JPS6241299A - 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 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/P r
(Otector & Gamble) describes paste or gel detergent compositions that are hexagonal, or 6'middle'' phase. Contains mixed with water-soluble soap.

The use of alkanolamines as the main cations
Promotes the formation of middle phase.

British Patent No. 21 published on 18th September 1985
No. 55031A (Unlever) describes detergent compositions of the hexagonal phase gel type. The main components of these gels are secondary surfactants, ie their polar head groups are located non-terminal in the hydrocarbon chain or have two or more hydrocarbon chains. Examples of "secondary" surfactants are alkylbenzene sulfonic acids and dialkyl sulfosuccinic acids. These surfactants do not naturally form a hexagonal phase at room temperature, and the gel does not contain "additives" (e.g. urea or sodium xylene sulfonate) to bring the composition into a hexagonal phase.

A simple gel of this kind is alkylbenzene sulfone 216
No. 12 (lyl 1ntaX) also discloses a detergent gel containing an alkylbenzenesulfonic acid, urea and water, but it makes no mention of a hexagonal phase.

Said British Patent No. 2155031A (U ni 1e
The "secondary" surfactants for (ver) have a tendency to form a lamellar phase rather than a hexagonal phase and require an [additive], e.g. urea, to stabilize this hexagonal phase. . [first (
primary) J surfactants pose different problems;
That is, they have a tendency to crystallize. Urea-type "additives" do not solve this problem. U.S. Patent No. 25
According to No. 80713, this problem is solved by using alkanolamines as the main cation.

This time, by including a second component in the gel, which can be either a specific type of auxiliary 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 sodium salt form can also be produced from xylated non-soap surfactants in a non-technical manner to considerably expand the concentration range.

Accordingly, the present invention provides an aqueous detergent composition consisting entirely or mainly of a hexagonal liquid crystal gel, wherein the gel in the present invention comprises (a) 5 to 85% of a ionic head and 10-20
a xylated micelle-forming non-soap surfactant in which the anionic head is located at or adjacent to the end of the hydrocarbon chain; and (b) a second component, i.e. (b) (i) 1- 75ffi at% of auxiliary micelle-forming non-soap surfactants selected from: (b) (i) (i) anionic non-soap surfactants other than those specified in (a) above; Ethoxylated nonionic surfactants and amine oxides having an HLB value of at least 12; or (b) (i) (ii) fatty acid mono- and di-ethanol-
and/or (bHii) 1 to 15% non-micelle-forming or weakly micelle-forming aliphatic, cycloaliphatic , aromatic or araliphatic with a melting point not exceeding 55°C and at least 2.
(b) (ii) a non-ionic substance having a dielectric constant in liquid form of 2 and selected from: (b) (ii)
(i) a hydroxyl group having at least 4 carbon atoms and located at or within 2 carbon atoms of the terminal position in the hydrocarbon chain or aromatic or cycloaliphatic ring and optionally one or more hydroxyl groups; with more than one other polar group: if the hydroxyl group is the only polar group present or if a second polar group is separated from the hydroxyl group by two or fewer carbon atoms present; or up to 12 aliphatic carbon atoms if the second polar group is present and separated from the hydroxyl group by three or more carbon atoms. (b) (ii) (ii) having at least 7 carbon atoms and 2 carbon atoms in terminal or terminal positions in a hydrocarbon chain or an aromatic or cycloaliphatic ring; a substance having at least one polar group located within and/or having ethylenic unsaturation;
(b) in a total amount in the range of 15 to 95% by weight, and optionally (c) 1 to 45% by weight of the polar head and optionally up to 6% by weight.
anionic or nonionic water-soluble non-micelle-forming or weakly micelle-forming substances with aliphatic or araliphatic hydrocarbon chains having up to 1 aliphatic carbon atoms, component (c) being an auxiliary Essential in the absence of either surfactant (b) (i) (i) and additive (b) (i iHi i); further characterized by containing (d) water.

The detergent gel of the present invention is wholly or primarily of hexagonal liquid crystal type (hexagonal liquid crystal type).
stalform). 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. Plug spacing in X-ray pattern (B
raaa spacing) are as follows: For this, for example, G, W, Gray and P,
A. Edited by Winsor [Liquid Crystals and Plastic Crystals J (EIlis l-1orwo1
-1or, (1974), Volume 2, Chapter 4, Page 88).

31! Among the liquid crystalline types (i.e. lamellar, hexagonal and cubic phases), hexagonal phase is intermediate in stiffness, but stiffness or viscosity is the absolute means to distinguish hexagonal phase gels from other gels. Not.

