JP2848536B2 - Heavy laundry detergent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Trialkylamine oxides are known as effective surfactants. Such an amine oxide is industrially produced by reacting an appropriate trialkylamine with an aqueous hydrogen peroxide solution. In this method, the moisture must be adjusted to at least 70% by weight of the final composition. Otherwise, the reaction mixture becomes a gel and cannot be stirred. Such dilute aqueous trialkylamine oxides cannot be used to produce free flowing, free flowing granular laundry detergents by dry blending.

Esposita et al. In US Pat. No. 3,489,687 mention the need to include tertiary amine oxides in laundry detergents. However, it does not give any suggestions on how to deal with high moisture.

U.S. Pat. No. 3,489,687 to Inamorato et al. Discloses a fragile and brittle hydrate salt / amine oxide which is added with an amount of an anhydrous salt, such as sodium sulfate and sodium tripolyphosphate, to react with the entire water in the amine oxide solution. To form free-flowing granular laundry detergents. However, this method requires the addition of a salt composition in addition to the separated solid amine oxide.

In accordance with the present invention, a free-flowing granular detergent for detergents containing a trialkylamine oxide surfactant is used to convert a laundry alkylamine oxide dihydrate into a suitable laundry detergent builder and optionally other laundry detergents. It can be produced by dry blending detergent components.

In summary of the present invention, a free-flowing, free-flowing, heavy-duty laundry detergent comprises (i) 1-30% by weight of the following formula R ₁ R ₂ R ₃ NO.2H ₂ O wherein R ₁ is 8-24 R ₂ is methyl, ethyl or alkyl having 12 to 24 carbon atoms, and R ₃ is methyl or ethyl. Separated tertiary amine oxide dihydrate And (ii) manufactured by blending a composition comprising 10 to 50% by weight of a detergent builder and optionally other conventionally used laundry detergent ingredients.

In a preferred embodiment of the invention, the detergent is (i) 1 to 30% by weight of the formula R ₁ R ₂ R ₃ NO.2H ₂ O wherein R ₁ is alkyl having 8 to 24 carbon atoms. R ₂ is methyl, ethyl or alkyl having 12 to 24 carbon atoms, and R ₃ is methyl or ethyl. Separated tertiary amine oxide dihydrate and (ii) 10 to 50 A free-flowing, free-flowing, granular, heavy-duty detergent for laundry, characterized in that it comprises by weight of a detergent builder.

The essential component of the heavy-duty laundry detergent of the present invention is the above formula: R ₁ R ₂ R ₃ N
O.2H trialkyl amine oxide dihydrate having ₂ O. Such solid tertiary amine dihydrate comprises about 1 to 50% by weight of the detergent composition. More preferably, the detergent comprises about 5 to 30% by weight, most preferably 10 to 25% by weight of the composition.

The requisite trialkylamine oxide dihydrate is prepared by converting the appropriate amine into at least a stoichiometric amount of a concentrated (eg, 50-70% by weight) hydrogen peroxide organic ester (eg, ethyl acetate) solution and the reaction mixture is a liquid. Can be produced by reacting in a sufficient amount of a solvent capable of retaining the above. The reaction temperature is about 25-100 ° C, preferably 60-7
5 ° C. The reaction can be promoted by injecting carbon dioxide gas. 7
Using 0% by weight of hydrogen peroxide at about 1.2 times the theoretical amount, the final reaction mixture contains about 2 moles of water per mole of amine oxide. If more water is present, the water must be distilled so that the water / amine oxide molar ratio is 2/1. The resulting organic ester solution is then cooled to crystallize the amine oxide dihydrate. Otherwise, the organic ester is distilled off under normal pressure or under vacuum to obtain the amine oxide dihydrate as a residue.
Surprisingly, it has been found that tertiary amine oxide dihydrate is not hygroscopic.

Trialkylamines useful for preparing tertiary amine oxide dihydrate have the formula: R ₁ R ₂ R ₃ N, wherein R ₁ , R ₂ and R ₃ are defined as above Compound.

 Typical examples are octyldiethylamine, decyldimethylamine, dodecyldiethylamine, tetradecyldimethylamine, hexadecyldiethylamine, octadecyldimethylamine, eicosyldimethylamine, docosyldimethylamine tetracosyldimethylamine dioctylmethylamine, octyldecylmethylamine , Didecyl methylamine, didodecyl ethylamine, ditetradecyl methylamine, dihexadecyl methylamine, eicosyl decyl methylamine, ditetracosyl methylamine and the like, and mixtures thereof.

Among the above, more preferred tertiary amines are those wherein R ₁ is a linear primary alkyl having 12 to 24 carbon atoms and R ₂ and R ₃ are methyl. .
Examples of these include n-dodecyldimethylamine, n-tetradecyldimethylamine, n-hexadecyldimethylamine, n-eicosyldimethylamine, n-docosyldimethylamine, n-tetracosyldimethylamine, and the like. Is a mixture of

The following example illustrates the preparation of the required trialkylamine oxide dihydrate.

