JPS61275393A - Detergent containing cloth conditioner - 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] Technical field The present invention relates to detergent compositions having fabric softening properties.

The amine (in intimate admixture with the dispersing aid) in the composition is
-wash) provides flexibility and antistatic benefits. A detergent composition in spray-dried form containing the amine is disclosed. Also preferred compositions are the use of fabric softeners to treat fabrics after the smek wash operation for additional softening benefits, which is a well-known laundering practice. Fabric softeners are primarily cationic materials that are incompatible with the anionic detergent surfactants used in most fabric cleaning compositions. For that reason, the softening operation is generally carried out in the laundry rinse bath after the surfactant has been removed from the washer. This imposes additional work on the user.

Formulators of fabric laundry compositions have long sought means by which fabric cleaning and softening can be performed simultaneously. The method of using clay softeners, mixtures of clay and various amine substances, etc. is disclosed in the following patents, namely West German patent no. q4II//'
Specification No. I, Specification No. 2'l l /1, 3, Review No. 3
9! 'II Specification, No. 113I1199 and KPO No. 0023347 Specification, No. 0026!
It is described in Specification No. 52S and Specification No. 002 Zada No. 32.

The use of mixtures of amines and soaps (salts of fatty acids) as through-the-wash fabric softeners is the first British patent! It is disclosed in the specification of 1-Hiro No. 276. The amine in this document has an isoelectric point S of 3 to 9. That is, it is selected on the basis of having an isoelectric point such that it does not have a positive charge during the cleaning cycle and becomes positively charged during the rinsing cycle.

The present invention uses a class of amines intimately mixed with dispersion aids in an otherwise conventional detergent composition matrix and optionally a clay to provide cleaning and simultaneous softening.

SUMMARY OF THE INVENTION The present compositions contain conventional detergent ingredients such as detergent surfactants (
(e.g., anionic surfactants), detergency builders, optical brighteners, detergent enzymes, fabric bleaches, etc. (all in normal amounts)
and a detergent composition (preferably in granular form) which may contain a clay fabric softener (preferably a smectite clay), the detergent composition having an isoelectric point of at least DE,! amines having the formula R1R2R,N, where R4 is C9-C2o hydrocarbyl and R2 and R5 are each C1
~C4 hydrocarbyl, C2-C10 alkoxylated hydrocarbyl or hydrogen, characterized in that the amine contains at least 0.1% (preferably /, 0%~Jti) in an intimate mixture with a dispersing aid It can be briefly described as a detergent composition.

As discussed below, the compositions of the present invention consist for the most part of conventional ingredients that are quite common to formulators of granular detergent compositions.

Surprisingly, the amines used in the present invention are quite compatible with such conventional detergent formulations, and even with anionic surfactants.

Amines Suitable amines for the present compositions have a molecular weight greater than 9.5, preferably 10.5. Ot- is selected to have an isoelectric point greater than Ot.

Examples include the general formula R, R2H, N (wherein R4 is C8-C
2°hydrocarbyl, preferably C8-C2o alkyl, more preferably C1o-C14 alkyl, most preferably C42 alkyl or C52 alkyl and cL4
is a mixture with alkyl).

R2 and R3 are each independently c1-C4°hydrocarpyl or hydrogen. Examples of suitable hydrocarbyl groups are C1-C4 alkyl or hydroxyalkyl, and C2-C4° alkoxylated alkyl, especially ethoxylated alkyl groups. C1-C where R2 and R3 are the same
Amines that are 4-alkyl, especially methyl, are preferred.

Prior to incorporation into the detergent matrix, the amine is intimately mixed with the dispersion aid. The dispersion aid can be any of a number of such materials. Specific examples include nonionic surfactants and emulsifiers such as those used in the food industry. Examples of the latter include glycerol esters such as lecithin.

Certain classes of compounds, the majority of which are not generally considered dispersing aids, have been found to be particularly suitable for use as dispersing aids in combination with the amines defined herein. It was done. Compounds of this type consist of Brønsted acids having a pKa value below A or below S.

