JPH07500637A - biodegradable fabric softener - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] biodegradable fabric softener The present invention relates to fiber softeners, particularly those having one or more long chain alkyl or alkenyl groups. amine compound.

1m textile softener, used to make textiles soft to the touch after washing, commercially available laundry products such as detergents, rinsing agents and washing Mixed with desiccant. A typical commercially available fabric softener is dimethylene Rudistearyl ammonium chloride and 1-methyl-2-chloroalkyl- Contains 3-tallowamide ethylimidazolinium mesosulfate. this Known fabric softeners such as Although it has only a sex, it is widely used mainly in households after passing through the sewage system. Finally, it becomes urban sewage, which is a serious problem with large amounts of them complicating its purification. Show shortcomings.

Therefore, there is a need for new fabric softeners that are more easily biodegradable.

Furthermore, neither these softeners nor their biodegradation products exhibit any toxicity. The present invention accomplishes this by providing fiber softeners based on amine compounds. The purpose is to meet the needs of

Amine-containing fabric softeners have been previously described.

Canadian Patent No. 1,464,470 for many formulations, including fabric softener formulations. As the addition side, protonated (prot.

nate+j) discloses a wide range of uses for amines. Which of the disclosed compounds? No suggestion is given as to whether any of them themselves exhibit softening activity.

European Patent Application No. 281.975 discloses a wide range of amines, which When formulated with carboxylic acids having from 1 to 24 carbon atoms, it has a softening effect. Are any of the disclosed compounds that serve as activating ingredients biodegradable? No indication is given as to whether or not.

European Patent Application No. 417.987 (published after priority 8, which the present invention has) Under certain conditions, it appears to be an effective softener when prescribed with pHg 8. Certain amines have been disclosed. This disclosure provides amine-based softeners. One major problem faced by those skilled in the art when attempting to provide: amine-containing fiber soft side compositions. Explain that objects often do not soften very well.

European Patent No. 293,953 describes a quaternary ammonium containing one ester group. The present invention relates to a fabric softener including a fabric softener.

The disclosed quaternary ammonium compounds are described to be biodegradable. However, further improvement is desired in this regard.This disclosure does not provide effective biodegradable It is not concerned with the issue of prescribing fabric softeners based on min.

German Patent Publication No. 2728841 describes quaternary ammonia with two ester moieties. discloses fabric softeners based on um compounds. This disclosure relates to biodegradable The above-mentioned advantages of formulating effective softeners based on amine compounds rather than those mentioned above It doesn't even mention the problem.

A select group of amine compounds makes them more effective textile softeners than other amines and exhibit unexpected favorable properties that make them more easily biodegradable. was looked up to here.

Therefore, the present invention provides the following formula 1: %formula% (Here, R represents an alkyl or alkenyl group having 7 to 22 carbon atoms. and Ro represents an alkyl or alkenyl group having 7 to 21 carbon atoms, R" and R°°" may be the same or different and have 1 to 6 carbon atoms represents an alkyl or hydroxyalkyl group, P is equal to 0 or 1, and X- represents an anion) is an ester group-containing cationic nitrogen compound. A biodegradable fabric softener comprising:

This amine needs to be protonated to provide the desired softening activity.

This is generally low enough to allow the amine to be present in protonated form during the rinse. achieved by using amines in fiber softening compositions with low pH. Ru. This means that the amine is present in the softener composition along with the acid.

Therefore, the counter ion X'' is an acid group.

Surprisingly, effective softeners can be protonated without the need for additional steps. It should be noted that the present invention's selected group of amines yields .gamma.

This is as described in the above-referenced European Patent Application No. 417.987. Such additional steps do not adversely affect the performance of the softeners of the present invention. So On the contrary, European patent application no. When applied to , compared to Armeen H211T (trademark) Even better softening performance is achieved. Rather, it does not require any additional steps This indicates an unexpected or unique performance of selected amines of the present invention. Emphasize.

Preferred implementation of the invention! Sa! According to the cationic nitrogen compound, the following formula 2: (Here, R represents an alkyl or alkenyl group having 8 to 22 carbon atoms. and R', R'', Rooo and X- may have the meanings disclosed above) has.

According to a further preferred solid line embodiment of the present invention, the cationic nitrogen compound has the following formula 3: %formula% (where R and Ro are alkyl or alkyl having 8 to 22 carbon atoms. R'', R° and X- may have the meanings disclosed above) do.

Amine compounds of the latter formula are the same as those disclosed in European Patent Application No. 417,987. It is more easily biodegradable than H2HT (trademark). In particular, R'' and R゛° are methyl and R and ■( “is a C15/1□ saturated hydrocarbon.

