JPH0735517B2 - Homogeneous concentrated liquid detergent composition containing a three-component surfactant system - Google Patents

Abstract

Homogeneous concentrated liquid detergent compositions with a ternary surfactant system are disclosed. The ternary system contains two anionic surfactants, an alkyl (aryl) - sulfonate and a succinate, and a nonionic surfactant. The compositions exhibit a pH in the neutral to mildly alkaline domain. Preferred compositions additionally contain low level of oleic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to concentrated homogeneous liquid detergent compositions containing a well-defined surface-active mixture. More specifically, the composition is characterized by the use of a three component surfactant system and contains less than 50% water. The ternary surfactant system has a sulfonate to succinate weight ratio of 3: 1 to 1: 4.
Containing most of the anionic surfactants represented by the binary mixture of alkyl (aryl) sulfonated surfactants and alkyl or alkenyl succinates and nonionic surfactant components.

The composition exhibits excellent and highly desirable detergency, is easy to prepare and exhibits excellent stability during long term storage.

Uniform concentrated heavy duty liquid detergents are well known in the art and find commercial application. Such compositions may consist of a three component active system, ie a synthetic anionic sulfonate or sulphate in combination with a nonionic ethoxylate and soap. Such prior art compositions are difficult to process, especially depending on the alkalinity. Prior art concentrated liquid detergents are in that respect susceptible to phase separation under neutral to weakly alkaline conditions. As a further result of such matrix criticality, it is quite difficult to modify the matrix in order to improve its performance for certain staining / cleaning situations. From the standpoint of detergency, prior art concentrated liquid compositions
It is known that while exhibiting excellent cleaning for most fibers, there can be desirable improvements in cellulosic fiber detergency compared to the performance obtained from the use of oxygen bleach-containing polyphosphate builder-containing granular detergents.

There is a wide variety of prior art relating to concentrated and uniform heavy duty liquid detergent compositions. As an example, U.S. Pat.
No. 285,841 describes an anionic synthetic surface-active compound,
Disclosed is a builder-free concentrated homogeneous liquid composition containing a combination of a nonionic surface-active compound and a fatty acid. The preparation of such a composition containing less than 50% water comprises
It requires the use of real masses of solvents and / or compatibilizers, and even under those circumstances, especially nonionic compounds, fatty acids, especially saturated compounds, and optional electrolytes, such as small amounts of organic builders and It remains borderline stable with respect to variety.

Succinate ingredients are well known in the detergent art and are disclosed in combination with detergent formulations of all types, mostly granular compositions. While such succinates have been recommended for use in liquid compositions, substantial formulation difficulties are associated with their use in such compositions, especially in the presence of small amounts of water and substantial amounts of nonionic compounds. It is well known that this will happen.

German patent 1768851 relates to the use of certain succinate derivatives as whipping boosters. These compositions contain an anionic surfactant alone and, in combination with an additional hydrotrope, a substantial amount of water.

West German Patent No. 1956671 discloses a two-component liquid formulation containing a substantial amount of alkyl or alkenyl succinate in combination with a nonionic surfactant.
West German Patent Application No. 3013904 relates to a solid or liquid alkaline cleaning agent composition containing a partially neutralized succinic acid derivative which appears to be utilized for its foaming properties.

EP-A-00017951 relates to the combined use of alkyl or alkenyl succinates or their monoesters in liquid detergent compositions containing high amounts of electrolytes with polyhydric alcohols which render the perfumes hydrotropic.

The main object of the present invention is to formulate a uniform concentrated liquid detergent composition having outstanding performance characteristics comparable to those obtainable from a polyphosphate builder-containing granular detergent composition containing an oxygen bleach. .

Yet another object of the present invention is a uniform high concentration containing a substantial amount of a three component surfactant system based on anionic sulfonates and succinates in combination with nonionic ethoxylates but containing less than 50% water. To formulate a liquid detergent composition.

Yet another object of the present invention is to define a high-concentration, storage-stable liquid detergent composition having excellent laundry cleaning properties under neutral to weakly alkaline conditions.

