JP2994035B2 - Stabilized bleach-containing liquid detergent composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an aqueous liquid detergent composition containing a solid water-soluble peroxygen compound.

The peroxygen compound is stabilized against decomposition due to contamination with transition metals such as iron and manganese.

BACKGROUND ART It has only recently become possible to formulate liquid detergent compositions containing solid water-soluble peroxygen bleaches. Such detergent compositions are described, for example, in EP 0 294 904.

Under normal circumstances, the chemical stability of the peroxygen compound in such liquid detergents is satisfactory, thus giving the product good storage stability properties.

However, some products show some instability of the peroxygen compounds, which raises problems with storage stability sufficient for adequate shelf life of these products.

The cause of this peroxygen instability has now been identified as contamination of the product with traces of transition metals that catalyze the decomposition of peroxygen compounds in the composition.

Product contamination by transition metal traces is a significant problem that cannot be avoided in normal industrial practice. In fact, it has been discovered that some of the raw materials used in the manufacture of the products themselves carry trace amounts of transition metals.

In addition, accidental contamination can occur during manufacturing, shipping, handling or stocking of products due to corroded pipes or containers.

A solution to this problem is described in co-pending European Patent Application 90 20
No. 0315, which describes an aqueous liquid detergent composition containing a peroxygen bleach, and the peroxygen bleach is an effective amount of hydroxyethylidene-1,1-
Diphosphonic acid (HEDP) protects against degradation by transition metals. In these compositions, the peroxygen compounds are efficiently stabilized, but with the new problem that HEDP tends to form large aggregates (which can precipitate) in the presence of calcium. Have encountered. It is believed that this precipitation phenomenon can have some adverse effect on maintaining the whiteness of fabrics washed with the HEDP-containing detergent composition.

A new encounter is also the fact that the use of HEDP in liquid detergent compositions appears to interfere with the stability in the finished product of enzymes that can be used in detergent compositions.

Of course, these problems can be solved by obvious methods, for example by adding enzyme stabilizing systems and anti-redeposition agents, or
It can be overcome by compromising DP usage.

The object of the present invention is instead a compound containing a solid water-soluble peroxygen bleach, which protects the bleach from degradation by transition metals, which compound is as efficient as HEDP in protecting the bleach. Wherein the compound does not include the risk of precipitation in the presence of calcium). Another object of the present invention is to provide a liquid detergent composition wherein said compound does not interfere with the stability of oxygen in the finished product.

DISCLOSURE OF THE INVENTION The present invention provides a solid water-soluble peroxygen compound and (Wherein, R is C ₂ -C ₅ alkyl or alkenyl group) and Wherein R ₁ is H or CO ₂ H, x and y are integers denoting molar ratios, and the molar ratio of x: y is less than 30: 1. And (iii) mixtures thereof 0.01 to 5.0% by weight of the selected compound, preferably 0.05%
To 1.5% by weight of an aqueous liquid detergent composition.

BEST MODE FOR CARRYING OUT THE INVENTION Compounds which have been found to be useful in protecting water-soluble peroxygen bleaches against degradation by transition metal traces, but which do not precipitate, have the formula (Wherein, R is C ₂ -C ₅ alkyl or alkenyl group) and Wherein R ₁ is H or CO ₂ H, x and y are integers denoting molar ratios, and the molar ratio of x: y is lower than 30: 1, preferably lower than 20: 1 , Most preferably 4: 1) (iii) mixtures thereof.

The x: y ratio can be measured by phosphorus nuclear magnetic resonance spectroscopy techniques well known to those skilled in the art.

The compound according to the formula (i) is described in, for example, Russian Chemical Reviews 43 (9), p.
744 (1974). These chemical reactions involve the acylation of phosphoric acid or phosphorus trichloride with carboxylic acids, their anhydrides or halides: (Wherein, R is C ₂ -C ₅ saturated or unsaturated linear or branched hydrocarbon chain.) These reactions would not be discussed further here and therefore are known from the person skilled in the art .

 The most preferred compounds of formula (i) are:

The compound according to the formula (ii) has a molecular weight of 1,000 to 20,000,
Preferably it may have between 1000 and 5000, most preferably about 2000. Weight average molecular weight can be measured by the low angle scattering technique known to those skilled in the art (hereinafter referred to as LALLS).

