EP1080172B1 - Stable quaternary ammonium compositions - Google Patents
Stable quaternary ammonium compositions Download PDFInfo
- Publication number
- EP1080172B1 EP1080172B1 EP99929121A EP99929121A EP1080172B1 EP 1080172 B1 EP1080172 B1 EP 1080172B1 EP 99929121 A EP99929121 A EP 99929121A EP 99929121 A EP99929121 A EP 99929121A EP 1080172 B1 EP1080172 B1 EP 1080172B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- quaternary ammonium
- ammonium material
- stabilising agent
- weight
- levels
- 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
Links
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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- 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
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium 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
- C11D3/2065—Polyhydric alcohols
-
- 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
- C11D3/32—Amides; Substituted amides
- C11D3/323—Amides; Substituted amides urea or derivatives thereof
Definitions
- the present invention relates to the stability of quaternary ammonium materials, in particular it relates to maintaining stable quaternary ammonium materials containing at least one ester group, in the raw material form or as a solution in a suitable solvent.
- Quaternary ammonium materials both solid or liquid are used extensively in fabric softener compositions.
- Such compositions contain a water insoluble quaternary ammonium fabric softening agent dispersed in water at a level of quaternary ammonium softening agent up to 8% by weight in which case the compositions are considered dilute or at levels from 8 to 50% in which case the compositions are considered concentrates.
- the problem is particularly noticeable in the storage of these materials at variable temperatures over time, especially at elevated temperatures eg in the region of 40-90°C, such as 50-85°C.
- the amount of discolouration is generally an indication of the level of decomposition occurring over time. This decomposition is of greatest concern when quaternary ammonium material is stored at temperatures above their melting points.
- Instability may also manifest itself by alkyl halide appearance in the sample, indicating decomposition of the quaternary ammonium material. Instability may be referred to as caused by, or indicated by, de-quaternisation of the quaternary ammonium material.
- EP 299 176 discloses soft-finishing agents comprising a di-long chained quaternary ammonium salt containing a single ester group and a decyldimethyl amine.
- EP 499 282 discloses compositions comprising a quaternary ammonium compound and an aliphatic amine.
- EP 332 270 discloses compositions comprising a quaternary ammonium fabric softening agent, an amine and an amphoteric material.
- US 5282983 discloses aqueous fabric softener compositions comprising a softener material obtained by neutralising a di-long chain type tertiary amine compound.
- EP 0547723 (Colgate-Palmolive) discloses free-flowing spraydried particulate fabric softening compositions comprising 45 to 85% by weight of urea.
- low and high temperature stability of the aforementioned solid or liquid quaternary ammonium compounds may be improved by the addition of at least one stabilising agent selected from specific group of compounds which improve the stability of the composition.
- improved stable compositions comprising a quaternary ammonium material of formula where each R 1 group is methyl; and each R 2 group is tallowyl; X - is chloride, T is and n is 2 characterised in that they further comprise one or more stabilising agent(s) chosen from;
- compositions show improved stability at varying temperatures.
- a process of stabilising the aforementioned quaternary ammonium material by the addition of one or more stabilising agents as defined above, at levels as defined above.
- a solid rinse conditioner comprising a composition as defined above.
- liquid rinse conditioner made by dilution of a composition as defined above with water.
- a further aspect of the invention is provided a method of reducing the alkyl halide levels in the aforementioned quaternary ammonium material over time by the addition of a stabilising as defined herein, at levels as defined herein.
- the quaternary ammonium materials of the invention preferably do not contain substantial amounts of non- ester containing material.
- the ester containing quaternary ammonium material is used in the absence of non-ester group quaternary ammonium containing material.
- small amounts eg less than 20% by weight based on the amount of total quaternary ammonium material, preferably less than 10% may be present.
- ester-linked quaternary ammonium material for use in the invention is represented by the formula: wherein each R 1 group is methyl; and wherein each R 2 group is tallowyl; X - is chloride T is and n is 2.
- the quaternary ammonium compound used in the present invention is substantially anhydrous, meaning containing less than 10% water in the context of the present invention.
- the quaternary ammonium material may contain optional additional components, as known in the art, in particular, low molecular weight solvents, for instance isopropanol and/or ethanol, and co-actives such as nonionic softeners, for example fatty acid or sorbitan esters.
