US3476505A - Bleaching fibrous material of natural cellulose - Google Patents

Bleaching fibrous material of natural cellulose Download PDF

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Publication number
US3476505A
US3476505A US511988A US3476505DA US3476505A US 3476505 A US3476505 A US 3476505A US 511988 A US511988 A US 511988A US 3476505D A US3476505D A US 3476505DA US 3476505 A US3476505 A US 3476505A
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parts
alkali metal
acid
sodium
moles
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US511988A
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English (en)
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Uwe Kirner
Bjarne Hartmark
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BASF SE
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BASF SE
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/30—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using reducing agents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/70—Multi-step processes

Definitions

  • the present invention relates to a process for bleaching fibrous material of natural cellulose by treatment with alkali metal hydroxide solutions of definite concentration in the presence of sequestring agents.
  • hydroxides of all the alkali metals may be used for the present process.
  • Potassium hydroxide and sodium hydroxide are however preferred because of their easy accessibility and their very good efficacy.
  • Alkali metal polyphosphaes are defined as those which contain two or more phosphorus atoms in the molecule, combined together linearly or reticularly.
  • Polyphosphates having the general formula: M P O (in which M denotes an alkali metal ion, preferably a sodium or potassium ion, and n denotes one of the integers from 2 to 10), for example sodium or potassium pyrophosphate, tripolyphosphate, tetrapolyphosphate and hexapolyphosphate and commercial mixtures of these polyphosphates are particularly emphasized.
  • the polyphosphates of the said type may be used alone in the amounts stated above.
  • These alkali metal polyphosphates are often referred to as alkali metal molecularly dehydrated polyphosphates.
  • A denotes a radical having the formula -no-cn- H20 om Hie-0H2 or preferably m denotes zero, 1 or 2 and Y denotes identical or different groups having the formula -COOH or CH OH.
  • Examples of complex-forming aminopolycarboxlic acids are: N-hydroxyethylethylene diamine triacetic acid, o-cyclohexylene diamine tetracetic acid, diethylene triamine pentacetic acid, triethylene tetramine hexacetic acid, N-hydroxyethyldiethylene triamine tetracetic acid, nitrilotriacetic acid and particularly ethylene diamine tetracetic acid.
  • the above-mentioned compounds may be used as alkali metal salts or as free acids, inasmuch as the acids are converted into the salts in the alkaline liquor.
  • the complex-forming aminopolycarboxylic acids or their alkali metal salts may be used alone instead of the polyphosphates in the amounts stated above. It has proved to be particularly suitable however to use the polyphosphates together with complex-forming aminopolycarboxylic acids or their alkali metal salts, the total concentration of the polyphosphates and aminopolycarboxylic acids or their salts in the treatment liquor being 1 to 4% by weight. Especially good bleaching results are achieved by using alkali metal polyphosphates and complex-forming aminopolycarboxylic acids or their salts in the weight ratio of 1:4 to 4:1.
  • the wetting agents may be conventional substances of this type which are active in alkaline solution.
  • the manu facturers of wetting agents give information concerning the activity of their products in alkaline medium in their technical literature. They are generally products which are recommended as kier boiling assistants.
  • Alkyl sulfonates, alkyl disulfonates, alkylaryl sulfonates, fatty acid condensates, protein cleavage products and sulfuric acid hemiesters of alkylphenol-ethylene oxide adducts or their salts are examples of anion-active wetting agents.
  • nonionic Wetting agents are adducts of ethylene oxide to fatty alcohols, fatty acid amides, alkylnaphthols and alkylphenols.
  • wetting agents which have proved to be very suitable are the following: sodium salt of the disulfonic acid of kogasin, diethanolamine salt of dodecylbenzene-sulfonic acid, sodium salt of bis-decanesulfonirnide, sodium salt of a sulfonated OC,fi-Olfifl having 12 to 14 carbon atoms, sodium salt of the sulfuric acid halfester of an adduct of 1 mole of nonyl phenol and 4 moles of ethylene oxide, adducts of 1 mole of colophony to 25 moles of ethylene oxide, of 1 mole of octyl phenol to 8 or 9 moles of ethylene oxide, of nonyl phenol to 10 moles of ethylene oxide, and of fatty alcohols of medium chain length, such as coconut fatty alcohol, to 7 to 9 moles of ethylene oxide, the condensation product of 2 moles of
  • kogasin denotes a hydrocarbon fraction from the Fischer-Tropsch sysnthesis having a boiling range of about 200 to 300 C. These mixtures are therefore preferred.
  • the wetting agents may furthermore contain antifoaming agents, such as triisobutyl phosphate, in the usual way.
  • the liquor ratio i.e. the ratio by weight of the textile material to the amount of liquor used, in the present process may be varied Within the range 0.5:1 to 3:1 and adapted to the apparatus available. It is preferable to use a liquor ratio of 0.8:1 to 2.521. This range is particularly suitable for continuous operation of the process. It is preferred to pad the treatment liquor onto the fibrous material and then to subject the impregnated material to the heat treatment. In general, the impregnated material is squeezed out in a padding machine to a liquor retention of 90 to 110% with reference to the weight of the dry fibrous material.
