CA2024699C - Fabric softening - Google Patents
Fabric softening Download PDFInfo
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- CA2024699C CA2024699C CA002024699A CA2024699A CA2024699C CA 2024699 C CA2024699 C CA 2024699C CA 002024699 A CA002024699 A CA 002024699A CA 2024699 A CA2024699 A CA 2024699A CA 2024699 C CA2024699 C CA 2024699C
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- pka
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- softening
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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
- 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
-
- 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
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic acids-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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
A fabric softening composition comprising one or more amine softening materials and one or more pH adjusting agents, wherein the pH of an aqueous liquor obtained by diluting said fabric softening composition to a concentration of 200 ppm of the amine materials has a pH
which is equal to or below the pK a of the amine materials.
Preferably the composition is a liquid satisfying the following condition:
1.5 < pK a (pH adjuster) < pK a (amine)
which is equal to or below the pK a of the amine materials.
Preferably the composition is a liquid satisfying the following condition:
1.5 < pK a (pH adjuster) < pK a (amine)
Description
FABRIC SOFTENING
The present invention relates to fabric softening compositions, in particular to fabric softening compositions containing one or more amines as active materials, which are intended for use in the rinse cycle of a fabric washing process.
It is an object of the present invention to formulate fabric softening compositions comprising one or more amines as the active materials. It is a further object of the present invention to provide fabric softening compositions which are environmentally acceptable and which show a good softening performance. One of the problems with amine-containing fabric softener compositions is that they often do not soften as well as conventional softeners containing quaternary ammonium softener materials.
It has now been found that the softening performance of amine containing fabric softener compositions can significantly be improved by carefully controlling the pH
of the aqueous rinse liquor for treating the fabrics.
__ 2024699 The concentration of amine materials in the rinse water will generally be from 30 to 1000 ppm, preferably around 200. It has been found that improved softening can be obtained when the pH of an aqueous rinse liquor comprising the amine softener materials at a concentration of 200 ppm is equal to or below the pKa of the amine.
Accordingly, the present invention relates to a fabric softening composition comprising one or more amine softening materials and one or more pH adjusting agents, wherein the pH of an aqueous liquor obtained by diluting said fabric softening composition to a concentration of 200 ppm of the amine materials has a pH which is equal to or below the pKa of the amine materials.
Tie amine material The one or more amine softening materials used in the composition of the invention is or are selected from amine softening materials of the following formula:
(i) amines of the formula R16 N (I) wherein either R15 or R16 are C6_24 hydrocarbyl groups and Rl~ is Cl_3 hydrocarbyl; or R15 is a hydrocarbyl group having at least 22 carbon atoms and R16 and Rl~ are Cl_3 hydrocarbyl.
J
The present invention relates to fabric softening compositions, in particular to fabric softening compositions containing one or more amines as active materials, which are intended for use in the rinse cycle of a fabric washing process.
It is an object of the present invention to formulate fabric softening compositions comprising one or more amines as the active materials. It is a further object of the present invention to provide fabric softening compositions which are environmentally acceptable and which show a good softening performance. One of the problems with amine-containing fabric softener compositions is that they often do not soften as well as conventional softeners containing quaternary ammonium softener materials.
It has now been found that the softening performance of amine containing fabric softener compositions can significantly be improved by carefully controlling the pH
of the aqueous rinse liquor for treating the fabrics.
__ 2024699 The concentration of amine materials in the rinse water will generally be from 30 to 1000 ppm, preferably around 200. It has been found that improved softening can be obtained when the pH of an aqueous rinse liquor comprising the amine softener materials at a concentration of 200 ppm is equal to or below the pKa of the amine.
Accordingly, the present invention relates to a fabric softening composition comprising one or more amine softening materials and one or more pH adjusting agents, wherein the pH of an aqueous liquor obtained by diluting said fabric softening composition to a concentration of 200 ppm of the amine materials has a pH which is equal to or below the pKa of the amine materials.
Tie amine material The one or more amine softening materials used in the composition of the invention is or are selected from amine softening materials of the following formula:
(i) amines of the formula R16 N (I) wherein either R15 or R16 are C6_24 hydrocarbyl groups and Rl~ is Cl_3 hydrocarbyl; or R15 is a hydrocarbyl group having at least 22 carbon atoms and R16 and Rl~ are Cl_3 hydrocarbyl.
J
3 _ C7203 Preferred amine materials are materials of formula (I), which comprise two long hydrocarbyl groups (C6-C24) and one short hydrocarbyl group (C1-C3). Especially preferred is the use of dihardened tallow methyl amine, as marketed under the tradename ARMEEN M2HT (Akzo). When the latter material is used the pH of a 200 ppm rinse liquor is preferably 4.5 or less, more preferred less than 3.5.
