RO121133B1 - Stabilized quaternary ammonium compositions, process for preparing the same and conditioner containing it - Google Patents

Abstract

The invention relates to a stabilized quaternary ammonium composition, to a process for preparing the same and to a conditioner containing it, meant to be used for cloths softening. According to the invention, the composition comprises besides the quaternary ammonium material represented by the formula: one or several stabilizing agents selected from among urea, urea derivatives, primary or secondary amides and/or polyhydric alcohols, which are present in amounts ranging from 0.05 to 10% by weight in respect of the weight of the quaternary ammonium material, the claimed composition being presented in liquid, melted, semi-solid or solid form, containing less than 10% by weight of water. The claimed process consists in including the stabilizing agent admixing stage during the manufacturing process, after the quaternarization stage, or during the storage of the quaternary ammonium material

Description

Any interested person has the right to file in writing and motivated, at OSIM, a request to revoke the decision to grant the patent, within 6 months from the publication of its mention.

RO 121133 Β1

The invention relates to the stabilized quaternary ammonium-based composition, to a process for obtaining it and to a conditioning product containing it, used for the fabric softening. In particular, the invention relates to maintaining the stability of quaternary ammonium-based materials containing at least one ester group, in the form of a starting material or as a solution in a suitable solvent.

Quaternary ammonium based materials, both solid and liquid, are widely used in fabric softening compositions. Typically, such compositions contain a quaternary ammonium-based, water-insoluble fabric softening agent, dispersed in water at a concentration of the quaternary ammonium-based emollient up to 8% by weight, which compositions are considered diluted or at concentrations from 8 to 50%, in which case the compositions are considered concentrated.

A problem associated with quaternary ammonium-based materials containing at least one steric group is storage instability.

The problem arises especially when storing these materials at varying temperatures over time.

The instability of quaternary ammonium-based materials, both solid and liquid, is manifested by discoloration of these materials during storage at different temperatures. The size of the discoloration is generally an indication of the level of decomposition that occurs over time. This decomposition is greatest when the quaternary ammonium material is stored at temperatures above their melting point.

In the past, the stability of quaternary ammonium compounds was improved by storing the compounds at low temperatures, ie at temperatures below the melting points of the compounds to be stored. Also, antioxidants were added to counteract the breakdown.

EP 299176 (Kao) discloses emollient finishing agents comprising a long, double chain quaternary ammonium salt, containing a single ester group and a decilimethyl amine.

US 4937008 (Kao) discloses concentrated emollient agents for fabrics comprising one or more quaternary ammonium salts and a di- or tn-valent polyol having 2 to 3 carbon atoms.

The technical problem to be solved by the invention is to determine the components, their proportions and working parameters, so as to ensure that a high level of quaternary ammonium compound is maintained and that high levels of decomposition products are avoided and, thus, improve the stability at low and high temperature of quaternary ammonium compounds.

In a first aspect, the invention relates to a stabilized quaternary ammonium based composition, which in addition to the quaternary ammonium material represented by the formula:

R ¹ * '- y— ichj ^ ta ² χ- w

Wherein each R ¹ group is independently selected from CM, hydroxyalkyl or 1 C 2-4 alkenyl groups; and wherein each R ² group is independently selected from C 8 alkyl groups. ₂₈ or alkenyl; X 'is any suitable counterion, 3

T is

OO ⁵

OC- or CO-; _q n is an integer from 1-5 or is 0, further comprising one or more stabilizing agents, wherein said stabilizing agent (s) is chosen (are chosen) from the group consisting of:

a) urea;

b) urea derivatives;

c) primary or secondary amides and / or

d) polyhydric alcohols and are present in quantities from 0.05 to 10% by weight, based on the weight of the material based on quaternary ammonium, preferably from 0.5 to 6.0% and even more preferably from 0.5 to 4%, provided that the composition is in liquid, molten, semi-solid or solid form, containing less than 10% by weight of water.

In a second aspect, the invention relates to a process for obtaining the quaternary ammonium-based composition, represented by the formula:

R ¹ —N * —— tC ^ gTR ⁸ χ; W "CWT-R ² wherein each R ¹ group is independently selected from C 1-6 alkyl, hydroxyalkyl or C ₂₄ alkenyl groups; and wherein each R ² group is independently selected from the alkyl or alkenyl X groups is any suitable counterion,

T is

O-C 'or-C-O-;

n is an integer from 1-5 or is 0 and further comprises the step of adding at least one stabilizing agent to the material on quaternary ammonium base 43, wherein the stabilizing agent is selected from one or more of the group consisting of: 45

a) urea;

b) urea derivatives; 47

c) primary or secondary amides, and / or

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d) polyhydric alcohols and is present in quantities of 0.05 to 10% by weight, based on the weight of the material based on quaternary ammonium, preferably 0.5 to 6.0% and even more preferably 0.5 to 4%, provided that the composition is in liquid, molten, semi-solid or solid form, containing less than 10% by weight of water.

