JPS6169895A - Liquid detergent composition - 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] definition The present invention is a novel aqueous flowable liquid detergent composition.

Preferably, the present invention relates to an aqueous flowable liquid detergent composition containing an effective amount of a detergent builder.

Unless otherwise noted, terms used herein have the meanings given in these definitions.

The term "builder" is sometimes used loosely in the detergent industry to refer to any non-surfactant present in a detergent composition to enhance the cleaning effectiveness of the composition. However, more commonly, the term "builder" is used primarily to prevent or ameliorate adverse effects during cleaning of calcium and magnesium ions, for example by chelation, sequestration, precipitation or adsorption of ions. The present invention is limited to representative virgoos which are useful as tools and, secondly, as sources of alkalinity and buffering agents. The term "builder" is used herein in the more limited sense described above, and the term "builder" relates to additives for the substantial amelioration of the effects of calcium. The builders are tripolyphosphoric acid and other sodium or potassium salts of phosphoric acid, and orthophosphoric acid, pyrophosphoric acid.

Included are condensed phosphates such as the sodium or potassium salts of metaphosphoric acid or tetraphosphoric acid, as well as phosphonates such as acetodiphosphonate, aminotrimethylenephosphonate, ethylenediaminetetradiphosphonate. The builders also include alkali metal carbonates, zeolites and organic compounds such as nitrilotriacetic acid, salts of citric acid, minced triacetic acid, high molecular weight polycarboxylic acids such as polyacrylic acid, and copolymers of maleic anhydride. Includes sequestering agents.

For the avoidance of doubt, the term "builder" as used herein includes water-soluble alkali metal silicates, such as sodium silicate, but also includes soil suspending agents or anti-redeposition agents. It does not include additives such as carboxymethylcellulose or polyvinylpyrrolidone, which act primarily as agents.

As used herein, the term "electrolyte" is defined as having a solubility in water of at least s %, expressed as a weight of anhydrous compound, at 0°C and at least partially dissociating in aqueous solution to form ions, and in the concentrations present, salts. It refers to water-soluble ionic compounds that tend to reduce the total solubility (including micelle concentration) of surfactants in aqueous solutions due to their catalytic effects. The term "electrolyte" refers to water-soluble inorganic salts such as alkali metal or ammonium chlorides, nitrates, phosphates, carbonates, silicates, perborates and polyphosphates, and surfactants that insolubilize, i.e. Includes water-soluble organic salts that salt out. The term "electrolyte" does not include salts of cations that form water-insoluble precipitates with surfactants present or that are only slightly soluble in the cleaning composition, such as calcium sulfate or sodium sulfate.

The electrolyte content or electrolyte concentration mentioned herein refers to all dissolved electrolytes, and also includes dissolved builders if the builder used is an electrolyte.

However, it does not include suspended solids.

The term "hydrotrope" refers to any water-soluble compound that tends to increase the solubility of a surfactant in aqueous solution. Typical hydrotropes include urea, or alkali metal or ammonium salts of lower alkylbenzene sulfonic acids such as sodium toluene sulfonate or sodium xylene sulfonate.

Whether a particular compound is an electrolyte or a hydrotrope may sometimes depend on the active ingredient present. Sodium chloride is usually considered the typical electrolyte, but for sultines (5u1tains) it behaves as a sodium chloride salt mudrotrope. Therefore, as used herein, electrolytes and hydrotropes should be interpreted in the context of the individual active ingredients.

As used herein, the term "soap" refers to an at least slightly water-soluble salt of a naturally occurring or synthetic aliphatic monocarboxylic acid, and the salt has surfactant properties. . The term "soap" refers to C8-22 naturally occurring and synthetic fatty acids such as stearic acid, palmitic acid, oleic acid, linoleic acid, ricinoleic acid, behenic acid, dodecanoic acid, resin acids and branched chain monocarboxylic acids. Includes sodium, potassium, ammonium and alkanolamine salts.

The term "common minor ingredients" includes ingredients other than water, active ingredients, bilters and electrolytes that can be included in detergent compositions in proportions of up to S%, and these "common minor ingredients" In suitable compositions, they are compatible with wash detergent compositions having a pourable, chemically stable, non-sedimenting composition. Terminology: "Ordinary minor ingredients"
is redeposition prevention agent 1 dispersant, antifoaming agent, fragrance.

Including dyes, optical brighteners, hydrotropes, solvents, buffers, bleaches, corrosion inhibitors, antioxidants, preservatives, scale inhibitors, humectants, enzymes and enzyme stabilizers and bleach activators, etc. do.

As used herein, the term "functional ingredients" refers to ingredients that provide a beneficial effect to the cleaning solution, and includes ingredients that contribute to the cleaning effectiveness of detergent compositions, such as surfactants, builders, and bleaching agents. agents, optical brighteners, alkaline buffers, enzymes, redeposition prevention agents.

This includes corrosion inhibitors and antifoaming agents.

but,! Water, solvents, dyes, fragrances, hydrotropes, sodium chloride, sodium sulfate, solubilizers and stabilizers whose sole function is to impart stability, fluidity or other desirable properties to the composition. The chemical agent is a technical term ``
It is not included in "functional ingredients". The term "payload" refers to the proportion of functional ingredients based on the total weight of the detergent composition. The term "active ingredient" refers to a surface-active substance.

Unless otherwise noted, the term "centrifugation" used herein all refers to 2 K' (j, 77 hours).

It should be interpreted as centrifugal processing with normal gravity and goo rotation.

The term “high-G centrifugation treatment” is 2! 'Q, so, oo
.

This means centrifugation at G. Unless otherwise specified, high-G centrifugation was performed for 5 minutes.

As used herein, the term "separable phase" separates from the flowable detergent composition upon centrifugation to form distinct layers. 74 or one or more components of the separable phase of the flowable detergent composition. Unless otherwise noted, all 1 separable phases relate to compositions of centrifugally separated phases and 1 composition structure refers to non-centrifuged compositions. The seven separable phases cannot be separated from each other by centrifugation. It can contain two or more different thermodynamically distinct phases, such as stable emulsions or flocs.

The term "dispersed" is used in the present invention to describe a phase that is dispersed discontinuously as discrete or liquid particles in at least one other phase. The term monocontinuous refers to two or more interpenetrating phases, each of which extends continuously through a common volume, or as a continuous network, or is otherwise stationary. Sometimes made up of discrete or fractional elements (components), each of which interacts to form a continuous matrix such that the position of each element in the matrix is maintained when the system is at rest. . The term "interdispersed" refers to co-continuous or one or more phases in which one or more phases are dispersed in seven or more other phases.

The term "solid layer" refers to materials actually present in the composition in a solid state at ambient temperature, and also includes water of crystallization or water of hydration, unless otherwise noted.

The term "solid" is meant to encompass microscopic solids or cryptographic solids, ie, solids whose crystals are not directly observed by optical microscopy and whose presence can be inferred. The term ``
A "solid layer" is a solid, paste or non-flowing gelatinous layer formed during centrifugation.

The term "total water" refers to water present primarily as liquid water in the aqueous phase as well as any other water in the detergent composition, such as water of crystallization, water of hydration, or dissolved or present primarily in the non-aqueous phase. It shows water. The term "dry weight" is / 40
'Q indicates the weight of the residue after drying to a constant weight.

The term "composition" is used to describe the combination of ingredients that make up the dry weight of a composition.

Therefore, the same composition can be exemplified by many compositions with different dry weight percentages.

The term "stable" is intended to mean that a layer containing more than the total volume of flatheads does not separate from the composition within three months at room temperature, usually under gravity.

The term ``shear test'' means that the sample is subjected to pressure 3! ;, 2 kg
/cys' gauge pressure (!; 00 psig) through a tube of length 1 lOttrtn with inner radius O and diameter S. The shear test, in the case of all measurements described herein, involves sucking the sample into a 300 ml pressure vessel through a tube with a wide opening, said tube having an inner radius of 0.2! t
Replace the tube with a 1 m long tube, and apply J j, J kg/an” gauge pressure (j (7
This was done by supplying nitrogen at a pressure of (1+psig).

The tube with inner radius O, cos mttr can then be replaced with a tube with the wide opening and the cycle can be repeated. Typically, the method described above produces a shear rate of about 721,000 sec-1.

The term "shear stability" means stable even after repeating the shear test three times, and the term "shear instability"
means instability after three or fewer repetitions of the shear test, or at slower shear rates.

The term "non-shear sensitive" means that there is no loss of stability or substantial increase in viscosity after being subjected to moderate shear. Shear sensitivity is determined by Contraves “Rheomat J”
OJ (C! ontraves”Rheomat
j O”) viscometer 1 cone and plate measuring device 2 !'
Q, increase the shear line to o-, tgo sec-1 for 7 min (upsweep) L/, also shear,
° - "1 straight line) rapidly decreases [descent (aow
nsweθp)). A composition is considered non-shear sensitive if it is stable after the above-described cycling and the viscosity at 750 s-1 upon decline is not more than 70% higher than the viscosity upon activation.

The term "temperature stability" is defined by immersing a cog sample in a water bath,
A layer containing more than 5 volumes of water should not separate from the composition within a few hours after heating by holding at 90"Q for 110 minutes, then immediately immersing in a 100°C water bath and holding for 70 minutes. It means.

The rpHJ of the detergent compositions described herein is a combination of a glass electrode and a calomel electrode.
p measured by Unicam) 410'I
It is H.

"Conductivity" is at SO kilohertz frequency.

Electrical conductivity measured at 2S°C. The results to be described are ODO
J/4 (using flow and pipette cells (!D
M,? The conductivity was measured using a radiometer (RAD OMKTKR).

The term "74th is the smallest value" is the active ingredient for conductivity:
A graph of conductivity as a function of increasing dissolved electrolyte concentration in a liquid detergent composition containing a given percentage of water, in which the conductivity typically first increases to a maximum value, decreases to a minimum value, and then increases again. do. This term refers to the concentration of electrolyte corresponding to the above-mentioned minimum value or the lowest concentration of dissolved electrolyte corresponding to seven of a number of such minimum values.

Unless otherwise noted, all percentages are by weight based on the total weight of the composition.

Unless otherwise stated, all viscosities used in one FIAls document are 7111, in a flat-bottomed cup with a height of 1.5 mm and a horizontal angle of This figure shows the viscometer measured after operating for a minute using a viscometer consisting of a cup and rotor with a rotor at both conical ends of !t'Q and a spindle with a diameter of em.The tip of the rotor is 2 J Im from the bottom of the cup. This is done using a C-type measuring device.
Compatible with 30” viscometer.

As used herein, the term "flowable" means having a viscosity of less than a covascal second at a shear rate of 134 seconds.

The term "viscosity drop" means a shear force of 11 s-1 and /34 s-1
It refers to the difference in viscosity of shear-thinning compositions measured at a shear force of .

The term "yield point" as used herein refers to RML series IJ -
, z: l 7'x-# 11 rheome fi -(
RML 5eries Deer Rheometa
r) at sr°C.

