US3619109A - Cobalt-phthalocyanine-polyamine complexes for the dyeing and printing of textiles - Google Patents

Cobalt-phthalocyanine-polyamine complexes for the dyeing and printing of textiles Download PDF

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Publication number
US3619109A
US3619109A US754709A US3619109DA US3619109A US 3619109 A US3619109 A US 3619109A US 754709 A US754709 A US 754709A US 3619109D A US3619109D A US 3619109DA US 3619109 A US3619109 A US 3619109A
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United States
Prior art keywords
cobalt
phthalocyanine
parts
process according
polyamine
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Expired - Lifetime
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US754709A
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English (en)
Inventor
Heinrich Vollman
Peter Mertens
Johannes Eibl
Ulrich Altmann
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Bayer AG
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Bayer AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
    • 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
    • D06P1/14—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 phthalocyanine dyes without vatting
    • D06P1/145—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 phthalocyanine dyes without vatting using phthalocyanine dyes prepared in situ
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/916—Natural fiber dyeing
    • Y10S8/918—Cellulose textile

Definitions

  • Tyner & Sandt ABSTRACT A process for dyeing and printing textile materials made of natural or regenerated cellulose wherein an insoluble cobalt-phthalocyanine is solubilized by oxidizing to a hexavalent state and complexing with two molecules of an amine which complex contains an anion. is dissolved in a solvent and is applied to the textile materials which materials are subsequently treated to a heating treatment above l()0 C. or to a treatment with reducing agents to convert the salts of cobalt-phthalocyanine to the original insoluble state.
  • the present invention relates to a process for dyeing and printing textile materials made of natural or regenerated cellulose. More particularly it concerns a process wherein the dyeing and printing is carried out by applying coordinatively hexavalent complex salts of trivalent cobalt. in which four of the six coordination points are occupied by the phthalocyanine ring which has a double negative charge. and each of the remaining two points is occupied by a primary. secondary or tertiary polyamine. and which contain an ion from the series Cl. Br. 1'. HCO;,'. N and CH;,COO as anion. dissolved in solvents to the textile materials and subsequently developing said complex salts into cobalt-phthalocyanines on the textile material by an aftertreatment.
  • the dyeing process is based on the property of the cobaltphthalocyanine-polyamine complex salts to be used according to the invention to separate quantitatively and in a pure form the cobalt-phthalocyanine from which they are derived within a few minutes when they are heated to 60-l00 C. in solvents. especially in weakly acidic aqueous solutions.
  • Dyeing according to the process of the invention therefore only requires padding of the textile materials with a solution of the cobalt-phthalocyanine-polyamine complex salts. for example with an approximately 0.5-3 percent acetic acid containing 3 percent ofthe complex salt. at about -30 C.. squeezing off and developing after drying by steaming or hot calendering at temperatures above 100 C.
  • the dyeings can subsequently be finished in the usual manner. for example. by rinsing. soaping at the boil. rinsing again and drying. Obviously. it is also possible to work in the presence of reducing agents. such as sodium bisulfite or sodium dithionite. whereby the short time of 1-5 minutes required for developing the dyestuff by steaming or dry heating. can be reduced to less than one minute.
  • the cobalt-phthalocyanine-polyamine complex salts can also be developed to cobalt-phthalocyanines on the fiber by the action oflight. for example. by hanging in sunlight or by illumination with ultraviolet rays
  • the weakly acidic complex salt solution is adjusted to the desired viscosity by the addition of a suitable thickening agent. and the prints are aftertreated as stated above for pad dyeing.
  • dilute acetic acid there may be used for dissolving the cobalt-phthalocyanine-polyamine complex salts also dilute aqueous solutions of other organic acids.