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 main surfactant (DrinCipal 5urractan);
t> and (b) a second component, i.e. (bHi) a co-surfactant, and/or (b) li
(c) an optional second additive; (d) water.

These layers will be explained in detail below.

Additionally, other ingredients of the type 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: (i)
Primary alkyl sulfuric acid of the general formula (1): R1-0-8o3X1 (I) in which R1 is an alkyl group having 10 to 20 carbon atoms and x1 is a solubilizing cation. The primary alkyl sulfates can be of substantially single chain length, such as in dodecyl sulfate, or they can be, for example, Quercus alkyl sulfates (010C14
, mainly C12 and C14) may also be composed of a mixture of substances of different chain lengths.

(ii) α-olefin sulfonic acid of the general formula ■: R2-8O3x2 (■) where R is an α,β-unsaturated cio C20 alkenyl group and x2 is a solubilizing cation.

(iii) General formula ■: R3-8O3X3 (■) [In the formula, R3 is the first 010"' C20 alkyl group, ×
3 is a solubilizing cation] primary alkanesulfonic acid.

(1v) An alkyl or alkenyl isethionic acid of the general formula ■: R4Co O(TV) CHCH-803x4 [wherein R4 is a C7C20 alkyl or alkenyl group, and x4 is a solubilizing cation].

(V) General formula V: 0OX6 [wherein, R5 is a C8C20 alkyl group, ×5 is a solubilizing cation, and ×6 is H or a solubilizing cation depending on the pH (even if it is the same as ×5) α-sulfonated fatty acid salts (SFAS), which may be different.

(vi) Fatty acid methyl ester sulfone II (FAES) of the general formula: [wherein R is a C-C2o alkyl group and x7 is a solubilizing cation].

The fatty acid methyl ester sulfonic acid can be of substantially single chain length or can be coconut FAES (cg-Ci
It can also be composed of a mixture of substances of different chain lengths, such as Q (mainly R6 being C4° and C1□).

All these preferred surfactants have a sulfonic acid or sulfate head group at or adjacent to the terminal position;
It will be appreciated that in the case of , this is modified by the presence of a vicinal carboxyl or carboxyl ester group.

The countercation of the main surfactant component (a) can be any solubilizing cation, provided that the Kraft point (K raf [t p
oint) is kept below room temperature as a whole.

Examples are for example alkali metals such as sodium, potassium, lithium or cesium; alkaline earth metals such as magnesium; ammonium; mono-, di- or tri-alkylamines or mono-, di- or trialkanolamines. Includes substituted ammonium. 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 powder. The choice of cation is therefore primarily a matter of choice.

The main surfactant component (a) of the composition according to the invention may consist of one or more of the above-mentioned substances.

In one preferred embodiment of the invention, the main surface-active surfactant (
a) is composed of one or more primary alkyl sulfates.

In the composition of the present invention, the main surfactant (a) is 5 to 8
It is present in an amount of 5% by weight, preferably from 5 to 75% by weight, particularly preferably from 8 to 55% by weight, a particularly preferred amount being the co-surfactant (b)m or "additive" (b)(ii) 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, preferred levels are 5-60% by weight
, more preferably 5 to 55% by weight.

Depending on whether (b) is a co-surfactant and/or an additive, the components present (
The total amount of a) and (b) ranges from 15 to 95% by weight, preferably from 15 to 85% by weight. 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 1 in all-sodium systems.
It is 5 to 85% by weight, preferably 40 to 70% by weight.

Particularly preferred ranges within these ranges, as described below, depend on whether component (b) is a co-surfactant (1) or an additive (11) or a mixture of the two. It depends.

The total surfactant level (i.e. the total level of primary surfactant (a) and any co-surfactant (bHi) 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.% will reduce the cation of one or both surfactants. This can only be achieved with high molecular weights such as triethanolamine. Of course, 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 are discussed in Motokawa II.
Examples are shown after the book.

(b)i) In a first embodiment of the invention, the composition of the invention comprises an auxiliary non-soap surfactant (b)(i) selected from certain anionic and nonionic surfactants. Contains.

In this first embodiment, the composition of the invention comprises 1 to 75
% by weight, preferably 5-50% by weight, more preferably 8
~40% by weight co-surfactant (b)(i);
More preferably 5 to 60% by weight, more preferably 5 to 60% by weight
It also contains 40% by weight of primary 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 "principal surfactant" does not necessarily mean that this component is the predominant surfactant, but in fact (
The ratio of a) to (b)(+) can range from 20:1 to G, 1:1, preferably from 10:1 to G, 1:1, the selection depending on the particular co-surface activity selected. Depends on the agent.

