EP0472178A1 - Fabric softener composition - Google Patents
Fabric softener composition Download PDFInfo
- Publication number
- EP0472178A1 EP0472178A1 EP19910113991 EP91113991A EP0472178A1 EP 0472178 A1 EP0472178 A1 EP 0472178A1 EP 19910113991 EP19910113991 EP 19910113991 EP 91113991 A EP91113991 A EP 91113991A EP 0472178 A1 EP0472178 A1 EP 0472178A1
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- European Patent Office
- Prior art keywords
- compound
- carbon atoms
- alkyl
- product
- fabric softener
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- 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.)
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- 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
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/528—Carboxylic amides (R1-CO-NR2R3), where at least one of the chains R1, R2 or R3 is interrupted by a functional group, e.g. a -NH-, -NR-, -CO-, or -CON- group
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- 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
- C11D1/40—Monoamines or polyamines; Salts thereof
-
- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
- C11D3/0015—Softening compositions liquid
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/005—Compositions containing perfumes; Compositions containing deodorants
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
- D06M13/228—Cyclic esters, e.g. lactones
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
- D06M13/342—Amino-carboxylic acids; Betaines; Aminosulfonic acids; Sulfo-betaines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/53—Polyethers
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
Definitions
- the present invention relates to a fabric softener composition and more particularly to a liquid fabric softener composition which imparts an improved softness and resiliency (fluffy feeling) to clothes of various fibers.
- compositions based on quaternary ammonium salts containing two long-chain alkyl groups within the molecule such as di-hydrogenated tallow-alkyl dimethylammonium chloride, for instance. This is because quaternary ammonium salts produce satisfactory softening effects on various fibers even when used in small quantities.
- the above-mentioned quaternary ammonium salts are less effective for synthetic fibers such as acrylic, polyester and polyamide fibers. Moreover, if they are used in high concentrations, the resiliency and the feel of clothes are adversely affected.
- the above quaternary ammonium salts are so hydrophobic that when put in rinse water, they are not well dispersed at low to moderate pulsator speeds and tend to be deposited unevenly on the clothes. In addition, particularly when they are stored at low temperature for a prolonged time, these compositions tend to gain in viscosity and form gels or undergo phase separation.
- the commercial softeners contain, in addition to the quaternary ammonium salts, such additives as polyoxyethylene nonionic surfactants, electrolytes, solvents, and the like for improving the dispersibility and shelf life but the effects are not as satisfactory as desired.
- Liquid softeners containing various amines as softener bases are also known.
- a textile softening composition containing a long-chain alkylamine such as methyl di-hydrogenated tallow-alkylamines is described in JP-A-52-59796 (the term "JP-A” as used herein means "unexamined published Japanese Patent Application”) (corresponding to GB-1514276);
- a textile finishing composition containing an acylated alkanolamine, a water-soluble quaternary ammonium salt and a fatty acid ester for imparting smoothness and the pleasing feel is disclosed in JP-A-58-60070 (corresponding to U.S.
- Patent 4,446,034 a highly-dispersible softener containing a quaternary ammonium compound, a higher fatty acid-hydroxy(lower)alkylpolyamine condensate, and an alkylamine polyglycol ether is disclosed in JP-A-61-167083 (corresponding to U.S. Patent 4,776,965); a stable aqueous dispersion for textile treatment which contains a di(higher alkyl)cyclic amine and a Br ⁇ nsted acid is disclosed in JP-A-61-275474 (corresponding to U.S.
- Patent 4,724,089 a softening composition containing a di-long chain alkylamine-anionic surfactant ion pair complex, a non-silicone wax and a liquid vehicle is disclosed in JP-A-64-85368 (corresponding to U.S.
- Patent 4,913,828 a textile conditioning composition containing an amine such as a hydroxy(lower)alkylalkylenediamine-higher fatty acid condensate and an amphoteric textile conditioner is disclosed in JP-A-2-6662 (corresponding to EP-332270); a textile conditioning composition containing a di(long chain) alkylamine-polycarboxylic acid complex for imparting flexibility and antistaticity to fabrics is disclosed in JP-A-2-14076 (corresponding to U.S. Patent 4,869,836).
- JP-A-52-5394 (corresponding to U.S. Patent 4,045,361) discloses a fabric conditioner comprising a mono- or di(long chain)alkyl-alkylenediamine antistatic agent and a quaternary ammonium softening agent.
- these amine-containing softeners are not sufficient in the ability to soften the substrate fabrics, although they are superior to those softening compositions based on quaternary ammonium salts in dispersibility and shelf life.
- the present inventors have conducted extensive studies of amine-containing softener compositions. As a result, they found that a neutralization or quaternization product of a specific di-long chain amine compound is superior in the softening effect and it imparts sufficient resiliency (fluffy feeling) to clothes.
