WO1984001972A1

WO1984001972A1 - Waterless dip dye composition and method of use thereof for textile-related materials

Info

Publication number: WO1984001972A1
Application number: PCT/US1983/001760
Authority: WO
Inventors: Robert B Wilson; William F Pomeroy; Louis Terrell Sovey Jr
Original assignee: Robert B Wilson; William F Pomeroy; Louis Terrell Sovey Jr
Priority date: 1982-11-10
Filing date: 1983-11-10
Publication date: 1984-05-24
Also published as: GB2140463A; EP0124606A4; DE3390325T1; NL8320374A; GB2140463B; EP0124606A1; GB8416539D0

Abstract

A waterless dip dye composition for apparel- and textile-related articles comprises an aromatic ester of the formula ArCOOR2, ArCOO-R1-OOCAr or (ArCOO)z-R3, wherein R1 is alkylene of 2 - 8 carbon atoms or polyoxyalkylene of the formula -CrH2r(OCrH2r)s, in which r is 2 or 3 and s is 1 to 15; R2 is substituted or unsubstituted alkyl or alkenyl of 8-30 carbon atoms; R3 in the residue of a polyhydric alcohol having z hydroxyl groups; Ar is substituted or unsubstituted mono- or bicyclic aryl of up to 15 carbon atoms and z is 3-6, admixed with at least 0.5% by weight of a dyeing assistant agent and an organic colorant. A process for coloring apparel- and textile-related articles, fabricated from polyester, polyamide, polyurethane, acrylic, halogenated polyolefin or epoxy plastic, comprises exposing an article to the foregoing compositions, maintained at a temperature between 100oC and the temperature at which the plastic is degraded, for a time adequate to achieve the desired degree of coloration.

Description

DESCRIPTION

WATERLESS DIP DYE COMPOSITION AND METHOD OF USE THEREOF

FOR TEXTILE-RELATED MATERIALS

REFERENCE TO RELATED APPLICATION This is a continuation in part of Serial No. 06/440,611, filed November

10, 1982.

TECHNICAL FIELD

This invention relates to waterless compositions, particularly adapted for immersion coloring of plastic articles, used in apparel- and textile-related appli- cations.

BACKGROUND ART

The use of a glycol ether or glycol ester in a dyeing composition has been disclosed, for example, in the following U.S. Patents: 1,891,520 Bowley 1,927,145 Whitehead

1,977,345 Moore et al.

2,537,177 Woodruff

2,723,899 Toulmin, Jr.

3,009,760 Lenz et al. 3,607,358 Dangl et al.

3,635,652 Streck

4,047,889 Hermes

4,055,971 Hermes

References disclosing the use of glycols or glycerol as media for dyeing compositions include:

2,302,760 Goodman, Jr.

2,320,426 Goodman, Jr.

2,882,119 Laucius et al.

3,241,906 Smith et al. 3,901,648 Arbaud

4,245,991 Haddad et al.

Of these, the Hermes reference appears of most interest with respect to clean, economically feasible waterless dyeing of textiles.

_"gTfRE

O PI

^Z The use of ethoxylated materials for coloring of objects has been disclosed by Lenz et al. (U.S. Patent 3,362,779) and Kressner et al. (4,332,587).

Compositions containing esterified derivatives of a Diels-Alder adduct of linoleic acid and acrylic acid, intended for use in various textile-treating compo- sitions, have been disclosed by Wilson, in U.S. Patents 4,293,305 and 4,394,126, incorporated herein by reference.

Although a variety of solvent systems have been suggested for dyeing of articles in waterless systems, none presently available provides rapid, failure-free dyeings, which are done without producing obnoxious effluents or otherwise being unacceptable from a commercial viewpoint.

It is an object of this invention to provide a composition for waterless immersion coloring of plastic articles, used in the apparel- and textile-industries.

Such articles include, but are not limited to buttons, zippers, garments, carpeting, ribbons, draperies, shoe strings, sewing thread, lace, socks and other notions, used in clothing manufacture.

It is a further object of this invention to provide a method for rapid waterless coloring of apparel- and textile-articles. Still an other object of this invention is to provide an apparatus suitable for waterless coloring of apparel- and textile-related articles.

DISCLOSURE OF THE INVENTION

In one aspect, this invention relates to a waterless dip dye composition for apparel- and textile-related articles, comprising an aromatic ester of the formula ArCOOR₂, ArCOO-R_j-OOCAr or (ArCOO) -R„, wherein R_χ is alkylene of 2-8 carbon atoms or polyoxyalkylene of the formula -C H„ (OC H„ ) , in which r is 2 or 3 and s is 1 to 15; R« is substituted or unsubstituted alkyl or alkenyl of 8-30 carbon atoms; R„ is the residue of a polyhydric alcohol having z hydroxyl groups; Ar is substituted or unsubstituted mono or bicyclic aryl of up to 15 carbon atoms and z is 3-6, admixed with at least 0.5% by weight of a dyeing assistant composition and an organic colorant. in another aspect, this invention relates to a process for waterless color¬ ation of apparel- and textile-related articles, fabricated from a plastic compo¬ sition, comprising exposing an article to the foregoing compositions, maintained at a temperature between 100° C and the temperature at which the plastic degrades, for a time adequate to achieve the desired degree of coloration. "Aromatic ester," as used in the specification and claims, means an ester formed by reaction between a mono-, di- or polyh dric alcohol and an aromatic acid, so as to accomplish complete esterification of all hydroxyl functions therein.