The term "rLs phase" refers to the transparent, fluid, aqueous surfactant.
It is an optically isotropic micelle solution, and the Ll phase occurs at a concentration above the critical micelle concentration, and the surfactant in the Ll phase aggregates to form spherical micelles, oblate spheroidal (aisC) micelles, or oblate (aisC) micelles. rod) appears to form micelles.

The term "bilayer" encompasses a phase approximately - molecules thick of surfactant, which bilayer is formed from one contiguous layer of surfactant molecules, and whose surface The hydrophobic sites of the active agent molecules are arranged such that they are located inside the bilayer membrane and on the outer surface of the bilayer membrane. As used herein, bilayer membranes also include an intermediate layer that is less than two molecules thick. An interlayer can be considered a bilayer in which two layers interpenetrate and overlap at least to some extent between the hydrophobic portions of the molecules of one of the layers.

The term "spherulite" means a spherical or ellipsoid with dimensions Q,/~50 microns. Spherulites are sometimes oblong.

It may be deformed into a flat sphere, Western shape, or bell shape. The term "bubbles" refers to spherules containing a liquid phase surrounded by a double membrane, and "multiple bubbles" refers to bubbles containing seven or more bubbles. "Plate phase" refers to bilayers separated by aqueous or aqueous solution phases that are arranged substantially parallel to each other, and when present as a substantial proportion of the composition, can be easily detected by neutron diffraction. can=s~7(1) means a hydrated solid phase or liquid phase with a regular lattice spacing of A. Here, this plate-like phase does not contain concentric multiple liquid bubbles.

"G phase" refers to a type of liquid crystal plate phase known in the literature as a "neat phase" or plate phase;
This G phase is usually present in a narrow concentration range for a given surfactant or surfactant mixture. Pure G phase can usually be identified by placing the sample between crossed polarizing plates and examining it under a polarizing microscope. The characteristic organization is JAOC
! Roaa in S volume 31 bit page (/93 years)
vear's paper, or Colloid Endo-Interfacial Science 7s (0011o1d and 1
interfacialScience) Volume 30, m
p., p. 00 (7969).

"Spherical G-phase" refers to a multi-liquid bubble consisting of substantially concentric outer shells of bilayer surfactant membranes in which aqueous and G phases are alternately arranged. Typically, the conventional G phase may include a small percentage amount of spherulite G phase.

"Lye" means an aqueous liquid phase containing an electrolyte, which aqueous liquid phase is separated from a λth liquid phase containing more active ingredients and less electrolyte than the lye phase; Scattered in layers.

"Platform composition" means a composition in which most of the surfactant is present as a platy phase, or in which the platy phase is a major factor in inhibiting sedimentation. By "spherulite composition" is meant a composition in which most of the surfactant is present as small spheres (spherulites) or is stabilized against sedimentation primarily by a spherulite surfactant layer.

Technical Background Liquid detergents have been used primarily for light detergents such as dishwashing. For example, the market for heavy wash detergents, for example laundry detergents, is dominated by powders due to the difficulty of incorporating effective amounts of surfactants into stable liquid compositions and especially builders into stable liquid compositions. was dominant. Such liquids should theoretically be cheaper than powdered detergents because they do not need to be dried and water can often replace the sulfate fillers traditionally used in powdered detergents. Liquid detergents are also more convenient than powdered detergents and dissolve more quickly in the wash water. Attempts to create solutions of functional components have been unsuccessful industrially. One of the reasons for this lack of success is that the most commonly used and cost effective builders, such as sodium tripolyphosphate, do not dissolve sufficiently well in aqueous compositions. Furthermore, increasing the amount of dissolved builder due to the salting-out effect tends to reduce the amount of surfactant that can be dissolved, and increasing the amount of surfactant dissolved reduces the amount of builder dissolved. Potassium pyrophosphate builders and amine salt surfactants (which have relatively higher solubility than others) have been tried in place of the sodium salts, but have not been found to be cost effective.

Builder-free liquid detergents are commercially available for laundry use, but they are unsuitable in hard-water areas, the use of effective amounts of builders is subject to legal restrictions, and competition with powder detergents is comparable. It has had only limited success, largely confined to less demanding markets.

A different approach to that described above consists in suspending an excess amount of the builder in a liquid micelle solution or emulsion of surfactant. However, in this case, there was a problem in that the system had to be stabilized to maintain the builder in suspension and prevent sedimentation. A number of relatively complex compositions have been proposed in the literature, which use expensive potassium salts instead of cheaper sodium salts and include additives such as hydrotropes, dispersants, or solvents. It involves the use of solubilizing agents. However, their use hinders the realization of cost reductions. Even with such external additives, it would be necessary to use relatively low concentrations of solid builders, and the cleaning effectiveness would be limited. This approach requires certain conditions: the active ingredient must remain as dissolved as possible; the amount of suspended solids must be minimal to prevent the suspended solids from settling and to avoid stabilizing difficulties. special thickeners or stabilizers are required to prevent sedimentation; and are improved by omitting or keeping electrolytes, which reduce the solubility of the surfactant, at very low concentrations.

A major feature of the prior art is its experimental nature. No acceptable general theory has yet been proposed to explain the stabilization of some compositions and the instability of others. Therefore, there is no way to predict which compositions will be stable, and there is no general procedure for creating new stable liquids. The prior art does not contain generally applicable teachings, and even most examples of prior patents relating to liquid detergents only provide compositions that separate within a few weeks. Relatively few exceptions are found only by chance and cannot be used as a basis for presuming improvement.

Products of this type have been commercially introduced in Europe and Australia, but have serious drawbacks. These products had relatively poor cleaning performance due to low builder/active ingredient weight ratios or low alkalinity. They also exhibit an undesirably high susceptibility to mechanical and/or thermal stresses, such as shear or storage under extreme weather temperature conditions.

Thus, some compositions separate under shear, while others become extremely viscous and most separate when stored at either 0°C or 1IO°C.

However, the prior art does not teach how to overcome the aforementioned drawbacks.

In addition to the compositions that have been developed industrially, a large number of compositions have been proposed in the literature, but these have been unsuitable for practical commercial use.

Typically, such compositions are not stable or sufficiently stable to permit normal storage without sedimentation, and cleaning effectiveness otherwise must be considered for commercial development. The manufacturing price was too high compared to

Compositions have recently been proposed in which the active ingredients form a network of plate-like phases that are separated from the aqueous phase by centrifugation, giving a gel structure in which this network is capable of maintaining suspended particles of solid builder. This gel structure is created by adding a sufficient amount of electrolyte to salt out the active ingredients to form an aqueous lye phase and a separable plate phase, and by adding a sufficient amount of electrolyte to salt out the active ingredient and form an aqueous lye phase and a separable plate phase, above a stability limit and below a fluidity limit. obtained by maintaining a solids content of . The amount of electrolyte required depends on the hydrophilicity and melting point of the surfactant and the presence of solubilizing agents such as hydrotropes and solvents. The aforementioned gel structures tend to have higher payloads, higher builder/active ingredient ratios, and are more cost effective than known commercial liquid compositions. In fact, the best of the aforementioned platy phases are more cost effective stain removers than the best powdered laundry detergents.

However, the laminar phase compositions disclosed heretofore exhibit flow properties that are less than optimal for some purposes.

INTRODUCTION TO THE INVENTION The present invention describes a novel method containing electrolytes, active ingredients, and water that can suspend solids such as builders to form stable compositions that combine improved cleaning performance with satisfactory flow properties. The composition of the group was found. We believe that the stability of the novel compositions of the present invention is due to the previously unreported spherulitic structure. We have also discovered a method for producing stable, flowable compositions with excellent cleaning performance from a wide variety of active ingredients.

According to a preferred embodiment of the invention, the invention has at least some of the following advantages over previously commercially available products: high payload; high builder/surfactant ratio; improved stability; Low cost due to the use of affordable ingredients and compact manufacturing methods; improved cleaning performance; high pH and/or alkalinity; good stability at high and/or low storage temperatures and satisfactory upon shearing Action.

It has been found that when the active ingredient, dissolved electrolyte and water are present in a predetermined proportion depending on the selected active ingredient and electrolyte, a stable spherulite composition is obtained which is capable of suspending solid particles such as builders. It was done. We have also found a method for producing such compositions and a method for identifying the compositions by various physical properties. We further provide active ingredients/compositions for obtaining compositions that are stable to shear stress and to temperature changes encountered during storage under widely varying weather conditions and are highly fluid. They also found a way to optimize the electrolyte ratio. Unlike compositions exemplified by recent prior art relating to platelet compositions, the novel compositions of the present invention are believed to be stabilized by surfactants present as spherulites rather than in a platelet phase. It will be done.

PRIOR ART The prior art relating to liquid detergents is extremely voluminous. However, for the purpose of the present invention lζ, the large number of publications on liquid light detergents in which all the components are present in solution and on clear liquid laundry detergents without builders or with builders are not worth considering.

The reason for this is that the content of builder is much lower than desired.

For a summary of the recent state of the art, JAOC! 5 (1
1991/Q) -, 7, t4A page I
Duty Laundr7 Detergent)
(this article evaluates representative commercially available liquid compositions) and Rutkowsky (2013).
Recent Change in Laundry in the Surfactant Science Series by Ski)
r7.

netergent) (published by Marcel Detzker-ψ Incorporated, /91/).

The three main avenues of attempt to define liquid detergent compositions containing sufficient amounts of builder are emulsifying the surfactant in an aqueous solution of the builder, emulsifying the solid builder in an aqueous solution or emulsion of the surfactant. and suspending the solid builder in a gel with a platy matrix of surfactants.

The first attempt was U.S. Patent No. J Co. J! ! ;0! No. 33
Hiro 4! OJ issue, same number 33! r/! ! No. 7, No. 3!09
0! No. 9, same No. 7j? Gu/Coco, No. 33 Yuza 30
No. 9 and Canadian Patent No. 9/70J/. In each of these patents, an aqueous solution of water-soluble virgoo is sufficiently concentrated to salt out a surfactant (usually a liquid non-ionic type), and the salted out surfactant is mixed into a colloidal liquid with various emulsifiers. It is dispersed in an aqueous medium.

In each case the system is a clear emulsion, which is generally
Although it contains a relatively low content of builder, this results in an undesirably high price due to the high cost of using soluble builders.

The first attempt is British patent number T! Jrt J No. 9
411AI No. 7, Dedacock/No. 11441
/l: No. 1, same IL/sob Hiroyuku issue, same No. koo kotJ
Le! No., European Patent No. ytioi, Australian Patent No. 3-Utah No. 13, US Patent No. 0/l Near 2
No. 0, No. 7 J, t x t 7 g -1%
, Same No. 307s9:12 and Same No. 00e
! exemplified by No. The compositions described in these patents are not stable, temperature stable, or shear stable. Commercial products corresponding to the two embodiments of these patents have recently been sold in Australia and Europe. In particular, compositions corresponding to Australian Patent No. J Yuko 91J achieved some commercial success, but were shear sensitive.

A third attempt is described in European Patent No. 00tttia. The compositions described in this inter-patent document represent platelet solid or liquid crystal surfactants. Such compositions have higher viscosities than desired for some applications.

