EP0044601B1 - Process for discharge printing of polyester materials - Google Patents

Process for discharge printing of polyester materials Download PDF

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Publication number
EP0044601B1
EP0044601B1 EP81200822A EP81200822A EP0044601B1 EP 0044601 B1 EP0044601 B1 EP 0044601B1 EP 81200822 A EP81200822 A EP 81200822A EP 81200822 A EP81200822 A EP 81200822A EP 0044601 B1 EP0044601 B1 EP 0044601B1
Authority
EP
European Patent Office
Prior art keywords
composition
discharge
discharging
dye
thiourea
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP81200822A
Other languages
German (de)
French (fr)
Other versions
EP0044601A1 (en
Inventor
Ronald Johannes Spierdijk
Willem Laurens Veltman
Louis Leonard Weerkamp
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EPEC-DINON
Original Assignee
EPEC-DINON
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EPEC-DINON filed Critical EPEC-DINON
Priority to AT81200822T priority Critical patent/ATE20100T1/en
Publication of EP0044601A1 publication Critical patent/EP0044601A1/en
Application granted granted Critical
Publication of EP0044601B1 publication Critical patent/EP0044601B1/en
Expired legal-status Critical Current

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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
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/15—Locally discharging the dyes
    • D06P5/155—Locally discharging the dyes with reductants
    • 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
    • D06P1/642—Compounds containing nitrogen
    • D06P1/649—Compounds containing carbonamide, thiocarbonamide or guanyl groups
    • D06P1/6491—(Thio)urea or (cyclic) derivatives