Examples of such acids are inorganic acids such as chlorine, HCI.

HBr%H2SO4, HNO, , HNaSO4, H2S
O,, HNas03, phosphate ester, e.g. R'(c
H2CH2O)mPO(OH)2 and (R'0(cH
2CH20)rn)2P00H (wherein, R' is c3~C
organic acids such as carboxylic acids, polycarboxylic acids, hydroxycarboxylic acids, hydroxypolycarboxylic acids, aminocarboxylic acids, phosphonic acids (phosphonic acids); acid),
Includes polymeric carboxylic acids, alkyl-ether carboxylic acids, and alkyl sulfonic acids. Formula RCOOH
(wherein R is hydrogen or C1-C15 alkyl)
carboxylic acids are particularly suitable for use as dispersing aids in the present invention. Preferred acids are formic acid (R is hydrogen) and lauric acid (R is C1,R25n-alkyl).

Without intending to be limited by theory, a possible mechanism by which the Brønsted acid acts as a dispersion aid may be as follows. The acid protonates a portion of the amine.

The protonated amine acts as a dispersion aid for the remaining unprotonated amine. This mechanism suggests that protonated amines themselves can be used as dispersion aids in place of or in combination with Brønsted acids.

The higher electric point of the amine (at least ?, 5, preferably 10
．． A criticality of 0 or more) suggests that if protonation is to occur, it is important that the amine remains protonated during the wash cycle of the wash program. On the other hand, it is critical that the dispersion aid is intimately mixed with the amine. Simply contacting the amine with a dispersion aid in the wash liquor is clearly not sufficient to obtain good softening performance.

Generally, the amine/dispersing aid mixture that is key to this invention is
It is prepared separately from the rest of the composition and then added to the usual detergent ingredients. If the dispersion aid is a Brønsted acid, this can be done by preparing a melt of acid and amine (preferably molar ratio /:/) and maintaining the melt stage for about 70 minutes under continuous mixing. By generating a complex,
can be done most conveniently.

If the detergent matrix is granular, the amine/dispersing aid melt can be sprayed onto the granules.

Alternatively, the melt can be solidified and then reduced to the desired particle size, for example in a colloid mill, and dry mixed with detergent granules.

If the detergent matrix is liquid, the amine/dispersing aid melt can be dispersed into the liquid detergent mixture or solidified to the desired particle size (typically smaller than that used with granules). It can be finely ground and then dispersed into a liquid.

The amine/dispersing aid may also be deposited onto the sheet, for example by coating with a SeeIf melt. The sheet may be added to the wash solution during the wash cycle of the laundry process. The sheet may further contain conventional detergent ingredients. Sheets of the type disclosed for use as delivery systems for detergent ingredients are generally suitable for use in the present invention.

If the dispersing aid is an acid, the molar ratio of amine to acid is preferably about 1:/, but good fabric softening results are obtained by mixing the amine with a substoichiometric amount of the acid. It can also be obtained by For good results K the acid to amine ratio should be at least 1:10, preferably at least 1
:Should be 3.

The amine/dispersing aid mixture typically accounts for at least 0.7% of the detergent composition, especially when softener clay is present.
% amount, typically 0. Tachi to Nichi, most preferably 1
% to 10%.

Protonated amines are preferably used in conjunction with detergent-compatible clay softeners, but are not limited to them. Such clay softeners are well known in the cleaning patent literature and have wide commercial use both in Europe and the United States. Such clay softeners include heat-treated kaolins and multilayered smectites. Preferred clay softeners are the smectite softener clays described in German Patent No. 2331119 and British Patent No. 11I001798. Softener clays are used in preferred compositions in an amount of at least /9g, generally /~7%, preferably ~7%.

Detergent Surfactants The compositions of the present invention will typically contain organic surfactants to provide the usual cleaning benefits associated with the use of such materials.