The total surfactant level in this embodiment is preferably from 16 to 60% by weight on a total sodium system.
is within the range of Of course, the above types (a) and (b) (i
) may be present.

Two types of co-surfactants have been identified that are suitable for use in the present invention. The first one (i.e. (b) (i
) (i)) is an anionic non-soap surfactant other than the same type as the main surfactant (a), i.e. the anionic head is at the end of the C10" C20 hydrocarbon chain or Anionic non-soap surfactant other than adjacent non-ethoxylated anionic surfactant; high (>1
2.0) Ethoxylated nonionic surfactants with HLB values; and amine oxides. (b)(i)(i
) Preferred types of cosurfactants are: (1) non-ethoxylated anionic surfactants in which the anionic head is located at the non-terminus of the aliphatic or araliphatic hydrocarbon chain; Ethoxylated anionic surfactant, ≧12
．． an ethoxylated nonionic surfactant with an HLB value of 0, and (4) an amine oxide.

A first group of non-ethoxylated surfactants is described in UK Patent No. 2,155,031A II (U nlever
) 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 Further short chains are attached directly to the head itself. The first type of "second" surfactants generally have the general formula: [where 2 is an anionic head group, e.g. a sulfonic acid or sulfate group in combination with a solubilizing cation, R7 and R8 are both aliphatic or araliphatic hydrocarbon chains having 8 to 20 carbon atoms, R7
and R8, the shorter of which has at least two aliphatic carbon atoms, and Y is a linking group such as,
The total number of aliphatic carbon atoms in RSR8 and Y corresponds to 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 is generally
General formula ■: [wherein Z is an anionic head group in combination with a solubilizing cation, R and Rlo are both aliphatic or It is an araliphatic hydrocarbon chain, and the chains R9 and R
10 with at least 2 aliphatic carbon atoms].

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, preferably 1
Linear or branched alkylbenzenesulfonic acids having 0 to 13 aliphatic carbon atoms.

Advantageously, the alkylbenzenesulfonic 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 the same ratio as (i). 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 from 4:1 to 1:1.

A preferred ethoxylated anionic surfactant for use in the compositions of the invention is the alkyl ether 1iil! It is an acid.

These have the general formula (1): R11-(OCH2CH2). -(IX)O-803x
8 In formula 1, R11 is 10 to 20, preferably 12 to 15
x8 is a solubilizing cation, and n, the average degree of ethoxylation, ranges from 1 to 12, preferably from 1 to 8.

As with the primary surfactant (a), the choice of solubilizing cation for the auxiliary anionic surfactant (b)(i)(i) is primarily a matter of choice.

Suitable high HLB ethoxylated nonionic surfactants are ethoxylated alcohols and alkylphenols of the general formula X: R-(c6H4), -12(X) (OC82CH2), -OH and In the formula, X is O (alcohol ethoxylate) or 1 (alkylphenol ethoxylate)
, R12 is an alkyl group having 6 to 20 carbon atoms, and m, the average degree of ethoxylation, is 5 to 3.
It is in the range of 0. Per alcohol ethoxylate, R
12 preferably has 8 to 18 carbon atoms, m is 5
~14. An example of a suitable alcohol ethoxylate is dopanol 9
1-8 and 9l-6 (Shefi) (c9-01
1 alcohol, respectively m-8 and 6, respectively HL
B values of 13.8 and 12.6). For alkylphenol ethoxylates, R12 is preferably 8 to 1
It has 2 carbon atoms and m is 6-16.

The ethoxylated co-surfactant (both anionic and non-ionic) preferably comprises the primary surfactant (a).
G10:1~0.1:1 f of (a) vs. (b) (+)
They can be combined at the f1l ratio. Main surfactant (a
) is one or more primary alkyl sulfates, preferred ratio ranges are from 5:1 to 0.1 (.1, more preferably from 3.5:1 to 14:1).

The amine oxide has the general formula xI: RN---1-→O(XI) [wherein R13 is C1o-C2° alkyl group,
14 is a C1-04 alkyl group, and R15 is a C1-04 alkyl group.
is a C4 alkyl group].

Advantageously, the amine oxide is combined with the main surfactant (a) by 20:
1 to 2: 1 (7) (a) to (b) (i) may be combined in a weight ratio of 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 from 7:1 to 3:1.
It is.