Definitions

  • the invention relates to a process for printing polyester containing textile materials by applying in one step wet on wet a first composition containing at least a dischargeable dye and a discharge composition containing a compound discharging said dischargeable dye onto a fabric, drying the fabric and fixing the dyes by heating.
  • Such a process for printing polyester or polyester/cotton fabrics in one step using a first composition containing a dischargeable dye and urea (thiourea is used for other fabrics) and a discharging composition containing only high amounts of stannous chloride and sodium sulphoxylate formaldehyde as discharging agent is known from GB-A-1.508.855.
  • This aim is attained in that the dischargeable dye is discharged by a thiourea or isothiourea compound present in the discharge composition.
  • GB-A-1.440.904 discloses a printing process wherein a composition containing at least one dischargeable dye is applied onto fabric of polyester fibres and after dying the polyester material a discharging composition is applied containing 7 parts by weight of stannous chloride and 5 parts by weight of an amine binding hydrochloric acid evolved in the action of stannous chloride.
  • This amine may be urea or thiourea.
  • the fabric is subjected to a steam treatment with superheated steam at a temperature of 180°C for 10 minutes for fixing the dyes. This process does not provide multicoloured designs of good quality.
  • DE-B-1.103.288 also describes a discharge printing process for printing cellulose ester containing fabrics by applying a two steps process, the discharging composition containing 15 parts by weight of sodium sulphoxylate formaldehyde as discharging agent and 10 parts by weight of thiourea. This process does not provide multicoloured design of good quality.
  • US-A-2.874.022 discloses the use of a discharging composition containing sodium sulphoxylate formaldehyde and thiourea for discharge printing cellulose acetate in two steps.
  • DE-A-2.727.327 and CH-A-612.307 describes a two step discharge printing process for polyester fabric the discharge composition containing 8 to 10% of zinc sulphoxylate formaldehyde and 1 to 3% of thiourea.
  • US-A-3.958.287 describes the use of thiourea as a hydrotroping or neutralizing agent in discharging compositions containing stannous chloride as discharging agent, the printing process is a two step process.
  • the discharging composition as used in the invention may contain an additional discharging agent preferably in the form of a salt of a metal of the second to fourth groups of the periodic system. However, this is unnecessary if suitable recipes are applied.
  • the composition may contain as such an additional discharging agent a halogen compound of a bivalent metal, in particular zinc chloride, and yet more advantageously a halogen compound of a quadrivalent metal, in particular tin, which tin compound is applied in the form of stannous chloride. It is recommended to use at most 5% of such an additional discharging agent.
  • the discharge composition may contain at most 4% of a dye discharging metal salt preferably of a halide or a halide of a metal of the second to fourth groups of the periodic system as additional discharge agent besides 0,1 to 10%, preferably 0,1 to 5% of a thiourea or isothiourea compound as discharge agent.
  • the metal halide is advantageously zinc or stannous chloride.
  • a composition may effectively be used for printing which contains 0,1 to 4% of a metal salt, more particularly 0,1 to 2% and 0,5 to 10% of organic discharging agent, still more particularly 1 to 4% and more effectively 0,5 to 1% of a metal salt, preferably stannous II chloride and 0,5 to 5% thiourea.
  • the fabric is subjected to heat treatment at a temperature exceeding 80°C and less than the decomposing temperature of the textile material, preferably to a steam treatment at a temperature of 150 to 180°C.
  • the process according to the invention is particularly used for rotation film-printing of textile materials containing synthetic and natural fibres, particularly cellulose fibres (cotton) mixed with polyester.
  • a discharge composition for use in the process of the invention contains at most 4% of a dye discharging metal salt preferably of a halide of a halide of a metal of the second to fourth groups of the periodic system as additional discharge agent besides 0,1 to 10%, preferably 0,1 to 5% of a thiourea or isothiourea compound as discharge agent.
  • the thickeners applied in the composition according to the invention may effectively consist of cellulose or starch derivatives thickening with water.
  • Other solvents can also be included in the composition such as e.g, benzene, in which case semi-emulsions are obtained.
  • a layer of one of the discharge-resistant printing pastes as described in one of the Examples II to VI is applied to the textile material to be printed (50% cotton fibre and 50% polyester fibre) and a print overlayer is applied to this of a known printing paste with dischargeable dyes.
  • Both printing pastes are printed wet on wet in a single stage with the aid of a printing machine.
  • the cloth is then dried, fixed at e.g. a temperature of 170°C within a period of e.g. 10 minutes, after which the textile material is further treated.
  • the printing paste according to the invention be first applied to the textile material and then the paste with dischargeable dye, as this produces optimum results.
  • Discharging Composition for e.g. Dispersed Dyes
  • 360 g of thickener (12% solution) is mixed with 40 g of emulsifier (12,5% solution), 16 g of sodium acetate and 2 g-of citric acid and 48 g of thiourea.
  • Discharging Composition Suitable for e.g. Dispersed Dyes
  • Example II The composition described in Example II is prepared but without 20-40 g stannous II chloride. Instead of stannous II chloride 30 g of "Solutionsalz" @ or an identical product and 30 g of Lyogene V @ or an identical product is added. It is filled up to 1000 g with water.
  • composition described in Examples II or III is taken but the quantity of citric acid is increased to 50 g and 80 g of polyethyleneglycol (specific weight 300) is also added, after which discharging on to polyester/cotton is possible.
  • an acid pigment cover printing paste is taken, to which is added 20 g of sodium acetate, 20 g of fixation agent, 50 g of tylose MH 300 (7% solution), 50 g of citric acid and 50 g of thiourea.
  • a certain quantity of discharge-resistant pigment dye and 20-40 g of stannous II chloride (depending on the properties and dye concentrations present of dischargeable dyes or dyes to be discharged) is further added to this composition. It is filled up to 1000 g with water.
  • Example V The composition described in Example V is taken but without 20-40 g of stannous II chloride and, instead, the products named in Example III are added.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

Composition for discharge printing of textile materials in one step consisting of cellulose fibers, such as cotton and synthetic fibers, such as polyester, containing thiourea as an agent discharging dischargeable dyes. Thiourea is present in an amount of not more than 5%. For rotation film printing the composition together with another composition is applied on to the textile material, whereafter the whole is subjected to a steam treatment at a temperature comprised between 150 and 180 DEG C.