Example 1 In a 250 ml glass reaction flask, 100 g of tetradecyldimethylamine (0.41 mol, amine value 230.0 mg KOH /
g amine) and 0.5 g (1.27 mmol) of diethylenetriaminepentaacetic acid. While stirring, heat to 65 ° C,
Then 23g (0.47mol) of 70% by weight aqueous hydrogen peroxide solution
It was added dropwise over 15 minutes. The reaction mixture is heated to 76 ° C,
And it stirred at that temperature for 7 hours. Ethyl acetate (34 ml) was added to the reaction mixture as needed, keeping it clear and gel-free. Analysis of the crude reaction mass by proton NMR showed 99% conversion of the amine. 40 additional crude reaction masses
Combine with 0 ml of ethyl acetate. Cool the solution to 15 ° C,
Tetradecyldimethylamine oxide dihydrate, a non-hygroscopic white crystalline solid, was obtained with a melting point of about 41 ° C. and 86% recovery yield.

Example 2 A glass reaction flask was charged with 100 g of tetradecyldimethylamine and 0.5 g of diethylenetriaminepentaacetic acid. Carbon dioxide was blown into the liquid phase, the resulting mixture was stirred and heated to 65 ° C. The blowing of carbon dioxide was stopped and the carbon dioxide phase was maintained above the reaction mixture. The dropping of a 70% by weight aqueous hydrogen peroxide solution was started. At the same time, the addition of ethyl acetate was started. After 10 minutes, all hydrogen peroxide,
And 28 ml of ethyl acetate were added. Cooling was required to keep the temperature at 75 ° C. Heat was applied and the reaction continued for another 2 hours. Ethyl acetate addition continued for the first 19 minutes of the 2 hour period. The feed rate of ethyl acetate was 43 ml in total. The reaction mixture was a clear, gel-free solution. When the reaction mixture was analyzed by NMR, the amine conversion was 100%. 106 g of needle-like crystals of tetradecyldimethylamine oxide dihydrate were obtained, and the yield was 87%.

Another essential component of the laundry detergent of the present invention is at least one detergent builder. As detergent builders, sodium aluminum silicate (for example, zeolite A), sodium tropophosphate (STPP), sodium salt of nitrilotriacetic acid, sodium carbonate, sodium bicarbonate, sodium citrate, potassium carboxymethyloxymalonate, carboxymethyloxysuccinic acid Sodium, sodium salt of ethylenediaminetetraacetic acid (EDTA), sodium pyrophosphate and the like. In the above,
The most preferred detergent builders are sodium carbonate, STPP and zeolite A.

The amount of builder can vary from about 10% to 85% by weight or more. The preferred amount is about 20 to
It is 80% by weight, most preferably 30 to 50% by weight.

The laundry detergent may further include a surfactant other than the tertiary amine oxide dihydrate of the present invention. As such a surfactant, for example, anionic, nonionic,
It is a zwitterionic and cationic detergent.

Anionic surfactants include fatty acid sodium, potassium, ammonium, or alkylol ammonium soaps such as tallow fatty acid, coconut fatty acid, oleic acid,
And sodium salts such as stearic acid. Other very useful anionic surfactants are the sodium, potassium, ammonium, and alkylol ammonium salts of alkylbenzene sulfonic acids having 10 to 16 carbon atoms, such as sodium tridecylbenzene sulfonate. Also useful are the sodium, potassium, ammonium, and alkylol ammoniums of alpha-olefin sulfonic acids having 12 to 16 carbon atoms and alkyl sulfates having 12 to 16 carbon atoms.

Yet another useful anionic surfactant is an alkyl glyceryl ether sulfonic acid, such as one having 12 carbon atoms.
There are from 16 to 16 alkali metal salts of alkyl monoglyceride sulfonic acid and sulfuric acid. Also useful are alkali metal salts of alkyl phenyl polyethoxy sulfonic acids or sulfuric acids having 8 to 12 carbon atoms and about 5 to 10 ethyleneoxy units per molecule.

Other anionic surfactants have 12 to 12 carbon atoms.
Of the 16 α-sulfonated fatty acids, 2 to 10 carbon atoms
Is a water-soluble salt of an alkyl ester. Also useful are water-soluble salts of 2-acyloxyalkane-1-sulfonic acids containing 2 to 9 carbon atoms in the aryl group. Similarly, fatty alcohol sulfates and ether sulfates are effective anionic surfactants. 12 to 18 carbon atoms
Alkyl polyethoxy sulfates are also useful combination surfactants.

Useful nonionic surface active agents, polyethyleneoxy (5-10 units) C ₁₂ -C ₁₆ - alcohol or C ₅ -
C ₁₀ - and the like alkylphenols. For example, polyethoxylated (5-9 units) dodecanol and polyethoxylated (5-9 units) nonylphenol. Cationic surfactants include, for example, quaternary ammonium, phosphonium, and sulfonium compounds having at least one detergent range, for example, an alkyl group having 12 to 18 carbon atoms, such as dodecyl dimethyl ammonium chloride.