In this specification the expression hydrocarbyl group refers to alkyl or alkenyl groups optionally substituted or interrupted by functional groups such as -OH, -O-, -CONH, -COO-, etc.
The pK value The pKa value is a well-known parameter related to the protonation of materials. For a certain amine material the pKa can be determined by considering the protonation reaction of the amine material:
r~ ~
amine + H+ -------- amineH+
~~~4699 The pKa of the amine is the pH value, at which the amount of unprotonated amine is equal to the amount of protonated amine. A possible method of determining the pKa of a substance is to determine the titration curve of a 1% dispersion of the material with increasing amounts of acid; the pKa of the material is the pH value at the midpoint of the steep part of the titration curve.
In table 1, the pKa value for a number of amine softening materials is given:
TABLE I
AMINE MATERIAL FORMULA TRADE NAME pKa methyl dihardened tallow (i) Armeen M2HT 4.5 1,2 dihardened tallow oxy dimethyl propane amine (i) DTDMPA 5.1 It is preferred to use amine materials having a pKa of less than 6.5, more preferred less than 5.5, especially preferred between 5.2 and 4Ø
If more than one amine material is present in a composition of the invention, the pKa value of the amine material should be taken as the weight average pKa value of the amine mixture.
Liquid products Compositions of the present invention may take a variety of forms such as liquids, pastes, gels, powders, tablets, flakes etc. Preferably compositions of the present invention are liquids, comprising an aqueous phase. Preferably the water level in such aqueous liquids B
__ 202469 ~
In this specification the expression hydrocarbyl group refers to alkyl or alkenyl groups optionally substituted or interrupted by functional groups such as -OH, -O-, -CONH, -COO-, etc.
The pK value The pKa value is a well-known parameter related to the protonation of materials. For a certain amine material the pKa can be determined by considering the protonation reaction of the amine material:
r~ ~
amine + H+ -------- amineH+
~~~4699 The pKa of the amine is the pH value, at which the amount of unprotonated amine is equal to the amount of protonated amine. A possible method of determining the pKa of a substance is to determine the titration curve of a 1% dispersion of the material with increasing amounts of acid; the pKa of the material is the pH value at the midpoint of the steep part of the titration curve.
In table 1, the pKa value for a number of amine softening materials is given:
TABLE I
AMINE MATERIAL FORMULA TRADE NAME pKa methyl dihardened tallow (i) Armeen M2HT 4.5 1,2 dihardened tallow oxy dimethyl propane amine (i) DTDMPA 5.1 It is preferred to use amine materials having a pKa of less than 6.5, more preferred less than 5.5, especially preferred between 5.2 and 4Ø
If more than one amine material is present in a composition of the invention, the pKa value of the amine material should be taken as the weight average pKa value of the amine mixture.
Liquid products Compositions of the present invention may take a variety of forms such as liquids, pastes, gels, powders, tablets, flakes etc. Preferably compositions of the present invention are liquids, comprising an aqueous phase. Preferably the water level in such aqueous liquids B
__ 202469 ~
is from 97 to 20% by weight of the composition, more preferred from 95 to 70%. The level of amine softener materials in products of the invention, especially liquid products of the invention, is preferably more than 1% by weight of the composition, more preferred more than 2%, most preferred more than 3%. Preferably the level of amine softener materials will not exceed 70% by weight of the composition, more preferred the level is less than 30%, especially preferred are compositions comprising from 3 to 20% by weight of amine softener materials.
A problem in the formulation of liquid products according to the invention is that the low pH requirement for the rinse liquor, generally requires high levels of pH
adjusting agents in the undiluted product. These high levels of pH adjusting agents, however, often cause the undiluted product to be unstable due to the flocculation of the dispersed amine phase resulting in phase separation. A second object of the present invention is to prevent instability of the undiluted product, while still ensuring that an adequate amount of pH adjusting materials are present.
It has been found that instability of liquid fabric softeners according to the invention can be prevented by ensuring that the pH adjusting agents are predominantly in their unionised form in the undiluted product.
Furthermore, the pH of the undiluted product may not be too low for consumer safety. Also the pH adjusting material should have a sufficiently low pKa to provide the required pH at a 200 ppm concentration of the amine. It has been found that a compromise between these factors can be reached by selecting a pH adjusting agent, which satisfies the following condition:
B
zo~4~99 1.5 < pKa (pH adjuster) < pKa (amine) More preferably:
2.0 < pKa (pH adjuster) < pKa(amine)-0.5 Most preferably:
2.5 < pKa (pH adjuster) < pKa(amine)-1.0 If pH adjusters are used which undergo more than one deprotonation step, then the pKa (pH adjuster) for use in the above given equations is the lowest pKa value of the pH adjusting material. For example citric acid has pKa values of 3.1, 4.8 and 6.4. In the above given equations the value 3.1 is used as the pKa (citric acid).
