η i-ι t Ο Ό Φ CM -Η Μ ω β φ φ Η C? V. Φ ι-H ί <*> «^· <*) ο ο ο Ο in <Η • Τ * 00 0 Ο «-4 Μ co Ο Φ Φ r4 CP 03 Α β Φ ο φ r4 φ Η CM J4 I 3 03 υ ο α ο m ιη co 00 Ο ι-4 ΙΟ ΙΟ co r4 Ο «-4 γ4 co Ο • •Η • r-4 Ο ο λ: ο φ Φ CP 03 Λ β Φ □ φ »-4 φ Μ & U υ β ί-ι ιΛ · Η Ο ϋ ο η Ο\ <ο m · τ4 ο Ό η -Ρ >, •Η tn χ: 43 Φ β 43 β ' 5 •Η φ Φ rti β g •«4 β Ό r4 Φ α Μ Φ Φ Ο ο Φ Μ Ο co •»4 tn ο -Η - Η β ο β r4 φ Φ Ό ί* Φ Λ Φ *τ4 & 5 43 -Η Ο 43 43 Η 43 φ m • Φ β ω *-* Μ 3 β S Φ ε , ο Ο Φ ί3 ο >4 •Η +3 Μ 43 υ Q ο β Φ >4 β ο α 42 β Μ4 0 Φ | —( 43 2 φ ΙΗ r-4 Ο ο β >1 φ X! Ο •ί-ί Φ ι4 ϋ H Φ 43 e &4 Ο Q Ο Μ φ -Η •9 Φ Μ § 01 Ο CO Ρ •3 β Φ r*4 τ4 β Φ 5? ι4 ΕΗ Ο Ρμ Ο Ε4 Q <# TMA is a measure of softening or melting tendency of yarn heated under a constant tension. The decrease in TMA and DSC of the test yarn indicates that the degree of crystallinity is lower than that of yam treated with a conventional spin finish. Accordingly, treated fibers could be texturized and would absorb dyes at lower temperatures than customary, resulting in decreased energy expenditure. (c) Photomicrographic studies of yam cross 10 sections indicated that both yarns maintained their configurations. Accordingly, it is thought that observed changes in heat history were caused by changes in crystallinity induced by the spin finish applied. Dye penetration of both yam lots was essentially equivalent, but dye absorption of the fibers treated with the compositions of this Example are higher. The photomicrographs (Figs. 1-4) also show that the crystallinity of the test specimens has been changed. (d) Lubricating properties of the yarns was evaluated on the Scragg X-2 machine under varying conditions. The yam was textured at 340 meters/min at 205-220°C.

The following results were obtained: Table fi β> ο tn-H fi +» X fi X. fi tn fi-d fi Φ O' fi Ό Λ4 (D fi 4J -d dfi fi P Φ Λ ffi CO fi Q CH B rH B 0) tP fi P CD > < o Λ 0) 5 -d •d fi -P fi P fi -d Q « fa in fi •d \ Ό a □ fi CD CO Ο P CD td •d fi p. O in COl fi fi o •d GJ -P σ» fi fi · CD X o > υ z c fi o o< u co rH \ ΙΛ CO tn to rH CO to rH p* ”3· © to co in tn CH tn co P* to to • .« • • • co co co CO © CO P- to to f- P* •rH rH rH rH rH rH rH rH rH rH rH \ \ \ \ \ \ \ \ \ tn cn CO to in ^P *3« rH tn P* d PH CM co CH co CO © © PH CO in tn tn tn tn tn in *3* in tn tn ID CO rH rH co ό* in d H rl in ^p ch rH rH rH ro in rH rH ©co^cotocotnottocoin Γ-lDtOtOlDtDtDtDtOlOO rHrHrHrHrHidrd*drHid rH r» ο ”?· tn in co co ot co μ· ό· tn o r* r* to co in ί· «Μ* ^3· tnf~rHr-in©cofHinto to to co co o © tn to in tn co co co © in © to to Γ co co co o © o to to to co co co to in to in in in in tn in in o tn O tn in in tn tn tn in PH PH CO CH CM ε PH PH PH PH PH • • • ·- \ • • • • • CO CO co CO CO ε o o CO CO co CO td rH rd rH rH CO rH rH tn to ot σ» Ot Ot Ot Ot Ot Ot r- Ot Ot • • • • • • • • • td td rH td «d td «d id td id HC4(0'3'in^DtsC0ClOd The frictional properties, breaking strength, elongation and heated shrinkage were judged equivalent. (e) The effect of texturing temperature on dye uptake of yarn knitted into a sock and dyed was studied from 180-230°C. Dye absorption by the fibre was measured using a Macbeth Colour Eye instrument.

