WO1990001084A1 - Composition et son procede d'utilisation pour traiter des articles plastiques - Google Patents

Composition et son procede d'utilisation pour traiter des articles plastiques Download PDF

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Publication number
WO1990001084A1
WO1990001084A1 PCT/US1988/002555 US8802555W WO9001084A1 WO 1990001084 A1 WO1990001084 A1 WO 1990001084A1 US 8802555 W US8802555 W US 8802555W WO 9001084 A1 WO9001084 A1 WO 9001084A1
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composition
article
carbon atoms
treated
temperature
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PCT/US1988/002555
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English (en)
Inventor
Robert B. Wilson
Original Assignee
Wilson Robert B
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Priority to PCT/US1988/002555 priority Critical patent/WO1990001084A1/fr
Publication of WO1990001084A1 publication Critical patent/WO1990001084A1/fr

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Classifications

    • 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
    • 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

Definitions

  • This invention relates to waterless compositions, particularly adapted for immersion treating and surface modification of plastic articles, whether intended for apparel or general utility applications.
  • Sears et aL (U.S. Patent 4,459,704) have provided a method for forming cloth into three-dimensional shapes by tentering the cloth over a preformed shell and heating the shell into the shape of a final product on a mold.
  • Hinton, Jr. et aL in U.S. Patent 3,824,125, have proposed the use of higher trialkyl trimellitates in laundry compostions to improve soil release properties of synthetic fibers, such as polyesters.
  • Such articles include, but are not limited to buttons, zippers, garments, carpeting, ribbons, draperies, shoe strings, sewing thread, lace, socks, plastic tubing and pipe, plastic coated wire, ropes, polyester and polyamide films, 0 toys, and housings for pencils, pens, kitchen utensils and telephones.
  • this invention relates to a waterless composition for treating 35 articles, made from plastic, comprising a hot liquid vehicle of at least one high- boiling ester at a temperature from about 100° C to the boiling point of the composition.
  • the vehicle comprises at least one high-boiling ester derived from a monohydric alcohol and one or more monocarboxylic acids; from a monocarboxylic acid and one or more monohydric alcohols; from a glycol or polyol and one or more 5 monocarboxylic acids; or from a dicarboxylic or polycarboxylic acid and one or more monohydric alcohols.
  • the vehicles of this invention can include mixtures of esters.
  • the waterless compositions of this invention will contain at least one high-boiling ester other than a bisterephthalate of an alkylphenoxypolyethoxyethanol, as defined by Wilson '405, supra.
  • this invention relates to a process for altering the characteristics of articles, made from plastics, by treating the articles at temperatures from 100° C to the temperature at which the plastic degrades, with a ⁇ t> composition containing an antistatic, ultraviolet stabilizing/absorbing or flame retardant adjuvant, for a time sufficient to impart to the article being treated antistatic, flame retardant or ultraviolet sta ilizing /absorbing properties.
  • This invention further relates to a process for decolorizing ester-based dye vehicles by contacting hot vehicle, containing organic colorant, with activated
  • Glycols and polyols include those of 2-10 carbon atoms, or more, including sugar alcohols and condensed sugar alcohols. Aromatic alcohols are included. Representative embodiments, as disclosed below, include but are not limited to, esters from alkylene glycols, including ethylene oxide, propylene oxide and 5 butylene oxide oligomers, polymers and copolymers. Other polyols inlcude glycer- ol, trimethylolpropane and hexanehexols.
  • Dicarboxylic aids include aliphatic, cycloaliphatic and aromatic acids, for example, adipie acid, benzenetetracarboxylic acid, phthalic acid, isophthalic acid, ellitic acid, cyclohexanedicarboxylic acids, and .substituted cyclohexanedicar- 0 boxylic acids, including dimer acids obtained by condensation of linoleic acid.
  • Tricarboxylic acids and polycarboxylic acids include aliphatic acids, e.g., butanetricarboxylic acid; cycloaliphatic tricarboxylic acids, e.g., trimer acid from the condensation of linoleic acid; and aromatic tricarboxylic and polycarboxylic acids, as recited below.
  • -_+- Monocarboxylic acids, from which the vehicles of this invention can be derived include those of 8 or more carbon atoms. Generally, acids of up to 30 carbon atoms can be used for making esters for the vehicle.
  • Monohydric alcohols will generally be of 8-30 carbon atoms. The monocarboxylic acids and alcohols can be substituted or unsubstituted and can be of straight-chain or branched-chain structure. Monohydric alcohols include polyoxyalkylated alkanols and phenols.