Compounds within this class include esters of the formula ArCOOR„, wherein Ar is substituted or unsubstituted mono- or bicyclic aryl of up to 15 carbon atoms and

is substituted or unsubstituted alkyl or alkenyl of 8-30 carbon atoms. Also included within the definition of aromatic esters are those of the formula Ar-COO-R_-

OOCAr, wherein Ar is as above and R. is alkylene of 2-8 carbon atoms or polyoxyalkylene of the formula -C rB, £ ((K- ΓH, *ύT ) s_, in which r is 2 or 3 and s is 1 to 15.

Accordingly, aromatic esters used in this aspect of the invention include, but are not limited to, esters of benzoic, toluic, di ethylbenzoic, trimethyl- benzoic, naphthoic, butylbenzoic and similar acids.

In the practice of this invention, the foregoing types of esters will preferably be used in combination with a cycloaliphatic diester of the formula

ⁿ-°6^H13- r' /- CH₂>-COOR

COOR wherein R is substituted or unsubstituted straight or branched chain alkyl of 4-20 carbon atoms, polyoxyalkylene of the formula HO(C x H y 0) nC x H y- or phosphated polyoxyalkylene of the formula

(HO)₂P(=O)O(C_χH_2χO)_nC_χH_2χ or a salt thereof, wherein (C_χH_2χO)_n is (CH₂CH₂O)_n, (C₃H_gO)_n or (CHgCHgO) - (CgHgO) and n is 2-22. Other cycloaliphatic diester compounds which can be used are those wherein R is ArCOO(CH₂CH₂O)_nCH₂CH₂-, ArCOO CgHgO^CgHg-, ArCOO(C₂H₄O)_p(C₃H₆O)_qC₃H₆- or ArCOO(C₃HgO)_p(C₂H₄O)_qC₂H₄- and n, p, q and Ar are as above. It is preferred that compositions of this invention contain at least 5% by weight of a diester of this composition.

Preferred aromatic esters employed in the practice of this invention include those based on tri- or polyhydric alcohols, such as glycerol, tri ethylolpropane, pentaerythritol, diglycerol, sorbitol, mannitol, and the like. The aromatic acids used for esterification are as above. When esters of this type are used, it has been found that entirely acceptable dyeings can be obtained, without the use of a cyclo¬ aliphatic diester, required for good results in combination with aromatic esters of mono- and dihydric alcohols. Aromatic esters of tri- and polyhydric alcohols can be represented by the formula (ArCOO)_z-Rg, wherein R_g is the residue of a polyhydric alcohol having z hydroxyl groups and z is 3-6. When aromatic di esters of dihydric alcohols are used, alkylene (R,) can be ethylene, propylene, hexylene, 2,2- dim ethyl trim ethylene, butylene, hepta- methylene and octylene, including various isomers thereof.

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

In the case of aromatic esters of monohydric alcohols, alkyl (R„) can be octyl, nonyl, decyl, dodecyl, tridecyl, hexadecyl, stearyl and alkenyl can be any corresponding monounsaturated function, e.g., oleyl.

Preferred among aromatic esters of mono-or dihydric alcohols are those wherein:

(a) Ar is phenyl,

(b) Ar is tolyl,

(c) R, is ethylene or propylene, including each of (a) and (b),

(d) R, is ethyleneoxyethylene or propyleneoxypropylene, including each of (a) and (b),

(e) R, is polyoxypropylene of molecular weight 200-250, including each of (a) and (b), and

(f) R„ is decyl, dodecyl, hexadecyl, tridecyl, octadecyl or oleyl, including each of (a) and (b). Contemplated equivalents of the aromatic esters described above include esters of benzyl alcohol and substituted or unsubstituted aromatic acids of 6 or more carbon atoms, or substituted or unsubstituted aliphatic acids of 8 or more carbon atoms, including but not limited to, benzyl laurate, benzyl pelargonate, benzyl octoate, benzyl palmitate, benzyl stearate, benzyl oleate, benzyl hydroxy- stearate or benzyl benzoate. It will be understood that esters of substituted benzyl alcohols can also be used.

Preferred aromatic esters based on trihydric or polyhydric alcohols are those of glycerol, trimethylolpropane or pentaerythritol. Most preferred are benzoate or toluate esters. It will be understood that mixtures of aromatic acids can be used to prepare any of the aromatic esters used in the practice of this invention.

The dibasic cycloaliphatic acid employed in making the compositions of this invention is a Diels-Alder adduet of aerylic acid and linoleic acid and can be prepared as described by Ward in U. S. Patent 3,753,968. The diacid has the formula

-ψJΕE

OMPI

and therefore is a mixture of (5 and 6)-carboxy-4-hexyl-2-cyclohexene-l-octanoic acids. The diacid is available commercially from Westvaco, designated as "Diacid 1550".