- the present invention is completed on the above findings.
- the present invention provides an aqueous fabric softener composition
- aqueous fabric softener composition comprising water and, as a softener raw material, a neutralization product of:
- the substituent R in the di-long chain tertiary amine compound (A) is an alkyl or alkenyl group containing from 11 to 21 carbon atoms, preferably from 13 to 19 carbon atoms and more preferably from 15 to 17 carbon atoms. These groups may be a straight-chain or branched, though straight-chain ones are preferred. Specific examples thereof include, for example, n-heptadecyl, n-pentadecyl, n-heptadecenyl and n-pentadecenyl.
- the di-long chain tertiary amine compound (A) (hereinafter referred to as "Compound (A)), which is a precursor of the softener raw material to be contained in the fabric softener composition of the invention, is any of the compounds of the following formulas (A-1) through (A-3): wherein, R1 represents an alkyl or hydroxyalkyl group containing from 1 to 4 carbon atoms; R2, R3 each represents an alkyl or alkenyl group containing from 11 to 21 carbon atoms; R4 represents a alkyl group containing from 1 to 4 carbon atoms; R5 represents an alkyl or alkenyl group containing from 12 to 22 carbon atoms; and m is 2 or 3.
- Specific and preferred examples of the group represented by R1 include, for example, methyl group and hydroxyethyl group.
- the alkyl or alkenyl group represented by R2 those containing from 13 to 20 carbon atoms are preferred and those containing from 15 to 18 carbon atoms are more preferred.
- Specific and preferred example of the group represented by R4 include, for example, methyl group.
- the symbol m is preferably 2.
- the alkyl or alkenyl group represented by R2 or R3 may be straight-chain or branched, though straight-chain ones are preferred.
- the compounds of formulas (A-1) though (A-3) can be used either alone or a mixture of two or more of them.
- the compound (A-1) can be synthesized by reacting: a compound of formula (AB-1): wherein R1 and m are as defined hereinbefore, which can be obtained by cyanoethylation and hydrogenation of an N-lower alkylalkanolamine or a dialkanolamine such as diethanolamine with a fatty acid containing 12 to 22 carbon atoms.
- the compound (A-2) can be synthesized by subjecting a compound of formula (AB-2): wherein R4 is as defined hereinbefore, which can be obtained by intramolecular dehydrative ring-formation reaction of an N-lower alkyldiethanolamine, to ring-opening amidation with an aliphatic amine such as laurylamine or stearylamine, and reacting the resulting amide with a fatty acid halide containing from 12 to 22 carbon atoms such as stearoyl chloride.
- the compound (A-3) can be synthesized by reacting: a compound of formula (AB-3): wherein R5 is as defined hereinbefore, which can be obtained by intramolecular dehydrative ring-formation reaction of an N-higher alkyl or alkenyldiethanolamine with a lower alkylamine such as methylamine, ethylamine or butylamine, and further with a fatty acid halide containing from 12 to 22 carbon atoms such as stearoyl chloride.
- the fatty acid to be used in the synthesis of the compounds of formulas (A-1) though (A-3) are those containing from 12 to 22 carbon atoms, preferably from 14 to 20 carbon atoms, and more preferably from 16 to 18 carbon atoms. Specific examples thereof include, for example, palmitic acid, stearic acid, oleic acid and elaidic acid.
- the acid (B) to be used to give the neutralization product of Compound (A) which is used as the softener raw material of the fabric softener composition of the invention includes inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid and so on; and organic acids containing from 1 to 6 carbon atoms, such as acetic acid, lactic acid, glycolic acid, citric acid, maleic acid and so on, although hydrochloric acid is preferred in that it is most inexpensive and effective.
- Compound (A) it is optional to neutralize Compound (A) beforehand and disperse it in water, or to pour Compound (A), whether in liquid form or in solid form, into an aqueous solution of the acid.
- Compound (A) and the acid may be simultaneously added to water.
- the quaternization of Compound (A) can be accomplished by the known method, for example, using methyl chloride or a dialkyl sulfate such as dimethyl sulfate or diethyl sulfate.
- the total amount of the neutralization product of Compound (A) and the quaternization product of Compound (A) in the fabric softener composition of the invention ranges from 4 to 40 % by weight, preferably 6 to 30 % by weight, and more preferably from 10 to 30 % by weight, based on the total weight of the composition, in view of the viscosity of the final product and ease of handling.
- the balance of the composition can be water.
- a silicone compound such as dimethylpolysiloxane or a partially amino- or polyoxyalkylene-modified dimethylpolysiloxane, particularly a partially polyoxyalkylene-modified dimethylpolysiloxane can be added in addition to the neutralization product of Compound (A) and/or the quaternization product of Compound (A) and water.
