EP2992075B1 - Kammpolymere als waschkraftverstärker für waschmittel - Google Patents

Kammpolymere als waschkraftverstärker für waschmittel Download PDF

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Publication number
EP2992075B1
EP2992075B1 EP14718618.3A EP14718618A EP2992075B1 EP 2992075 B1 EP2992075 B1 EP 2992075B1 EP 14718618 A EP14718618 A EP 14718618A EP 2992075 B1 EP2992075 B1 EP 2992075B1
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EP
European Patent Office
Prior art keywords
acids
monoethylenically unsaturated
acid
textile
comb polymers
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.)
Active
Application number
EP14718618.3A
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German (de)
English (en)
French (fr)
Other versions
EP2992075A1 (de
Inventor
Bernd Horrer
Heike Witzel-Wilhelm
Andrea Fischer-Sturm
Michael Hees
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.)
CHT Germany GmbH
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CHT R Beitlich GmbH
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Publication date
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Publication of EP2992075A1 publication Critical patent/EP2992075A1/de
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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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • 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

Definitions

  • the present invention relates to the use of comb polymers in textile pretreatment, in particular in textile finishing and corresponding agents.
  • the comb polymers used according to the invention are obtainable by A) a free-radical polymerization of monoethylenically unsaturated monomers a group A1) monoethylenically unsaturated acids and their salts and a group A2) monoethylenically unsaturated polyethers.
  • Detergents and cleaners contain surfactants as indispensable ingredients for the washing and cleaning process.
  • the surfactants as a main component influence primarily the result of the To assist the washing performance, a variety of laundry aids, such as builders to mask the water hardness, graying and color transfer inhibitors, foam regulators, bleaching agents and bleach activators in household washing and cleaning agents are already used today.
  • Such excipients also include substances which enhance the detergency of the surfactants. Such substances are often referred to as "soil-release" agents or detergency boosters. As a rule, such substances themselves have no pronounced surfactant properties.
  • Hydrophobic polymers consisting of styrene, methacrylic acid, hydroxyethyl methacrylate and methyl methacrylate are known, which show a very good dirt-removing effect especially on cotton-containing textiles.
  • the EP 2 065 403 A1 discloses the preparation of polymers via esterification of polyacrylic acids with end-capped polyols or amines.
  • a potential application as Builder component for hardness masking in liquid household detergents called.
  • JPH03185184 such as JP 2005 187 742
  • Detergents for textile pretreatment such as desizing, scouring, bleaching and soaps are disclosed which contain methoxy-PEG-methacrylate / (meth) acrylic acid copolymers.
  • US 2005/0113541 discloses polymers as a builder substance in detergents containing acrylic acid, methacrylic acid, acrylic acid PEG esters and polyamine polyethers.
  • sulfonic acid-containing copolymers consist of at least one monoethylenically unsaturated carboxylic acid, at least one monomer containing sulfonic acid groups and at least one nonionic monomer are formed and should be used as an additive to detergents and cleaners.
  • the process conditions in the textile pretreatment of natural or synthetic fibers or mixtures thereof are fundamentally different from the conditions of household laundry.
  • textile finishing processes in the strongly acidic range such as the “acid demineralization” at a pH of about 2
  • strongly alkaline processes such as "alkaline boiling", “cold bleaching” and “pad-steam bleaching” at pH Values from 13 to 14 are performed.
  • the treatment temperatures in the textile pretreatment also differ significantly from those which are usual in household washing.
  • the majority of the finishing processes are carried out at approx. 95 to 100 ° C. In some countries, high-temperature bleaching at 110 ° C is favored.
  • the types of dirt are also fundamentally different from the types of household waste.
  • the natural In textile pretreatment, the natural must Adjacent substances such as fats, waxes and the preparations used for the production of the synthetic fibers or textile fabrics, such as knitting oils and sizes, are removed.
  • the object of the present invention is to overcome the disadvantages described above with regard to insufficient effectiveness for the textile pretreatment of natural or synthetic fibers or mixtures thereof. It is intended to provide polymers which effectively support surfactants and thereby enable a reduced amount of surfactants to be used for optimum washing and cleaning performance.
  • the alkaline bleaching processes are carried out at pH values between 10 and 14 and temperatures between 80 and 130 ° C.
  • the cleaning performance is checked after the bleaching process by a good and uniform hydrophilicity (absorbency) of the cotton.
  • the invention is therefore based, in particular, on the problem of providing polymers having an excellent washing-power-enhancing effect under these conditions.
  • Another object is for the washing of elastane-containing materials (mesh or woven fabric) a polymer which effectively removes the silicone oil used for production and stably emulsifies in the washing solution.
  • the comb polymers used according to the invention thus contain the components A1 + A2 in the first embodiment.
