EP0969080B1 - Flüssige Reinigungsmittel - Google Patents

Flüssige Reinigungsmittel Download PDF

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Publication number
EP0969080B1
EP0969080B1 EP99112847A EP99112847A EP0969080B1 EP 0969080 B1 EP0969080 B1 EP 0969080B1 EP 99112847 A EP99112847 A EP 99112847A EP 99112847 A EP99112847 A EP 99112847A EP 0969080 B1 EP0969080 B1 EP 0969080B1
Authority
EP
European Patent Office
Prior art keywords
acid
liquid detergent
detergent composition
surfactant
salt
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 - Lifetime
Application number
EP99112847A
Other languages
English (en)
French (fr)
Other versions
EP0969080A1 (de
Inventor
Makoto c/oKAWASAKI WORKS SHOWA DENKO K.K. Saito
Tohru KAWASAKI WORKS SHOWA DENKO K.K. Yamamoto
Nobuyoshi c/oYOKKAICHI WORKS Nambu
Masanori c/oYOKKAICHI WORKS Furukawa
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.)
Resonac Holdings Corp
Original Assignee
Showa Denko KK
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 Showa Denko KK filed Critical Showa Denko KK
Publication of EP0969080A1 publication Critical patent/EP0969080A1/de
Application granted granted Critical
Publication of EP0969080B1 publication Critical patent/EP0969080B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D3/43—Solvents