Another approach is to suspend a solid builder in an anhydrous liquid non-ionic surfactant, as shown for example in British Patent No. 1 RO9G1. This system is expensive, limited in the selection of surfactants, and has unsatisfactory scouring properties. Although the amount of builder relative to the total composition is high, its proportion to the active ingredient is low and therefore not cost effective.

Several patent specifications describe emulsions in which the builder is not suspended, but rather forms the dispersed phase of the emulsion. US Patent No. 'l0jr7! ;01. No. 1, which describes a clear emulsion of sodium tripolyphosphate, U.S. Pat.
No. 107,067 describes an inverse emulsion in which an aqueous solution of a builder is dispersed in a liquid crystal surface-active system.

A number of patents describe hard surface cleaners, usually with abrasives suspended in a surfactant water bath, and such patents include U.S. Patent No. 03/'I!
! r, U.S. Patent No. 3 Co. 11347, U.S. Patent No. 31/3J
'lt issue, same issue J de Art/! No. and M4'JO
There is Kojda No. 7.

However, it is not possible to create laundry detergent compositions from these patents due to their low content of surfactants, lack of builders, and high concentrations of abrasives.

Other publications of interest include Australian Patent No.! r07
'1.7/, this patent describes a suspension of a builder in an aqueous surfactant stabilized with sodium methylcellulose or clay as a thickener.

However, the content of functional ingredients, particularly the content of builders in the exemplified compositions, is not sufficient for a well-accepted commercial product, and the stability is also insufficient to provide a useful shelf life.

US Pat. No. 303'/97/ describes detergent pastes containing dissolved builders.

FR 2 213 911 describes suspensions of zeolite virgoos in nonionic surfactant systems. However, this composition is not a free-flowing fluid but a hard paste.

U.S. Pat. No. 3,341,63011 and U.S. Pat. No. 33'
1Al; No. 73 describes the solubilization of sultines with a hydrotrope (referred to as an electrolyte in these IMM books).

A, O, S, Symposium 1? f regular meeting ``Silicates in Detergent''
Detergenta) I describes the effect of silicates on liquid detergents.

The above-mentioned patent documents have been selected from a very wide range of prior art, and the relevant annotations have been provided by the inventors using the knowledge of the present invention to highlight the selection of the above-mentioned prior art and its main points. This was done in addition to post-mortem observations. At the time of the present invention, without prior knowledge of the present invention, one skilled in the art would not necessarily select the above-mentioned prior art as particularly important or the annotations of the above-mentioned prior art as particularly interesting and relevant. Probably.

Accordingly, the above summary of the prior art is available to those skilled in the art and does not represent a comprehensive overview of the prior art.According to a first embodiment of the present invention: , and having solid/11 turbidity properties, wherein the proportion of electrolyte is sufficient to provide a temperature stable, non-shear sensitive, and substantially non-platform composition;
A flowable liquid detergent composition is provided.

According to a first embodiment, the invention has solid suspension properties;
and a stable, flowable liquid detergent composition containing water, an active ingredient, and an electrolyte, wherein the proportion of electrolyte is sufficient to provide a space-filling spherulite floc that is temperature stable and non-shear sensitive. It's about providing things.

According to a third embodiment, the invention has solid suspension properties;
The trough in the graph of electrolyte concentration versus conductivity containing water, active ingredient and a first conductivity minimum is sufficient to form a dispersion stable phase containing at least 7 parts of the corresponding active ingredient. The present invention provides a stable, flowable, liquid detergent composition containing an amount of electrolyte, the proportion of which is within a range such that the detergent composition is temperature stable and non-shear sensitive.

In each of the embodiments described above, the concentration of electrolyte is preferably sufficient to provide a shear stable performance acid.

Compositions according to each of the embodiments described above advantageously contain suspended solids such as builders and/or abrasives. This suspended solid is either insoluble in the aqueous fluid medium already present in saturated amounts, or encapsulated in a substance that prevents the solid from dissolving in the medium.

According to a ninth embodiment, the invention comprises water, an active ingredient, an electrolyte and a suspended solid, wherein the proportion of electrolyte is between 7 and 7.
The object of the present invention is to provide a stable, flowable liquid detergent composition in an amount sufficient to form a shear-stable spherulite composition with a yield point of Dyne/cIL-2.

The drop point of the detergent composition is preferably 5 dynes α-2 or higher, more preferably 5 dynes α-2 or higher, more preferably 3 dynes CIE-” or higher, such as 3 dynes CIE-” or higher, and most preferably 3 dynes CIE-” or higher. is less than lθdyne a. /
31. The viscosity at -1 seconds is preferably less than 1 Pascal second, more preferably less than 1 Pascal second, for example 0.2 Pascal seconds or less. λ~0
．． It is 4 pascal seconds.

According to a fifth embodiment, the invention provides water as an essential component, by weight of the composition! -2r% of active ingredient, electrolyte and suspended solid builder, the total weight proportion of builder/active acid is /, (<Δ~ri//, and the proportion of electrolyte is shear stable, non-shear-stable, The objective is to provide a stable, flowable, liquid detergent composition in sufficient quantity to provide a plate composition.

The detergent compositions may further contain conventional minor ingredients. The active ingredient is preferably present in a proportion of 10-20 wt-1, more preferably 10-19 wt-1, the total weight ratio or builder/active ingredient ratio being /, yo// to J//, for example /, li/ /~ko, 1//.

According to a sixth embodiment, the invention provides water, 5% by weight of the composition.
~Ko! - contains an active ingredient, an electrolyte and a suspended solid builder, and has a payload of at least 35 weight -
The proportion of electrolyte herein is in an amount sufficient to provide a shear stable, spherulite composition to provide a stable, flowable, liquid detergent composition.

According to a seventh embodiment, the invention comprises water, 5 to 25 weight percent of active ingredient, an electrolyte and a suspended solid builder;
The total proportion by weight of builder/active ingredient is /, r//
~4t// and the proportion of electrolyte is sufficient to provide a spherulite composition that is temperature stable to storage at qoC. There are many things to offer.

According to a first embodiment, the invention comprises water, j to -0 weight of active ingredient, an electrolyte and a suspended solid builder;
the total weight ratio of builder/active ingredient is ///-q/l, the proportion of electrolyte is sufficient to provide a temperature stable, non-shear sensitive composition, and the composition is centrifuged; an aqueous layer containing 50- or more of the total weight of active ingredients;
and to provide a stable, fluid, liquid detergent composition that separates into solid phases.

According to a second embodiment, the present invention contains as essential ingredients water, dissolved electrolyte, composition t-/II weight of active ingredient, as well as suspended solid builder and optionally customary minor ingredients, and Upon centrifugation of the composition, the composition separates into a solid phase and a single liquid phase having a yield point greater than 5 d as-'' to provide a stable, flowable detergent composition. .

According to a first O embodiment, the present invention comprises substantially water, an active ingredient and an electrolyte, and contains solid suspension properties, wherein the active ingredient is capable of forming a stable composition at a first conductivity minimum. and the amount of electrolyte present is sufficient to provide a composition having a yield point of greater than or equal to 5 dynes (II-2) and a viscosity of less than 00-t Pascal seconds measured at 736 seconds-1. It's about providing things.

According to a first/embodiment, the present invention comprises water as an essential component;
containing an electrolyte, an active ingredient and a builder, having at least a portion of the dissolved electrolyte and the total weight of the active ingredient;
To provide a stable, free-flowing, water-based detergent composition comprising a first predominant aqueous liquid phase containing o- and at least seven dispersed solid separated phases containing at least seven parts of a builder as solids. be.

The main aqueous separate phase is at least 4 L of total water.

It is preferred to contain at least 50-1, such as at least 60-1.

According to a first co-embodiment, the present invention has a payload of 35 wt. or more and a pH of 9 or more, water, dissolved electrolyte, at least 5 wt.
5 by weight of the builder and the electrolyte is sufficient to impart a shear stable composition, but in an amount insufficient for the active ingredient to form a substantial division of the platy phase. The object of the present invention is to provide a water-based detergent composition with excellent fluidity and stability.

According to the first J embodiment, the present invention contains sufficient active ingredient to form space-filling flocs of surfactant containing interspersed spherulites in the aqueous phase, and the amount of electrolyte is at a conductivity relative to the electrolyte concentration. an amount that is greater than or equal to the first conductivity minimum value in the graph of the degree of conductivity, and less than or equal to the amount that corresponds to the formation of a plate-like phase, and sufficient to provide a non-shear sensitive composition. An aqueous liquid detergent composition is provided.

According to the 11I embodiment, the present invention comprises water, an electrolyte, an active ingredient and a builder, wherein upon centrifugation as defined above the composition contains at least 70% by weight of the total amount of water - dissolved electrolyte and total activity. Provided is a flowable, stable liquid detergent composition that separates into at least one layer comprising an aqueous layer containing at least a to-go weight of the active ingredient and a solid layer containing at least 7 parts of the builder. It is in.

According to another embodiment, the present invention comprises an active ingredient, an electrolyte, and water, and is stable, spherulite-like, and free from the appearance of a separated clear aqueous phase after high-G centrifugation at -0, -000 G for 90 minutes. Compositions are provided.

More particularly, the present invention provides stable, free-flowing liquid detergent compositions containing water, active ingredients, and electrolytes, all of which exhibit at least some of the following properties: , but need not all be indicated: the composition contains a co-continuous phase of lye or lye, interspersed with spherulite phases, preferably lye or 11 phases; the composition preferably contains a floc system that is space-filling; the composition usually contains an aqueous phase alternating with an aqueous phase, e.g.
k, preferably the height ~θ~? OA, often
The active ingredient consists of flocs formed from active ingredient-containing particles, preferably surfactant-containing spherulites, with concentric shells of surfactant with a repeating space of X, e.g. Preferably diameter 0.4-3
The composition is composed of micron spherulites (small spheres), which exhibit a so-called "Maltese cross" when placed between so-called crossed polarizers and observed under appropriate magnification; the composition is shear-thinning; has a viscosity drop of 0.3; II '7, t~/, j Pascal seconds, especially o
, a viscosity drop of tar~8/pahecal seconds; the composition has a high payload of functional components, usually -0 weight or more; Usually less than weight -1 (both 3
0 wt-1 preferably at least 35% by weight, optimally at least q.