  • the monoethylenically unsaturated acids and their salts include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, Vinylphosphonic.
  • the monomers of group A1 can be used individually or as a mixture of different monomers in an amount of 5 to 95 wt .-%, in particular with an amount of 10 to 90 wt .-% based on the polymer. Preference is given to acrylic acid, methacrylic acid and maleic acid and particular preference is given to acrylic acid or methacrylic acid.
  • the monoethylenically unsaturated polyethers include polyethylene glycol monoallyl ether, polypropylene glycol monoallyl ether and polyethylene-polypropylene monoallyl ether; these are commercially available, for example, from Clariant under the Polyglykol® A product line and from BASF under the Pluriol® A ... R product line. Further examples include polyethylene glycol monovinyl ether (product series from Clariant: Polyglycol® R), isoprenyl ethoxylates (product series from BASF: Pluriol® A ... I) and vinyloxybutyl ethoxylates (product series from BASF: Pluriol® A ... V).
  • the monomers of group A2 can be used individually or as a mixture of different monomers in an amount of from 2 to 25% by weight, based on the polymer, in particular in an amount of from 5 to 20% by weight, based on the polymer.
  • Polyalkyl glycol monoallyl ethers are preferred, and polyethylene glycol monoallyl ether and polyethylene-polypropylene monoallyl ether are particularly preferred.
  • the use according to the invention can be carried out as part of a washing, decoction, enzyme, desizing, demineralization or bleaching process in a continuous or discontinuous production process such that the comb polymer is added separately to a detergent-containing liquor, or the comb polymer as a constituent of the detergent in bring in the fleet.
  • Another object of the invention is therefore a detergent for the textile pretreatment of natural or synthetic fibers or mixtures thereof, which contains 0.1 to 20 wt .-%, in particular 0.5 to 15 wt .-%, of a corresponding comb polymer.
  • Detergents containing the comb polymer used in the invention may contain all the usual ingredients of such agents which do not undesirably interact with it.
  • such a detergent contains surfactants, such as fatty alcohol alkoxylates, fatty acid alkoxylates, fatty alkyl polyglycosides, fatty amine alkoxylates and / or fatty acid amides from the field of nonionic surfactants.
  • surfactants such as fatty alcohol alkoxylates, fatty acid alkoxylates, fatty alkyl polyglycosides, fatty amine alkoxylates and / or fatty acid amides from the field of nonionic surfactants.
  • anionic surfactants it is possible to use alkylcarboxylates, alkyl ether carboxylates, alkane sulfates, alkane ether sulfates, alkane sulfonates, alkyl phosphates, alkyl ether phosphates, taurides and / or sarcosides.
  • Table 1 comb polymer Monoethylenically unsaturated polyethers Quantity [g] Monoethylenically unsaturated acid Quantity [g] KP-1 Polyglycol® A 31/1000 61 acrylic acid 365 KP-2 Polyglycol® A 11/1800 61 acrylic acid 365 KP-3 Pluriol® A 10 R 61 acrylic acid 365 KP-4 Polyglycol® A 1100 61 acrylic acid 365
  • the content of residual monomer for the side chains was determined semiquantitatively by thin-layer chromatography.
  • the residual monomer results were always below 0.5% by weight in the polymer solution.
  • a raw cotton jersey knit fabric with a base white of 17 Berger units was bleached in a Labomat from Mathis for 30 minutes at 98 ° C.
  • the liquor ratio was 1:10 and the water used had a set water hardness of 5 ° dH, adjusted with CaCl 2 ⁇ 2 H 2 O.
  • the heating or cooling gradient was 3 ° C / min.
  • the product was rinsed for 10 min at 80 ° C, then neutralized with 0.5 g / L acetic acid 60% for 10 min at 30 ° C and rinsed once more for 10 min at 30 ° C.
  • the product was spun for 30 seconds and dried for 30 seconds at a surface temperature of 120 ° C in the tenter.
  • the bleaching formulations are shown in Table 4.1 and the associated whiteness and absorbency results for the product in Table 4.2.
  • the absorbency also referred to as hydrophilicity
  • the product is dependent on the cleaning performance of the detergent used. It is tested using the TEGEWA Drip Test, which measures the amount of time a stained drop of water needs to sink into the fabric. The exact description is in the Journal Melliand Textilberichte 68 (1987), pages 581-583 released. A better differentiating method is the determination of absorbency according to the riser method according to DIN 53924.
  • the surfactants used were Lutensol® AO 5 and Lutensol® AO 7 from BASF, C 13/15 fatty alcohol ethoxylates with 5 or 7 mol of ethylene oxide.
  • the comb polymers were used as polymer solutions with a solids content of 46% by weight.
  • As comparison polymer V-1 was Sokalan® PA 25 CL PN from BASF, an acrylic acid homopolymer having an average molecular weight of 4,000 g / mol and a solids content of 49% by weight and Comparative Polymer V-2 was Alcosperse® 747 from Akzo Nobel, a hydrophobically modified copolymer having an average molecular weight of 3,000 g / mol and a solids content of 40 wt .-% used.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (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)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polyethers (AREA)
EP14718618.3A 2013-04-29 2014-04-22 Kammpolymere als waschkraftverstärker für waschmittel Active EP2992075B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013207778.5A DE102013207778A1 (de) 2013-04-29 2013-04-29 Kammpolymere als Waschkraftverstärker für Wasch- und Reinigungsmittel
PCT/EP2014/058131 WO2014177423A1 (de) 2013-04-29 2014-04-22 Kammpolymere als waschkraftverstärker für wasch- und reinigungsmittel