Preparation of adducts from conjugated octadecadienoic acid and unsatu- rated acids and/or their hydrogenation has also been described by Teeter et al, J. Org. Che ., vol. 22 (1957) at 512-514, Ward in U. S. Patent 3,899,476 and Ward et al in U. S. Patent 3,981,682. The preparation of esters from the C„, diacid adduet was reported by Ward et al, J. Arner. Oil Chemists' Soc, vol. 57 (1957) at 219-224. Ethoxylated esters containing 4-119 ethylene oxide units are said to be effective lime soap dispersants. The alkyl esters are reported as being useful in lubricant applications, including users as textile lubricants and plasticizers for PVC. The diacid can be esterified with alcohols using, for example, acidic catalysts such as p-toluenesulfonic acid, methanesulfonic acid or sulfuric acid. During the esterification, the reaction mixture is preferably also treated with a decolorizing agent, e.g., carbon or clay.

The diacid is reduced following esterification to a saturated compound cycle. A nickel catalyst such as Raney Nickel, nickel on kieselguhr or nickel on alumina can be used. The required amount varies up to 5 - 10% by weight of the ester.

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

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. 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:

OMPI r- WIPO -6-

CH₃-(CH₂)₅ (CH₂)₇CO-(OCH₂CH₂)_χ-OH

HO-(CH₂CH₂O) OC x + y = 5 - 25

The phosphorylated product is readily obtained by reaction with phosphorus pentoxide. The saturated diester can be obtained by nickel-catalyzed hydro- genation.

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 in which R is ArCOO(CH₂CH₂O) CHgCHg-, etc. 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.

Representative of substituted alkyl R which ay be used in the products of this invention are butoxybutyl, 10-hydroxystearyl, 10-hydroxydecyl, IO-halostearyl, t -alkanoyloxyalkyl or the like.

Preferred diesters for use in accordance with the principles of the invention are those wherein:

(a) R is 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(C₃HgO)_nC₃H₆-,

(e) R is HO(C₂H₄O) (C₃HgO) C₃Hg-,

(f) R is (HO)₂P=O(OCH₂CH₂)_nOCH₂CH₂- or a salt thereof, (g) R is C₆H₅CO(OC₂H₄)_nOC₂H₄-,

(h) R is CH₃C_gH₄CO(OC₂H₄)_nOC₂H₄-

(i) R is CgH₅CO(OC₃H₆)_nOC₃H₆-, and

(j) R is CH₃CgH₄CO(OC₃H₆)_nOC₃H₆-.

"Dyeing assistant agent," as used in the specification and claims, includes alkoxylated alkylphenols and their esters, alkoxylated castor oil compounds, alkoxylated hydrogenated castor oil compounds, alkoxylated primary alkanols, salts of phosphated alkoxylated primary alkanols and mixtures thereof. The amount of dyeing assistant agent, employed in the compositions of this invention, is at least about 0.5% by weight of the composition. However, it is preferred that the compositions contain at least 5%, more preferably up to about

80% by weight, of dyeing assistant agent. Preferred compositions can also contain 60 -80% by weight of the dyeing assistant agent.

Preferred dyeing assistant agents are alkoxylated alkylphenols and their esters. These are compounds of the formula

^Ca^H2a ₊ 1^6^H4-°^(Cx^H2x⁰⁾b^R"' wherein a is 1 - 12; b is 1 - 24; R" is H, aroyl of mono- or bicyclic aromatic acids of up to 15 carbon atoms or substituted or unsubstituted alkanoyl of 8 - 30 carbon atoms. Accordingly, exemplary dyeing assistant agents include ethoxylated and propoxylated alkyl phenols and corresponding esters, such as the laurate, myristate, palmitate, coconate, oleate, stearate, isostearate, benzoate and toluate esters. Preferred alkylphenols are nonylphenol, octylphenol, and dodecylphenol. It will be understood that the alkylphenols and the acids used to esterify the alkoxylated alkylphenols can include mixtures.

Most preferably, the alkoxylated alkylphenols will be ethoxylated deriv¬ atives, having 5 - 10 ethylene oxide units.

Preferred dyeing assistant agents will be those wherein: (a) R" is alkanoyl of 12 - 18 carbon atoms, including mixtures thereof;

(b) R" is n-C_1?H₃₃CO;

(c) R" is n-C_1?H₃₅CO;

(d) R" is iso-C_1?H₃₅CO;

(e) R" is benzoyl; (f) R" is n-C_uH₂₃CO;

(g) R" is H;

(h) a is 5 - 10, including each of (a) - (g);

(i) b is 6 - 15, including each of (a) - (h);

(j) b is 8 - 11, including mixtures thereof and including each of (a) - (h); (k) a is 9, b is 8 - 10 and R" is n-C_uH₂₃CO;

(1) a is 9, b is 6 - 10 and R" is H and

(m) x is 2, including each of (a) - (1). Alkoxylated castor oil used as an optional additive in the compositions of this invention will contain 15 - 100 oxyalkylene units, preferably 40 -85 oxyethylene units. The hydrogenated cator oil derivatives will contain 5 - 200 oxyalkylene units, preferably 20 - 30 oxyethylene units. These types of materials can be purchased from ICI America and Whitestone Chemical Co.