of functional components by weight; the composition has a high builder/active ingredient ratio, e.g. 777 or higher, preferably /, co//~
lI//, more preferably 7.4t/1S-1I//,
Optimally /β// %, 7. of the weight of the composition; weight % or more, preferably t weight % or more and co5 or less, preferably 10 or less, usually 1596 or less, more preferably /lI, 6% or less, optimally /dar or less, such as 1o-iJ, r - contains active ingredients;
The composition forms a mono-aqueous layer and a solid phase upon centrifugation, the aqueous layer usually having at least /J dynes m-', preferably at least /J dynes am-2, e.g. of the active ingredient in the main aqueous layer formed after centrifugation, based on the total active ingredient in the composition. The weight proportion is greater than or equal to 50, preferably greater than or equal to j, such as greater than or equal to tOS, but less than or equal to yos, preferably less than or equal to tS, such as ?
o- or below; no clear lye layer is observed upon high-G centrifugation for 90 minutes; the pH of the composition is above t, r, preferably ~13, e.g. De, S~/co; the composition When the product is diluted with water to a dry weight of 0.2%, the pH decreases to 7 or more, preferably 10 or more.
A cleaning solution with /, / can be produced; the alkalinity is the pH of 100rnl of a cleaning solution with a dry weight of 00S-? In order to reduce the normal Hα to 1/10, the alkalinity requires Ant to at least o, r-1 preferably at least /d1, e.g. a total amount of at least 0.3 g ions of alkali metal cations and/or ammonium cations,
Preferably at least an O6j gram ion, more preferably at least an 8-gram ion, such as ρ~ri,!
contains sufficient electrolyte to provide a concentration of gram ions; the concentration of electrolyte is greater than or equal to the concentration corresponding to the first conductivity minimum tζ of the graph of electrolyte concentration versus conductivity; The electrolyte concentration is not more than -ms above the conductivity at the highest value; the electrolyte concentration is less than that which forms a substantial section of the platelet phase; the electrolyte concentration is preferably not less than the minimum concentration that provides a stable composition. the minimum concentration that provides a shear stable composition; the composition is non-shear sensitive; the composition is temperature stable; the composition is stable at HO; Sex is/! Millisiemens/
lxh or less; the composition has a weight of at least /
The builder preferably contains 20% by weight of builder; the builder is at least a predominant amount of sodium tripolyphosphate; the builder is an alkali metal silicate and/or alkali metal carbonate, preferably sodium silicate and/or sodium carbonate. the viscosity of the composition at a shear rate of /36 s −1 is between 0.7 Pa sec and covascal sec, preferably between 0.1 Pa sec and /Pa sec, for example (7
, jPascal seconds to 0.6 Pascal seconds; the composition preferably has at least 7 dynes/as2, more preferably at least 3 dynes/as2, such as at least 1 dynes/(as)2. , preferably JO dyne/42 or less,
For example, 20 dynes/cm' or less, more preferably /j
have a yield point of less than 10 dynes/(up to) 2; the builder-containing phase contains solid particles with a maximum number dimension below the limit at which the particles settle; the composition is shear stable; The active ingredient contains at least two ingredients, one of which is a non-ethoxylated anionic surfactant and the other a stable foam-forming surface such as an ether sulfate, alkanolamide or amine oxide. It is an activator.

When the concentration of fζ-dissolved electrolyte in a suitable aqueous surfactant mixture is gradually increased from zero, the detergent composition passes through a readily recognizable series of stages that typically occur below.

/””− 1/′ 1′/ /′ Stage I First, the conductivity increases to its maximum value, during this stage the viscosity increases and the phase becomes initially transparent optically isotropic and forms spherulites. begins to show signs of The spherulites are visible under a microscope and, when viewed between crossed polarizers, exhibit a texture called Maltese cross, which is usually characteristic of the spherulitic G phase. However, neutron diffraction shows no evidence of G phase or any other liquid crystal phase;
Substantially compatible with micellar compositions.

Although Stage I compositions are usually clear and stable.

However, it does not have the ability to suspend solid particles.

Stage ■ In stage ■, the conductivity drops with increasing electrolyte concentration and the composition becomes cloudy. The high-G centrifugation treatment 1ζ separates the composition into a transparent aqueous phase and an opaque emulsion phase, and the volume fraction of the opaque emulsion phase increases as the electrolyte concentration increases. Under the microscope, the spherulites were observed to gradually increase in size and become smaller in size, producing loosely aggregated flocs separated by optically isotropic ranges, which became more numerous as the electrolyte concentration increased. Ru.

However, according to neutron diffraction studies, the micelle concentration decreases and the proportion of larger substances increases.

There is no G phase in a proportion that can be recognized as G phase. The composition of the stage is cloudy, unstable and rapidly settles.

Stage ■ The conductivity drops to a minimum value and begins to rise to the first order.

The spaces between the spherulite flocs disappear and one spherulite forms a space-filling floc that expands throughout the liquid phase. High G centrifugation treatment? O
The aqueous phase does not separate, even when continued for minutes. A yield point was observed and increased to a maximum value and one composition became shear thinning and a significant viscosity drop was observed.

Neutron diffraction provides no evidence of substantial division of the platelet phase. Nuclear magnetic resonance absorption likewise shows virtually no G-phase content, indicating a low concentration of micellar surfactant. Electron microscopy shows that at least some of the spherulites are multiple bubbles with a substantially concentric arrangement of shells or partially overlapping shells, perhaps more widely spaced than in normal G-phase cells.

In step ζζ the composition is stable and it is possible to suspend solid particles to form a stable suspension.

The composition of this step (2) constitutes the present invention.

Step 2: Adding more dissolved electrolyte gradually reduces the size of the spherulites and increases the luster of the Maltese cloth structure. Spherulites are space-filling and form discrete flocs separated by optically isotropic ranges. The yield point and viscosity drop decrease and the conductivity increases to a maximum value or begins to level off. Neutron diffraction shows evidence of substantial G phase.

High-G centrifugation 1 Separate the clear lye phase from the turbid layer. The composition is unstable, tends to settle, and is unable to suspend solid particles.

Stage■ The plate composition has a European patent number 00! It is formed in the form of the type described in No. j46/'I. Adjusting the water content to the degree necessary to obtain a stable composition results in a relatively high viscosity.

The sequence of steps described above is typical of the interaction of electrolytes with a wide variety of aqueous surfactant mixtures. If the composition already contains some dissolved electrolyte, such as in a suspended TolipoIJ phosphate-containing builder-containing detergent, or if the initial surfactant mixture is not completely dissolved in water, step 1 ■ cannot be observed. Similarly, if the solubility of the electrolyte is limited, as is the case for example with sodium tripolyphosphate or sodium carbonate, subsequent additions of electrolyte above the saturation limit of the electrolyte will not take the composition to a further stage. There will be no migration.

Preferred compositions of the invention fall within step 1 of the above series. There are metastable intermediate compositions between stage (i) and stage H, and between stage (i), respectively. The composition exhibits flocs of surfactant spherulites which, upon continuous high-G centrifugation for 10 minutes, may form a clear aqueous layer or cause irreversible disintegration of the spherulites. It is not completely space-filling, as evidenced by certain facts. Even if the composition is stable when it is left at ambient temperature, it often fails when exposed to various stresses such as high shear, elevated temperature, reduced temperature, or pH changes. It becomes stable. The composition's ability to suspend finely divided solids is often limited. Many compositions proposed in the prior art are within the metastable range described above.

We have now discovered that typical compositions within the marginal metastability range described above can be modified by the teachings of the present invention by adjusting the electrolyte content to bring them closer to the stage II stability range. .

Typically, during centrifugation, the composition of step (1) of the present invention is 90-50% by weight of the electrolyte and total active ingredients.

Normal go-so weight%, more normal? ! -3! ;weight%.

For example, 70-! ;! separated into an aqueous layer containing % by weight of the active ingredient and at least 7 other layers, said at least one other layer containing from 73 to 50 % by weight of the total active ingredient, as well as a substantial fraction of the bilgoux; do. The viscosity of the composition of the invention at a shear rate of 736 s-1 is typically 0. /-2 pascal seconds, preferably 0.2 to 7.5 pascal seconds, e.g.
23-0.6 pass force per second, and the viscosity drop is typically O0a
~Cobascal seconds 1 For example, o, lIs~/j Pascal seconds.

The composition of stage (1) is non-shear sensitive and usually shear stable. In contrast, high shear forces tend to destabilize metastable border range compositions. The viscosity often increases considerably with even mild shear, and the composition settles rapidly. This creates practical difficulties during manufacturing and bottling. The compositions of step 1 of the present invention, unlike many metastable compositions, are generally stable to high pH and to storage at temperatures below about IIoC or s'Q. The composition of step (1) is generally temperature stable even when heated to 100"C.

Compositions of stage (2) usually show no evidence of platelet layers when analyzed by neutron diffraction, although some compositions near the boundary range with stage (1) may show evidence of small amounts of G phase.

It should be appreciated that the proposed structure of the surfactant is that the behavior at each stage described above can be most easily explained based on the assumption that the electrolyte undergoes a gradual transition from a micellar phase to a spherulite phase with increasing electrolyte concentration. Spherulites are initially obtained in the form of multiple bubbles with a large number of double membranes arranged substantially concentrically, but with wider and more irregular spacing (spaces) than the normal G phase. I want to be understood.

There can be one aqueous phase L1 phase and one lye phase;
The lye phase can also be an L1 phase containing fewer micelles and a larger amount of electrolyte than the L1 phase. Seven or more of these phases, possibly the lye phase, can form the internal phase of a multiple liquid bubble.

We have found that increasing the electrolyte content and decreasing the proportion of active ingredients tends to provide less viscous compositions with equal stability and payload, which is due to the fact that substantial spherulite It should be understood that it is a reduction in the proportion of micellar surfactant without a reduction in quantity. Lower micelle content reduces viscosity, while sufficient spherulite phase remains to maintain stability.

In preferred stable compositions of the present invention, the 9-spherulites are packed closely enough to form substantially space-filling, ie, cohesive flocs that increase the total volume of the liquid. The spherulites probably interact to form a weak three-dimensional matrix that is strong enough to support the suspended particles, but breaks down under the action of shear forces and quickly disintegrates. It has a weak strength that makes it fluid,
The matrix is reformed when the shear force is no longer applied. Spherulite dimensions correlate with stability;
Compositions with large spherulites of 3 microns or more are less stable than compositions in which a large proportion of the surfactant is o,s-s micron spherulites.

As the electrolyte content increases, the single spherulite becomes smaller.

It also probably tends to be denser and more regularly spaced than the spherulite G phase. As a result, the G-phase spherulites have narrower space filling;
The composition also tends to settle.

Active Ingredients The compositions of the present invention preferably contain at least 3% by weight of surfactants, and up to 30% by weight and usually up to 23% by weight. The surfactant more preferably comprises 5 to 2 of the composition.
0% by weight 1 e.g. S to 75% by weight 1 usually 10-/4',
! % by weight, particularly preferably less than / da % by weight, often 7% by weight
Consists of 3% or less.

The concentration of active ingredient is a critical factor in obtaining the compositions of the invention. Below a certain minimum amount, which varies depending on the particular active ingredient system, a composition cannot be stabilized by adding larger amounts of electrolyte, but a maximum amount also 'avoids an overly viscous composition. It is important for

Prior art metastable spherulitic compositions often contain relatively large amounts of active ingredient. This makes the viscosity of the aqueous suspension medium relatively high and severely limits the amount of builder that can be suspended to achieve a given viscosity limit. Therefore, the overall builder/active ingredient ratio will be lower compared to powdered detergent compositions, resulting in lower cleaning performance.

It has been extremely difficult to reduce the active ingredients in detergent compositions without destabilizing the entire system.

We have surprisingly found that by increasing the electrolyte concentration sufficiently, the concentration of active ingredient can be substantially reduced and provide an aqueous medium with equal or greater stability and even lower viscosity. The aqueous medium is able to suspend a larger amount of builder without losing sufficient fluidity, and the greatly increased builder/active ingredient ratio likewise substantially increases the cost-effectiveness of production. do.