The step of adding at least one stabilizing agent takes place during the manufacture of the quaternary ammonium material, preferably after the quaternization step, in the synthesis of the quaternary ammonium material or after the manufacture of the quaternary ammonium material, preferably during material storage. of quaternary ammonium.

In a third aspect, the invention relates to the use of a stabilizing agent, as defined above, to reduce the bleaching level of the quaternary ammonium-based material containing at least one ester group.

In a fourth aspect, the invention relates to a rinse aid product, liquid or solid, comprising the stabilized composition, based on quaternary ammonium, as defined above.

As mentioned, in a first aspect the invention relates to a quaternary ammonium-based composition, with improved stability, which contains at least one ester group characterized in that it further comprises one or more stabilizing agents, stabilizing agents. mentioned being strong donors of hydrogen bonds.

In a second aspect, the invention relates to a process for obtaining the stabilized quaternary ammonium-based composition, which contains at least one ester group, through the steps of adding at least one stabilizing agent to the ammonium-based material. Quaternary, wherein the stabilizing agent is a strong hydrogen bond donor.

In a third aspect, the invention provides for a reduction in the level of bleaching of the quaternary ammonium material containing at least one ester group over time, by the addition of a stabilizing agent, as mentioned.

In a fourth aspect of the present invention, the defined composition is incorporated into a conditioning agent for solid and / or liquid rinsing.

In the present invention, the term "ester group" in the quaternary ammonium composition includes an ester group, which is a bonding group in the molecule. References to the quaternary ammonium material include, in the present invention, those having at least one ester group in their structure.

Preferably, the stabilizing agent (s) is (are) chosen from one or more of the following groups comprising:

a) urea;

b) urea derivatives;

c) primary or secondary amides, and / or

d) polyhydric alcohols.

The compositions according to the invention have improved stability at different temperatures, in the present specification, quaternary ammonium compounds containing at least one ester group are referred to as quaternary ammonium compounds having an ester bond.

It is preferred that the quaternary ammonium compounds contain two or more ester groups. In both monoesteric and diesteric quaternary ammonium compounds, according to the invention, it is preferred that the ester group (s) represent a bonding group between the nitrogen atom and an alkyl group. The ester group (s) are preferably attached to the nitrogen atom via another hydrocarbon group.

The invention has the highest efficacy for quaternary ammonium compounds containing at least one ester group, preferably two, wherein at least one high molecular weight group containing at least one ester group and two or three mass groups

These small molecular molecules are linked to a common nitrogen atom to produce a cation and wherein the anion of electric equilibrium is a halide, acetate or lower alkosulfate ion, such as chloride or metosulfate. The high molecular weight nitrogen substituent is preferably an upper alkyl group, containing 12 to 28, preferably 12 to 22, for example 12 to 20 carbon atoms, such as coco-alkyl, fats. alkylated amines, 5 hydrogenated alkylated animal fats or substituted higher alkyls and low molecular weight substituents are preferably lower alkyl with 1 to 4 carbon atoms, such as 7 methyl or ethyl or substituted lower alkyl. One or more of the aforementioned low molecular weight substituents may include an aryl residue or may be replaced with an aryl, such as benzyl, 9 phenyl or other suitable substituents.

Preferably, the quaternary ammonium compound used in the present invention is a compound having two C ₁₂ -C ₂₂ alkyl or alkenyl groups linked to a quaternary ammonium end group via at least one ester bond, preferably two ester 13 bonds. or a compound comprising a single long chain with an average chain length equal to or greater than C ₂₀ . 15

More preferably, the invention is useful for quaternary ammonium-based materials, comprising a compound having two long alkyl or alkenyl chains having an average chain length 17 equal to or greater than C ₁₄ . Even more preferably, each chain has an average chain length equal to or greater than C ₁₆ . Most preferably at least 50% of each alkyl group 19 or long chain alkenyl has a length of chain C ₁₆ . Long chain alkyl or alkenyl groups are preferred which are predominantly linear. 21