The types of plastic materials which can be colored using the compositions and method of this invention include, but are not limited to, polyesters, poly- amides, polyurethanes, acrylics, halogenated polyolefins and epoxy plastics. How¬ ever, notions, and textile- and apparel-related articles are commonly made from polyesters, polyamides, polyurethanes and acrylics, which substrates are preferred for the practice of this invention.

Polyester articles include those made from poly(alkylene terephthalates), such as poly(ethylene terephthalate), or polyesters made from cyclohexanedi- m ethanol. Typical of polyester articles are presewn garments, including slacks, jeans, dresses, shirts, scarves and the like. Also included within the scope of polyester articles are buttons, draperies, laces, seatbelts, ribbons, zippers and other notions.

Polyamides particularly contemplated as substrates in the practice of this invention include those known as nylons 6; 6,6 or 6,10. Articles which can be colored in accordance with the invention include the same types of articles as for polyesters, as well as lingerie and hosiery. It is common, for example, to employ polyamide teeth in zipper constructions. Also, polyamide is often used for carpeting.

Acrylic plastics, contemplated within the scope of this invention include straight acrylics, such as polyacrylonitrile, and modacrylics. The latter are copolymers of acrylonitrile or methacrylonitrile, generally with vinyl chloride or vinylidene chloride. Articles made from acrylics include clothing, carpeting and notions.

Polyurethanes include a myriad of compositions, made by reaction, for example, between glycols and organic di- or polyisocyanates. Among the glycols, used to make polyurethanes, are simple glycols, such as the alkylene glycols, and polymeric glycols, including polyether and polyester glycols. Articles containing polyurethane, used in textile and garment manufacture include rain wear and artificial leather, which can be colored by the teachings of the instant invention.

OMPI VvIPO In some instances, the foregoing types of plastics can be blended with natural or synthetic cellulosic materials and colored according to this invention.

"Organic colorant," as used in the specification and claims, includes both dyes and pigments of any structure. Normally, the dyes or pigments which are employed need not be soluble in water. Therefore, such dyes and pigments will not usually contain water-solubilizing functions, such as a plurality of sulfonic acid groups. The dyes/pigments used in the practice of this invention generally will be chosen from among water-insoluble dyes, which may also be known as disperse dyes. Included within this class of dyes, which can be used on fibers such as cellulose actate, polyamides or polyesters, from any kind of dyeing medium are colors of the azo, azomethine, nitroarene and anthraquinone structures. It will be understood that the dyes useful in the practice of the present invention are not limited to these classes of compounds.

The dyes or pigments used in the practice of this invention may be identified by their chemical names, for example:

3-nitro-N -phenylsulfanilanilide, a yellow dye; p-[p-(phenylazo)phenylazo] - phenol, a red-yellow dye; ethyl 4-hydroxy-l-anthraquinonecarbamate (an orange dye); l-amino-4-hydroxyanthraquinone, a red dye; l-amino-2-bromo-4-hydroxy- anthraquinone, a red-blue dye or 4,5-diamonochrysazin, a blue dye. The dyes alternatively may be identified in accordance with standard chemical handbooks, such as "The Color Index," third edition, The Society of Dyes and Colors and the American Association of Textile Chemists and Colorists (1971). This sort of handbook correlates dye structure with trade names. Typical of colorants identified in accordance with this handbook, which can be used in the practice of this invention, are Solvent Orange 20; Acid Blue 83 (C.I. 42660), Acid Blue 59 (C.I. 50315), Direct Blue 86 (C.I. 74180); Direct Red 81 (C.I. 28160) and Acid Yellow 36 (C.I. 13065).

Cationic dyestuffs can also be used in the practice of this invention, for example Rhodamine 6G, Rhodamine B, Rhoduline Blue 6G and Methylene Blue BB. Similarly, metallized azo dyestuffs can be employed in the practice of this invention. Representative metallized azo dyes which can be employed are Co, Ni, Cu or Cr complexes of coupling products of 2-amino-4-nitrophenol and resorcinol; 2-amino-4-chloro-5-nitrophenol and acetoacetanilide; dianisidine and 3-hydroxy-2- naphthanilide; 2-amino-4-chloro-5-nitrophenol and 2-aminonaphthalene or the like.

ξ fRE OMPI , WIPO It will further be understood that other textile-treating agents, such as optical brighteners, e.g. styrylnaphoxazole compoαnds, can be applied, along with dyes or pigments.

The dyes/pigments can be used in any form, that is as presscake or as dried pressed dye. The addition of dispersing agents is optional. Alternatively, the dyes or pigments can be added to the dye bath in a solvent/dispersing medium compatible with the dye bath. It is convenient and preferred, in the practice of this invention, to use solid disperse dyes free of additives.

It has been found, in accordance with this invention that articles can be dyed or colored very rapidly and very homogeneously. Normally, i mersion in the dye bath for as little as 30 seconds at 160° C will give significant coloration.

However, for even faster results, the dyeings can be done at 180 - 200° C. or higher.