SUMMARY OF THE INVENTION The present invention relates to a uniform concentrated liquid detergent composition having less than about 50% water and containing a three component surfactant system. In detail,
The composition represents (a) a three-component surfactant system 35% to 75%, (b) a three-component surfactant system 50% to 90%, and (1) an alkyl (aryl) sulfonated surfactant. Agent and formula (2) Wherein R ₁ is an alkyl or alkenyl group having 10 to 20 carbon atoms and R ₂ is hydrogen or C _{1 to} C ₄ alkyl) and a binary mixture with an alkyl or alkenyl succinate ( The weight ratio of sulfonate to succinate is in the range of 3: 1 to 1: 4), and (c) a nonionic representing 50% to 10% of the ternary surfactant system. Characterized by the presence of a surfactant component, the composition has a pH of about 7 to about 9 as measured in a 1% solution at 20 ° C.
Have.

DETAILED DESCRIPTION OF THE INVENTION The present invention may be embodied by a highly concentrated uniform liquid detergent composition containing a three-component surfactant system and having a pH in the neutral to weakly alkaline range.

The essential parameters that qualify the invention are detailed below.

Unless otherwise stated, "percentage indication" means "wt%" of the composition.

Anionic surfactant component is 50% of ternary surfactant system
˜90%, and (1) an alkyl (aryl) sulfonated surfactant and (2) a formula Wherein R ₁ is an alkyl or alkenyl group having 10 to 20 carbon atoms and R ₂ is hydrogen or C _{1 to} C ₄ alkyl) and a binary combination with an alkyl or alkenyl succinate ( The weight ratio of sulfonate to succinate is in the range 3: 1 to 1: 4).

As is clear from the above, the three-component surfactant system in the detergent composition of the present invention comprises an anionic surfactant and a nonionic surfactant, and two components of the three components are anionic. It is a surfactant, and the remaining one component, which is the third component, is a nonionic surfactant. The two components of the anionic surfactant consist of an alkyl (aryl) sulfonate and an alkyl or alkenyl succinate. The ternary surfactant system comprises 35-75% by weight of the composition, 50-90% by weight of the ternary surfactant system is the anionic surfactant consisting of the binary mixture, the remaining 50-10%.
Weight percent is nonionic surfactant.

Anionic sulfonate surfactants are known to be suitable for use in liquid detergent compositions, and in fact all the alkyl (aryl) sulfonated surfactants widely used in commercial detergent formulations. Can be represented by

Such anion-synthesized sulfonates have the general formula R ¹ SO ₃ M
(Wherein R ¹ is a hydrocarbon selected from the group consisting of a linear or branched alkyl group having about 8 to about 24 carbon atoms and an alkylphenyl group having about 10 to about 18 carbon atoms in the alkyl group. Can be represented by). M is typically a salt-forming cation selected from the group consisting of sodium, potassium, magnesium, ammonium, monoalkanol ammonium, dialkanol ammonium, trialkanol ammonium and mixtures thereof.

Preferred synthetic anionic sulfonate surfactants are water-soluble salts of alkylbenzene sulfonic acids having from about 10 to about 18 carbon atoms in the alkyl group, most preferred for use in the present invention are those with carbon number in the alkyl chain. 12 to 16 (C _{12 to} C
₁₆ ) have.

Alkyl or alkenyl succinates are those of the above formula wherein R ₁ is either a saturated or unsaturated group having 10 to 20 carbon atoms, preferably an unsaturated derivative having 12 to 16 carbon atoms in the alkenyl moiety. ) Has. Hydrogen is preferred, but R ₂ can be hydrogen or C ₁ -C ₄ alkyl. The terms "succinate" and "succinic acid" refer to
Used interchangeably. Suitable succinates include sodium, potassium, lithium, ammonium, mono-, di- and tri-alkanolamine salts and mixtures thereof.

Preferred succinic acid derivatives for use in the present invention are 2-
Dodecenyl succinic acid, 2-tetradecenyl succinic acid, 2
-Hexadecenyl succinic acid, decyl succinic acid, dodecyl succinic acid and tetradecyl succinic acid and their water-soluble salts. The alkyl or alkenyl chain attached to succinic acid can be either straight or branched. Straight chain alkyl or alkenyl moieties are preferred.