The test lot was texturized using the composition of Example 15(a) and contained no other additives.

The control lot contained Hipochem TA-3, a commercial dye carrier containing chlorinated solvents» methylnaphthalene and emulsifiers.

The K/S values (Kubelk-Munk/Scattering) were calculated as follows: _ (1 reflectance) ' ~2XreSectance The K/S value is directly proportional to the amount of dye on the fabric.

The following results were obtained: % Color Increase Temperature °C K/S with Carrier K/S with Finish Of Example 180 5.999 6.580 9.7 185 5.907 6.510 10.2 190 5.814 6.556 12.8 195 5.814 6.432 10.6 200 5.721 6.426 12.3 205 5.719 6.484 13.4 210 5.715 6.490 13.6 215 5.816 6.542 12.5 220 5.879 6.614 12;5 225 5.993 6.734 12.4 230 6,151 6.888 12.0 These results show that the test fabrics had K/S values about 10% higher than a fabric dyed using a conventional carrier. In additon, dye uptake was relatively uniform over a wide temperature range for texturing. These data further indicate that spin finish application is relatively more uniform than heretofore. (f) Large scale quantities of polyester texturized following use of the spin finish of Example 15 (a, were knitted into fabric and dyed in Gaston County Jet Machines without addition of lubricant, leveller, dyeing assistant or dye carrier. The treated polyester consistently gave 7-12% higher color yields than usual. Heat history barre seconds dropped 3-30%, depending on the style and shade.

Example 16 Lubricant of the following composition was prepared: Parts by Weight Cycloaliphatic bis (2-ethyl- hexyl)ester 20.0 Dipropylene glycol dibenzoate 39.3 POE (9.5) nonylphenol laurate 20.0 POE (10) nonylphenol 10.0 Butylated hydroxytoluene 0.1 POE (9.5) nonylphenol phosphate '6.3 Triethanolamine, 98% 2.5 Water 1.8 Example 17 Coning oil, for application at a level of 2-· after texturizing, was prepared from: Weight Percent Cycloaliphatic bis(2-ethyl- hexyl)ester 7.50 Lauryl benzoate 7.50 POE (9.5) nonylphenol coconate 3.75 POE (3.5) lauryl alcohol 10.00 POE (25) Hydrogenated castor oil Weight Percent 2.50 POE (10) nonylphenol phosphate 2.50 Ucon IB-65 64.15 Butylated hydroxytoluene 0.10 Triethanolamine 1.00 Water 1.00 This coning oil provided necessary lubrication to allow the yarn to be rapidly coned, knitted or woven. It did not smoke, yellow or discolor during processing temperatures of up to 65®C, Example 18 Knitting lubricant in accordance with the invention was prepared from: Weight Percent Cycloaliphatic bis(2-ethyl20 hexyl)ester 10.0 Propylene glycol dibenzoate 41.0 Lauryl (POE 9) laurate 10.0 POE (9) lauryl alcohol 10.0 Butylated hydroxytoluene 0.1 Ucon LB-6 5 21.9 POE (9) lauryl acid phosphate 5.0 Dibutylethanolamine 2.0 The lubricant was applied to the knitting needles at a level of 1-2% by dripping or misting and was effective as a lubricant at 38-65®C.

Example 19 Into a three-neck 1000 ml glass flask fitted with stirrer, thermometer, nitrogen purge and DeanStark trap were charged: 122.0 g benzoic acid 191.0 g di-n-butylaminoethanol 1.3 g 0.3 g 200.0 ml methanesulfonic acid (70%) hypophosphorous acid (50%) toluene The resulting mixture was heated to 70-85°C and held at reflux until the theoretical amount (18 g) of water was removed. The sample was cooled and washed in a separatory funnel. Toluene was removed in a rotary evaporator. Approximately 260 grams of di-nbutylaminoethyl benzoate were recovered.

Amino-substituted alkyl esters of aromatic acids, as prepared above, can be used in the compositions of this invention to replace all or part of the unsubstituted aromatic esters which would otherwise be used.