Preparation of spherulite flocs from mixtures of one surfactant is usually substantially easier than preparing the flocs from a single surfactant. Thus, a stable foam-building co-surfactant such as an alkyl ether sulfate and/or an alkanolamide or an amine oxide with one or more non-ethoxylated anionic surfactants such as alkyl benzene sulfonates and/or alkyl sulfonates. A mixture of one or more surfactants is usually more suitable than any single surfactant. Minor amounts of ethoxylated nonionic surfactants or minor amounts of amphoteric surfactants or minor amounts of cationic fabric softeners may additionally be present.

The surfactant mixture i can be, for example, an at least slightly water-soluble salt of a sulfonic acid or a monoesterified sulfuric acid 1, such as alkylbenzene sulfonates; alkyl sulfates, alkyl ether sulfates, olefin sulfonates, alkanesulfonates, alkylphenol sulfates, alkylphenol eratilsulfates. neat.

Alkylethanolamide sulfate, alkylethanolamide ether sulfate.

or 8 to 22, more commonly - ζ may contain one or more α-sulfo fatty acids or esters thereof having at least one alkyl or alkenyl group having 10 to 20 aliphatic carbon atoms. can. The alkyl or alkenyl group is preferably a straight chain 11i & group, but can optionally be a primary or branched group. The above term "ether" refers to polyoxyethylene, polyoxypropylene, glyceryl, mixed polyoxyethylene-oxypropylene, mixed glyceryl-oxyethylene, or glyceryl-oxypropylene. Usually 01~. . It contains an oxyalkylene group. For example, sulfonated or sulfated surfactants include sodium dodecylbenzenesulfonate, potassium hexadecylbenzenesulfonate, sodium dodecyldimethylbenzenesulfonate, sodium lauryl sulfate, sodium tallow sulfate, potassium oleyl sulfate,
Ammonium lauryl monoethoxy sulfate or cetyl 1
0 mole ethoxylate sulfate monoethanolamine.

Other anionic surfactants useful in the present invention are paraffin sulfonates, olefin sulfonates, fatty alkyl sulfosuccinates, fatty alkyl ether sulfosuccinates, fatty alkyl sulfosuccinamates, fatty alkyl ether sulfosuccinamates, and fatty alkyl ether sulfosuccinates. mate, acyl sarcosinate, acyl tauride, inthionate, stearate, palmitate, resinate, oleate,
Includes soaps such as lylate, and alkyl ether carboxylates. Anionic phosphate esters can also be used. In each case, the anionic surfactant is usually g--2, preferably 10-20
containing at least 7 aliphatic hydrocarbon chains with 5 carbon atoms, in the case of ethers, one or more of glyceryl groups and/or/-20 ethyleneoxy and/or propyleneoxy groups; Contains.

A preferred anionic surfactant is IJ salt.

Another salt of industrial interest is potassium.

Lithium, calcium, magnesium, ammonium,
Includes monoethanolamine, jetanolamine, triethanolamine and salts of alkylamines containing up to 7 aliphatic carbon atoms.

The surfactant mixture may optionally contain nonionic surfactants, although those consisting of nonionic surfactants are less preferred. Nonionic surfactants are, for example, mono- or di-lower alkanolamine C1° alkanolamides, such as monoethanolamide of coconut oil. Other surfactants that may optionally be present include ethoxylated alcohols, ethoxylated carboxylic acids,
Propoxylation of ethoxylated amines, ethoxylated alkylolamines, ethoxylated alkylphenols, ethoxylated glyceryl esters, ethoxylated sorbitan esters, ethoxylated phosphate esters, and all ethoxylated nonionic substances mentioned above. Congeners.

or with ethoxylated and propoxylated congeners.

08-1. of alkyl or alkenyl groups and up to 20 ethyleneoxy and/or propyleneoxy groups or other nonionic surfactants that have been mixed into powder or liquid detergent compositions to date. Examples include amine oxides. Said other nonionic surfactants usually contain at least 7 C8 to 2°, preferably C1 to 2° alkyl or alkenyl groups and up to -lower (e.g. C4 to 4, preferably C
I-, has an alkyl group.

Active ingredients or mixtures suitable for the invention include, for example, HLB
7 or more, preferably 3 or more, more preferably 70
Above, optimally 72 or more, and preferably 1g or less,
More preferably it is 16 or less, most preferably 1S or less.

Some of the detergent compositions of the present invention may contain cationic surfactants and especially cationic fabric softeners and/or disinfectants, usually as a minor fraction of the total actives. Fabric softeners useful in the present invention contain one long chain (e.g. Ctt~11 usually C16~2°) alkyl or alkenyl group and two short chain (e.g. 01-4) alkyl groups or one short chain (e.g. 01-4) alkyl group. It includes secondary amines having a chain and one benzyl group. The softeners also include imidacillines and formalized imidacillines having one long-chain alkyl or alkenyl group, and amidoamines and di-classified amidoamines having two long-chain alkyl or alkenyl groups. Dated fabric softeners are usually all formates.

Salts of anions that confer some degree of water solubility, such as acetate, lactate, tartrate, chloride, methosulfate, ethosulfate, sulfate and nitrate. The composition used in the present invention with fabric softening properties is a particular finely-woven clay.

The compositions of the present invention may also contain amphoteric surfactants, although amphoteric surfactants are commonly included in surfactants that include cationic fabric softeners.

However, they can also be normally included as a minor component of the active ingredients in any of the other detergent types mentioned above.

Amphoteric surfactants include betaines, sulfobetaines and phosphobetaines formed by the reaction of a suitable tertiary nitrogen compound with a long chain alkyl or alkenyl group with a suitable agent such as monochloroacetic acid or propane sultone. includes. Examples of suitable tertiary nitrogen compound-containing compounds include 27 or one long chain alkyl or alkenyl group, optionally a benzyl group and other optional substituents such as a tertiary nitrogen group with one or more short chain alkyl groups. Tertiary amines; imidacillins with 7 or 2 long-chain alkyl or alkenyl groups and amidoamines with 7 or 1 long-chain alkyl or alkenyl groups.

Detergent manufacturers will recognize that the specific types of surfactants described above are merely illustrative of suitable common surfactants for use in accordance with the present invention. Any surfactant that can serve a useful function in the wash liquor can be included. A more detailed description of the major types of commercially available surfactants can be found at M+1nuf! LOturin
gConfectioners Publishing
"Ma Cutcheon'a I" published by the Ma cutcheon division of the Company.
Mulsifiers & Detergenta J
described in the modern edition of

Electrolytes Electrolytes are essential to interact with surfactants to form spherulite systems. However, the concentration of electrolyte is preferably not sufficient to allow substantial stacking of planar bilayers and to form non-spherical plate-like phases. In the case of a plate-like phase, the payload is sufficiently high, ・European Patent 0016//IA
The platelet phase provides an unstable or shear unstable composition unless it forms a stable structure. Moreover, the relatively strong matrix characteristic of the compositions of the European Patent Oogtil A usually results in undesirably high viscosities. At appropriate concentrations and for a suitable surfactant system, we have found that the system can be stabilized in the present invention by including an appropriate amount of electrolyte in the composition.

Insufficient electrolyte results in unstable, shear- or temperature-sensitive systems and/or systems with undesirably high viscosities. Therefore, in order to provide a composition according to the invention, the proportion of electrolyte must be chosen according to the nature of the surfactant and the amount of hydrotrope present.

The optimum proportion of electrolyte is usually determined by gradually adding the electrolyte to an aqueous micelle solution of the active ingredient (usually containing about 15 to 0% by weight of active ingredient), resulting in turbidity and conductivity.

It is determined by observing several characteristic properties such as yield point, appearance under a polarized light microscope or behavior in high-G centrifugation. Characteristic 1 of the above-mentioned stage (1), for example, shows an opaque isotropic range.

And if a turbid composition at or near the first conductivity minimum is detected with flocs of spherulites exhibiting an opaque layer in high-G centrifugation, a primary spherulite range is identified.

The proportion of electrolyte can be optimized within the above spherulitic range by observing the amount required to obtain an opaque layer during 90 minutes of high-G centrifugation. If the composition is intended for a market where low viscosity is more important than shelf life at low temperatures, for example, until the desired viscosity is achieved or signs of destabilization can be observed.

The optimized composition may be gradually diluted. If signs of instability occur, further electrolyte can be added until a sufficiently stable composition is obtained.

The amount of electrolyte is preferably at least the concentration at the first minimum value of conductivity in the conductivity/electrolyte concentration graph, and in order to provide a composition having a yield point of /, j dyne-2 or more. corresponding to the amount required. Although it is preferred to use functional electrolytes such as carbonates, silicates, pyrophosphates, polyphosphates, nitriloacetates, citrates (all of which are builders), some of these electrolytes.

For example, the effective concentration of carbonates is undesirably limited by their solubility. In such cases it has been found necessary to add more soluble non-functional electrolytes. Sodium chloride and sodium nitrate have been found to be particularly effective in this context. Often the proportion of electrolyte in the at least 7 predominantly aqueous layer is at least 0.3 g ions per il of alkali metal cations, alkaline earth metal cations and/or ammonium cations, preferably at least 2 g ions per il, for example 2.
0 to 4 (, j is sufficient to give a concentration of gram ions.

Builder It is to be understood that in the preferred compositions of the present invention, the builder is usually present at least in part as discrete crystalline particles suspended in the composition. The crystal dimensions are usually tso
It is 1 to a micron, for example, /-30 microns.

Compositions containing sodium tripolyphosphate as a builder or compositions containing at least a major proportion of sodium tripolyphosphate in the form of a mixture with other builders are more stable and flowable over a wider range of dry weights than corresponding compositions using other builders. We found that it shows the sex.

The composition is therefore preferred. However, one aspect of the present invention is potassium tripolyphosphate, carbonate, zeolite, nitrilotriacetate, citrate, metaphosphate, pyrophosphate,
Phosphonates.

Compositions are also provided which contain other builders such as KDTA and/or polycarboxylate salts, optionally but preferably in the form of a mixture with tripolyphosphate salts. Orthophosphates may be present, but trypoIJ I as well as alkali metal silicates and carbonates
Preferably, it is present as a minor component of the mixture with the J-phosphate salt.

Silicates and carbonates are particularly suitable because they exhibit several beneficial effects. Silicates and carbonates provide the desired free alkalinity to saponify fats in the soil;
Effective as a builder, and in the case of silicates,
Suppresses corrosion on aluminum surfaces of cleaning equipment. Additionally, the salts mentioned above are effective as electrolytes necessary to form a spherulite system.

When silicates are used to prepare the compositions of the invention, the silicates usually have a NatO/5iOt ratio l/l-7
//'2 or //i, s -i/i, X. but.

Na! Sodium silicate or even silicic acid in any ratio of O (or other base)/S i Ot can be used in the composition provided the necessary alkalinity is provided by the addition of other bases such as sodium carbonate or sodium hydroxide. Can be used to provide silicates inside. Compositions not intended for use in cleaning equipment do not require silicates if another source of alkalinity is provided.

In the present invention, the builder is present in a substantially fixed form, such as sodium nitrilotriacetate, sodium phosphate,
Compositions containing sodium silicates or mixtures thereof are not excluded.