The weight ratio of sulfonate to succinate surfactant in the binary mixture is in the range of 3: 1 to 1: 4, preferably 2: 1.
To 1: 2.

The three component surfactant system usually represents 35% to 75% of the composition. The anionic surfactant component is defined in salt form.

The nonionic surfactant component contains an organic hydrophobic group condensed with the ethylene oxide hydrophilic moiety. All ethoxylated nonionic surfactants known to be suitable for use in detergent applications can be used in the compositions of the present invention. The nonionic surfactant preferable in the present invention has 8 carbon atoms.
Derived from primary and secondary fatty alcohols having ˜24 and having an HLB (hydrophilic / lipophilic balance) of about 8-15
Is a polyethoxylate. These preferred ethoxylates often provide 2 per mole of hydrophobic moiety.
Contains about 14 moles of ethylene oxide. The hydrocarbyl chain (hydrophobic portion) may be represented by a linear or branched fatty alcohol.

Preferred types of nonionic ethoxylates have 12 to 12 carbon atoms.
It is represented by a condensate of a fatty alcohol having 15 and about 4 to 10 moles of ethylene oxide per mole of fatty alcohol. A suitable class of ethoxylates of this class is C
₁₂ -C ₁₅ oxo alcohol with an alcohol per mole 7
Condensate of moles of ethylene oxide; Condensate of C _13-15 oxo alcohol and 5 moles of ethylene oxide; narrow cut C ₁₄ -C ₁₅ 7 or 9 moles per mole of oxo alcohol and fatty (oxo) alcohol Condensation product of ethylene oxide with ethylene oxide; narrow-cut C ₁₂ -C ₁₃ fatty (oxo) alcohol and 6.
Condensate with 5 moles of ethylene oxide; and C with a degree of ethoxylation (EO moles / fatty alcohol moles) 5-8
₁₀ -C ₁₄ include condensation products of coconut fatty alcohol. Fat oxoalcohols are mainly linear,
Depending on the processing conditions and the raw olefin, it is possible to have some degree of branching, especially short chains, for example methyl branching. 15%
A degree of branching within the range of -50% (wt%) is often found in commercial oxo alcohols.

Also, the preferred nonionic ethoxylated component may be represented by a mixture of two separately ethoxylated nonionic surfactants having different degrees of ethoxylation. For example,
The nonionic ethoxylate is 3 to 3 mol per 1 mol of the hydrophobic part.
It may be represented by a mixture of a first ethoxylated surfactant containing 7 moles of ethylene oxide and a second ethoxylated surfactant having 8 to 14 moles of ethylene oxide per mole of hydrophobic moiety. A preferred nonionic ethoxylated mixture is a C ₁₂ -C ₁₅ oxo alcohol having up to 50% branching (by weight) and about 3 per mole of fatty oxo alcohol / mole.
To 7 moles of condensate at a lower ethoxylate of ethylene oxide, and C ₁₆ -C ₁₉ oxo alcohols and branched oxo alcohol 1 with branching greater than 50% (by weight)
It contains about 8 to 14 moles of higher ethoxylate per mole, which is a condensate with ethylene oxide.

Nonionic surfactant component is 50% of ternary surfactant system
Represents 10%, preferably 15% to 40%.

The composition contains less than 50% water, usually 15% -40%.

The composition also has a pH measured at 1% aqueous solution at 20 ° C.
Characterized by about 7 to about 9. This pH range is such that the anionic surfactant component, ie, the sulfonate, salcinate, and binary mixture, especially succinate, is neutralized substantially completely (ie, greater than 90%) in the composition as is. Indicates.

In addition to the essential ingredients mentioned above, the compositions often contain, in conventional amounts, a series of optional ingredients used for their known functions.

Examples of such optional ingredients are saturated and / or unsaturated fatty acids and the corresponding soaps, synthetic anionic surfactants different from sulfonates (non-sulfonate anionic surfactants), water-insoluble solvents, enzymes, Enzyme stabilizers, polyacids, antifoams, brighteners, perfumes, dyes, antioxidants, bactericides, corrosion inhibitors, fabric softeners, phase modifiers and the like can be included.

