JPH0457720B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to detergent compositions in the form of stable and transparent, translucent or opaque, wholly or primarily hexagonal liquid crystalline water-soluble gels. The compositions of the invention are particularly suitable for cleaning hard surfaces such as dishes, but can also be used for other cleaning purposes, such as for example fabric washing. U.S. Patent No. 2580713 (Wood/
Protector & Gamble) describe paste or gel detergent compositions that are hexagonal, or "middle" phase. These compositions contain some anionic detergent (particularly triethanolamine lauryl sulfate), generally mixed with a water-soluble soap. The use of alkanolamines as the main cation promotes the formation of a middle phuse. British Patent No. published on 18th September 1985
2155031A (Unilever) describes detergent compositions of the hexagonal phase gel type. The main component of these gels is a "secondary" surfactant, i.e. its polar head group is located non-terminal in the carbon-hydrogen chain, or
They each have a hundred or more hydrocarbon chains.
Examples of "secondary" surfactants are alkylbenzenesulfonic acids and dialkylsulfosuccinic acids. These surfactants do not naturally form a hexagonal phase at room temperature, and the gels contain "additives" (such as urea or sodium xylene sulfonate) to bring the composition into a hexagonal phase. A simple gel of this type can contain an alkylbenzenesulfonic acid, urea and water. Torque Patent Publication No. 21612 (Mintax), published December 5, 1984, also discloses a detergent gel containing an alkylbenzene sulfonic acid, urea, and water, which has a hexagonal phase. doesn't mention anything. The "second" surfactant mentioned above, according to UK Patent No. 2155031A (Unilever), has a tendency to form a lamellar phase rather than a hexagonal phase, and to stabilize this hexagonal phase, e.g. urea is used. Requires "additives". "Primary" surfactants, such as alkyl sulfates, whose head is located at or adjacent to the end of the hydrocarbon chain, present a different problem, ie they have a tendency to crystallize. Urea-type "additives" do not solve this problem. According to the above US Pat. No. 2,580,713,
This problem is solved by using alkanolamines as the main cation. By including a second component in the gel, which can be either a specific type of co-surfactant or a specific type of non-surfactant "additive," we have created a hexagonal phase gel that is stable at 22°C. It has now been discovered that the range of concentrations that can also be produced in sodium salt form can be significantly expanded from non-ethoxylated non-soap surfactants. Accordingly, the present invention provides an aqueous detergent composition consisting entirely or primarily of a gel of hexagonal liquid crystal type, wherein the gel of the present invention comprises: (a) 5 to 85% by weight of anionic head and A non-ethoxylated, micelle-forming, non-soap surfactant with an aliphatic or araliphatic hydrocarbon chain having 10 to 20 aliphatic carbon atoms (the anionic head is at the end of the hydrocarbon chain). (b) a second component, i.e. (b)()() an auxiliary micelle-forming non-soap surfactant selected from 1 to 75% by weight of: (b)()() Anionic non-soap surfactants other than those specified in (a) above, at least 12
an ethoxylated nonionic surfactant and an amine oxide having an HLB value, or (b)()() fatty acid monomer and diethanolamine and an ethoxylated nonionic surfactant having an HLB value of less than 12; and/ or (b)() 1 to 15% by weight of a non-micelle-forming or weakly micelle-forming aliphatic, cycloaliphatic, aromatic or araliphatic in liquid form with a melting point not exceeding 55°C and at least 2.2 (b)()() having at least 4 carbon atoms and having a hydrocarbon chain or an aromatic or cycloaliphatic having a hydroxyl group located at or within two carbon atoms of the terminal position in the ring and optionally one or more other polar groups; when the hydroxyl group is the only polar group present; or having up to 6 aliphatic carbon atoms if the second polar group is separated from the hydroxyl group by two or fewer carbon atoms; or present and separated from the hydroxyl group by three or more carbon atoms, or (b)()() having at least 7 carbon atoms; and has at least one polar group located at or within two carbon atoms of the terminal position in the hydrocarbon chain or aromatic or cycloaliphatic ring and/or has ethylenic unsaturation. ; including (a) and
The total amount with (b) is within the range of 15 to 95% by weight, and optionally (c) 1 to 45% by weight of aliphatic carbons having polar head groups and optionally up to 6 aliphatic carbons. an anionic or nonionic water-soluble non-micelle-forming or weak micelle-forming substance having an aliphatic or araliphatic hydrocarbon chain with atoms, and component (C) is a co-surfactant (b). () () and additives (b) () () are essential if none of them are present; further characterized by (d) containing water. The detergent gel of the present invention is generally and primarily of the hexagonal liquid crystal type.