The compounds according to formula (ii) here are described in particular in U.S. Pat. No. 4,207,405 to BF Goodrich Company. As described in this document, the expression (i
The compounds of i), the precursor of phosphoric acid capable of generating the phosphoric acid or phosphoric acid in aqueous solution, for example, can be obtained by reacting a water-soluble carboxylic polymer in a polar organic solvent PCl ₃ . The starting materials and reaction conditions, as well as the proportions of the starting materials, are discussed in more detail in the above-mentioned literature, which is available to the person skilled in the art.

Here, the compound of formula (i) or (ii) or a mixture thereof is present in an amount of 0.01 to 5% by weight of the total composition, preferably 0.05%.
Formulated in an amount of ~ 1.5% by weight.

Synthetic anionic surfactants have the general formula R ₁ SO ₃ M, where R ₁ has about 9 to about 15 carbon atoms in the linear or branched alkyl group and the alkyl group having about 8 to about 24 carbon atoms. A hydrocarbon group selected from the group consisting of an alkylphenyl group). M is a salt-forming cation typically selected from the group consisting of sodium, potassium, ammonium, and mixtures thereof.

Preferred synthetic anionic surfactants are water-soluble salts of alkyl benzene sulfonic acids having 9 to 15 carbon atoms in the alkyl group. Another preferred synthetic anionic surfactant is an alkyl sulfate or alkyl group having from about 8 to about 24.
And preferably from about 10 to about 18 carbon atoms and from about 1
Water-soluble salts of alkyl polyethoxylate ether sulfates having from about to about 20, preferably from about 1 to about 12, ethoxy groups. Other suitable anionic surfactants are described in October 9, 1979
This is disclosed in US Pat. No. 4,170,565 to Fresher et al.

Nonionic surfactants are usually formed by condensing a hydrocarbon having a reactive hydrogen atom, for example, a hydroxyl, carboxyl, or amino group, with ethylene oxide in the presence of an acid or base catalyst and forming a nonionic surfactant. As the activator, the general formula RA (CH ₂ CH ₂ O) _n H (wherein, R represents a hydrophobic moiety, A represents a group carrying a reactive hydrogen atom, and n represents the average number of ethylene oxide moieties) ). R typically has about 8 to 22 carbon atoms. They can also be formed by condensation of propylene oxide or a copolymer of ethylene oxide and propylene oxide with a low molecular weight compound. n typically varies from about 2 to about 24.

The hydrophobic portion of the nonionic compound is preferably a primary or secondary linear or branched aliphatic alcohol having about 8 to about 24, preferably about 12 to about 20, carbon atoms. A more complete disclosure of suitable nonionic surfactants is found in U.S. Pat.
It can be found in the No. 5 specification. Mixtures of nonionic surfactants may be desirable.

Suitable cationic surfactants include those of the formula R ₁ R ₂ R ₃ R ₄ N
⁺ Wherein R ₁ , R ₂ and R ₃ are methyl groups and R ₄ is C ₁₂
A C ₁₅ alkyl group, or R ₁ is an ethyl or hydroxyethyl group, R ₂ and R ₃ are methyl groups,
R ₄ is a C ₁₂ -C ₁₅ alkyl group).

As amphoteric surfactants, the aliphatic portion can be straight or branched and one of the aliphatic substituents is about 8 to
Having about 24 carbon atoms and at least one further substituent
Derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds containing a single anion solubilizing group. Particularly preferred zwitterionic substances are U.S. Pat. No. 3,925,262 to Laurin et al. Issued Dec. 9, 1975 and U.S. Pat.
Ethoxylated ammonium sulfonates and ethoxylated ammonium sulfates disclosed in 929,678.

As the semipolar nonionic surfactant, a carbon number of about 8 to about
Contains one alkyl or hydroxyalkyl moiety of 28 and two moieties selected from the group consisting of alkyl and hydroxyalkyl groups having 1 to about 3 carbon atoms, which may optionally combine to form a ring structure Water-soluble amine oxides.

Suitable anionic synthetic surfactant salts are selected from the group of the sulfonates and sulfates. Such anionic detergents are well known in the detergent art and have found widespread application in commercial detergents. Preferred anionic synthetic water-soluble sulfonate or sulfate salts have an alkyl group having about 8 to about 22 carbon atoms in the molecular structure.

Examples of such preferred anionic surfactant salts are tallow and the reaction products obtained by sulfating C ₈ -C ₁₈ fatty alcohols derived from coconut oil; alkyl group of about 9 to 15 carbon atoms Sodium alkyl glyceryl ether sulfonate; ether sulfates of fatty alcohols derived from tallow and coconut oil; coconut fatty acid monoglyceride sulfate and coconut fatty acid monoglyceride sulfonate; and about 8 to about
It is a water-soluble salt of paraffinsulfonic acid having 22 carbon atoms. For example, sulfonated olefin surfactants as detailed in US Pat. No. 3,332,880 can also be used. Neutralizing cations for anionic synthetic sulfonates and / or sulfates are represented by common cations such as sodium, potassium, etc., which are widely used in detergent technology.

