RU2693486C1 - Stable bleaching composition - Google Patents

Abstract

FIELD: chemistry.SUBSTANCE: present invention relates to a hypohalite liquid bleaching composition. Described is a hypohalite liquid bleaching composition having a pH of at least 7.5, containing at least one copper phthalocyanine pigment, or at least one optical bleach, or mixtures thereof, wherein the copper phthalocyanine pigment is present in amount of 0.0005 to 0.005 wt% of total weight of composition, and optical bleaching agent is present in amount of 0.005 to 0.5 wt% of total weight of composition; at least a system of surfactants selected from a group consisting of: a) at least 0.01 wt% anionic surfactant; b) at least 0.01 wt% cationic surfactant; c) at least 0.5 wt% zwitterionic surfactant; d) at least 0.01 wt% nonionic surfactant; or e) a mixture of at least two of a), b), c) and d); and a stabilizer of formula (I) R-O-(RCHCHO)-H (I), where Ris a phenyl group or a benzyl group; Rdenotes a hydrogen atom or a methyl group; and s is integer from 1 to 2; buffering component for maintaining pH is selected from a group consisting of carbonate, polycarbonate, sesquicarbonate salts of alkali metals, boron salts, phosphates, stannates, aluminates and mixtures thereof.EFFECT: development of hypohalite bleaching compositions possessing excellent bleaching ability, which are stable for a long time.12 cl, 4 ex, 4 tbl

Description

The technical field to which the invention relates.

The present invention relates to bleaching compositions, in particular, to hypohalogenitic bleaching compositions that can be used to treat various surfaces.

BACKGROUND OF THE INVENTION

Bleaching compositions for bleaching various surfaces, for example fabrics, are well known in the art. Among the various bleaching compositions available, those that resort to bleaching with a hypohalogenitic bleach, such as hypochlorite, are often preferred, mainly because of its bleaching ability.

However, when using such a hypo-halogen bleaching composition, often faced with stability problems. Thus, the goal of bleach manufacturers has always been to obtain bleach, which is chemically and physically stable for a long time, for example, during certain periods of storage.

In addition, to improve the aesthetic properties of such compositions, it is often desirable to add additional ingredients, such as dyes or pigments, to the hypohalogenic compositions containing bleach. Indeed, highly preferred compositions are colored whitening compositions. As a matter of fact, the individual appearance of the composition facilitates its recognition by consumers, thereby reducing the possibility of improper use of the composition or use of the composition, which can potentially cause irritation.

However, the preparation of such a colored whitening composition is a difficult task due to the aggressiveness of hypohalogenitic bleaching agents. Such compositions often cause many problems associated with their stability.

One of the drawbacks of colored hypohalogen bleaching compositions is that the pigments and / or dyes present in them are decomposed by the bleach. Indeed, hypohalogen bleaches are oxidizing agents, and pigments and dyes are highly susceptible to chemical attack. In some cases, such compounds can be completely decomposed by these oxidizing agents.

As a result, such a decomposition leads to a loss of color of the composition, and in some cases to the deposition of pigments on the bottom of containers containing a similar composition. In addition, as a result of the interaction of such components with the oxidizing agent, premature decomposition of the oxidizing agent and other active substances present in the composition occurs, which reduces the effectiveness of the composition, for example, from the point of view of its cleaning ability. In addition, during the oxidation process, dyes and / or pigments form ions that attack oxidizing agents, which accelerates the decomposition of these agents.

In addition, it is known that the oxidizing agents of the bleaching composition can also cause the degradation of optical brighteners present in the composition in order to increase the effectiveness of the bleaching.

Disclosure of the invention

Thus, an object of the present invention is to develop a composition comprising a hypohalogenoate comprising a pigment and / or an optical bleach, in which the said compound is chemically stable and in which the cleaning ability is retained.

The addition of a stabilizing agent to hypohalogenitic whitening compositions in order to prevent or at least reduce the decomposition of additional ingredients, in particular pigments and / or dyes present in such compositions, is known in the art.

For example, EP-A-0668345 and EP-A-1001010 relate to bleaching compositions containing a hypohalogen bleach and a radical scavenger. However, despite the fact that such stabilizing systems and, in particular, radical scavengers are able to stabilize additional ingredients, it has been found that pigments and / or dyes are still exposed to hypohalogen bleaches and, therefore, it is extremely difficult to reliably incorporate into bleaches compositions containing known stabilizing systems.

Thus, while systems known in the art provide stabilization of additional ingredients in bleaching compositions containing hypohalogenite, it has been found that additional enhancement may be required to stabilize the pigments and / or dyes and compositions.

EP 2112218 describes the use of trimethoxybenzoic acid (TMBA) or its salt as a stabilizer for pigments and / or dyes in a hypohalogenitic whitening composition. TMBA is also able to stabilize Brightener 49, which is rapidly oxidized by hypochlorite. However, TMBA is a costly chemical, and therefore a cheaper and effective substitute for TMBA would be really attractive.

Another stabilizing system is disclosed in JP2006077199, which describes the use of a compound of the formula R ₂ -O- (R ₃ CHCH ₂ O) _s H, such as phenoxyethanol, for stabilizing synthetic dyes in a whitening composition containing a hypohalogenate, an alkaline agent, an alkali metal salt of sulfonic acid. However, a composition containing phenoxyethanol, although it is stable, causes staining of solid surfaces on which it is applied, in the case when the dye is a pigment based on copper phthalocyanine.

Therefore, an object of the present invention is to develop a stable bleaching composition containing phthalocyanine pigments, where the decomposition of these ingredients is significantly reduced, and staining is prevented. In addition, another object of the present invention is the development of hypohalogen bleaching compositions with excellent whitening ability and containing optical bleach, which are stable for a long time.

It was shown that this problem can be solved using the compositions according to claim 1 of the claims. In addition, in accordance with the present invention, the use of the compound of formula (I) according to claim 10 or 11 of the claims and the surface treatment method of claim 12 are proposed.

The best way of carrying out the invention

Whitening composition

The bleaching compositions described in this specification are formulated as liquid compositions, including gel form and paste form. Bleaching compositions are preferably, but not necessarily, formulated as aqueous compositions. Preferred liquid whitening compositions of the present invention are aqueous compositions, and therefore preferably may contain water, more preferably, may contain water in an amount of from 60 to 98%, even more preferably in an amount of from 80 to 96% and, most preferably, in an amount 85% to 97% of the mass. from the total weight of the composition.

An essential aspect of the present invention is that the composition is shelf stable. Under "stable during storage" it should be understood that the compositions of the present invention, as a rule, do not undergo more than 36% loss of available oxidant after 10 days of storage at a temperature of 50 ° C ± 0.5 ° C and, more preferably, not over 32% loss. The percentage loss of available chlorine (% AvCl) can be measured using the method described, for example, in "Analyzes des Eaux et Extraits de Javel" in "La chambre syndicale nationale de l'Eau de Javel et des produits connexes", pp. 9-10 (1984). This method consists in measuring the available oxidant in freshly prepared compositions, i.e. immediately after their preparation, and in the same compositions after 5 days at 50 ° C.

The compositions of the present invention are preferably alkaline compositions. The pH of the liquid compositions of the present invention is from 9.0 to 14, preferably from 10.5 to 14, if measured at a temperature of 25 ° C. It is in the indicated alkaline range that the optimum stability and effectiveness of the composition is achieved, as well as the whiteness of the fabric and / or safety of use.