The second type of co-surfactant (b)(i)(ii) is:
Consists of ethoxylated nonionic surfactants with low (<12.0> HLB values) and fatty acid mono- and di-ethanolamides.

Suitable ethoxylated nonionic surfactants are ethoxylated alcohols and alkylphenols of general formula X above, but generally have a low degree of ethoxylation m, ie higher HLB substances. An example is Dopanol® 91-5 (shell) (cg-C
11) Alcohol; m=5; HL B = 11.7)
It is. Advantageously, these include the main surfactant (a) and 10
: 1 to 0.1: Can be combined at a weight ratio of (a) to (b) (+) of 1. When the main surfactant (a) is one or more primary alkyl sulfates, the preferred ratio ranges from 5:1 to 0.1:1, more preferably 3.
The ratio is 5:1 to 0.14:1.

Fatty acid mono- and di-ethanolamides have the general formula
: R16Go N C82CH208 (XII) where R16 is an alkyl group having 7 to 20 carbon atoms and R is H or -CH, 2CH, 20H.

The fatty acid mono- and di-ethanolamides are preferably 2
It can be combined with the main surfactant (a) in an end ratio of (al to (b)(i) of 0:1 to 2:1, where the main surfactant is one or more primary alkyl In the case of sulfuric acid, the preferred ratio range is 10:1 to 3:1, more preferably 7:1 to 3:1.

Two broad classes of co-surfactants (b)(i)(i)
The meaning of the difference between That is to say. Co-surfactant (b)(i) In the case of type (i), the second additive (c) can be present if desired and is not necessarily required.

If desired, the compositions of the invention can also contain mixtures of cosurfactants of the same or different types.

[2] EO process U process In the second embodiment of the present invention, the composition contains, in addition to the main surfactant (a), an additive J that is not a surfactant.
(b) Contains (ii). This additive (b) (ii
) is a non-micelle-forming or weakly micelle-forming aliphatic, l
- an aliphatic, aromatic or araliphatic nonionic substance with a melting point not exceeding 55° C. and a dielectric constant of at least 2.2. Additive (b)(ii) has the ability to reduce the kraft temperature of the surfactant system below room temperature.

When using co-surfactant (bHi), additive (b)
(ii) are classified into two broad types (b) (i 1) (i) and (b) (iiHii), and additives (bHi
The optional second additive (c) is mandatory only if i) is of type (b)(ii)(iiJ, and additive (b)(ii)
It is optional or advantageous if is of type (b)(i 1)(i).

The first type of additives (b)(ii)(i) consists 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, carboxylic acid amides, amines, aldehydes or ketone groups. can. This (b)(i
i) Type (i) additives have at least 4 carbon atoms, and the maximum number of carbon atoms present is such that the number and arrangement of any polar groups present other than the hydroxyl group is such that no less than 4 carbon atoms When separated from groups, (bHii) type (i) additives have up to 6 aliphatic carbon atoms. On the other hand, if there is a second polar group separated from the hydroxyl group by 3 or more carbon atoms, type (b)(ii)(i) additives contain up to 12 aliphatic carbon atoms. must have. These limitations are caused by the need for type (b)(++)(i) additives to have some, but not too great, affinity for water.

Examples of suitable type (b)(ii)(i) additives with various melting points and dielectric constants (exceeding the melting point) include: [spoon] 2-phenylethanol <20 °C 11.5 Hydroxycitronellal < 20 °C 11-12 Benzyl alcohol <20 °C 13.1 Thymol 51 °C Approximately 9 The second type of additive (bHii) (ii) is in the hexagonal phase range Although it is not possible to enlarge the surfactant or surfactant mixture, it lowers the kraft temperature of the surfactant or surfactant mixture present, thus solving the problem of crystallization, and also allows the composition to be in a lamellar rather than hexagonal phase. As mentioned above, the additive (b) (
If ii) is of this type, then the above British Patent No. 21550
No. 31A! It is essential that a second type of additive (c) is also present to bring the composition into a hexagonal phase, as described in LlnNever. The additive (c) will be explained in detail later.

Additive (b) (+ tot +) is an amphoteric substance of low water solubility such that its overall character is hydrophobic despite the presence of polar groups. These may have at least 7 carbon atoms and have a polar group located at or within two carbon atoms of the terminal position in the hydrocarbon fast chain or aromatic or cycloaliphatic ring; and or can have ethylenic unsaturation.

