Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3937—Stabilising agents
  • C11D3/394—Organic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3937—Stabilising 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
  • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
  • D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
• • 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
  • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
  • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
  • Y10S516/03—Organic sulfoxy compound containing

Definitions

• the invention relates to alkaline, silicate-containing compositions of a polymeric aminophosphonic or carboxylic acid, a polyhydroxy compound and a magnesium salt and the use of such compositions for bleaching cellulosic fiber materials in the presence of e.g. B. hydrogen peroxide.
• EP-A-0 100 300 discloses a process for the aftertreatment of cellulose-containing fiber materials in a combined bleaching and washing bath, stabilizers being an adduct of aminoalkanediphosphonic acids and epihalohydrins, oligomers of phosphonic acid esters or a reaction product of phosphorous acid and carboxylic acid anhydrides or halides or mixtures thereof are used. These stabilizers have insufficient stability in the strongly alkaline range.
• US Pat. No. 3,860,391 discloses an alkaline, silicate-free, peroxide-containing composition composed of a polymeric aminophosphonic or carboxylic acid, optionally a polyhydroxy compound and optionally a non-ionogenic or anionic dispersant, e.g. B. an alkaryl monosulfonate, which are used for bleaching cellulosic fiber materials.
• the known compositions which optionally contain an alkaryl monosulfonate, have at high pH values of z. B. 13 to 14, however, insufficient storage stability.
• silicates when bleaching cellulosic fiber materials with the known compositions, high ash contents of the bleached materials have to be accepted.
• compositions which always contain an alkyl, aryl or alkaryl disulphonic acid or salts thereof as an anionic dispersant.
• the aminopoly (alkylenephosphonic acid) as component (a) of the composition according to the invention is above all an amino-bis (C, -C 3 -alkylenephosphonic acid), an amino-tris (C, -C 3 -alkylenephosphonic acid), a diamino-tetra (methylenephosphonic acid) or triamino-penta (methylenephosphonic acid), which is derived from a saturated, aliphatic or cycloaliphatic hydrocarbon with 2 to 6 carbon atoms, the alkane-polyphosphonic acid is primarily a hydroxy, amino, C t -C 4 alkylamino or C 1 -C 4 dialkylamino substituted C 1 -C 4 alkane di- or triphosphonic acid and in the alkali metal salt of polyamino carboxylic acid especially about the potassium, especially the sodium salt of a polyaminocarboxylic acid with 1 to 3 nitrogen atoms and 3 to 5 carboxymethyl groups or 1 carboxymethyl group
• Mixtures of the polyphosphonic acids and the alkali metal salts of the polycarboxylic acids of the budding type are also suitable as component (a).
• component (a) several or preferably a single polyphosphonic acid or the alkali metal salt of several or preferably a single polycarboxylic acid are used.
• Polycarboxylic acids in the form of their alkali metal salts are used both alone and in a mixture with polyphosphonic acids, while polyphosphonic acids are preferably used alone.
• the polyphosphonic acids are preferred over the alkali metal salts of the polycarboxylic acids.
• the aminopoly (alkylenephosphonic acids) are preferred over the alkane polyphosphonic acids.
• C 1 -C 3 alkylene radicals in the amino bis and triS (C 1 -C 3 alkylene phosphonic acids) come especially Isopropylene, preferably ethylene and especially methylene.
• polyphosphonic acids such as B. amino-bis (methylenephosphonic acid), especially amino-tris (isopropylene-phosphonic acid), amino-tris (ethylene-phosphonic acid) and in particular amino-tris (methylene-phosphonic acid).
• the aliphatic or cycloaliphatic hydrocarbon with 2 to 6 carbon atoms, from which the diamino-tetra (methylenephosphonic acids) and triamino-penta (methylenephosphonic acids) are derived, is primarily cyclobutane, cyclopentane, cyclohexane and in particular propane and ethane.
• cyclobutane primarily cyclopentane, cyclohexane and in particular propane and ethane.
• Preferred alkane di- or tri-phosphonic acids have an n-propane or ethane residue which is substituted by amino or especially hydroxy.
• polyphosphonic acids of this type for. B. 1-hydroxypropane-1,1,3-triphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, especially 1-hydroxyethane-1,1,2-triphosphonic acid and especially 1-hydroxyethane-1,1-diphosphonic acid.
