EP0426876A1 - Waschmittelzusammensetzung - Google Patents

Waschmittelzusammensetzung Download PDF

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Publication number
EP0426876A1
EP0426876A1 EP90907473A EP90907473A EP0426876A1 EP 0426876 A1 EP0426876 A1 EP 0426876A1 EP 90907473 A EP90907473 A EP 90907473A EP 90907473 A EP90907473 A EP 90907473A EP 0426876 A1 EP0426876 A1 EP 0426876A1
Authority
EP
European Patent Office
Prior art keywords
acid
surface active
active agent
detergent composition
carbon atoms
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.)
Withdrawn
Application number
EP90907473A
Other languages
English (en)
French (fr)
Other versions
EP0426876A4 (en
Inventor
Isao 4594 Ichihana Ichikaimachi Yamada
Nobuyoshi 4599-1 Ichihana Yamaguchi
Akira 4-12 Izumigaoka 2-Chome Suzuki
Tatsuhiro 3-45 Wakaurahigashi 4-Chome Imanaka
Hiromoto 44 Tosacho 1-Chome Mizushima
Shoji 3-30-301 Nishikoniri 3-Chome Nakagawa
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.)
Kao Corp
Original Assignee
Kao Corp
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 Kao Corp filed Critical Kao Corp
Publication of EP0426876A1 publication Critical patent/EP0426876A1/de
Publication of EP0426876A4 publication Critical patent/EP0426876A4/en
Withdrawn legal-status Critical Current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
    • C11D1/66—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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention concerns a detergent composition and, more in particular, it relates to a detergent composition having excellent detergent power to inorganic contaminations on cloths.
  • Contaminations on cloths are generally classified into organic dirts and inorganic dirts.
  • the organic dirts mainly comprise skin fat dirts derived from bodies.
  • Detergents containing non-ionic surface active agents show excellent detergent power to oil contaminations such as skin fat dirts.
  • inorganic dirts mainly comprise dusts suspending in air or mud derived from soils.
  • organic and inorganic contaminations are present together in cloth contaminations and conventional detergents have insufficient detergent power to inorganic dirts, in particular, mud deposited to socks, etc.
  • the present inventors have made an earnest study and, as a result, have accomplished the present invention based on the finding that a detergent composition remarkably improved with a detergent power to inorganic dirts can be obtained by using a non-ionic surface active agent and a specific anionic surface active agent together.
  • the present invention provides a detergent composition containing:
  • the non-ionic surface active agent (a) having HLB of 6 to 19, preferably 8 to 17 is usually used. Among all, the non-ionic surface active agent represented by (1), (2), (5) or (10) is particularly preferred.
  • the non-ionic surface active agent (a) is blended by 1 to 90 % in the composition.
  • the anionic surface active agent used as the ingredient (b) in the present invention is an anionic surface active agent having at least one hydrophobic group with 6 to 24 carbon atoms and two or more anionic groups, in which the chelate stabilization constant to calcium ions is not less than 2 and the kraft point upon chelating calcium ions is not higher than 5°C.
  • the anionic surface active agent having the foregoing feature is different from Na salt of linear alkyl benzene sulfonic acid or sodium salt of polyoxyethylene alkyl ether sulfuric ester in view of the following points.
  • contaminations comprise polyvalent cations such as calcium, magnesium, iron and aluminum in the contamination ingredients, which are present between negatively charged fibers and negatively charged contamination particles and serve to bond them. It is considered that such polyvalent cation bridges are rather important factor for the deposition of contaminations and the anionic surface active agent in the present invention has a nature of chelating such metal ions and those having Ca2+ chelate stabilization constant of not less than 2 particularly contribute to the improvement of the detergent power.
  • ions such as Ca2+ and Mg2+ present in water in particular, Ca2+ cause undesired effects such as recontaminations if they are not chelated and the anionic surface active agent in the present invention is useful also in this point.
  • the surface active agent has a kraft point upon chelating the calcium ions of not higher than 5°C, preferably, not higher than 0°C, such an anionic surface active agents remains to serve as the surface active agent after chelating the calcium ions and, accordingly, can provide a detergent power being free from the effect of the hard ingredient even under low temperature washing conditions as in Japan.
  • anionic surface active agent in the present invention has a plurality (two or more) of anionic groups, they are adsorbed on solid particles to increase negative zeta potential to, thereby increase the repulsion between solid particles having identical static charges. Since these charges are scarcely lost under usual washing conditions, contaminations are detached from the surface to be washed.