(b)(ii)(ii) The dielectricity of the additive is at least 2.
．． It is 2. If present, polar groups can be, for example, hydroxyl, carboxylic azide, amine, aldehyde or ketone groups.

Examples of these materials with various melting points and dielectric constants (at the 1m point and above) include: Decane-1
-all 7℃ approx. 7 dodecane-1-ol 26℃ approx. 5 coconut alcohol
40-45℃ 4-5 oleyl alcohol
6-7℃ approx. 4 decanoic acid
31.5℃ Approximately 2.4 dodecanoic acid
44℃ approx. 2.4 oleic acid
16.3℃ 2.4 Coconut fatty acids
40-45°C Approximately 2.4 (hereinafter referred to as margin/white) Ingredients such as fragrances can also be used as (bHii) (ii) additives. Examples of these materials with various melting points and dielectric constants (above the melting point) include:

Melting point Dielectric constant d-limonene <20℃ 2.3 Linalool <20℃ Approx. 3 Terpineol <20℃ Approx. 3 Amylcinnamic aldehyde <20℃ Approx. 127 Diethyl talate
<20℃ approx. 87 nisole
<20°C 4.3 Commercial perfume formulations can also be used. Ingredients such as fragrances typically contain 30 to 6
It is used in amounts of 1 to 5% by weight with 0% by weight of the main surfactant (a).

Both types of additives (b)(ii)(i) and (b)(i
In the case of i)(ii), a melting point of 55°C or lower is essential to avoid crystallization of the additive.

(b)(ii)(i) type or (b)(ii)(ii)
Relatively low levels (1-15% by weight) of any type
, preferably 2 to 10% by weight) of the additive (bHii) is sufficient. The preferred amount of surfactant (a) present in this embodiment depends, of course, on its countercation, and for all sodium systems ranges from 25 to 60% by weight, more preferably from 30 to 50% by weight. The total level of surfactants and additives in this embodiment is preferably between 16 and 60% bart water per total sodium system, more preferably 35%
~57% by weight. The ratio of surfactant to additive can range from 30:1 to 3:1, for example.

For type (b)(iiHi) additives and primary alkyl sulfates, the preferred ratio range is from 27.5:1 to 3.5:1.

If desired, the compositions of the invention may contain a co-surfactant (b) (
i) and additive (b)(11).

Optional Additives (c) The compositions of the invention can also contain a second type of additive (c), which in fact means that component (b) is
i) A co-surfactant of the type (ii) or by itself does not act as a hexagonal phase promoter (bo+te (essential if it is an m-type additive). The second additive (c) is useful for counteracting the effects of electrolytes that tend to reduce range, and is therefore particularly useful in compositions containing electrolytic components such as builders.

Additive (c) is described in detail in the aforementioned GB 2155031A (Unilever). This is a water-soluble non-containing compound that can move the 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 micelle-forming or weakly micelle-forming substance. The mechanism of action of additive (c) is not clearly understood. Although this would act to increase the micelle or liquid crystal curvature, the scope of the invention is not limited by this hypothesis. It has been experimentally observed that certain types of materials useful as hydrotropes in light duty liquid detergent compositions may 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 more hydrophobic groups it can tolerate.

The polar group of additive (c) carries an ionic charge, in which case it must be of the same polarity as that of 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 an -0ON- group. The general characteristics of this second type are that it increases the dielectric constant of water and has a structure-bending effect on water.
This seems to be the ability to exhibit a reaking effect. 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, urea itself is not desirable.

When additive (c) is urea, a buffer is advantageously present to minimize hydrolysis, especially alkaline hydrolysis, of the urea. A suitable buffer is boric acid, preferably 3
It is used in amounts of less than 1% by weight, more preferably 1-2% by weight. Buffering is achieved by including triethanolamine as a countercation in the surfactant system. buffering capacity as well as greater electrolyte tolerance (e
lectrolyte tolerance) allows higher levels of electrolytic components (eg tripolyte@sodium builder) to be incorporated into the compositions of the present invention.

Advantageously, additive (c) is present in an amount of 1 to 45% by weight, preferably 5 to 35% by weight. Additive (b) (ii)
) The greater the amount of (ii) present and the more electrolyte salts present, the greater the amount of additive (c) required.

Mizuyu Fallenji In all embodiments of the invention, water is an essential ingredient.