In the formula L, R and Ro are preferably derived from fatty acids or mixtures thereof. 6 does not represent an essentially linear alkyl or alkenyl group that can be derived from For this purpose, alkyl derivatives derived from natural fatty acid mixtures (r2t LIX, Example i - tallow alkyl, hydrogenated Tallowargyl (H-tallowalkyl) and cocoalkyl (cocoalk) yl), these groups are also useful because they are readily available at low cost. It is preferably used in the biodegradable cod softener of the present invention.

The nature of the short-chain (hydroxy)alkyl groups depends on the starting materials. actual Methyl and 2-hydroxyethyl are preferred.

As mentioned above, the fluorons in the detonated amine are acidic fiber softeners. It can be hydrogen derived from the side medium.

The counterion X- is an acid group, preferably an organic carboxylic acid, especially a hydroxycarboxylic acid Citric acid, malic acid and glycolic acid are suitable for 1Ml of acid groups. be. Of course, acids are known to those skilled in the art and need not be further explained here. To affect the protonation of the amines of this invention, the acid is added to the grass with an equivalent amount of amine. Complex systems such as those disclosed in European Patent Application No. 281.975, which require mixing No additional melting step is required.

The cationic nitrogen compounds of the invention can be prepared by methods known for the preparation of similar compounds. It can be manufactured by In later examples, prismatic cationic nitrogen compounds of the invention The production of the remaining biodegradable fabric softeners of the invention is described in detail and the remaining biodegradable fabric softeners of interest are l) are directly available to those skilled in the art through adaptation of one-shot materials.

The method to which the biodegradable fabric softener of the present invention is applied is based on the conventional and currently commercially available Same as available fabric softeners. The usual possibility in this respect is to mix with detergents Use this formulation or add it to another/Z, i.e. rinse cycle Can be added as a rinse agent in the Dinse-cycle or else in the dryer. That is. The softener of the present invention is particularly useful as a softener added to Susuki° cycles. It is advantageous.

The fiber softening effect intended and achieved here is at least as strong as the conventional quaternary anhydride. Same as Monium fiber softener.

Inevitably, some of the fabric softener will become sewage after rinsing and dripping. However, because of the present invention, the accelerated biodegradability results in less harm to the environment. do not have.

The biodegradable fiber softener of the present invention was tested for fiber softening performance and dimethylamino (dihardened)riX':! Ammonium chloride, distearylua Ammonium chloride and 1-methyl-2-crowalkyl-3-tallowamide - was found to be comparable to ethylimidazolinium mesosulphate.

In the test, towels treated with the textile softener in question were line dried for 24 hours, then I It was cut into strips of Gx2Gcn.

The test panel evaluated the softening action in comparison to a standard test detergent (IEc), where: The observation takes were statistically processed according to DIN standard 10954.

The quaternary ammonium compound of the present invention, EEC10ECD Kiteline 0ECD 301 [1r closed test M (closed bo mouth 1e test L+) Once tested for biodegradability. In this fruit @, the test compound is 1 1! When added to a hot aqueous solution of salts, it kills a relatively small number of microorganisms for 28 days in an atmospheric environment. Interspersed:.

The official test regulations deviate from the following non-critical points in the EEC guidelines: The activated slump, adjusted by T. Remove the inoculum from the V-sludc+e (sludc+e) device and -Ammonium chloride is used as a medium to avoid valueization! 414.1 Not included Ta.

Dissolved oxygen a degree, oxygen electric% (IITW TrioxIIatic EO200 ) and an oxygen gauge (formerly W OXI 530). Biodegradability is defined by the theory of biological oxygen demand i fBOD) n (j oxygen demand slope flhO D) to 1' ratio: 6L calculated as BOD, 'Th01) Compared to the 1m soft shaved cod that is available in the market, significantly accelerated biodegradation performance was observed. It was noticed.

The invention will be further illustrated with reference to the following examples.

K1■” 544 g (2 mol) of hydrogenated tallow fatty acid was melted and heated using a temperature control device and rectification. 3-dimethylamino-1,2 in a 3-day nine-bottomed flask with equipment. - 130 g (], t mol) of propanediol. Homogeneous mixture at 190 °C and 1 (10 mbar for 4 hours, then 190' (: and 5 mbar) The mixture was stirred for 2 hours.

Conversion was monitored using rLC or <; After 6 hours, the raw dTh power composition is: - Diester amine 90.4%, monoester amine 4.9% and and free fatty acids 47? fruit.

Diester amines can be converted into corresponding diester amines by oxidation of 1 C and 1 C of citric acid. It was converted into a cationic nitrogen compound. Is this bundling 5 weight? 6 Jesus Tellamine and our! 1.66 weight? While stirring the hydrate in citric acid 17 of t. This was done by adding it to water. In embodiments using per-t1 acids, 5 Add a heavy diesteramine and 5% by weight of citric acid monohydrate to water. Ta. 7 Example 2 where stable 5'T adhesive was produced by adding ester amine to water 272 g (1 mol) of hydrogenated tallow fat fi was melted and prepared as described in Example 1. In the same manner as above, 3-dimethylamino, 2-propanediol 130+g (1,1 mol).