Detergent surfactants useful in the present invention include the well-known synthetic anionic surfactants, synthetic nonionic surfactants, synthetic amphoteric surfactants, and synthetic zwitterionic surfactants. Among these are alkylbenzene sulfonates, alkyl sulfates, alkyl ether sulfates, paraffin sulfonates, olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and alkylphenols, amine oxides, alpha-sulfonates of fatty acids and fatty acid esters, which are well known from cleaning technology. α-sulfonate and the like are typical. Generally, such detergent surfactants contain alkyl groups within the C2 to C1B range. Anionic detergent surfactants may be used in the form of their sodium, potassium or triethanolammonium salts. Nonionic surfactants generally contain about 5
Contains ethylene oxide groups of ~Noah. U.S. Patent No. 4, ///, g! ;! No. r contains a detailed list of such typical detergent surfactants. 011~C16
Alkylbenzene sulfonates, C1□-C18 halafine sulfonates and alkyl sulfates, and ethoxylated alcohols and ethoxylated alkylphenols are particularly preferred in compositions of the invention type.

Also, water-soluble soaps, such as common sodium and potassium coconut or tallow soaps well known in the art, are useful as surfactants in the present invention.

The surfactant component can constitute as little as % of the composition, but preferably the composition contains a surfactant! It will contain rq6 to Shunchi, preferably /θ Chi to 30 Chi. Mixtures of ethoxylated nonionic surfactants and anionic surfactants such as alkylbenzene sulfonates, alkyl sulfates, halaffin sulfonates, etc. are preferred for through-the-wash cleaning of a wide range of soils and smears from fabrics.

Detergent Adjuvants The present compositions can contain other ingredients that aid their cleaning performance. For example, the detergent composition may contain a detergent builder and/or a sequestering agent.
Highly preferred. Compounds that can be classified as detergent builders and are well known in the art include nitrilotriacetates, polycarboxylates, citrates, water-soluble phosphates such as tripolyphosphate and sodium orthophosphates and birophosphates, silicates, and mixtures thereof. include. Sequestering agents include all of the above-mentioned materials, as well as materials such as ethylenediaminetetraacetate, aminopolyphosphonate (DEQUEST) and various other polyfunctional organic acids and salts too numerous to be detailed here. do. See US Pat. No. 3.5, Futatei for typical examples of the use of such materials in various cleaning compositions. Generally, the builder/sequestering agent will be about 0.0% of the composition. ! ; %~ will constitute the company. West German Patent No. 1, Ko 2, 6s!
The size/-70μ zeolite (e.g., zeolite) builders disclosed in this patent are particularly preferred for use in low phosphate compositions containing amine-fatty acid complexes.

The laundry compositions of the present invention also preferably contain enzymes that enhance through-the-bone cleaning performance against various soils and stains.

Amylase, protease and lipase enzymes suitable for use in detergents are well known in the art and are found in commercially available liquid and granular detergents. Commercial detergent enzymes (preferably mixtures of amylase and protease) are typically used in the present compositions in amounts of 0.00 to 1/4 inch and higher.

Additionally, the compositions can contain, in addition to the ingredients already mentioned, b9 or a variety of other optional ingredients typically used in commercial products to provide additional product performance benefits. Typical ingredients include pH adjusters, fragrances, dyes, bleaches, optical brighteners, soil suspending agents, hydrotropes and gel control agents, freeze-thaw stabilizers, bactericides, preservatives, antifoam agents, Includes bleach activators and the like.

In the through-the-Φwash format, the composition typically contains at least 17 ppm, preferably 0,000 g of phosphorus at pH 7 to 11, preferably pH 9 to 11, in an aqueous wash bath for washing fabrics. Concentrations of 10% to 3% are used.Washing can be carried out over a range from 5°C to boiling with excellent results.

Industrial Applications The following examples are representative of preferred compositions of the invention containing smectite softener clays, but are not intended to limit the scope of the invention.

Example I Lauric acid and lauryl-N,N-dimethylamine (molar ratio /: /)'i mixed in a jacketed batch, melted and maintained as a melt under continuous mixing for about 70 minutes (overheating will cause yellow ).

A detergent composition is formulated as follows.