Here, particularly preferred anionic synthetic surfactant components are:
Represented by water-soluble salts of alkyl benzene sulfonic acids, preferably sodium alkyl benzene sulphonates having about 10 to 13 carbon atoms in the alkyl group.

A preferred type of non-ionic ethoxylate has 12 carbon atoms.
Represented by the condensate of ~ 15 fatty alcohols with about 2 to 10, preferably 3 to 7 moles of ethylene oxide per mole of fatty alcohol. Preferable examples of such ethoxylates, C ₁₂ -C ₁₅ condensation product of oxo alcohols and alcohol per mole 7 moles of ethylene oxide; narrow-cut C ₁₄ -C ₁₅ oxo alcohol and fatty (oxo) alcohol 1 mole condensates of per 7 or 9 moles of ethylene oxide; narrow-cut C ₁₂ -C ₁₃ fatty (oxo) condensates of alcohol and fatty alcohol per mole 6.5 moles of ethylene oxide; and the degree of ethoxylation (EO mole / fatty alcohol mole ) C ₁₀ -C having 5-8
Condensates of ₁₄ coconut fatty alcohols. Fatty oxo alcohols are mainly linear, but can have a certain degree of branching, especially short chains such as methyl branches, depending on the processing conditions and the starting olefin.

A degree of branching of 15% to 50% (% by weight) is often found in commercially available oxo alcohols.

Also, a preferred non-ionic ethoxylated component may be represented by a mixture of two separately ethoxylated non-ionic surfactants having different degrees of ethoxylation.
For example, a nonionic ethoxylate surfactant having 3 to 7 moles of ethylene oxide per mole of hydrophobic moiety and a second ethoxylate having 8 to 14 moles of ethylene oxide per mole of hydrophobic moiety. Preferred nonionic ethoxylated mixture comprises a lower ethoxylate which is the condensation product of C ₁₂ -C ₁₅ oxo alcohols and fatty oxo alcohols per mole to about 3-7 moles of ethylene oxide with up to branch 50% (by weight), Has branching higher than 50% (by weight)
Containing a higher ethoxylate which is the condensation product of C ₁₆ -C ₁₉ oxo alcohols and branched oxo alcohol per mole to about 8 to 14 moles of ethylene oxide.

Suitable bleaching agents in the present compositions are solid water-soluble peroxygen compounds. Preferred compounds include perborate, persulfate, peroxydisulfate, perphosphate and crystalline hydrogen peroxide, preferably percarbonate, formed by reacting hydrogen peroxide with sodium carbonate or urea. Preferred peroxygen bleach compounds are sodium perborate monohydrate and sodium perborate tetrahydrate, and sodium percarbonate. The perborate bleach in the present composition is preferably in the form of small particles, i.e. small particles having a diameter of 0.1-20 [mu] m. The particles are formed by in-situ crystallization of perborate. The term "in-situ crystallization" relates to a process in which perborate particles are formed from larger particles or solutions in the presence of a water / anionic surfactant / detergent builder matrix. Thus, the term includes processes that involve chemical reactions, such as when sodium perborate is formed by reacting a stoichiometric amount of hydrogen peroxide with sodium metaborate or borax. It also includes methods involving dissolution and recrystallization to produce perborate tetrahydrate after dissolving perborate monohydrate. Recrystallization may occur by allowing perborate monohydrate to take up the water of crystallization, so that the monohydrate can be converted to 4 without a dissolution step.
Recrystallization of the hydrate directly.

For example, a perborate compound, such as sodium perborate monohydrate, can be added to an aqueous liquid containing an anionic surfactant and a detergent builder. The resulting slurry is agitated. During this stirring, the perborate compound is
It undergoes a dissolution / recrystallization process. Due to the presence of an anionic surfactant and a detersive builder, this dissolution / recrystallization process results in particles having the desired particle size. Monohydrate is preferred for this aspect of the invention because monohydrate is more susceptible to recrystallization. For reasons of physical stability, it is preferred that the particle size distribution is relatively narrow, ie, less than 10% (wt) has a particle size greater than 10 μm.