Thus, the compositions of the present invention may contain an acid or alkalinity source so as to adjust the pH accordingly. Suitable alkalinity sources are caustic alkalis, such as sodium hydroxide, potassium hydroxide and / or lithium hydroxide, and / or alkali metal oxides, such as sodium and / or potassium oxide. The preferred alkalinity source is caustic alkali, more preferably sodium hydroxide and / or potassium hydroxide. A typical content of such alkalinity sources, if they are present, is from 0.1 to 2% by weight, preferably from 0.5 to 1.5% by weight. by weight of the composition.

Hypohalogen bleach

As the first main ingredient, the whitening compositions of the present invention contain a hypohalogen bleach.

Suitable hypohalogen bleaches can be obtained from various sources, including bleach, which leads to the formation of positive halide and / or hypohalogenic ions, as well as bleach, which are sources of organic-based halides, such as chloro-isocyanurates.

Hypohalogenite Suitable bleaches for use herein include alkaline hypochlorites and alkaline earth metal hypobromites, gipoiodity, chlorinated trisodium phosphate dodecahydrate, potassium and sodium dichloroisocyanurates, potassium and sodium trihlortsianuraty, N-hlorimidy, N-chloroamides, N-chloramines, and hlorgidantoiny. In a preferred embodiment of the present invention, said hypohalogen bleach is an alkali metal and / or alkaline earth metal hypochlorite. More preferably, said hypohalogen bleach is an alkali metal and / or alkaline earth metal hypochlorite selected from the group consisting of sodium hypochlorite, potassium hypochlorite, magnesium hypochlorite, lithium hypochlorite and calcium hypochlorite, and mixtures thereof. Even more preferably, said hypohalogen bleach is sodium hypochlorite.

Preferably, the liquid whitening compositions of the present invention include a hypohalogen bleach, so that the content of active halide (for hypochlorite: AvCl2) in the composition is from 0.01% to 15% by weight, more preferably from 0.1% to 10% by weight. , even more preferably, from 0.5% to 7% of the mass. and, most preferably, from 1% to 6% of the mass. by weight of the composition.

Surfactants

As another main ingredient, the whitening compositions of the present invention contain a surfactant system. Said surfactant system may be present in compositions of the present invention in amounts equal to at least 0.01% by weight, preferably from 0.5% to 50% by weight, more preferably from 0.5% up to 30% of the mass. and, more preferably, from 0.5% to 10% of the mass. by weight of the composition. The amount of surfactant should exceed 0.5% in order to avoid staining surfaces.

The surfactant system suitable for use in the present invention is selected from the group consisting of:

a) at least 0.01% of the mass. anionic surfactant;

(b) at least 0.01% of the mass. cationic surfactant;

c) at least 0.5% of the mass. zwitterionic surfactant;

d) at least 0.01% of the mass. nonionic surfactant; or

d) a mixture of at least two of a), b), c) and d).

Anionic surfactants suitable for use in the compositions of the present invention include water-soluble salts or acids of the formula ROSO ₃ M, where R is preferably a C ₁₀ -C ₂₄ hydrocarbon radical, preferably a linear or branched alkyl, having a C ₁₀ -C ₂₀ alkyl a component, more preferably a C ₁₂ -C ₁₈ linear or branched alkyl, and M is H or a cation, in particular, an alkali metal cation (for example, sodium, potassium, lithium) or ammonium or substituted ammonium cations (for example, ka Methyl-, dimethyl- and trimethylammonium cations and quaternary ammonium cations, such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations, derived from alkylamines, such as ethylamine, diethylamine, triethylamine and their mixtures, etc.).

Other suitable for use in the present invention anionic surfactants are water-soluble salts or acids of formula (II)

R ₃ O (A) _m SO ₃ M ₁ (II)

where R ₃ represents an unsubstituted C ₆ -C ₂₄ linear or branched alkyl group, having a C ₆ -C ₂₄ alkyl fragment, preferably C ₁₀ -C ₂₀ linear or branched alkyl, more preferably C ₁₂ -C ₁₈ linear or branched alkyl, A is an ethoxy or propoxy group, m is greater than zero, usually in the range of from about 0.5 to about 30, more preferably from about 0.5 to about 5, and M ₁ is H or a cation, which can be for example, a metal cation (for example, sodium, Alia, lithium, calcium, magnesium etc.), ammonium cation or substituted ammonium. In this description are considered ethoxylated alkyl sulfates, as well as propoxylated alkyl sulfates. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethylammonium and quaternary ammonium cations, such as tetramethylammonium, dimethylpiperidinium and cations derived from alkanolamines, such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like. Typical surfactants are C ₁₂ -C ₁₈ alkyl polyethoxylate (1.0) sulfate, C ₁₂ -C ₁₈ E (1.0) sulfate, C ₁₂ -C ₁₈ alkyl polyethoxylate (2.25) sulfate, C ₁₂ -C ₁₈ E (2.25) sulfate, C ₁₂ -C ₁₈ alkyl polyethoxylate (3.0) sulfate, C ₁₂ -C ₁₈ E (3.0) sulfate and C ₁₂ -C ₁₈ alkyl polyethoxylate (4.0) sulfate, C ₁₂ -C ₁₈ E (4.0) sulfate, where the counterion usually selected from sodium and potassium.

In the most preferred embodiment of the present invention, the surfactant system used is an anionic surfactant system, namely an individual alkyl alkoxy (preferably ethoxy) sulfate, for example, alkyl (ethoxy) 3 sulfate (AE3S) or a combination with an auxiliary surfactant active agent, preferably, C ₂ -C ₁₀ alkyl sulfate and / or C ₈ -C ₂₂ alkyl or aryl sulfonates such as C ₈ -C ₂₂ benzenesulfonate, and / or another alkyl alkoxy sulfates ethoxylated besides 3 vannogo compound. Indeed, the presence of said alkyl (ethoxy) 3 sulfate, alone or in combination with an auxiliary surfactant, provides the desired viscosity to the compositions of the present invention and provides said compositions with an excellent ability to remove stains, especially when used for any wash. Typically, the compositions of the present invention have a viscosity from 25 cPs to 1500 cPs, preferably from 50 to 200 cPs, depending on the ratio of AE3S and auxiliary surfactant when measured using a rheometer, such as Carri-med CSL2-100 ^® with following viscosity measurement parameters: angle: 1 ° 58; clearance: 60; diameter: 4.0 cm; inertia: 63.60 at a temperature of 25 ° C and shear rate 30 1 / s.

Other suitable for use in the present invention anionic surfactants are water-soluble salts or acids of formula (III)

R ₄ O (A) _m CH ₂ COOM ₁ (III)

where R ₄ represents an unsubstituted C ₆ -C ₂₄ linear or branched alkyl group, having a C ₆ -C ₂₄ alkyl fragment, preferably, C ₁₀ -C ₂₀ linear or branched alkyl, more preferably, C ₁₂ -C ₁₈ linear or branched alkyl , A denotes an ethoxy or propoxy group, m is greater than zero, usually has a value from about 0.5 to about 30, more preferably from about 0.5 to about 5, and M ₁ values are as indicated above. This description covers ethoxylated alkyl carboxylates as well as propoxylated alkyl carboxylates. Typical surfactants are C ₁₂ -C ₁₈ alkyl ethoxylated (2.0) carboxylate, C ₁₂ -C ₁₈ alkyl ethoxylated (5.0) carboxylate, C ₁₂ -C ₁₈ alkyl ethoxylated (7.0) carboxylate, where the counterion is usually selected from sodium and potassium .

Other anionic surfactants suitable as detergents may also be used in the present invention.

In accordance with an embodiment of the present invention, the anionic surfactant may be selected from the group consisting of alkyl sulfates, alkyl ether sulfates, sarcosinates, taurates, ether carboxylate, ethoxylated alkyl sulfates, propoxylated alkyl sulfates, or mixtures thereof.