- low molecular weight solvents for instance isopropanol and/or ethanol
- co-actives such as nonionic softeners, for example fatty acid or sorbitan esters.
- any of the above-mentioned stabilising agents may be used according to the invention.
- the stabilising agent is added to the composition of the present invention at levels of 0.05 to 10% by weight of the weight of the quaternary ammonium material, more preferably 0.5 to 8.5% and even more preferably 0.75 to 7.5%, eg 1 to 5%.
- R 1 R 2 R 3 substituents include OCOR4 substituents wherein R 4 is a C 12 -C 22 alkyl or alkenyl chain.
- the most preferred stabilising agents are urea and tertiary amines where R 1 and R 2 are C 1 - C 2 alkyl groups and R 3 is a C 2 - C 4 hydroxyalkyl group eg N,N-dimethyl ethanolamine (DMEA).
- R 1 and R 2 are C 1 - C 2 alkyl groups and R 3 is a C 2 - C 4 hydroxyalkyl group eg N,N-dimethyl ethanolamine (DMEA).
- the stabilising agent may be introduced to the quaternary ammonium material at any stage during its manufacture or after manufacture, eg on storage.
- the stabilising agent may be added in any form, as a powder direct to the molten quaternary ammonium material or as a solution in a suitable solvent, for instance isopropanol.
- the addition of the stabilising agent can take place during the synthesis of the quaternary ammonium material preferably following the quaternisation step.
- the addition may alternatively, or additionally, be made during storage of the quaternary ammonium material.
- the stabilising agent is most effectively introduced at any stage following the quaternisation step of the synthesis of the quaternary ammonium material.
- composition is in a liquid, molten or semi molten form containing less than 10% by weight of water.
- These compositions may be incorporated into a solid rinse conditioner which is preferably in a powdered or granular form.
- the compositions may also be diluted with water to produce a liquid rinse conditioner.
- the reflectance was measured on a datacolor international Spectraflash SF600 plus reflectometer after 3 days storage at 82°C. R540 after 3 days at 82°C DEQ (control) 19.8 DEQ + 3.6% urea 25.1 DEQ + 7.3% urea 27.4 DEQ is di(2-[hardened tallow]oxyl oxyethyl) dimethyl ammonium chloride ex Hoechst. It includes approximately 10% mono ester and minor amounts of unquaternised amine/amine salt as well as approximately 2% fatty acid and 14% isopropanol.
- Alkyl halide is produced by the following decomposition reaction: R 2 Me 2 N + Cl - ⁇ R 2 NMe+ MeCl R 1 Me 3 N + Cl - ⁇ R 1 NMe 2 + MeCl
- R is a C 8 to C 22 hydrocarbyl group, optionally interrupted by functional groups, e.g. ester [O-CO., CO.O], amide, ether, amine, carbonate), optionally branched, optionally unsaturated and R 1 is a C 8 to C 40 hydrocarbyl group similarly defined.
- the chloromethane levels were determined by capillary gas chromatography.
- Formulation MeCl (ppm) after 3 days at 82°C DEQ (control) 283 DEQ plus 3.6% urea 52 DEQ plus 7.3% urea 24 DEQ is di(2-[hardened tallow]oxyl oxyethyl) dimethyl ammonium chloride ex Hoechst. It includes approximately 10% mono ester and minor amounts of unquaternised amine/amine salt as well as approximately 2% fatty acid and 14% isopropanol.
- DMEA was added to the DEQ following storage of the DEQ overnight at 82°C. Chloromethane was determined by gas chromatography after a further day at 82°C. Formulation MeCl (ppm) after storage at 82°C DEQ (control) 80 (1 day) DEQ plus 0.76% DMEA 32 (1 day) DEQ plus 2.28% DMEA 5 (30 minutes) DEQ plus 2.28% DMEA 2 (1 day) DMEA is N,N-dimethylethanol amine (99% ex Aldrich)
- Glycerol was added at a level of 7.5% by weight to a sample of DEQ to produce example 4A.
- a control sample of DEQ which did not contain any glycerol (Comparative example 4B) and example 4A were sealed in separate Gas Chromatograph (GC) vials and were stored at 80.5°C. At the end of the storage period the level of 'total' methyl chloride in each sample was measured. The results are given below.