If more than one pH adjuster is used then the pKa value for the mixture of pH adjusters is the weight average pKa of the mixture of pH adjusting materials.
Other possible methods for increasing the stability of liquid products according to the invention are~for example, the use of pH adjusting agents, which are relatively insoluble in the undiluted product, but sufficiently soluble in the rinse liquor, and the use of ingredients which prevent flocculation of the dispersed phase. Examples of suitable deflocculating materials are disclosed in Canadian Patent application number 2,023,950, published March 1, 1991.
The ~H adiusting agents Compositions according to the invention also comprise one or more pH adjusting agents. As described above, the B
pH adjusting agents should provide a certain pH for the rinse water. As soon as the required pH for the rinse water has been determined in line with the teaching as given above, it is believed to be well within the ambit of the skilled person, to select the types and amounts of pH
adjusting materials necessary to obtain the required pH.
Generally the pH adjusting agents will be acid materials.
When the product of the invention is a liquid product, comprising an aqueous base it is preferred that the pH adjusting materials have a pKa which is above 1.5, but below the pKa of the amine. Again it is believed that as soon as the desired pKa for the pH adjusting agents has been found with help of the above teaching, then it is well within the ambit of the skilled person to select suitable acids and their amounts.
Typical concentrations for the pH adjusting materials in the liquid undiluted products are from 0.1 to 2.0 mole per litre, more preferably from 0.2 to 1.5 mole per litre, especially preferred from 0.25 to 1.0 mole per litre.
Preferred pH adjusting materials have a pKa of between 2.5 and 3.5. Examples of these materials are p-Aminobenzosulphonic acid, bromoacetic acid, chloroacetic acid, o-chloroacetic acid, alpha chlorobutyric acid, citric acid, dihydroxybenzoic acid, dimethylmalic acid, dimethylmalonic acid, dinicotinic acid, fumaric acid, furancarboxylic acid, iodoacetic acid, lactic acid, malic acid, malonic acid, methyl malonic acid, quinolinic acid, sulfanilic acid and tartaric acid. For environmental reasons the use of tartaric acid, lactic acid, citric acid, malonic acid or mixtures thereof is preferred.
t a - $ - C7203 Preferably the pH adjusting materials having a pKa of between 2.5 and 3.5 are used in combination with amines of formula (i), which comprise two long hydrocarbyl groups (C6-C24) and one short hydrocarbyl group (C1-C3).
Especially preferred is the use of these pH adjusting materials in combination with dihardened tallow methyl amine, as marketed under the tradename ARMEEN M2HT (Akzo).
Optional ingredients Compositions of the present invention may comprise in addition to the above mentioned amine and pH adjusting materials one or more other softener materials selected from cationic, amphoteric and nonionic softening materials. Suitable materials are for example described in EP 239 910 (P&G), US 3 915 865 (STEPAN) and US
4 137 180 (LEVER BROTHERS). Preferably the weight ratio of these additional softening materials to the total of the amine softening materials is less than 3:1, more preferred less than 1:1, especially preferred less than 0.5:1.
The composition can also contain one or more optional ingredients selected from non-aqueous solvents such as C1-C4 alkanols and polyhydric alcohols, rewetting agents, viscosity modifiers such as electrolytes or long (e. g.
25-40 EO) alkoxylated fatty alcohols, for example calcium chloride, antigelling agents, perfumes, perfume carriers, fluorescers, colourants, hydrotropes, antifoaming agents, antiredeposition agents, enzymes, optical brightening agents, opacifiers, stabilisers such as guar gum and polyethylene glycol, emulsifiers, anti-shrinking agents, anti-wrinkle agents, fabric crisping agents, anti-spotting agents, soil-release agents, germicides, linear or branched silicones, fungicides, anti-oxidants, B, 2oz4~9~
g - C7203 anti-corrosion agents, preservatives such as Proxel, ascorbic acid, Bronopol (Trade Mark), a commercially available form of 2-bromo-2-nitropropane-1,3-diol, dyes, bleaches and bleach precursors, drape imparting agents, antistatic agents and ironing aids.
These optional ingredients, if added, preferably are present at levels up to 5% by weight of the composition.
The compositions according to the invention may be prepared by a variety of methods. One suitable method to prepare liquid products according to the invention is to form a molten mixture of the amine materials eventually in combination with other softening materials, and adding this premix to water under stirring to form a dispersion and thereafter adding the pH adjusting materials and any optional ingredients.