Suitable for use in the present invention nonionic surfactants are nonionic ethoxylated surfactants of the formula (IV):

R ₅ (OR ₆ ) _n OR ₇ (IV)

where R ₅ is a C ₈ -C ₁₈ linear or branched alkyl or alkenyl group, aryl group, alkaryl group, preferably, R ₅ is a C ₁₀ -C ₁₅ alkyl or alkenyl group, more preferably, C ₁₀ -C ₁₅ alkyl group ; R ₆ represents a C ₂ -C ₁₀ linear or branched alkyl group, preferably a C ₄ group; R ₇ is a C ₁ -C ₁₀ alkyl or alkenyl group, preferably a C ₁ -C ₅ alkyl group, and n is an integer ranging from 1 to 20, preferably from 1 to 10, more preferably from 1 to 5; or mixtures thereof. These surfactants are commercially available from BASF Company under the trade name Plurafac ^®, from HOECHST company under the trade name Genapol ^® or from ICI companies under the trade name Symperonic ^®. Preferred consecutively oxylated non-ionic ethoxylated surfactants mentioned above are those commercially available under the Genapol® L 2.5 NR trademark from Hoechst and Symperonic® LF / CS 1100 from ICI.

Other nonionic surfactants suitable for use in the present invention include a class of compounds that can be broadly defined as compounds formed by the condensation of alkylene oxide groups (having hydrophilic properties) with a hydrophobic organic compound, which can be a branched or linear aliphatic ( for example, Coat of arms or secondary alcohol) or an alkyl aromatic compound. The length of the hydrophilic or polyoxyalkylene radical condensed with any particular hydrophobic group can be easily chosen to produce a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic moieties.

Other suitable for use in the present invention zwitterionic surfactants are those that include oxides of amines corresponding to the formula (V):

R ₈ R ₉ R ₁₀ N → O (V)

where R ₈ is a primary alkyl group containing 6 to 24 carbon atoms, preferably _{10 to 18} carbon atoms, and where each R ₉ and R ₁₀ independently represents an alkyl group containing from 1 to 6 carbon atoms. The arrow in the formula is the usual designation of a semi-polar connection. Preferred oxides of amines are those in which the primary alkyl group has a straight chain, at least in most molecules, usually at least 70%, preferably at least 90% of molecules, and oxides are particularly preferred amines in which R contains 10-18 carbon atoms, and both R ₈ and R ₉ denote methyl. Typical examples of preferred amine oxides are N-decyldimethylamine oxide, N-dodecyl dimethylamine oxide, the corresponding amine oxides in which one or both methyl groups are replaced by ethyl or 2-hydroxyethyl groups, and mixtures thereof. The most preferred amine oxide for use in the present invention is N-decyldimethylamine oxide.

Other suitable zwitterionic surfactants for the purposes of the present invention are phosphine or sulfoxide surfactants of the formula (VI):

R ₁₁ R ₁₂ R ₁₃ A → O (VI)

where a denotes a phosphorus atom or sulfur, R ₁₁ represents a primary alkyl group containing 6-24 carbon atoms, preferably 10-18 carbon atoms, and where each R ₁₂ and R ₁₃ each is independently selected from methyl, ethyl and 2-hydroxyethyl. The arrow in the formula is the usual designation of a semi-polar connection.

Suitable surfactants with multiple charges for use in the present invention are zwitterionic detergents, which are betaine and betaine-like detergents, where the molecule contains both basic and acidic groups that form an internal salt, which give the molecule both cationic and anionic hydrophilic groups in a wide range of pH values. Some typical examples of these detergents are described in US Pat. Nos. 2,082,275, 270,227,279 and 2,255,082.

Amphoteric and ampholytic detergents, which can be either cationic or anionic depending on the pH of the system, are represented by such detergents as dodecyl-beta-alanine, N-alkyl taurines, such as those obtained by reacting dodecylamine with sodium isethionate according to the procedure, described in US patent No. 2658072, N- (higher alkyl) aspartic acids, such as those obtained by the method described in US patent. No. 2438091, and products sold under the trademark Miranol, and described in US Pat. No. 2,528,378. Additional synthetic detergents and lists of their commercial sources can be found in McCutcheon's Detergents and Emulsifiers, North American Ed. 1980

Other suitable for use in the present invention zwitterionic detergents include quaternary alkyl ether sulfate amine (or diamine) of the formula (VII):

R ₁₄ [N (A _m SO ₃ M ₁ ) ₄ ] _n (VII)

where R ₁₄ represents an unsubstituted C ₂ -C ₂₄ linear or branched alkyl group, having a C ₄ -C ₂₄ alkyl fragment, preferably, C ₄ -C ₂₀ linear or branched alkyl, more preferably, C ₄ -C ₁₈ linear or branched alkyl , and the values of A, m and M _{1 are} defined above, in particular, m is usually from about 0.5 to about 50, more preferably from about 5 to about 30.

In this description, alkyl ether sulfates of the quaternary diamine are considered, as well as alkyl ether sulfates of the quaternary amine. Typical examples of surfactants are Lutensit z96 from BASF ^® .

Cationic surfactants suitable for use in the compositions of the present invention are those that have a long chain hydrocarbon group. Examples of such cationic surfactants include ammonium surfactants, such as alkyltrimethylammonium halides, and surfactants, which have the formula (VIII):

[R ₁₅ OR ₁₆ ) _y ] [R ₁₇ (OR ₁₆ ) _y ] ₂ R ₁₈ N ⁺ X ^- (VIII)

wherein R ₁₅ represents an alkyl or alkylbenzyl group having from 8 to 18 carbon atoms in the alkyl chain, each R ₁₆ is selected from the group consisting of -CH ₂ CH ₂ -, -CH ₂ CH (CH _3), -CH ₂ CH ₂ CH ₂ - and their mixtures; each R _{17 is} selected from the group consisting of C ₁ -C ₄ alkyl, benzyl ring structures formed by combining two R ₁₇ groups, and a hydrogen atom, when “y” is different from 0; R ₁₈ has the same meaning as R ₁₇ or is an alkyl chain, where the total number of carbon atoms in R ₁₅ plus R ₁₈ does not exceed about 18; each yy is 0 to 10, and the sum of yy is 0 to 15; and X is any compatible anion.

Quaternary ammonium surfactant suitable for the present invention has the formula (IX):

(Ix)

where R ₁₉ is a short-chained alkyl (C ₆ -C ₁₀ ),

where R ₂₀ denotes H or C ₁ -C ₃ alkyl,

where x is 0-4, preferably 0-2, most preferably 0,

where R ₂₁ , R ₂₂ and R _{23 are the} same or different and can be either a short chain alkyl (C ₁ -C ₃ ) or an alkoxylated alkyl of formula X,

where X ^- is a counterion, preferably a halide, for example, chloride, or methyl sulfate.

(X)

where R ₂₄ represents a C ₁ -C ₄ and z is 1 or 2.

Highly preferred cationic surfactants are water soluble quaternary ammonium compounds suitable for use in the present composition, having the formula:

R ₂₅ R ₂₆ R ₂₇ R ₂₈ N ⁺ X ^- (i)

where R ₂₅ represents a C ₈ -C ₁₆ alkyl, each of R ₂₆ , R ₂₇ and R ₂₈ independently represents a C ₁ -C ₄ alkyl, benzyl and (C ₂ H ₄ ) _x H, where x has a value from 2 to 5, and X is an anion. Not more than one of R ₂₆ , R ₂₇ and R ₂₈ must be benzyl.