  • the anionic surface active agent according to the present invention is a surface active agent capable of remarkably improving a detergent power to inorganic dirts, in particular, mud deposited to socks, etc. which can not be cleaned sufficiently with conventional detergent containing anionic surface active agent.
  • the chelate stabilization constant to calcium ions and the kraft point upon chelating the calcium ions of the anionic surface active agent as the ingredient (b) in the present invention are values measured by the following measuring methods.
  • Buffer solution 0.1M-NH4Cl-NH4OH buffer (pH 10.0)
  • a standard calcium ion solution is prepared and a calibration curve showing a relationship between the calcium ion concentration (log) and the potential as shown in Fig. 1 is prepared.
  • the aqueous solution of CaCl2 is added each by 0.1 - 0.2 ml upon dropping and the potential is read on every dropping to determine a calcium ion concentration based on the calibration curve shown in Fig. 1.
  • the calcium ion concentration at the dropping amount A of the specimen shows a calcium ion capturing performance of the specimen (in Fig. 2).
  • An anionic surface active agent and an equimolar amount of CaCl2 are added to an aqueous solution of the anionic surface active agent at 0.1 wt% concentration.
  • the solution is cooled to not higher than 0°C and then the temperature is elevated at a rate of less than 1°C for one min.
  • the kraft point is defined as not higher than 0°C if there is no insoluble matters and the temperature at which insoluble matters, if any, are dissolved is defined as the kraft point.
  • the anionic surface active agent used in the present invention has a chelate stabilization constant to calcium ions (pKCa2+) of not less than 2, preferably, not less than 3 and, more preferably, not less than 4 and the kraft point upon chelating the calcium ions of not higher than 5°C and, preferably, not higher than 0°C.
  • the anionic surface active agent having such physical property can effectively catch the hard ingredients in tap water, as well as effectively improve the detergent power when used together with the non-ionic surface active agent.
  • the anionic surface active agent in the present invention preferably has the calcium ion capturing performance of not less than 50 mg/g, preferably, 100 mg/g and, more preferably, 200 mg/g converted as CaCO3.
  • the anionic group of the anionic surface active agent according to the present invention is carboxylic acid group, sulfonic acid group, etc. and, preferably, it has at least one and, more preferably, two or more carboxylic acid groups.
  • Such physical property is not found in anionic surface active agents used so far in conventional detergents such as alkylbenzene sulfonate salt, alkyl ether sulfonate salt, olefin sulfonate salt, ⁇ -sulfo fatty acid ester salt, alkane sulfonate salt, higher fatty acid salt, alkenyl succinic acid salt, sulfosuccinic acid salt, etc.
  • anionic surface active agent usable in the present invention is to be exemplified with no particular restrictions.
  • the anionic surface active agent represented by the general formula (II) can be synthesized from commercially available phenol or phenol derivatives by means of one step Mannich reaction. Specifically, it can be synthesized by the method described in Helv. Chim. Acta 35, 1785 (1952) or "Chemistry of EDTA Complexane” edited by Keihei Ueno, p 99 - 105, published from Nankodo (1977).
  • the kraft point for each of the compounds shows a value when chelating calcium ions.
  • the anionic surface active agent for the ingredient (b) in the present invention is blended by 0.1 to 90% in the composition.
  • the ingredients (a) and (b) are blended at the composition ratio (a)/(b) (by weight ratio) of 100/1 - 1/20, preferably, 100/1 - 1/10, more preferably, 10/1 - 1/10. If the weight ratio is less than 100/1, no sufficient effect for improving the detergent power to inorganic dirts can be obtained.
  • amphoteric surface active agent and anionic surface active agent can be blended in addition to the essential ingredients as described above.
  • alkali metal ion such as of sodium and potassium
  • alkaline earth metal ion such as of magnesium
  • ammonium ion or alkanol amine having 1 to 3 alkanol groups with 2 or 3 carbon atoms (for example, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine).
  • organic or inorganic alkali agents such as silicate, carbonate, hydrogen carbonate, caustic alkali or ethanolamine can be blended.
  • inorganic bivalent metal ion chelating agent such as synthetic zeolite or layerous silicate, or organic bivalent metal ion chelating agent shown below can be blended.
  • solubilizing agent used for enhancing the viscosity reducing effect and coagulation preventive effect at low temperature in the case of preparing the detergent composition according to the present invention into a liquid detergent, particularly, with less content of the ingredient (b), there can be mentioned lower alcohols such as ethanol and isopropanol; polyhydric alcohols such as ethylene glycol, propylene glycol, glycerine and sorbitol; aromatic sulfonate salts such as benzene sulfonate salt, acetylbenzene sulfonate salt, p-toluene sulfonate salt and m-xylene sulfonate salt; acetoamides, pyridine carboxylic acid amides, benzoic acid salt or urea.