- the feel of the clothes finished by such a fabric softener composition can be improved without detracting the water-absorbing property of the clothes.
- Such a silicone compound is preferably used in the fabric softener composition of the invention in a proportion of from 0.3 to 5 % by weight based the total weight of the neutralization product of Compound (A) and the quaternization product of Compound (A) according to the invention.
- the fabric softener composition of the invention imparts to clothes of various fibers a softness with bouncy while giving the softening effect equivalent to that of di-hydrogenated tallow-alkyl dimethylammonium chloride, which has been widely used in the art.
- an aqueous liquid fabric softener composition of the invention it is preferable to control the viscosity of the final product by adding an inorganic electrolyte, such as sodium chloride, calcium chloride, magnesium chloride or the like, in a proportion of from 0.05 to 0.4 % by weight based on the total weight of the composition.
- an inorganic electrolyte such as sodium chloride, calcium chloride, magnesium chloride or the like
- the fabric softener composition of the invention has a long shelf life, it can be further stabilized for assurance of the quality of the composition under severe storage conditions by incorporating additives including nonionic surfactants such as polyoxyethylene (5-50 moles)-alkyl or alkenyl(C12 ⁇ 24) ethers, polyoxyethylene (5-50 moles)-alkyl or alkenylamines; solvents such as ethanol, isopropyl alcohol, propylene glycol and ethylene glycol; and/or urea.
- nonionic surfactants such as polyoxyethylene (5-50 moles)-alkyl or alkenyl(C12 ⁇ 24) ethers, polyoxyethylene (5-50 moles)-alkyl or alkenylamines
- solvents such as ethanol, isopropyl alcohol, propylene glycol and ethylene glycol
- urea such as ethanol, isopropyl alcohol, propylene glycol and ethylene glycol
- esters, nonionic or cationic compounds, long-chain alcohols, and the like which are known as a softener raw material, may be incorporated in the fabric softener composition of the invention.
- a pigment or a dye for improving appearance of the product may be further incorporated in the fabric softener composition of the invention a pigment or a dye for improving appearance of the product, a fluorescent whitener for improving finished whiteness, and a perfume for improving a sensory value during use and after finishing.
- the fabric softener composition of the invention can be prepared in the form of a solution, a suspension, an emulsion or the like in a conventional manner.
- the fabric softener composition of the present invention imparts the sufficient softness, the antistaticity and the resiliency (fluffy feeling) to clothes of various fabrics.
- compositions indicated in Table 2 were evaluated for the softness and the resiliency by the following test.
- a polyoxyethylene-modified dimethylpolysiloxane was incorporated in the amount of 1 % by weight based on the total amount of the compound according to the invention.
- the balance was water.
- the fabrics treated as above were dried in the interior atmosphere and, then, allowed to stand in a constant temperature-humidity chamber controlled at 25°C and 65% RH.
- the evaluation of the softness and the resiliency was performed by five expert panelists by the method of paired comparison using a fabric treated with 10 cc of a softening agent containing 15 % by weight of di-hydrogenated tallow-alkyl dimethylammonium chloride as a reference control.
- the scoring schema was as follows.
- the results are indicated by the mean values of the evaluation results of the five panelists.
- An aqueous fabric softener composition of the following formulation was prepared.
- This aqueous fabric softener composition imparted to clothes of softness with good resiliency. Also, this aqueous fabric softener composition showed good dispersion stability at storage for a long period of time.
Abstract
- (A) a di-long chain type tertiary amine compound containing one
- (B) an inorganic acid or an organic acid containing from 1 to 6 carbon atoms,
Description
- The present invention relates to a fabric softener composition and more particularly to a liquid fabric softener composition which imparts an improved softness and resiliency (fluffy feeling) to clothes of various fibers.
- The large majority of home laundering agents available on the market today under the name of softeners are compositions based on quaternary ammonium salts containing two long-chain alkyl groups within the molecule, such as di-hydrogenated tallow-alkyl dimethylammonium chloride, for instance. This is because quaternary ammonium salts produce satisfactory softening effects on various fibers even when used in small quantities.
- However, despite their remarkable softening effects on cotton and the like, the above-mentioned quaternary ammonium salts are less effective for synthetic fibers such as acrylic, polyester and polyamide fibers. Moreover, if they are used in high concentrations, the resiliency and the feel of clothes are adversely affected.