The preferred alkyl chain length for R ₁ is C ₁₂ -C ₁₅ , in particular, the alkyl group is a mixture of chains of different lengths derived from coconut or palm kernel fat or synthetically synthesized in the production of olefins or in the synthesis of OXO alcohols. Preferred groups for R ₂ R ₃ and R ₄ are methyl, and the anion X can be selected from halogen ions, methosulfate, acetate and phosphate.

Examples of quaternary ammonium compounds of formula (i) suitable for use in the present invention are:

coconut trimethylammonium chloride or bromide;

decyltriethylammonium chloride;

C _12-15 trimethylammonium chloride or bromide;

methyl ethyl ammonium methyl sulfate;

lauryl dimethyl benzyl ammonium chloride or bromide;

ammonium chloride or bromide lauryl dimethyl (ethenoxy) ₄ ;

choline ethers (compounds of formula (i), where R ₂₅ is

dialkyl imidazolines

alkyl, and R ₂₆ R ₂₇ R ₂₈ denote methyl.

The stabilizer of the formula I

As another significant ingredient, the compositions of the present invention contain a stabilizer of the formula (I):

R ₁ -O- (R ₂ CHCH ₂ O) _s -H (I)

where R ₁ represents an optionally substituted phenyl group or benzyl group; R ₂ denotes a hydrogen atom or a methyl group; and s is an integer from 0 to 4.

Preferably, R ₁ is a phenyl group, R ₂ is a hydrogen atom, and s is an integer from 1 to 2.

More preferably, the stabilizer of formula (I) is phenoxyethanol.

Typically, the whitening composition of the present invention may contain from 0.001% to 5%, preferably from 0.005% to 3.0% and, more preferably, from 0.03% to 2.0% by weight. the specified stabilizer of formula (I) by weight of the total composition.

The use of a stabilizer of formula (I), such as phenoxyethanol, in combination with the particular surfactant system described above, has been found to have a synergistic effect on the stability of the pigment and / or optical brightener and on the bleaching composition itself.

Pigment

As another ingredient, the compositions of the present invention may contain at least one metal phthalocyanine pigment. The presence of the pigment in the composition of the present invention is important to obtain a color whitening composition.

The metal in the metal phthalocyanine pigment can be any metal with which the phthalocyanine forms a metal chelate complex, such as Cu, Ni, Mg, Pt, Al, Co, Pb, Ba. Preferably, the metal phthalocyanine pigments contained in the whitening composition of the present invention are copper phthalocyanine pigments. In a highly preferred embodiment of the present invention, the pigment used in the present invention is blue or green copper phthalocyanine pigment.

Blue copper phthalocyanine is commercially available under the brand name Dye Pigmosol Blue 15 ^® from BASF; Direct Blue 86 (sold under the trademark Iragon Blue DBL86 ^® by Clariant); Pigment Blue 15: 1 (commercially available under the brand name Disperse Blue 69-007 ^® from BASF); and Pigment Blue 15: 3 (sold under the brand name Hostafine Blue B2G ^® by the company Clariant). The pigment or their mixture is present in the compositions of the present invention in an amount of from 0.0001% to 0.5% by weight, preferably from 0.0002% to 0.05%, more preferably from 0.0005% to 0.005% and , most preferably, from 0.0005% to 0.003% of the mass.

Optical bleach

The compositions of the present invention may also contain an optical bleach or mixture thereof.

Naturally, for the purposes of the present invention, the bleach must be resistant to the hypo-halogen bleach. Optical bleaches may be required in the present invention to further increase the effectiveness of the whitening compositions of the present invention.

Optical bleaches are compounds that have the ability to fluoresce, absorbing ultraviolet waves and again emitting visible light. Optical brighteners, also called fluorescent whitening agent (FWA), are widely described in the art, see, for example, EP-A-0265041, EP-A-0322564, EP-A-0317979 or “Fluorescent whitening agentsʺ by A.K. Sarkar, published MERROW, in particular, on pp. 71-72.

Commercial optical brighteners, which may be suitable for use in the present invention, can be classified into subgroups, which include, but not necessarily or limited to, stilbene, pyrazoline, coumarin, carboxylic acid, methincyanin, dibenzothiophene-5,5-dioxide derivatives, azoles, 5- and 6-membered heterocycles and other various agents. Examples of such bleaches are described in “The Production and Application of Fluorescent Brightening Agents”, M. Zahradnik, published by John Wiley & Sons, New York (1982). Additional optical brighteners that may also be used in the present invention include naphthyl imide, benzoxazole, benzofuran, benzimidazole, and any mixtures thereof. Examples of optical brighteners that are suitable for use in the compositions of the present invention are those indicated in US Pat. No. 4,790,856. These optical brighteners include the PHORWHITE ^® optical bleachers from Verona. Other optical brighteners listed in this link include: Tinopal-UNPA ^® , Tinopal CBS ^® and Tinopal 5BM ^® , available from Ciba-Geigy; Artic White CC ^® and Artic White CWD ^® ; 2- (4-styrylphenyl) -2H-naphtho [1,2-d] triazoles; 4,4'-bis (1,2,3-triazol-2-yl) stilbenes; 4,4'-bis (styryl) bisphenyls; and aminocoumarins.

Additional specific examples of optical brighteners suitable for use in the present invention include polycyclic oxazole derivatives, such as benzoxazole derivatives or mixtures thereof, and benzoxazole derivatives are most preferred in the present invention. An example of such an optical brightener is 2,2 '- (thiophenaldil) bisbenzoxazole having the following formula C ₁₈ H ₁₀ N ₂ O ₂ S, which is commercially available from Ciba-Geigy under the trademark Tinopal SOP ^® . The bleach indicated is practically insoluble in water, i.e. has a solubility below 1 g per liter. Another example of such an optical bleach is bis (sulfobenzofuranyl) biphenyl, commercially available from Ciba-Geigy under the trademark Tinopal PLC ^® .

Typically, the compositions of the present invention contain bleach or mixtures thereof in amounts up to 1.0% by weight. of the total weight of the composition, preferably, from 0.005% to 0.5%, more preferably, from 0.005% to 0.3% and, most preferably, from 0.008% to 0.1% by weight.

Silicate component

As an optional ingredient, the compositions of the present invention may contain an alkali metal silicate salt. In fact, when the specified ingredient is present in the composition of the present invention, a synergistic effect is achieved, which affects the stability of the pigment and oxidant.

As the alkali metal silicate salt in this specification, silicate or polysilicate alkali metal salts or mixtures thereof are meant. The preferred alkali metal silicate salt used in the present invention is sodium silicate. Preferred compositions of the present invention contain from 0.005% to 5% by weight. alkali metal silicate salt of the total mass of the final composition, preferably from 0.01% to 2% and, more preferably, from 0.05% to 1%.

An alkali metal silicate salt, such as sodium silicate, has been found to have a significant effect on the chemical stability of the whitening composition. In fact, without associating themselves with any theory, the authors of the present invention believe that such compounds protect pigments from the effects of an oxidizing agent originating from hypochlorite. This leads, therefore, to stabilize the amount of pigment in the composition.

In addition, it was found that the presence of silicate salts of alkali metals, such as sodium silicate, in the composition also indirectly leads to less decomposition of the bleaching agent present in said composition. In fact, it is believed that pigments, such as copper phthalocyanine, when decomposed by an oxidizing agent, release a free metal ion, such as copper, which accelerates the decomposition of the hypohalogenite.

Thus, an additional advantage of the whitening compositions of the present invention is that they demonstrate the preservation of high whitening ability during storage. Thus, the cleansing ability of the whitening composition is maintained.