- the above results demonstrate the ability of the stabilising agent, here glycerol, to reduce the level of MeCl in a quaternary ammonium material on closed, high temperature, storage.
- the level of MeCl measured here is the 'total' level in a sealed system.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Detergent Compositions (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9810656 | 1998-05-18 | ||
GBGB9810656.0A GB9810656D0 (en) | 1998-05-18 | 1998-05-18 | Stable ammonium compositions |
PCT/EP1999/003367 WO1999060082A1 (en) | 1998-05-18 | 1999-05-12 | Stable quaternary ammonium compositions |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1080172A1 EP1080172A1 (en) | 2001-03-07 |
EP1080172B1 true EP1080172B1 (en) | 2005-05-04 |
Family
ID=10832261
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99929121A Expired - Lifetime EP1080172B1 (en) | 1998-05-18 | 1999-05-12 | Stable quaternary ammonium compositions |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP1080172B1 (tr) |
CN (1) | CN1280389C (tr) |
AR (1) | AR019556A1 (tr) |
AU (1) | AU4604599A (tr) |
BR (1) | BR9910550B1 (tr) |
CA (1) | CA2329959C (tr) |
DE (1) | DE69925119T2 (tr) |
ES (1) | ES2241289T3 (tr) |
GB (1) | GB9810656D0 (tr) |
HU (1) | HUP0101902A3 (tr) |
TR (1) | TR200003385T2 (tr) |
WO (1) | WO1999060082A1 (tr) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1493424B1 (en) * | 2002-04-08 | 2009-01-21 | Kao Corporation | Cosmetic hair preparation |
DE602004008217T2 (de) * | 2004-03-29 | 2008-05-15 | Clariant Produkte (Deutschland) Gmbh | Einfach dispergierbare konzentrierte Esterquat Zusammensetzungen |
US20090312428A1 (en) | 2008-06-13 | 2009-12-17 | Fernando Figueredo | Biocide Compositions Comprising Quaternary Ammonium and Urea and Methods for Their Use |
US8257720B2 (en) | 2009-04-20 | 2012-09-04 | Conopco, Inc. | Stabilized cationic ammonium compounds and compositions comprising the same |
US8324255B2 (en) * | 2009-09-15 | 2012-12-04 | Conopco, Inc. | Chelator stabilized cationic ammonium compounds and compositions comprising the same |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2454465A1 (de) * | 1974-11-16 | 1976-05-20 | Hoechst Ag | Pulverfoermige waescheweichspuelmittel mit desinfizierenden eigenschaften |
EP0258923B1 (en) * | 1986-09-02 | 1993-10-06 | Akzo Nobel N.V. | Fabric softening composition and detergent-composition comprising the same |
GB8805837D0 (en) * | 1988-03-11 | 1988-04-13 | Unilever Plc | Fabric conditioning composition |
US5282983A (en) * | 1990-08-22 | 1994-02-01 | Kao Corporation | Fabric softener composition and ammonium salt |
US5259964A (en) * | 1991-12-18 | 1993-11-09 | Colgate-Palmolive Co. | Free-flowing powder fabric softening composition and process for its manufacture |
US5543067A (en) * | 1992-10-27 | 1996-08-06 | The Procter & Gamble Company | Waterless self-emulsiviable biodegradable chemical softening composition useful in fibrous cellulosic materials |
DE4307186A1 (de) * | 1993-03-08 | 1994-09-15 | Henkel Kgaa | Wäßrige Textilweichmacher-Zusammensetzung |
DE19629666A1 (de) * | 1996-07-23 | 1998-01-29 | Henkel Kgaa | Verfahren zur hydrophilen Ausrüstung von Fasern oder Vliesstoffen |
-
1998
- 1998-05-18 GB GBGB9810656.0A patent/GB9810656D0/en not_active Ceased
-
1999
- 1999-05-12 HU HU0101902A patent/HUP0101902A3/hu unknown
- 1999-05-12 EP EP99929121A patent/EP1080172B1/en not_active Expired - Lifetime
- 1999-05-12 CA CA2329959A patent/CA2329959C/en not_active Expired - Fee Related
- 1999-05-12 TR TR2000/03385T patent/TR200003385T2/tr unknown
- 1999-05-12 AU AU46045/99A patent/AU4604599A/en not_active Abandoned
- 1999-05-12 WO PCT/EP1999/003367 patent/WO1999060082A1/en active IP Right Grant
- 1999-05-12 DE DE69925119T patent/DE69925119T2/de not_active Expired - Lifetime