  • the hydroxyl and carboxyl functions of the acids or alcohols, from which the ester vehicles are derived will be essentially completely esterified. . That is, the vehicles will contain essentially no free hydroxyl or carboxyl groups.
  • the ester vehicles are high-boiling materials, preferably boiling above about 250° C, most preferably boiling above about 300° C at 760 mm. Vehicles preferred for use in the practice of this invention are therefore those of which the constituent ester or esters boils above about 300° C at 760 mm or at eorresponding- ly lower temperatures at reduced pressures.
  • the esters comprising the vehicle will preferably contain at least 18 carbon atoms, more preferably at least 24 carbon atoms, e.g., glyceryl tridecanoate, tris(2-ethylhexyl) trimellitate, lauryl laurate, stearyl benzoate, phenyl stearate, ethylene didodecanoate or bis(2-ethylhexyl)cycloaliphatic diester, as defined below.
  • glyceryl tridecanoate tris(2-ethylhexyl) trimellitate, lauryl laurate, stearyl benzoate, phenyl stearate, ethylene didodecanoate or bis(2-ethylhexyl)cycloaliphatic diester, as defined below.
  • this invention relates to a vehicle for waterless dip dyeing of thermoplastic articles, comprising an aliphatic polyester of a higher alkanoic acid and a polyol, of the formula (ACOO)neig _ ⁇ B, wherein A is alkyl of 8 -22 carbon atoms and B is the residue of a polyhydric alcohol, other than glyeerol-, of 2 - 6 hydroxyl groups.
  • the compositions also comprise glyceryl esters of acids having 9, 11, 13, 15, 17, 19 or 21 carbon atoms.
  • the compositions can comprise an aromatic polyester of the formula C g H .
  • the vehicle When used as a dye bath for the coloring of thermoplastic articles, the vehicle will also contain sufficient amounts of an organic colorant to permit coloring of the thermoplastic articles being dyed. If heat treatment, without coloration of the treated article is desired, the compositions will contain little or no organic colorant.
  • this invention relates to a process for waterless coloring of articles, fabricated from a thermoplastic composition, comprising exposing an article to the foregoing compositions, containing an organic colorant, 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.
  • compositions containing little or no organic colorant can be used under similar conditions to treat an article, made from plastic.
  • the heat history of an article can be corrected. This treatment increases the dimensional stability or strength of the article, particularly webs or films.
  • Dyeing and heat treatment of polyethylene terephthalate might be accomplished simultaneously to provide films of increased strength and stability.
  • the vehicles can include aliphatic polyesters of the formula (ACOO) B , wherein A is alkyl of 8 - 22 carbon atoms and B is the residue of a polyhydric alcohol, other than glycerol, of 2 - 6 hydroxyl groups.
  • the higher alkanoic acid can be selected from acids of even or odd numbers of carbon atoms, including substituted, unsubstituted, saturated, unsaturated, branched and linear acids. Representative of acids within this class are pelargonic, decanoic, undecanoic, palmitic, myristic, oleic, stearic, linolenic and linoleic acids.
  • the acids may be pure compounds or may be mixture of compounds, e.g., acids derived by hydrolyz- ihg naturally-occurring fats and oils, including palm oil, corn oil, lard and the like.
  • the aliphatic polyesters can be made in the same fashion as the aromatic polyesters, described below.
  • Polyols of 2 - 6 hydroxyl groups include, but are not limited to ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, butylene glycol, dipropylene glycol, tripropylene glycol, trimethylolpropane, tri- ethylolpropane, erythritol, pentaerythritol, mannitol, dulcitol, sorbitol and other isomeric hexanehexols.
  • Preferred aliphatic polyesters are those derived from pentaerythritol, partic ⁇ ularly pentaerythritol esters of acids having 9 - 21 carbon atoms, more particularly those of 9 - 13 carbon atoms. Pentaerythritol tetrapelargonate, trimethylolpropane tripelargonate and triethyleneglycol dipelargonate are most preferred.
  • the vehicles can further include triglycerides, as recited in U.S. Patent 4,581,035, herein incorporated by reference.
  • the vehicles can also contain aromatic polyesters formed by reaction between a polybasic aromatic acid of the benzene series and a higher alkanol, so as to accomplish complete esterification of all carboxyl functions therein.