Buffering ingredients to maintain pH

In the compositions of the present invention, the presence of a buffering component to maintain pH is not mandatory, but is preferred.

The authors of the present invention believe that the presence of a buffering component to maintain pH in the compositions of the present invention further contributes to the stabilization of these compositions, effective whitening ability, and also safety to the fabric. In fact, the buffering component for maintaining the pH makes it possible to control the alkalinity in the bleaching solution, i.e. maintain the pH of the whitening solution at a pH of at least 7.5, preferably at least 8, and more preferably at least 8.5 for a longer period starting from the moment the dilution is completed (for example when the whitening composition of the present invention is diluted in a whitening solution with a dilution level of 500: 1 (water: composition)). The authors of the present invention believe that the buffering component to maintain pH can also contribute to the stabilization of the unstable whitening ingredients of the present invention.

The pH buffering component ensures that the pH of the composition is buffered to a pH in the range of 7.5 to 13, preferably from 8 to 12, more preferably from 8.5 to 11.5 after the composition has been diluted in 1- 500 times the weight of water.

Suitable buffering components for use in the present invention are selected from the group consisting of carbonate, polycarbonate, sesquicarbonate, silicate, polysilicate alkali metal salts, boron salts, phosphates, stannates, aluminates, and mixtures thereof. More preferred are carbonate, silicate, and borate alkali metal salts. Preferred alkali metal salts for use in the present invention are sodium and potassium salts.

Particularly preferred buffering components for pH maintenance are selected from the group consisting of sodium carbonate, sodium silicate, sodium borate, sodium metaborate and mixtures thereof.

The starting materials involved in the preparation of the hypohalogen bleach usually contain by-products, for example, calcium carbonate, which leads to the amount of the by-product in the hypo-halogen composition reaching 0.4% by weight. However, in a similar amount, the by-product does not have the buffering effect indicated above.

The liquid whitening compositions of the present invention may contain a mixture of inorganic alkaline compounds, preferably a mixture of at least hydroxide and at least carbonate.

The liquid whitening compositions of the present invention may contain a buffering component to maintain a pH in an amount in the range from 0.5% to 9% by weight, preferably from 0.5% to 5% by weight. and, more preferably, from 0.6% to 3% of the mass. by weight of the composition.

Additional chelating agents

The compositions of the present invention optionally may also contain a chelating agent as an optional ingredient.

Suitable chelating agents may be any chelating agent known to those skilled in the art, such as those selected from the group including phosphonate chelating agents, phosphate chelating agents, polyfunctionally substituted aromatic chelating agents, ethylenediamine-N, N'-diyanthane or mixtures thereof.

Chelating agents, preferably, such phosphate chelating agents, such as phytic acid, may be desirable in the compositions of the present invention, since they provide additional advantages beyond those that the stabilizer used in the present invention, by further improving the stability of optical brighteners, and most allow for effective whitening with any washing in case of aging of the compositions, i.e. after long periods of storage.

Phosphonate chelating agents suitable for use in the present invention may include ethane-1-hydroxydiphosphonates (a) abypdrapdpans (HEDP) alkali metal, alkylenepoly (alkylenphosphonate), and aminophosphonate compounds, including amino aminotri (methylenephosphonic) acid (ATMP), nitrilotrimethylenphosphine, and nitrophenylmethinephosphate (NTPA), nitrile trimethinephosphate (NPMP), methylenphosphonic acid (ATMP), nitrile trimethinephosphate, and nitrophenylphosphate, which are used for the present invention. diethylenetriamine pentamethylene phosphonates (DTPMP). Phosphonate compounds may be present either in their acid form or in the form of salts of various cations in some or all of their acidic functional groups. Preferred phosphonate chelating agents for use in the present invention are diethylenetriamine pentamethylene phosphonate (DTPMP) and ethane-1-hydroxydiphosphonate (HEDP). These phosphonate chelating agents are commercially available from Monsanto under the trade name REQUEST ^® .

Phosphate chelating agents suitable for use in the compositions of the present invention are described in EP-A-0867502 in the section titled “Phosphate Ingredient”, and similar ingredients are specifically included in this description by reference, in particular due to the advantages they provide in bleaching tissue (example is the effect of preventing yellowing) and / or safety benefits for the fabric. All the phosphate ingredients described in EP-A-0867502 in the section titled “Phosphate Ingredient” are suitable for use in the present invention. Preferred phosphate chelating agents for use in the present invention are linear phosphate ingredients, where R in the formula in the Phosphate Ingredient section of EP-A-0867502 is M and where n is 1 (pyrophosphate) or n is 2 (tripolyphosphate (STPP) ), most preferably, where n is 2. The most accessible form of these phosphates is the form, where M is sodium. Indeed, the preferred phosphate chelating agents for use in the compositions of the present invention are pyrophosphate and / or tripolyphosphate (STPP), more preferably sodium phosphate and / or sodium tripolyphosphate (STPP).

Phytic acid, which is particularly suitable for use in the present invention, is hexaphosphoric acid, which is naturally found in the seeds of many cereal grains, usually in the form of an insoluble calcium-magnesium salt. It can also be obtained from corn syrup. Commercial grade phytic acid is commercially available from J.T. Baker Co., for example, in the form of a 40% aqueous solution. The present invention is intended to encompass the acidic form of phytic acid, as well as its derivatives in the form of an alkali metal salt, in particular, sodium or potassium salts. Sodium phytate is available from Jonas Chemical Co (Brooklyn, N.Y.). In fact, since the typical pH of the compositions of the present invention is in the alkaline pH range, the phytic acid component exists in the liquid compositions of the present invention mostly as an ionized salt, even if phytic acid is added in its acid form. Mixtures of such phytic acid salts are also covered. Polyfunctionally substituted aromatic chelating agents can also be used in the compositions of the present invention. See U.S. Patent 3,812,044, issued May 21, 1974 to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes, such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelating agent for use in the present invention is ethylenediamine-N, N'-disuccinic acid or its salts with an alkali metal or alkaline earth metal, its ammonium or substituted ammonium salts, or mixtures thereof. Ethylenediamine-N, N'-disuccinic acid, in particular, the (S, S) isomer is described in detail in US Patent No. 4,704,233, issued November 3, 1987 in the name of Hartman and Perkins. Ethylenediamine-N, N'-disuccinic acid, for example, commercially available under the tradename ssEDDS ^® from the company Palmer Research Laboratories.

The most preferred chelating agents for use in the present invention are phosphate chelating agents, such as sodium pyrophosphate, sodium tripolyphosphate, phytic acid, and mixtures thereof.

Typically, the compositions of the present invention contain up to 10%, preferably from 0.01% to 5% by weight, more preferably from 0.03% to 2% by weight. chelating agent or mixture of chelating agents by weight of the composition.

Washing component

Another optional ingredient of the composition of the present invention is a detergent component. The most preferred detergent components for use in the present invention are water-soluble phosphate detergent components. Specific examples of water-soluble phosphate detergent components include alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymetaphosphate, in which the degree of polymerization varies from 6 to 21, and phytic acid salts.

Specific examples of water-soluble phosphate detergent components include alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymetaphosphate, in which the degree of polymerization varies from 6 to 21, and phytic acid salts.

Other optional ingredients

The whitening compositions of the present invention may additionally contain a variety of optional ingredients, such as bleach activators, dirt removers, dirt repellent polyamine polymers, polymer dirt removers, foam reduction systems / agents, catalysts, dye transfer agents, fragrances, hydrotropic substances and solvents.