Description

  • The invention relates to a process for printing polyester containing textile materials by applying in one step wet on wet a first composition containing at least a dischargeable dye and a discharge composition containing a compound discharging said dischargeable dye onto a fabric, drying the fabric and fixing the dyes by heating.
  • Such a process for printing polyester or polyester/cotton fabrics in one step using a first composition containing a dischargeable dye and urea (thiourea is used for other fabrics) and a discharging composition containing only high amounts of stannous chloride and sodium sulphoxylate formaldehyde as discharging agent is known from GB-A-1.508.855.
  • However, the use of a high concentration of the discharging agent such as stannous chloride or zinc sulphoxylate formaldehyde presents the disadvantage that
    • a) a small dying range is obtained as if more stannous chloride or sulphoxylate is used, the less dyes are dischargeproof. In practice, this results in printed fabrics having dischargeproof dyes which are relatively dull in colour.
    • b) When the dyes are fixed on the textile material hydrochloric acid escapes from stannous chloride during this reaction mechanism which gives rise to high corrosion and attack of the metal of the steamer in which the fixation takes place.
    • c) Stannous chloride and zinc sulphoxylate formaldehyde are expensive products so that the process is very costly.
  • It is now the aim of the invention to provide a process for printing of polyester containing textile materials by applying a discharging agent whereby the abovementioned disadvantages do not arise and, in particular, improved colour patterns can be obtained with an appreciable saving in raw materials. The opportunity is also created for discharging textile materials without using any stannous chloride, depending on the dyes and materials to be processed.
  • This aim is attained in that the dischargeable dye is discharged by a thiourea or isothiourea compound present in the discharge composition.
  • In this way the following advantages are obtained:
    • a) A more extensive range of dyes can be used as more dyes will be proof to the discharging agent in the form of an thiourea or an isothiourea compound.
    • b) Owing to the fact that no or at least less stannous chloride need be used, less corrosion of the installation takes place.
    • c) Through an appreciable smaller use of stann ous chloride or even without stannous chloride important economic advantages are obtained.
    • d) A multi-colured design can be obtained by making use of masks both in the stencils for the first composition and the stencils for applying the discharging composition, which may contain a second colour being proof against the discharging compound thiourea or isothiourea.
    • e) The textile material need be passed over a printing machine once only, while drying after applying the first dye-containing composition can be omitted; this leads to major economic advantages.
    • f) Since the drying of the first colour-containing composition is superfluous, no additional problems can result with parts of the textile material containing dye already fixed, so that the percentage of waste is reduced.
    • g) The composition containing the first dye and the discharging composition can be printed in relation to each other so that the opportunities for design and artistic work are much greater. In particular, this process allows designs hitherto impossible to be printed onto textile materials.
    • h) Single-stage printing allows thicker, coarser polyester qualities to be worked with.
  • It should be noted that GB-A-1.440.904 discloses a printing process wherein a composition containing at least one dischargeable dye is applied onto fabric of polyester fibres and after dying the polyester material a discharging composition is applied containing 7 parts by weight of stannous chloride and 5 parts by weight of an amine binding hydrochloric acid evolved in the action of stannous chloride. This amine may be urea or thiourea. Subsequently the fabric is subjected to a steam treatment with superheated steam at a temperature of 180°C for 10 minutes for fixing the dyes. This process does not provide multicoloured designs of good quality.
  • DE-B-1.103.288 also describes a discharge printing process for printing cellulose ester containing fabrics by applying a two steps process, the discharging composition containing 15 parts by weight of sodium sulphoxylate formaldehyde as discharging agent and 10 parts by weight of thiourea. This process does not provide multicoloured design of good quality.
  • US-A-2.874.022 discloses the use of a discharging composition containing sodium sulphoxylate formaldehyde and thiourea for discharge printing cellulose acetate in two steps.
  • Chemical Abstracts, Vol. 93, no. 12, September 1980, page 63 no. 115853t describes discharge printing of acrylic fibres in two steps using a discharge composition containing stannous chloride as a dye discharging agent and thiourea.
  • DE-A-2.727.327 and CH-A-612.307 describes a two step discharge printing process for polyester fabric the discharge composition containing 8 to 10% of zinc sulphoxylate formaldehyde and 1 to 3% of thiourea.
  • US-A-3.958.287 describes the use of thiourea as a hydrotroping or neutralizing agent in discharging compositions containing stannous chloride as discharging agent, the printing process is a two step process.