  • the treatment temperature should be within the range of from 90 to 150 C. and should be correlated to the treatment period so that it does not fall short of or exceed the limits set by the abovementioned equations I and II. This means that for a given treatment period 1, the higher of the two lower limits 90 C. and t and the lower of the two higher limits 150 C. and t determine the temperature range to be used. When falling short of or exceeding the working range thus defined, the eifect of the treatment falls off so rapidly and so markedly that any appreciable whitening of the fibrous material no longer takes place.
  • the fibrous material is freed from alkali metal hydroxide by conventional methods, for example by thorough rinsing and if necessary by acidification.
  • Particularly good bleaching of the material being treated is obtained when it is rinsed at least once at boiling temperature to free it from alkali metal hydroxide. It has proved to be outstandingly suitable to carry out rinsing first twice at the boiling temperature and then once or twice at about 60 to 80 C., then to acidify with very dilute hydrochloric acid and finally to rinse once cold.
  • the upper portion of the range from 110 to 150 (3., preferably from 115 to 150 C., is significant chiefly for short treatment periods up to about fifteen minutes
  • the lower portion of the range from 90 to 110 0, preferably from 90 to 105 C. is significant chiefly for long treatment periods of from about thirty minutes.
  • Particularly improved results are obtained when the concentration of alkali metal hydroxide within the range of concentration of from 4 to 13% is correlated to the treatment temperature in each of the said portions of the temperature range so that the concentration is low at the higher temperatures and high at the lower temperatures.
  • a preferred embodiment of the process according to this invention therefore comprises choosing the concentration of alkali metal hydroxide in percent by weight so that in the upper portion of the temperature range from to 150 C., preferably from to 150 C., it remains within the limits c and c defined by the equations:
  • the upper portion of the temperature range is preferably used for short treatment periods of up to fifteen minutes and the lower portion of the temperature range for long treatment periods of from thirty minutes.
  • the present process may be carried out batchwise or preferably continuously.
  • the procedure may preferably be to carry out the treatment for thirty seconds to fifteen minutes, preferably from one to fifteen minutes, at temperatures of from to 150 C.
  • the process according to this invention permits the achievement, without oxidizing bleaching agents, of a bleaching effect which is better than that with a medium oxidizing bleach without damage to the fiber which occurs in oxidizing bleaching having to be tolerated.
  • An even better degree of whiteness may be achieved by adding reducing bleaching agents, such as sodium dithionite, a-hydroxyalkanesulfinic acids and their salts, reaction products of a-hydroxyalkanesulfinic acids with ammonia or amines and salts of such reaction products, in amounts of at least 2.5% by Weight, to the bleaching liquor but for reasons of economy it is preferred not to use reducing agents in amounts which produce an appreciable additional bleaching effect.
  • liquor ratio 0.5 :1 to 50:1; duration of bleaching: one to sixty minutes at 90 to 150 C.
  • EXAMPLE 1 Desized and dried unbleached cotton cloth is impregnated with a solution having the following composition:
  • the material treated with the said solution is squeezed out on a padding machine to 100% liquor retention and treated with saturated steam at C. for ten minutes a cottage steamer. It is then rinsed with desalted water twice at 100 C. and one at 60 C. It is then acidified with an aqueous solution which contains 3 to 5 ml./l. of con centrated hydrochloric acid and again rinsed at room temperature.
  • a material entirely free from husks is obtained having a degree of whiteness which varies from 83.0 to 86.0% (measured on the Elrepho apparatus of the firm of Carl Zeiss, Oberkochen, with filter R 46 T) depending on the quality of the cotton.
  • the material treated with the said solution is squeezed out on a padding machine to 100% liquor retention and treated with saturated steam at 130 C. for fifteen minutes in a cottage steamer. It is then rinsed twice at 100 C. and once at 60 C. with desalted water, then acidified with an aqueous solution containing 3 to 5 m1./l. of concentrated hydrochloric acid and rinsed again at room temperature.
  • the material which has been treated with the said solution is squeezed out to liquor retention on a padding machine and treated with saturated steam at 100 to 103 C. for three hours in a pad-roll plant.
  • the plant should be equipped so that it can be operated free from air as far as possible.
  • the material is then risend twice at 100 C. and once at 60 C. with desalted water, then acidified with an aqueous solution which contains 3 to 5 ml./l. of concentrated hydrochloric acid and again rinsed at room temperature.
  • a completely husk-free material is obtained having a degree of whiteness, depending on the quality of the cotton, of from 82.0% to 85.0% (measured as in Example 1).
  • An entirely husk-free material is obtained having a degree of whiteness, depending on the quality of the material, of from 83.0% to 86.0%.
  • EXAMPLE 5 Desized and dried unbleached cotton cloth is impregnated with an aqueous solution having the following composition:
  • the impregnated material is squeezed out to 100% liquor retention on a padding machine and treated in a pad-roll plant with saturated steam for three hours at 100 to 103 C.
  • the plant should be equipped to operate free from air as far as possible.
  • the material is then rinsed twice at 100 C. and once at 60 C. with desalted water. It is then acidified with an aqueous solut1on containing 3 to 5 ml./l. of concentrated hydrochloric acid and rinsed again at room temperature.
  • a completely husk-free material is obtained having a degree of whiteness varying, depending on the quality 7 of the cotton, from 79.0% to 83.0% (measured as in Example 1).
  • EXAMPLE 6 Desized and dried unbleached cotton cloth is impregnated with a solution having the following composition:
  • the impregnated material is squeezed out on a padding machine to 100% liquor retention and treated with saturated steam at 135 C. for ten minutes in a cottage steamer. Then it is rinsed twice at 100 C. and once at 60 C. with desalted water. It is then acidified with an aqueous solution containing 3 to 5 ml./l. of concentrated hydrochloric acid and again rinsed at room temperature.
  • a completely husk-free material is obtained which has a degree of whiteness, depending on the quality of the cotton, of from 80.0% to 84.0% (measured as in Example 1).
  • EXAMPLE 7 Desized and dried unbleached cotton cloth is impregnated with a solution having the following composition:
  • the material treated with the said solution is squeezed out in a padding machine to 110% liquor retention and treated with a mixture of steam and air at 90 C. for 5 hours in a pad-roll plant. It is then rised twice at 100 C. and once at 60 C. with desalted water, then acidified with an aqueous solution containing 3 to 5 ml./l. of concentrated hydrochloric acid and rinsed again at room temperature.
  • EXAMPLE 8 Desized and dried unbleached cotton cloth is impregnated with a solution having the following composition:
  • the material'treated with the said solution is squeezed out in a padding machine to 90% liquor retention and treated with saturated steam at 110 C. for 4 hours in a cottage steamer. It is then rinsed twice at 100 C. and once at 60 C. with desalted water, then acidified with an aqueous solution containing 3 to 5 ml./l. of concentrated hydrochloric acid and rinsed again at room temperature.
  • EXAMPLE 9 Desized and dried unbleached cotton cloth is impregnated with a solution having the following composition:
  • the material treated with the said solution is squeezed out in a padding machine to liquor retention and treated with saturated steam at C. for 10 minutes in a cottage steamer. It is then rinsed twice at 100 C. and once at 60 C. with desalted water, then acidified with an aqueous solution containing 3 to 5 rnL/l. of concentrated hydrochloric acid and rinsed again at room temperature.
  • EXAMPLE 10 Desized and dried unbleached cotton cloth is treated in a jigger (which can be hermetically sealed) for two hours at a liquor ratio of 1:3 in a liquor having a temperature of C. and the following composition:
  • EXAMPLE 11 Desized and dried unbleached cotton cloth is impregnated with a solution having the following composition:
  • the material treated with the said solution is squeezed out in a padding machine to 100% liquor retention and treated with steam at C. for 1 minute in a cotton steamer. It is then rinsed twice at 100 C. and once at 60 C. with desalted water, then acidified with an aqueous solution containing 3 to 5 ml./l of concentrated hydrochloric acid and rinsed again at room temperature.
  • the aqueous liquor contains (i) 4 to 13% by weight of an alkali metal hydroxide, (ii) 1 to 4% by weight of an alkali compopund selected from the class consisting of a polyphosphate of the formula M P O wherein M represent an alkali metal ion and n denotes one of the integers from 2 to and alkali metal salts of complex-forming aminopolycarboxylic acids of the general formula 110000112 our-00011 Y--CH ja CHzY wherein p represent one of the integers 1 or 2, A represents a radical selected from the group consisting of the formulae and wherein m denotes one of the integers 0, 1 and 2 and Y represents a member selected from the group consisting of carboxy and hydroxymethyl;
  • a wetting agent selected from the group consisting of anion-active and nonionic wetting agents, which are active in alkaline solution.
  • aqueous liquor contains (i) 4 to 13% by weight of an alkali metal hydroxide selected from the group consisting of sodium hydroxide and potassium hydroxide;
  • a wetting agent selected from the group consisting of anion-active and nonionic wetting agents, which are active in alkaline solution.
  • the liquor contains as component (ii) a mixture of (a) alkali metal polyphosphates and (b) complex-forming alkali amino polycarboxylates, the ratio of (a) to (b) by weight between 1:4 to 4:1.
  • concentration c, measured in percent by weight, of the alkali metal hydroxide (i) is so correlated to the treatment temperature t in C. that it is between the limits c and 0 c representing the lower and c the upper concentration limits, both limits inclusive, as defined by the equations c 10-0.1 (t and 1 being a temperature in the range of from to C.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Detergent Compositions (AREA)
  • Paper (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
US511988A 1964-12-10 1965-12-06 Bleaching fibrous material of natural cellulose Expired - Lifetime US3476505A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1964B0079687 DE1273480C2 (de) 1964-12-10 1964-12-10 Verfahren zum bleichen von fasergut aus nativer cellulose
DE1965B0081807 DE1273481C2 (de) 1964-12-10 1965-05-07 Verfahren zum bleichen von fasergut aus nativer cellulose