Publications (2)

Publication Number Publication Date
EP2992075A1 EP2992075A1 (de) 2016-03-09
EP2992075B1 true EP2992075B1 (de) 2018-10-31

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP14718618.3A Active EP2992075B1 (de) 2013-04-29 2014-04-22 Kammpolymere als waschkraftverstärker für waschmittel

Country Status (8)

Country Link
EP (1) EP2992075B1 (pt)
CN (1) CN105102604B (pt)
BR (1) BR112015027088B1 (pt)
DE (1) DE102013207778A1 (pt)
ES (1) ES2707956T3 (pt)
MX (1) MX2015015006A (pt)
TR (1) TR201816403T4 (pt)
WO (1) WO2014177423A1 (pt)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102017200430A1 (de) * 2017-01-12 2018-07-12 CHT Germany GmbH Ablagerungsverhinderung in der Zellstoff-Herstellung nach dem Sulfatverfahren (Kraft-Aufschluss)
CN112708068B (zh) * 2020-12-21 2022-08-09 杭州有氧品牌管理有限公司 一种水溶性梳状聚合物超分子体系及其应用

Family Cites Families (17)

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Publication number Priority date Publication date Assignee Title
DE69015424T2 (de) * 1989-04-28 1995-08-17 Nippon Catalytic Chem Ind Verfahren zur Herstellung und Verwendung von Salzen von Polymeren der Maleinsäure mit verbesserter Biodegradabilität.
FR2651888B1 (fr) * 1989-09-14 1993-10-22 Superba Sa Procede et appareil pour caracteriser et mesurer la qualite de rubans et de meches de fibres textiles.
JP2901294B2 (ja) * 1989-12-12 1999-06-07 日華化学株式会社 繊維製品用洗浄性向上剤
EP0537870A1 (en) 1991-10-18 1993-04-21 W.R. Grace & Co.-Conn. Copolymers of ethylenically unsaturated ethers useful as hydraulic cement superplasticizers
US6180589B1 (en) 1999-01-05 2001-01-30 National Starch And Chemical Investment Holding Corporation Polyether hydroxycarboxylate copolymers
DE19906367A1 (de) * 1999-02-16 2000-08-17 Clariant Gmbh Verwendung von Kammpolymeren als Schutzablösepolymere
GB0130499D0 (en) 2001-12-20 2002-02-06 Unilever Plc Polymers for laundry cleaning compositions
DE10225794A1 (de) * 2002-06-10 2003-12-18 Basf Ag Verwendung von sulfonsäuregruppenhaltigen Copolymeren als Zusatz in Wasch- und Reinigungsmitteln
DE10323180A1 (de) * 2003-05-22 2004-12-09 Basf Ag Mischung, umfassend ein Tensid und ein Cotensid
TW200517406A (en) * 2003-10-29 2005-06-01 Nippon Catalytic Chem Ind Polymer, process for preparing the same, and use of the same
JP4489422B2 (ja) * 2003-12-26 2010-06-23 花王株式会社 液体洗浄剤組成物
DE102005026544A1 (de) 2005-06-08 2006-12-14 Henkel Kgaa Verstärkung der Reinigungsleistung von Waschmitteln durch Polymer
FR2900930B1 (fr) * 2006-05-12 2008-08-08 Coatex Sas Procede de fabrication de polymeres peigne par sechage puis fonctionnalisation de la chaine principale (meth)acrylique, polymeres obtenus et leurs utilisations
JP4975714B2 (ja) * 2007-11-28 2012-07-11 ローム アンド ハース カンパニー ポリマーの製造法
DE102009020299A1 (de) 2009-05-07 2010-11-11 Clariant International Ltd. Kammpolymere und deren Verwendung in Wasch- und Reinigungsmitteln
DE102011112777A1 (de) 2011-09-09 2013-03-14 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Die Primärwaschkraft verbessernde polymere Wirkstoffe
DE102011112778A1 (de) 2011-09-09 2013-03-14 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Die Primärwaschkraft verbessernde polymere Wirkstoffe

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Also Published As

Publication number Publication date
BR112015027088A2 (pt) 2017-07-25
TR201816403T4 (tr) 2018-11-21
CN105102604A (zh) 2015-11-25
CN105102604B (zh) 2018-08-07
BR112015027088B1 (pt) 2021-09-21
ES2707956T3 (es) 2019-04-08
DE102013207778A1 (de) 2014-10-30
WO2014177423A1 (de) 2014-11-06
EP2992075A1 (de) 2016-03-09
MX2015015006A (es) 2016-03-09

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