JPH02272099A - Normally liquid detergent and/or bleaching composition containing low-molecular-weight tertiary amine of n-oxide form - Google Patents

Abstract

PURPOSE: To obtain a composition which can exhibit decontamination action even in the presence of a builder-free liquid detergent by using a specified N-oxide-form low-molecular tert. amine.

CONSTITUTION: This composition contains an N-oxide-form lowmolecular-weight tert. amine selected from the group consisting of Noxide-form trialkanolamines represented by formula I (R is a 1-4C alkylene), N-oxide-form trialkanolamines represented by formula II (R' is a 1-4C alkyl) and heterocyclic compounds selected among triethyleneamine-N-oxide, triethylenediamine N,N'-dioxide, Nmethylmorpholine N-oxide and N-methylpiperidine N-oxide.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to normally liquid cleaning and/or bleaching compositions containing low molecular weight tertiary amines, such as triethanolamine; 2.197. ! The present invention relates to aqueous liquid detergent compositions commonly used in automatic washing machines such as those described in No. 34G.

The aqueous liquid detergents for washing machines currently on the market are (a) transparent compositions consisting of highly concentrated solutions of surfactants and, because they do not contain water softeners, are "R-builder-free"compositions; The viscosity of these compositions is quite low (500 @Pa at room temperature,
(below s), - as a neutralizer for acid components in boat fishing and/
or (b) a milky white composition containing a low concentration of surfactant components and a significant amount of water softening. agents (e.g. - for boat fishing, zeolite (zeol!tes) 4A, which is present in the form of a suspension);
), it is defined as a "built" composition as it contains a relatively high viscosity (1.00
0 sPa, s) compositions, which can essentially be divided into two types:

Both the "built with" and "non-builder" products mentioned above do not contain any decontaminating (bleaching) ingredients; contrary to what happens with washing machine (powdered) detergents, they are decontaminants. (Chemical bleaching) does not show sufficient activity, so its performance is low.

2) Consideration of the prior art A non-negligible disadvantage of this liquid cleaning agent compared to powdered products is that, at the beginning of the cleaning, the presence of bases such as perborates, percarbonates, hypochlorites, etc. It is generally believed that it can only be overcome by adding regular bleach additives to the liquid.

However, the Applicant has found that similar bleaching results are only obtained with "builder-containing" liquid cleaning products at the dosages suggested for bleach, and in "builder-free" products, perborate It has been surprisingly observed that in practice, such additives are of little use since their decontamination action is negligible. Considering that the use of liquid detergents for washing machines has great potential for development and that detergent compositions of the "builder-free" type are very widely available, the latter The inefficiency of the bleaching action (even with the addition of bleaching agents that have proven to be highly effective in other cases) is a significant problem.

Therefore, it is an object of the present invention to enable bleach to exhibit decontamination action even in the presence of "builder-free" liquid detergents,
The result is to make it possible to obtain a bleaching action with such detergents even when conventional bleaching additives are added in the indicated dosages. Applicants have successfully improved the composition of ``Builder-free'' liquid detergents by eliminating the inhibitory effect of ``Builder-free'' liquid detergents on bleaching agents.

DETAILED DESCRIPTION OF THE INVENTION In its broadest aspects, the present invention relates to normally liquid cleaning and/or bleaching compositions comprising low molecular weight tertiary amines in the form of N-oxides, comprising (a) %(1) in the form of N-oxides in which the radicals R are the same or different from each other and are straight-chain or branched alkylene radicals having 1 to 4 carbon atoms. trialkanolamine, having the formula (b) in which the radicals R' are the same or different from each other and are straight-chain or branched alkyl radicals having 1 to 4 carbon atoms; a trialkylamine in the form of N-oxide and (c) triethylenediamine-N
and a heterocyclic compound selected from - oxide, triethylenediamine-N,N'-dioxide, N-methylmorpholine-N-oxide, N-methylpiperidine-N-oxide. relating to things.