The invention will further be illustrated by means of the following examples.
EXAMPLE I
A di hardened tallow methyl amine (Armeen M2HT) was dispersed in water of ambient temperature to a concentration of 200 ppm of the amine. The pKa of the amine is 4.5. For tests 1-6, 1 litre of the 200 ppm amine dispersion was adjusted to the pH as indicated with HC1~.
Pieces of terry towelling of a total weight of 40g were rinsed for 5 minutes in the amine dispersion. The pieces were line dried. The amount of deposited amine was determined by measuring the change in turbidity of the rinse liquor. A higher deposition percentage corresponds to a better softening.
The following results were obtained.
TEST pH % deposited amine 1 3.0 (pKa-1.5) 95 2 3.5 (pKa-1.0) 81 3 4.0 (pKa-0.5) 68 4 4.5 (pKa) 50 5.0 (pKa+0.5) 40 6 6.0 (pKa+1.5) 30 These results indicate that a good deposition (over 50%) can be obtained when the pH of the rinse liquor is equal to or below the pKa of the amine. Especially good results are obtained when the rinse pH is at least 0.5 unit below the pKa of the amine.
EXAMPLE II
The performance and stability of several amine containing liquid fabric softening compositions was tested as follows:
A wash load of 1.25 kg of terry towelling and 1.25 kg *
of cotton sheeting fabrics was washed at 40°C in a Miele 756 automatic with 100g of*Persil Automatic (UK). 90 mls (corresponding to about 200 ppm for the amine concentration) of a rinse conditioner containing 5wt%
Armeen M2HT, lwt% tallow 35E0 and a variable amount of pH
adjusting material was added to the last rinse cycle. In table 3, the stability of the undiluted product, the pH of the undiluted product and the pH of the rinse water are given. A lower value for the pH of the rinse corresponds to a better softening performance.
*denotes trade mark B
-- 2~24fi99 pH adjuster undiluted product rinse type pKa conc(M) stability pH pH
HC1 <0.0 0.7 unstable 0.2 5.2 HC1 <0.0 0.9 unstable 0.1 4.4 HC1 <0.0 1.0 unstable 0.1 3.7 Oxalic 1.2 0.3 unstable 1.0 6.0 Oxalic 1.2 0.4 unstable 0.9 4.8 Oxalic 1.2 0.6 unstable 0.8 3.3 o-H3P04 2.1 0.6 stable 1.3 5.6 o-H3P04 2.1 0.9 stable 1.0 4.6 o-H3P04 2.1 1.2 unstable 0.8 3.8 Malonic 2.8 0.5 stable 1.7 5.4 Malonic 2.8 0.7 stable 1.5 4.7 Malonic 2.8 0.9 stable 1.4 3.4 Tartaric 3.2 0.4 stable 1.8 5.7 Tartaric 3.2 0.5 stable 1.7 4.5 Tartaric 3.2 0.8 stable 1.5 3.9 Citric 3.1 0.3 stable 2.0 5.6 Citric 3.1 0.5 stable 1.8 4.5 Citric 3.1 0.9 stable 1.6 3.8 Succinic 4.2 1.0 stable 2.3 4.5 Succinic 4.2 1.5 stable 2.2 4.2 These results show that if acids of low pKa such as HC1 and Oxalic acid are used, then stable products which give the required pH in the rinse cannot be formulated.
This illustrates the lower limit of 1.5 for the pKa of the pH adjuster in liquid products. If orthophosphoric acid is used for pH adjustment, stable products may be formulated, but at higher levels of the acid instability occurs, with orthophosphoric acid, these high levels of acids ar however necessary to lower the pH of the rinse liquor to a value below the pKa of the amine. Therefore for formulating Armeen M2HT systems, the use of orthophosphric acid as the pH adjusting material is less preferred.
If malonic, citric or tartaric acid are used stable compositions are obtained, which provide the preferred pH
value in the rinse only at relatively low levels of the ' acid material. Similar results may be obtained by using lactic acid. These materials are therefore preferred for use in Armeen M2HT systems.
If succinic acid is used, also stable products are obtained, but high levels of the acid material are necessary to obtain the preferred pH in the rinse liquor, these high levels of acid materials are sometimes less preferred for cost reasons.
A problem in the formulation of liquid products according to the invention is that the low pH requirement for the rinse liquor, generally requires high levels of pH
adjusting agents in the undiluted product. These high levels of pH adjusting agents, however, often cause the undiluted product to be unstable due to the flocculation of the dispersed amine phase resulting in phase separation. A second object of the present invention is to prevent instability of the undiluted product, while still ensuring that an adequate amount of pH adjusting materials are present.