Suitable saturated or unsaturated fatty acids have 10 to 18 carbon atoms in the alkyl chain. Unsaturated species having 14 to 18 carbons in the alkyl chain are preferred, most preferably oleic acid. Corresponding soaps could equally be used. The optional fatty acid / soap is used in an amount of up to 10% of the composition, preferably 1% to 8%. Among other things, the fatty acids / soaps act as foam control / foam control agents.

Also, synthetic non-sulfonate anionic surfactants may be used in the composition in relatively minor amounts, eg, in amounts not exceeding 25% of the three component surfactant system. Examples of suitable non-sulfonate anionic surfactants have 12 to 20 carbon atoms in the alcohol chain.
And salts of sulfated fatty alcohols having

Also, water insoluble solvents such as terpenes, phthalates and liquid paraffins can generally be used in amounts of less than 5%.

Detergent enzymes generally help and enhance the removal of certain stains. Suitable enzymes may be represented by proteases, amylases, lipases, glucose oxidases, cellulases, or mixtures thereof. Proteases and amylases are preferred in the liquid concentrate compositions of the present invention.
They are often used in amounts of about 0.01% to about 1%.

All commonly known enzyme stabilization systems can be used in the compositions in art-established amounts. Examples of suitable stabilizing systems include short chain C _1-4 carboxylic acids, especially formic acid, in combination with small amounts of calcium, boric acid and its water-soluble salts (possibly in combination with polyols).

Another preferred optional ingredient is represented by a polyacid or mixture of polyacids in an amount of about 0.05% to about 2%. Suitable polyacids are those having a pK value of at least 5.
Preferred polyacid species for use in the present invention may be represented by organophosphonic acids, especially alkylene-polyamino-polyalkylenephosphonic acids such as ethylenediaminetetramethylenephosphonic acid, and diethylenetriaminepentamethylenephosphonic acid or salts thereof.

Non-fatty acid detergent defoamers can also be used. The preferred one is
Includes alkylated polysiloxanes such as dimethyl polysiloxane, often also referred to as silicone. Silicones are often used in amounts not exceeding 0.5%, most preferably 0.01% to 0.2%.

The present compositions also contain known antioxidants, often radical scavengers, for their known utility in technically established amounts, i.e. 0.01% to 0.25% (based on the total composition). it can. These antioxidants are often introduced with unsaturated organic acids. Many suitable antioxidants are readily known and available for that purpose, but also 2,6-ditert-butyl-p-cresol, commonly known as butylated hydroxytoluene BHT, and 2
-Tert-Butyl-4-hydroxyanisole is particularly preferred for use in the present composition. Other suitable antioxidants are 4,4'-thiobis (6-tert-butyl-m-cresol) and 2-methyl-4,6-dinonylphenol.

A stain release polymer can also be included in the composition. A suitable class of such stain release polymers is described in U.S. Patent Application No. 684,511 filed December 21, 1984.

Phase modifiers are yet another optional ingredient in the composition. This component, together with water, can form the solvent matrix for the concentrated liquid compositions of the present invention. Suitable components include lower aliphatic alcohols having 2 to 6 carbon atoms and 1 to 3 hydroxyl groups, ethers of diethylene glycol and lower aliphatic monoalcohols having 1 to 4 carbon atoms. Specific examples of phase modifiers are ethanol; n-propanol; isopropanol; butanol; 1,2-propanediol; 1,3-propanediol; monomethyl-, ethyl-, propyl-, and monobutyl ethers of diethylene glycol.

The present invention is illustrated and clarified by the following examples.

Example I By mixing the indicated ingredients in the following proportions,
A liquid detergent composition according to the present invention is prepared.

From the viewpoint of cleaning performance, the above composition is a registered trademark of Ariel (AR
IEL), i.e. a granular tripolyphosphate builder containing oxygen bleach. The test is carried out in a horizontal drum washing machine in cycles up to 60 ° C. Comparative performance is measured on various artificial soils such as cotton strips soiled with bleach-builder sensitive soils, enzyme sensitive soils, particulate soils and grease-oil soils. It has been found that the composition according to the invention gives a cloth cleaning performance on all types of soils comparable to that obtained from Ariel.