Useful amphoteric surface active agent C ₁₂ -C ₁₈ - include alkyl dimethyl betaines e.g. hexadecyl dimethyl betaine.

As other formulation components, optional optical brighteners, for example,
4,4'-bis (triazin-2-ylamino) stilbene-2,2-disulfonic acid, 2- (stilben-4-yl) naphthotriazole, 1,4-bis (styryl) benzene, 1,3-diphenyl- 2-pyrazolin and the like can be mentioned. Laundry detergents may also contain dry peroxide bleaches, such as sodium perborate, bleach activators, such as
C ₉ acyloxy sodium benzenesulfonate, and anti-redeposition agents, for example, can also include sodium polyacrylate.

A water-soluble bulk filler, such as sodium sulfate, can be constantly included. A typical laundry detergent formulation contains about 5 to 50% by weight of a filler to facilitate handling.

A series of heavy duty laundry detergent formulations containing the tertiary amine oxide dihydrate of the present invention are shown in the table below.

The main features and aspects of the present invention are as follows.

1. In a free-flowing, heavy-duty laundry detergent, the detergent is (i) 1 to 30% by weight of the following formula R ₁ R ₂ R ₃ NO.2H ₂ O In the formula, R ₁ is 8 to 24 R ₂ is methyl, ethyl or alkyl having 12 to 24 carbon atoms, and R ₃ is methyl or ethyl. Separated tertiary amine oxide dihydrate And (ii) 10 to 50% by weight of a detergent builder.

2. A laundry detergent according to the above item 1, wherein R ₂ and R ₃ are methyl.

3. A laundry detergent according to the above item 1 or 2, wherein R ₁ is a linear alkyl group having 12 to 24 carbon atoms.

4. The detergent according to any one of the above, wherein the detergent builder is selected from the group consisting of sodium tripolyphosphate, sodium carbonate, sodium nitrilotriacetate, sodium aluminum silicate, and a mixture thereof.

5. In any one of the above items, the detergent is at least one surfactant selected from an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a cationic surfactant, and a mixture thereof. A laundry detergent comprising:

6. The method of claim 1, wherein (a) 5 to 30% by weight of tetradecyldimethylamine oxide dihydrate, (b) 80% by weight of zeolite A, (c) 5 to 30% by weight of sodium alkylbenzene sulfonate. (D) a laundry detergent comprising 10 to 60% by weight of sodium carbonate.

7. A laundry detergent according to the above item 1, comprising: (a) 5 to 30% by weight of tetradecyldimethylamine oxide dihydrate; and (b) 70 to 95% by weight of sodium tripolyphosphate.

8. A method for producing a free-flowing, free-flowing, heavy-duty laundry detergent, comprising the steps of: (i) in the following formula: R ₁ R ₂ R ₃ NO.2H ₂ O wherein R ₁ is 8 to 24 carbon atoms R ₂ is methyl, ethyl or alkyl having 12 to 24 carbon atoms, and R ₃ is methyl or ethyl. A separate tertiary amine oxide dihydrate (Ii) A method for producing a heavy-duty laundry detergent comprising dry blending with a detergent builder.

9. In item 8 above, (a) 5 to 30% by weight of an independent solid non-hygroscopic tetradecyldimethylamine oxide dihydrate; (b) 20 to 80% by weight of zeolite A; (C) dry blending of 5 to 30% by weight of sodium alkylbenzene sulfonate having 10 to 16 carbon atoms, and (d) 10 to 60% by weight of sodium carbonate. Law.

10. In the above item 8, wherein (a) 5 to 30% by weight of an independent solid non-hygroscopic tetradecyldimethylamine oxide dihydrate; (b) 20 to 80% by weight of sodium tripolyphosphate (C) 5 to 30% by weight of sodium alkylbenzene sulfonate having 10 to 16 carbon atoms; and (d) 10 to 60% by weight of sodium carbonate, which is dry-blended. Manufacturing method.

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Claims (2)

(57) [Claims] 1. A free-flowing, free-flowing, heavy-duty laundry detergent comprising (i) 1 to 30% by weight of the following formula: R ₁ R ₂ R ₃ NO.2H ₂ O wherein R ₁ is 8 R ₂ is methyl, ethyl or alkyl having 12 to 24 carbon atoms, and R ₃ is methyl or ethyl. A heavy-duty laundry detergent comprising: oxide dihydrate; and (ii) 10 to 50% by weight of a detergent builder. 2. A free-flowing free-flowing non-hygroscopic laundry granules heavy-duty detergent manufacturing process, the manufacturing method (i) the following formula _{R 1 R 2 R 3 NO.2H 2} O formula R ₁ is R ₂ is methyl, ethyl or alkyl having 12 to 24 carbon atoms, and R ₃ is methyl or ethyl. A method for producing a heavy-duty laundry detergent, comprising dry-blending an amine oxide dihydrate and (ii) a conventional laundry detergent component containing a detergent builder.