It has been found that instability of liquid fabric softeners according to the invention can be prevented by ensuring that the pH adjusting agents are predominantly in their unionised form in the undiluted product.
Furthermore, the pH of the undiluted product may not be too low for consumer safety. Also the pH adjusting material should have a sufficiently low pKa to provide the required pH at a 200 ppm concentration of the amine. It has been found that a compromise between these factors can be reached by selecting a pH adjusting agent, which satisfies the following condition:
B
zo~4~99 1.5 < pKa (pH adjuster) < pKa (amine) More preferably:
2.0 < pKa (pH adjuster) < pKa(amine)-0.5 Most preferably:
2.5 < pKa (pH adjuster) < pKa(amine)-1.0 If pH adjusters are used which undergo more than one deprotonation step, then the pKa (pH adjuster) for use in the above given equations is the lowest pKa value of the pH adjusting material. For example citric acid has pKa values of 3.1, 4.8 and 6.4. In the above given equations the value 3.1 is used as the pKa (citric acid).
If more than one pH adjuster is used then the pKa value for the mixture of pH adjusters is the weight average pKa of the mixture of pH adjusting materials.
Other possible methods for increasing the stability of liquid products according to the invention are~for example, the use of pH adjusting agents, which are relatively insoluble in the undiluted product, but sufficiently soluble in the rinse liquor, and the use of ingredients which prevent flocculation of the dispersed phase. Examples of suitable deflocculating materials are disclosed in Canadian Patent application number 2,023,950, published March 1, 1991.
The ~H adiusting agents Compositions according to the invention also comprise one or more pH adjusting agents. As described above, the B
pH adjusting agents should provide a certain pH for the rinse water. As soon as the required pH for the rinse water has been determined in line with the teaching as given above, it is believed to be well within the ambit of the skilled person, to select the types and amounts of pH
adjusting materials necessary to obtain the required pH.
Generally the pH adjusting agents will be acid materials.
When the product of the invention is a liquid product, comprising an aqueous base it is preferred that the pH adjusting materials have a pKa which is above 1.5, but below the pKa of the amine. Again it is believed that as soon as the desired pKa for the pH adjusting agents has been found with help of the above teaching, then it is well within the ambit of the skilled person to select suitable acids and their amounts.
Typical concentrations for the pH adjusting materials in the liquid undiluted products are from 0.1 to 2.0 mole per litre, more preferably from 0.2 to 1.5 mole per litre, especially preferred from 0.25 to 1.0 mole per litre.
Preferred pH adjusting materials have a pKa of between 2.5 and 3.5. Examples of these materials are p-Aminobenzosulphonic acid, bromoacetic acid, chloroacetic acid, o-chloroacetic acid, alpha chlorobutyric acid, citric acid, dihydroxybenzoic acid, dimethylmalic acid, dimethylmalonic acid, dinicotinic acid, fumaric acid, furancarboxylic acid, iodoacetic acid, lactic acid, malic acid, malonic acid, methyl malonic acid, quinolinic acid, sulfanilic acid and tartaric acid. For environmental reasons the use of tartaric acid, lactic acid, citric acid, malonic acid or mixtures thereof is preferred.
t a - $ - C7203 Preferably the pH adjusting materials having a pKa of between 2.5 and 3.5 are used in combination with amines of formula (i), which comprise two long hydrocarbyl groups (C6-C24) and one short hydrocarbyl group (C1-C3).
Especially preferred is the use of these pH adjusting materials in combination with dihardened tallow methyl amine, as marketed under the tradename ARMEEN M2HT (Akzo).
Optional ingredients Compositions of the present invention may comprise in addition to the above mentioned amine and pH adjusting materials one or more other softener materials selected from cationic, amphoteric and nonionic softening materials. Suitable materials are for example described in EP 239 910 (P&G), US 3 915 865 (STEPAN) and US
4 137 180 (LEVER BROTHERS). Preferably the weight ratio of these additional softening materials to the total of the amine softening materials is less than 3:1, more preferred less than 1:1, especially preferred less than 0.5:1.
The composition can also contain one or more optional ingredients selected from non-aqueous solvents such as C1-C4 alkanols and polyhydric alcohols, rewetting agents, viscosity modifiers such as electrolytes or long (e. g.
25-40 EO) alkoxylated fatty alcohols, for example calcium chloride, antigelling agents, perfumes, perfume carriers, fluorescers, colourants, hydrotropes, antifoaming agents, antiredeposition agents, enzymes, optical brightening agents, opacifiers, stabilisers such as guar gum and polyethylene glycol, emulsifiers, anti-shrinking agents, anti-wrinkle agents, fabric crisping agents, anti-spotting agents, soil-release agents, germicides, linear or branched silicones, fungicides, anti-oxidants, B, 2oz4~9~
g - C7203 anti-corrosion agents, preservatives such as Proxel, ascorbic acid, Bronopol (Trade Mark), a commercially available form of 2-bromo-2-nitropropane-1,3-diol, dyes, bleaches and bleach precursors, drape imparting agents, antistatic agents and ironing aids.