Stable hexagonal or predominantly hexagonal phase in any particular system consisting of surfactant (a), component (b) (co-surfactant or additive), optional second additive (c), and water. The relative proportions of phases that give rise to gels can be ascertained by experiment and by construction of phase diagrams. Samples of various ratios were prepared by mixing and the phases present were visually observed and the gross flow properties
), can be easily identified by the appearance of polarized light and tissue observation under a polarized light microscope.

111 Gua Lu 1 The non-build compositions of the present invention consist essentially entirely of surfactant component (a), component (b), optional additives (c), water, and conventional agents such as colorants, fragrances, and fungicides. and small amounts of ingredients such as preservatives. Non-build compositions of this type are useful in light duty applications such as dishwashing, jump or fabric laundering in soft water areas.

Further within the scope of this invention, there are also heavy duty fabric laundry compositions containing ingredients such as builders, bleaches, fluorescent agents, photobleachs, enzymes, anti-redeposition deodorizers and disinfectants.

Water-soluble organic or inorganic builders such as phosphates,
Citrate or nitrilotriacetate may also be incorporated into the compositions of the present invention, but 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 bilgoux 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 suitable bleaching substance is European Patent No. 16
No. 0542A! 1,12-diperoxide dodecanedioic acid as described in Book A (Unilever).

1-1-1-1 Hereinafter, the present invention will be explained by way of examples, although not limited, and the %
and the ratio is by weight.

An experiment was conducted to prepare a hexagonal phase gel containing coconut alkyl sulfate and water by mixing.

Alkyl sulfur 111 (sodium salt) was Emal (registered trademark) 10 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.

Alkyl sulfuric acid Product description A 30 70 Crystallographer's solution B
35 65 Crystal + Solution C4555 Crystal solid [) 50 50 Crystal solid support 1
1-Top 2'' These examples demonstrate a first embodiment of the invention in which co-surfactant (b) (i >) is present.

A composition containing coconut alkyl sulfuric acid, alkyl ether 1iRIffl, and water used in Comparative Examples △ to D was prepared by mixing. The alkyl ether sulfate was Synperonic® 3-8-708 (c,3EO 1 sodium salt) from IO2. These compositions are shown in the corresponding table, where numbers are used 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 designated as (al) and alkyl ether sulfates are designated as (b)(i).

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 non-ionic surfactant was Dopanol® 91 from 5he11.
-8 (c9-C,,,8EO), which is 13.
It has an HLB value of 8. These compositions are shown in the corresponding tables, where (b)(i) indicates the nonionic surfactant. In this table, the expression "two phases" indicates separation into two liquid crystal (hexagonal and lamellar) phases.

A composition similar to Example 6-12 was prepared using an ethoxylated alcohol with a low average degree of ethoxylation, namely Dopanol 91-6 (c
9-C,6EO) (This is 1-I L B of 12.6
lit! ) was used as co-surfactant (b)(i). These compositions are shown in the corresponding table.

-16 and 17 Lower ethoxylation, i.e. Dopanol 91-5 from 5hel1 <C3C11,5EO1HLB
Compositions with a value of 11.7) were made 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.

Dopanol 91-2.5 from 5hel1 company without urea
Attempts to create a gel using (c-C, 2,5EO, 1-ILB 8.2) were unsuccessful. No hexagonal phase was present at 22° C. in the absence of component (c).

Tomo 11 Once coconut sodium alkyl sulfate and non-ethoxylated nonionic surfactant and coconut jetanolamide (EthVlan® LD, Rank
ro) and are shown in the corresponding table. The gel of Comparative Example AA contained some hexagonal phase but did not exhibit flowability.

Examples 19 and 22 Primary alkyl sulfuric acid in the sodium salt form (dodecyl in Example 22, coconut in its base metal) was added to coconut dimethylamine oxide (Enbigen).
EIIlpigen) (registered trademark) OB, ^Ibri
Ght and Wilson, Inc.) and are shown in the corresponding table. Sodium dedocyl sulfate is Br1tish Drug Houses
Ltd., pure experimental reagents.

-C12 alkylbenzenesulfonic acid, i.e. 11
Compositions containing Harlon® A from JLS were prepared and are shown in the corresponding table.

27 and 28 Compositions containing ethoxylated nonionic surfactants as co-surfactants (b) (+) and sodium tripolyphosphate builder were made and are shown in the corresponding tables. The base formulation of 20% sodium dodecyl sulfate and 20% Dopanol 91-8 is similar to Example 9 above. When urea is not used (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.

A comparative experiment using 40% sodium dodecyl sulfate without co-surfactant gave solid crystals (Comparative Example PP-8S).

