WO1984001971A1 - Waterless dip dye composition and method of use thereof for synthetic articles - Google Patents

Waterless dip dye composition and method of use thereof for synthetic articles Download PDF

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Publication number
WO1984001971A1
WO1984001971A1 PCT/US1983/001759 US8301759W WO8401971A1 WO 1984001971 A1 WO1984001971 A1 WO 1984001971A1 US 8301759 W US8301759 W US 8301759W WO 8401971 A1 WO8401971 A1 WO 8401971A1
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WIPO (PCT)
Prior art keywords
composition
article
ester
temperature
coloring
Prior art date
Application number
PCT/US1983/001759
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English (en)
French (fr)
Inventor
Robert B Wilson
William F Pomeroy
Louis Terrell Sovey Jr
Original Assignee
Robert B Wilson
William F Pomeroy
Louis Terrell Sovey Jr
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Filing date
Publication date
Application filed by Robert B Wilson, William F Pomeroy, Louis Terrell Sovey Jr filed Critical Robert B Wilson
Priority to BR8307604A priority Critical patent/BR8307604A/pt
Priority to NL8320379A priority patent/NL8320379A/nl
Priority to GB08416540A priority patent/GB2140828B/en
Priority to JP84500056A priority patent/JPS59502113A/ja
Publication of WO1984001971A1 publication Critical patent/WO1984001971A1/en
Priority to SE8403598A priority patent/SE8403598L/sv

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
    • D06P1/613—Polyethers without nitrogen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/651—Compounds without nitrogen
    • D06P1/65106—Oxygen-containing compounds
    • D06P1/65125—Compounds containing ester groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/90—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof
    • D06P1/92—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof in organic solvents
    • D06P1/928—Solvents other than hydrocarbons
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/001—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated using acid dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/002—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated using basic dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/004—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated using dispersed dyes