  • solubilizing agents as described above, use of ethanol is particularly preferred since it can serve also for preventing bacteria growth occurring upon long time storage of the liquid detergent.
  • the blending ratio of the ingredient (a) and the ingredient (b) is from 20/1 to 1/10, preferably, 10/1 to 1/5 as (a)/(b) (weight ratio) and 5 to 60 wt% and, preferably, 20 to 60 wt% as the total for (a)+(b).
  • the heavy liquid detergent composition as described above can further be blended with a saturated or unsaturated fatty acid with 10 to 20 carbon atoms such as coconuts oil, beef tallow fatty acid, palm fatty acid or the salts thereof for further improving the detergent power, without deteriorating the store stability.
  • a saturated or unsaturated fatty acid with 10 to 20 carbon atoms such as coconuts oil, beef tallow fatty acid, palm fatty acid or the salts thereof for further improving the detergent power, without deteriorating the store stability.
  • the fatty acid or the salts thereof is an ingredient also desired for the improvement of rinsing property and is preferably blended by 0.5 to 5 wt% in the composition.
  • the store stability is kept satisfactory if the bivalent metal ion chelating is blended by a great amount than usual composition.
  • liquid detergent composition there can be further blended as other optional ingredients depending on the purpose, for example, extender such as sodium sulfate; re-contamination preventive agent such as carboxymethyl cellulose, polyethylene glycol, polyacrylic acid salt, copolymer of maleic acid anhydride and acrylic acid or olefin; bleaching agent such as percarbonate or perborate; enzyme such as protease, lipase, cellulase or amylase, enzyme stabilizer such as calcium chloride; bleaching activator, fluorescent dye, pigment, preserver, perfume, etc.
  • extender such as sodium sulfate
  • re-contamination preventive agent such as carboxymethyl cellulose, polyethylene glycol, polyacrylic acid salt, copolymer of maleic acid anhydride and acrylic acid or olefin
  • bleaching agent such as percarbonate or perborate
  • enzyme such as protease, lipase, cellulase or amylase, enzyme stabilizer such as calcium chloride
  • Remarkable merits of the detergent composition according to the present invention are that it can provide a detergent effect, particularly, for inorganic solid contaminations, for example, contaminations with fine mud that can not be washed off sufficiently by conventional detergents, that it is effective also for contaminations such as dirts on collars and cuffs and oil stains, as well as that it is extremely useful for the improvement of the detergent power of non-phosphorus inorganic detergents.
  • Detergents containing phosphates have been effective for the removal of contaminations with fine mud intruding between the fibers.
  • the blending amount of the phosphates in the detergents, etc. has tended to be reduced in view of the eutrophication problems and non-phosphatization is obliged at present, removal of mud contaminations becomes difficult.
  • removal of contaminations with mud intruding into cotton cloths is quite difficult.
  • the detergent composition according to the present invention can provide a solution for such problems. That is, when the composition according to the present invention is applied, for example, to non-phosphate alkaline detergent, a detergent having excellent detergent power which is comparable with or superior to a weakly alkaline detergent containing a sufficient amount of phosphate can be obtained for cleaning contaminations with mud intruding mixed-spun cloths of cellulose fibers and other fibers.
  • Kanuma Akadama soils horticultural soils
  • fractions passing at 150 mesh (100 ⁇ m) size were dried at 120°C ⁇ 5°C for 2 hr and ⁇ 150 g was dispersed in 1000 liter perchloroethylene.
  • unbleached muslin #2023 cloth was brought into contact with the liquid, and brushed, to remove liquid dispersion and remove contaminations deposited in excess (Japanese Patent Laid-Open Sho 55-26473).
  • the model skin fat contamination comprising the above mentioned composition was uniformly coated by 2g on a 10 x 10 cm cotton cloth.
  • the reflectance at 460 m ⁇ of cloths not contaminated and contaminated cloths before and after washing was measured by self recording color meter (manufactured by Shimazu Seisakusho) and the detergent rate (%) was determined in accordance with the following equation (the ratio is shown in the table as the average of measured value for 5 sheets).
  • pKCa2+ kraft point upon chelating calcium ions and Ca capturing performance (mg/g, as CaCO3) of II-5, II-9, II-10, II-15, III-3, III-5 and III-6 for the ingredient (b) in Table-2 are as shown below
  • liquid detergent compositions having ingredients shown in Table-3 were prepared and their store stability were evaluated respectively by the following method.
  • the evaluation standards are as shown below.
  • Liquid detergent compositions having ingredients shown in Table-4 were prepared and their store stability were evaluated in the same procedures as in Example 3 and the detergent power was evaluated by the following method.
  • the washing conditions are as below.
  • Powdery detergent compositions having ingredients as shown in Table-5 were prepared and their detergent performance was evaluated respectively in the same procedures as those in Example 2.