Surface Treatment Method

In the present invention, a whitening composition can be used for surface treatment. By "surfaces" in this description is meant any inanimate surface. These inanimate surfaces include, but are not limited to, solid surfaces commonly found in homes, particularly in kitchens, bathrooms, or inside cars, such as tiles, walls, floors, chrome surfaces, glass, smooth vinyl, any plastic, plasticized wood, countertops, sinks, cooking plates, dishes, plumbing fixtures such as sinks, showers, shower curtains, washbasins, toilets, etc., as well as fabrics, including clothes, curtains, curtains, bedding, towels for bathroom, tablecloths, sleeping bags, awnings, upholstered furniture, etc., as well as carpets. Inanimate surfaces also include household appliances, including, but not limited to, refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers, etc.

The term "surface treatment" means in this description the bleaching and / or disinfection of these surfaces, since the compositions of the present invention contain a hypohalogenitic bleach, and cleaning, i.e. removal of various types of stains from surfaces.

Thus, the present invention also encompasses a method for treating (e.g., bleaching) fabric as an inanimate surface. In a similar way, the fabric is contacted with the composition of the present invention.

This treatment can be carried out either in the so-called “pre-treatment mode”, where the liquid whitening composition, as defined in this specification, is applied undiluted onto the indicated fabrics before the fabrics are rinsed or washed, after which the fabrics are rinsed, or in soaking mode ", where the liquid whitening composition, as defined herein, is first diluted with water in the bath, and the fabrics are immersed and soaked in the bath before washing, or" in the wash mode ", where the liquid whitening the position, as defined herein, is added in addition to the washing solution formed by dissolving or dispersing a typical laundry detergent. In any case, it is also important that the fabrics are washed after they have been in contact with the specified composition and before the composition is completely dry.

The method of treating the surfaces of the knitted fabric of the present invention, in particular the fabric, provides effective whitening and / or effective removal of stains, excluding staining of the treated surface due to aging of the compositions.

The compositions of the present invention are preferably contacted with tissues in liquid form. By "liquid form" in this description refers to the liquid compositions of the present invention by themselves in a concentrated form or in a diluted form.

The compositions of the present invention in washing are usually used in diluted form. By "in diluted form" in this description it is meant that the bleaching compositions for fabrics of the present invention can be diluted by the user, preferably with water. Such dilution can be carried out, for example, by hand washing, as well as by other means, for example, in a washing machine. These compositions can be diluted 500 times, preferably from 5 to 200 times and, more preferably, from 10 to 80 times.

More specifically, the method of bleaching fabrics according to the present invention includes the steps of first contacting the fabrics with the bleaching composition of the present invention in its diluted form, and then said fabrics are allowed to remain in contact with the specified composition for a period of time sufficient to bleach these fabrics, usually from 1 to 60 minutes, preferably from 5 to 30 minutes, and then these fabrics are washed with water. If these fabrics are to be washed, for example, with a conventional composition containing at least one surfactant, then this washing can be carried out together with bleaching these fabrics by simultaneously contacting these fabrics with the bleaching composition of the present invention or this washing can be carried out before or after bleaching the specified fabric.

Accordingly, this method allows to bleach fabrics and, optionally, to erase fabrics with a detergent composition containing at least one surfactant, prior to the stage of contacting said fabrics with the specified bleaching composition, and / or at the stage when said fabrics are in contact with specified bleaching composition, and / or after the stage when these fabrics are in contact with the bleaching composition and before the stage of rinsing and / or after the stage of rinsing.

In another embodiment of the present invention, the method of bleaching fabrics comprises the step of contacting the fabrics with the liquid whitening composition of the present invention in its concentrated form, allows said fabrics to remain in contact with said bleaching composition for a period of time sufficient to bleach said fabrics, as a rule for 5 seconds to 30 minutes, preferably from 1 minute to 10 minutes, and then these fabrics are rinsed with water. If these fabrics are going to be washed, for example, with a conventional composition containing at least one surfactant, then this washing can be carried out before or after the fabrics are bleached. In an embodiment of the present invention, when the fabric is in contact with the whitening composition of the present invention in its undiluted form, it is preferable that the amount of the hypohalogen bleach is from 0.01% to 6%, preferably from 0.1% to 5%, more preferably , from 0.3% to 4.5% and, most preferably, from 1.0% to 4.0%. The present invention advantageously relates to hypohalogenite-containing liquid whitening compositions, which can be applied without diluting to a fabric, with the aim of bleaching, despite persistent prejudice against the use of hypohalogenite-containing compositions in undiluted form for treating fabrics.

The bleaching method of the present invention is preferably carried out before washing the fabric. Indeed, it was noted that bleaching these fabrics with the compositions of the present invention (methods using diluted and / or undiluted bleaches) before washing them with a detergent composition provides excellent bleaching and stain removal with less energy and less detergent consumption, than if these fabrics were first washed and then bleached.

Alternatively, instead of carrying out the rinsing stage with water after bleaching using the non-diluting method, as described above (pretreatment), and / or the conventional washing stage with a conventional liquid or powder detergent, treatment using the bleaching method may follow the pre-bleaching stage. dilution, as already indicated in this description, which is carried out both in the bucket (manual treatment) and in the washing machine.

In another embodiment, the invention also includes a method for treating a solid surface as an inanimate surface. In a similar way, the composition, as indicated in this description, is in contact with the treated solid surfaces. Thus, the present invention also relates to a method for treating a solid surface with a composition as described herein, wherein said method comprises the step of applying said composition onto said hard surface, preferably only on contaminated parts, and optionally rinsing said hard surface.

In the method of treating solid surfaces according to the present invention, the composition, as indicated in this specification, may be applied to the surface to be treated in its concentrated form or in diluted form, usually diluted up to 200 times more by mass of water, preferably 80-2 times more water and, more preferably, 60–2 times more water.

When used as bleaching / disinfecting compositions for hard surfaces, the compositions of the present invention are easily washed off and give shine to treated surfaces. By "hard surfaces" is meant any hard surface, as described above in this description, as well as dishes.

The following examples further illustrate the present invention.

Example 1

The following compositions are prepared by mixing the listed ingredients in the indicated proportions (in weight percent, unless otherwise indicated).

Table 1

Compositions I (comparative) II III IV V Sodium hypochlorite 3,000 3,000 3,000 3,000 3,000 Sodium hydroxide 1,200 1,200 1,200 1,200 1,200 Sodium carbonate 1,200 1,200 1,200 1,200 1,200 STPP 0.049 0.049 0.049 0.049 0.049 Incomplete NaCl Chloride 2,500 2,500 2,500 2,500 2,500 AE3S / AS 1,064 1,064 1,064 1,064 1,064 Amine Oxide C ₁₂ -C ₁₄ - - - - - Fatty acid 0.078 0.078 0.078 0.078 0.078 Odorant 0.085 0.085 0.085 0.085 0.085 Tmba 0.100 --- --- --- --- 2-PE --- 0,100 0.150 0,200 0.066 Copper phthalocyanine blue 0,0015 0,0015 0,0015 0,0015 0,0015 Sodium silicate 0,100 0,100 0,100 0,100 0,100 Br49 - - - - - Components in trace amounts and water ---- Balance up to 100% ----

Table 1 (continued)