- 1999-05-12 ES ES99929121T patent/ES2241289T3/es not_active Expired - Lifetime
- 1999-05-12 CN CN99806166.2A patent/CN1280389C/zh not_active Expired - Fee Related
- 1999-05-12 BR BRPI9910550-0A patent/BR9910550B1/pt not_active IP Right Cessation
- 1999-05-18 AR ARP990102346A patent/AR019556A1/es active IP Right Grant
Also Published As
Publication number | Publication date |
---|---|
CA2329959A1 (en) | 1999-11-25 |
BR9910550B1 (pt) | 2009-05-05 |
CA2329959C (en) | 2010-04-27 |
GB9810656D0 (en) | 1998-07-15 |
CN1301292A (zh) | 2001-06-27 |
HUP0101902A2 (hu) | 2001-10-28 |
BR9910550A (pt) | 2001-01-30 |
CN1280389C (zh) | 2006-10-18 |
EP1080172A1 (en) | 2001-03-07 |
WO1999060082A1 (en) | 1999-11-25 |
DE69925119D1 (de) | 2005-06-09 |
DE69925119T2 (de) | 2005-10-06 |
HUP0101902A3 (en) | 2002-08-28 |
ES2241289T3 (es) | 2005-10-16 |
AU4604599A (en) | 1999-12-06 |
TR200003385T2 (tr) | 2001-02-21 |
AR019556A1 (es) | 2002-02-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP3902783B2 (ja) | 濃縮生分解性四級アンモニウム布帛柔軟剤組成物、および中間ヨウ素価不飽和脂肪酸鎖を含む化合物 | |
JP3739429B2 (ja) | 透明または半透明の濃縮布帛柔軟剤組成物 | |
JPS636168A (ja) | 生物分解性繊維柔軟化剤 | |
IE860830L (en) | Fabric conditioner | |
JPH10508622A (ja) | 中間ヨウ素価脂肪酸鎖を含有する濃縮生分解性第四級アンモニウム布帛柔軟剤組成物 | |
DE69519579T2 (de) | Nachspülzusätze enthaltend oxydationsinhibitoren in wäscheweichmacherzusammensetzungen | |
EP1080172B1 (en) | Stable quaternary ammonium compositions | |
US4622154A (en) | Aqueous fabric softening composition | |
CA1204563A (en) | Liquid fabric-softening composition | |
JPH07505189A (ja) | 濃縮布帛柔軟化組成物 | |
EP1080171B1 (en) | Stabilised quaternary ammonium compositions | |
US4627925A (en) | Aqueous concentrated fabric softening composition | |
EP0681604B1 (en) | Fabric softener composition | |
GB2157730A (en) | Aqueous concentrated fabric softening composition | |
JPH11511802A (ja) | 布帛柔軟化組成物 | |
JP3279397B2 (ja) | 液体柔軟剤組成物 | |
EP1254203B2 (en) | Fabric conditioning compositions | |
CA1226407A (en) | Aqueous fabric softening composition | |
GB2157726A (en) | Aqueous fabric softening composition | |
TH33640C3 (th) | องค์ประกอบแอมโมเนียมที่เสถียร | |
TH59263A3 (th) | องค์ประกอบแอมโมเนียมที่เสถียร |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20000926 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): BE DE ES FR GB IT |
|
17Q | First examination report despatched |
Effective date: 20030721 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE ES FR GB IT |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 69925119 Country of ref document: DE Date of ref document: 20050609 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2241289 Country of ref document: ES Kind code of ref document: T3 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
ET | Fr: translation filed | ||
26N | No opposition filed |
Effective date: 20060207 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20150527 Year of fee payment: 17 Ref country code: DE Payment date: 20150528 Year of fee payment: 17 Ref country code: ES Payment date: 20150526 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20150527 Year of fee payment: 17 Ref country code: BE Payment date: 20150527 Year of fee payment: 17 Ref country code: FR Payment date: 20150519 Year of fee payment: 17 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160531 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 69925119 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20160512 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160512 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20170131 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20161201 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160531 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160512 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160513 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20181126 |