The abovementioned problems are specifically associated with quaternary ammonium compounds having an ester bond and wherein the compound has two or three attractive groups of 23 electrons bound to the quaternary nitrogen atom by one or two carbon atoms from different substituents and a methyl group. all attached to said nitrogen atom. This arrangement 25 is presented in formula (A). Such compounds having a chloride counterion have been found to have the advantage of stability. 27

The applicant considers that the discoloration / instability problems are most common in quaternary ammonium compounds containing an ester bonding group and having a methyl group of nitrogen and a chloride counterion and two or three attractive groups of electrons attached separately to the atom. of quaternary nitrogen. 31

Although quaternary ammonium compounds of the general formula (B), presented below, may suffer from discoloration and instability, these problems are the most dominant in the case of type (A) compounds presented below and in particular in the aforementioned compounds. 35

The ester-bonded quaternary ammonium compound, especially preferred for use in the present invention, can be represented by the formula: 37 ^r1 39, U (A) ^R - t - (CW ^{T 4.2} x 'in which each group R ¹ is independently selected from C 1-6 alkyl, hydroxyalkyl or 45 C 2-4 alkenyl groups; and wherein each R ² group is independently selected from C 8 alkyl or alkenyl groups. ₂₈ ; X is any suitable counterion, i.e., a halide, acetate or alkosulfate ion. 47, such as chloride or metosulfate.

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T is

Ο Ο

O-C- or-C-O-, and η is an integer from 1-5 or is 0.

It is particularly preferred that each R ¹ group is methyl and each n is 2, as such compounds are particularly susceptible to the aforementioned stability problems.

Hoechst's dimethyl ammonium di (thaloyloxyethylate) chloride is particularly preferred, as is Hoechst's dimethyl ammonium di (thaloyloxyethylate chloride).

Another preferred type of quaternary ammonium based material with an ester bond can be used according to the invention is represented by the formula:

OOCR ² (B) (R ¹ > 3 * · * --- (CH2) _n - CH X “

I _t

CHjQCOR ² wherein R ¹ , n, R ² and X 'have the meanings presented above.

It has been found that these materials do not exhibit such a tendency for instability, especially at elevated temperatures, for example 60-70 ° C compared to the compounds of the preceding formula.

For environmental reasons it is advantageous for the quaternary ammonium material to be biodegradable.

Preferred materials of this class, such as 1.2 bis (cured thalloxy) 3-trimethylammonium propane chloride and its method of preparation, are described, for example, in US 4137180 (Lever Brothers). Preferably, these materials comprise small amounts of Suitable monoester, as described in US 4137180, for example 1-thaloyloxy hardened chloride -2-hydroxy-3-trimethylammonium propane.

It is particularly preferred that the quaternary ammonium material according to the invention comprises at least one methyl group attached to the quaternary nitrogen atom, with two or three substituents on the nitrogen atom containing attractive groups of electrons and having chloride counterion. It is particularly preferred to use those compounds having the general formula A and even more preferred is that such compounds have two methyl substituents on nitrogen and in the rest of the radicals n is 1 or 2 and R ² is C ₁₂ -C. ₂₂ , especially C ₁₆ -C ₂₂ , for example, natural fat.

It is also preferred that the quaternary ammonium compound used in the present invention is practically anhydrous, ie containing less than 10% water.

The quaternary ammonium material may contain optional additional components known in the art, in particular low molecular weight solvents, for example isopropanol and / or ethanol, and co-active agents, such as nonionic emollient agents, for example esters of an acid. fat or sorbitan.

The types of stabilizing agents that can be used are those that are powerful hydrogen bond donors.

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The stabilizing agent may be urea or a derivative thereof, a primary or secondary amide or a polyhydric alcohol or mixtures thereof. Two or more stabilizing agents may be used.

The stabilizing agent is added to the composition according to the invention, preferably in amounts of 0.05 to 10% by weight, based on the weight of the quaternary ammonium material. However, smaller quantities are preferred, more preferably 0.1 to 7.5% is added relative to the weight of the quaternary ammonium material, in particular 0.5 to 6.0% and even more preferably 0.5 to 4%.

The stabilizing agent may be introduced into the quaternary ammonium material at any stage during the manufacture of the quaternary ammonium material or after manufacture, for example during storage. The destabilizing agent may be added in any form, in powder form directly to the melt of quaternary ammonium material or as a solution in a suitable solvent, for example isopropanol.

The addition step may occur during the synthesis of the quaternary ammonium material, preferably after the quaternization step. Addition may occur, alternatively or additionally, during storage of the quaternary ammonium material.