These optional ingredients, if added, preferably are present at levels up to 5% by weight of the composition.
The compositions according to the invention may be prepared by a variety of methods. One suitable method to prepare liquid products according to the invention is to form a molten mixture of the amine materials eventually in combination with other softening materials, and adding this premix to water under stirring to form a dispersion and thereafter adding the pH adjusting materials and any optional ingredients.
The invention will further be illustrated by means of the following examples.
EXAMPLE I
A di hardened tallow methyl amine (Armeen M2HT) was dispersed in water of ambient temperature to a concentration of 200 ppm of the amine. The pKa of the amine is 4.5. For tests 1-6, 1 litre of the 200 ppm amine dispersion was adjusted to the pH as indicated with HC1~.
Pieces of terry towelling of a total weight of 40g were rinsed for 5 minutes in the amine dispersion. The pieces were line dried. The amount of deposited amine was determined by measuring the change in turbidity of the rinse liquor. A higher deposition percentage corresponds to a better softening.
The following results were obtained.
TEST pH % deposited amine 1 3.0 (pKa-1.5) 95 2 3.5 (pKa-1.0) 81 3 4.0 (pKa-0.5) 68 4 4.5 (pKa) 50 5.0 (pKa+0.5) 40 6 6.0 (pKa+1.5) 30 These results indicate that a good deposition (over 50%) can be obtained when the pH of the rinse liquor is equal to or below the pKa of the amine. Especially good results are obtained when the rinse pH is at least 0.5 unit below the pKa of the amine.
EXAMPLE II
The performance and stability of several amine containing liquid fabric softening compositions was tested as follows:
A wash load of 1.25 kg of terry towelling and 1.25 kg *
of cotton sheeting fabrics was washed at 40°C in a Miele 756 automatic with 100g of*Persil Automatic (UK). 90 mls (corresponding to about 200 ppm for the amine concentration) of a rinse conditioner containing 5wt%
Armeen M2HT, lwt% tallow 35E0 and a variable amount of pH
adjusting material was added to the last rinse cycle. In table 3, the stability of the undiluted product, the pH of the undiluted product and the pH of the rinse water are given. A lower value for the pH of the rinse corresponds to a better softening performance.
*denotes trade mark B
-- 2~24fi99 pH adjuster undiluted product rinse type pKa conc(M) stability pH pH
HC1 <0.0 0.7 unstable 0.2 5.2 HC1 <0.0 0.9 unstable 0.1 4.4 HC1 <0.0 1.0 unstable 0.1 3.7 Oxalic 1.2 0.3 unstable 1.0 6.0 Oxalic 1.2 0.4 unstable 0.9 4.8 Oxalic 1.2 0.6 unstable 0.8 3.3 o-H3P04 2.1 0.6 stable 1.3 5.6 o-H3P04 2.1 0.9 stable 1.0 4.6 o-H3P04 2.1 1.2 unstable 0.8 3.8 Malonic 2.8 0.5 stable 1.7 5.4 Malonic 2.8 0.7 stable 1.5 4.7 Malonic 2.8 0.9 stable 1.4 3.4 Tartaric 3.2 0.4 stable 1.8 5.7 Tartaric 3.2 0.5 stable 1.7 4.5 Tartaric 3.2 0.8 stable 1.5 3.9 Citric 3.1 0.3 stable 2.0 5.6 Citric 3.1 0.5 stable 1.8 4.5 Citric 3.1 0.9 stable 1.6 3.8 Succinic 4.2 1.0 stable 2.3 4.5 Succinic 4.2 1.5 stable 2.2 4.2 These results show that if acids of low pKa such as HC1 and Oxalic acid are used, then stable products which give the required pH in the rinse cannot be formulated.
This illustrates the lower limit of 1.5 for the pKa of the pH adjuster in liquid products. If orthophosphoric acid is used for pH adjustment, stable products may be formulated, but at higher levels of the acid instability occurs, with orthophosphoric acid, these high levels of acids ar however necessary to lower the pH of the rinse liquor to a value below the pKa of the amine. Therefore for formulating Armeen M2HT systems, the use of orthophosphric acid as the pH adjusting material is less preferred.
If malonic, citric or tartaric acid are used stable compositions are obtained, which provide the preferred pH
value in the rinse only at relatively low levels of the ' acid material. Similar results may be obtained by using lactic acid. These materials are therefore preferred for use in Armeen M2HT systems.