Definitions

  • This invention relates to waterless compositions, particularly adapted for immersion coloring of plastic articles, intended for non-textile or general-utility use.
  • references disclosing the use of glycols or glycerol as media for dyeing compositions include:
  • compositions containing esterif ⁇ ed 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, incorporated herein by reference.
  • plastic articles include, but are not limited to plastic tubing and pipe, plastic coated wire, ropes, polyester and polyamide chips, metals coated with synthetic resins, flowers made of synthetic resins, synthetic resin films, toys, synthetic resin constructions used in cars and planes, housings for pencils and pens, kitchen utensils and telephones.
  • this invention relates to a waterless dip dye composition for non-textile and general-utility articles, comprising an aromatic ester of the formula ArCOOR place, ArCOO-R.-OOCAr or (ArCOO) -R «, wherein R.
  • this invention relates to a process for waterless color ⁇ ation of non-textile, general utility articles, fabricated from a plastic material, comprising exposing an article to the foregoing compositions, maintained at a temperature from about 100° C to the temperature at which the plastic degrades, for a time adequate to achieve the desired degree of coloration.
  • Aromatic ester means an ester formed by reaction between a mono-, di- or polyhydric 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 classroom, 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.
  • 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.Hg (O-C H 2 ) , in which r is 2 or 3 and s is 1 to 15.
  • aromatic esters used in this aspect of the invention include, but are not limited to, esters of benzoic, toluic, dimethylbenzoic, trimethyl- benzoic, naphthoic, butylbenzoic and similar acids.
  • esters will preferably be used in combination with a cydoaliphatic diester of the formula
  • R is substituted or unsubstituted straight or branched chain alkyl of 4-20 carbon atoms, polyoxyalkylene of the formula HO(C H O) C H - or phosphated
  • compositions of this invention will contain at least 5% by weight of this type of cydoaliphatic diester.
  • aromatic esters employed in the practice of this invention include those based on tri- or polyhydric alcohols, such as glycerol, trimethylolpropane, 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 cydo ⁇ 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) -R 3 , wherein R 3 is the residue of a polyhydric alcohol having z hydroxyl groups and z is 3-6.
  • alkylene (R,) can be ethylene, propylene, hexylene, 2,2- dimethyltrimethylene, butylene, hepta- methylene and octylene, including various isomers thereof.
  • Polyoxyalkylene diesters include those derived from polyethylene glycol or polypropylene glycol.
  • alkyl Rêt
  • alkyl R should
  • alkyl can be octyl, nonyl, decyl, dodecyl, tridecyl, hexadecyl, stearyl and alkenyl can be any corresponding monounsaturated function, e.g., oleyl.
  • aromatic esters of mono-or dihydric alcohols are those wherein: (a) Ar is phenyl,
  • R is ethylene or propylene, including each of (a) and (b),
  • R. is ethyleneoxyethylene or propyleneoxypropylene, including each of (a) and (b), (e) R, is polyoxypropylene of molecular weight 200-250, including each of
  • R 2 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.
  • aromatic esters based on trihydric or polyhydric alcohols are those of glycerol, tri ethylolpropane 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 cydoaliphatic acid employed in making the compositions of this invention is a Diels-Alder adduct of acrylic acid and linoleic acid and can be prepared as described by Ward in U. S. Patent 3,753,968.
  • the diacid has the formula
  • esters from the C diacid adduct was reported by Ward et al, J. Amer. 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.
  • acidic catalysts such as p-toluenesulfonic acid, methanesulfonic acid or sulfuric acid.
  • the reaction mixture is preferably also treated with a decolorizing agent, e.g., carbon or clay.
  • 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.
  • O PI IFO 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:
  • the phosphorylated product is readily obtained by reaction with phosphorus pentoxide.
  • the saturated diester can be obtained by nickel-catalyzed hydro ⁇ genation.
  • 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(CH 2 CH 2 O) n CH 2 CH 2 -, 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 cydoaliphatic ring can be done before or after esterification with the aromatic acid.
  • substituted alkyl R which may be used in the products of this invention are butoxybutyl, 10-hydroxystearyl, 10-hydroxydecyl, 10-halostearyl, c -alkanoyloxyalkyl or the like.
  • Preferred diesters or 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,
  • R is 2-ethylhexyl, lauryl or stearyl
  • R is HO(CH 2 CH 2 O) n CH 2 CH 2 -,
  • R is HO(C 3 H 6 O) n C 3 H 6 -
  • R is HO(C 2 H 4 O) p (C 3 H 6 O) q C 3 H 6 -
  • R is C 6 H 5 CO(OC 2 H 4 ) n OC 2 H 4 -
  • R is CH 3 C g H 4 CO(OC 2 H 4 ) n OC 2 H 4 -
  • R is CgH 5 CO(OC 3 Hg) n OC 3 Hg-
  • R is CH 3 C 6 H 4 CO(OC 3 Hg) n OC 3 Hg-.
  • “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 10 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
  • compositions can also contain
  • Preferred dyeing assistant agents are alkoxylated alkylphenols and their esters. These are compounds of the formula
  • exemplary dyeing assistant agents include ethoxylated and propoxylated alkyl phenols and corre-sponding esters, such as the laurate, myris- tate, palm i tat e, coconate, oleate, stearate, isostearate, benzoate and toluate esters.
  • Preferred alkylphenols are nonylphenol, octylphenol, and dodecylphenol. 5 It will be understood that the alkylphenols and the acids used to esterify the alkoxylated alkylphenols can include mixtures.
  • the alkoxylated alkylphenols will be ethoxylated deriv ⁇ atives, having 5 - 10 ethylene oxide units.
  • Preferred dyeing assistant agents will be those wherein: 0 (a) R" is alkanoyl of 12 - 18 carbon atoms, including mixtures thereof;
  • R" is n-C 1? H 33 CO;
  • R" is benzoyl
  • R" is n-C u H 23 CO;
  • (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 n H 23 CO; (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.
  • Polyester articles include those made from poly(alkylene terephthalates), such as poly( ethylene terephthalate), or polyesters made from cyclohexanedi- methanol.
  • Typical of polyester articles are chips of polyester resin, polyester coating on wires or metal, flowers, polyester film, toys, glass-filled polyester articles, including styrenated polyester articles, components of cars and planes and housings for pencils and pens.
  • 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 ar tides as for polyesters, as well as ropes.
  • 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. Also included within the classification of acrylics are high impact resins, whether comprising blends or graft copolyers, such as are co monly identified as ABS (acrylonitrile, butadiene, styrene resins). Articles made of these types of resins include resin chips, coatings on metal or wire, telephones, toys, impact-resistant moldings for cars and planes, housings for pencils and pens and kitchen utensils.
  • Polyure thanes include a myriad of compositions, made by reaction, for example, between glycols and organic di- or polyisocyanates.
  • glycols used to make polyurethanes, are simple glycols, such as the alkylene glycols, and polymeric glycols, including polyether and polyester glycols.