  • formic acid lactic acid. oxalic acid and citric acid or inorganic acids. such as phosphoric acid. sulfuric acid or hydrochloric acid.
  • solvents such as lower alcohols. e.g. methanol. ethanol. propanol. acetonitrile. formamide or dimethylformamide. advantageously in mixture with water.
  • the acid concentration in the dilute aqueous solutions of the acids generally amounts to 0.5-3 percent by weight.
  • cobalt-phthalocyanine-polyamine complexes used in the present dyeing and printing process are prepared according to one of the processes described below. starting from cobalt-phthalocyanine or from its easily obtainable substitution products. for example. cobalt-phthalocyanine compounds which are substituted in their benzene nuclei by halogen. C,-C.,,'""- ",-C.-alkoxy or phenyl radicals. but which are free from water-solubilizing radicals:
  • the cobalt-phthalocyanine (l) is first converted with a halogenating agent. such as chlorine. into a dihalo-cobaltphthalocyanine of the structure (II) and this is subsequently converted with a primary. secondary or tertiary polyamine. preferably l-amino-3-dimethylamino-propane. into the complex (III) which is soluble in acetic acid.
  • a halogenating agent such as chlorine.
  • a dihalo-cobaltphthalocyanine of the structure (II) is subsequently converted with a primary. secondary or tertiary polyamine. preferably l-amino-3-dimethylamino-propane. into the complex (III) which is soluble in acetic acid.
  • the cobalt-phthalocyanine is first stirred with the polyamine whereupon a loose amine--cobalt-phthalocyanine complex (IV) is primarily formed. and this is subsequently converted into the dyestuff (III) in the presence of halide. acetate. carbonate or nitrate ions by means of an oxidizing agent. preferably atmospheric oxygen.
  • polyamines examples include ethylenediamine. bis- 1 .Z-dimethylamino-ethane. l.3-diaminopropane. bis-lJ-amino-propyll-methylamine and especially the diamines of the formula lii lI:Y ⁇ .' ⁇ -N
  • A a straight or branched C C -.-alkylene radical.
  • R hydrogen or a C,-C.-alkyl radical and R a C,C -alkyl or a cyclohexyl radical.
  • diamines of the above formula are mentioned: l-amino-2-dimethylamino-ethane. l-amino-3- methylamino-propane and especially -l-amino-3- dimethylamino-propane and l-amino-3-diethylaminopropane.
  • cobalt-phthalocyanine-polyamine complex salts to be used according to the invention possess an excellent texturing power on natural or regenerated cellulose fibers. that means. the depth of color of the dyeings produced increases corresponding to the increasing concentration of the complex salts in the dyeing liquor.
  • cobalt-phthaloeyanine-polyamine complex salts are well applicable together with other types of dyestuffs. since for developing the complex salts to cobaltphthalocyanines no reducing agents or other auxiliaries are necessary and. therefore. no turbidity of the accompanying dyestuffs which often results from the use of reducing agents. occurs.
  • the cobalt-phthalocyanine-polyamine complex salts can excellently be used together with acid-soluble basic dyestuffs for dyeing or printing mixed fiber materials of natural and regenerated cellulose and polyacrylonitrile in a single bath or together with dispersion dyestuffs for dyeing and printing mixed fiber materials of natural and regenerated cellulose and polyesters in a single bath.
  • acid-soluble basic dyestuffs for dyeing or printing mixed fiber materials of natural and regenerated cellulose and polyacrylonitrile in a single bath
  • dispersion dyestuffs for dyeing and printing mixed fiber materials of natural and regenerated cellulose and polyesters in a single bath.
  • EXAMPLE 1 A cotton fabric is padded with a liquor which is prepared from 1-60 parts of the cobalt-phthalocyaninecomplex salt described below 10-15 parts of 50 percent acetic acid 989-925 parts of water of l5-25 C. After squeezing to a weight increase of about -90 percent and drying the dyestuff is fixed by neutral steaming at l00-l02 C. for 1-2 minutes. The fabric is subsequently rinsed. soaped at the boil. rinsed and dried. A clear blue dyeing of excellent fastness properties is obtained if. instead ofsteaming. the padded and dried fabric is heated to l30-l50 C. by means of hot air or by contact action for 3-5 minutes. the development of the dyestuff is equally complete and the same blue clear dyeing is obtained by the usual finishing.