  • "Higher alkanol” means a substituted or unsubstituted alkanol of at least six carbon atoms, for example, hexanol, octanol, 2-ethylhexanol, isodecanol, decanol, hexadecanol, octadecanol, docosanol, oleyl alcohol, linoleyl alcohol or the like.
  • alkylphenol ethers of alkoxyalkanols having the formula
  • the esters can be made by reaction between, for example, trimellitic acid, and the selected alkanol, conveniently in a fashion so as to remove or entrain by ⁇ product water.
  • the aromatic polyesters can be prepared by trans- ester if ication between a lower ester, e.g. trimethyl trimeUitate and the higher alkanoL In such a reaction, the lower boiling alcohol will normally be removed from the reaction site by distillation.
  • Contemplated among aromatic polyesters are esters of benzene tri-, tetra-, penta- and hexacarboxylic acids, wherein R is as above.
  • esters of prehnitic, mellophanic, pyromellitic, trimesic, trimellitic and hemimellitic acids are included, as well as esters of benzenepentacarboxylic acid and mellitic acid.
  • esters are tris(2-ethylhexyl) trimeUitate, trisisodeeyl trimeUitate, trisisooetyl trimeUitate, tridecyl trimeUitate, and trihexadeeyl tri ⁇ meUitate. It wiU be understood that mixed esters, such as hexyl, oetyl, decyl trimeUitate can also be used. Most preferred is tris(2-ethylhexyl) trimeUitate (CAS No. 3319-31-1), also known as trioctyl trimeUitate, which can be purchased ⁇ > from Eastman Chemical Products, Inc., Kingsport, Tennessee, as Kodaflex TOTM.
  • the aliphatic polyesters or other esters can also be admixed with one or more cycloaliphatic diesters of the formula
  • Other cycloaliphatic diester compounds which can be used are those wherein R is ArCOO(CH 2 CH 2 0) n CH-,CH 2 -, ArCOO(C 3 HgO) n C 3 Hg-,
  • compositions of this invention can contain at least 5% by weight of one or more of these cycloaliphatic diesters. It is preferred that the compositions contain a maximum of 95% by weight of the cycloaliphatic diester.
  • the dibasic cycloaliphatic 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
  • the alkyl esters are reported as being useful in lubricant applications, including use 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.
  • the diacid is reduced foUowing esterification to a saturated compound.
  • 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 aUowed 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.
  • 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(CH 2 CH 2 0) 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 cycloaliphatic 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, omega-alkanoyloxyalkyl or the like.
  • Preferred cycloaliphatic 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,
  • 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 HgO) n C 3 H 6 -
  • R is CgH 5 CO(OC 2 H 4 ) n OC 2 H 4 -
  • R is CH 3 CgH 4 CO(OC 2 H 4 ) n OC 2 H 4 -
  • R is CgH 5 CO(OC 3 Hg) n OC 3 H ⁇ -
  • R is CH 3 C 6 H 4 CO(OC 3 Hg) n OC 3 Hg-.
  • textile-and apparel-related articles are commonly made from polyesters, polyamides, poly ⁇ urethanes and acryUcs, which substrates are preferred for the practice of this invention.
  • Pipe and tubing are commonly made from chlorinated polyethylene (CPE) or post-chlorinated PVC (PCPVC).
  • 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 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, as weU as chips of polyester resins, polyester coatings on wire or metal, polyester articles (including those made from styreneated polyesters), polyester film, toys, components of automobiles and airplanes and housings for pencils, pens or household articles.
  • Polycarbonates are a type of polyester, that is, a polymer containing repeating -O-CO-0 groups in the main chain.
  • the most significant polycarbonates of commerce are those derived from 4,4'-dihydroxydiphenylalkanes.
  • the preferred polymer for treatment in accordance with the teachings of this invention is derived from 2,2-bis(4'-hydroxyphenyl)propane.
  • a particularly preferred utility for colored polycarbonate films or sheets is in window glazing, for example, poly ⁇ carbonate sheets tinted "neutral gray.”
  • Polycarbonate sheets are used as solar control windows in motor vehicles and in home and office construction.
  • Poly ⁇ carbonate film can also be used for food packaging. It will be understood that the distinction between sheets and films is essentiaUy based on thickness and that the treatments set forth herein are equaUy applicable to sheets, films and other articles.
  • Polya ides 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 weU as lingerie and hosiery. It is common, for example, to employ polyamide teeth in zipper constructions. Polyamides are often used for carpeting and ropes.