- Furthermore, the above quaternary ammonium salts are so hydrophobic that when put in rinse water, they are not well dispersed at low to moderate pulsator speeds and tend to be deposited unevenly on the clothes. In addition, particularly when they are stored at low temperature for a prolonged time, these compositions tend to gain in viscosity and form gels or undergo phase separation. The commercial softeners contain, in addition to the quaternary ammonium salts, such additives as polyoxyethylene nonionic surfactants, electrolytes, solvents, and the like for improving the dispersibility and shelf life but the effects are not as satisfactory as desired.
- Liquid softeners containing various amines as softener bases are also known. By way of illustration, a textile softening composition containing a long-chain alkylamine such as methyl di-hydrogenated tallow-alkylamines is described in JP-A-52-59796 (the term "JP-A" as used herein means "unexamined published Japanese Patent Application") (corresponding to GB-1514276); a textile finishing composition containing an acylated alkanolamine, a water-soluble quaternary ammonium salt and a fatty acid ester for imparting smoothness and the pleasing feel is disclosed in JP-A-58-60070 (corresponding to U.S. Patent 4,446,034); a highly-dispersible softener containing a quaternary ammonium compound, a higher fatty acid-hydroxy(lower)alkylpolyamine condensate, and an alkylamine polyglycol ether is disclosed in JP-A-61-167083 (corresponding to U.S. Patent 4,776,965); a stable aqueous dispersion for textile treatment which contains a di(higher alkyl)cyclic amine and a Brønsted acid is disclosed in JP-A-61-275474 (corresponding to U.S. Patent 4,724,089); a softening composition containing a di-long chain alkylamine-anionic surfactant ion pair complex, a non-silicone wax and a liquid vehicle is disclosed in JP-A-64-85368 (corresponding to U.S. Patent 4,913,828); a textile conditioning composition containing an amine such as a hydroxy(lower)alkylalkylenediamine-higher fatty acid condensate and an amphoteric textile conditioner is disclosed in JP-A-2-6662 (corresponding to EP-332270); a textile conditioning composition containing a di(long chain) alkylamine-polycarboxylic acid complex for imparting flexibility and antistaticity to fabrics is disclosed in JP-A-2-14076 (corresponding to U.S. Patent 4,869,836).
- Furthermore, JP-A-52-5394 (corresponding to U.S. Patent 4,045,361) discloses a fabric conditioner comprising a mono- or di(long chain)alkyl-alkylenediamine antistatic agent and a quaternary ammonium softening agent.
- However, these amine-containing softeners are not sufficient in the ability to soften the substrate fabrics, although they are superior to those softening compositions based on quaternary ammonium salts in dispersibility and shelf life.
- The present inventors have conducted extensive studies of amine-containing softener compositions. As a result, they found that a neutralization or quaternization product of a specific di-long chain amine compound is superior in the softening effect and it imparts sufficient resiliency (fluffy feeling) to clothes. The present invention is completed on the above findings.
- Accordingly, the present invention provides an aqueous fabric softener composition comprising water and, as a softener raw material, a neutralization product of:
- (A) a di-long chain tertiary amine compound containing one
- (B) an inorganic acid or an organic acid containing from 1 to 6 carbon atoms,
- The substituent R in the di-long chain tertiary amine compound (A) is an alkyl or alkenyl group containing from 11 to 21 carbon atoms, preferably from 13 to 19 carbon atoms and more preferably from 15 to 17 carbon atoms. These groups may be a straight-chain or branched, though straight-chain ones are preferred. Specific examples thereof include, for example, n-heptadecyl, n-pentadecyl, n-heptadecenyl and n-pentadecenyl.
- The di-long chain tertiary amine compound (A) (hereinafter referred to as "Compound (A)), which is a precursor of the softener raw material to be contained in the fabric softener composition of the invention, is any of the compounds of the following formulas (A-1) through (A-3):
wherein, R¹ represents an alkyl or hydroxyalkyl group containing from 1 to 4 carbon atoms;
R², R³ each represents an alkyl or alkenyl group containing from 11 to 21 carbon atoms;
R⁴ represents a alkyl group containing from 1 to 4 carbon atoms;
R⁵ represents an alkyl or alkenyl group containing from 12 to 22 carbon atoms; and
m is 2 or 3. - Specific and preferred examples of the group represented by R¹ include, for example, methyl group and hydroxyethyl group. As the alkyl or alkenyl group represented by R², those containing from 13 to 20 carbon atoms are preferred and those containing from 15 to 18 carbon atoms are more preferred. As the alkyl or alkenyl group represented by R³, those containing from 13 to 19 carbon atoms are preferred and those containing from 15 to 17 carbon atoms are more preferred. Specific and preferred example of the group represented by R⁴ include, for example, methyl group. As the alkyl or alkenyl group represented by R⁵, those containing from 14 to 20 carbon atoms are preferred and those containing from 16 to 18 carbon atoms are more preferred. The symbol m is preferably 2. The alkyl or alkenyl group represented by R² or R³ may be straight-chain or branched, though straight-chain ones are preferred.