Compositions VI VII (comparative) Viii Ix X Sodium hypochlorite 3,000 3,000 3,000 3,000 3,000 Sodium hydroxide 1,200 1,200 1,200 1.00 1.00 Sodium carbonate 1,200 1,200 1,200 1.00 1,200 STPP 0.049 0.049 0.049 0.049 0.049 Incomplete NaCl Chloride 2,500 2,500 2,500 2,500 2,500 AE3S / AS 1,064 1,064 1,064 1,064 1,064 Amine Oxide C ₁₂ -C ₁₄ - - - - - Fatty acid 0.078 0.078 0.078 0.078 0.078 Odorant 0.085 0.085 0.085 0.085 0.085 Tmba --- 0,100 --- --- --- 2-PE 0.033 --- 0,100 0.150 0,200 Copper phthalocyanine blue 0,0015 0,0015 0,0015 0,0015 0,0015 Sodium silicate 0,100 0,100 0,100 0,100 0,100 Br49 --- 0.020 0.020 0.020 0.020 Components in trace amounts and water ---- Balance up to 100% ----

Table 1 (continued)

Compositions Xi Xii XIII (comparative) XIV (comparative) Sodium hypochlorite 3,000 3,000 3,000 3,000 Sodium hydroxide 1,200 1,200 1,000 1,000 Sodium carbonate 1,200 1,200 1,700 1,700 STPP 0.049 0.049 0.049 0.049 Incomplete NaCl Chloride 2,500 2,500 --- --- AE3S / AS 1,064 1,064 0.1 0.2 Amine Oxide C ₁₂ -C ₁₄ - - - - Fatty acid 0.078 0.078 --- --- Odorant 0.085 0.085 --- --- Tmba --- --- --- --- 2-PE 0.066 0.33 --- --- Copper phthalocyanine blue 0,0015 0,0015 --- --- Sodium silicate 0,100 0,100 --- --- Br49 0.020 0.020 0.020 0.020 Components in trace amounts and water ---- Balance up to 100% ----

Table 1 (continued)

Compositions XV (comparative) XVI XVII XVIII Sodium hypochlorite 3,000 3,000 3,000 3,000 Sodium hydroxide 1,000 1,000 1,000 1,000 Sodium carbonate 1,700 1,700 1,700 1,700 STPP 0.049 0.049 0.049 0.049 Incomplete NaCl Chloride --- --- --- --- AE3S / AS 0.3 0.1 0.2 0.3 Amine Oxide C ₁₂ -C ₁₄ - - - - Fatty acid --- --- --- --- Odorant --- --- --- --- Tmba --- --- --- --- 2-PE --- 0,100 0,100 0,100 Copper phthalocyanine blue --- --- --- --- Sodium silicate --- --- --- --- Br49 0.020 0.020 0.020 0.020 Components in trace amounts and water ---- Balance up to 100% ----

Table 1 (continued)

Compositions XIX Xx XXI XXII XXIII XXIV Sodium hypochlorite 3,000 3,000 3,000 3,000 3,000 3,000 Sodium hydroxide 1,000 1,000 1,000 1,200 1,200 1,200 Sodium carbonate 1,700 1,700 1,700 1,200 1,200 1,200 STPP 0.049 0.049 0.049 0.049 0.049 0.049 Incomplete NaCl Chloride --- --- --- 2,500 2,500 2,500 AE3S / AS 0.1 0.1 0.1 - - - Amine Oxide C ₁₂ -C ₁₄ - - - 1.1 0.4 1.1 Fatty acid --- --- --- 0.078 0.078 0.078 Odorant --- --- --- 0.085 0.085 0.085 Tmba --- --- --- --- --- --- 2-PE 0.2 0.3 0.1 0,100 0,100 - Copper phthalocyanine blue --- --- --- 0,0015 0,0015 0,0015 Sodium silicate --- --- --- 0,100 0,100 0,100 Br49 0.020 0.020 0,010 - - - Components in trace amounts and water ---- Balance up to 100% ----

The pH of these samples is from 13.0 to 14.0.

STPP = Na tripolyphosphate

TMBA = 3,4,5-trimethoxybenzoic acid

2-PE = 2-phenoxyethanol

Br49 = disodium salt of 4,4'-bis (2-sulfostil) diphenyl

Example 2

The compositions of Table I were tested in the Accelerated Aging Test (RAT) for 10 days at 50 ° C.

Accelerated aging test was performed by storing 100 ml of the sample at 50 ° C (± 0.5 ° C) in a ventilated oven. The bottles used for the test were square 100-ml bottles with caps made of high-pressure polyethylene.

To assess the characteristics of the stabilizer, the following parameters were considered at the end of the RAT:

- Stability of pigment (% residual absorption depending on time ): The decomposition of the pigment over time was assessed using a spectrophotometer in the UV and visible regions of the spectrum (the wavelength λ = 610 nm was chosen). Assuming that the absorption of the composition is directly proportional to the concentration of the pigment, one can trace the decomposition of blue copper phthalocyanine (CuPc) in the RAT process. The “% residual absorption versus time” plot is shown only for relevant pigment stabilization related.

- Hyperstability (% loss of AvCl): Hypochlorite stability was estimated as% loss of AvCl after 10 days. Used the following criteria:

- AvCl loss up to 30%: good stability;

- AvCl loss in the range from 30 to 36%: medium stability;

- AvCl loss of more than 36%: unacceptable stability.

- Stability Brightener 49 (% loss Br49): Stability Brightner 49 was estimated as% loss Br49 after 10 days (for compositions VII-XXI).

The results are presented in table II.

table 2

Composition Loss AvCl (%) Loss of pigment (%) Br49 loss (%) I
(TMBA 0.10%) 22 26 --- II
(2-PE 0.10%) 28 20 --- III
(2-PE 0.15) 32 25 --- IV
(2-PE 0.20%) 36 17 --- V
(2-PE 0.066%) 26 21 --- VII
(TMBA 0.10% + Br49) 21 26 92 Viii
(2-PE 0.10% + Br49) 28 24 67 Ix
(2-PE 0.15+ Br49) 32 13 66 X
(2-PE 0.20% + Br49) 34 17 56 Xi
(2-PE 0.066% + Br49) 26 24 91 XXII
(2-PE 0.100% + AO) 27 nineteen --- XXIII
(2-PE 0.100% + AO) 25 18 --- XXIV
(AO) 60 90 ---

As can be seen from Table II, stabilization of the pigment (blue copper phthalocyanine) using 2-PE is better when compared with TMBA at the same concentration of 0.10% (composition I versus composition II in table 2). In general, as the concentration of 2-PE increases, stabilization of the pigment increases (composition II versus composition IV in table 2), but the loss of AvCl increases, probably due to oxidation of 2-PE itself. In accordance with this trend, with a decrease in the concentration of 2-PE, the stabilization of the pigment is somewhat reduced (composition II versus composition V in table 2), however, the loss of AvCl is also reduced.

Amine oxides are suitable surfactants for these systems (formulations XXII, XXIII and XIV from table I), but it should be noted that the content of surfactant in an amount of less than 0.5% w / w. causes the pigment to stain the surfaces on which the product is applied (see composition XXIII).

Similar trends in pigment and AvCl were observed when samples were prepared with Br49 (compositions VII-XII). Moreover, the stabilization of optical brightener under the action of 2-PE is better compared with TMBA at the same concentration of 0.10% (composition VIII compared with composition VII in table 2). With an increase in the concentration of 2-PE, the stabilization of Br49 increases (composition VIII in comparison with compositions IX-XII in table 2). The stabilization of optical bleach, which is provided by 0.10% TMBA, is comparable to stabilization, which is achieved with a content of 0.066% 2-PE (composition VII versus composition XI in table 2).

Example 3

To further test the suitability of 2-PE as a replacement for TMBA, a test for gas evolution rate (GER) was performed on formulations I and II of table 1.