  • AcryUc plastics contemplated within the scope of this invention include straight acrylics, such as polyaerylonitrile, and modacrylics. The latter are copolymers of acrylonitrile or methacrylonitrile, generaUy with vinyl chloride or vinylidene chloride. Articles made from acrylics include clothing, carpeting and notions.
  • acrylics are also included among acrylics.
  • high impact resins whether comprising blends or graft copolymers. These are commonly identified as ABS resins.
  • Articles made therefrom include chips, coatings for wire and metal, telephone housings, toys, impact-resistant moldings for automobiles and airplanes, and housings for pencils, pens and kitchen utensils.
  • Acrylic plastics also include opticaUy clear sheets, such as those based on methyl methacrylate monomer.
  • Polyurethanes 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.
  • Articles containing polyurethane include rain wear, artificial leather, toys, and moldings and extrus ⁇ ions for automobiles and airplanes. Any of these articles can be colored and/or treated by the teachings of the instant invention.
  • Epoxy resins include polymers in which cross-linking is brought about by an epoxy function, such as that in bisphenol A diglycidyl ether or other glycidyl ethers.
  • the epoxy function reacts with materials containing a reactive group, for example amines, such as triethylenetetramine, and acid anhydrides, e.g. maleic anhydride and substituted maleic anhydrides.
  • amines such as triethylenetetramine
  • acid anhydrides e.g. maleic anhydride and substituted maleic anhydrides.
  • Most commercially available epoxy resins are based on bisphenol A diglycidyl ether. Epoxy resins are used in coatings and for encapsulating electrical components.
  • 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. NormaUy, the dyes or pigments which are employed need not be soluble in water. Therefore, such dyes and pigments wiU not usually contain water-solubilizing functions, such as a plurality of sulfonic acid groups.
  • the dyes/pigments used in the practice of this invention generaUy wiU 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 acetate, polyamides or polyesters, from any kind of dyeing medium are colors of 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: 4 3-n ⁇ tro-N -phenylsulfanilanilide, a yeUow dye; p-[p-(phenylazo)phenylazo] - phenol, a red-yeUow dye; ethyl 4-hydroxy-l-anthraquinoneearbamate (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, 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).
  • 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.
  • metaUized azo dyestuffs can be employed in the practice of this invention.
  • Representative metallized azo dyes which can be employed are Co, Ni,
  • textile-treating agents such as optical brighteners, e.g. styrylnaphthoxazole compounds, 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.
  • 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.
  • Ultraviolet absorbing or stabilizing adjuvants can be appUed to articles, made from plastic, using the treating compositions of this invention.
  • Thus-treated articles wiU have enhanced stability to ultraviolet radiation and/or increased ultra ⁇ violet absorption. Stabilization toward ultraviolet radiation is significant for articles, exposed to sunlight. Stabilization may occur with or without an increase -5 in the ultraviolet absorption of the treated article, for example, a treated poly ⁇ carbonate sheet might have improved stability and also filter out ultraviolet radiation.
  • Effects of treatment with ultraviolet stabilizing/absorbing agents therefore include both stabilization and optical effects, regardless of the mech ⁇ anism by which produced.
  • more than one kind of adjuvant can be used in the compositions of this invention, assuming eompatability. This can be determined by routine experimentation.
  • articles can be both colored and treated with an antistatic agent, using a composition containing an organic colorant and an antistatic adjuvant.
  • Representative antistatic agents include, but are not limited to, long chain polyamines, for example, l-amino-3,6-diazatetracosane or l-amino-3,6-diazahexa- decane; unsaturated sulfonic acid betaines, for example, from methacrylic acid- (oxamido-N,N-dimethylhydrazide)-ethyl ester or cinna ic acid-(3-oxamido-N,N- dimethylhydrazide)-phenyl ester; quaternary ammonium salts, for example, tri- ° methyl stearyl ammonium chloride, stearyl dimethyl ethyl ammonium ethyl sulfate, lauryl dimethyl benzyl ammonium propyl sulfate or choline chloride; fluorinated alkyl polyoxyethylene ethanols and potassium perfluoroalkyl
  • Fire retardant adjuvants include, but are not limited to organophosphorus compounds. These agents include halogenated and unhalogenated esters of 5 phosphoric, phosphorous, phosphonic and phosphinic acids, as weU as corresponding phosphines and phosphine oxides. Particularly preferred fire retardant adjuvants for the practice of this invention include cyclic phosphite esters, e.g., those based on ethylene glycol; tris(beta-chloroethyl) phosphate and dialkyl alkylphosphonates, especially dimethyl methyl phosphonate.