Example 20 A representative benzyl ester was prepared as in Example 19 from: 227.0 g benzyl alcohol 400.0 g lauric acid 2.4 g 0.6 g methanesulfonic acid (70%) hypophosphorous acid (50%) The resulting mixture was heated and held, at 165-175°C until the theoretical amount (37 g) of water was removed. Approximately 580 grams benzyl laurate were recovered.

The benzyl esters of pelargonic, octanoic, palmitic, stearic, oleic and hydroxystearic acids were prepared in a similar fashion.

Example 21 A diester of Formula II was synthesized in a two-liter autoclave fitted with nitrogen purge, condenser and receiver for water removal. Charge weights were: 510 g diacid 1550 2.0g flake caustic 636.0 g ethylene oxide After purging with nitrogen, Diacid 1550 and caustic were heated to 5 130°C. Ethylene oxide was added over a four hour period, during which the temperature was kept at 150-165°C. The resulting ethoxylate was cooled to 90°C, sampled and the molecular weight determined by hydroxyl value. A value of 139 was found. The following were added: 3.5 g acetic acid (glacial) 7.5 g methanesulphonic acid (70%) 340.0 g benzoic acid After purging thoroughly with nitrogen, the temperature was raised to and held at 165-170°C until the acid value was less than 5 mg KOH per gram. The theoretical amount of water was removed during the reaction and collected in the receiver. The sample was cooled and filtered.

The above composition was hydrogenated 1000.0 g example above 50.0 g Raney nickel QS hydrogen In the two-liter autoclave: The reduction was run at 100-125°C and 200-250 psig (say 1.3 to 1.7 MPag) until hydrogen consumption ceased. The product was cooled and filtered.

A propoxylated dibenzoate ester was prepared in a similar fashion. Example 22 To a three-necked flask fitted out as above was charged: 750.0 g polyoxyethylated nonylphenol (NP 9.5) 317.0 g hydroxystearic acid 4.0 g methanesulphonic acid (70%) 1.0 g hypophosphorous acid (50%) The mixture was heated to 160-170°C under nitrogen purge until the acid value was below 10 mg KOH/gm. The product was cooled and filtered. Approximately 1035 grams of polyoxyethylene nonylphenyl hydroxystearate were removed.

Claims (10)

CLAIMS 1. (1) an ester of the formula ArCOO-R^-OOCAr 10 [wherein Ar is substituted or unsubstituted monocyclic aryl and R^ is alkylene of up to 8 carbon atoms or polyoxyalkylene of the formula -C H. (0-C H„ ) - in which r is 2 or 3 and s_ is up to 15]; Γ 2Γ IT 22? S (Ii) an ester of the formula ArCOOR 2 15 [wherein Ar is as defined above and R 2 is alkyl or alkenyl of 8 to 30 carbon atoms]; (iii) an ester of a substituted or unsubstituted benzyl alcohol with a substituted or unsubstituted aromatic acid of 6 or more carbon atoms; (iv) an ester of a substituted or unsubstituted benzyl alcohol with a 20 substituted or unsubstituted aliphatic acid of 8 or more carbon atoms; or (v) an amino-substituted alkyl ester of an aromatic acid.

1. A base suitable for a fibre and textile-treating composition, the base comprising (a) a cycloaliphatic diester of formula (ch 2 ) 7 coor wherein R is substituted or unsubstituted straight or branched chain alkyl of 4 to 20 carbon atoms, polyoxyalkylene of the formula HO(CH 2 CH 2 O) n CH 2 CH 2 -, H0(C 3 H 60) a C 3 H 6 -, 10 HO(CH 2 CH 2 O) (C 3 H 6 0) q C 3 H 6 -, or Ηθ(ε 3 Η 6 θ) ρ^2 Η 4 θ \°2 Η 4- or phosphated polyoxyalkylene or a salt thereof wherein n is 2 to 22 and £ + 3. ~ ’ an ^ (b) a high boiling aromatic ester which is: 15 (i) an ester of the formula ArCOO-Rj-OOCAr [wherein Ar is substituted or unsubstituted monocyclic aryl and R^ is alkylene of up to 8 carbon atoms or polyoxyalkylene of the formula -C H, (0-C H„ ) — in which r is 2 or 3 and s is up to 15]; Γ Αΐ ΐ Λ,ΐ S ““ 44, (ii) an ester of the formula ArCOOR, '2 [wherein Ar is as defined above and R£ Is alkyl or alkenyl of 8 to 30 carbon atoms]: (ill) an ester of a substituted or unsubstituted benzyl alcohol with a substituted or unsubstituted aromatic acid of 6 or more carbon atoms; (Iv) an ester of a substituted or unsubstituted benzyl alcohol with a substituted or unsubstituted aliphatic acid of 8 or more carbon atoms; or (v) an amino-substituted alkyl ester of an aromatic acid.