crsytalform). This crystalline form, also known as the middle phase, can be recognized by various microscopic techniques, of which X-ray diffraction is the most obvious. Hexagonal phase compositions exhibit characteristic X-ray diffraction patterns unique to this liquid crystal type. The ratio of Bragg spacing in the X-ray pattern is: 1:1/√3:1/√4:1/√7;
'Liquid and Plastic Crystals', edited by John Winsor, Ellis Horwood Ltd. (1974), vol.
(Vol. 4, p. 88). Among the three liquid crystal types (i.e., lamellar, hexagonal, and cubic), the hexagonal phase is intermediate in stiffness, but the stiffness or viscosity is the absolute one that distinguishes hexagonal phase gels from other gels. It's not a good method.
This is because, for example, softer lamellar phase gels can be thickened with polymers or electrolytes to yield products of comparable viscosity. The products of this invention are inherently stiff gels and do not require thickeners. Preferred embodiments are transparent or translucent and have a sufficiently attractive appearance for packaging in transparent containers. The detergent gel of the present invention consists of the following components: (a) a principal surfactant; (b) a second component, namely (b)() a co-surfactant; and/or (b) a co-surfactant; )() an additive; (c) an optional second additive; and (d) water. These will be explained in more detail below. Additionally, certain other ingredients conventionally used in detergent products may also be present and are also discussed below. Primary Surfactant (a) This primary surfactant (a) can be any non-ethoxylated non-soap anionic surfactant, the anionic head containing 10 to 20 aliphatic carbon atoms. located at the terminal carbon atom of the hydrocarbon chain or the carbon atom adjacent to the terminal. Examples of this type of surfactant include: () General formula: R ₁ -O-SO ₃ X ₁ () where R ₁ is an alkyl group having 10 to 20 carbon atoms and X ₁ is a solubilizing cation] primary alkyl sulfate. The primary alkyl sulfates can be of substantially single chain length, such as in dodecyl sulfate, or they can be of different chain lengths, such as in coconut alkyl sulfates ( _C10 - _C14 , primarily _C12 and _C14 ). It can be composed of a mixture of substances of different chain lengths. _{( )} General _formula : _{R 2 −SO 3}
α-olefin sulfonic acid. () General formula: R ₃ −SO ₃ X ₃ () [wherein R ₃ is a primary C ₁₀ to C ₂₀ alkyl group,
X ₃ is a solubilizing cation] primary alkanesulfonic acid. _{( )} General _formula : R ₄ -CO-O- _{CH 2} CH _{2 -SO 3} ] alkyl or alkenyl isethionic acid. () General formula V: [Wherein, R ₅ is a C ₈ -C ₂₀ alkyl group, X ₅ is a solubilizing cation, and X ₆ is H or a solubilizing cation depending on the pH (whether the same or different _from α-sulfonated fatty acid salts (SFAS). () General formula: Fatty acid methyl ester sulfonic acid (FAES) in which R ₆ is a C ₈ -C ₂₀ alkyl group and X ₇ is a solubilizing cation.
The fatty acid methyl ester sulfonic acid can be of substantially single chain length, or coconut FAES
( _C8 - _C18 , mainly _R6 is _C10 and _C12 )
It can also be composed of a mixture of substances with different chain lengths, such as. All these preferred surfactants have a sulfonic acid or sulfate head group at or adjacent to the terminal position, and in some cases this is modified by the presence of a vicinal carboxyl or carboxyl ester group. You will find that it will be done. The counter cation of the main surfactant component (a) can be any solubilizing cation, provided that the Krallt point of the surfactant or surfactant/additive system as a whole is below room temperature. do.
Examples include alkali metals such as sodium, potassium, lithium or cesium; alkaline earth metals such as magnesium; ammonium; mono-, di- or tri-
Includes substituted ammoniums such as alkylamines or mono-, di- or tri-alkanolamines. Trialkanolamine salts have higher molecular weight cations that reduce the water content of a given composition compared to similar sodium salt compositions and increase the concentration of surfactants and (if necessary) additives. It has the advantage of Indeed, this increases the range of compositions from which stable commercially available gels can be produced. On the other hand, sodium salts are easy to produce by neutralization of caustic soda. The choice of cation is therefore primarily a matter of choice. The main surfactant component (a) of the composition according to the invention is:
It can be composed of one or more of the above substances. In one preferred embodiment of the invention, the primary surface-active surfactant (a) is comprised of one or more primary alkyl sulfates. Ratio of components present In the composition of the present invention, the main surfactant (a) is 5%
Present in an amount of ~85% by weight, preferably 5-75%, particularly preferably 8-55% by weight, particularly preferred amounts of co-surfactant (b) () or "additive" (b)
() depends on whether either or both are present. The preferred level also depends on the counter cation of the primary surfactant, and is greater when the cation is high molecular weight, such as triethanolamine, than when the cation is low molecular weight, such as sodium. For sodium salts, the preferred level is 5-60
% by weight, more preferably 5-55% by weight. Depending on whether (b) is a co-surfactant or an additive or both, the total amount of components (a) and (b) present is between 15 and 95% by weight, preferably between 15 and 85% by weight. % range. Again, the suitable amount depends on the countercation of the primary surfactant and also on the countercation of the anionic cosurfactant, if present. For all sodium systems, the combined level of (a) and (b) is preferably within the range of 30-60% by weight. The water content is preferably generally from 15 to 85% by weight, preferably from 40 to 70% by weight, based on the total sodium system. As described below, particularly preferred ranges within these ranges depend on whether component (b) is a co-surfactant () or an additive () or a mixture of the two. different. Total surfactant level (i.e. main surfactant (a)
and optional co-surfactant (b) () present) preferably ranges from 15 to 80% by weight. While the lower end of this range (15-60 wt.%) can be used specifically for all-sodium systems, total surfactant levels of 60-80 wt.% are This can only be achieved with high molecular weights such as triethanolamine. It goes without saying that the region forming the hexagonal phase changes with the main surfactant, the auxiliary surfactant (if present), and the ratio of the two types, and these changes will be explained in the practical examples later in this specification. Shown below. Co-surfactant (b) () In a first embodiment of the invention, the composition of the invention comprises a co-surfactant (b) selected from certain anionic and non-ionic surfactants. ()
Contains. In this first embodiment, the composition of the invention comprises 1 to 75% by weight, preferably 5 to 50% by weight, more preferably 8 to 40% by weight of cosurfactant (b)().
and more preferably 5 to 60% by weight, more preferably 5 to 40% by weight of the main surfactant (a). Again, suitable levels will depend on the countercation of the primary surfactant as well as the countercation of the cosurfactant if it is anionic. The term "predominant surfactant" does not necessarily mean that this component is the predominant surfactant; in fact, (a) versus (b)
The ratio in parentheses is 20:1 to 0.1:1, preferably 10:1
~0.1:1, the selection depending on the particular co-surfactant selected. The total surfactant level in this embodiment is preferably in a total sodium system, preferably 16
~60% by weight. Of course, two or more of each surfactant selected from each of the above types (a) and (b)() can be present. Two types of co-surfactants have been identified that are suitable for use in the present invention. The first (i.e. (b)()()) is an anionic non-soap surfactant other than the same type as the main surfactant (a), i.e. the anionic head is C ₁₀ to C ₂₀ Anionic non-soap surfactants other than non-ethoxylated anionic surfactants located at or adjacent to the terminus of a carbon-hydrogen chain; ethoxylated non-ionic surfactants with high (12.0) HLB values (b)()() Preferred types of cosurfactants are: (1) The anionic head is a non-aliphatic or araliphatic hydrocarbon chain. a terminally located non-ethoxylated anionic surfactant, (2) an ethoxylated anionic surfactant, (3) an ethoxylated nonionic surfactant with an HLB value of 12.0, and (4) amine oxidation. A first group of non-ethoxylated surfactants are disclosed in the above-mentioned GB 2155031A (Unilever) as components of hexagonal phase gels, and these are referred to as "secondary" surfactants. In the "secondary" anionic surfactant, the anionic head is attached to the hydrophobic hydrocarbon chain in a non-terminal position, or occupies itself a non-terminal position within the chain, i.e. Two or more short chains are attached directly to the head itself. "Second"
The first type of surfactant generally has the general formula: [wherein Z is an anionic head group, such as a sulfonic acid or sulfate group in combination with a solubilizing cation, and R ₇ and R ₈ are both aliphatic or araliphatic with 8 to 20 carbon atoms. a hydrocarbon chain, the shorter of R ₇ and R ₈ has at least 2 aliphatic carbon atoms, and Y is for example