The stabilizing agent is most efficiently introduced at any stage subsequent to the quaternization step in the synthesis of quaternary ammonium material.

An example of an amide that can be used in the present invention is acetamide. Polyhydric alcohols, such as glycerol, can be used as stabilizing agents. Another preferred stabilizing agent is urea. Particularly preferred is a combination of glycerin and a quaternary ammonium compound of the general formula (A), especially where both R ¹ are CH ₃ , n is 2 and R ² is natural fat.

The stabilized composition may be in liquid, molten or semi-solid form, containing less than 10% by weight of water.

The invention further includes a solid-state rinse conditioning product comprising a stabilized composition as defined above, preferably a granular or powdered composition. Another type of conditioning product according to the invention is a liquid conditioning product, comprising the stabilized composition defined above.

The invention has the following advantages:

- increasing the storage stability of the composition based on quaternary ammonium material;

- the possibility of conditioning in different forms.

Following are examples of embodiments of the invention. Other examples that fall within the scope of the invention will be obvious to those skilled in the art.

Examples. Urea is added to a quaternary ammonium powder material and heated to 82 ”C. The obtained composition was stored for three days.

The reflectance was measured with a Spectraflash SF 600 reflectometer after 3 days of 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

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DEQ is the di (2- [hardened natural fat] oxyloxyethyl) dimethyl ammonium chloride from Hoechst. This includes about 10% mono ester and small amounts of non-quaternized amine salt / amine, as well as about 2% fatty acid and 14% isopropanol.

These results show that by the presence of urea in the compositions containing quaternary ammonium compound, decomposition at high temperature is counteracted. This fact is indicated by the high values of the R540 reflectance determined in the case of the composition samples according to the invention containing quaternary ammonium compound in the presence of urea, stored under the conditions specified in the table.

Claims (6)

claims 1. Stabilized quaternary ammonium based composition comprising quaternary ammonium material represented by the formula: R ¹ (A) | ⁺ - MWir ^T * x (CH -TR * wherein each R ¹ is independently selected from CM alkyl, CM hydroxyalkyl, or alkenyl; and wherein each R ² is independently selected from C8 alkyl groups. _2B or alkenyl; X 'is any appropriate counterion, T is O O I I O-C- or -C-O-; n is an integer from 1-5 or is 0, characterized in that it also comprises one or more stabilizing agents, in which the mentioned stabilizing agent (s) is chosen (are chosen) from the group consisting of: a) urea; b) urea derivatives; c) primary or secondary amides and / or d) polyhydric alcohols and are present in quantities from 0.05 to 10% by weight, based on the weight of the material based on quaternary ammonium, preferably from 0.5 to 6.0% and even more preferably from 0.5 to 4%, provided that the composition is in liquid, molten, semi-solid or solid form, containing less than 10% by weight of water. 2. Process for obtaining the stabilized composition, defined in claim 1, based on quaternary ammonium material, represented by the formula: R ¹ (A) - y ⁺ - IC »W ^T ** x (CH ^ -TR * Wherein each R ¹ group is independently selected from C 14 alkyl, hydroxyalkyl or 1 C 2 alkenyl groups; and wherein each R ² group is independently selected from C 8 alkyl or alkenyl groups. ₂₈ ; X 'is any suitable counterion, 3 T is OC- or CO-; ₉ n is an integer from 1-5 or is 0 which comprises the step of adding to the quaternary ammonium material of at least one stabilizing agent, wherein the stabilizing agent is selected from one or more of the group. of: 13 a) urea; b) urea derivatives; 15 c) primary or secondary amides, and / or d) polyhydric alcohols and is present in quantities of 0.05 to 10% by weight, relative to the weight of the material based on quaternary ammonium, preferably 0.5 to 6.0% and even more preferably 0, 5 to 4%, provided that the composition is in liquid, melted, 19 semi-solid or solid form, containing less than 10% by weight of water. The process of claim 2, wherein the step of adding at least one stabilizing agent 21 occurs during the manufacture of the quaternary ammonium material, preferably after the quaternization step, in the synthesis of the quaternary ammonium material. 2. 3 The process of claim 2, wherein the step of adding at least one stabilizing agent occurs after the manufacture of the quaternary ammonium material, preferably 25, during the storage of the quaternary ammonium material. 5. The use of a stabilizing agent, as defined in claim 1, for reducing the bleaching level of the quaternary ammonium material containing at least one ester group. 29 6. A rinse aid product, liquid or solid, comprising a stabilized composition, as defined in claim 1. 31