In fact, the hypochlorite-containing compounds release molecular oxygen as the main decomposition product of the oxidizing agent. This reaction is catalytically enhanced by metallic impurities that are commonly present in water, such as copper and iron. This phenomenon is important for bleaching products, since high gas release rates can cause the bottles to swell, which can be inconvenient from the point of view of aesthetics and packaging safety. For this reason, GER is a key parameter for assessing the sustainability of new formulations.

Test Gas velocity was performed by measuring the pressure increase in a closed bottle containing a known volume of product at 50 ° C (± 0.5 ° C). The increase in pressure and gas velocity are related by the following equation:

,

,

where: V _{S =} solution volume (L);

V _hs = amount of free space above the product (in cubic centimeters);

ΔP / Δt = rate of pressure increase in free space above the product (bar);

T = temperature (K);

R = Universal gas constant [8.31 (j / mol K)]

The equation takes into account:

1) The amount of product in the bottle through the following components:

The increase in pressure in the bottle increases significantly if the filling level increases, for two reasons: (a) the amount of gas released is proportional to the volume of the solution; (b) an increase in pressure for every mole of gas evolved is inversely proportional to the volume of free space.

2) The distribution of released O ₂ between the gas and liquid phases through the following components: This component is a function of temperature and filling level and takes into account the fact that an increase in the partial pressure of O ₂ leads to an increase in the amount of dissolved O ₂ (Henry's Law).

To test the worst case product, compositions I and II were also tested with contamination with iron (500 parts per billion) and copper (250 parts per billion), which were added in addition to the product. As a rule, the product already contains approximately 200 parts per billion of iron and 200 parts per billion of copper that have fallen into it from the starting materials.

For composition II, the following results are obtained (table 3).

Table 3

GER ((ml O ₂ / (500 ml * day)) Day 0 Day 1 Day 3 Day 7 Day 10 Day 14 Composition I
(TMBA 0.10%) 1.0 1.7 1.8 1,3 1,3 0.47 Composition II
(2-PE 0.10%) 1.7 0.7 1,3 1.0 1.0 0.59 Composition I
(Tmba 0.10%) + metals 9.6 9.0 8.0 7.4 11.2 12.22 Composition II
(2-PE 0.10%) + metals 6.0 5.4 4.6 3.6 4.6 4.01

The results of the GER test indicate the exceptional stability of a composition containing 2-PE, with and without metals.

Example 4

The characteristics of the stabilizer were also evaluated in compositions XIII-XXI. Hyperstability (% loss of AvCl) and resistance to bleach (% Br49) were measured in accordance with the methods indicated in Example 2.

The results obtained are illustrated in table 4.

Table 4

Composition Freshly prepared 18 hours 3 days Loss AvCl (%) Br49 loss (%) Loss AvCl (%) Br49 loss (%) Loss AvCl (%) Br49 loss (%) XIII (0.1% AE3S + 0.020% Br49) 0 37 one 78 four 100 XIV (0.2% AE3S + 0.020% Br49) 0 38 one 76 five 100 XV (0.3% AE3S + 0.020% Br49) 0 39 2 76 6 100 XVI (0.1% AE3S + 0.020% Br49 + 0.1% 2-PE) 0 42 one 50 eight 61 XVII (0.2% AE3S + 0.020% Br49 + 0.1% 2-PE) 0 39 2 54 eight 65 XVIII (0.3% AE3S + 0.020% Br49 + 0.1% 2-PE) 0 48 2 56 7 65

It should be noted that the main consumption of Br49 occurs within a few hours, since freshly prepared foods are already losing from 37% to 48% Br49. No effects on the presence of 2-PE are reported at this stage. With longer aging, the stabilizing effect of 2-PE becomes more noticeable, and in products without a stabilizer after 3 days Br49 does not remain at all (the original composition XIII compared to composition XVI in Table 4). The effect of changes in the concentration of AE3S was not observed (composition XVI in comparison with composition XVII and in comparison with composition XVIII in table 9).

Claims (31)

1. Hypalogenolitic liquid whitening composition having a pH of at least 7.5, containing - at least one copper phthalocyanine pigment or at least one optical bleach or mixtures thereof, where the copper phthalocyanine pigment is present in an amount of from 0.0005 to 0.005% wt. by weight of the total composition, and the optical brightener is present in an amount of from 0.005 to 0.5% wt. from the total weight of the composition; - at least a system of surfactants selected from the group consisting of a) at least 0.01% wt. anionic surfactant; b) at least 0.01% wt. cationic surfactant; c) at least 0.5% wt. zwitterionic surfactant; d) at least 0.01% wt. nonionic surfactant; or e) mixtures of at least two of a), b), c) and d); and - stabilizer of formula (I)

, where R ₁ represents a phenyl group or a benzyl group; R ₂ denotes a hydrogen atom or a methyl group; and s is an integer from 1 to 2, - the buffering component for pH maintenance is selected from the group consisting of carbonate, polycarbonate, sesquicarbonate salts of alkali metals, boric salts, phosphates, stannates, aluminates and their mixtures. 2. Hypalogenated liquid whitening composition according to claim 1, containing at least one copper phthalocyanine pigment and at least one optical bleach. 3. Hypalogenated liquid whitening composition according to claim 2, where the copper phthalocyanine pigment is a blue or green copper phthalocyanine pigment. 4. Hypalogenated liquid whitening composition according to claim 1, where the anionic surfactant has the following formula (II)

where R ₃ is an unsubstituted C ₆ -C ₂₄ linear or branched alkyl group, having a C ₆ -C ₂₄ alkyl fragment, A is an ethoxy or propoxy group, m is greater than zero, and M ₁ is H or a cation. 5. Hypalogenated liquid whitening composition according to claim 1, where the anionic surfactant is selected from the group consisting of alkyl sulfates, alkyl ether sulfates, sarcosinates, taurates, ether carboxylate, alkyl ethoxylated sulfates, alkyl propoxylated sulfates or mixtures thereof. 6. Hypalogenated liquid whitening composition according to claim 1, wherein the cationic surfactant is a quaternary ammonium compound. 7. Hypalogenated liquid whitening composition according to claim 1, where the surfactant having a plurality of charges is selected from the group consisting of betaines and amine oxides. 8. Hypohalogenic liquid whitening composition according to claim 1, wherein the stabilizer of formula (I) is 2-phenoxyethanol. 9. The use of the stabilizer of formula (I)

in combination with a buffering component to maintain a pH selected from the group consisting of carbonate, polycarbonate, sesquicarbonate salts of alkali metals, boron salts, phosphates, stannates, aluminates, and mixtures thereof to stabilize a hypohalogenic liquid whitening composition containing at least one copper phthalocyanine pigment, where R ₁ is an optionally substituted phenyl group or a benzyl group; R ₂ represents a hydrogen atom or a methyl group; and s denotes an integer from 1 to 2. 10. Use of a stabilizer of formula (I)

in combination with a buffering component to maintain a pH selected from the group consisting of carbonate, polycarbonate, sesquicarbonate salts of alkali metals, boron salts, phosphates, stannates, aluminates, and mixtures thereof to stabilize a hypohalogenic liquid whitening composition containing at least one optical bleach, where R ₁ is an optionally substituted phenyl group or benzyl group; R ₂ represents a hydrogen atom or a methyl group; and s denotes an integer from 1 to 2. 11. The method of surface treatment composition, such as the composition defined in any of paragraphs. 1-8, while the method includes the stage of applying the specified composition in its concentrated form, in its diluted form or in its dissolved or dispersed form, at least part of the surface for a period of time sufficient to bleach the specified surface, before as the specified surface is optionally washed and / or rinsed. 12. The method according to claim 11, wherein said surface is a fabric.