• Preferred polyaminocarboxylic acids have 1 to 3, especially 2 or 3 nitrogen atoms and 4 or 5 carboxymethyl groups and are optionally substituted by a hydroxyethyl or hydroxyl group. Unsubstituted polyaminocarboxylic acids are preferred. As specific representatives of such polyaminocarboxylic acids such. B.
• Component (a) acts as a complexing agent for alkaline earth metals and heavy metals when using the composition according to the invention in aqueous liquors which contain a per-compound, e.g. B. contain hydrogen peroxide, during pretreatment, especially bleaching cellulosic fiber materials.
• component (a) in the bleaching liquor suppresses the decomposition of the per-compound by free, i.e. heavy metals which are not present as a complex and which may be present in process water.
• Component (a) is preferably used as 35 to 70, in particular 40 to 60 percent by weight aqueous solution in the composition according to the invention.
• polymeric aminophosphonic or carboxylic acids are used as component (a), they are hydrolyzed in the aqueous composition according to the invention in the presence of an alkali metal hydroxide, both during storage and when used in bleaching liquors, at least in part to give the corresponding monomers.
• Component (b) acts as a complexing agent when the composition according to the invention is used in bleaching liquors for pretreating cellulosic fiber materials. This effect is also guaranteed in bleaching liquors with pH values above 11.
• Component (b) is generally used as a solid substance.
• the alkali metal silicates as component (c) are generally water-soluble. Above all, sodium water glass comes into consideration, which as a commercial product has a preferred SiO 2 content of about 24 to 28 percent by weight. In particular, commercially available, aqueous, about 30 to 40 percent by weight solutions of sodium water glass are used as component (c).
• Component (c) enables longer treatment times in bleaching liquors for the pretreatment of cellulose-containing fiber materials.
• Potassium hydroxide or, in particular, the less expensive sodium hydroxide are particularly suitable as alkali metal hydroxide for component (d).
• Mixtures of potassium hydroxide and sodium hydroxide are particularly suitable with regard to the homogeneity of the composition to be used as component (d).
• Component (d) is preferably used in the undiluted state and in amounts of not less than 9%, based on the total weight of the composition. Accordingly, solid caustic potash, especially solid caustic soda and very particularly a mixture of solid caustic potash and solid caustic soda, is of primary interest for component (d), the weight ratio (caustic soda): (caustic alkali) generally 1: 0.01 to 1 : 2, especially 1: 0.05 to 1: 0.25.
• the addition of component (d) gives strongly alkaline compositions which have a pH of > 14. The alkalinity of the compositions when higher amounts of component (d) are added is determined by the concentration of alkali hydroxide.
• component (s), z. B. the acetate, especially the sulfate or its heptahydrate and especially the chloride or its hexahydrate.
• Component (e) is generally used as a solid, with solid magnesium chloride hexahydrate being of primary interest.
• Component (e) forms a water-soluble magnesium complex with component (a), which acts as a bleach stabilizer.
• the presence of the magnesium complex from components (a) and (e) causes it to persist over a longer period of time or at least to a reduced decrease in the original per-compound content, e.g. B. of hydrogen peroxide in the bleaching liquors which contain the composition according to the invention.
• Suitable anionic dispersants for component (f) are, in particular, the potassium or, in particular, sodium salts of an alkyl disulfonic acid, aryl disulfonic acid or alkaryl disulfonic acid, which in the undiluted state, for. B. as a powder or paste or as an aqueous, at least 40 percent by weight, preferably 40 to 95 percent by weight solution.
• the alkyl radical of the alkyl disulfonic acid generally has 8 to 20 carbon atoms.
• An example is the disodium salt of pentadecane-1,8-disulfonic acid, in the form of an aqueous 40 to 60 percent by weight solution.
• Aryl disulfonic acid is primarily a derivative of naphthalene monosulfonic acid, which is preferably present as a reaction product with formaldehyde, 2 or 3 moles of naphthalenesulfonic acid being generally used per 1 or 2 moles of formaldehyde.
• the u.a. Suitable alkaryl disulfonic acids have straight-chain or branched alkyl chains with at least 4, preferably 4 to 22, in particular 4 to 18 carbon atoms.
• alkaryl disulfonic acids are e.g. B. dodecylbenzene disulfonic acids or 3,7-diisobutytnaphthatinedisu) fonic acids or especially disulfonated benzyl-alkyl-benzimidazoles, which preferably have 8 to 22 carbon atoms in the alkyl radical.