【formula】 【formula】

【formula】 or

A bonding group of the formula [Formula] in which the total number of aliphatic carbon atoms in R ₇ , R ₈ and Y is at least 8, preferably 10 to 28]. Examples of "secondary" anionic surfactants of this first type include alkylbenzene sulfonic acids, secondary alkanesulfonic acids, and secondary alkyl sulfates. All of these substances are generally random mixtures of isomers and are not "secondary" (i.e. do not have a head located in or adjacent to a terminal position, but the average composition of the substance is "secondary"). It includes several types of substances such as The second type of "second" anionic surfactant generally has the general formula: [wherein Z is an anionic head group in combination with a solubilizing cation and R ₉ and R ₁₀ are both at least 8
, preferably 10 to 20 aliphatic carbon atoms, the shorter of the chains R ₉ and R ₁₀ having at least 2 aliphatic carbon atoms] corresponds to An example of this second type of "secondary" anionic surfactant is dialkyl sulfosuccinic acid. For purposes of the present invention, suitable "secondary" non-ethoxylated anionic surfactants include an average of 8 to 15,
Preference is given to linear or branched alkylbenzenesulfonic acids having 10 to 13 aliphatic carbon atoms. Advantageously, the alkylbenzene sulfonic acid is present in a ratio of 10:1 to 0.25:1 (a) to (b) () with the main surfactant (a).
They can be combined at a weight ratio of When the primary surfactant (a) is one or more primary alkyl sulfates, the preferred range of ratios is from 5:1 to 0.67:1;
More preferably, the ratio is 4:1 to 1:1. Preferred ethoxylated anionic surfactants for use in the compositions of the invention are alkyl ether sulfates. These have _the general formula: R ₁₁ -(OCH ₂ CH _{2 ) o} -O-SO ₃ X ₈ is a solubilizing cation, and n, which is the average degree of ethoxylation, is in the range of 1 to 12, preferably 1 to 8]. As with the primary surfactant (a), the choice of solubilizing cation for the auxiliary anionic surfactant (b) () is primarily a matter of choice. Suitable high HLB ethoxylated nonionic surfactants are ethoxylated alcohols and alkylphenols having the general formula: R ₁₂ −(C ₆ H ₄ ) _x −(OCH ₂ CH ₂ ) _n −OH (). A substance, in the above _formula , m ranges from 5 to 30. For alcohol ethoxylates, R ₁₂ preferably has 8 to 18 carbon atoms and m is 5 to 14. Examples of suitable alcohol ethoxylates are Dodanol® 91-8 and 91-6.
(Shell) ( _C9 - _C11 alcohols, m=8 and 6, respectively, HLB values 13.8 and 12.6, respectively). For alkylphenol ethoxylate,
R ₁₂ preferably has 8 to 12 carbon atoms and m
is 6 to 16. The ethoxylated cosurfactant (both anionic and nonionic) is preferably used with the primary surfactant (a) in a weight ratio of (a) to (b) () from 10:1 to 0.1:1. Can be combined. Main surfactant
When (a) is one or more primary alkyl sulfates, a suitable ratio range is from 5:1 to 0.1:1, more preferably from 3.5:1 to 0.14:1. Amine oxides have general formula XI: [In the formula, R ₁₃ is a C ₁₀ -C ₂₀ alkyl group, and R ₁₄ is
_{and R15} is _{a C1-C4 alkyl group} ]. Advantageously, the amine oxide is combined with the main surfactant (a).
They can be combined in a weight ratio of (a) to (b) () of 20:1 to 2:1. When the main surfactant is one or more primary alkyl sulfates, the preferred ratio ranges from 10:1 to 3:1, more preferably 7:1.
~3:1. The second type of co-surfactant (b)()() is
Ethoxylated nonionic surfactants with low (<12.0) HLB values and fatty acid mono- and di-
It is more similar to ethanolamide. Suitable ethoxylated nonionic surfactants are ethoxylated alcohols and alkylphenols of the general formula above, but generally have a low degree of ethoxylation m, ie high HLB substances. An example is Dovanol® 91-5
(Shell) ( _C9 - _C11 ) Alcohol; m=5; HLB
= 11.7). Advantageously, these can be combined with the main surfactant (a) in a weight ratio of (a) to (b) () from 10:1 to 0.1:1. The main surfactant (a) is 1
For primary alkyl sulfates of one or more species, preferred ratios range from 5:1 to 0.1:1, more preferably from 3.5:1 to 0.14:1. Fatty acid mono- and di-ethanolamides have the general formula: [wherein R ₁₆ is an alkyl group having 7 to 20 carbon atoms, and R ₁₇ is H or -CH ₂ CH ₂ OH
] is the substance. Fatty acid mono- and di-ethanolamides can advantageously be combined with the primary surfactant (a) in a final ratio of (a) to (b) () from 20:1 to 2:1. When the primary surfactant is one or more primary alkyl sulfates, preferred ratios range from 10:1 to 3:
1, more preferably 7:1 to 3:1. Two broad classes of cosurfactants (b) ()
The meaning of the difference between () and (b)()() is that when the co-surfactant is of the type (b)()(), an optional second additive ( c). Co-surfactant (b) ()
In the case of type (), the second additive (c) can be present as desired and is not necessarily essential. If desired, the compositions of the invention can also contain mixtures of cosurfactants of the same or different types. Additive (b)() In a second embodiment of the invention, the composition contains, in addition to the main surfactant (a), an "additive" (b)() that is not a surfactant. This additive (b) () is a non-micelle-forming or weakly micelle-forming aliphatic,
A cycloaliphatic, aromatic or araliphatic nonionic substance having a melting point not exceeding 55° C. and a dielectric constant of at least 2.2. Additive (b)() has the ability to lower the kraft temperature of the surfactant system below room temperature. When using co-surfactant (b) (), the additive amount
(b)() is classified into two broad categories (b)()() and (b)()(), with additives (b)()
The optional second additive (c) is required only if the type (b) () (), and the additive (b) () is (b) ().
It is optional or advantageous if it is of type ( ). The first type of additives (b)()() is composed of substances in which the hexagonal phase is present and which can further extend the range of stable compositions. These are relatively short-chain organic substances with alcoholic or phenolic hydroxyl groups. If desired, one or more additional polar groups can be present in the molecule, for example other hydroxyl or carboxyl groups, carboxylic acid esters, alboxylic acid amides, amines, aldehydes or ketone groups. can. This (b)
( ) ( ) type additives have at least 4 carbon atoms, and the maximum number of carbon atoms that may be present is governed by the number and arrangement of any polar groups present other than the hydroxyl group. If no other polar group is present, or if a second polar group is present but separated from the hydroxyl group by two or fewer carbon atoms, the (b)()() type additive has six It has the following fatty carbon atoms: In contrast, when a second polar group is present separated from the hydroxyl group by three or more carbon atoms, a (b)()() type additive has 12 or fewer fatty carbon atoms. Must be. These limitations are caused by the need for type (b)()() additives to have some, but not too great, affinity for water. Various melting points and dielectric constants (above the melting point)
An example of a suitable (b)()() type additive having
Includes:

[Table] Additives of the second type (b) () () cannot by themselves expand the hexagonal phase range, but they do lower the craft temperature of the surfactant or surfactant mixture present. It is composed of a material that solves the problem of crystallization and allows the composition to be in a lamellar phase rather than a hexagonal phase. As mentioned above, additive (b)
If () is of this type, then the above British patent number
It is essential that a second type of additive (c) is also present to bring the composition into a hexagonal phase, as described in 2155031A (Unilever). Additive
(c) will be explained in detail later. Additive (b)()() is an amphoteric substance of low water solubility such that its overall character is hydrophobic despite the presence of polar groups. They have at least 7 carbon atoms and can have polar groups located at or within 2 carbon atoms of the terminal position in the hydrocarbon chain or the aromatic or cycloaliphatic ring, and or Can have ethylenic unsaturation. (b)()() The inductivity of the additive is at least 2.2
It is. If present, polar groups can be, for example, hydroxyl, carboxyl, carboxylic ester, carboxylic amide, amine, aldehyde or ketone groups. Various melting points and dielectric constants (above the melting point)
Examples of these substances with include:

[Table] Ingredients such as fragrances can also be used as (b)()() additives. Examples of these materials with various melting points and dielectric constants (above the melting point) include:

【table】

[Table] Commercially available perfume formulations can be used. Ingredients such as perfumes are typically used in amounts of 1 to 5% by weight, with 30 to 60% by weight of the primary surfactant (a). Both types of additives (b) () () and (b) ()
For (), a melting point of 55°C or lower is essential to avoid crystallization of the additive. Relatively low levels (1-15% by weight, preferably 2-10%) of additives (b)(), whether of the (b)()() type or the (b)()() type. is sufficient. The preferred amount of surfactant (a) present in this embodiment will of course depend on its countercation,
In the case of a total sodium base, it is in the range of 25 to 60% by weight, more preferably 30 to 50% by weight. The total level of surfactant and additives in this embodiment preferably ranges from 16 to 60% by weight, more preferably from 35 to 57% by weight of the total sodium system. The ratio of surfactant to additive can range from 30:1 to 3:1, for example. (b) For () () type additives and primary alkyl sulfates, the preferred ratio range is
The ratio is 27.5:1 to 3.5:1. If desired, compositions of the invention may contain co-surfactants.
It can contain both (b)() and additive (b)(). Optional additive (c) The composition of the invention may further include a second type of additive (c)
In fact, these components (b)
This is essential in the case of a ()() type auxiliary surfactant or a (b)()() type additive that does not itself act as a hexagonal phase promoter. Furthermore, in other embodiments the second additive (c) is useful for antagonizing the action of the electrolyte which tends to reduce the hexagonal phase range and therefore contains electrolyte components such as builders. It is particularly useful in compositions where Additive (c) is described in detail in the above-mentioned GB 2155031A (Unilever). This is a water-soluble, non-micellar material that can transition a surfactant mixture or surfactant/additive mixture from a lamellar phase to a hexagonal phase, or increase the range of stable hexagonal phases obtainable for a particular composition. It is a forming or weakly micelle-forming substance. The mechanism of action of additive (c) is not clearly understood. Although this may act to increase micelle or liquid crystal curvature, the scope of the invention is not limited by this hypothesis. It has been experimentally observed that certain primary substances useful as hydrotropes in light duty liquid detergent compositions can behave as type (c) additives. These are generally molecules having large polar groups and optionally small hydrophobic groups, such as aliphatic or araliphatic chains having up to 6, preferably 4 or less, aliphatic carbon atoms.
The larger the polar head, the larger the hydrophobic group that can be tolerated. The polar group of additive (c) can have an ionic charge, but
In that case it must be of the same polarity as the surfactant, ie anionic.
Examples of anionic additives (c) are lower aryl or alkylaryl sulfonic acids, such as toluene and xylene sulfonic acid. Alternatively, additive (c) can be a highly polar but uncharged material. A preferred type of non-charged additive (c) is typically a lower amide having a -CON- group. A general feature of this second type appears to be the ability to increase the dielectric constant of water and exhibit a structure-braking effect on water. A preferred substance that is inexpensive and has no environmental objections is urea. Short-chain urea congeners and analogues, such as methyl and ethyl ureas, thioureas, formamides and acetamides, are possible substances, which have various disadvantages such as cost, toxicity or simply poor effectiveness as additives. In view of this, it is not as desirable as urea itself. When additive (c) is urea, a buffer is advantageously present to minimize hydrolysis, especially alkaline hydrolysis, of urea. A suitable buffering agent is boric acid, preferably less than 3% by weight, more preferably 1% by weight.
It is used in an amount of ~2% by weight. Buffering is achieved by including triethanolamine as a countercation in the surfactant system. The buffering capacity and greater electrolyte tolerance of triethanolamine as a countercation compared to sodium makes it possible to incorporate higher levels of electrolyte components (e.g., sodium tripolyphosphate builder) into the compositions of the present invention. enable. Advantageously, additive (c) is present in an amount of 1 to 45% by weight, preferably 5 to 35% by weight. Additive (b)
The greater the amount of ()() and the greater the amount of electrolyte present, the greater the amount of additive (c) required. Water (d) In all embodiments of the invention, water is an essential ingredient. A stable or predominantly hexagonal phase in any particular system of surfactant (a), component (b) (cosurfactant or additive), optional second additive (c), and water. The relative proportions that give a gel of can be confirmed by experiment and construction of a phase diagram. Samples of various proportions can be prepared by mixing and the phases present can be easily identified by visual observation, gross flow properties, appearance of polarized light and texture observation in a polarized light microscope. Optional Additional Ingredients The non-build compositions of the present invention consist essentially of surfactant component (a), component (b), optional additives (c), water and the usual colorants, fragrances, fungicides and the like. It can be composed of small amounts of ingredients such as preservatives. This primary non-build composition is useful in light duty applications such as dishwashing, shampooing, or fabric laundering in soft water areas. Additionally within the scope of this invention there are also baby duty fabric laundry compositions containing ingredients such as builders, bleaches, fluorescent agents, photobleachs, enzymes, anti-redeposition agents, deodorizers and disinfectants. Water-soluble organic or inorganic builders such as phosphates, citrates or nitrilotriacetates can also be incorporated into the compositions of the invention;
Care must be taken to ensure that the electrolyte level does not rise to such an extent that it destabilizes the hexagonal gel.
As mentioned above, the amount of electrolyte builder that can be tolerated can also be increased by including additive (c), preferably urea. The same is true for other electrolyte components, such as sodium sulfite bleach. Alternatively, water-insoluble inorganic builders, such as zeolites, can also be suspended in the gels of the invention. Similarly, other useful insoluble materials can be present as suspended solids, such as, for example, abrasives or peroxy acid bleaches. A particularly preferred bleaching material is 1,12-diperoxide dodecanedioic acid, as described in European Patent No. 160,542A (Unilever). EXAMPLES The invention will now be illustrated by means of non-limiting examples, in which percentages and proportions are by weight. Comparative Examples A-D Tests were conducted to prepare a hexagonal phase gel containing coconut alkyl sulfate and water by mixing.
The alkyl sulfate (sodium salt) was Emal 10 (registered trademark) manufactured by Kao Soap Co., Ltd. The composition prepared and its physical state at room temperature (22° C. in this case) are shown in the following table; as can be seen, no stable hexagonal phase gel was formed.