Kaoru natural smectite; ion exchange capacity greater than 3θm@q/clay/θop++ U.S. Pat.
Spray dry to granulate. Spray the amine/lauric acid mixture as well as perfume onto the granules. Dry mix the enzymes.

The composition of Example I is free-flowing and provides excellent through-the-flow properties when fabrics washed with it are line dried.
Showing wash fabric softening performance.

Example■ The phosphorus-free spray-dried detergent formulation is as follows.

Kaoru Gel White (gelvrhit*) GP (registered trademark); Ion exchange capacity Omeq//θop
++ mixed coconut fatty acids and mixed coconut two N,
prepared separately from N-dimethylamine (molar ratio l:l);
In the spray-dried granulate optional form as a dry powder, the composition of example
It can be modified by substituting an equivalent (in terms of softening performance) amine/acid mixture.

In another composition, clay is replaced with sitallomethylamine.

Example■ The following composition is prepared as in Example I.

s +4 oooc> pay () 5
Cheers ~ ) 11B2-Kiutamu quasi 91Z MiR to light λ Sobeso λ λ Δ 11, / Enter li I h~ ) Lead ) ) θ too
qooS (＞ 鵠 ~ なぎうび！ ＼He - , 1) Ethylenediamine-N, N, N', N'-tetramethylene phosphonic acid 2) Tetraacetylethylenediamine Previously Preparation of dry mixture Dissolve citric acid in methanol (approx. at 30°C).

After the amine addition is complete, the mixture is stirred for approximately 73 minutes.

The methanol is then evaporated (e.g. by heating),
The solid residue (citric acid/dimethylmyristylamine mixture) is then dried and ground to the desired particle size.

This method of preparing the amine/dispersing aid mixture is suitable when the melting point of the dispersing aid is very high.

Claims (1)

[Scope of Claims] 1. A detergent composition comprising a detergent surfactant, a builder, and conventional detergent ingredients, which has an isoelectric point of at least 9.5.
An intimate mixture of an amine and a dispersing aid having at least 0
．． A detergent composition characterized in that it contains 1%. 2. The composition of claim 1, wherein the amine has an isoelectric point of at least 10.0. 3. The amine has the formula R_1R_2R_3N (wherein R_1
is C_8-C_2_0 hydrocarbyl, and R
3. The composition of claim 1 or 2, wherein _2 and R_3 are each C_1-C_4 hydrocarbyl, C_2-C_1_0 alkoxylated hydrocarbyl, or hydrogen. 4. Claims 1 to 4, wherein the dispersion aid is a Brønsted acid having a pKa value of 6 or less, preferably 5 or less.
The composition according to any of paragraph 3. 5. Any one of claims 1 to 4, wherein the dispersing aid is a carboxylic acid of the formula RCOOH, where R is hydrogen or C_1-C_1_5 hydrocarbyl, preferably formic acid or lauric acid. The composition described in . 6. Claims 1 to 6, wherein the amine and the dispersing aid are present in an amine to dispersing aid molar ratio of 10:1 to 1:5.
The composition according to any of paragraph 5. 7. The composition according to any one of claims 1 to 6, containing 0.5% to 20% of an amine/dispersing aid mixture. 8. The amine/dispersing aid is prepared by mixing the materials at a temperature above the melting point of both the amine and the dispersing aid. Composition. 9. A composition according to any one of claims 1 to 8, which additionally contains a clay softener, preferably a smectite clay. 10. (a) an intimate mixture of lauryl-N,N-dimethylamine and lauric acid in a molar ratio of 1:0.9 to 1:1.1 from 1% to 10%; (b) a smectite clay softener from 2% to 10%; 10. A composition according to any one of claims 1 to 9, in the form of spray-dried granules, consisting of 7%, (c) the balance consisting of conventional detergent ingredients in conventional amounts. 11. A sheet suitable for addition to a cleaning liquid, wherein the fabric softening amount of the amine/dispersing aid mixture according to any one of claims 1 to 10 is dispersibly related thereto.