2. A fibre or textile treating composition containing: (a) a cycloaliphatic dlester of formula n _ c 6 H 13_ —(CH 2 ) 7 C00R COOR wherein R is substituted or unsubstituted straight of branched chain alkyl o f 4 to 20 carbon atoms, polyoxyalkylene of the formula ho(ch..ch„o) αι,αι,-, Z z η Z Z IIO(C 3 H 6 0) n (C 3 H 6 -, H0(CH 2 CH 2 O) p (C 3 H 6 0) q C 3 H 6 -, or

3. A composition according to claim 2, wherein the weight ratio of cycloaliphatic diester to high boiling aromatic ester is 0.1:1 to 10:1 and wherein the combination of cycloaliphatic dlester and high boiling aromatic 25 constitutes 10-90% by weight of the composition.

4. A composition according to claim 2 or 3, and further comprising a dye-levelling agent. 5. Fibre can be texturized and lowering the temperature at which the fibre absorbs dye, the method comprising applying to the fibre to a pick-up of 0.4-0.75% by weight of a composition made from a base according to claim 1 and comprising the cycloaliphatic diester of formula I and the high boiling aromatic ester, wherein the ratio of cycloaliphatic diester to high boiling 5 ArCOOR^ [wherein Ar is phenyl or tolyl, and R 2 is decyl, dodecyl, hexadecyl, tridecyl, octadecyl or oleyl]. 29. A fibre or textile treated with a composition according to any preceding claim. 10 30. A fibre or textile according to claim 29, which fibre or textile contains a polyester, polyamide, polyacrylic or polymodacrylic. 31, A fibre or textile according to claim 29, which fibre or textile further contains a cellulosic or wool. 32. A fibre or textile according to claim 29, 30 or 31 which has been dyed 15 33. A method for treating a fibre or textile with one or more fibre or textile treating compositions, wherein at least one composition is a composition according to any of claims 2 to 32. 34. A method according to claim 33 which includes dyeing the fibre or textile. 20 35. A method of making fabric or an article from a synthetic fibre or fabric comprising coating the fibre or fabric with 1-2% by weight of a knitting or weaving lubricant composition made from a base according to claim 1 and comprising 5-15 parts by weight of cycloaliphatic diester of formula (I), 30-50 parts by weight of high boiling aromatic ester, 5-15 25 parts 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 fibre into fabric or a knitted or woven article and dyeing the fabric or knit or woven article. 36. A method for treating a synthetic fibre comprising applying to the 30 fibre to a pick-up of 0.4-0.75% by weight a spin finish composition made from a base according to claim 1 together with a dye-levelling agent; texturing the thus-coated synthetic fibre at 180-230°C; knitting or 50. weaving the resulting textured fibre into fabric or knitting the textured fibre into a knit article and dyeing the fabric or knit article. ')/. A method for lowering the heat history characteristics and the degree of crystallinity of a synthetic fibre, lowering the temperature at which the 5 wherein a is 0-12 and b is 1-24, or R^ is an ethoxylated alkanol residue of the formula CH 3 (CH 2 ) c _0 (CH 2 CH 2 C)) d“ CH 2 CH 2 whereln £ is 7-12 and d Is 1-24.