Definitions

  • the present invention relates to a liquid detergent composition comprising a surfactant and an aminopolycarboxylic acid-based organic builder. More specifically, the present invention relates to a high concentration liquid detergent composition having excellent compatibility with a surfactant, superior resistance against white turbidity and good biodegradability.
  • liquid detergents particularly in liquid detergents used as a household detergent, a nonionic surfactant and/or an anionic surfactant are used as the surfactant and a builder of various types is added to increase detergency.
  • a builder of various types is added to increase detergency.
  • organic or inorganic builders can be used but almost all builders have a Na salt structure
  • US-A-3 914 185 discloses clear, liquid, heavy-duty detergents based on mixed surfactant systems with nitrilotriacetic acid salt builders, which can be prepared in the absence of heat, without gel formation.
  • JP-A-10-36888 discloses a liquid detergent comprising an aminopolycarboxylic acid builder, where an amine salt is disclosed on the same level with an alkali metal salt and in Examples, a Na salt is used. Moreover, the maximum concentration of the surfactant in this composition is as low as 10 wt%, thus, the problem of white turbidity on the high concentration side is not solved.
  • the use of a builder has a problem in that the solubility or clouding point of the surfactant as the main agent decreases and thereby the compatibility is deteriorated to cause, for example, white turbidity or separation of the white turbidity into two layers with the elapse of time.
  • a technique of diluting the liquid detergent composition with water to reduce the concentration of the surfactant or a technique of adding a solubilizing agent has been heretofore used.
  • the former case of diluting the liquid detergent composition with water inevitably results in an increase in the cost of transporting the detergent and this is commercially disadvantageous.
  • the effect is not sufficiently high for obtaining a high concentration liquid detergent composition.
  • An object of the present invention is to obtain a liquid detergent which has excellent biodegradability, which does not assume strong alkalinity, which has excellent compatibility even if the surfactant concentration is increased, and which is free of white turbidity.
  • the present inventors have found that when a nonionic surfactant and/or anionic surfactant is used at a high concentration as the main surfactant of a liquid detergent and an aminopolycarboxylic acid chelating agent is used as a builder, by using an amine salt or an alkali metal-amine mixed salt as the counter ion of the builder and at the same time, adding an alcohol thereto, the compatibility is increased and the white turbidity can be prevented.
  • the present invention has been accomplished based on this finding.
  • the present invention relates to the liquid detergent composition described below.
  • the invention provides a liquid detergent composition comprising:
  • the invention provides a liquid detergent composition comprising:
  • a further embodiment comprises a liquid detergent composition as described in (1) or (2), wherein the aminopolycarboxylic acid is an amino acid-N,N-diacetic acid.
  • An even further embodiment is a liquid detergent composition as described in (1) or (2), wherein the aminopolycarboxylic acid is glutamic acid-N,N-diacetic acid, ⁇ -alanine-N,N-diacetic acid, ⁇ -alanine-N,N-diacetic acid, aspartic acid-N,N-diacetic acid, glycine-N,N-diacetic acid or serine-N,N-diacetic acid.
  • the aminopolycarboxylic acid is glutamic acid-N,N-diacetic acid, ⁇ -alanine-N,N-diacetic acid, ⁇ -alanine-N,N-diacetic acid, aspartic acid-N,N-diacetic acid, glycine-N,N-diacetic acid or serine-N,N-diacetic acid.
  • another embodiment is a liquid detergent composition as described in any one of (1) to (4), wherein the alcohol is a glycol.
  • the surfactant used as component (A) in the present invention is one or more selected from a nonionic surfactant and an anionic surfactant.
  • a nonionic surfactant has a higher solubility than an anionic surfactant, accordingly, it is suitable for preparing a high concentration liquid detergent composition.
  • the surfactant is used at a concentration of 20 wt% or more in the liquid detergent composition.
  • nonionic surfactants examples include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, fatty acid diethanolamide, amine oxide and amidoamine oxide.
  • suitable anionic surfactants include alkyl sulfate, alkylpolyoxyethylene sulfate, alkylbenzenesulfonate, ⁇ -olefinsulfonate, fatty acid salts, ether carboxylates and monoalkylphosphates. A number of these may be commercially available.
  • the aminopdycarboxylic acid-based chelating agent used in the builder as component (B) of the present invention is a chelating agent containing one or more, preferably one or two amino groups and two or more, preferably three or four carboxyl groups, and having a chelating action.
  • the amino group may be a secondary amino group or a tertiary amino group.
  • the chelating agent is preferably an amino acid-N,N-diacetic acid.
  • An amino acid-N,N-diacetic acid is a compound represented by the following formula (1) A-N-(CH 2 COOH) 2 wherein A-NH 2 represents an amino acid, and -N represents an amino group in the amino acid.
  • amino acid-N,N-diacetic acids examples include glutamic acid-N,N-diacetic acid, ⁇ -alanine-N,N-diacetic acid, ⁇ -alanine-N,N-diacetic acid, aspartic acid-N,N-diacetic acid, glycine-N,N-diacetic acid and serine-N,N-diacetic acid.
  • amino acid-N,N-diacetic acids may be synthesized by the known Strecker reaction using, for example, an amino acid as the raw material or may be synthesized from a monochloroacetic acid.
  • aminopolycarboxylic acid chelating agents include ethylenediaminedisuccinic acid and iminodisuccinic acid. These may also be synthesized by a known method and used. Examples of preferred aminopolycarboxylic acid chelating agents are shown below by their structural formulae.
  • amino acid-N,N-diacetic acids and other aminopolycarboxylic acid-based chelating agents are generally obtained as an aqueous solution where all carboxyl groups have a Na salt as the counter ion.
  • the aminopolycarboxylic acid for use in the builder as component (B) is used in the form of an amine salt or an alkali metal-amine mixed salt.
  • the amine salt used is preferably an alkanolamine salt, more preferably triethanolamine salt or diethanolamine salt.
  • the alkali metal salt in the alkali metal-amine mixed salt is preferably a K salt because it has a higher compatibility with the surfactant than an Na salt, however, in view of the cost, a Na salt is more preferred.
  • the Na salt aqueous solution obtained may be treated to remove Na using an H-type cation exchange resin or by electrodialysis, or may be subjected to acid deposition to obtain a crystal having an H type carboxyl group. Thereafter, the resulting solution as it is or in the case of a crystal, a solution obtained by dissolving the crystals in water, is mixed with a mixture of an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide with an amine and thereby an aqueous solution of the objective salt can be obtained. Also, after the removal of Na, the solution or crystal may be added to the formulation of a liquid detergent and then an amine or another alkali metal hydroxide may be added thereto so as to obtain the objective salt.
  • an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide
  • an aminopolycarboxylic acid-based chelating agent particularly the aminodiacetic acid-type chelating agent is known to exert a good chelate effect namely a builder effect, on the neutral to weakly alkali side at a pH of from 8 to 12. Therefore, the amount of the amine or alkali metal hydroxide added is preferably controlled so that the above-described pH region can be created.
  • the alcohol used as the solubilizing agent in the present invention is not particularly limited. However, a primary, secondary or tertiary alcohol, preferably a primary or secondary alcohol, having from 1 to 5 carbon atoms, preferably from 2 to 4 carbon atoms is preferred.
  • the alcohol may be a general alcohol such as ethanol and isopropyl alcohol, however, since these are volatile and highly inflammable, a commonly used and inexpensive glycol such as propylene glycol and ethylene glycol is preferably used.
  • the liquid detergent composition of the present invention preferably has a composition ratio such that the surfactant as component (A) is from 20 to 60 wt%, preferably from 30 to 50 wt%, the builder as component (B) is from 0.1 to 15 wt%, preferably from 1 to 10 wt%, the solubilizing agent as component (C) is from 0.5 to 30 wt%, preferably from 1 to 20 wt%, and the balance is water as component (D).
  • This composition ratio is the proportion among four components (A) to (D).
  • the ratio of builder as component (B) based on the surfactant as component (A) is preferably from 2 to 20 wt%, more preferably from 5 to 15 wt%, and the solubilizing agent as component (C) based on the surfactant as component (A) is preferably from 5 to 40 wt%, more preferably from 10 to 30 wt%.
  • the ratio of the surfactant as component (A) is less than the above-described range, the cost for transportation or packaging of the liquid detergent increases and this is commercially disadvantageous. If it exceeds the range, the desired compatibility can be attained only within narrow limits. As a result, flexibility in the formulation may decrease or the viscosity may increase and the handleability is disadvantageously impaired.
  • the ratio of the builder as component (B) is less than the above-described range, the cleaning effect of the liquid detergent composition decreases, whereas if it exceeds the range, the compatibility with the surfactant occurs only within narrow limits and flexibility in formulation disadvantageously decreases.
  • the liquid detergent composition of the present invention may contain, if desired, other additives in any optional ratio, such as a viscosity controlling agent, a moisture retaining agent, an antiseptic, an antifungal agent, a dye and perfume.
  • the detergent composition of the present invention may be used for all uses as a detergent. However, this is suitably used in particular as a home detergent for cleaning clothes or household materials.
  • the detergent composition of the present invention may be used as it is or may be used after diluting it with water because the concentration is high.
  • a builder comprising an amine salt or amine-alkali metal mixed salt of an aminopolycarboxylic add and a solubilizing agent comprising an alcohol are mixed each in a specific ratio with a specific surfactant, therefore, a high-concentration liquid detergent composition which does not have strong alkalinity, which has excellent compatibility even if the surfactant concentration is increased, and which is free of white turbidity can be obtained.
  • Example 3 and Comparative Example 11 and Comparative Example 6 Example 9 and Comparative Example 12, Example 10 and Comparative Example 13, Example 11 and Comparative Example 14, Example 15 and Comparative Example 17, and Example 16 and Comparative Example 18.
  • a high-concentration liquid detergent composition having excellent compatibility and free of white turbidity can be obtained.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Claims (5)

