JPH01268800A - Liquid detergent - Google Patents

Abstract

PURPOSE: To provide an aqueous liquid detergent which contains a detergent active material, a dissolved electrolyte, and a specific stabilized surfactant and has physical stability, solid suspending capability, and proper flow characteristics.

CONSTITUTION: This composition, containing (A) a detergent active material (e.g. nonionic surfactant, (non)alkoxy-converted anionic surfactant) having an alkyl chain of at least 6 carbon atoms on the average, (B) a dissolved electrolyte, and (C) a stabilized surfactant (e.g. alkylpolyalkoxy-converted phosphate, dialkyl diphenyl oxide disulfonate, etc.), having salting out resistance of at least 6.4, forms substantially no transparent liquid active layer even when applied with a centrifugal force of 750 G at 25°C for 20 hours.

COPYRIGHT: (C)1989,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a surfactant structure (Stlrf) inside the composition.
aCtant 5truCtLlre). Such compositions can be added to the unstructured compositions by adding an "external structure material"
structurant) J because its structuring derives from the secondary component, rather than from secondary additives such as cross-linked polyacrylates, which are added as "internally structured" J.
It is sometimes said that

Internal structuring is known to those skilled in the art and is intended to provide consumer-preferred flow characteristics and/or hazy appearance. Many internally structured liquids can also suspend solid particles such as detergent builders and abrasive powders. Examples of structured liquids without suspended solids are U.S. Pat.
No. 840, an example of suspended solid particles is shown in E.
P-A-160342:E P=A-3810
1;Er''-A-104452113 and the above-mentioned US Pat. No. 4,244,840.

Various surfactant structurings possible
tructurino) in the literature, Wa
ltcrs (IQ collection), “Reometry 2 Industrial Applications”
J.

Wiley & 5ons, Letchworth (1
980), Chapter 2, H, A., Barnes, “Detergent Pa.”

Generally, this stability increases with increasing surfactant and/or electrolyte concentration. When surfactants and/or electrolytes are added to the grains, a structured (anisotropic) system is formed. These are rod-shaped micelles and
It is referred to by various names such as planar lamellar structure, lamellar droplet, and liquid crystal phase. Others skilled in the art often use other terms to refer to substantially the same structure. The presence of surfactant structured systems in the liquid can be detected by means known to those skilled in the art, such as optical techniques, various flow measurements, xm or neutron diffraction, and possibly electron microscopy.

One well-known type of internal surfactant structure is called lamellar droplet dispersion (lamellar fraction 010).

Each lamellar droplet is
It consists of two concentric layers of surfactant molecules arranged in an onion-like arrangement, between which water or an electrolyte solution (aqueous phase) is trapped. Systems with close packing of lamellar droplets have a highly desirable combination of physical stability, solids suspension, and suitable flow properties.

As used herein, the term "electrolyte" refers to an ionic water-soluble substance. However, in a structured liquid, not all of the electrolyte is necessarily dissolved, and the electrolyte may be suspended as solid particles. This is because the m-electrolyte concentration of the liquid is ff1W1. This is because it is higher than the solubility limit of quality. Mixtures of electrolytes may also be used, in which case one or more electrolytes may be in the dissolved aqueous phase and the other one or more may be present substantially only in the suspended solids phase.

Two or more electrolytes may be distributed approximately proportionally between these two phases. In part this depends on the processing, ie, the order of component addition. The term "salt" refers to all forms of inorganic substances (formulation ingredients), whether ionic or not, except for surfactants and water, and the term is a subcategory of electrolytes (water-soluble substances). It also includes.

The types and types of surfactants and salts (eg, builders, buffers, WI base stabilizers, preservatives) that are ideally incorporated into such systems vary widely depending on the type of ingredients that are included. Unfortunately, this may be hampered by component incompatibility. One is salting-out of the surfactant due to the salts present.
(precipitation). This means that although salting out depends on the properties of the substance in question, it also depends on the concentration of salt and the amount of surfactant.
This becomes a problem when one or both of the 11 degrees are relatively high. This is often (though not always) a problem when the salt contains too many electrolytes.

This has given rise to a desire to identify surfactants and surfactant mixtures that can be stably incorporated into such liquids to allow improved and wider latitude in salt type and concentration. .

This is basically patent Ill. EP-A-178,000.
This is the issue raised in 6. However, the same E-P-A
The surfactants (alkyl polycarboxylates) described in 178,006 do not provide the electrolyte tolerance that the present invention seeks to provide.