5. A composition according to claim 4, wherein the dye-levelling agent Is at least one compound of the formula K..C00K, J 4 IwliiTeln la a linear or branched ulkyl or alkenyl group of 1-21 carbon atoms, phenyl or tolyl and la an ethoxylated alkylphenol residue of the formula C a H 2a +1 \\ // 0{CH 2 CH 2 0) b CH 2 CH 2 -, 5 HO(C.H,0) (C„H,0) (C H - or phosphated polyoxyalkylene or a Jo p 2 4 24 salt thereof wherein n is 2 to 22 and £ + £ = n]; and (b) a high boiling aromatic ester which is:

6. A composition according to claim 5, wherein R^ has 11-17 carbon 10 atoms.

7. A composition according to any of claims 2 to 6, which is a spinfinish composition of the following composition: Parts by weight cycloaliphatic diester of formula I 20-40 15 high boiling aromatic ester 20-40 dye-levelling agent 10-20 emulsifiers, dispersing agents and/or anti-static agents 20-30.

8. A composition according to claim 7, wherein the cycloaliphatic 20 diester is one in which R is alkyl of 4-20 carbon atoms.

9. A composition according to claim 8, wherein the cycloaliphatic diester is one in which R is alkyl of 6-12 carbon atoms. 10. A composition according to claim 7, 8 or 9, wherein the high boiling aromatic ester is an ester of a glycol. 11. A composition according to claim 10, wherein the high boiling aromatic ester Is a diester from ethylene, propylene, or butylene glycol and benzoic or toluic acid. 12. A composition according to any of claims 2 to 6, which is a knitting lubricant composition of the following composition: Parts by weight cycloaliphatic diester of formula I 5-15 high boiling aromatic ester 30-50 dye-levelling agent 5-15 emulsifiers, etc. 10-20 ethylene oxide-propylene oxide copolymer 10-30. 13. A composition according to claim 12, wherein the cycloaliphatic diester is one In which R is alkyl of 4-20 carbon atoms. 14. A composition according to claim 13, wherein the cycloaliphatic diester is one in which R is alkyl of 6-12 carbon atoms. 15. A composition according to claim 12, 13 or 14, wherein the high boiling aromatic ester is a dibenzoate or ditoluate of ethylene or propylene glycol. 16. A composition according to claim 15, wherein the high boiling aromatic ester is propylene glycol dlbenzoate. 17. A composition according to any of claims 2 to 6, which is a coning oil composition of the following composition: Parts by weight cycloaliphatic diester of formula I 5-10 high boiling aromatic ester 5-10 dye-levelling agent 2-5 emulsifiers, dispersing agents and/or anti-static agents 10-20 ethylene oxide-propylene oxide copolymer 60-70. 18. A composition according to claim 17, wherein the cycloaliphatic diester is one in which R is alkyl of 4-20 carbon atoms. 48, Γ). Λ corapoaltIon according to claim 18, wherein the cycloaliphatic dlester is one in which R is alkyl of 6-12 carbon atoms. 20. A composition according to claim 17, 18 or 19, wherein the high boiling aromatic ester Is an ester of an alkanol of 8-30 atoms. 5 21. A composition according to claim 20, wherein the high boiling aromatic ester is decyl, lauryl or myristyl benzoate or toluate. 22. A composition according to any of claims 2 to 6, which is a dyeing assistant composition of the following composition: Parts hy weight 10 cycloaliphatic diester of Formula I 15-40 high boiling aromatic ester 20-55 dye-levelling agent 10-25 emulsifiers, etc. 10-30. 23. A composition according to claim 22, wherein the cycloaliphatic 15 diester is one in which R is alkyl of 4-20 carbon atoms. 24. A composition according to claim 23, wherein the cycloaliphatic diester is one in which R is alkyl of 6-12 carbon atoms. 25. A composition according to claim 23, 24 or 25, wherein the high boiling aromatic ester is a dibenzoate or ditoluate of mono- or diethylene 20 or propylene glycol. 26. A composition according to any of claims 2 to 25, wherein the cycloaliphatic diester is a dilauryl, bis(2-ethylhexyl), distearyl, bis(15-mole ethoxylated or phosphated 15-mole ethoxylated) ester. 27. A composition according to any of claims 2 to 26, wherein the high boiling aromatic ester is of the formula ArC00-R^-00CAr 49. 53003 [wherein Ar Is phenyl or tolyl, and R Is ethylene, propylene, ethyleneoxyethylene, or propyleneoxypropylene]. 28. A composition according to any of claims 2 to 26, wherein the high boiling aromatic ester is of the formula

10. Aromatic ester is 0.1:1 to 10:1 and wherein the combination of cycloaliphatic diester and high boiling aromatic constitutes 10-90% by weight of the composition, and texturing the thus-coated fibre at 180-230°C