Employing the compositions of this invention at 200° C. or more does not result in smoking or pollution of the processing plant, which is a problem when ethylene glycol or diethylene glycol are the dyeing solvents. In practice, it is feasible to use a temperature, up to that at which the plastic being dyed, will degrade. However, temperatures between 120 - 235^CC, most preferably 140 - 235° C, will be preferred.

Although it is preferred to dye the articles being treated by immersion in a bath of the dye composition, the dyes can also be applied by spraying. Then, the sprayed articles should be heated in a bath to at least 140° C to complete uptake of the dye into the article.

Whether the article is dyed by immersion or otherwise, the dyed article is normally cleaned with a solvent to remove excess dye. Preferably, the solvents used for cleaning are chlorinated or fluorinated hydrocarbons. However, highly chlorinated solvents, such as perchloroethylene and trichloroethylene are preferred for cleaning by immersion in a liquid bath. Fluorochlorocarbons, such as dichloro- difluororo ethane, chlorotrifluorom ethane, which are gases at ambient temperatures or slightly above, can be used for vapor-phase cleaning of the dyed articles. Normally, means will be used to recover and recycle the cleaning solvent, rather than discharging it to the atmosphere.

A further advantage of the process of the invention is that it is essentially self-contained and effluent free, that is, little or no material is lost or discharged to the atmosphere.

OMPI eΛ, WHO -11- In the apparatus of this invention, as shown in Fig. 1, the major components include a dip tank, a dye recovery unit, a solvent cleaning tank, a solvent recovery still and a drier. The dip tank will be provided with heating means and stirring means, so as to permit circulation of the dyeing solution within the dip tank and to a dye recovery unit external thereto.

The dye recovery unit normally includes filtration means for removal of solid debris from used dye solutions and distilling and condensing means for recovery of the solvent. The purified dye solution can be recycled to the dip tank, with addition of dye or other additives to provide the desired composition in the dip tank, or can be stored for later use.

It is preferred, in coloring many types of textile-related articles, including jeans, shorts, lingerie, carpeting, hosiery, zippers and lace, as exemplary, to provide squeeze roller means, essentially functioning as wringers, to remove excess dye solution from treated articles. The dye solution removed at this point can be cycled to the external recovery unit or can be returned directly to the dip tank.

Articles leaving the squeeze roll station are passed into the solvent cleaning tank to complete removal of any excess or unadherent dye matter. It is preferred to use a plurality of solvent cleaning tanks. It is also preferred to circulate solvent from the tank through an external solvent recovery unit, provided with filters to remove solid materials and distilling and condensing means for purifying solvent, and to return purified solvent to the system. Dye recovered on the filter or as residue from the distiUaticxi can be returned to the system for recycle. When a plurality of solvent cleaning tanks are employed, it is preferred to flow solvent countercurrently to the direction in which the articles being treated, are moved. The final component of the apparatus is the drying means, such as a hot air drier, from which articles leaving the system can be inspected and packaged.

Solvent vapors from the hot air drier can be condensed and returned to the system.

BRIEF DESCRIPTION OF THE DRAWING

In Fig. 1 is shown an apparatus, suitable for use in accordance with the invention.

_*- WIP BEST MODE FOR CARRYING OUT THE INVENTION

In a most preferred aspect, the compositions of this invention will ^"be those wherein the aromatic ester is of the formula (ArCOO) -R,, Ar is phenyl or tolyl, ₃ is the residue of glycerol, trimethylolpropane or pentaerythritol and the composition contains at least 5% by weight of an alkoxylated alkylphenol or an ester thereof. It is further preferred that the compositions of this invention contain at least 5% by weight of a diester, obtained from the hydrogenated adduet of linoleic acid and acrylic acid and that the organic colorant is a disperse dye.

A most preferred process in accordance with this invention is one wherein the article being treated is exposed to the foregoing composition, maintained at a temperature of 140 - 235° C for a time adequate to achieve the desired degree of coloration.

Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to the fullest extent. The following specific embodiments are, therefore, to be construed as merely illustrative and not limitative of the remainder of the disclosure in any way whatsoever. In the following examples, the temperatures are set forth uneorrected in degrees Celsius. Unless otherwise indicated, all parts and percentages are by weight.

EXAMPLE 1

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 purged 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 product 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

(4) glycerol and benzoic acid, 1 : 3 molar ratio

(5) pentaerythritol and toluic acid, 1 : 4 molar ratio (6) trimethylolpropane and mixture of benzoic and toluic acids, 1 : 3 molar ratio.

OMFI EXAMPLE 2

Preparation of Polyoxyethylene Nonylphenyl Laurate

To a three-necked flask fitted out as in Example 1 was charged 750 g (1.1 moles) 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 nitrogen and the mixture was heated to 160 - 170° C until an acid value below 10 g/KOH was obtained. The product was cooled and filtered.