Since many useful salts are also electrolytes, a suitable surfactant that provides the required improvement can be found by dissolving it in water and testing its tolerance by increasing the amount of electrolyte added. It is thought that it can be confirmed. however,
We have found that this does not always work as expected.

The reason is that the aqueous solution of surfactant is a molecular solution (mol
ecular solution) or spherical micelle solution. This is completely different from the arrangement of surfactant molecules in structured liquids. Therefore, when an electrolyte is added sequentially to a molecular or spherical micellar solution of surfactant, the behavior of the surfactant does not necessarily mimic its behavior in structured systems.

However, it was unexpected that particularly suitable surfactants (hereinafter "stabilis7i")
It has been found that, when framed in an appropriate manner, the general test described above can define an appropriate threshold for determining whether a particular surfactant passes the test.

This allows for advantageous selection of surfactants that can be used in novel internally structured detergent liquids.

Kanmei l111! The test for electrolyte tolerance is called salting-out resistance measurement. For this test, 200 ai! of a 5ffiffi% aqueous solution of the surfactant in question! Prepare. !
Toro [trisodium cotriacetate r! A(NTA
) at room temperature (approximately 25
Add at ℃). 1 of the NTA added up to this point (
1 mole of NTA is 3 equivalent losses) is the salting-out resistance of the surfactant. (This amount is added to 1 liter of surfactant solution.)
Expressed as Durham equivalent of TA. ) For convenience, SOR is used as an abbreviation for salting-out resistance.

The aqueous liquid detergent compositions of the present invention contain sufficient detergent active materials and dissolved electrolytes to produce surfactant structuring in the composition and are centrifuged at 750 G for 20 hours at 25°C. does not form a substantially transparent liquid active layer even when the detergent active material has an average alkyl chain length of 6 carbon atoms.
or more, and is characterized by containing a stabilizing surfactant having a salting-out resistance (as defined above) of 6.4 or more.

Compared to known surfactant structured liquid detergents, the selection of surfactants of the present invention provides considerable flexibility in that a large number of salts, particularly soluble salts (i.e. electrolytes), may be added to the compositions of the present invention. It also allows the addition of polymeric builders, especially water-soluble building blocks. This results in
It also becomes possible to achieve the desired viscosity reduction of the product. The addition of higher amounts of surfactant is advantageous for the removal of lipid stains. Especially when the stabilizing surfactant is nonionic,
It is also advantageous for the stability of the existing enzyme to add more nonionic surfactant than anionic surfactant later. Enzymes are generally more sensitive to anionic systems than to non-ionic systems. Generally, in the present invention, it has been found that the larger the actual 15OR, the lower the concentration of surfactant required to exhibit a predetermined effect.

In addition to containing at least the type of stabilizing surfactant described above, the composition of the present invention provides a liquid active layer that is substantially transparent even after centrifugation at 750 G for 20 hours at 25°C. activeri
It is necessary to prevent the formation of ch + ayer). The symbol G refers to Earth's normal Doshi gravity value. This requirement excludes compositions that do not exhibit the effects of the compositions of the present invention, and also excludes detergent compositions and their I! It also excludes the compositions of the same applicant's patent application (c, 3218) entitled ``Method for Preparing I''.

In Book I, the term "transparent" with respect to a liquid active layer means completely or substantially transparent to the naked eye. the non-active liquid layer is less than 10% by weight, preferably less than 5% by weight;
More preferably, it contains less than 2% by weight of surface-active (detergent-active) substances.

Stabilizing surfactants may constitute all or part of the detergent active material. The only limitation on the total output of detergent active materials and electrolytes is that they must together form a structured system. Therefore, a wide variety of variations in the type and range of W surface active agents are possible within the scope of the present invention. Selection of the type and amount of surfactant to be used is within the ability of those skilled in the art in light of the teachings of the present invention to obtain a stable liquid with the desired structure. However, an important subclass of useful compositions are those in which the detergent active material contains one or more conventional or "primary" surfactants along with one or more stabilizing surfactants. Typical blends useful in fabric cleaning compositions include non-ionic and/or non-alkoxylated anionic and/or alkoxylated anionic surfactants. It is like containing.