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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)
  • Detergent Compositions (AREA)
EP19900907473 1989-05-29 1990-05-29 Detergent composition Withdrawn EP0426876A4 (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP13509189 1989-05-29
JP135091/89 1989-05-29
JP16606789 1989-06-28
JP166067/89 1989-06-28
JP71464/90 1990-03-19
JP7146490 1990-03-19

Publications (2)

Publication Number Publication Date
EP0426876A1 true EP0426876A1 (de) 1991-05-15
EP0426876A4 EP0426876A4 (en) 1991-12-11

Family

ID=27300648

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19900907473 Withdrawn EP0426876A4 (en) 1989-05-29 1990-05-29 Detergent composition

Country Status (3)

Country Link
EP (1) EP0426876A4 (de)
JP (1) JP2843112B2 (de)
WO (1) WO1990015128A1 (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995006095A3 (de) * 1993-08-26 1995-08-03 Basf Ag Phenolische komplexbildner
US5531939A (en) * 1994-03-23 1996-07-02 Amway Corporation Concentrated glass and window cleaning composition and method of use
US5575864A (en) * 1994-03-23 1996-11-19 Haley; Kalliopi S. Method for cleaning a hard surface with an all-purpose liquid cleaning composition
WO2003010276A1 (en) * 2001-07-24 2003-02-06 Kao Corporation Laundering pretreatment composition for clothing
US8067354B2 (en) 2005-12-28 2011-11-29 Kao Corporation Softening detergent composition

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4418634C2 (de) * 1993-09-14 2001-08-30 Fujitsu Ltd Aus bioabbaubarem Harz geformter Artikel, Modifikationsverfahren eines Harzes, Harzzusammensetzung und geformter Harzartikel
JP3596912B2 (ja) * 1994-07-25 2004-12-02 旭化成ケミカルズ株式会社 リンス不要洗浄剤
JP3558375B2 (ja) * 1994-07-25 2004-08-25 旭化成ケミカルズ株式会社 リンス不要低残渣洗浄剤
RU2447138C2 (ru) 2006-03-31 2012-04-10 Као Корпорейшн Композиция смягчающего детергента

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS512708A (ja) * 1974-06-28 1976-01-10 Lion Fat Oil Co Ltd Senjozaisoseibutsu
JPS53141309A (en) * 1977-05-17 1978-12-09 Agency Of Ind Science & Technol Phosphorus-free detergent composition
JPS55104400A (en) * 1979-02-06 1980-08-09 Kureha Chemical Ind Co Ltd Detergent composition
JPS55160099A (en) * 1979-05-18 1980-12-12 Kureha Chemical Ind Co Ltd Detergent composition
JPS55157695A (en) * 1979-05-18 1980-12-08 Kureha Chemical Ind Co Ltd Detergent composition
JPS5851994B2 (ja) * 1979-12-05 1983-11-19 呉羽化学工業株式会社 無リン洗剤組成物
JPS58160400A (ja) * 1982-03-17 1983-09-22 花王株式会社 洗浄剤組成物
US4396520A (en) * 1982-04-26 1983-08-02 The Procter & Gamble Company Detergent compositions
JPS6055098A (ja) * 1983-09-05 1985-03-29 第一工業製薬株式会社 液状洗浄剤
JPH0768539B2 (ja) * 1986-06-24 1995-07-26 ライオン株式会社 ビリルビン汚れのしみ抜き剤

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995006095A3 (de) * 1993-08-26 1995-08-03 Basf Ag Phenolische komplexbildner
EP0785250A1 (de) * 1993-08-26 1997-07-23 Basf Aktiengesellschaft Phenolische Komplexbildner
US5531939A (en) * 1994-03-23 1996-07-02 Amway Corporation Concentrated glass and window cleaning composition and method of use
US5575864A (en) * 1994-03-23 1996-11-19 Haley; Kalliopi S. Method for cleaning a hard surface with an all-purpose liquid cleaning composition
US5837065A (en) * 1994-03-23 1998-11-17 Amway Corporation Concentrated all-purpose light duty liquid cleaning composition and method of use
WO2003010276A1 (en) * 2001-07-24 2003-02-06 Kao Corporation Laundering pretreatment composition for clothing
US8067354B2 (en) 2005-12-28 2011-11-29 Kao Corporation Softening detergent composition

Also Published As

Publication number Publication date
JPH03277696A (ja) 1991-12-09
EP0426876A4 (en) 1991-12-11
JP2843112B2 (ja) 1999-01-06
WO1990015128A1 (fr) 1990-12-13

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