It was also found that the liquid composition of Example I remained homogeneous and stable after storage for at least 2 weeks at temperatures varying from 4 ° C to 50 ° C and also after exposure to several freeze / thaw cycles. Was done.

The following examples illustrate additional formulations of the present invention. Abbreviations for the individual components of the examples have the following meanings.

C ₁₂ HLAS: Cotton-like dodecylbenzene sulfonic acid C ₁₆ HLAS: Cotton-like hexadecylbenzene sulfonic acid C ₂₀ AS: Sodium salt of eicosene α-sulfonic acid TEACnAS: Coconut (C _12-14 ) alcohol Sulfate triethanolamine C _xy EOn: _Cx-y alcohol ethoxylated with n moles of ethylene oxide _Cx- y EOnS: sodium salt of _sulfated Cx- _y EOn DSA: 2-dodecenyl succinic acid HDSA: dodecyl succinic acid TSA: 2-tetradece Nylsuccinic acid C _12-14 FA: Coconut fatty acid DETPMP: Diethylenetriaminopentamethylphosphonic acid TEA: Triethanolamine TPG-EO ₃₀ : Poly (terephthalate propylene glycol ester) ethoxylated with about 30 mol of ethylene oxide

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI technical display part C11D 1:72) (72) Inventor Jean, Pol, Boutique Belgian country B-5150, Bepion, Ryu, Ah. De, Basage, 28 (56) Reference JP 58-196296 (JP, A) JP 59-15495 (JP, A) JP 50-70408 (JP, A) JP 61-145298 ( JP, A)

Claims (9)

[Claims] 1. A homogeneous concentrated aqueous liquid detergent composition containing less than 50% by weight of water, a three component anionic-nonionic surfactant system, and, if desired, conventional additives, comprising: (a) three components Surfactant system, 35-75% by weight of the composition
(B) the anionic surfactant component is 50 to 90% by weight of the three-component surfactant system, and (1) an alkyl (aryl) sulfonated surfactant and (2) a formula Wherein R ₁ is an alkyl or alkenyl group having 10 to 20 carbon atoms and R ₂ is hydrogen or C _{1 to} C ₄ alkyl) and a binary mixture with an alkyl or alkenyl succinate ( The weight ratio of sulfonate to succinate is in the range of 3: 1 to 1: 4) and (c) the nonionic surfactant component comprises 50% to 10% of the ternary surfactant system. A uniform concentrated aqueous liquid detergent composition characterized in that it has a pH of about 7 to about 9 as measured in a 1% solution at 20 ° C. 2. An alkyl (aryl) sulfonate is an alkylbenzene sulfonate having 10 to 18 carbon atoms in the alkyl group, and a salt-forming cation is sodium, potassium, magnesium, ammonium, monoalkanol ammonium, dialkanol ammonium. A composition according to claim 1 which is, trialkanol ammonium and mixtures thereof. 3. An alkyl or alkenyl succinate is 2-dodecenyl succinic acid, 2-tetradecenyl succinic acid, 2-hexadecenyl succinic acid, decyl succinic acid,
Claim 1 selected from the group of dodecyl succinic acid and tetradecyl succinic acid and their water-soluble salts.
The composition according to the item. 4. An alkyl or alkenyl group is a linear moiety and the weight ratio of sulfonate surfactant to succinate surfactant is in the range of 2: 1 to 1: 2. The composition according to the item. 5. A composition according to claim 3 in which the nonionic surfactant component represents 15 to 40% by weight of the three component surfactant system. 6. A composition according to claim 1 containing 15-40% by weight of water. 7. The composition according to claim 1, further comprising 1 to 8% by weight of C _{10 to} C ₁₈ fatty acids. 8. The composition according to claim 7, further comprising 0.01 to 0.25% by weight of an antioxidant. 9. The composition according to claim 8, wherein the fatty acid is oleic acid.