  1. Flüssige Detergens-Zusammensetzung, umfassend:
    (A) ein oder mehrere oberflächenaktive Mittel, die aus der Gruppe ausgewählt sind, die aus einem nicht-ionischen oberflächenaktiven Mittel und einem anionischen oberflächenaktiven Mittel besteht,
    (B) ein oder mehrere Gerüststoffe, die aus der Gruppe ausgewählt sind, bestehend aus einem Aminsalz und einem Alkalimetall-Amin-Mischsalz eines Chelatbildners auf Aminopolycarbonsäure-Basis, und
    (C) ein oder mehrere Solubilisierungsmittel, die aus der Gruppe ausgewählt sind, die aus Alkoholen besteht,
    wobei Bestandteil (A) in einer Konzentration von 20 Gew.-% oder mehr vorliegt.
  2. Flüssige Detergens-Zusammensetzung, umfassend:
    (A) 20 bis 60 Gew.-% eines oder mehrerer oberflächenaktiver Mittel, die aus der Gruppe ausgewählt sind, die aus einem nicht-ionischen oberflächenaktiven Mittel und einem anionischen oberflächenaktiven Mittel besteht,
    (B) 0,1 bis 15 Gew.-% eines oder mehrerer Gerüststoffe, die aus der Gruppe ausgewählt sind, bestehend aus einem Aminsalz und einem Alkalimetall-Amin-Mischsalz eines Chelatbildners auf Aminopolycarbonsäure-Basis,
    (C) 0,5 bis 30 Gew.-% eines oder mehrerer Solubilisierungsmittel, die aus der Gruppe ausgewählt sind, die aus Alkoholen besteht, und
    (D) als Restbestandteil Wasser.
  3. Flüssige Detergens-Zusammensetzung nach Anspruch 1 oder 2, wobei die Aminopolycarbonsäure eine Aminosäure-N,N-diessigsäure ist.
  4. Flüssige Detergens-Zusammensetzung nach Anspruch 1 oder 2, wobei die Aminopolycarbonsäure Glutaminsäure-N,N-diessigsäure, α-Alanin-N,N-diessigsäure, β-Alanin-N,N-diessigsäure, Asparaginsäure-N,N-diessigsäure, Glycin-N,N-diessigsäure oder Serin-N,N-diessigsäure ist.
  5. Flüssige Detergens-Zusammensetzung nach einem der Ansprüche 1 bis 4, wobei der Alkohol Glycol ist.
EP99112847A 1998-07-03 1999-07-02 Flüssige Reinigungsmittel Expired - Lifetime EP0969080B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP18872398A JP4061420B2 (ja) 1998-07-03 1998-07-03 液体洗剤組成物
JP18872398 1998-07-03