If succinic acid is used, also stable products are obtained, but high levels of the acid material are necessary to obtain the preferred pH in the rinse liquor, these high levels of acid materials are sometimes less preferred for cost reasons.
Claims (8)
1. A fabric softening composition comprising at least one amine softening material and at least one pH adjusting agent, wherein the pH of an aqueous liquor obtained by diluting said fabric softening composition to a concentration of 200 ppm of the amine materials has a pH which is equal to or below the pKa of the amine materials, the pka of the amine material being determined from the titration curve of a 1% dispersion of the amine material, said at least one amine softening material being selected from fabric softening amines of formula (I):
wherein either: (a) R15 and R16 are C6-24 hydrocarbyl groups and R17 is C1-3 hydrocarbyl; or (b) R15 is a hydrocarbyl group having at least 22 carbon atoms and R16 and R17 are C1-3 hydrocarbyl.
wherein either: (a) R15 and R16 are C6-24 hydrocarbyl groups and R17 is C1-3 hydrocarbyl; or (b) R15 is a hydrocarbyl group having at least 22 carbon atoms and R16 and R17 are C1-3 hydrocarbyl.
2. A fabric softening composition according to claim 1, wherein the pH of the diluted amine liquor is at least 0.5 unit below the pKa of the amine.
3. A fabric softening composition according to claim 1, being a liquid comprising an aqueous base, wherein the pH adjusting agent satisfies the following equation:
1.5 < pKa (pH adjuster) < pKa (amine)
1.5 < pKa (pH adjuster) < pKa (amine)
4. A fabric softening composition according to claim 3, wherein the pKa of the pH adjuster is from 2.5 to 3.5.
5. A fabric softening composition according to claim 3, wherein the pH adjusting agents are selected from the group of tartaric acid, lactic acid, citric acid and malonic acid or mixtures thereof.
6. A fabric softener composition according to claim 3, claim 4 or claim 5, wherein the concentration of the pH adjusting material is from 0.25 to 1.0 mole per litre.
7. A fabric softener composition according to claim 1 comprising, as fabric softening amine of formula (I)(b), 1,2 dihardened tallow oxydimethyl propane amine.
8. A method for the production of a fabric softening composition comprising combining at least one amine softening material and at least one pH adjusting agent which composition when diluted to a concentration of 200 ppm of the amine material has a pH which is equal to or below the pKa of the amine material, the pKa of the amine material being determined from the titration curve of a 1% dispersion of the amine material, said at least one amine softening material, said at least one amine softening material being selected from fabric softening amines of formula (I):
wherein either: (a) R15 and R16 are C6-24 hydrocarbyl groups and R17, is C1-3 hydrocarbyl ; or (b) R15 is a hydrocarbyl group having at least 22 carbon atoms and R16 and R17 are C1-3 hydrocarbyl.
wherein either: (a) R15 and R16 are C6-24 hydrocarbyl groups and R17, is C1-3 hydrocarbyl ; or (b) R15 is a hydrocarbyl group having at least 22 carbon atoms and R16 and R17 are C1-3 hydrocarbyl.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB898920468A GB8920468D0 (en) | 1989-09-11 | 1989-09-11 | Fabric softening |
| GB8920468.9 | 1989-09-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2024699A1 CA2024699A1 (en) | 1991-03-12 |
| CA2024699C true CA2024699C (en) | 2002-01-08 |
Family
ID=10662857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002024699A Expired - Fee Related CA2024699C (en) | 1989-09-11 | 1990-09-05 | Fabric softening |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0417987B1 (en) |
| JP (1) | JP2566177B2 (en) |
| AU (1) | AU635767B2 (en) |
| BR (1) | BR9004440A (en) |
| CA (1) | CA2024699C (en) |
| DE (1) | DE69025246T2 (en) |
| ES (1) | ES2084004T3 (en) |
| GB (1) | GB8920468D0 (en) |
| ZA (1) | ZA907142B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5312558A (en) * | 1991-04-04 | 1994-05-17 | Ibc Manufacturing Company | Pesticide composition |