Builders usually constitute at least it% by weight of the composition, preferably at least 20% by weight. The builder's active agent ratio is at least ///, preferably 1. ko／／～gu／l
It is.

From a cation economics point of view, it is usually preferred that the cations present contain at least a major amount of sodium salt. Therefore,
For example, a suitable builder is sodium tripolyphosphate, a suitable anionic surfactant is a sulfated or sulfonated anionic surfactant or any anti-redeposition agent, such as the sodium salt of carboxymethyl cellulose, and a base, such as silicon Preferably, the acid salt or carbonate is present as the sodium salt. Calcium is usually only present if the active ingredient contains a surfactant such as an olefin sulfonate or a nonionic material that tolerates the presence of calcium. Magnesium salts may also be present and are more miscible with surfactants than calcium salts.

Alternatively, it is possible, but less preferred, to choose from salts of salts, ammonium, lower amines, alkanolamines, or mixtures of cations. but.

Compared to conventional detergent powders, compositions containing high proportions of these cations are not very powerful due to their substantial cost implications.

Alkalinity The composition of the present invention is preferably alkaline, and the pH of the composition as measured with a glass calomel electrode is f...! - or more, preferably 9 or more, more preferably 9.2 or more, for example, De, 5~/-,'l? It is desirable to buffer with an alkaline buffer so that the ratio is 1o-ii. In the washing liquor containing the composition of the invention diluted to 0.5% dry weight, the pH is above 7, for example above io, in particular from 10 J to
//,! It is particularly preferred to adapt the composition according to the invention so that: Diluted solution 1 of composition according to dry weight O1j
To lower the pH of 00d to 9/10N Hot,
at least 0. 'l trtl, preferably at least 0. Irn1゜more preferably 7-1゜d1, for example 3
~10tnl, typically Gu~? Although it is desirable to have sufficient free alkalinity to meet the requirements of d, compositions with higher alkalinity are also commercially acceptable.

In general, lower alkalinity makes commercial implementation less acceptable, even if it is not excluded from the scope of the invention.

The alkaline buffer is preferably sodium tripolyphosphate and the alkalinity is preferably provided at least 7 parts by sodium carbonate. Other suitable alkaline buffers include sodium silicate.

Solubilizing Agents Hitherto, liquid diarrhea compositions have been prepared using hydrotropes and/or organic water-miscible hydroxyl-containing solvents such as methanol, ethanol, ingropanol, glycols, glycerol.

They usually contained significant concentrations of polyethylene glycol and polypropylene glycol.

However, these materials are expensive and are not functional ingredients. In certain circumstances, these materials promote fluidity and also allow the surfactant to form a spherulite phase more easily.

Therefore, it is not intended to exclude these materials from all compositions of the present invention, but the presence of these materials should be limited to the minimum amount necessary to give the spherulite composition a desired flowability. It is preferable to do so. You may be absent if it is not necessary.

Solvents are sometimes needed to be used as ingredients in perfumery or other common minor ingredients.

Dry weight The dry weight of the composition affects stability and flowability. The optimum dry weight can vary considerably from one type of composition to another and can be selected to obtain the required viscosity. Even though some types of compositions can obtain stable forms at less than 30% by dry weight, sometimes as low as 3% by dry weight, stable compositions are generally less than 3% by dry weight. Nothing has been found that can be guaranteed. The invention does not exclude the possibility of producing stable compositions with dry weight up to 10% by weight.

For a given composition according to the present invention, the range of dry weight can be determined within which the composition is stable and flowable. Below this range, sedimentation generally occurs; above this range, the composition becomes too viscous. An acceptable range is to prepare suspensions using the minimum amount of water necessary to maintain a stirrable composition, dilute a large number of samples to progressively higher dilutions, and allow settling to occur over a reasonable period of time. A given composition can usually be determined by observing the sample for symptoms. For some compositions, the acceptable range of dry weight can extend from 30% or 33% to 60% or even 70%, while for other compositions it is much narrower, e.g.
IO-Hiroshi! Weight%.

If the stability, flowability range cannot be determined by the methods described above, the composition may be modified, for example by adding further sodium carbonate solution, sodium silicate solution or other electrolytes when the composition exhibits characteristics of stage I or H. By this,
Also, when the composition exhibits Stage I or V characteristics, the composition should be modified by reducing the electrolyte content or adding hydrotropes. Alternatively, it is possible to simply change the electrolyte content. If it is therefore difficult to find a stable spherulite system, the alkyl ether sulfate The active ingredient can be modified by adding foam-stabilizing surfactants, such as alkanolamides or amine oxides, and when stage I or 'is predominant, alkylbenzene sulfonates or alkyl sulfates. The active ingredient can be denatured by addition.

In many cases, the compositions of the present invention can be prepared in bulk by generally stirring the ingredients.

However, it is a feature of the preferred compositions of the invention that they do not become unstable or thicken due to high shear forces.

In preparing stable structural mixtures according to the present invention, the order in which the components are mixed and the mixing conditions are sometimes important.

Compositions of the invention typically contain suitable active ingredients.

First, a clear aqueous L1 solution of the active ingredient at a suitable concentration (e.g. /jt-30% by weight) is prepared, with heating if necessary, and the electrolyte is dissolved in the L1 solution until the mixture becomes opaque, or It can be obtained by adding a concentrated electrolyte solution (preferably a functional electrolyte). The mixture is then centrifuged at 212,000 G for 3 minutes. If a clear aqueous phase is observed, in a high-G centrifugation process,
Additional electrolyte is added to the mixture until no more evidence of a separate, substantially clear aqueous phase is obtained. The active ingredient/dissolved electrolyte weight ratio is then recorded.

A composition containing all the desired ingredients and a previously determined active ingredient/electrolyte weight ratio can now be prepared at the desired dry weight percentage (usually 140-37%). The composition of the clear aqueous lye phase in high-G centrifugation indicates the presence of a platelet phase, in which case the amount of electrolyte is reduced in high-G centrifugation until no clear phase is observed. Samples of the latter composition at different dry weights can be prepared to determine appropriate flowability/stability properties.

If it is difficult to find a suitable active ingredient/electrolyte ratio in the first stage of the above procedure.

The procedure may be repeated using further soluble electrolytes, such as non-functional electrolytes such as sodium chloride or sodium nitrate. Alternatively, if Stage ■ or Stage V characteristics are observed.

By adding surfactants that aid in stable dispersions according to the invention, such as ether sulfates, -amine oxides or alkanolamines, and when step-processing or H properties are readily available, non-ethoxylated The active system can be modified by adding anionic surfactants.

Typically, mixing is done at ambient temperature if sufficient dispersion is obtained at ambient temperature, but for specific components.

To fully disperse nonionic surfactants, such as monoethanolic acid in coconut oil, gentle heating,
For example, aO 0 C is required.

This degree of heating can usually be achieved by water heating of sodium tripolyphosphate. In order to provide sufficient heating, high temperature rise metamorphism, commonly referred to as Phase 1,
It is preferred to add triboIJ IJ phosphate in anhydrous form containing a sufficiently high proportion of IJ modification). The operations described above are just seven of several methods that can be used satisfactorily with all or most of the compositions of the present invention. Some compositions are more sensitive to mixing order and temperature than others.

Compositions Considering the different types of compositions according to the invention in more detail, a distinction can be made in particular between high-foam and low-foam compositions of the sulfate or sulfonate type.

The composition is usually a non-ethoxylated anionic surfactant.

Preferably, seven or more sulfated surfactants or sulfonated surfactants are combined with a stable anionic surfactant, such as an ethoxylated anionic surfactant, an ethoxylated amide/oxide or an ethoxylated aliphatic alkanolamide. It is mainly composed of seven types or a mixture of two or more types of co-surfactants that form bubbles. The first active ingredient, i.e. a non-ethoxylated anionic surfactant, may be e.g. C+O-18 alkyl sulfate and/or C
10-14 alkylbenzene sulfonate. The first component or co-surfactant is C1゜-1゜ straight or branched chain alkyl Cl ~ 50 mole ether sulfate or alkylphenol ether sulfate, amine ether sulfate, alkanolamide ether sulfate or fatty acid ether sulfate. can be. Alternatively or additionally, the second component can contain an amine oxide or an aliphatic alkylolamide. The total proportion by weight of non-ethoxylated surfactant/co-surfactant is usually from j// to //3;
Preferably, it can be from //2, for example from J// to ///.

A small amount of soap (eg up to 7% by weight of the composition) may be present to aid in rinsing the fabric. Nonionic ethoxylates may represent up to 20% by weight of the total active ingredients, preferably up to 15% by weight.

It can be present in small proportions, usually up to 70% by weight.

Sodium alkyl sulfates or sodium alkylbenzene phosphonates in the above compositions may be substituted by aliphatic alkyl xylenes or other sulfonated non-ethoxylated surfactants, including toluene sulfonates, or by paraffins, including sulfosuccinates or sulfosufucinamates. Sulfonates, olefin sulfonates.

Can be fully or partially substituted by sulfocarboxylates or their esters or amides. The alkyl ether sulfonates can be wholly or partially substituted with other ether sulfates such as alkylphenyl ether sulfates, aliphatic acyl monoethanolamide ether sulfates, or mixtures thereof.

Therefore, according to a particular embodiment, the present invention provides water, 12 to 0% of the active ingredient by dry weight, based on the dry weight of the composition, and co-o-tro %, based on the dry weight of the composition.
of a dry weight of builder, at least 7 parts of the builder being present as a suspended solid and at least partially dissolved as an electrolyte, and wherein the active ingredient is between 30% and 0% by weight of the active ingredient. of non-alkoxylated anionic sulfated or sulfonated surfactants (Al
and 20-70% by weight of total surfactants of at least one cell-stabilizing surfactant and/or a non-ionic surfactant). There is something to do.

Optionally, the compositions described above may contain up to one hundred percent of the dry weight of the composition of soap. Preferably the non-alkoxylated sulfated matahasulfonated anionic surfactant consists essentially of an alkyl sulfate or an alkylbenzene sulfonate, preferably a sodium alkylhensensulfonate, such as a C1o-I4 alkylbenzene sulfonate.

Alternatively, the anionic surfactant may be an alkylbenzene sulfonate and/or alkyl sulfur nitride, alkyl ether sulfate and alkyl phenol ether sulfate, such as //3~! r//,
It may consist of a mixture in a weight ratio of usually 1/cog//, preferably //I to 3//1, for example, y//.

Low foam forming compositions according to the invention can be prepared using suitable foam suppressants. Certain commercially available foam suppressants may lose their suppressive effect upon storage of the compositions of the present invention, and other suppressants may only be used at concentrations high enough to affect the viscosity or stability of the composition. In order to be effective,
Some care must be taken in the selection of bubble suppressants.

We have found that mixtures of organopolysiloxanes and colloidal silica are particularly effective.

According to another particular embodiment, the present invention provides 71 to 140% of the active ingredient, based on the dry weight of the composition, wherein the active ingredient is non-alkoxylated, based on the dry weight of the active ingredient. sulfated anionic surfactant and/or non-alkoxylated phosphonated anionic surfactant and the remainder is an alkyl ether sulfate and/or alkanolamide or amine oxide)
, an aqueous phase containing sufficient dissolved electrolyte to form space-filling spherulites interspersed in the aqueous phase, suspended particles of a builder, and at least one bubble suppressant; The object of the present invention is to provide stable, free-flowing, liquid aqueous detergent compositions containing effective amounts of agents and, where appropriate, common minor ingredients.