• the focus of interest is e.g. B. a 1-benzyl-2-heptadecylbenzimidazole disulfonic acid disodium salt, which is mainly used in powder form.
• the preparation of the composition according to the invention is generally carried out by adding half the total amount of component (d) to an aqueous solution (A) of components (c) and (f), then adding an aqueous solution to solution (A) Solution (B), which contains components (a), (b) and (e) and finally the mixture of solutions (A) and (B) with the remaining amount of component (d).
• the aminopoly (alkylenephosphonic acids) and alkane polyphosphonic acids as component (a) of solution (B) by the remaining amount of component (d) in the corresponding alkali metal salts, for. B. the potassium or in particular sodium salts.
• the procedure is preferably such that mixing solution (A) with the first half of component (d) and then with solution (B) and finally with the second half of component (d ) at a temperature of at most 80 ° C, preferably 60 to 70 ° C.
• the procedure described has the essential advantage that the addition of component (d) in two portions does not result in any undesired precipitation during the production process.
• the solution (A) from components (c) and (f) and solution (B) from components (a), (b) and (e), which are generally in the form of aqueous solutions can be used thanks to their excellent properties Storage stability kept in stock and processed at any time by adding component (d) in the manner described to the compositions according to the invention.
• the aqueous bleaching liquors mentioned at the outset for carrying out the application process in which the composition according to the invention is used contain, for example, B. alkali metal peroxydisulfates or especially alkali metal peroxysulfates, with potassium and in particular sodium peroxodisulfate being preferred.
• sodium peroxosulfate Na 2 S 2 0 8
• the per compound is hydrogen peroxide (H 2 0 2 ) in the foreground of interest, which is generally used as a concentrated, approximately 30 to 60 percent by weight solution because of its higher stability.
• the bleaching liquors optionally contain wetting agents or detergents, defoaming or deaerating agents and / or optical brighteners.
• wetting agents or detergents are generally used as an optional component of the bleaching liquors, provided that the cellulose in the cellulose-containing fiber material to be treated is in the raw state, or in particular consists of raw cotton.
• Anionic or nonionic surfactants are suitable as wetting agents or detergents.
• Preferred anionic surfactants are e.g. B. alkaryl monosulfonates, fatty acid condensation products, protein cleavage products or their salts and especially alkyl monosulfate salts and alkylbenzene monosulfonic acids with 12 to 22 carbon atoms in the alkyl radical.
• Preferred non-ionic surfactants are e.g. B.
• adducts of alkylene oxides especially propylene and especially ethylene oxide and alkylphenols with z.
• Silicone surfactants or silicone oils are suitable as further components in these mixtures.
• Defoamers or deaerators are required as optional components of the bleaching liquor, but in the presence of a wetting agent or detergent in the bleaching liquor. This is e.g. B. to higher alcohols, especially isooctanol, but above all defoaming and / or deaerating agents based on silicone, in particular silicone oil emulsions.
• optical brighteners used as an optional component of the bleaching liquors to achieve a particularly high degree of whiteness of the treating materials generally belong to the styryl and stilbene series, such as, for. B. distyrylarylenes, diaminostilbenes, ditriazolylstilbenes, phenylbenzoxazolylstilbenes, stilbene naphthotriazoles and dibenzoxazolylstilbenes.
• Optical brighteners of the distyrylbiphenyl or bistriazinylaminostilbene type which contain sulfonic acid groups, e.g. B.
• sulfonated distyrylbiphenyl and bistriazinyl derivatives especially those present as alkali metal salts, especially as potassium or preferably as sodium salts, bis (phenylamino-morpholino-s-triazinyl) -stilbene-disulfonic acids.
• alkali metal salts especially as potassium or preferably as sodium salts
• bis (phenylamino-morpholino-s-triazinyl) -stilbene-disulfonic acids are preferably used as commercially available aqueous, about 20 to 30 percent by weight liquid formulations, if appropriate.
• the application process for bleaching cellulose-containing fiber materials using the compositions according to the invention is generally carried out in such a way that the bleaching liquor is first applied to the fiber material, as a rule, for. B. by immersion, padding and preferably by padding at z. B. 10 to 60 ° C, but preferably at room temperature (15 to 25 ° C), the liquor pickup after squeezing is about 50 to 120, preferably 90 to 110 weight percent.