  • Ultraviolet absorbing or stabilizing adjuvants generaUy include materials which are compatible with the treating compositions and with the article being treated and which absorb incident radiation in the range between about 2700 A and about 4000 A.
  • materials known to function as ultraviolet absorbing or stabilizing agents are coumarin ethers; esters of para-aminobenzoic acid, such as the glyceryl ester; esters of substituted para-aminobenzoic acids and para- methoxycinnamic acid, for example the 2-ethoxyethyl esters; benzophenone deriva ⁇ tives, e.g., 2-hydroxy-4-methoxybenzophenone; triazolyl ketones, such as 2-phenyl- 4-2,',4 , -dihydroxybenzoyl)-v-triazoles and corresponding ethers and esters; hydra- zones derived from aromatic aldehydes; 2-phenylbenzoxazole derivatives; bisoxalic acid diamides; beno
  • waterless dye baths can be decolorized by contacting the baths with activated carbon at elevated temperatures.
  • Dye baths containing at least 5% by weight of an aromatic polyester can be decolorized readily using activated carbon, whereas baths of prior art compositions, containing no aromatic polyester, are not readily decolorized in this fashion.
  • these compositions being decolorized contain at least 5% by weight of trialkyl trimeUit ⁇ ate, wherein alkyl is of 6-22 carbon atoms.
  • the compositions being decolorized are other than the compositions claimed in U.S. Patents 4,602,916 and 4,608,056.
  • compositions containing 0.1 - 2.0% by weight of triphenyl phosphite are preferred.
  • the baths can contain, in addition to or instead of triphenyl phosphite, 0.1 - 2.0% by weight of 2,2 * -oxamido bistethyl 3- (3,5-di-tert.-butyl-4-hydroxyphenyl)propionate] .
  • Optional emulsifiers or dyeing assistant agents used in the compositions of this invention, include, but are not limited to, alkoxylated alkylphenols, alkoxylated castor oil compounds, alkoxylated hydrogenated castor oil compounds, alkoxylated primary alkanols, salts of phosphated alkoxylated primary alkanols or alkylphenols, ethoxylated sorbitan esters and mixtures thereof. It wiU be understood that corresponding esters of the optional dyeing assistant agents can be used as a component of the high-boiling ester vehicle.
  • the amount of optional emulsifier or dyeing assistant agent, employed in the compositions of this invention, is at least about 0.5% by weight of the composition a nd can be as high as 60 - 80% by weight.
  • Waterless dye bath compositions wiU preferably contain 5 - 10% by weight of one or more optional emulsifiers.
  • Ethoxylated alkanols used as optional emulsifiers, wiU be of alkanols of 8 -24 carbon atoms, ethoxylated so as to contain 2 - 30 ethyleneoxy units.
  • Typical ethoxylated alkanols which can be used are lauryl alcohol 3.5 ethoxylate (POE 3.5) or POE (18) tridecyl aleohoL
  • Preferred optional dyeing assistant agents are alkoxylated alkylphenols.
  • exemplary dyeing assistant agents include ethoxylated and propoxylated alkylphenols.
  • 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 derivatives, having 5 - 10 ethylene oxide units.
  • Preferred emulsifiers or optional dyeing assistant agents will be those wherein:
  • 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 castor oil derivatives wiU contain 5 - 200 oxyalkylene units, preferably 20 - 30 oxyethylene units. These types of materials can be purchased from ICI America and Whitestone Chemical Co.
  • 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.
  • a temperature up to that at which the plastic being dyed, wiU degrade.
  • 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 treated article is normally cleaned with a solvent to remove excess treating agent or adjuvant.
  • the solvents used for cleaning are chlorinated or fluorinated hydro- carbons.
  • highly chlorinated solvents such as perchloroethylene and trichloroethylene are preferred for cleaning by immersion in a liquid bath.
  • Fluorochlorocarbons such as dichlorodifluoromethane, chlorotrifluoromethane, which are gases at ambient temperatures or slightly above, can be used for vapor- phase cleaning of the treated 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.
  • 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 wiU 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 normaUy includes filtration means for removal of soUd 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.
  • the dye bath contains at least 5% by weight of aromatic polyester and is free of other optional dyeing assistant agents, it is preferred to recover clean dye vehicle by treatment with activated carbon. This treatment permits reuse of the dyeing vehicle with a plurality of different organic colorants and avoids the need for recovering the dyeing vehicle by distillation.