The stabilizing surfactant has a carbon atom number of 6L:1. Generally, it is preferred that the stabilizing surfactant has an average alkyl chain length of 8 or more carbon atoms. Particularly preferred classes of stabilizing surfactants, used alone or in combination, include: alkyl polyalkoxylated phosphates; alkyl polyalkoxylated sulfolyuccinates; dialkyl diphenyl oxide disulfonates J5 and alkyl polysaccharides. be. A wide variety of such stabilizing surfactants are known to those skilled in the art. For example, E r' −A −
70074+70075;70076;70077;7
5994 Near 5995, 75996 and 92355
It is an alkyl polysaccharide described in .

Particularly preferred are stabilizing surfactants (regardless of chemical structure) having an SOR of 9.0 or more.

In many cases (but not all cases >Vl), the total detergent active materials will be between 2 and 50% of the total composition, preferably 5%.
It can be present in the range of 10 to 30% by weight, more preferably 10 to 30% by weight. These values apply both to blends of secondary surfactants and stabilizing surfactants and to cases where the detergent active material consists entirely of stabilizing surfactants. However, in blends of secondary surfactants and stabilizing surfactants, the amount of stabilizing surfactant is typically 0.1 to 45% by weight of the total composition, especially 0.5 to 3%.
0% by weight, more preferably 1-30% by weight. In such blends, the stabilizing surfactant often ranges from 5 to 90% by weight of the total detergent active materials, particularly from 1.5 to 90%, most preferably from 10 to 90% by weight.

It is generally highly desirable for the composition to have a rheology and a minimum stability that is compatible with most commercial and retail requirements. Thus, in general, the compositions of the present invention exhibit a phase separation of less than 2% by volume after storage at 25° C. for 21 to 1 hour from the time of manufacture, and a viscosity of 2.5 Pas at a shear rate of 218''.
It is desirable that it be less than 1 Pas, preferably less than 1 Pas.

For blends of primary and stabilizing surfactants, the exact proportions of each component that provide such stability and viscosity will depend on the type and amount of electrolyte, as in conventional structured liquids. It's decided. Thus, by way of example, FIG. 1 shows a typical three-component blend of dodecylbenzel sulfonate (Does), a C fatty acid alcohol ethoxylated with an average of 7 moles of eburene oxide, and a stabilizing surfactant. A stability diagram is shown. Locus ■ indicates the limit of a stable composition at a certain amount of electrolyte (for example, 10% by weight). Dashed lines A and B for this limit.

C has the following meanings.

Δ=minimum weight ratio of stabilizing surfactant to total surfactant amount to obtain a stable liquid detergent composition (in this case 0
．． 06) B=minimum weight ratio of ethoxylated aliphatic alcohol to the total amount of surfactant that can be stably added (here 0.
34) C - Minimum weight ratio of formulation surfactant to total surfactant amount (here 0.3) to obtain a stable liquid detergent composition.
37) (assuming that the stabilizing surfactant is nonionic) The locus ■ has a higher 7i solution mass (for example, 12.51ff
i%). It is understood that when determining the composition buffmeter at various electrolyte amounts, it is necessary to vary the surfactant proportions so that the test compositions are always effectively in the same position with respect to the stability limit. Such adjustments must be made in the determination of threshold values A, B and C for the various electrolytes m, as shown in the examples above.

In such ternary surfactant blends, the use of a stabilizing surfactant as a co-surfactant along with one or more primary surfactants will result in the expected additive behavior of each binary combination. An exceptionally large stability region is obtained in the stability diagram. (1, i.e., stable compositions can be obtained over a wide range of surfactant ratios.) Figure 2 shows 23% total surfactant, 10% total surfactant.
A system of sodium citrate and 67% water is shown in which the surfactants are dodecylbenzecysulfonate, C,,E and stabilizing surfactants C,,G (see (it) at the end of Example 1).
). The ternary diagram a) shows the expected additive behavior from a binary system, and the diagram b) shows the actually observed stability region. [Note] The numbers written on each axis in these diagrams indicate the ratio of each surfactant to the total surfactant in the composition.

Detergent actives generally consist of one or more surfactants, whether secondary surfactants or stabilizing surfactants, anionic, cationic, nonionic, zwitterionic and zwitterionic. It is possible to select from among systems and mixtures thereof (if they are mutually compatible). For example, these are “Surfactants” Volume 1, Sil.
Waltz & Berry, Interscience 1949 and
``Surfactants'' Volume 1 [Schwartz, Perry & Birch (Interscience 1958), ``McCutchan Emulsifiers &Detergents'' or ``Tenside,'' published by Manufacturing, Confectioners, Inc., McCutchan Division. Pocket book ``H.