  • This two-stage method presents the disadvantage, of a high percentage of waste being a consequence of the fact that the process is difficult to check. Moreover, when the dischargeable dye has been applied by means of the first composition and has dried the dischargeable dye may be fixed to the fibres in certain parts of the fabic in such a way that the discharge agent stannous chloride is not able to discharge these parts printed by the first dye. Furthermore, the opportunities for design and artistic work are restricted since the print with the composition containing the discharging agent and the first composition cannot be printed to match in relation to each other, while finally, this process can virtually be applied only on thin polyester-materials.
  • The discharging composition as used in the invention may contain an additional discharging agent preferably in the form of a salt of a metal of the second to fourth groups of the periodic system. However, this is unnecessary if suitable recipes are applied.
  • The composition may contain as such an additional discharging agent a halogen compound of a bivalent metal, in particular zinc chloride, and yet more advantageously a halogen compound of a quadrivalent metal, in particular tin, which tin compound is applied in the form of stannous chloride. It is recommended to use at most 5% of such an additional discharging agent.
  • The discharge composition may contain at most 4% of a dye discharging metal salt preferably of a halide or a halide of a metal of the second to fourth groups of the periodic system as additional discharge agent besides 0,1 to 10%, preferably 0,1 to 5% of a thiourea or isothiourea compound as discharge agent. The metal halide is advantageously zinc or stannous chloride.
  • A composition may effectively be used for printing which contains 0,1 to 4% of a metal salt, more particularly 0,1 to 2% and 0,5 to 10% of organic discharging agent, still more particularly 1 to 4% and more effectively 0,5 to 1% of a metal salt, preferably stannous II chloride and 0,5 to 5% thiourea.
  • Preferably after having applied the first and the discharge composition, the fabric is subjected to heat treatment at a temperature exceeding 80°C and less than the decomposing temperature of the textile material, preferably to a steam treatment at a temperature of 150 to 180°C.
  • The process according to the invention is particularly used for rotation film-printing of textile materials containing synthetic and natural fibres, particularly cellulose fibres (cotton) mixed with polyester.
  • Preferably a discharge composition for use in the process of the invention contains at most 4% of a dye discharging metal salt preferably of a halide of a halide of a metal of the second to fourth groups of the periodic system as additional discharge agent besides 0,1 to 10%, preferably 0,1 to 5% of a thiourea or isothiourea compound as discharge agent.
  • The thickeners applied in the composition according to the invention may effectively consist of cellulose or starch derivatives thickening with water. Other solvents can also be included in the composition such as e.g, benzene, in which case semi-emulsions are obtained.
  • The invention will now be explained by mean of some examples.
    • Example I Printing of Textile
  • A layer of one of the discharge-resistant printing pastes as described in one of the Examples II to VI is applied to the textile material to be printed (50% cotton fibre and 50% polyester fibre) and a print overlayer is applied to this of a known printing paste with dischargeable dyes.
  • Both printing pastes are printed wet on wet in a single stage with the aid of a printing machine.
  • The cloth is then dried, fixed at e.g. a temperature of 170°C within a period of e.g. 10 minutes, after which the textile material is further treated.
  • It is recommended that the printing paste according to the invention be first applied to the textile material and then the paste with dischargeable dye, as this produces optimum results.
    • Example II Discharging Composition for e.g. Dispersed Dyes
  • 360 g of thickener (12% solution) is mixed with 40 g of emulsifier (12,5% solution), 16 g of sodium acetate and 2 g-of citric acid and 48 g of thiourea.
  • Further, 10 g of carrier and 320 ml of TerpentoiO are added to this composition, together with a desired quantity of discharge-proof dispersed dyes and 20 to 40 g of stannous II chloride (depending on the properties and concentrations present of the dischargeable dyes or those to be discharged). This is filled up to 1000 g with water or another solvent.
    • Example III Discharging Composition Suitable for e.g. Dispersed Dyes
  • The composition described in Example II is prepared but without 20-40 g stannous II chloride. Instead of stannous II chloride 30 g of "Solutionsalz"@ or an identical product and 30 g of Lyogene V@ or an identical product is added. It is filled up to 1000 g with water.
    • Example IV Discharging Composition Suitable for Dispersed Reactive Dyes
  • The composition described in Examples II or III is taken but the quantity of citric acid is increased to 50 g and 80 g of polyethyleneglycol (specific weight 300) is also added, after which discharging on to polyester/cotton is possible.
    • Example V Discharging Composition Suitable for Pigment Dyes
  • 700 g of an acid pigment cover printing paste is taken, to which is added 20 g of sodium acetate, 20 g of fixation agent, 50 g of tylose MH 300 (7% solution), 50 g of citric acid and 50 g of thiourea. A certain quantity of discharge-resistant pigment dye and 20-40 g of stannous II chloride (depending on the properties and dye concentrations present of dischargeable dyes or dyes to be discharged) is further added to this composition. It is filled up to 1000 g with water. By means of this printing paste cover printing is possible on polyester/cotton with discharge-resistant pigment-dyes.
    • Example VI Discharge Composition Suitable for Pigment Dyes
  • The composition described in Example V is taken but without 20-40 g of stannous II chloride and, instead, the products named in Example III are added.