  • Articles leaving the squeeze roU 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 distiUing and condensing means for purifying solvent, and to return purified solvent to the system. Dye recovered on the filter or as residue from the distiUation 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. It has surprisingly been found that non-aqueous dye baths containing aromatic polyester, with or without emulsifiers or other optional dyeing assistant additives, but no cycloaliphatic diester, have better high temperature stabiUty than composi ⁇ tions containing both the aromatic polyester and the eycloaUphatic diester.
  • compositions of this invention will comprise a vehicle of at least one high-boiling ester derived from a glycol or polyol and one or more monocarboxylic acids or derived from a dicarboxylic or polycarboxylic acid and one or more monohydric alcohols.
  • the vehicles wiU boU above about 300° C at 760 mm and the esters will be of at least 24 carbon atoms.
  • a most preferred process in accordance with this invention is one wherein the article being treated is exposed to the foregoing composition, containing a fire retardant, antistatic or ultraviolet absorbin /stabilizing adjuvant, maintained at a temperature of 140 - 235° C for a time adequate to achieve the desired degree of antistatic, ultraviolet absorbing/stabilizing or fire retardant properties.
  • Articles most preferably treated in t is fashion are polyester or polycarbonate sheets or films.
  • the vehicle wiU contain an organic colorant and the process will comprise exposing an article made from polycarbonate to the composition, maintained at 140-235° C, for a time adequate to achieve the desired degree of coloration.
  • esters are prepared using the foUowing reactants: (1) trimethylolpropane and dodecanoic acid 1 : 3 molar ratio (2) pentaerythritol and palmitic acid 1 : 4 molar ratio
  • diethyleneglycol and undecanoic acid 1 : 2 molar ratio (6) trimethylole thane and a mixture of stearic and oleic acids 1 : 3 molar ratio
  • polyoxyethylene compounds are made in a similar fashion from: (l) NP 9.5 and coconut fatty 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:
  • Diacid 1550 and Neodol 25 (a mixture of 12 - 15 carbon alcohols), 1 : 2 molar ratio.
  • 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.
  • 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 the iodine value was less than 0.5 g/100 g of sample.
  • Ethoxylated castor and hydrogenated castor oils were prepared as in Example 4. Ethylene oxide adds to the hydroxyl group of castor oiL
  • a waterless dyeing composition was prepared from bis(2-ethylhexyl) cyclo ⁇ aliphatic diester of Example 3 and tris(2-ethylhexyl) trimeUitate (Eastman) in 20 : 80 weight ratio, containing 5 grams/liter of Disperse Blue 60 and 0.1% by weight of triphenyl phosphite. 5 This composition was kept at 185° C and stirred while a piece of polyester carpet was immersed therein for 30 sec. The carpet section was removed, washed in perchloroethylene and dried. The carpet was homogeneously colored with good dye fixation. There was little or no smoking during the coloring operation.
  • EXAMPLE 9 0 Dip dye solution was made from 80 parts by weight of tris(2-ethylhexyl) trimeUitate, 20 parts by weight of bis(2-ethylhexyl) cycloaliphatic diester and 0.1% by weight of triphenyl phosphite.
  • a dye bath was prepared from a mixture of 50 g of tris(2-ethylhexyl) trimeUitate and 50 g of pentaerythritol tetrapelargonate, to which was added 0.5 g of Disperse Blue 56 dye.
  • the resulting dark blue mixture was heated to 185° C and maintained at that temperature to dye a swatch of polyester fabric.
  • the immersion time was 1 min.
  • the dyed swatch was washed with perchloroethylene and dryed. The dyed sample was a level, dark blue shade.
  • EXAMPLE 12 Baths were made from tris(2-ethylhexyl) trimeUitate and pentaerythritol tetrapelargonate in 20 : 80 and 80 : 20 ratios by weight.
  • EXAMPLE 13 (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.
  • BCN 356 (crude ground dye) was heated externaUy to provide a temperature of
  • 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 roUer 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 15 An apparatus for removal of dye solutions of the invention consisted of three stainless steel columns, each 5 cm in diameter and 50 cm long. Each column was fitted with a circular pad (5 microns), in the center of which was a hole 0.64 cm in diameter. The pad was covered with a disc of stainless steel screen and topped with Whatman no. 1 filter paper. The first column of the series was packed with 100-200 g of activated granular carbon (Calgon Corp.) and was used as a holding tank for heating the dye solution to about 185° C.
  • activated granular carbon Calgon Corp.
  • Each of the second and third columns was packed with about 500 g of activated carbon.