  • Halogenated polyolefins include polyvinyl chloride and polyvinylidene chlor ⁇ ide, including their ⁇ opolymers. Also included among halogenated polyolefins are post-chlorinated materials, such as chlorinated polyethylene (CPE) and post- chlorinated PVC. These resins are commonly employed in pipes and tubing, for above and below ground installation, for wire and metal coating, for building sidings and for films.
  • CPE chlorinated polyethylene
  • PVC post- chlorinated PVC
  • Epoxy resins are the reaction products of a polyglycidyl ether and a curing agent, particularly a polyamine. These resins often have very high impact resistance and will, accordingly, be used in fiberglass filled compositions for boats and automobiles.
  • the foregoing types of plastics can be blended with natural or synthetic cellulosic materials and colored according to this invention.
  • Organic colorant 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 or pigments used in the practice of this invention generally will be chosen from among water-insoluble dyes, which are also known as disperse dyes. Included within this class of dyes, which can be used on fibers such as cellulose acetate, polyamides or polyesters, from any kind of dyeing medium are colors having azo, azomethine, nitroarene and anthraquinone structures. It is to be understood that the dyes useful in the practice of this 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-diaminochrysazin
  • blue dye a blue dye.
  • the dyes may be identified by standard chemical textbooks, such as "The Color Index,” third edition, The Society of Dyes and Colours and The American Association of Textile Chemists and Colorists (1971). This type of handbook correlates dye structure with trade names. Typical of colorants thus identified, which dyes 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. 74810); 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.
  • metallized azo dyestuffs can be employed in the practice of this invention.
  • Representative azo dyestuffs which can be used are Co, Ni, Cu or Cr complexes of coupling products of 2-amino-4-nitrophenol and resorcinol; 2-amino-
  • textile-treating agents such as optical brighteners, e.g., styrylnaphthoxazole compounds, can be applied, along with dyes or pigments.
  • the dyes or pigments can be used in any form, that is, as presscake or as dried pressed dye.
  • the addition of dispersing agents is optional.
  • the dyes or pigments can be added to the dye bath in a solvent or dispersing medium, compatible with the dye bath. It is convenient and preferred, in the practice of this invention, to use additive-free, solid disperse dyes.
  • 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.
  • the dyed article is normally cleaned with a solvent to remove excess dye.
  • the solvents used for cleaning are chlorinated or fluorinated hydrocarbons.
  • highly chlorinated solvents such as perchloroethylene and trichloroethylene are preferred when cleaning is to be done in a liquid bath.
  • a more volatile solvent particularly a chlorofluorocarbon, such as dichloro- difluorom ethane or chlorotrifluorom ethane, will be selected. 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.
  • 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, as 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. Alternatively, the purified dye solution can be stored for later use.
  • porous belt or squeeze roller means for removal of excess dye solution from treated articles.
  • the dye removal means employed at this point will be selected according to the shape and size of the articles being colored in the dip tank.
  • 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 or belt 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 the distillation residue 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 an air dryer, from which articles leaving the system can be inspected and packaged. Solvent vapors from the hot air dryers can be condensed and returned to the system.
  • drying means such as an air dryer
  • compositions of this invention will be those wherein the aromatic ester is of the formula (ArCOO) z ⁇ R 3 , Ar is phenyl or tolyl,
  • R- 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. Most preferably, the compositions will contain at least 5% by weight of a hydrogenated cydoaliphatic diester, obtained from linoleic acid and acrylic acid, and the organic colorant will be 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.
  • esters are prepared using the following reactants:
  • Example 2 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.
  • 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
  • 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.
  • Esters are prepared similarly from: (1) Diacid 1550 and decyl alcohol, 1 : 2 molar ratio
  • Diacid 1550 and Neodol 25 (a mixture of 12 - 15 carbon alcohols), 1 : 2 molar ratio.
  • OMPI (2.3 moles) of ethylene oxide was added to the reactor.
  • the pressure inside the reactor im ediately built up to 30 - 50 psig.
  • 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 5 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. 5 B. Reduction to the Polyoxyethylene Diester
  • Example 4A 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 o the iodine value was less than 0.5 g ⁇ 00 g of sample.
  • 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
  • a propoxylated dibenzoate ester was prepared in a similar fashion.
  • a representative benzyl ester was prepared from: 227.0 g benzyl alcohol
  • 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.
  • benzyl esters of pelargonic, octanoic, palmitic, stearic, oleic and hydroxystearie acids were prepared in a similar fashion.
  • Ethoxylated castor and hydrogenated castor oils were prepared as in Example 4. Ethylene oxide adds to the hydroxyl group of castor oil.
  • This composition was kept at 180° C and stirred while a fiberglass-polyester composite was immersed therein for one minute. The sample was removed, washed in perchloroethylene and dried. The sample was homogeneously colored with good dye fixation. There was little or no smoking during the coloring operation.
  • compositions similar to that of Example 9 were used to color the following articles, under the conditions indicated: ( a ) 180° C, 2 min nylon ring electrical cord screen wire nylon beads nylon cord
  • EXAMPLE 12 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 i ersed 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.
  • Dip dye solution is made from the following ingredients, as above: parts by weight 40 hydrogenated cydoaliphatic diester with 2-ethylhexyl alcohol (Example 3)
  • Dip dye solution is made as above from: parts by weight (a) 20 POE nonylphenol (N.P. 8.5)
  • compositions are used for coloration of general-utility articles, with results similar to those obtained 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.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Coloring (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/US1983/001759 1982-11-10 1983-11-10 Waterless dip dye composition and method of use thereof for synthetic articles WO1984001971A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BR8307604A BR8307604A (pt) 1982-11-10 1983-11-10 Composicao de corante de imersao isenta de agua e processo de uso da mesma para artigos sinteticos
NL8320379A NL8320379A (nl) 1982-11-10 1983-11-10 Watervrij dompelkleurmengsel alsmede werkwijze voor het gebruik ervan voor synthetische voorwerpen.
GB08416540A GB2140828B (en) 1982-11-10 1983-11-10 Waterless dip dye composition and method of use thereof for synthetic articles
JP84500056A JPS59502113A (ja) 1982-11-10 1983-11-10 無水浸漬染料組成物および合成品に対するその使用法
SE8403598A SE8403598L (sv) 1982-11-10 1984-07-06 Vattenfri doppfergkomposition och sett att anvenda densamma for syntetiska artiklar