- The compounds of formulas (A-1) though (A-3) can be used either alone or a mixture of two or more of them.
- The compound (A-1) can be synthesized by reacting:
a compound of formula (AB-1):
wherein R¹ and m are as defined hereinbefore,
which can be obtained by cyanoethylation and
hydrogenation of an N-lower alkylalkanolamine or a dialkanolamine such as diethanolamine with
a fatty acid containing 12 to 22 carbon atoms. - The compound (A-2) can be synthesized by subjecting a compound of formula (AB-2):
wherein R⁴ is as defined hereinbefore, which can be obtained by intramolecular dehydrative ring-formation reaction of an N-lower alkyldiethanolamine,
to ring-opening amidation with an aliphatic amine such as laurylamine or stearylamine, and reacting the resulting amide with a fatty acid halide containing from 12 to 22 carbon atoms such as stearoyl chloride. - The compound (A-3) can be synthesized by reacting:
a compound of formula (AB-3):
wherein R⁵ is as defined hereinbefore,
which can be obtained by intramolecular dehydrative ring-formation reaction of an N-higher alkyl or alkenyldiethanolamine with
a lower alkylamine such as methylamine, ethylamine or butylamine, and further with
a fatty acid halide containing from 12 to 22 carbon atoms such as stearoyl chloride. - The fatty acid to be used in the synthesis of the compounds of formulas (A-1) though (A-3) are those containing from 12 to 22 carbon atoms, preferably from 14 to 20 carbon atoms, and more preferably from 16 to 18 carbon atoms. Specific examples thereof include, for example, palmitic acid, stearic acid, oleic acid and elaidic acid.
- The acid (B) to be used to give the neutralization product of Compound (A) which is used as the softener raw material of the fabric softener composition of the invention includes inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid and so on; and organic acids containing from 1 to 6 carbon atoms, such as acetic acid, lactic acid, glycolic acid, citric acid, maleic acid and so on, although hydrochloric acid is preferred in that it is most inexpensive and effective.
- Regarding the neutralization process of Compound (A), it is optional to neutralize Compound (A) beforehand and disperse it in water, or to pour Compound (A), whether in liquid form or in solid form, into an aqueous solution of the acid. Of course, Compound (A) and the acid may be simultaneously added to water. The quaternization of Compound (A) can be accomplished by the known method, for example, using methyl chloride or a dialkyl sulfate such as dimethyl sulfate or diethyl sulfate.
- For the preparation of a fabric softener composition containing the neutralization or quaternization product of Compound (A) according to the invention as an essential ingredient, it is preferable that the total amount of the neutralization product of Compound (A) and the quaternization product of Compound (A) in the fabric softener composition of the invention ranges from 4 to 40 % by weight, preferably 6 to 30 % by weight, and more preferably from 10 to 30 % by weight, based on the total weight of the composition, in view of the viscosity of the final product and ease of handling. The balance of the composition can be water.
- In the fabric softener composition of the invention, a silicone compound such as dimethylpolysiloxane or a partially amino- or polyoxyalkylene-modified dimethylpolysiloxane, particularly a partially polyoxyalkylene-modified dimethylpolysiloxane can be added in addition to the neutralization product of Compound (A) and/or the quaternization product of Compound (A) and water. In this case, the feel of the clothes finished by such a fabric softener composition can be improved without detracting the water-absorbing property of the clothes. Such a silicone compound is preferably used in the fabric softener composition of the invention in a proportion of from 0.3 to 5 % by weight based the total weight of the neutralization product of Compound (A) and the quaternization product of Compound (A) according to the invention.
- The fabric softener composition of the invention imparts to clothes of various fibers a softness with bouncy while giving the softening effect equivalent to that of di-hydrogenated tallow-alkyl dimethylammonium chloride, which has been widely used in the art.
- In an aqueous liquid fabric softener composition of the invention, it is preferable to control the viscosity of the final product by adding an inorganic electrolyte, such as sodium chloride, calcium chloride, magnesium chloride or the like, in a proportion of from 0.05 to 0.4 % by weight based on the total weight of the composition.
- Although the fabric softener composition of the invention has a long shelf life, it can be further stabilized for assurance of the quality of the composition under severe storage conditions by incorporating additives including nonionic surfactants such as polyoxyethylene (5-50 moles)-alkyl or alkenyl(C₁₂₋₂₄) ethers, polyoxyethylene (5-50 moles)-alkyl or alkenylamines; solvents such as ethanol, isopropyl alcohol, propylene glycol and ethylene glycol; and/or urea.