Other polyoxyethylene compounds 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 3

Preparation of Unsaturated Cycloaliphatic Diester (R is 2-ethylhexyl) To a three-necked flask fitted with stirrer, thermometer, nitrogen purge, condenser, side-arm receiver and heating mantle were charged 352 g (I mole) of

Diacid 1550, 273 g (2.1 moles) of 2-ethylhexanol, 1.5 g of p-toluenesulfonic acid and

2 g of decolorizing carbon. Air was purged from the flask with nitrogen and the reaction mixtue 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 with hydrogen. A sample was removed after 6 - 8 hours for determination of the iodine value. The reaction was continued until the iodine value was below 0.5 g of iodine/100 g of sample.

The product was cooled to 50^® C and the catalyst was 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 12 - 15 carbon alcohols), 1 : 2 molar ratio. -14- EXAMPLE 4

A. Preparation of Polyoxyethylene Unsaturated Cycloaliphatic Diester, R is

To a stirred autoclave fitted with heating and cooling coils was charged 352 g (1 mole) 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 reaetants or catalyst. The reactor was purged with nitrogen to remove air, evacuated again and purged again with nitrogen. The contents of the reactor were 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. After 30 -60 minutes' induction time, an exothermic polymerization reaction (to 150 - 160° C) began. The reaction was accompanied by a pressure drop to zero (0 psig) as the ethylene oxide was consumed. Ethylene oxide was added to the reactor to a total of 660 g (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 30 minutes more. The reactor was cooled to 90 - 100° C and purged twice with nitrogen.

A sample of the product had a hydroxyl value of 110 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 treated with 3 g of hydrogen peroxide to bleach and lighten the color of the product. The reactor was cooled to 30° C prior to removing the product, which was filtered through filter paper, using a porcelain filter. B. Reduction to the Polyoxyethylene Diester

The product of Example 4A and 25 g of nickel on kieselguhr were charged to a stirred, heated pressure vessel. The mixture was heated to 160 - 170° C and pressurized with hydrogen to 400 psig. 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 5

Preparation of Phosphated Polyoxyethylene Diester (R is (HO)_oP(=O)(OCH₂CH₂) -

(15 moles of ethylene oxide) diacid, obtained as in Example 4B was heated to 50 - 60° C, stirred and purged thoroughly with nitrogen to remove air. To about 1015 g (1 mole) of this material was added 24 g (0.17 mole) of phosphorus pentoxide. An exothermic reaction began immediately, with an exotherm to 85 -95° C. The reaction mixture was maintained at this temperature by cooling and an additional 24 g (0.17 mole) of phosphorus pentoxide was added. The reaction was continued for three hours after all of the phosphorus pentoxide was added. The reactor was cooled to 50° C prior to removal of a sample. The acid value of the product was 32 mg KOH/g, indicating that the reaction was complete. The batch was bleached at 85 - 95° C with 5 g of hydrogen peroxide, cooled to 30° C and filtered.

EXAMPLE 6

Aroylpolyoxyethylene Cycloaliphatic Diester

An aroylpolyoxyethylene cycloaliphatic diester was synthesized in a two- liter autoclave fitted with nitrogen purge, condenser and receiver for the removal of by-product water. Charge weights were: 510.0 g. Diacid 1550

2.0 g. flake caustic

636.0 g. ethylene oxide

After purging the system with nitrogen, Diacid 1550 and caustic were heated to 130° C. Ethylene oxide was added over a four-hour period, during which the temperature was kept at 150 -165° C. The resulting ethoxylated product was cooled to 90° C for removal of a sample. The (by hydroxyl value) was 139. To this intermediate was added:

3.5 g. acetic acid (glacial)

7.5 g. methanesulfonic acid (70%) 340.0 g. benzoic acid

After purging with nitrogen, the temperature of the mixture 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 filtered product was hydrogenated in a two-liter autoclave:

1000.0 g ethoxylated product, above

50.0 g Raney nickel

QS hydrogen

OMPI *tøV_AT The reduction was run at 100 - 125° C 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 7 A representative benzyl ester was prepared from:

227.0 g benzyl alcohol

400.0 g lauric acid

2.24 g methanesulfonic acid (70%)

0.6 g hypophosphorous acid (50%) The resulting mixture was heated and held at 165 -175° C until the theo¬ retical amount (37 g) of water was removed. Approximately 580 grams of benzyl laurate were recovered.

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

EXAMPLE 8

Ethoxylated castor and hydrogenated castor oils were prepared as in Example 4. Ethylene oxide adds to the hydroxyl group of castor oil.

EXAMPLE 9

A waterless dyeing composition was prepared from glyceryl tribenzoate (Velsicol Chemical Corp.) and nonylphenol 7 (7 oxyethylene units, Union Carbide Corp.) in 20 : 80 weight ratio, containing 1 gram/liter of presscake blue dye.

This composition was kept at 180° C and stirred while a six-inch section of polyester zipper was immersed therein for one minute. The zipper was removed, washed in perchloroethylene and dried. The zipper was homogeneously colored with good dye fixation. There was little or no smoking during the coloring operation.

EXAMPLE 10

(a) Polyester buttons were dyed with a composition, as in Example 9, which contained 2.5 g/liter of disperse blue 56 dye. After 30 seconds' immersion, the

i JR > ^ιp buttons were homogeneously colored a light blue. At the end of three minutes, the buttons were deep blue. The buttons were washed with perchloroethylene as in

Example 9.