  • EXAMPLE 2 A cotton fabric is printed with a printing paste which is prepared from 1-60 parts of the cobalt-phthalocyanine-polyamine complex salt described below,
  • the cobalt-phthalocyanine-polyamine complex salt used above was prepared as follows: 7.5 parts chlorine were passed into a suspension of 57 parts cobalt-phthalocyanine in 300 parts by volume o-dichlorobenzene. Stirring was continued for minutes, air was then blown through the black-brown suspension of dichloro-cobalt-phthalocyanine in order to remove any excess chlorine which may be present. 35 parts N.N-dimethyl-ethylene-diamine were then added and the mixture was heated to 80 C. After cooling to room temperature the product was filtered off with suction, washed with benzene and dried at 60-70 C., in a vacuum. There were obtained 62.5 parts of a dark-green crystalline powder which was freed from any adhering amine hydrochloride by stirring in a 5 percent sodium chloride solution.
  • EXAMPLE 3 A cotton fabric is printed with a printing paste which is prepared from -40 parts of the complex salt described in example 1. parts of crystalline tartaric acid, 455-435 parts of water and 500 parts of a mixture of wheat starch/tragacanth and dextrinated starch (2:1 After drying the fabric is padded with a liquor which is prepared from 40 parts of the dyestuff described in example 216 of the British Patent Specification No. 1 120 761, 675 parts of water of -50 C.. 25 parts of calcined sodium carbonate, 10 parts of the sodium salt of m-nitrobenzene-sulphonic acid and 100 parts ofcarrageenatc /100 dissolved in water.
  • EXAMPLE 4 A cotton fabric is padded at room temperature with a liquor which contains per liter l-60 parts of the cobalt-phthalocyanine-polyarnine complex salt described below and 10-15 parts of 50 percent acetic acid.
  • the cobalt-phthalocyanine-polyamine complex salt used above was prepared as follows: To a suspension of 32.5 parts dichloro-cobalt-phthalocyanine (prepared from cobaltphthalocyanine and chlorine as mentioned in example 2) in 150 parts by volume dioxan 50 parts of volume ethylenediamine were added in portions at below 15 C. The product was filtered off with suction and washed with dioxan and cyclohexane. The precipitate was dried at 40 C. in a vacuum and then well stirred in 250 parts by volume of 10 percent aqueous acetic acid. From the solution which was freed from undissolved matter by filtration the complex salt was precipitated by the addition of sodium chloride. The precipitate was washed with a sodium chloride solution until neutral and dried in a vacuum at 40 C. The resultant deepgreen crystal powder dissolved in dilute acids without a residue.
  • EXAMPLE 5 A cotton fabric is padded with a liquor which contains per liter 5-40 parts of the complex salt described in example 2.
  • the fabric After squeezing to a weight increase of 80-90 percent the fabric is aftertreated with a 3-5 percent sodium dithionite solution at 50 C., for 30 seconds. It is then rinsed. acidified with 3-5 percent hydrochloric acid at 70 C. for 30 seconds, rinsed. soaped at the boil, and finished in the usual manner. As in example 1, there is obtained a clear-blue dyeing.
  • EXAMPLE 6 A cotton fabric which has been bottomed with the dyestuff color index no. 37 610 is printed with a printing paste which is prepared as follows:
  • I. Process for dyeing and printing textile materials made of natural or regenerated cellulose which comprises dissolving in a solvent an insoluble cobalt-phthalocyanine which has been solubilized by oxidizing to the hexavalent state and complexing with a polyamine selected from the group consisting of an alkylene polyamine. an N-alkyl-alkylene polyaminc. an N.N- dialkyl-alkylene polyamine. an N-cyclohexyl-alkylene polyamine. an N-alkyl-N-cyclohexyl-alkylene polyamine and an Nlalkyl-polyalkylene-polyamine. and which contains an anion.
  • the solvent is a member selected from the group consisting of aqueous solutions of formic acid. acetic acid. lactic acid. oxalic acid. citric acid. phosphoric acid. sulfuric acid. hydrochloric acid; and methanol. ethanol. propanol. acetonitrile. formamide, dimethylformamide. and mixtures of said solvents with water.
  • R hydrogen oraC,-C.-alkyl radical and R; a C.C.-alkyl or a cyclohexyl radical.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Coloring (AREA)
US754709A 1967-08-31 1968-08-22 Cobalt-phthalocyanine-polyamine complexes for the dyeing and printing of textiles Expired - Lifetime US3619109A (en)