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US3476505A true US3476505A (en) 1969-11-04

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US511988A Expired - Lifetime US3476505A (en) 1964-12-10 1965-12-06 Bleaching fibrous material of natural cellulose

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US (1) US3476505A (enrdf_load_stackoverflow)
AT (1) AT266760B (enrdf_load_stackoverflow)
BE (1) BE673508A (enrdf_load_stackoverflow)
CH (1) CH467374A (enrdf_load_stackoverflow)
DE (2) DE1273480C2 (enrdf_load_stackoverflow)
DK (1) DK129952B (enrdf_load_stackoverflow)
FI (1) FI42818B (enrdf_load_stackoverflow)
FR (1) FR1459527A (enrdf_load_stackoverflow)
GB (1) GB1073807A (enrdf_load_stackoverflow)
NL (2) NL6515967A (enrdf_load_stackoverflow)
NO (1) NO121441B (enrdf_load_stackoverflow)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3617206A (en) * 1969-08-27 1971-11-02 Monsanto Co Processes for scouring textiles
US3645670A (en) * 1970-03-03 1972-02-29 Monsanto Co Processes for scouring textiles
US4489455A (en) * 1982-10-28 1984-12-25 The Procter & Gamble Company Method for highly efficient laundering of textiles
US4489574A (en) * 1981-11-10 1984-12-25 The Procter & Gamble Company Apparatus for highly efficient laundering of textiles
US4555019A (en) * 1981-11-10 1985-11-26 The Procter & Gamble Company Packaged detergent composition with instructions for use in a laundering process
US5131915A (en) * 1988-01-11 1992-07-21 Arler Corporation/Arler International Method of forming designs on cellulose fabrics: discharge print, a dyed cellulose fabric

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2343816C3 (de) * 1973-08-30 1988-03-24 Chemische Fabrik Tübingen, R.Beitlich, 7400 Tübingen Verfahren zum alkalischen Abkochen von Fasergut aus nativer Cellulose
DE2554360C2 (de) * 1975-12-03 1982-09-30 Degussa Ag, 6000 Frankfurt Verfahren zum Vorbehandeln und Veredeln von Fasergutaus nativer Cellulose

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3617206A (en) * 1969-08-27 1971-11-02 Monsanto Co Processes for scouring textiles
US3645670A (en) * 1970-03-03 1972-02-29 Monsanto Co Processes for scouring textiles
US4489574A (en) * 1981-11-10 1984-12-25 The Procter & Gamble Company Apparatus for highly efficient laundering of textiles
US4555019A (en) * 1981-11-10 1985-11-26 The Procter & Gamble Company Packaged detergent composition with instructions for use in a laundering process
US4489455A (en) * 1982-10-28 1984-12-25 The Procter & Gamble Company Method for highly efficient laundering of textiles
US5131915A (en) * 1988-01-11 1992-07-21 Arler Corporation/Arler International Method of forming designs on cellulose fabrics: discharge print, a dyed cellulose fabric

Also Published As

Publication number Publication date
DE1273480B (de) 1978-04-27
DK129952B (da) 1974-12-02
DE1273481B (de) 1978-02-16
GB1073807A (en) 1967-06-28
NL128428C (enrdf_load_stackoverflow)
NL6515967A (enrdf_load_stackoverflow) 1966-06-13
CH467374A (de) 1969-02-28
CH1648365A4 (enrdf_load_stackoverflow) 1968-09-30
AT266760B (de) 1968-11-25
FI42818B (enrdf_load_stackoverflow) 1970-08-03
FR1459527A (fr) 1966-11-18
DK129952C (enrdf_load_stackoverflow) 1975-05-20
DE1273480C2 (de) 1978-04-27
BE673508A (enrdf_load_stackoverflow) 1966-06-09
DE1273481C2 (de) 1978-02-16
NO121441B (enrdf_load_stackoverflow) 1971-03-01

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