- Moreover, esters, nonionic or cationic compounds, long-chain alcohols, and the like, which are known as a softener raw material, may be incorporated in the fabric softener composition of the invention.
- Furthermore, there may be further incorporated in the fabric softener composition of the invention a pigment or a dye for improving appearance of the product, a fluorescent whitener for improving finished whiteness, and a perfume for improving a sensory value during use and after finishing.
- The fabric softener composition of the invention can be prepared in the form of a solution, a suspension, an emulsion or the like in a conventional manner.
- The fabric softener composition of the present invention imparts the sufficient softness, the antistaticity and the resiliency (fluffy feeling) to clothes of various fabrics.
- The present invention is illustrated by the following examples in further detail. However, the present invention is not restricted thereby.
-
- The compositions indicated in Table 2 were evaluated for the softness and the resiliency by the following test.
- Using a 30 ℓ laundering machine, 2 kg of commercial cotton towels and 1 kg of acrylic jersey fabrics were laundered in 3.5° DH hard water with a commercial detergent (Attack, tradename, a product of Kao Corporation) 5 times to remove the textile finishes from the respective fibers. Then, 1.5 g of one of the compositions indicated in Table 2 was added and the wash load was treated under pulsation at 25°C for 1 minute.
- In each of the test compositions, a polyoxyethylene-modified dimethylpolysiloxane was incorporated in the amount of 1 % by weight based on the total amount of the compound according to the invention. The balance was water.
- The fabrics treated as above were dried in the interior atmosphere and, then, allowed to stand in a constant temperature-humidity chamber controlled at 25°C and 65% RH.
- The fabrics were then evaluated for the softness and the resiliency.
- The evaluation of the softness and the resiliency was performed by five expert panelists by the method of paired comparison using a fabric treated with 10 cc of a softening agent containing 15 % by weight of di-hydrogenated tallow-alkyl dimethylammonium chloride as a reference control. The scoring schema was as follows.
- +2:
- Definitely superior to control in the softness or the resiliency
- +1:
- Slightly superior to control in the softness or the resiliency
- 0:
- Equivalent to control
- -1:
- Slightly inferior to control in the softness or the resiliency
- -2:
- Definitely inferior to control in the softness or the resiliency
-
- It is apparent from Table 2 that the use of the compound of the invention leads to satisfactory results in both terms of the softness and resiliency.
- Using the compositions indicated in Table 3, the stacking height of cotton towels was measured for evaluation of the resiliency.
- Three cotton towels, treated as in the manner of Examples 1 through 12 and each folded in 8, were stacked up and compressed under a pressure load of 5 g/cm² for 5 minutes. The pressing load was then removed and the height of the stack was measured. The higher height of the stack indicates the higher resiliency of the towels.
-
- This aqueous fabric softener composition imparted to clothes of softness with good resiliency. Also, this aqueous fabric softener composition showed good dispersion stability at storage for a long period of time.
- While the invention has been described in detail and with reference to specific examples thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (4)
- An aqueous fabric softener composition comprising water and a neutralization product of:(A) a di-long chain tertiary amine compound containing one(B) an inorganic acid or an organic acid containing from 1 to 6 carbon atoms,a quaternization product of said Compound (A) or a mixture of said neutralization product of said Compound (A) with said Compound (B) and said quaternization product of said Compound (A).
- An aqueous fabric softener composition of claim 1, wherein said Compound (A) is at least one compound selected from the compounds represented by formulas (A-1) through (A-3):
R², R³ each represents an alkyl or alkenyl group containing from 11 to 21 carbon atoms;
R⁴ represents an alkyl group containing from 1 to 4 carbon atoms;
R⁵ represents an alkyl or alkenyl group containing from 12 to 22 carbon atoms; and
m is 2 or 3. - An aqueous fabric softener composition of claim 1, wherein said quaternization product of said Compound (A) is a compound obtained by quaternization of said Compound (A) with methyl chloride or a dialkyl sulfate.