The class described in To Stala, 2nd edition, Karl Hanser Bookstore, Munich & Vienna, 1981,
You can choose from subclasses and specific substances.

- In the case of surfactants, suitable nonionic surfactants are reaction products of compounds with hydrophobic groups and compounds with reactive hydrogen atoms, such as aliphatic alcohols, aliphatic acids,
It includes the products obtained by reacting an aliphatic amide or alkylphenol with an alkylene oxide, especially ethylene oxide alone or in a mixture with p[]pyrene oxide. Certain nonionic detergent compounds include:
Alkyl containing ethylene oxide (C6-018)1
There are products obtained by condensing ethylene oxide with primary or secondary straight-chain or branched-chain alcohols, and reaction products of propylene oxide and ethylenediamine. Other so-called non-ionic detergent compounds include long chain tertiary amine oxides, long m-grade phosphine oxides and dialkyl sulfoxys.

Primary anionic detergent surfactants are typically water-soluble alkali metal salts of organic sulfuric and sulfonic acids containing alkyl groups of about 8 to 22 carbon atoms.

The term "alkyl" herein includes the alkyl portion of higher acyl groups.

Examples of suitable synthetic anionic detergent compounds include alkyl derivatives such as high-grade detergents made from tallow or coconut oil.
C8-018) What is obtained by sulfurizing alcohol and chlorinating it, alkyl (C9-C2o) benzene 11, this-page→-k II r'7/, upper γf potassium, especially Naobo secondary alkyl ( C1o-015) Sodium benzene sulfonate; sodium alkyl glyceryl ether sulfonate, especially ether of higher alcohols derived from tallow or coconut oil and ether of synthetic alcohols derived from petroleum: coconut oil fat monoglyceride sulfate and sodium sulfonate :High class (C8-C
18) Reaction products of sodium and potassium salts of sulfuric esters of fatty alcohols with alkylene oquinides, especially ethylene oquinide: reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralized with sodium hydroxide; methyltaurine sodium and potassium salts of fatty acid amides; alpha olefins (C8-C
2o) obtained by reacting with sodium bisulfite, paraffin with SO2.

Alkane monosulfone olefins, such as those reacted with C12 and then derived from random sulfonate salts, especially C1
Examples include olefin sulfonate salts obtained by reacting o-02o alpha olefin with S03 and then neutralizing and hydrolyzing the reaction product. The preferred anionic detergent compound is (C, 1-0 1.)
Sodium alkylbenzene sulfonate and (C16
-C18) alkyl 5AM sodium.

For example, oleic acid, linoleic acid, and castor oil. Fatty acid soaps derived from rapeseed oil, peanut oil, coconut oil, palm kernel oil or mixtures thereof may be included. Sodium or potassium soaps of these acids can be used, preferably potassium soaps.

The compositions of the present invention also include an amount of electrolyte sufficient to structure the detergent active material. Preferably, the composition contains 1% to 60%, especially 10 to 45%, of salting-out electrolyte. Salting-out electrolyte has the meaning given in EP-A-79646.

Such compositions are also within the scope of this invention. Some or all of the electrolytes (saltino-in and salt or the substantially water-insoluble salts present may have detergent builder properties. Some or all of the detergent builder substances may be electrolytes.A builder substance is a substance that can reduce the amount of free calcium ions in the wash solution, and can also reduce the amount of free calcium ions removed from the fabric by creating an alkaline pH. It would be desirable to have other beneficial properties in the composition, such as soil suspension and fabric softening clay material dispersion.

Examples of inorganic detergents containing phosphorus include water-soluble salts, especially pyrophosphates and orthophosphates of alkali metals.

Contains polyphosphates and phosphonates. Specific examples of the inorganic detergent virgoo include the sodium and potassium salts of tripolyphosphoric acid, phosphoric acid and hexametaphosphoric acid, respectively.

Examples of phosphorus-free inorganic detergents are water-insoluble alkali metal carbonates, bicarbonates, silicates and crystalline or amorphous aluminosilicates! ! Add salt. Specific examples include sodium carbonates (including those with and without calcite cores), potassium carbonates, tuthorium and potassium retraction salts, silica and zeolites.

Examples of organic detergent virgoos include alkali metal, ammonium and substituted ammonium polyacetyl carboxylates and polyhydroxysulfonates. Specific examples include ethylenediaminetetraacetic acid and nitrilotriacetic acid. Oxydisuccinic acid.