According to yet another particular embodiment, the present invention comprises 1 to eo% active ingredient, based on the dry weight of the composition, at least 30% builder, based on the dry weight of the composition; / active ingredient ratio of /// or more, and the active ingredient is an alkylbenzene sulfonate having t to /j aliphatic carbon atoms, a C11l-11 alkyl monoethanolamide and a C1゜-1, alkyl jetanolamide. consisting essentially of an alkyl ethanolamide selected from, with an alkylbenzene sulfonate/ethanolamide weight ratio of /,! r// to a/i, and the builder is selected from sodium tripolyphosphate, sodium carbonate, zeolite, sodium nitrilotriacetate, sodium silicate and mixtures thereof;
The melting builder is to! Sufficient amount to provide a yield point of greater than Dyne/Engine, 3o-! The object of the present invention is to provide a flowable, stable detergent composition with a payload of rO%.

A particularly preferred embodiment of the invention comprises A(i) sodium alkylbenzenesulfonate having from /θ to /r, preferably from 10 to /da aliphatic carbon atoms and (II) on average from ~it, preferably is 10~/lI
alkyl groups with 7 to 20 carbon atoms, preferably 1 to IO, for example 3 to ! is a mixture of alkyl ether sodium sulfates having ethyleneoxy groups and/or propyleneoxy groups, the ratio of (iXii) being / 0/ / ~ // / 0, especially / 0//, ! r
-/ 0/! ? , for example from 10/U to 10/A; B a builder selected from sodium tripolyphosphate, zeolites, sodium nitrilotriacetate and mixtures thereof, with a weight ratio of B/A of 8//1;
-1I//, preferably /, 2// to 3. yo//1 builder, for example co//-j//; C an electrolyte selected from sodium carbonate, sodium silicate, sodium nitrate, sodium chloride and mixtures thereof, the concentration of the electrolyte being equal to the weight of the composition; -0%, preferably j
-/f%, especially from 7 to /j; the composition is from 30 to 50
% by weight, preferably J! The composition has a payload of ~0% by weight, for example 3g-% by weight; suitably the composition contains a small and effective amount of an anti-redeposition agent, preferably sodium carboxymethyl cellulose, perfume, colorant and firefly. The object of the present invention is to provide two or more substantially free-flowing, stable liquid detergent compositions containing optical brighteners.

All of the SuI-IJum cations in the above compositions.

Alternatively, one portion can be appropriately substituted with potassium, lithium or ammonium, but this is not so preferred. Preferably, sodium tripolyphosphate accounts for 5 to 90% of the total weight of the builder, such as 'I! Consists of r-40%. Preferably the self-cleaning composition contains at least seven bubble suppressants.

The above compositions may optionally contain a small proportion of an alkanolamide or ethoxylated nonionic surfactant, such as coconut monoethanolamide or coconut jetanolamide.

Minor Components The compositions of the present invention may contain conventional minor acids. The main ingredients that are commonly used in small quantities are anti-redeposition agents, dispersants,
It is a fluorescent brightener and bleaching agent.

The most commonly used anti-redeposition agent in the manufacture of detergents is sodium carboxymethylcellulose (SOMO), and SCMCj may be present in the compositions of the invention in an effective amount that does not impair the desired viscosity and stability, for example. can. In general, 50M0 is effective at concentrations of about 100%, and larger amounts of 50M0 can greatly increase the viscosity of the liquid composition, and may also affect stability beyond the normal effective concentration. is not desirable.

Other anti-redeposition and/or stain removers include carboxymethyl cellulose (OMO), CMO ammonium or other soluble OMO salts, phosphonates,
Contains methyl cellulose, polyvinylpyrrolidone, carboxymethyl starch and similar polyelectrolytes, BOM
All of these can be used instead of C.

Although an optical brightener (OBA) is an optional component of the compositions of the present invention, its presence is preferred. Unlike some prior art compositions, the compositions of the present invention do not rely on OBA for stability and are therefore free to choose and use OBA due to its convenience and cost effectiveness. You can also omit it altogether. OB in liquid detergent
Fluorescent dyes which have heretofore been recommended for use as A may be used, as well as many dyes which are normally suitable for use in powdered detergents. OBA can be present in conventional amounts.

The concentration of OBA is usually o, o r ~ o, r %, for example 0.07! r~0.3%, more commonly o, i~O,
Flathead is enough. Lower IIk degrees can also be used, but
However, although not effective and also within the scope of the present invention.

Higher concentrations are undesirable for cost reasons and may in some cases cause compatibility problems.

Representative examples of OBAs that can be used in the present invention include: ethoxylated heco(benzimidazolyl)ethylene; caustyrylnaphtho(l, cod-)
Oxazole: l, -bis(demethyl-nibenzoxazolyl)ethylene: 4'+4''-bis(rumethylethanolamine-J-anilino-t, J, r
-) riazin-l-yl)-1, co-1-stilbenesulfonic acid disodium;' (-1-hydroxyethyl)
-da, da 1-bis(benzimidazolyl)stilbene:
"#"'-bis(am-bis(=1-hydroxyethyl)-amino-, n (,7M-sulfophenyl)amino-/11°3N, 1N) riazine-co"-ylamino-2, co-stilbendisulfone Tetranatrichum acid; Hiro-(6″-sulfonaphtho [l″, co-1d))
Disodium lyazole-niyl)-costilbensulfonate; 1-bis(<4n (2+11-
hydroxyethoxy)-6n-amino-%, Jl,
jl F riazine-noylamino) “#Nice stilbendisulfonate disodium: Dermethyl-7
-dimethylaminocoumarin; and an alkoxylated group.

4t'-His-(benzimidazolyl)stilbene.

Bleach agents can be appropriately mixed into the liquid detergent composition of the present invention, subject to chemical stability and compatibility. The encapsulated bleaching agent can form part of the suspended solid. The action of peroxy bleaches in the compositions of this invention can be enhanced by the presence of an effective amount of a bleach activator such as tetraacetylethylenediamine. Photoactive bleaches such as sulfonated zinc 7-phthalocyanine or sulfonated aluminum phthalocyanine
bleach) may also be present.

Fragrances and colorants are present in the prior art in amounts up to 7% or flathead in detergents and can likewise be present in the compositions of the invention. Care is sometimes required in the selection of suitable perfumes, since solvents present in perfumes can alter the behavior of the active ingredients.

Proteolytic and amylolytic enzymes and enzyme stabilizers and killers may optionally be present in amounts similar to those of the prior art.

Encapsulated enzymes can be suspended in the composition.

Other minor ingredients include defoamers, alkalis, buffers, disinfectants such as formaldehyde, opacifiers such as vinyl latex emulsions, inert abrasives such as silica, and corrosion inhibitors such as benzotriazole. include.

The compositions of the present invention are generally suitable for laundering, and the present invention provides a method of cleaning fabrics by dipping and agitating the fabrics in a wash solution containing any of the compositions described herein. be. The low foam compositions described herein can also be used for dishwashing or hard surface cleaning; in particular, the low foam products are suitable for use in mechanical dishwashing.

These uses constitute other aspects of the invention.

The compositions of the invention are generally suitable for cleaning fabrics in boiling water or at moderate temperatures, such as from 0 to 50°C, especially from 3 to 65°C.
, or low temperature e.g. -〇-! It can be used for cleaning at 0°C, especially at 30-40°C. Typically, the composition is at a concentration of O,OS to J% of the wash water, preferably o,i-flat, more usually from 0.3 to 0.1:% dry weight of the wash water. Can be added to wash water.

EXAMPLES The invention is further illustrated by the examples listed in the table below: Example 1 Sodium carbonate θ 4 (
jSodium tripolyphosphate /lJ
/9J) Zeolitem
De, 0 / DJ) C1 to 11 alcohol 1 mole ethoxytoxy -- 1 increase whitening agent
o, is o, i, example 1 example = J example - da sodium carbonate da, 4,? ,?
Dirt sodium tripolyphosphate 6.2 lids /! r, 0 sodium nitrilotriacetate
/J,t //,ri r,,7C1jl
,,alcohol 57-ethoxyle-1--/,7-coconut oil jetanolamide /J/,1!1
-Example 3 Example Coconut oil monoethanolamide-
1. Sodium carbonate
-Sodium tripolyphosphate /?
KoS, 3 Zeolite people
Yo -carboxymethylcellulogen sodium -7
,4! Brightener 0
．． /! (7, /, ?Sodium silicate ('Si
O, :Na, O, /A:/) j
! J Silicone defoamer l
-Coconut oil monoethanolamide
1. j Sodium carbonate
Sodium tripolyphosphate
Kokko! , A brightener
-o, i Hiroqz-147-Katashiro dimethyamine amine oxide j Yu J Silicone defoaming agent l
-Town~-1-nee j, +”$1 1s warehouse ゝ 1
ゝ 1 Conduct+):l! 'q Ko 1 1 Meeting Mi 11 Mi o 1 Smell 1 1 o 1 Ro IS
) cumulative, (:111 smell 1 mi 1 de 1
Example 36 Example 37 Example 3t C1゜-n Linear Sodium Alkylbenzenesulfonate 10 7. Hirot, = C12-11 alkyl 3 mole ethoxy sulfate sodium salt -/, de
-Coconut oil monoethanolamide! ;
/,! +, /zeolite A
/7 Ko ff uA, lI Sodium tripolyphosphate l - Sodium silicate (SiO, :Na2O, #;:/)
//j Za-phantom o
＼ -4h ＠＠＠ ＋ll ′
= = l h ゛ 1\
0) Conductivity ~50'-+1'-
” ～ ～Kure 4 Bay 1
1 1) -1 book
1° o.

~ Gloss o o e'
(1) Surprise -)
1 turtle; ~ 1 ゝ 0)
ゝKare 4 Pei -11ゝ) 1 Surprise;
~5ku)
″′ Kame 4Q Kure Jun
Ue"'1 I,, l
; C3,s,l''.

Book -1c″″. 0 pattern
-o -11 Kurei 4 I I, + 1 1) 1 Surprise E
``o'' ゛mi 1111 琐 q GO GO MATTER 4Q くら 勺 無 -飄 6 MI BE 1 KYO
1 Example 4c6 Example 7 Example dag Coconut oil monoethanolamide, 7J
4t, 0 4AA sodium carbonate
Transfer -- Sodium tripolyphosphate /j
;;, 7 /9.0 /9.0 Zeolite A ri, De 9.0 9
．． 0 brightening agent 0. /3
0. /! 0.1! r＜c′,′,′
4. Example 7 Example 7J Oleic acid 47
/Sodium hydroxide Oo
Ri o,! , sC8゜-8Ji-like alkylbenzene sulfone λryo -, -acid sodium coconut oil jetanolamide Jjj
J, 7, sodium tripolyphosphate
Yude, Yu 29. sodium chloride
/, 7 2.0 Example 7 Sodium Gutripolyphosphate Co3.4
Sodium carbonate Sodium carboxymethyl cellulona 1. O brightener 0. /Fragrances, dyes, water Other references 1koni+
+++ Ie:II disease 11) Hiden
-1 false ゝ' ) ζ disease 111 Crow ;ko 11 disease 〆 1 9 1 book -81 = steam 111
"-11"-1' = 1;
ゞIkkoni, II: Hllll 1 gu 1 town - 1 book
−1′:″(″,,i<
” ' l, l : : l : I + ,,1
ゝ ＼ 5
The figure shows the conductivity due to changes in the concentration of electrolytes and active ingredients,
Shows changes in yield point and viscosity.