TABLE Examples 1-30 These examples demonstrate a first embodiment of the invention in which co-surfactant (b)() is present. Examples 1 to 5 Compositions containing coconut alkyl sulfuric acid, alkyl ether sulfuric acid, and water used in Comparative Examples A to D were prepared by mixing. Alkyl ether sulfate is
Synperonic® 3-S-70S ( _C13-15 , 3EO, sodium salt) from ICI. These compositions are shown in the corresponding table,
Numbers are used here to indicate compositions according to the invention (stable gels) and letters are used to indicate comparative compositions outside the scope of the invention. Alkyl sulfates are shown as (a) and alkyl ether sulfates are shown as (b).
Shown as (). Examples 6-12 Compositions containing the sodium coconut alkyl sulfate used in the previous examples along with an ethoxylated nonionic surfactant and water were made by mixing. The nonionic surfactant was Dovanol® 91-8 ( _C9 - _C11 , 8EO) from Shell, which has an HLB value of 13.8. These compositions are shown in the corresponding tables, where (b)() indicates the nonionic surfactant. In this table, “2
The expression "two phases" indicates separation into two liquid crystal (hexagonal and lamellar) phases. Examples 13-15 A composition similar to Example 6-12 was prepared, with an ethoxylated alcohol having a low average degree of ethoxylation, namely Dovanol 91 from Shell.
-6( _C9 - _C11,6EO ), which has an HLB value of 12.6, was used as co-surfactant (b) (). These compositions are shown in the corresponding table. Examples 16 and 17 A lower ethoxylated product, Dovanol 91-5 from Shell ( _C9 - _C11 , 5EO, HLB value
11.7) and these are shown in the corresponding table. The gel of Comparative Example W contained some hexagonal phase but did not exhibit fluidity. In the absence of component (c), no overall hexagonal phase gel was formed from these components. Dovanol 91−2.5 from Shell without urea
Attempts to create gels using ( _C9 - _C11 , 2.5EO, HLB8.2) were unsuccessful. In the absence of component (c), no hexagonal phase existed at 22°C. Example 18 Sodium Coconut Alkyl Sulfate and Non-Ethoxylated Non-Ionic Surfactant and Coconut Diethanolamide (Ethylan(TM))
LD, Lankro).
These are shown in the corresponding table. The gel of Comparative Example AA contained some hexagonal phase but did not exhibit fluidity. Examples 19-22 Sodium salt form of primary alkyl sulfuric acid (Example 22
dodecyl in all others and coconut in all others) to coconut dimethylamine oxide (Empigen® OB,
(Albright and Wilson) and are shown in the corresponding table. Sodium dodecyl sulfate was a pure laboratory reagent from British Drug Huoses Ltd. Examples 23-26 Coconut sodium alkyl sulfate linear C ₁₀
-C ₁₂ alkylbenzenesulfonic acid, i.e.
Marlon from Hu¨ls (registered trade)
Compositions were made containing A and these are shown in the corresponding tables. Examples 27 and 28 Compositions containing an ethoxylated nonionic surfactant as co-surfactant (b) () and sodium tripolyphosphate builder were made and are shown in the corresponding tables. The base formulation was similar to Example 9 above, but included sodium dodecyl sulfate instead of coconut alkyl sulfate. That is, it contained 20% sodium dodecyl sulfate and 20% Dovanol 91-8. Without urea (comparative examples KK and LL), an unstable hexagonal phase was obtained, which melted at approximately room temperature. Using 10% urea, stable hexagonal phase gels were obtained both at 50°C and room temperature. Comparative experiments using 40% sodium dodecyl sulfate without co-surfactant gave fixed crystals (Comparative Examples PP-SS). Example 29 A stable hexagonal phase gel was prepared containing the triethanolamine salt of coconut alkyl sulfate (80%), Dovanol 91-8 (5%) and water (15%). The ratio of (a) to (b) () was 16:1. Very high total active detergent levels were observed. Due to the high molecular weight of the triethanolamine cation, a range of stable hexagonal gel formation occurs at higher active detergent levels, which is the case for the sodium salt. Examples 30-33 Compositions containing sodium α-olefin sulfonate (AOS) with various chain lengths as the main surfactant (a) were prepared and these are shown in the corresponding tables. C ₁₄ and C _14-18 substances are from Lion Corporation, Japan, and C _14/16 AOS is from Aekyung, Korea.
It was a Shell product. The co-surfactants used were Dovanol 91-8 and Dovanol 91-5.
As expected, urea was required to obtain stable gels with the latter (low HLB) material. In each case, the total active detergent level shall be 50% by weight, and (a)
(b) The ratio in () was 4:1. Examples 34-38 Stable compositions containing various primary non-ethoxylated anionic surfactants (a) together with the nonionic surfactant Dovanol 91-8 as co-surfactant (b) (). Hexagonal phase gels were created and are shown in the table of correspondence. Examples 39-70 These examples illustrate a second embodiment of the invention in which additive (b)() is present. Examples 39-41 Compositions containing sodium coconut alkyl sulfate as surfactant and 2-phenylethanol as additive (b)()() were prepared by mixing and these compositions were combined into corresponding tables. Shown inside. Examples 42-47 Sodium coconut alkyl sulfate and additives (b)
Hydroxycitronellal ( _CH3 ) _2C (OH)−( _CH2 ) ₃₋ HC( _CH3 )− as ()()
Compositions containing CH ₂ CHO were made by mixing and these compositions are shown in the corresponding table. Example 48-52 Sodium coconut alkyl sulfate and additive (b)
( ) and benzyl alcohol as ( ) were prepared by mixing and these compositions are shown in the corresponding tables. Examples 53-57 Compositions containing a single chain length alkyl sulfate, i.e. sodium dodecyl sulfate, and 2-phenylethanol as additive (b)()() were made by mixing and these compositions are shown in the corresponding table. Example 58 Stable hexagonal phase gel prepared by mixing 35
% coconut sodium alkyl sulfate and additives (b)
() Contained 5% thymol (2-isopropyl-5-methylphenol) as () and 60% water. Examples 59 and 60 Sodium coconut alkyl sulfate (35% by weight)
and linalool (5) as an additive (b)()()
% by weight) were prepared with and without urea as additive (c) and these are shown below.