- An aqueous fabric softener composition of claim 1, wherein an amount of said neutralization product of said Compound (A), said quaternization product of said Compound (A) or a mixture of said neutralization product of said Compound (A) and said quaternization product of said Compound (A) ranges from 4 to 40 % by weight.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2221742A JPH0759792B2 (en) | 1990-08-22 | 1990-08-22 | Softening agent |
JP221742/90 | 1990-08-22 | ||
CA002061513A CA2061513A1 (en) | 1990-08-22 | 1992-02-19 | Fabric softener compositon and ammonium salt |
AU11111/92A AU643874B2 (en) | 1990-08-22 | 1992-02-19 | Fabric softener composition and ammonium salt |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0472178A1 true EP0472178A1 (en) | 1992-02-26 |
EP0472178B1 EP0472178B1 (en) | 1995-05-10 |
Family
ID=27151879
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91113991A Expired - Lifetime EP0472178B1 (en) | 1990-08-22 | 1991-08-21 | Fabric softener composition |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0472178B1 (en) |
JP (1) | JPH0759792B2 (en) |
AT (1) | ATE122419T1 (en) |
AU (1) | AU643874B2 (en) |
CA (1) | CA2061513A1 (en) |
DE (1) | DE69109579T2 (en) |
ES (1) | ES2074614T3 (en) |
HK (1) | HK159995A (en) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0510879A2 (en) * | 1991-04-26 | 1992-10-28 | Kao Corporation | Liquid softener |
EP0643128A1 (en) * | 1993-09-10 | 1995-03-15 | Kao Corporation | Aqueous fabric softener composition, novel quaternary ammonium salt, and process for the preparation of said salt |
US5399272A (en) * | 1993-12-17 | 1995-03-21 | The Procter & Gamble Company | Clear or translucent, concentrated biodgradable quaternary ammonium fabric softener compositions |
US5427697A (en) * | 1993-12-17 | 1995-06-27 | The Procter & Gamble Company | Clear or translucent, concentrated fabric softener compositions |
EP0760243A1 (en) | 1995-08-31 | 1997-03-05 | The Procter & Gamble Company | Use of allylic alcohol perfumes as a malodour reduction agent |
US5734069A (en) * | 1992-08-05 | 1998-03-31 | Sherex Chemical Co., Inc. | Biodegradable amidoaminoesters |
EP0839899A1 (en) | 1996-10-30 | 1998-05-06 | The Procter & Gamble Company | Fabric softening compositions |
WO2001025384A1 (en) * | 1999-10-05 | 2001-04-12 | Ciba Specialty Chemicals Holding Inc. | Fabric softener compositions |
WO2001036736A1 (en) * | 1999-11-12 | 2001-05-25 | Kao Corporation | Softener composition |
DE102007012909A1 (en) | 2007-03-19 | 2008-09-25 | Momentive Performance Materials Gmbh | Fragrance-modified, reactive polyorganosiloxanes |
DE102007012910A1 (en) | 2007-03-19 | 2008-09-25 | Momentive Performance Materials Gmbh | Fragrance-modified, branched polyorganosiloxanes |
WO2015164677A1 (en) | 2014-04-23 | 2015-10-29 | Gregory Van Buskirk | Cleaning formulations for chemically sensitive individuals: compositions and methods |
WO2016115408A1 (en) | 2015-01-14 | 2016-07-21 | Gregory Van Buskirk | Improved fabric treatment method for stain release |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3553142B2 (en) * | 1994-07-29 | 2004-08-11 | 花王株式会社 | Method for producing quaternary ammonium salt and intermediate diamino alcohol |
US6818610B2 (en) | 2001-07-27 | 2004-11-16 | Procter & Gamble Company | Fabric care systems for providing anti-wrinkle benefits to fabric |
EP3773298A1 (en) | 2018-04-03 | 2021-02-17 | Convergent Dental, Inc. | Laser system for surgical applications |
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GB1514276A (en) * | 1975-10-22 | 1978-06-14 | Unilever Ltd | Fabric-softening compositions |
US4137180A (en) * | 1976-07-02 | 1979-01-30 | Lever Brothers Company | Fabric treatment materials |
GB2160421A (en) * | 1984-06-08 | 1985-12-24 | Dominion Chemicals Limited | Hair and fabric conditioning preparation |
US4724089A (en) * | 1985-03-28 | 1988-02-09 | The Procter & Gamble Company | Textile treatment compositions |
US4869836A (en) * | 1988-05-03 | 1989-09-26 | Colgate-Palmolive Co. | Wash cycle fabric conditioning compositions: tertiaryamine-multi-functional carboxylic acid complex |
US4913829A (en) * | 1987-11-19 | 1990-04-03 | Henkel Kommanditgesellschaft Auf Aktien | Aqueous fabric softener composition: optionally quaternized aliphatic amine and sulfonic or phosphonic acid compound |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3138181A1 (en) * | 1981-09-25 | 1983-04-14 | Bayer Ag, 5090 Leverkusen | TEXTILE TREATMENT AGENTS AND THEIR USE FOR FINISHING TEXTILE MATERIALS |