For example, - triethanolamine (T
E A) in a liquid "builder-free" cleaning agent with the formula (
m) (HO-CH-CH2-)3-N-0 (III) with the respective N-oxide (TE-AO), the level of bleaching obtained is , comparable to that obtained in liquid "built" detergents and powder detergents, the use of said N-oxide (m)
It does not pose any particular technical problems and can be used in the same manner as triethanolamine. TEAO is T
Since it does not have the alkalinity of EA, the neutralization of acid components (fatty acids, alkylbenzenesulfonic acids, etc.) in liquid detergents, which is normally carried out with TEA, is performed in the presence of TEAO.
a OHs or more preferably KOH can be completed without compromising the homogeneity of the solution, and by using caustic potassium instead of caustic soda, obtaining high stability of the liquid detergent composition at low temperatures. You will be able to do this. The amount of alkali can be advantageously reduced if the amine is not completely replaced by N-oxide.

According to known technology, N-oxides can be obtained, for example, by oxidizing the corresponding tertiary amines with hydrogen peroxide. The oxidation can be carried out with either a deficient or an excess amount of H2O2. If the N-oxide is synthesized using an excess of hydrogen peroxide, at the end of the reaction there will be traces of H2O2 present, the amount of which will vary depending on the excess used, e.g. if the excess H2O2 is 10%
, the resulting residue is 0.5% of the reaction mixture
~1% by weight. Therefore, if suitable improvements fail,
This type of synthesis poses significant technical difficulties due to the inherent explosion hazard, which precludes immediate evaporation of the solvent and/or direct use of the reaction mixture for the production of liquid detergents. arise.

H2O without loss of N-oxide. It has been suggested to remove residual H202 with MnO, which is considered to be an excellent compound for decomposing H202. However, it is not possible in practice to use s M n O2, and in fact even after careful filtration, which is itself already a complex operation, traces of M n O2 remain in the N-oxide and its As a result, N-oxides may also remain in cleaning products, and these residues can also have a degrading effect on the bleach peroxides added to the liquid detergent during the cleaning cycle, thus impairing its performance. decreases sharply.

Other techniques, such as heating, typically
Temperatures higher than ℃ are undesirable because they decompose, and H2
Metals known for their decomposition effects on O2 (such as Fe or Cu) cannot also be used because they effectively cause decomposition of the N-oxide and are unsuitable in many aspects during detergent application processes.

Applicant has determined that if the amount of hydrogen peroxide is kept below the stoichiometric value, substantially H2O. Get a product that does not contain
The product thus obtained, which can be used immediately in detergent formulations (and water evaporation if concentrated N-oxides are desired), contains small amounts of tertiary amines that are not converted to N-oxides and is not bleachable. without compromising the ability at all.
Moreover, I realized that it makes it easier to mix detergents.

- For boat fishing, the amount of H202 is between 70% and 9% of the stoichiometric value.
It is desirable that it be 9%.

Also, the presence of unconverted amines is balanced by the low alkalinity of the corresponding N-oxides, thus increasing the homogeneity of the detergent with a low neutralizing capacity towards fatty acids, yet keeping the formulation at a given pH value. Reduces the amount of alkali required to

As used herein, including in the Examples, triethanolamine (T E A
Although described in detail with respect to the use of other types of low molecular weight tertiary amines, in particular triethylamine, triethylenediamine (PABCO), N-
Also included are methylmorpholine, N-methylpiperidine, and the like. Replacement of the amine with the corresponding N-oxide does not adversely affect the storage stability of the detergent even at low temperatures, high humidity and long periods of time.

Oxidation of tertiary amines with hydrogen peroxide reduces the amine itself,
Alternatively, salts of amines and fatty acids (TEA soaps) or other acid compounds can also be used, and liquid detergents containing this amine can also be used by adding H2O2 to the detergents.

The following examples are merely illustrative and are not intended to limit the scope of the invention.

N-oxide of triethanolamine (TEAO) was synthesized by the reaction of triethanolamine and hydrogen peroxide according to the reaction formula %.

150 g of triethanolamine (TEA) in a 2-neck, 1,000 d flask equipped with a bulb cooler.

After charging 300 g of water and 150 mg of EDTA (sodium ethylenediaminetetraacetate) and heating the mixture to 55 °C by an external water bath, an approximately 10% excess of H2O relative to the stoichiometric value was added. That's 33.81! % of H2O2 was gradually introduced (using a dropping funnel). The rate of addition was such that the temperature was kept below 80°C, and once the addition was complete, the temperature was held at 55°C for 90 minutes. After the residual H20□ decomposed naturally over several days, the product was dried by evaporating the water at a temperature not exceeding 40° C. (in a rotary evaporator under 14 atmospheres). A dry residue of 185° was obtained, corresponding to an almost quantitative yield.