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DEF0053376 1967-08-31

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US (1) US3619109A (enrdf_load_stackoverflow)
AT (1) AT284776B (enrdf_load_stackoverflow)
BE (1) BE719863A (enrdf_load_stackoverflow)
CH (2) CH1168368A4 (enrdf_load_stackoverflow)
DE (1) DE1619546A1 (enrdf_load_stackoverflow)
DK (1) DK133344B (enrdf_load_stackoverflow)
ES (1) ES357756A1 (enrdf_load_stackoverflow)
FI (1) FI46086C (enrdf_load_stackoverflow)
FR (1) FR1580613A (enrdf_load_stackoverflow)
GB (1) GB1242449A (enrdf_load_stackoverflow)
IL (1) IL30530A (enrdf_load_stackoverflow)
NL (1) NL161828C (enrdf_load_stackoverflow)
NO (1) NO127358B (enrdf_load_stackoverflow)
OA (1) OA02882A (enrdf_load_stackoverflow)
SE (1) SE336772B (enrdf_load_stackoverflow)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3927967A (en) * 1972-06-02 1975-12-23 Procter & Gamble Photoactivated bleaching process and composition
US4284560A (en) * 1976-01-24 1981-08-18 Bayer Aktiengesellschaft Process for the preparation of complex compounds of the cobalt Phthalocyanine series
CN101775232A (zh) * 2009-12-12 2010-07-14 汕头市粤钿化工有限公司 一种酸溶性酞菁染料及其制造方法
CN103570734A (zh) * 2013-11-05 2014-02-12 福建华天裕科学技术发展有限公司 一种酞菁钴二胺化合物的合成方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2772284A (en) * 1951-10-20 1956-11-27 Du Pont Solvent-soluble, complex, phthalocyanine-yielding compounds

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2772284A (en) * 1951-10-20 1956-11-27 Du Pont Solvent-soluble, complex, phthalocyanine-yielding compounds

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3927967A (en) * 1972-06-02 1975-12-23 Procter & Gamble Photoactivated bleaching process and composition
US4284560A (en) * 1976-01-24 1981-08-18 Bayer Aktiengesellschaft Process for the preparation of complex compounds of the cobalt Phthalocyanine series
CN101775232A (zh) * 2009-12-12 2010-07-14 汕头市粤钿化工有限公司 一种酸溶性酞菁染料及其制造方法
CN101775232B (zh) * 2009-12-12 2012-10-10 汕头市正亨化工实业有限公司 一种酸溶性酞菁染料及其制造方法
CN103570734A (zh) * 2013-11-05 2014-02-12 福建华天裕科学技术发展有限公司 一种酞菁钴二胺化合物的合成方法
CN103570734B (zh) * 2013-11-05 2015-07-15 福建华天裕科学技术发展有限公司 一种酞菁钴二胺化合物的合成方法

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CH1168368A4 (enrdf_load_stackoverflow) 1972-08-31
FI46086C (fi) 1972-12-11
FI46086B (enrdf_load_stackoverflow) 1972-08-31
DK133344B (da) 1976-05-03
BE719863A (enrdf_load_stackoverflow) 1969-02-03
NL6812409A (enrdf_load_stackoverflow) 1969-03-04
CH533202A (de) 1972-08-31
NL161828C (nl) 1980-03-17
NO127358B (enrdf_load_stackoverflow) 1973-06-12
ES357756A1 (es) 1970-03-16
OA02882A (fr) 1970-12-15
DE1619546A1 (de) 1969-09-04
IL30530A0 (en) 1968-10-24
SE336772B (enrdf_load_stackoverflow) 1971-07-19
GB1242449A (en) 1971-08-11
AT284776B (de) 1970-09-25
NL161828B (nl) 1979-10-15
IL30530A (en) 1971-12-29
DK133344C (enrdf_load_stackoverflow) 1976-10-04
FR1580613A (enrdf_load_stackoverflow) 1969-09-05

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