Figure 7 shows Na, 0:Sin, molar ratios tHt, t
, parts by weight of sodium dodecylbenzenesulfonate for various concentrations of sodium silicate and ' tz -t
a Shows the electrical conductivity of a 20.6% aqueous solution of the active ingredient consisting of 1 part by weight of 3-mole alkyl sodium ethoxysulfate. The horizontal axis of the figure shows the amount of silicate in the composition expressed as solid weight.

An added silicic acid solution of between 0 and 7% produces a substantially clear, optically isotropic composition representative of step 1 described herein. Between (1) and (2), a stage I composition is obtained, which is cloudy, unstable, and consists of non-space-filling flocs of spherulites. Between (1) and (2), the composition of step (2) according to the present invention is obtained. Although the composition is cloudy, it is a stable composition containing substantially space-filling flocs of spherulites, exhibiting a "yield point" and exhibiting only a single liquid phase upon high-G centrifugation. Beyond (1), a stage (2) composition is obtained, which contains non-space-filling flocs of G-phase spherulites.

It can be seen that the composition of stage (1) is obtained at a conductivity trough near the first conductivity minimum.

FIG. 2 shows the effect of adding sodium nitrate to the same active ingredient aqueous system as in FIG. When exceeding ■ in stage ■, the first conductivity maximum value is passed, and then the first conductivity maximum value is reached, which corresponds to the formation of a plate-like composition by step my in stage ■. shows the changes in viscosity, conductivity and yield point when sodium carbonate is added to the same active ingredient system.

The vertical axis on the left is the viscosity in /JA seconds-steam (unit: Pascal・
seconds), and the numbers in parentheses are milliSiemens and
-” (ms-of).

The vertical axis on the right is the yield point (dyne cIR"). The horizontal axis is the total weight of sodium carbonate expressed as the dry weight of sodium carbonate per total weight of the composition.

In the case of IJium carbonate, no minimum value is found in the conductivity (dashed line). The reason for this is that since the solubility limit of sodium carbonate has been reached, even if more sodium carbonate is added, it will only become suspended and the amount of dissolved sodium carbonate will not increase. Therefore, stage ■ is not observed.

The rapid increase in yield point (peak on the right) coincides with the onset of stage I at ■. This is a representative composition of the present invention. Figure 7 shows sodium dodecylbenzenesulfonate, sodium tripolyphosphate, sodium carbonate, and water at 0.00%. Figure 2 shows the effect of varying the relative proportions of sodium dodecylbenzenesulfonate and coconut oil monoethanolamide in a composition containing a ratio of o,s:o,t:t,o. The horizontal axis shows the weight ratio of coconut oil monoethanolamide/sodium dodecylbenzene sulfate, and the vertical axis shows the conductivity (ms-an-') (O mark) and viscosity (Pascal seconds x l0) (Δ mark). .

FIG. 5 shows a similar relationship to FIG. 7 when coconut oil monoethanolamide is replaced with CIf-II alkyl 3 mole sodium ethoxysulfate. The horizontal axis is the weight ratio of the above sodium ether sulfate/the above sodium alkylbenzene sulfonate.

Figures 3 and 3 illustrate how the compositions of the present invention may be prepared by varying the active ingredients.

Figure 6 contains suspended bilgoo and has the following composition: tt% sodium dodecylbenzenesulfonate
? 012-18 Alkyl 3 mole ethoxy sodium sulfate Hiroshi silicone defoamer
l Fragrance 0.6 01114 Mixed Seven-No/Di-Alkyl Sulfate
o, r Fluorescent brightener 0. /
! ; Sodium tripolyphosphate
19 shows the conductivity (ms-cm'''') when sodium nitrate is added in various proportions to a detergent with zeolite A/2.

Step l due to the already present sodium tripolyphosphate
cannot be seen in this graph. The conductivity decreases from the maximum value at ■ to the beginning of stage summer at ■.

Figure 7 shows the yield point (dyne an-”) of the same system as in Figure 6.
), and Figure 5 shows the viscosity of the same system at /, 74 s-1 (
Pascal seconds) (lower curve), also the viscosity at 21 s-1 (upper curve) and also the viscosity drop (Pascal seconds x
io> (center curve).

Figure 9 shows dodecylbenzenesulfonic acid prepared by mixing sodium dodecylbenzenesulfonate and coconut oil monoethanolamide at a weight ratio of IO:tI. This shows the change in conductivity when changing .

Again, stage I was not observed. The reason for this is that the active ingredient is completely soluble in water even at room temperature; the composition is therefore cloudy and unstable in the absence of electrolyte.

Fig. 10 and Fig. 1/Fig.
times).

This photomicrograph was made on a transmission electron microscope at Lancaster University, USA, and the composition of the sample is as follows: Weight - Dodecylbenzenesulfone'tt-ts alkyl 3 moles Sodium ethoxy sulfate
Sodium ninedisilicate (Ha, O: day 10
,/． 4:/) /ri,tI water
The remaining micrographs have a diameter of O. It shows ~1 micron spherulites, evidence of multiple bubbles in a concentric structure with a repeating space of tOx (containing one surfactant shell and an adjacent aqueous layer).

[Brief explanation of the drawing]

Figure 1 shows sodium dodecylbenzenesulfonate and C1
! - Gramme diagram showing the relationship between the conductivity of the active ingredient 10.6 weight by weight consisting of 3 moles of 11 alkyl sodium ethoxyl sulfate and the amount of added sodium silicate. Figure 3 is a graph showing the relationship between the amount of sodium carbonate added and the conductivity of the active ingredient aqueous solution. The figure shows a composition consisting of sodium dodecylbenzenesulfonate, sodium tripolyphosphate, sodium carbonate, and water (the phosphoric acid sl-I when coconut oil monoethanolamide was added).
The relationship between conductivity and viscosity when the relative proportions of Jium and the monoethanolamide are changed is shown. Figure 6 shows the conductivity when sodium nitrate is added to the builder-containing active ingredient composition, Figure 7 shows the change in yield point of the same system as in Figure 6, and Figure 7 is the same as Figure 6. FIG. 9 is a graph showing the relationship between the conductivity of an aqueous solution of a mixture of sodium dodecylbenzenesulfonate and coconut oil monoethanolamide and the amount of sodium silicate added; FIG. 70 and FIG. 1/FIG. 70 are Pt10 replicas after freezing a composition consisting of sodium dodecylbenzenesulfonate (!-c, z-1a 7 /L/kil 3 mol sodium ethoxysulfate, sodium silicate, and water). This is a transmission electron micrograph (71,000 times (Fig. 1O) and tro, ooo times (Fig. 1/))]. Dodecyl ``Gunsafe'' summer sodium tsum weight reduction - ~ 坩 3rd stage (＞"rr'・°巳) CO2 station ('"
p-p, e-man) ■! l bound mail (g'g) hand r: amendment 1. 1. Muho Patent Application No. 271682, filed in 1982, 2. Name of the invention: Liquid detergent composition 3. Relationship with the Jlli Registrar. 11 Address: 4th floor, Marunouchi Building, 2-4-1 Marunouchi, Chiyoda-ku, Tokyo Procedural amendment March 1, 1985

Claims (1)

[Scope of Claims] 1. Has one or more of the following properties: (i) non-shear sensitivity, (ii) shear stability, (iii) temperature stability, and (iv) preferably 60 to 100 Å, for example 80 Å. (v) a suspension such as sodium tripolyphosphate and/or zeolite; (vi) contains a dissolved electrolyte consisting of sodium carbonate, sodium silicate, sodium trinitrilotriacetate, tripolyphosphate sodium salt, sodium chloride and/or sodium nitrate; (vii) 1 to 15 dyne cm^ -^2, (viii) contains not more than 15% by weight of active ingredient, and (i
x) If centrifuged, solid phase and 90-50% of total active ingredient
(x) When diluted with water to a 0.5% dry weight component concentration, p
contains a free alkali that requires at least 0.8 ml, preferably 1 to 12 ml, of 1/10N hydrochloric acid per 100 ml to reduce H to 9; (xi) 1.2:1 or more, preferably 1. builder:active ingredient in a weight ratio of 5:1 or more, e.g. 1.5:1 to 3.5:1; (xii) having a payload of 32% or more, preferably 36% or more by weight; A stable, flowable, aqueous liquid composition comprising water, an active ingredient, and a dissolved electrolyte and having solid suspension properties. 2. The active ingredient is (i) an alkylbenzene sulfonate;
(ii) at least one stable foam-producing co-surfactant such as an ethoxylated anionic surfactant such as an alkyl ether sulfate; and/or or 5:1 to 1:3, preferably 3:1 with alkyl alkanolamide and/or amine oxide.
Ethoxylated alcohols, ethoxylated fatty acids, ethoxylated glycerol esters or ethoxylated fatty acids, ethoxylated fatty acids, ethoxylated glycerol esters, with a relative ratio of (i):(ii) of ~1:1, optionally from 0 to 20%, preferably from 2 to 10%, of the weight of the active ingredient. A composition according to claim 1, comprising a mixture of ethoxylated nonionic surfactants such as ethoxylated sorbitan esters or ethoxylated amines. 3. The composition contains 10 to 18 (A)(i), preferably 10
sodium alkylbenzenesulfonate having ~14 aliphatic carbon atoms; (ii) an average of 8 to 18, preferably 10 to 14 carbon atoms and 1 to 20, preferably 2 to 10 alkyl groups; For example, alkyl ether sodium sulfate having 3 to 5 ethyleneoxy groups and/or propyleneoxy groups in a ratio of 10:1 to 1:10, especially 10:
(i) of 1.5-10:5, e.g. 10:2-10:4:
(ii) and (B) a builder selected from sodium tripone phosphate, zeolite, sodium nitrilotriacetate and mixtures thereof, wherein the weight ratio of B:A is from 1.1:1 to 4:1. , preferably 1.2:1-3
．． 5:1, e.g. 2:1 to 3:1, and (C) 2 to 20%, preferably 3 to 18%, especially 7 to 1% by weight of the composition.
sodium carbonate, sodium silicate in a concentration of 5% by weight;
and an electrolyte selected from sodium nitrate, sodium chloride and mixtures thereof, wherein the payload of the composition is from 30 to 50% by weight, preferably from 35 to 50%, such as from 38 to 45%, and the composition is preferably 3. A composition according to claim 1 or claim 2, wherein the composition comprises a small but effective amount of an anti-redeposition agent such as sodium carboxymethyl cellulose, a fragrance, a colorant and an optical brightener.