Example 1 was repeated by reducing the amount of hydrogen peroxide (at 33.8%) to 103 g, an amount corresponding to about 98% of the stoichiometric value, and the final product was prepared by the paper method (for H2O2). Peroxide test, MERKOQUANTloll
), the analysis results were negative.

Not even the slightest trace of residual H2O2 was observed.

Example 3 (Concentrated N-oxide) To obtain a more concentrated TEAO, Example 1 was repeated without performing one or more steps of water evaporation, and water (added in Example 1 as reaction solvent) was added. Remove 300g,
TEA was reacted directly with H2O2. For details, see 33.
111 g of 8 wt% H2O2 at 55°C with 150 g of TEA
After addition, the temperature was held at 55° C. for 2 hours. An aqueous TEAO solution of approximately 67% by weight was thus obtained, which was much higher than the N-oxide concentration obtained in Example 1 (29%).

Example 4 A commercial washing machine REX (RF 2
A bleaching test was conducted under the following conditions.

Washing water: Tap water with hardness of 1B@F, Washing program: 80°C (maximum temperature specified for liquid cleaning agents), Washing load: 3 kg of clean white cotton cloth (for each wash) + EMPA study with standard contamination with red wine Manufactured 10XIOC
Two cotton test pieces EMPA 114 of II, detergent jl:
180 g for each wash (average addition specified by the manufacturer), Bleach amount: 40 g for each wash (average addition j:1 specified by the manufacturer).

As a bleaching agent, sodium perborate hydrate (PBS-
A commercially available product (product 1) based on 1) and an activator (TAED-tetraacetylethylenediamine) was used. The composition of the bleach was as follows.

PBS-1-47%, TAED-13%, fillers and trace ingredients - remaining amount making the total amount 100%.

As a liquid cleaning agent, commercially available products that contain a builder (Product ■) and commercially available products that do not contain a builder (Product III)
, a laboratory-reconstituted formulation with a similar composition (with respect to the most important ingredients, including TEA) as the above-described product; and a laboratory-reconstituted similar formulation with no TEA.
-oxide (TEAO) and the latter two formulations were compared with I[[/TEA and m/T E
They are shown in Table 1 as AO.

Table-1 Formulations ■ and III/TEA exhibit pH values of 8 to 8.5, while in formulation ■ the pH value is approximately 10 and formulation I [I/TEAO is T E A 0f7 )Furka+
Since the J degree is lower than TEA, the pH value was 8.8.

For the purposes of the present invention, the pI of formulation I11/TEAO
to a value of 8 to 8.5 by adding NaOH (i.e.
(up to the value of ``builder-free'' cleaning agent).

pH value a! ! The addition of NaOH to do this does not affect the effectiveness of the present invention as it is a normal step in the formulation of liquid detergents even in the absence of TEAO. The following combination (detergent + bleach) was used in the washing machine test:

A Product ■ only B Product ■ 10 bleaching additives C Product ■ only D Product ■ 10 bleaching additives E III/TEA 10 bleaching additives F III/TEAO + bleaching additives The bleaching results obtained are reported below, but bleaching is possible. It was expressed as the removal rate (D) of the dirt (red wine) and was calculated as follows.

However, a - whiteness of the test piece cleaned during the test, b - whiteness of the test piece before cleaning, C - whiteness of the uncontaminated test piece.
pho-Zeiss) and assumed to be blank.
It was compared with O (whiteness -100) and measured using a No. 6 filter. The results are shown in Table-2.

Table 2 mb These data show that when bleach is added to liquid detergent, T
Leads to the expected bleaching effect only in the case of "builder-containing" detergents that do not contain EA (see cases A and B), but is noticeable when the liquid detergent consists of the "non-builder" type. It shows that no effect is seen (see cases C and D). Furthermore, these data show that replacing TEA with TEAO in "builder-free" detergents significantly improves the whiteness (see cases E and F), which can be obtained with built formulations. It shows that the value will be changed again.