The reaction was stopped after 2.5 hours. The product contains 65% monoester amine there was.

Protonation with citric acid monohydrate converts the monoester amine into the corresponding cation. was converted into a nitrogenous compound. This protonation was performed using 5% by weight of monoester amine. and an equivalent amount of 2.8% by weight of citric acid monohydrate to the water with stirring. I went there. For embodiments using excess acid, 5% by weight monoester Ruamine and 5% by weight of citric acid R1 hydrate were added to the water. monoester to water Addition of amine resulted in a clear solution.

The results achieved with the 11" Ilonized amine softeners of the present invention demonstrate the softening performance and Call/! ：It can be summarized as follows by decomposing the physical property of the substance.

The softening performance is expressed as follows: - Insufficient + Satisfied +10 good 10++ l is missing Biodegradability is indicated by the percentage of degradation after 28 days.

A compound is considered "readily biodegradable" when biodegradability is ≧60%.

A percentage above 70% indicates further improved biodegradability, which is the highest Can be considered biodegradable. The margin of error in these tests is typically 10%. 6 The following compounds according to the formula given in claim 1 were used: AIR and Ro are saturated C15/1□ hydrocarbons, BAR and Ro are saturated C carbonized hydrogen, CAR - saturated C hydrocarbon, Ro-hydrogen atom In order to compare amines according to the invention with amines not according to the invention, Arneen 8211 (Commercial W) was used. This is the formula: (where Ro is a hardenecl tallow alkyl group) Not satisfied.

The results were as follows: Compound Protonated Softening Pure Amine Amine Formula Biodegradable A Citric acid, equivalent weight +→ 78 A Citric acid, excess amount 10++ B Citric acid, equivalent weight 4 63 B Citric acid, excess amount 10+ C citric acid, equivalent weight +4 59 C citric acid, excess 1 now Arneen H2HT citric acid, equivalent -60Arneen H2HT Enoic acid, excess amount ++ From the table above, protonated amine according to the invention appears to be a preferred biodegradable softener. Also, according to the present invention Non-protonated amine formulations may compromise the fabric softener, but additional steps may be required. It is also clear that it would not exhibit this amazing softening effect without it.

Algae (^1 (lael) - Acute poisoning using Daphnia fDaphnia and fish In the tests, low values were established for the amine compounds of the present invention, i.e. That is, the LC50 and [C50 values are at least above and above I ODIm, respectively. For the preferred ester amine (A) identified above, these values are 1 It was above 0pp1m. These tests were performed according to Hirabe known to those skilled in the art. Therefore, there is no need to write it here.

International Inquiry Assistance 1. , ++1mu~+PCT/EP 9110217g

Claims (11)

[Claims] 1. The following formula 1: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (Here, R represents an alkyl or alkenyl group having 7 to 22 carbon atoms. and R' represents an alkyl or alkenyl group having 7 to 21 carbon atoms, R'' and R''' may be the same or different and have 1 to 6 carbon atoms; represents an alkyl or hydroxyalkyl group, p is equal to 0 or 1, and X An essential component is a cationic nitrogen compound containing an ester group (- represents an anion). As a biodegradable fabric softener. 2. The cationic nitrogen compound has the following formula 2: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (Here, R represents an alkyl or alkenyl group having 8 to 22 carbon atoms. However, R', R'', R''' and X- have the meanings disclosed in claim 1. The fabric softener according to claim 1, which has the following properties: 3. The cationic nitrogen compound has the following formula 3: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (where R and R' are alkyl or alkyl having 7 to 14 carbon atoms) represents a nyl group, and R'', R''' and X- have the meaning disclosed in claim 1. The fabric softener according to claim 1, which has the following properties: 4. R represents one or more alkyl groups having 12 to 18 carbon atoms, more particularly is H-tallowalkyl or cocoalkyl according to any of claims 1 to 2. The fiber softener according to item 1. 5. R' represents one or more alkyl groups having 11 to 17 carbon atoms, more particularly is derived from H-tallowacyl or cocoacil. The fiber softener according to any one of items 1 and 2. 6. R' represents one or more alkyl groups having 11 to 13 carbon atoms, more particularly The fiber according to claim 1 or 2, which is derived from cocoa sil. fiber softener. 7. Claims 1 to 3 in which R'' represents a methyl or 2-hydroxyethyl group The fiber softener according to any one of the above. 8. According to any one of claims 1 to 3, wherein X- represents a citrate ion. Fiber softener. 9. protonated (2-H-tallowacyloxy-2-cocoalkylethyl ) Dimethylamine. 10. Protonated (2,3-dicocoacyloxypropyl)dimethylamine hmm. 11. Ester group-containing cation according to any one of claims 1 to 10 A method of using synthetic nitrogen compounds as fiber softeners for fabrics.