(b) Polyester buttons were immersed in the same solution as in part (a), but the solution was held at 160° C. The following results were obtained as a function of immersion time:

Time Result

5 sec no color

10 sec very pale blue 0 15 sec pale blue

1 in pale blue

2 min pale blue

3 min medium blue

(c) A similar run was made at 180° C. Results were: Time Result

5 sec no color

10 sec very pale blue

15 sec pale blue

30 sec pale blue 1 ^min ^fll^e blue

2 min medium blue

3 min medium deep blue

(d) Results for a similar experiment, done at 200° C, were: Time Results 5 sec pale blue

10 sec medium pale blue

15 sec medium pale blue

30 sec medium blue

1 min deep blue 2 min deep blue

3 min very deep blue

These results show that rapid uptake of dye occurred at 180 - 200° C. It was further found that cycling of the dye bath to and above 200° C did not result in smoking or destruction of the dye bath. Only periodic replenishment of the dye was required.

OMPI ^K. IPO

Φ?Λ'ATI EXAMPLE 11

Compositions similar to those of Examples 9 and 10 were used to color the following articles, under the conditions indicated:

(a) 140° C., 1 minute enamel paint-coated metal zipper travelers

(b) 170° C, l minute nylon sock (c) 180°C, 2 min nylon carpet polyester buttons nylon ring polyester zipper seat belt nylon bead nylon cord

In each case, the article was colored evenly. No splotches were observed. The products were cleaned easily with perchloroethylene.

EXAMPLE 12

(a) Dye solution comprising ethylene glycol, containing 1 gram/liter of pure presscake blue dye, was heated to 180° C with constant stirring. The solution began to smoke at about 107° C. Smoking became very troublesome at 125° C and even worse at 180° C.

Into the solution at 180° C was immersed a six-inch piece of polyester zipper. After one minutes' immersion, the zipper was removed, cooled in air and cleaned in perchloroethylene solution, to remove residual dye solution. The zipper was difficult to clean. The zipper was unevenly colored and had many splotches.

(b) A similar experiment was done, using diethylene glycol as solvent. The dyed product was unevenly dyed and had many splotches.

These experiments demonstrate that use of glycol solvents are unacceptable from a pollution standpoint and that unacceptable dyeings are obtained.

EXAMPLE 13

A 3/16 inch stainless steel tank of 70 gallon capacity containing 520 pounds of dip dye solution, as in Examples 9 and 10, at a dye level of 0.5 pound of Latyl Blue BCN 356 (crude ground dye) was heated externally to provide a temperature of 182° C.

A pump was used to circulate material in the dye bath during heating and while a polyester zipper about two feet long was immersed in the stirred bath for about 30 seconds. The zipper was removed from the bath and lightly squeezed with a roller to remove excess dye solution. The zipper was washed in a tank containing a mixture of trichloroethylene and perchloroethylene. After 30 seconds' immersion in the bath, the zipper was dried in a hot air chamber. The zipper was ready for final inspection and shipment. The zipper was rapidly dyed by this method and was pleasant in appearance.

EXAMPLE 14

Dip dye solution is made from the following ingredients, as above: parts by weight

40 hydrogenated cycloaliphatic diester with 2-ethylhexyl alcohol (Example 3) 40 propylene glycol dibenzoate

20 POE nonylphenyl laurate (Example 2)

1 Latyl Blue BCN 356

The dip dye solution is used as in Examples 9-11 with similar results.

EXAMPLE 15 Dip dye solution is made as above from: parts by weight

(a) 20 POE nonylphenol (N.P. 8.5)

50 glyceryl tribenzoate

30 hydrogenated cycloaliphatic diester of Example 3 (Neodol 25) 2 presscake blue

(b) 10 hydrogenated cycloaliphatic diester of Example

3 (decyl alcohol)

50 diethylene glycol toluate

50 ethoxylated octylphenol oleate

1 presscake yellow dye (c) 50 , benzyl benzoate

10 hydrogenated cycloaliphatic diester with

2-ethylhexanol

40 ethoxylated dodecylphenol

1.5 presscake green dye. The foregoing are used for coloration of textile-related articles with results similar to those described above.

The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples. From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.

- tJRE OMPI ^ WIPO

Claims

Claims:

1. A waterless dip dye composition for apparel- and textile-related articles, comprising an aromatic ester of the formula ArCOOR„, ArCOO-R,- OOCAr or (ArCOO) Z -R₀, wherein R 1, is alkylene of 2-8 carbon atoms or polyoxy- alkylene of the formula -C rH Δ.T (OC r H„ ΔV ) s , in which r is 2 or 3 and s is 1 to 15; R₀ -> is substituted or unsubstituted alkyl or alkenyl of 8-30 carbon atoms; R_g is the residue of a polyhydric alcohol having z hydroxyl groups; Ar is substituted or unsubstituted mono- or bicyclic aryl of up to 15 carbon atoms and z is 3 - 6, admixed with at least about 0.5% by weight of a dyeing assistant agent and an organic colorant.