Otherwise, perborate compounds can be produced in situ by chemical reactions. For example, sodium metaborate can be added to an aqueous liquid containing an anionic surfactant and a detersive builder. Then a stoichiometric amount of hydrogen peroxide is added with stirring. Stirring is continued until the reaction is completed.

Instead of metaborate, other borate compounds can be used, such as borax and boric acid. If borax is used as the boron compound, a stoichiometric amount of base, such as sodium hydroxide, additionally ensures the reaction of borax to metaborate. The process then proceeds as described above for the metaborate conversion. Instead of hydrogen peroxide, other peroxides (eg, sodium peroxide) may be used as is known in the art.

Preferred liquid detergent compositions contain a water-miscible organic solvent in addition to water. The solvent reduces the solubility of the solid water-soluble peroxygen bleach in the liquid phase, thereby increasing the chemical stability of the composition.

The organic solvent need not be completely miscible with water if sufficient solvent is mixed with the water of the composition to affect the solubility of the solid water-soluble peroxygen bleach in the liquid phase .

Of course, the water-miscible organic solvent must be compatible with the solid water-soluble peroxygen bleach at the pH used.

Examples of suitable water-miscible organic solvents include lower aliphatic monoalcohols, and diethylene glycol and ethers of lower monoaliphatic monoalcohols. Preferred solvents are ethanol, isopropanol, 1-methoxy-2-propanol, ethyl diglycol ether and butyl diglycol ether.

When using sodium perborate, polyalcohols with vic hydroxy groups (eg, 1,2-propanediol and glycerol) are less desirable and the preferred solvent will be ethanol.

In addition, the composition according to the present invention can contain a detergent enzyme. Suitable enzymes include detergent proteases, amylases, lipases, cellulases and mixtures thereof. Preferred enzymes are highly alkaline proteases,
For example, Maxacal (R), Savinase (S
avinase) and Maxapem (R). Silicone coated enzymes as described in EP 0238216 can also be used.

Preferred compositions of the present invention optionally contain a fatty acid component as a builder. However, preferably, the amount of fatty acid is less than 5% by weight of the composition, more preferably less than 4%. Preferred saturated fatty acids are 10
It has 1616, more preferably 12-14, carbon atoms.
Preferred unsaturated fatty acids are oleic acid and palmitoleic acid.

Preferred compositions contain an inorganic or organic builder. Examples of inorganic builders include phosphorus-based builders, such as sodium tripolyphosphate, sodium pyrophosphate, and aluminosilicates (zeolites).

Examples of organic builders are represented by polyacids such as citric acid, nitrilotriacetic acid, and mixtures of tartrate monosuccinate and tartrate disuccinate. Preferred builders for use herein are citric acid and alkyl or alkenyl substituted succinic compounds wherein the alkyl or alkenyl has from 10 to 16 carbon atoms. One example of this group of compounds is dodecenyl succinic acid. High molecular carboxylate builders, including polyacrylates, polyhydroxyacrylates and polyacrylate / polymaleate copolymers, can also be used.

The composition may contain a series of further optional ingredients which are usually used in amounts of additives, usually up to about 5%. Examples of such additives include foam control agents, opacifiers, agents that improve mechanical compatibility in relation to the enamel coated surface, bactericides, dyes, fragrances, brighteners and the like.

In addition to the peroxygen stabilizing compound, preferred liquid compositions of the present invention may further contain other chelating agents in an amount of 0.05% to 5%.

These chelating agents include polyaminocarboxylates, for example, ethylenediaminotetraacetic acid, diethylenetriaminopentaacetic acid, ethylenediaminodisuccinic acid or their water-soluble alkali metals. Other additives include organophosphonic acids. Ethylenediaminetetra (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and aminetri (methylenephosphonic acid) are particularly preferred.

Ascorbic acid, dipicolinic acid, sodium stannate,
A bleach stabilizer such as 8-hydroxyquinoline is also used in an amount of 0.01%.
-1% can be incorporated into these compositions.

The beneficial use of the composition under various conditions of use may require the use of a foam control agent. Generally, all detergent suds are available, but alkylated polysiloxanes, such as dimethylpolysiloxane, often also referred to as silicone, are preferred for use herein. The silicone is often present in an amount not exceeding 1.5%, most preferably 0.05%.
% To 1.0% used.

It may also be desirable to utilize an opacifier, as the opacifier contributes to producing a uniform appearance of the concentrated liquid detergent composition. Examples of suitable opacifiers include LYTRON manufactured by Monsanto Chemical Corporation.
621 includes commercially known polystyrene. Opacifiers are often used in amounts of 0.3% to 1.5%.