  • the temperature of the liquid being passed through these columns was about 185° C and 120° C, respectively.
  • Dye solutions (Disperse Blue 60 at a concentration of 5 g/1) in 80 : 20 tris(2- ethylhexyl) trimeUitate : bis(2-ethylhexyl) cycloaliphatic diester by volume were decolorized in the foregoing series of three columns. About 15.5 liters of dye solution was decolorized by about 500 g of activated granular carbon. At a dye concentration of 5 g/liter, 1 pound of carbon wiU accordingly decolorize about 30 pounds of dye mixture.
  • the dip dye solution is used as in Example 12, with similar results.
  • Example 17 Experiments similar to those of Example 17 are done with an 80 : 20 dye bath, containing 5 - 10 g/1 of one of Disperse Red 60, Disperse Yellow 54, Nylanthrene Blue 2RFF (an acid dye) or Roma Violet Pigment RL 9613.
  • treatment with about 10% by weight of activated carbon, referred to colorant weight, at 100 - 200° C results in essentiaUy clean dye bath solution, which can be recycled without distillation.
  • Dye bath was prepared from triethyleneglycol dipelargonate, containing 0.5% by weight of Disperse Blue 60. A polyester swatch, dipped into the bath at 185° C for 1 min, gave a good level blue shade dyeing.
  • Dye bath is prepared from phenyl stearate and tris(2-ethylhexyl) trimeUitate (20 : 80), containing L0% by weight of Disperse Red 60. The bath is used to dye a swatch of polyester as in Example 19. Similar results are obtained.
  • Dye bath containing lauryl laurate instead of phenyl stearate, is prepared as above. Similar results are obtained with a polyester fabric sample.
  • Diester is prepared from dimer acid (Diels-Alder condensate of linoleic acid) and 2-ethylhexanol as in Example 3.
  • Dye solution is made from tris(2-ethylhexyl) trimeUitate and the bis(2- ethylhexyl) ester of dimer acid (20 : 80) and 0.5% by weight of Disperse Yellow dye.
  • the solution is used as in Example 12 to dye and treat poly(ethylene terephthalate) film. An even dyeing is obtained and the film is stronger than untreated film.
  • Example 22(b) A sample of polycarbonate is treated as in Example 22(a), except that the treating composition contains no colorant. The treatment improves the dimensional stabiUty and strength of the film.
  • the treated specimen did not ignite under conditions of the vertical butane flame test.
  • the treated sample did not ignite during the vertical butane flame test and was colored an even light blue. This experiment shows that both colorant and flame retardant can be appUed simultaneously to an article made from plastic.
  • EXAMPLE 24 A sample of polyester tow (polyethylene terephthalate in rope form, 2.73 meters in length) was immersed in a 20:80 mixture of bis(2-ethylhexyl) cycloali ⁇ phatic diester and tris(2 -ethylhexyl) trimeUitate, maintained at 199° C, for three min. The sample was scoured with perchloroethylene and dried.
  • the product had a weU-defined crimp, which appeared to be permanently set.
  • Polyester or polycarbonate films are treated at 150-200° C for 30 sec-2 min with mixtures of pentaerythritol tetrapelargonate and tris(2-ethylhexyl) trimeUi ⁇ tate, containing 3% by weight of antistatic agents, such as trimethyl stearyl ammonium chloride and lauryl dimethyl benzyl ammonium propyl sulfate.
  • antistatic agents such as trimethyl stearyl ammonium chloride and lauryl dimethyl benzyl ammonium propyl sulfate.
  • the treated samples are scoured and dried.
  • the film specimens have antistatic properties.
  • the treated fabric was evaluated for lightfastness using GM Test Method 30- 2 in a GM twin carbon arc weatherometer.
  • the specimen treated with solution containing Tinuvin P was rated 3.0/480, that is, 480 h to failure.
  • a control, using the same solution without Tinuvin P, was rated 3.0/360, that is, 360 h to failure. Therefore, treatment with an ultraviolet absorber increased the lightfastness by 120 h.