Example 5 Another bleaching test was conducted using sodium perborate-hydrate (PBS
-1) and TAED in a substantially stoichiometric proportion (
This was done by adding a bleaching mixture of about 48% PBS-1 and about 52% TAED to the bilgoo-free liquid detergent. The second test consisted of 7 g of liquid detergent and 0.0 ml of bleach mixture in 250 ml of deionized water at 130°C in a 500 m flask.
．． A 5x5 cm cotton specimen EMPA114 (as in Example 4) 2 with 7 g added and finally stained with red wine
introduced.

The specimens were kept at a constant temperature of 60° C. with stirring and after 1 hour the specimens were rinsed under running water, dried, ironed and the whiteness was measured as described in Example 4. As a detergent, another commercially available liquid product (Product IV), T
A laboratory-reconstituted formulation with a composition similar to Product ■ in terms of essential ingredients, including EA (Product IV/TEA)
, and a formulation similar to the previous formulation (Formulation IV/TEAO) in which TEA was replaced by TEAO.

Table 3 shows the weight percentages of the components.

Table-3 The bleaching results are shown in Table 4.

Table-4 Bleaching tests were conducted using the following combinations.

A Product ■ only B Product ■ 10 bleach additives CIV/TEA 10 bleach additives D IV/TEAO + bleach additives If it exists in
The effect of bleach is negligible, but the corresponding N-
This shows that this effect is fully exerted in the presence of oxides.

Implementation f! 46 "Builder-free" formulation (having a similar basic composition to Composition III/TEA of Example 4) with the addition of a commercial bleaching product (Product I) at the time of washing, and TEA as shown in Table-5. By partially replacing TEAO with TEAO, TEA+TEA
Example 4 Using another formulation where the sum of O was held constant
repeated.

Table-5 Table-6 If necessary, the pH of the formulation was raised to 8-8.5 with NaOH. The bleaching results were evaluated and expressed as in Example 4 and are shown in Table-6.

These tests show that good bleaching performance is obtained even when TEA is partially replaced with TEAO, and that
TE corresponding to a TEA/TEAO mixture with a ratio of 0 to 0
It shows that at the AO level, results are clearly superior to those seen with TEA alone.

Example 7 Formulations A-G of Example 6 were subjected to low temperature stability testing to determine the potential for precipitation or immiscibility to occur as the internal temperature of the detergent decreases. Specifically, the formulation was immersed in a water bath and gradually cooled to an internal temperature of +3° C., and then held at the same temperature for 30 minutes. The visual observation results are shown in Table-7.

Table 7 b) The pH value was adjusted to 8 to 8.5 with NaOH, and the sum of TEA+TEAO was kept constant as in Example 7.

The detergent was then subjected to a cold storage test in a manner similar to that described in Example 7, with the product held at +2°C for 30 minutes. The results are shown in Table-8.

Table-8 Table-7 shows that replacing TEA with TEAO does not adversely affect the storage stability of the formulation at low temperatures.

Example 8 A series of formulations containing mixtures of TEA and TEAO were prepared based on mV/TEA as described in Example 5, and for all formulations (if desired, Example 9 In the production of "containing" formulations, it may be preferable to use TEA salts of coconut oil fatty acids (TEA soaps) as starting materials instead of using fatty acids and TEA individually, as is usually done. There is nothing to preclude replacing TEA with TEAO; in fact, the tests below show that TEA soap reacts with H202 to form TEAO.

Test Description TEA soap (from coconut oil fatty acids) soap 18 in two loaf flasks of capacity t, ooo i equipped with a bulb cooler
Add 0 q of water, 500 g of water and 100 g of EDTA, bring the mass to 55°C, and add 255 g of 3-3.8 wt% H20 to 8
After adding gradually so as not to exceed 0℃, the temperature was increased to 55℃.
It was held for about 90 minutes. Conversion of TEA to TEAO was evident by the fact that the solution changed from a clear state (before reaction) to a cloudy, jelly-like state. This is due to the lower alkalinity of TEAO compared to TEA and the resulting lower neutralizing activity toward fatty acids, which are (partially) present in the form of water-insoluble free acids at the end of the reaction. Ta.