2. The composition of claim 1, wherein the dyeing assistant agent is an alkoxylated alkylphenol or an ester thereof.

3. The composition of claim 1, wherein the aromatic ester is (ArCOO) -

R,

4. The composition of claim 3, wherein z is 3 or 4.

5. The composition of claim 1, wherein the dyeing assistant agent is an alkoxylated alkylphenol or an ester thereof and constitutes at least 5% by weight of the composition.

6. The composition of claim 1, wherein the dyeing assistant agent is an alkoxylated alkylphenol or ester thereof and constitutes up to 80% by weight of the composition.

7. The composition of claim 3, which further comprises an alkoxylated castor oil compound, an alkoxylated hydrogenated castor oil compound, an alkoxyl¬ ated primary alkanol, a salt of a phosphated alkoxylated primary alkanol or a mixture thereof.

8. The composition of claim 3, wherein Ar is phenyl or tolyl; R₃ is the residue of glycerine, trimethylolpropane or pentaerythritol and the composition contains at least 5% by weight of an alkoxylated alkylphenol or an ester thereof.

9. The composition of claim 3, wherein Ar is phenyl or tolyl; R_g is the residue of glycerine, trimethylolpropane or pentaerythritol and the composition contains up to 80% by weight of an alkoxylated alkylphenol or an ester thereof.

10. The composition of claim 1, wherein the organic colorant is a disperse dye.

11. A process for coloring apparel- and textile-related articles, made from plastic, comprising exposing an article being treated to a composition of claim 1, maintained at a temperature from 100° C to the temperature at which the plastic degrades, for a time adequate to achieve the desired degree of coloration.

12. The process of claim 11, wherein the plastic is polyester, polyamide, polyurethane, acrylic, halogenated polyolefin or epoxy.

13. The process of claim 11, wherein the article is immersed in the coloring composition at a temperature of at least 140° C for at least 1 minute.

14. The process of claim 11, wherein the article is sprayed with the coloring composition and heated in a bath or oven to at least 140° C.

15. The process of claim U, including the further steps of cleaning the colored article with a halogenated solvent and drying the thus-cleaned article.

16. The process of claim 15, wherein the halogenated solvent is perchloro¬ ethylene or trichloroethylene and the halogenated solvent is collected and recycled to the process.

17. A process for coloring apparel- and textile-related articles, made from polyester, polyamide, polyurethane, acrylic, halogenated polyolefin or epoxy plastic, comprising exposing an article being treated to a waterless coloring composition of claim 3, maintained at 120 - 235° C, for a time adequate to achieve the desired degree of coloration.

18. The process of claim 17, wherein the article is immersed in the coloring composition at a temperature of at least 140° C for at least 1 minute.

19. The process of claim 17, including the further steps of drying the colored article, cleaning the article with a halogenated solvent and drying the thus- cleaned article.

20. A process for coloring apparel- and textile-related articles, made from polyester, polyamide, polyurethane, acrylic, halogenated polyolefin or epoxy plastic, comprising exposing the article being treated to a composition of claim 8, maintained at 100° C to a temperature at which the plastic degrades, for a time adequate to achieve the desired degree of coloration.

21. The process of claim 20, wherein the article is immersed in the coloring composition at a temperature of at least 140° C for at least one minute.

22. The process of claim 15, wherein a portion of the waterless dip dye composition is recovered and a portion of the halogenated solvent used to clean the article is recovered by distillation and recycled to the process for cleaning additional articles.

23. The process of claim 22, wherein solvent removed from the article by drying is recycled to the process and colorant is recovered from the solvent by distillation and recycled to the process.

24. A process for coloring apparel- and textile-related synthetic articles comprising dipping an article being treated in a waterless liquid composition including a high boiling aromatic ester, a dyeing assistant agent and an organic colorant, maintained at about 120 -235° C for a time adequate to achieve the desired degree of coloration.

25. A process for coloring apparel- and textile-related articles, made from plastic, comprising exposing the article being treated to a composition of claim 1, wherein the aromatic ester is ArCOOR₂ or ArCOO-R.-OOCAr and the composition contains at least 5% by weight of a cycloaliphatic diester of the formula

wherein R is substituted or unsubstituted straight or branched chain alkyl of 4 - 20 carbon atoms, polyoxyalkylene of the formula R'(OC x H * Λ ) Π or phosphated poly- oxyalkylene of the formula

or a salt thereof, wherein (C_χH_2χO)_n is (C₂H₄O)_n~, (CgHgO)..- or (C₂H₄O) -

(C₃HgO) -; R' is H or ArCO; Ar is substituted or unsubstituted mono- or bicyclie aryl of up to 15 carbon atoms; x is 2 or 3; n is 2 - 22 and the sum of p + q is n, and maintaining the composition at a temperature from 100 C to the temperature at which the plastic degrades;, for a time adequate to achieve the desired degree of coloration.

26. The process of claim 25, wherein the composition contains at least 5% by weight of dyeing assistant agent selected from an alkoxylated alkylphenol or ester thereof.

27. The process of claim 25, wherein the composition contains at least 5% by weight of dyeing assistant agent selected from an alkoxylated alkylphenol or an ester thereof and the organic colorant is a disperse dye.