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US44056782A 1982-11-10 1982-11-10

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WO1984001971A1 true WO1984001971A1 (en) 1984-05-24

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PCT/US1983/001759 WO1984001971A1 (en) 1982-11-10 1983-11-10 Waterless dip dye composition and method of use thereof for synthetic articles

Country Status (8)

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EP (1) EP0126752A4 (sv)
JP (1) JPS59502113A (sv)
BR (1) BR8307604A (sv)
DE (1) DE3390326T1 (sv)
GB (1) GB2140828B (sv)
NL (1) NL8320379A (sv)
SE (1) SE8403598L (sv)
WO (1) WO1984001971A1 (sv)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0174341A1 (en) * 1984-02-27 1986-03-19 WILSON, Robert Buchanan Dye composition and method of use thereof for coloring thermoplastic materials
US5884643A (en) * 1994-07-18 1999-03-23 Kawasaki Steel Corporation Cleaning method and cleaning apparatus for surface of sheet steel

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113026382A (zh) * 2021-02-22 2021-06-25 苏州图延模具有限公司 一种cnc加工pmma透明件的上色技术

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4293305A (en) * 1979-11-01 1981-10-06 Northwestern Laboratories, Inc. Diester composition and textile processing compositions therefrom
US4394126A (en) * 1979-11-01 1983-07-19 Wilson Robert B Diester composition and textile processing compositions therefrom

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR81369E (fr) * 1954-09-09 1963-09-13 Hoechst Ag Procédé de modification des propriétés d'objets moulés en polyesters aromatiques
DE86374C (sv) * 1971-09-24
CH651603A5 (en) * 1981-12-24 1985-09-30 Sandoz Ag Dyeing assistant

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4293305A (en) * 1979-11-01 1981-10-06 Northwestern Laboratories, Inc. Diester composition and textile processing compositions therefrom
US4394126A (en) * 1979-11-01 1983-07-19 Wilson Robert B Diester composition and textile processing compositions therefrom

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0174341A1 (en) * 1984-02-27 1986-03-19 WILSON, Robert Buchanan Dye composition and method of use thereof for coloring thermoplastic materials
EP0174341A4 (en) * 1984-02-27 1987-01-22 Robert B Wilson DYE COMPOSITION AND THEIR USE IN DYING THERMOPLASTIC MATERIALS.
US5884643A (en) * 1994-07-18 1999-03-23 Kawasaki Steel Corporation Cleaning method and cleaning apparatus for surface of sheet steel

Also Published As

Publication number Publication date
NL8320379A (nl) 1984-10-01
GB8416540D0 (en) 1984-08-01
DE3390326T1 (de) 1985-01-24
GB2140828A (en) 1984-12-05
SE8403598D0 (sv) 1984-07-06
EP0126752A1 (en) 1984-12-05
JPS59502113A (ja) 1984-12-20
EP0126752A4 (en) 1985-09-16
BR8307604A (pt) 1984-10-02
SE8403598L (sv) 1984-07-06
GB2140828B (en) 1987-05-20

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