-
1990
- 1990-08-22 JP JP2221742A patent/JPH0759792B2/en not_active Expired - Lifetime
-
1991
- 1991-08-21 DE DE69109579T patent/DE69109579T2/en not_active Expired - Fee Related
- 1991-08-21 ES ES91113991T patent/ES2074614T3/en not_active Expired - Lifetime
- 1991-08-21 EP EP91113991A patent/EP0472178B1/en not_active Expired - Lifetime
- 1991-08-21 AT AT91113991T patent/ATE122419T1/en not_active IP Right Cessation
-
1992
- 1992-02-19 AU AU11111/92A patent/AU643874B2/en not_active Expired
- 1992-02-19 CA CA002061513A patent/CA2061513A1/en not_active Abandoned
-
1995
- 1995-10-12 HK HK159995A patent/HK159995A/en not_active IP Right Cessation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1514276A (en) * | 1975-10-22 | 1978-06-14 | Unilever Ltd | Fabric-softening compositions |
US4137180A (en) * | 1976-07-02 | 1979-01-30 | Lever Brothers Company | Fabric treatment materials |
GB2160421A (en) * | 1984-06-08 | 1985-12-24 | Dominion Chemicals Limited | Hair and fabric conditioning preparation |
US4724089A (en) * | 1985-03-28 | 1988-02-09 | The Procter & Gamble Company | Textile treatment compositions |
US4913829A (en) * | 1987-11-19 | 1990-04-03 | Henkel Kommanditgesellschaft Auf Aktien | Aqueous fabric softener composition: optionally quaternized aliphatic amine and sulfonic or phosphonic acid compound |
US4869836A (en) * | 1988-05-03 | 1989-09-26 | Colgate-Palmolive Co. | Wash cycle fabric conditioning compositions: tertiaryamine-multi-functional carboxylic acid complex |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0510879A3 (en) * | 1991-04-26 | 1993-03-17 | Kao Corporation | Liquid softener |
EP0510879A2 (en) * | 1991-04-26 | 1992-10-28 | Kao Corporation | Liquid softener |
US5734069A (en) * | 1992-08-05 | 1998-03-31 | Sherex Chemical Co., Inc. | Biodegradable amidoaminoesters |
US5580481A (en) * | 1993-09-10 | 1996-12-03 | Kao Corporation | Aqueous fabric softener composition, novel quaternary ammonium salt, and process for the preparation of said salt |
EP0643128A1 (en) * | 1993-09-10 | 1995-03-15 | Kao Corporation | Aqueous fabric softener composition, novel quaternary ammonium salt, and process for the preparation of said salt |
US5476597A (en) * | 1993-09-10 | 1995-12-19 | Kao Corporation | Liquid softener composition, novel quaternary ammonium salt, and process for the preparation of said salt |
US5427697A (en) * | 1993-12-17 | 1995-06-27 | The Procter & Gamble Company | Clear or translucent, concentrated fabric softener compositions |
US5399272A (en) * | 1993-12-17 | 1995-03-21 | The Procter & Gamble Company | Clear or translucent, concentrated biodgradable quaternary ammonium fabric softener compositions |
EP0760243A1 (en) | 1995-08-31 | 1997-03-05 | The Procter & Gamble Company | Use of allylic alcohol perfumes as a malodour reduction agent |
EP0839899A1 (en) | 1996-10-30 | 1998-05-06 | The Procter & Gamble Company | Fabric softening compositions |
WO2001025384A1 (en) * | 1999-10-05 | 2001-04-12 | Ciba Specialty Chemicals Holding Inc. | Fabric softener compositions |
WO2001036736A1 (en) * | 1999-11-12 | 2001-05-25 | Kao Corporation | Softener composition |
US6660710B1 (en) | 1999-11-12 | 2003-12-09 | Kao Corporation | Softener composition |
DE102007012909A1 (en) | 2007-03-19 | 2008-09-25 | Momentive Performance Materials Gmbh | Fragrance-modified, reactive polyorganosiloxanes |
DE102007012910A1 (en) | 2007-03-19 | 2008-09-25 | Momentive Performance Materials Gmbh | Fragrance-modified, branched polyorganosiloxanes |
WO2015164677A1 (en) | 2014-04-23 | 2015-10-29 | Gregory Van Buskirk | Cleaning formulations for chemically sensitive individuals: compositions and methods |
WO2016115408A1 (en) | 2015-01-14 | 2016-07-21 | Gregory Van Buskirk | Improved fabric treatment method for stain release |
Also Published As
Publication number | Publication date |
---|---|
JPH04108174A (en) | 1992-04-09 |
EP0472178B1 (en) | 1995-05-10 |
DE69109579T2 (en) | 1995-12-21 |
AU643874B2 (en) | 1993-11-25 |
CA2061513A1 (en) | 1993-08-20 |
JPH0759792B2 (en) | 1995-06-28 |
ATE122419T1 (en) | 1995-05-15 |
DE69109579D1 (en) | 1995-06-14 |
ES2074614T3 (en) | 1995-09-16 |
HK159995A (en) | 1995-10-20 |
AU1111192A (en) | 1993-09-02 |
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