Publications (2)

Publication Number Publication Date
EP0969080A1 EP0969080A1 (de) 2000-01-05
EP0969080B1 true EP0969080B1 (de) 2004-10-27

Family

ID=16228663

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99112847A Expired - Lifetime EP0969080B1 (de) 1998-07-03 1999-07-02 Flüssige Reinigungsmittel

Country Status (4)

Country Link
EP (1) EP0969080B1 (de)
JP (1) JP4061420B2 (de)
AT (1) ATE280820T1 (de)
DE (1) DE69921394T2 (de)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6034046A (en) * 1999-03-26 2000-03-07 Colgate Palmolive Company All purpose liquid bathroom cleaning compositions
ATE284946T1 (de) * 2000-02-17 2005-01-15 Bode Chemie Gmbh & Co Reinigungs- und desinfektionssysteme für medizinische instrumente
DE10007323A1 (de) * 2000-02-17 2001-08-23 Bode Chemie Gmbh & Co Kg Reinigunsmittel für medizinische Instrumente
DE10100720A1 (de) * 2001-01-10 2002-07-11 Beiersdorf Ag Kosmetische und dermatologische waschaktive Zubereitungen, enthaltend eine wirksame Menge an Iminodibernsteinsäure und/oder ihren Salzen
ITCR20060016A1 (it) * 2006-06-07 2007-12-08 Silvia Palladini Formulazioni di detersivi a basso impatto ambientale
US20100311998A1 (en) * 2007-08-02 2010-12-09 Akzo Nobel N.V. Chelating agent based ionic liquids, a process to prepare them, and their use
CN102666828B (zh) * 2009-12-24 2014-07-30 阿克佐诺贝尔化学国际公司 谷氨酸n,n-二乙酸盐螯合剂的涂覆颗粒
JP5580353B2 (ja) * 2012-02-22 2014-08-27 エコラボ インコーポレイティド アルミニウム表面を洗浄するためのアルカリ洗浄剤
EA201690001A1 (ru) 2013-06-12 2016-05-31 Юнилевер Н.В. Жидкий моющий состав, включающий суспендированные частицы

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3914185A (en) * 1973-03-15 1975-10-21 Colgate Palmolive Co Method of preparing liquid detergent compositions
US4020016A (en) * 1975-02-28 1977-04-26 The Drackett Company Cleaning compositions effective in dissolving soap curd
DE2836567C2 (de) * 1977-08-29 1986-12-11 Sandoz-Patent-Gmbh, 7850 Loerrach Reinigungsmittel und -verfahren
GB8619064D0 (en) * 1986-08-05 1986-09-17 Unilever Plc Detergent compositions
JPH0684514B2 (ja) * 1986-08-20 1994-10-26 ライオン株式会社 浴室用液体洗浄剤組成物
US5254290A (en) * 1991-04-25 1993-10-19 Genevieve Blandiaux Hard surface cleaner
DK0513948T3 (da) * 1991-05-15 1998-10-26 Hampshire Chemical Corp Sammensætninger indeholdende biologisk nedbrydelige chelateringsmidler til rensning af hårde overflader
US5186856A (en) * 1992-06-02 1993-02-16 Basf Corp. Aqueous prewash stain remover compositions with efficacy on tenacious oily stains
US5536452A (en) * 1993-12-07 1996-07-16 Black; Robert H. Aqueous shower rinsing composition and a method for keeping showers clean

Also Published As

Publication number Publication date
JP2000017298A (ja) 2000-01-18
EP0969080A1 (de) 2000-01-05
ATE280820T1 (de) 2004-11-15
DE69921394T2 (de) 2005-06-30
DE69921394D1 (de) 2004-12-02
JP4061420B2 (ja) 2008-03-19

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