The liquid detergent composition of the present invention may further comprise an agent that improves washing machine compatibility, especially in relation to the enamel coated surface.

0.1% further known anti-redeposition and / or compatibilizer
It may be desirable to add ~ 5%. Examples of such additives are sodium carboxymethylcellulose; hydroxy- _C1-6 alkylcellulose; polycarboxylic acid homopolymer or copolymer components, such as polymaleic acid; maleic anhydride in a molar ratio of 2: 1 to 1: 2. A copolymer of an acid and methyl vinyl ether; and having 5 or less carbon atoms,
Preferably, a copolymer of 3 or 4 ethylenically unsaturated monocarboxylic acid monomers, for example, a copolymer of (meth) acrylic acid and an ethylenically unsaturated dicarboxylic acid monomer having 6 or less carbon atoms, preferably 4 The molar ratio of the monomers is in the range from 1: 4 to 4: 1 and the copolymer is described in detail in EP-A-0 066 915 filed May 17, 1982). No.

The composition according to the invention has a pH at room temperature of at least 8.5,
More preferably it has at least 9.0, most preferably at least 9.5.

Examples Example I: A polymer according to formula (ii) is synthesized as follows. 125.0 g of polyacrylic acid (1.44 mol, average molecular weight 2100 as measured by LALLS), 25.9 g (1.44 mol) of distilled water, and 300.0 g of sulfolane (tetramethylene sulfone) were mixed in a 2 liter round bottom flask. This solution was stirred at 45 ° C. until the polyacrylic acid was dissolved. Then, PCl ₃
125.6 ml (197.76 g, 1.44 mol) were added dropwise to the solution over about 1 hour with continuous stirring. Free HCl was removed from the flask with an argon purge. The solution was heated to 100 ° C. by placing the flask in an oil bath and maintained at that temperature for 2 hours before allowing the solution to cool to room temperature. Once at room temperature, CH
600 ml of Cl ₃ was poured into the flask, which caused a yellow solid precipitate to fall out of solution. The precipitate was collected by vacuum filtration, washed 5 times with CHCl _3. (250ml CHC per wash
l ₃ ). The residual CHCl ₃ is removed in vacuo and the precipitate is
And the aqueous solution was refluxed at 100 ° C. for 18 hours to produce a crude gem diphosphonate polymer product. The aqueous solution containing the crude product is concentrated under vacuum at 50 ° C. to about 200 ml, then
The oily gem diphosphonate polymer to which acetone 1.2 was added was recovered by decantation.

The precipitation was carried out four additional times to give compound 72 of formula (ii)
g was produced. Examination of the product by P ³¹ NMR analysis indicated that 43 mol% of the phosphorus in the product was present as hydroxydiphosphonic acid. The product is 12.28% by weight of total phosphorus
Was contained. When the molar ratio of x: y was calculated, it was about 4.0.

Examples II-XI: The following examples illustrate compositions according to the present invention. The composition is obtained by mixing the indicated components in the indicated proportions.

Continuation of the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C11D 3 / 395,3 / 37,3 / 36 D06L 3/02

Claims (11)

(57) [Claims] An aqueous liquid detergent composition comprising a solid water-soluble peroxygen bleach, comprising: Wherein R is a C ₂ -C ₅ alkyl or alkenyl group; Wherein R ₁ is H or CO ₂ H, x and y are integers denoting a molar ratio, and the molar ratio of x: y is lower than 30: 1. (Iii) a mixture thereof. An aqueous liquid detergent composition comprising 0.01 to 5% by weight of a compound to be prepared and further comprising an enzyme. 2. The compound according to claim 2, wherein The composition of claim 1, wherein 3. The compound has the formula (ii) and the ratio of x: y is
The composition of claim 1, wherein the composition is 4: 1. 4. The composition according to claim 1, wherein said compound has the formula (ii) and said compound has a molecular weight of 1,000 to 5,000. 5. The composition according to claim 4, wherein said compound has a molecular weight of 2000. 6. The composition according to claim 1, wherein the solid water-soluble peroxygen bleach is selected from salts of perboric acid or percarbonate. 7. The composition according to claim 6, wherein the solid water-soluble peroxygen bleach is sodium percarbonate. 8. The composition according to claim 1, further comprising diethylenetriaminepenta (methylenephosphonic acid). 9. The composition according to claim 1, further comprising a water-miscible organic solvent. 10. The composition according to claim 9, wherein the water-miscible organic solvent is ethanol. 11. The composition according to claim 1, which has a pH of at least 9.