Abstract

Une composition de traitement anhydre pour des vêtements et autres articles, réalisés en matières plastiques, comporte un véhicule liquide chaud d'au moins un ester à point d'ébullition élevé, dérivé d'un ou de plusieurs alcools monovalents et d'un ou de plusieurs acides monocarboxyliques; d'un glycol ou d'un polyol et d'un ou de plusieurs acides monocarboxyliques; ou bien d'un acide dicarboxylique ou d'un acide polycarboxylique et d'un ou de plusieurs alcools monovalents; à condition que la composition parvienne à ébullition au-dessus d'environ 250°C à 760 mm, que le ou les esters à point d'ébullition élevé comporte au moins 18 atomes de carbone et que le véhicule se trouve à une température comprise entre environ 100°C et le point d'ébullition de la composition. Ces compositions s'utilisent pour influer sur le bilan thermique des articles, améliorer leur stabilité dimensionnelle et leur appliquer des agents antistatiques, absorbant/stabilisant les ultraviolets ou d'ignifugation.
PCT/US1988/002555 1988-07-27 1988-07-27 Composition et son procede d'utilisation pour traiter des articles plastiques WO1990001084A1 (fr)

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Publication number Priority date Publication date Assignee Title
EP1855638B1 (fr) * 2005-02-28 2011-06-22 L'Oréal Teinture de matieres contenant de la keratine, notamment de la keratine humaine, par transfert thermique a sec d'un colorant direct d'anthraquinone, composition comportant ce colorant et son procede de preparation
CN113005790A (zh) * 2021-02-09 2021-06-22 绍兴文理学院 助染剂及其在偶联型分散染料仿麂皮织物染色中的应用

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US2461612A (en) * 1944-04-18 1949-02-15 Celanese Corp Dyeing of resins with polyhydroxy alcohol assistants
US3362779A (en) * 1963-11-02 1968-01-09 Hoechst Ag Process for dyeing, printing and painting polyacetal resins
US3824125A (en) * 1968-07-25 1974-07-16 Burlington Industries Inc Soil release composition
US3950419A (en) * 1972-10-13 1976-04-13 Sandoz Ltd., (Sandoz Ag) Aromatic carboxylic acid esters and amides as fixing agents
US4115054A (en) * 1976-01-09 1978-09-19 Martin Processing, Inc. Process for the rapid, continuous and waterless dyeing and texturizing and heat-setting of textile and plastic materials
US4215992A (en) * 1977-12-26 1980-08-05 Kao Soap Co., Ltd. Dyeing assistant for printing
US4332587A (en) * 1980-02-16 1982-06-01 Bayer Aktiengesellschaft Colorant preparations, a process for their production and their use for coloring plastics
US4581035A (en) * 1984-11-08 1986-04-08 Crucible Chemical Company Waterless dye composition and method of use thereof for coloring thermoplastic articles
US4722738A (en) * 1984-02-27 1988-02-02 Crucible Chemical Company Process to decolorize dye composition and method of use thereof for coloring thermoplastic articles

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2461612A (en) * 1944-04-18 1949-02-15 Celanese Corp Dyeing of resins with polyhydroxy alcohol assistants
US3362779A (en) * 1963-11-02 1968-01-09 Hoechst Ag Process for dyeing, printing and painting polyacetal resins
US3824125A (en) * 1968-07-25 1974-07-16 Burlington Industries Inc Soil release composition
US3950419A (en) * 1972-10-13 1976-04-13 Sandoz Ltd., (Sandoz Ag) Aromatic carboxylic acid esters and amides as fixing agents
US4115054A (en) * 1976-01-09 1978-09-19 Martin Processing, Inc. Process for the rapid, continuous and waterless dyeing and texturizing and heat-setting of textile and plastic materials
US4215992A (en) * 1977-12-26 1980-08-05 Kao Soap Co., Ltd. Dyeing assistant for printing
US4332587A (en) * 1980-02-16 1982-06-01 Bayer Aktiengesellschaft Colorant preparations, a process for their production and their use for coloring plastics
US4722738A (en) * 1984-02-27 1988-02-02 Crucible Chemical Company Process to decolorize dye composition and method of use thereof for coloring thermoplastic articles
US4581035A (en) * 1984-11-08 1986-04-08 Crucible Chemical Company Waterless dye composition and method of use thereof for coloring thermoplastic articles

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1855638B1 (fr) * 2005-02-28 2011-06-22 L'Oréal Teinture de matieres contenant de la keratine, notamment de la keratine humaine, par transfert thermique a sec d'un colorant direct d'anthraquinone, composition comportant ce colorant et son procede de preparation
CN113005790A (zh) * 2021-02-09 2021-06-22 绍兴文理学院 助染剂及其在偶联型分散染料仿麂皮织物染色中的应用
CN113005790B (zh) * 2021-02-09 2023-07-25 绍兴文理学院 助染剂及其在偶联型分散染料仿麂皮织物染色中的应用

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