Claims (7)

1. A process for printing polyester containing textile materials by applying in one step wet on wet a first composition containing at least a dischargeable dye and a discharge composition containing a compound discharging said dischargeable dye onto a fabric drying the fabric and fixing the dyes by heating, characterized in that the dischargeable dye is discharged by a thiourea or isothiourea compound present in the discharge composition.
2. A process according to claim 1, characterized in that the discharge composition contains at most 4% of a dye discharging metal salt as additional discharge agent besides 0,1 to 10%, of thiourea or isothiourea compound as discharge agent.
3. A process according to claim 2, characterized in that the dye discharging metal salt is a halide of a metal of the second to fourth group of the Periodic System.
4. A process according to claim 2 or 3, characterized in that the discharge composition contains 0,1 to 5% of a thiourea or isothiourea compound as discharge agent.
5. A process according to claim 2-4, characterized in that the metal halide is zinc or stannous chloride.
6. A process according to any one of the preceding claims, characterized in that the discharging composition is first applied onto the fabric textile and the first composition containing - the dischargeable dye is deposited upon said discharging composition.
7. A process as claimed in any one of the preceding claims, characterized in that after having applied the first and the discharge composition, the fabric is subjected to heat treatment at a temperature exceeding 80°C and less than the decomposing temperature of the textile material, preferably to a steam treatment at a temperature of 150 to 180°C.
EP81200822A 1980-07-18 1981-07-20 Process for discharge printing of polyester materials Expired EP0044601B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81200822T ATE20100T1 (en) 1980-07-18 1981-07-20 METHOD OF ETCHING POLYESTER MATERIALS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL8004160 1980-07-18
NL8004160A NL8004160A (en) 1980-07-18 1980-07-18 COMPOSITION FOR ETCHING OF TEXTILE MATERIALS.

Publications (2)

Publication Number Publication Date
EP0044601A1 EP0044601A1 (en) 1982-01-27
EP0044601B1 true EP0044601B1 (en) 1986-05-28

Family

ID=19835643

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81200822A Expired EP0044601B1 (en) 1980-07-18 1981-07-20 Process for discharge printing of polyester materials

Country Status (5)

Country Link
EP (1) EP0044601B1 (en)
JP (1) JPS57101086A (en)
AT (1) ATE20100T1 (en)
DE (1) DE3174709D1 (en)
NL (1) NL8004160A (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3209327A1 (en) * 1982-03-15 1983-09-15 Cassella Ag, 6000 Frankfurt METHOD FOR PRODUCING ETCH RESERVE PRINTS ON HYDROPHOBIC TEXTILE MATERIALS
DE3339158A1 (en) * 1983-10-28 1985-05-09 Cassella Ag, 6000 Frankfurt METHOD FOR PRODUCING ETCH RESERVE PRINTS ON HYDROPHOBIC TEXTILE MATERIALS

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1103288B (en) * 1955-06-22 1961-03-30 Ciba Geigy Process for reductive etching of colorings produced with disperse dyes on fabrics containing cellulose esters
US2874022A (en) * 1956-06-14 1959-02-17 Ciba Company Inc Composition and process for application and discharge printing
US3097045A (en) * 1959-02-05 1963-07-09 Hoechst Ag Process for producing white or color resists on dyeings with vat dyestuffs on native or regenerated cellulose
DE1086209B (en) * 1959-04-18 1960-08-04 Basf Ag Printing pastes for the direct or etch printing process
GB986895A (en) * 1960-10-25 1965-03-24 Hoechst Ag Process for producing white or coloured discharge effects on dyed yarns or fabrics of vegetable fibres
GB1502861A (en) * 1974-05-24 1978-03-08 Sumitomo Chemical Co Dischargeable black dyeing of acidmodified polyester fibr
GB1440904A (en) * 1975-01-02 1976-06-30 Toray Industries Discharge printing of polyester fibre materials
CH616040GA3 (en) * 1976-06-25 1980-03-14 Discharge printing of synthetic textile materials
SU657049A1 (en) * 1977-06-28 1979-04-15 Московский Ордена Трудового Красного Знамени Текстильный Институт Composition for printing cotton textile material
CH612307GA3 (en) * 1977-08-22 1979-07-31 Discharge printing process for synthetic textile fibres using redox buffers
JPS6227980A (en) * 1985-07-30 1987-02-05 株式会社　タカラ Line-of-magnetic force generator for toy

Also Published As

Publication number Publication date
NL8004160A (en) 1982-02-16
DE3174709D1 (en) 1986-07-03
ATE20100T1 (en) 1986-06-15
EP0044601A1 (en) 1982-01-27
JPS57101086A (en) 1982-06-23

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