A stable hexagonal phase gel containing the triethanolamine salt of coconut alkyl sulfate (80%), Dopanol 9l-8 (5%) and water (15%) was prepared. (a) vs. (
b) The ratio of (i) 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 (AO8) with various chain lengths as the main surfactant (a) were prepared and these are shown in the corresponding tables. C and C1
Substance 4-18 is manufactured by Uion Co., Ltd. in Japan, and CAO
No. 3 was manufactured by ^ekyung-5hel1, Korea. The cosurfactants used were Dopanol 91-8 and Dopanol 91-5, and as expected urea was required to obtain stable gels with the latter (low HLB) material. In each case, the total active detergent level was 50% by weight and the ratio of (a) to (b)(i) was 4:1.

111 Bigram Various non-ethoxylated anionic surfactants (a)
Stable hexagonal phase gels were prepared containing the nonionic surfactant Dopanol 91-8 as co-surfactant (b)(i) and these are shown in the corresponding table.

Support 11 - Danjiri These examples illustrate a second embodiment of the invention in which an additive (bHii) is present.

A composition containing sodium coconut alkyl sulfate as a surfactant and 2-phenylethanol as an additive (bHii) (i) was prepared by mixing, and these compositions were added to the corresponding table. Shown inside.

Examples 42-47 Coconut sodium alkyl sulfate and additives (b) (ii
) (i) as hydroxycitronellal (cll
3) 2C(OH) -(cH2) 3- CH(cH
3) Compositions containing -CH2CHO were prepared by mixing and these compositions are shown in the corresponding tables.

115 Once 2H Coconut sodium alkyl sulfate and additives (b) (ii
benzyl alcohol as Ni) were made by mixing and these compositions are shown in the corresponding table.

Examples 53-57 A composition containing a single, long-chain alkyl sulfate, namely sodium dodecyl sulfate, and 2-phenylethanol as an additive (bHiiNi) was prepared by mixing,
These compositions are shown in the corresponding table.

Example 58 Stable hexagonal phase gel made by mixing 35% sodium coconut alkyl sulfate and additives (b)(ii)
(i) 5% thymol (2-isopropyl-
5-methylphenol) and 60% water.

Examples 59 and 60 A composition containing sodium coconut alkyl sulfate (35% by weight) and linalul (5% by weight) as additive (b) (ii) (ii) was used as additive (c). with or without urea, and these are shown below.

% % product sss
eo Fluid composition 59 10
50 Mainly hexagonal gel 60 20
40 Mainly hexagonal gel coconut alkyl sodium sulfate (40% by weight) Commercial fragrance (1ntern
ational Flours & Frang
lFF114.5% by weight from Lances Inc.
) were made with or without urea as additive (c) and these are shown below.

χ% TTT 55 solution + lamellar phase 61
10 45 Mainly hexagonal gel supporting 1λ
- Sodium coconut alkyl sulfate and flavor additives (b)
ii) Terpineol (terpiO) as (ii)
neo+) were made with or without urea as additive (c) and these are shown in the corresponding table.

Example 65 Coconut alkyl@acid sodium and additive (b) (ii
) coconut fatty acids as (ii) and compositions were prepared with or without urea as additive (c) and these are shown in the corresponding tables. As can be seen, when using additives (b)(ii)(ii) of this type, additive (c) is also essential for gel formation, but this level must be chosen carefully.

Example 66 The procedure of Example 65 is repeated using decane-1-ol as additive (b) (iiHii) and is shown in the corresponding table. Similar results are obtained, with higher levels of urea required than in Example 65 to obtain stable gel formation.

Sodium α-olefin sulfonate (AO8) as the main surfactant (a) and benzyl alcohol or limonene additive (b) (
ii) Prepare compositions containing (i) or (b)(ii) and (ii) and indicate these in the corresponding tables.

In each case, the total active detergent level was 401 i1% and the surfactant to additive ratio was 8:1. When using limonene, urea was required to obtain a stable gel.

Support 11-” Sodium coconut fatty acid methyl ester sulfonate (
A stable hexagonal phase gel containing benzyl alcohol (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.

*Example: JJJJ -LLLL To show that limitations on m-length and melting point are important when specifying additive (b) (11), neither sodium coconut alkyl sulfate (40% by weight) meets these requirements. Two [additives], namely ethanol (number of carbon atoms only 2) and stearyl alcohol (melting point 5
7°C) was prepared. The results were as follows.