[Table] Examples 61-63 Coconut sodium alkyl sulfate and flavor additives
(b) terpineol as ()();
and are shown in the corresponding table. Example 64 Sodium coconut alkyl sulfate and additives (b)
Compositions containing coconut fatty acids as ( ) and ( ) were made with or without urea as additive (c) and these are shown in the corresponding tables. As you can see, this type of additive (b) () ()
When using additive (c), additional additive (c) is essential for gel formation, but this level must be carefully selected. Example 65 The procedure of Example 64 is repeated using decane-1-ol as additive (b)()() and is shown in the corresponding table. Similar results are obtained, with higher levels of urea required than in Example 64 to obtain stable gel formation. Examples 66-68 Sodium α-olefin sulfonate (AOS) as the main surfactant (a) with benzyl alcohol or limonene additive (b) respectively
Compositions containing () () or (b) () () were made and these are shown in the corresponding tables. In each case, the total active detergent level was 40% by weight and the surfactant to additive ratio was 8:1. When using limonene, urea was required to obtain a stable gel. Example 69 A stable hexagonal phase gel containing sodium coconut fatty acid methyl ester sulfonate (55% by weight), benzyl alcohol (5% by weight), and water was prepared. The total active detergent level was 55% by weight and the surfactant to additive ratio was 11:1. Comparative example JJJJ~LLLL To show that limitations on chain length and melting point are important when specifying additives (b) (), we used coconut sodium alkyl sulfate (40% by weight) and 2, which do not meet these requirements. A composition was made containing seed "additives": ethanol (only 2 carbon atoms) and stearyl alcohol (melting point 57°C). The results were as follows.