Melidic acid, benzene polycarboxylic acid, phosphoric acid.

Includes sodium, potassium, lithium, ammonium and substituted ammonium salts of Tartaric Mm disuccinic acid and Tartaric 111 salt monosuccinic acid.

Apart from the additives already mentioned, a number of other additives may be used if desired. For example, foam promoters such as alkanolamides, especially monoethanolamides derived from palm kernel oil fatty acids and coconut oil fatty acids, fabric softeners such as clays, amines and amine oquinides;
antifoaming agents, R1s-releasing bleaches such as trichloroisocyanuric acid, salt-free V1 salts such as sodium 5A acid and fluorescent agents usually present in very small amounts, 6 agents, enzymes such as protea-U and amylase, disinfectants and It is a coloring agent.

The present invention will be further explained based on the following actual drop examples.

- Example 1: Salting-out resistance of interface duality I Cx Example 9 Demonstration of the decomposition of the lamellar phase (and the resulting instability of the corresponding detergent) when replacing CI2-15E7 (in whole or in part) with Cl3-1s229.

Composition: Surfactant tog/- NTA 151 W/W 1 liter plus NTA, equivalent of 5OR1) 3.2
2) 6.4 3> 2.14) Phase: Ll, low activity isotropic phase L2, high activity isotropic phase LAN, lamellar liquid crystal phase Note: C1□-15E7 is treated with one or more salting-out resistant surfactants. In case of substitution, it can only become stable if the lamellar phase (LAN) does not decompose into the highly active isotropic phase (L2).

This decomposition appears when using C13-+5E2s.

(Margin below)

[Brief explanation of the drawing]

Figure 1 shows dodecylbenzene sulfonate (DoBS)
, C fatty acid alcohol (7EO) and a stabilizing surfactant. a) # and b) in Fig. 2 are ooBs. Regarding the three-component stability of the system containing Cl2-15 [7 and CI2-13G3, predicted values and actual values are shown, respectively. Lee U Rito Patent Attorney Funa Yama Takeshi Proceedings ♀ 117 JE 7”-? March 1989) 0 Kuchi 181 Office Commissioner Furuguchi 1 Moon Yi 2, R Ming's name Liquid detergent 3 N1 I11 [Ro・ 16 people・IYl'l Relationship Specialty Section 1 Applicant Name
! Nilibar) - - Mu - Topen Note (Hoop, 19th, 3rd grade, 1-14, Shinjuku 1-chome, Shinjuku-ku, Tokyo: U+ Ut Building 5, Supplementary Date of 1st Order
spontaneous

Claims (11)

[Claims] (1) containing a detergent active material and a dissolved electrolyte in an amount sufficient to produce surfactant structuring in the composition;
Even if centrifugal force of 750 G is applied for 20 hours at An aqueous liquid detergent composition comprising a stabilizing surfactant of 6.4 or more. 2. The composition of claim 1, wherein the detergent-active material contains a nonionic surfactant and/or a non-alkoxylated anionic surfactant and/or an alkoxylated anionic surfactant. (3) The stabilizing surfactant is selected from alkyl polyalkoxylated phosphates; alkyl polyalkoxylated sulfosuccinates; dialkyl diphenyl oxide disulfonates; alkyl polysaccharides; and mixtures thereof. Composition of. (4) The composition according to any one of claims 1 to 3, wherein the stabilizing surfactant or at least one thereof has a salting-out resistance of 9.0 or more. (5) The composition according to any one of claims 1 to 4, wherein the stabilizing surfactant has an average alkyl chain length of more than 8 carbon atoms. 6. A composition according to claim 1, wherein the detergent active material represents from 2 to 50% by weight of the total composition. (7) The stabilizing surfactant is 0.1 to 45% of the total composition.
Composition according to any of claims 1 to 6, which accounts for % by weight. (8) The stabilizing surfactant is 5 to 90% of the detergent active material.
Composition according to any one of claims 1 to 7, which accounts for % by weight. (9) Claim 1 comprising 1 to 60% by weight of a salting-out electrolyte, all or part of which forms the dissolved electrolyte.
9. The composition according to any one of 8 to 8. (10) Salting-out electrolyte is 10 to 45% by weight of the total composition
10. The composition of claim 9, comprising: (11) Even after being left at 25°C for 21 days after production, there was no phase separation.
% by weight, and the viscosity is at a shear rate of 21s^
The composition according to any one of claims 1 to 10, wherein -^1 does not exceed 1 Pas.