1 presentation 1-J" mouth l -11dan 1 1-"L-1JJJJ
A stable gel according to the invention suitable for use in laundering fabrics was prepared by mixing an ethanol solution with a few crystals. These compositions are shown in the corresponding table. The base gels of Examples 71-74 were those of Example 2, and the base gels of Examples 75-79 were those of Example 31.

The blended fabric washing ingredients are as follows: Anti-redeposition agent: Sodium carboxymethylcellulose, Court
Aulds (62% active substance), Disinfectant: formalin (37%), Protease: Alcalase solution, Novo, active 1600 glycine units ■, Fluorescent agent: Tinopal (registered trademark) CBS-X , Ciba-Geigy, this is 4
゜4'-di(2-sulfostyryl) diphenyl disodium salt, photobleaching agent Nialuminum phthalocyanine sulfonate, Ciba-Geig V, deodorizing agent: PPE International 1, solid peroxy acid bleach: 1.12 - Diperoxide dodecanedioic acid ([1PODA) (12% available oxygen, made with DPDD eight particles from Oegussa, slurried in water and -filtered to remove water-soluble inorganic salts), buffered. Agent (to maintain good peroxyIl bleach stability during storage): Citric acid.

All of these compositions were stable, translucent hexagonal phase gels.

Examples 80-82 These examples illustrate the electrolyte component (i.e. tripoly[sodium) as the pirda and
No. (tlnilever) and British Patent Application No. 860
6145 (Unilever) as a mild bleaching agent.

These compositions are shown in the corresponding tables and were all stable, translucent hexagonal phase gels.

”L 匡１ Fotn + collapses the dirty plate (fotn + collapses)
The dishwashing performance of the three gels according to the invention was evaluated using the standard test method of washing to end point e). 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! 5 g of the product dissolved in water (French hardness: 4°) at 45°C,
That is, the total product concentration was 197It. The gels tested were those of Examples 13 and 30, and Example 23.
Similar but different alkylbenzene sulfonic acids, namely Dobane from Shell
(registered trademark) sodium salt) (composition 83). The results are shown in the last table.

Ax 8 5g 2 i g g
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M Toichi no ■ko = Σ♀ 'S l, 6 0 f 0 0 0 6 0 0
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Claims (1)

[Claims] (1) An aqueous detergent composition consisting entirely or primarily of a hexagonal liquid crystal type gel, wherein the gel comprises: (a) 5 to 85% by weight of anionic head and 10 to 20% by weight of anionic head;
A non-ethoxylated, micelle-forming, non-soap surfactant with an aliphatic or araliphatic hydrocarbon chain having 5 aliphatic carbon atoms (the anionic head is at or adjacent to the end of the hydrocarbon chain) (b) a second component, namely: (b) (i) 1 to 75% by weight of an auxiliary micelle-forming non-soap surfactant selected from: (b) (i) (i) Anionic non-soap surfactants other than those specified in (a) above, ethoxylated non-ionic surfactants and amine oxides having an HLB value of at least 12, or (b) (i) ( ii) fatty acid mono- and diethanolamides and ethoxylated nonionic surfactants with HLB values less than 12; and/or (b) (ii) 1 to 15% by weight of non-micelle-forming or weakly micelle-forming an aliphatic, cycloaliphatic, aromatic, or araliphatic nonionic substance having a melting point not exceeding 55°C and a dielectric constant in liquid form of at least 2.2, selected from the following: (b) (ii) (i) having at least 4 carbon atoms and within the terminal position or within 2 carbon atoms of the terminal position in the hydrocarbon chain or aromatic or cycloaliphatic ring; with a hydroxyl group present and optionally one or more other polar groups; if the hydroxyl group is the only polar group present or if a second polar group is present and there are two or fewer 6 or fewer aliphatic carbon atoms if the second polar group is present and separated from the hydroxyl group by 3 or more carbon atoms; (b) (ii) (ii) having at least 7 carbon atoms and terminating in a hydrocarbon chain or an aromatic or cycloaliphatic ring; a substance having at least one polar group located within two carbon atoms in a position or a terminal position and/or having ethylenic unsaturation; and the total amount of (a) and (b) is (c) 1 to 45% by weight of a polar head and optionally up to 6% by weight;
anionic or nonionic water-soluble non-micelle-forming or weakly micelle-forming substances with aliphatic or araliphatic hydrocarbon chains having up to 3 aliphatic carbon atoms; component (c) is an auxiliary an aqueous detergent characterized in that it is essential in the absence of both surfactant (b)(i)(i) and additive (b)(ii)(i); and further comprises (d) water. Composition.