• the fiber material is usually subjected to a so-called wet storage or wet storage process without drying while still wet, in which the rolled-up material is optionally packed airtight in a plastic film and optionally under pressure at a maximum of 150 ° C for about 10 Minutes, but preferably under normal pressure at 80 to 98 ° C for about 1 to 5 hours or in particular at room temperature (15 to 25 ° C) for about 10 to 30 hours.
• the treatment of the fiber materials can also in so-called long liquors (exhaust process) with a liquor ratio of z. B. 1: 3 to 1: 100, preferably 1: 8 to 1:25 at 20 to 100, preferably 80 to 98 ° C for about 1/4 to 3 hours under normal conditions, i.e. under atmospheric pressure in conventional equipment, e.g. B. a jigger or a reel run. If necessary, however, it is also possible to pull out to 150.degree. C., preferably 105 to 140.degree. C., under pressure in so-called high-temperature equipment (HT equipment).
• HT equipment high-temperature equipment
• Treatment temperatures of 98 ° C are advantageously not exceeded in order to prevent any fiber damage.
• the fiber materials can also be used in industrial continuous processes under pressure up to z. B. 2.5 bar at higher temperatures z. B. up to 150 ° C, are treated, if excluded.
• the fiber materials are usually rinsed thoroughly with hot water at about 90 to 98 ° C and then with warm and finally with cold water, if necessary with z. B. neutralized acetic acid and then preferably dehydrated and dried at elevated temperatures (z. B. to 150 ° C).
• the cellulosic material to be treated can be in a wide variety of processing stages, e.g. B. as loose material, yarn, fabric or knitted fabric. As a rule, these are always textile fiber materials which are produced from pure textile cellulose fibers or from mixtures of textile cellulose fibers with textile synthetic fibers.
• cellulosic fibers come e.g. B. those made of regenerated cellulose, such as. B. cellulose and viscose, such as native cellulose, such as. B. hemp, linen, jute and especially cotton and synthetic fibers such as those made of polyacrylonitrile and especially polyester and polyamide.
• Fabrics made of cotton or regenerated cellulose or blended fabrics made of cotton and polyester and made of cotton and polyamide are particularly well suited for being treated according to the invention, with cotton fabrics and knitted fabrics being of primary interest.
• Surfactants prewashed materials are also suitable. It is also possible to bleach sized cotton fibers, bleaching after or before desizing.
• the fiber materials treated using the composition according to the invention are notable for their shell freedom, their good rewettability, their low ash content and, above all, their high degree of whiteness.
• component (c) silicates, especially water glass
• the compositions according to the invention when used, cause little or no incrustation of the bleaching apparatus and incrustations on the treated fiber material.
• compositions according to the invention are their particularly high storage stability over several months.
• the composition After 2 months of storage at room temperature, the composition is homogeneous.
• the treated fabric is peel-free and has excellent rewettability.
• the increase in whiteness of the bleached fabric in comparison with the raw fabric before bleaching is assessed using the CIBA-GEIGY white scale (cf. R. Griesser, "Tenside Detergents", Volume 12, No. 2, pages 93 to 100 (1975)). You get -45 as the value of the raw fabric compared to +62 as the value of the bleached fabric.
• the DP degree of the bleached is only insignificantly reduced compared to the DP degree of the unbleached fabric. After the treatment, the residual peroxide content is still 41%. This bleaching liquor can be used for further bleaching processes; it usually becomes unusable when the concentration of hydrogen peroxide has dropped below about 20%.
• the impregnated fabric is then steamed at 100 ° C. for 5 minutes and then washed, hot and cold, neutralized and dried for 1 minute each.
• the bleaching process increases the whiteness of the treated blended fabric from 0 to 55 CIBA-GEIGY whiteness units.
• the hydrogen peroxide content of the steamed fabric after treatment is still 58% of the original value.
• the bleached fabric has practically not been damaged by the bleaching process: the DP level is 2760 before bleaching and 2690 after bleaching.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Inorganic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Textile Engineering (AREA)
• Detergent Compositions (AREA)

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• 1986
  • 1986-07-10 US US06/884,253 patent/US4725281A/en not_active Expired - Fee Related
  • 1986-07-14 DE DE8686810312T patent/DE3665201D1/de not_active Expired
  • 1986-07-14 EP EP86810312A patent/EP0210952B1/de not_active Expired
  • 1986-07-18 ZA ZA865369A patent/ZA865369B/xx unknown
  • 1986-07-19 JP JP61169071A patent/JPS6268900A/ja active Granted

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