[Table] Alcohol
Examples 70-78 Stable gels according to the invention suitable for use in fabric laundering were made by mixing. These compositions are shown in the corresponding table. The base gels of Examples 70-73 were those of Example 2, and the base gels of Examples 74-78 were those of Example 31. The fabric washing ingredients formulated are as follows: Anti-redeposition agent: Sodium carboxymethylcellulose, Courtaulds (62% active), Disinfectant: Formalin (37%), Proteolytic enzyme: Alcalase solution, Novo, active. 1600 Glycine Units mg Fluorescent Agent: Tinopal® CBS
-X, Ciba-Geigy, which is 4,4′-di(2
-sulfostyryl) diphenyl disodium salt Photobleach: Aluminum phthalocyanine sulfonate, Ciba-Geigy; Deodorizer: PPE International; Solid peroxyacid bleach: 1,12-diperoxidedodecanedioic acid (DPDDA) ( 12% usable enzyme, made from DPDDA particles from Degussa, slurried in water and filtered to remove water-soluble inorganic salts), buffer (good peroxy acid bleach stability during storage) (To maintain sex): Citric acid. All of these compositions were stable, translucent hexagonal phase gels. Examples 79-81 These examples demonstrate the use of electrolyte components (i.e. sodium tripolyphosphate as a builder) and British Patent No. 1417870 (Unilever) and British Patent Application No.
8606145 (Unilever) and sodium sulfite as a mild bleaching agent. These compositions are shown in the corresponding tables and were all stable, translucent hexagonal phase gels. Dish Washing Test The dish washing performance of three gels according to the invention was evaluated using a standard test method in which soiled plates are washed to the end of form collapse. Each plate was pre-soiled with 5 g of standard cooking oil/starch/fatty acid emulsion in water and in each case the cleaning solution was 5 g of product dissolved at 45°C in 5°C water (French hardness 4°), i.e. 1 g/ The total product concentration consisted of: The gels tested were Example 13 and
30, as well as that of Example 23, but with a different alkylbenzene sulfonic acid, namely Dobane® from Siel.
A gel containing sodium salt (composition 82) was prepared. The results are shown in the last table.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

[Table] Sulfo fatty acid salts

38 NaCoconut α-Sulfo Fatty Acid Methyl S
55 10 35 60 Stable gel Tell salt

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】
solution
68 C ₁₄ AOS 40 Limonene
5 3 52 Stable gel

【table】

【table】

【table】

[Table] Thorium sulfonic acid

30 C ₁₄ α-Olefin Insul 40 Dovanol 10 20
Fonic acid (Na salt)

Claims (1)

(b)()() 1 to 75% by weight of fatty acid mono- and diethanolamides and less than 12% by weight of fatty acid mono- and diethanolamides; of
An auxiliary micelle-forming non-soap surfactant selected from ethoxylated non-ionic surfactants having an HLB value [with the proviso that component (b)
() () may contain from 1 to 45% by weight of aliphatic or aromatic aliphatic hydrocarbon chains having polar head groups and up to 6 aliphatic carbon atoms. A second compound consisting of a good anionic or nonionic water-soluble non-micelle-forming or weakly micelle-forming substance.
(b)()() 1 to 15% by weight of non-micelle-forming or weakly micelle-forming aliphatics, cycloaliphatics, aromatics or araliphatics above 55°C; a non-ionic substance having a melting point of not less than or substances having a hydroxyl group located on a cycloaliphatic ring and optionally having one or more other polar groups [provided that if the hydroxyl group is the only polar group present or have up to 6 aliphatic carbon atoms if the second polar group is present and separated from the hydroxyl group by 2 or fewer carbon atoms, or if the second polar group is present and 3 (b)()() from 1 to 15% by weight; Non-micelle-forming or weakly micelle-forming aliphatic, cycloaliphatic, aromatic or araliphatic nonionic substances having a melting point not exceeding 55°C and a dielectric constant in liquid form of at least 2.2; from a substance having at least 7 carbon atoms and at least one polar group located at a terminal position or within two carbon atoms from the end in a hydrocarbon chain or on an aromatic or cycloaliphatic ring; Selected additives [provided that this additive (b)
() () may have (c) 1 to 45% by weight of aliphatic or araliphatic hydrocarbon chains with polar head groups and up to 6 aliphatic carbon atoms. a second substance consisting of an anionic or nonionic water-soluble non-micelle-forming or weakly micelle-forming substance;
and (d) water [provided that the total amount of (a) and (b) is within the range of 15 to 95% by weight]. thing.