Example 10 Conversion of TEA to TEAO can also be carried out using a liquid (TEA-containing) detergent by adding an appropriate amount of H2O2 to said detergent. 33.8% by weight H2O2B, 8ffj (>60°C After the addition, the temperature was increased to 55°C.
After holding for 50 minutes, the pH value of the cleaning agent was adjusted to 8~8 with NaOH.
It was set at 8.5. In order to confirm that the reaction actually occurred,
A commercially available cleaning agent (product ■) was prepared as a blank according to the method described in Example 5 using a cleaning agent (without O2).
A bleaching test was conducted using In detail, (80℃)
PBS-1 (48%) and TEA described in Example 5 were added to 5.3 g of cleaning agent dissolved in 250 d of distilled water with stirring.
0.7 g of a bleaching mixture consisting of O (52%) was added, followed immediately by two 5×5 cm cotton specimens EMPA 114 stained with red wine. After 80 minutes, the two specimens were rinsed under running water, air-dried, and ironed.
A whiteness measurement as described in Example 4 was carried out and the bleaching values were as follows.

Formulation Contamination removed (%) Product m
57.5III/TEA+H2O
2go, 9 These tests are H2O. This shows that replacement of TEA by TEAO occurred in the detergent m/TEA treated with .

Example 11 The pH of a liquid builder-free detergent containing TEAO instead of TEA can be brought to a predetermined value, typically 8 to 8.5, using NaOH or KOH.

However, the stability of the formulation at low temperatures is even higher when using KOI. The tests below show that.
H to 862 and subjected to the low temperature stability test described in Example 8. This composition was clear and homogeneous at temperatures down to -1°C.

Applicant's agent: Mr. Sato

Claims (1)

[Claims] 1. A normally liquid cleaning and/or bleaching composition containing a low molecular weight tertiary amine in the form of an N-oxide, which has the following formula: (a) a mathematical formula, a chemical formula, a table, etc. ▼(I) in the form of N-oxides with the radicals R being the same or different from each other and being straight-chain or branched alkylene radicals having 1 to 4 carbon atoms; Trialkanolamine and (b) Formula ▲ Numerical formula, chemical formula, table, etc. ▼ (II) (In the formula, the groups R' are the same or different from each other and have 1 to 4 carbon atoms. (c) triethylenediamine=N-oxide, triethylenediamine=N,N'-dioxide, N-methylmorpholine=N - a heterocyclic compound selected from N-oxide, N-methylpiperidine=N-oxide. 2. The composition according to claim 1, wherein the tertiary amine in the form of N-oxide is triethanolamine N-oxide having the formula ▲ which may be a mathematical formula, a chemical formula, a table, etc. ▼. 3. The tertiary amine in the form of N-oxide is triethylenediamine=N-oxide, triethylenediamine=N
, N'-dioxide, N-methylmorpholine N-oxide, N-methylpiperidine N-oxide and triethylamine N-oxide.
The composition described in. 4. The composition according to any one of claims 1 to 3, which also has NaOH or KOH as a pH regulator. 5. In addition to the tertiary amine in the form of N-oxide, it also contains the tertiary amine in free (non-oxidized) form, and the ratio (N-oxidized amine)/(non-oxidized amine) is preferably 70 by weight: 5. A composition according to any one of claims 1 to 4, ranging from 30 to 99:1. 6. Low molecular weight tertiary amines, in particular (a) of claim 1,
Use of amines in the form of N-oxides as specifically mentioned under (b) and (c), and if desired in mixtures with the corresponding tertiary amines in free form, for use in automatic washing machines. Use to obtain aqueous liquid detergent compositions of the "builder-free" type for use. 7. The method according to claims 1 to 5, characterized in that the selected tertiary amine is reacted with hydrogen peroxide to convert it into an N-oxide, and the resulting N-oxide is added to the other components of the composition. A method for producing the composition according to any one of the items. 8. Claim characterized in that the selected tertiary amine is added in free form to the other components of the composition and then converted "in situ" to the corresponding N-oxide by reaction with hydrogen peroxide. Item 6. A method for producing the composition according to any one of Items 1 to 5. 9. The method according to any one of claims 7 and 8, wherein the amount of H_2O_2 is substoichiometric. 10. Oxidation to N-oxide (e.g. with an acid moiety such as a fatty acid or an alkylbenzene sulfonic acid)
carried out on the corresponding tertiary amine in salt-formed form,
A method according to any one of claims 7 to 9.