| US5612372A (en) * | 1990-09-04 | 1997-03-18 | Ibc Manufacturing Company | Liquid dispersants for pesticides |
| NZ239522A (en) * | 1990-09-04 | 1993-10-26 | Chapman Chem Co | Pesticidal compositions containing an amine salt of a phosphonic or orthophosphoric acid |
| WO1994004642A2 (en) * | 1992-08-21 | 1994-03-03 | Colgate-Palmolive Company | Fabric conditioning composition |
| US5750491A (en) * | 1993-08-02 | 1998-05-12 | The Procter & Gamble Company | Super concentrate emulsions with fabric actives |
| EP0637625A1 (en) * | 1993-08-02 | 1995-02-08 | The Procter & Gamble Company | Super concentrate emulsions with fabric actives |
| EP0799887B1 (en) * | 1996-04-01 | 2003-06-11 | The Procter & Gamble Company | Fabric softener compositions |
| KR102582518B1 (en) * | 2016-02-29 | 2023-09-26 | 케미라 오와이제이 | softener composition |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3904359A (en) * | 1972-09-07 | 1975-09-09 | Colgate Palmolive Co | Post-wash fabric treating method |
| GB1514276A (en) * | 1975-10-22 | 1978-06-14 | Unilever Ltd | Fabric-softening compositions |
| US4157307A (en) * | 1978-08-07 | 1979-06-05 | The Procter & Gamble Company | Liquid fabric softener |
| DE2841076C2 (en) * | 1978-09-21 | 1980-02-14 | Basf Ag, 6700 Ludwigshafen | Process for the liquefaction of aqueous fabric softeners |
| US4320013A (en) * | 1980-06-10 | 1982-03-16 | The Procter & Gamble Company | Fabric conditioning compositions |
| ATE13562T1 (en) * | 1981-01-16 | 1985-06-15 | Procter & Gamble | TEXTILE TREATMENT AGENTS. |
| GB8508129D0 (en) * | 1985-03-28 | 1985-05-01 | Procter & Gamble Ltd | Textile treatment composition |
| GB2172910B (en) * | 1985-03-28 | 1989-06-21 | Procter & Gamble | Detergent containing a fabric conditioner |
| DE3661481D1 (en) * | 1985-05-28 | 1989-01-26 | Unilever Nv | Liquid cleaning and softening compositions |
| MX169902B (en) * | 1986-07-10 | 1993-07-30 | Colgate Palmolive Co | IMPROVEMENTS TO FABRIC CONDITIONING COMPOSITIONS THROUGH WASHING |
| US4828722A (en) * | 1986-07-10 | 1989-05-09 | Colgate-Palmolive Co. | Through the wash fabric conditioning compositions |
| NO170944C (en) * | 1987-01-24 | 1992-12-30 | Akzo Nv | THICKNESSED, MOISTURE PREPARATIONS, AND USE OF SUCH |
| GB8804555D0 (en) * | 1988-02-26 | 1988-03-30 | Procter & Gamble | Imidazole compounds & textile treatment compositions containing them |
| US4869836A (en) * | 1988-05-03 | 1989-09-26 | Colgate-Palmolive Co. | Wash cycle fabric conditioning compositions: tertiaryamine-multi-functional carboxylic acid complex |
| US4863620A (en) * | 1988-10-18 | 1989-09-05 | The Procter & Gamble Company | Acidic liquid fabric softener with yellow color that changes to blue upon dilution |
| GB8916308D0 (en) * | 1989-07-17 | 1989-08-31 | Unilever Plc | Fabric softening |
-
1989
- 1989-09-11 GB GB898920468A patent/GB8920468D0/en active Pending
-
1990
- 1990-09-05 CA CA002024699A patent/CA2024699C/en not_active Expired - Fee Related
- 1990-09-06 BR BR909004440A patent/BR9004440A/en not_active IP Right Cessation
- 1990-09-07 ES ES90309792T patent/ES2084004T3/en not_active Expired - Lifetime
- 1990-09-07 ZA ZA907142A patent/ZA907142B/en unknown
- 1990-09-07 AU AU62234/90A patent/AU635767B2/en not_active Ceased
- 1990-09-07 DE DE69025246T patent/DE69025246T2/en not_active Revoked
- 1990-09-07 EP EP90309792A patent/EP0417987B1/en not_active Revoked
- 1990-09-11 JP JP2241031A patent/JP2566177B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0417987B1 (en) | 1996-02-07 |
| JPH03137280A (en) | 1991-06-11 |
| EP0417987A3 (en) | 1991-08-14 |
| JP2566177B2 (en) | 1996-12-25 |
| EP0417987A2 (en) | 1991-03-20 |
| ES2084004T3 (en) | 1996-05-01 |
| DE69025246D1 (en) | 1996-03-21 |
| BR9004440A (en) | 1991-09-10 |
| AU635767B2 (en) | 1993-04-01 |
| DE69025246T2 (en) | 1996-06-27 |
| CA2024699A1 (en) | 1991-03-12 |
| ZA907142B (en) | 1992-05-27 |
| GB8920468D0 (en) | 1989-10-25 |
| AU6223490A (en) | 1991-03-14 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |