JP2003524671A - Stable bleaching composition - Google Patents

Abstract

  (57) [Summary] The present invention is a liquid composition comprising a hypohalite bleach and a surfactant mixture of greater than 1.5%, wherein the surfactant mixture comprises an alkyl alkoxylated sulfate surfactant and an alkyl sulfate surfactant. Composition comprising the agent. These compositions exhibit excellent soil removal performance while achieving excellent chemical stability on storage of the composition.

Description

Detailed Description of the Invention

[0001] Technical Field The present invention is, but not limited to various surfaces, e.g. fabric, garments, carpets, and hard surfaces, for example walls, tiles, floors, glass, bathroom surfaces, kitchen surfaces, toilet, dishes, etc. It relates to a liquid bleaching composition which can be used for bleaching, in particular a liquid hypochlorite bleaching composition.

BACKGROUND various surfaces of the invention, for example, bleach-containing compositions for bleaching fabrics, are well known in the art. Of the different bleaching compositions available, those relying on bleaching with hypohalite bleaching agents such as hypochlorite are often selected primarily for reasons of bleaching performance.

When formulating such a liquid bleaching composition, a surfactant, preferably an alkylalkoxylated sulphate surfactant, is added to it to give various stains, including greasy stains and / or enzymatic stains. On top of that it is desirable to achieve good cleaning performance, i.e. good soil removal performance. However, such hypohalite bleach-based compositions containing surfactants, especially high levels of surfactants,
Thus, a problem associated with those containing more than 1.5% by weight of the total composition, preferably more than 3% by weight, is their tendency to become unstable during long term storage. In particular, there is a need for liquid bleaching compositions based on hypohalite bleaches and surfactants, especially high levels of alkylalkoxylated sulphate surfactants, which are chemically stable for long-term storage after manufacture. Sex exists.

Accordingly, a stable liquid hypohalite bleach-containing composition that achieves excellent soil removal performance on a variety of soils while also being chemically stable during storage of the composition. It is an object of the present invention to provide an article.

Thus, the problem is a liquid bleaching composition comprising a hypohalite bleaching agent and a mixture of surfactants greater than 1.5%, wherein the surfactant mixture is an alkylalkoxylated sulfate surfactant. Applicants have surprisingly found here that it is solved by formulating a composition consisting of an agent and an alkylsulfate surfactant. In fact, the combination of alkylalkoxylated sulphate surfactants and alkyl sulphate surfactants in a liquid bleaching composition containing a hypohalite bleach is similar to that of a similar composition without an alkyl sulphate surfactant. Provides superior soil removal performance and improved chemical stability to the composition on storage.

Another advantage of the composition of the present invention is that the presence of the alkylalkoxylated sulphates described above achieves the desired viscosity without the need for further special thickening aids. The level of alkylalkoxylated sulfate and / or its degree of alkoxylation is adjusted by the desired viscosity.

Another advantage of the composition of the invention is that even after storage of the composition, lipsticks, makeup, sebum, oils (mineral and vegetable oils), oily stains such as mayonnaise, eggs and / or grass, cocoa. In addition to effective stain removal performance against various stains including enzymatic stains such as blood, effective bleaching performance, especially whiteness performance effective when used in any laundry application, Is achieved.

Beneficially, the compositions of the present invention provide for different types of surfaces, including fabrics and the like, as well as floors,
Suitable for bleaching hard surfaces such as walls, tiles, glass, kitchen surfaces, bathroom surfaces, toilet bowls and / or dishes. The liquid bleaching composition of the present invention is used both in a diluted state, for example as a detergent additive or a fully formulated laundry detergent composition, and in a net state, for example as a liquid pretreatment (stain remover). And is particularly suitable for various laundry bleaching applications.

SUMMARY OF THE INVENTION The present invention is a liquid composition comprising a hypohalite bleach and greater than 1.5% of a surfactant mixture, wherein the surfactant mixture is an alkylalkoxylated sulfate interface. It relates to compositions comprising an active agent and an alkyl sulphate surfactant.

The present invention also includes a method of bleaching a surface, such as a fabric, wherein said surface is contacted with a bleaching composition as described herein.

The present invention further relates to the use of a surfactant mixture in a liquid bleaching composition comprising a hypohalite bleach, said surfactant mixture comprising an alkylalkoxylated sulfate surfactant and an alkyl. Includes uses that consist of sulphate surfactants, whereby good chemical stability of the composition on storage is achieved.

[0012] The composition detailed description liquid bleaching compositions of the Invention The present invention is formulated as a liquid, including gels and pastes form.
The preferred liquid bleaching compositions of the present invention are aqueous and therefore preferably include water, more preferably from 60% to 98% by weight of the total composition, more preferably from 80% to 97%, most preferably. Includes water in an amount of 85% to 97% by weight.

Hypohalite Bleach As a first essential ingredient, the compositions of the present invention include a hypohalite bleach.
Any hypohalite bleaching agent known to those of ordinary skill in the art may be suitable for use herein. Suitable hypohalite bleaching agents are provided by a variety of sources, examples of which include bleaching agents which produce positive halide and / or hypohalite ions, and organic based delivery of halides. Sources include bleaching agents which are, for example, chloroisocyanurate.

Suitable hypohalite bleaching agents for use herein include alkali metal and alkaline earth metal hypochlorites, hypobromite, hypoiodite, Included are chlorinated trisodium phosphate dodecahydrate, potassium and sodium dichloroisocyanurate, potassium and sodium trichlorocyanurate, N-chloroimide, N-chloroamide, N-chloroamine and chlorohydantoin.

With respect to the bleaching compositions herein, preferred hypohalite bleaching agents among those mentioned above are the group consisting of sodium, potassium, magnesium, lithium and calcium hypochlorite salts and mixtures thereof. Alkali metal or alkaline earth metal hypochlorite selected from. Sodium hypochlorite is the most preferred hypohalite bleach.

Preferably, the bleaching composition of the present invention has a content of active halide in the composition of 0.01% to 20% by weight, preferably 0.25% to 15% by weight of the total composition.
, More preferably 0.1% to 10% by weight, further preferably 0.5% by weight
The hypohalite bleaching agents described above may be included so that they are -8% by weight, most preferably 1% -6% by weight.

Surfactant Mixture As a second essential ingredient, the composition of the present invention is greater than 1.5% by weight of the total composition, preferably 1.51% to 20%, more preferably 3. 0% by weight to 1
5% by weight, more preferably 3.5% to 10% by weight, most preferably 4% to 8% by weight of the surfactant mixture are included. The surfactant mixture includes an alkylalkoxylated sulfate surfactant and an alkylsulfate surfactant.

Suitable alkylalkoxylated sulfate surfactants for use herein are those represented by the formula RO (A) _m SO ₃ M; wherein R is substituted or unsubstituted, linear or branched C ₆ -C _24, preferably of C ₈ -C _20, more preferably of C ₁₂ -C _20, more preferably from C ₁₂ -C _18, most preferably alkyl C ₁₂ -C ₁₄ Is a group; A is an ethoxy or propoxy or butoxy unit; m is greater than zero, preferably at least 0.1, more preferably 0.1-15, more preferably 0.5-6, most preferably 0. .5-4; and M is H or a cation, such as a metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or a substituted anion. It is a monium cation. Alkyl ethoxylated sulphates, and alkyl propoxylated sulphates and alkyl butoxylated sulphates,
Considered herein. Highly preferred herein as alkylalkoxylated sulphate surfactants are alkyl ethoxylated sulphates, ie A is an ethoxy group. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethylpiperdinium, and, for example, ethylenediamine, diethylamine, triethylamine. Examples include cations obtained from alkanolamines, mixtures thereof, and the like. Examples of surfactants are C _{12 to} C ₁₈ alkyl polyethoxylates (1.0) sulfate (C _{12 to} C ₁₈ E (1.0) SM), C _{12 to} C ₁₈ alkyl polyethoxylates ( 2.25) sulfate (C ₁₂ -C ₁₈ of E (2.25) SM), C 12 ~
C ₁₈ alkyl polyethoxylate (3.0) sulfate (C ₁₂ -C ₁₈ E (
3.0) SM), C ₁₂ alkyl polyethoxylate (3.0 -C ₁₄₎ sulfate (C ₁₂ -C ₁₄ of E (3.0) SM) and alkyl polyethoxylate of C ₁₂ -C ₁₈ ( 4.0) is a sulfate (E of _{C 12 ~C 18 (4.0) SM} ). Here, M is conveniently selected from sodium and potassium. Sodium C ₁₂ / C ₁₄ E3 sulphate is for example EMPICOL ESC
It is marketed by Albright & Wilson under the name of 3 (trade name).

The composition of the invention is typically greater than 0.5% by weight of the total composition, preferably 1% to 10% by weight, more preferably 2% to 8% by weight, more preferably 3% to 7% by weight of alkylalkoxylated sulfate surfactant may be included.

Suitable alkyl sulphate surfactants for use herein are of the formula R ₁
It is represented by SO ₄ M. In the formula, R ₁ is an alkyl group having 6 to 24 carbon atoms,
Preferably 8-18, more preferably 10-16, more preferably 12-1.
4 represents a hydrocarbon group selected from the group consisting of a linear or branched chain alkyl group of 4 and an alkylphenyl group of 6 to 18 carbon atoms, and M is H or a cation, for example, an alkali metal cation (eg, Sodium, potassium, lithium, calcium, magnesium, etc. or ammonium or substituted ammonium (eg, methyl-, dimethyl- and trimethyl-ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethylpiperdinium cations. , And quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof). Illustrative surfactants are sulfates of sodium _{C 12 ~C 14 (NaC 12/14 S} ). Preferred alkyl sulphate surfactants are linear alkyl sulphate surfactants or branched chain alkyl sulphate surfactants.

As used herein, the term “linear alkyl sulphate” refers to alkyl chains of 6-24.
Carbon atoms, preferably 8-18, more preferably 10-16, more preferably 12-14 carbon atoms, and the alkyl chain is sulfated at one end. Means fate.

The term “branched-chain alkyl sulfate” as used herein refers to a total of 6 to 24, preferably 8 to 18, more preferably 10 to 16, and further preferably 12 to 14.
With 1 carbon atom, the main alkyl chain being replaced by at least one other alkyl chain, and the alkyl chain being one terminally sulfated alkyl chain.

Particularly preferred branched chain alkyl sulphates for use herein are those having a total carbon number of 10 to 16, preferably 12 to 14, such as Isalchem 123AS (trade name).
Is. Isalchem 123AS®, commercially available from Enichem, is a 94% branched chain C _12-13 surfactant. This _{material, CH 3 - (CH 2)} m -CH (
_{CH 2 OSO 3 Na) - (} CH 2) n -CH 3 ( wherein, n + m = 8~9) can be described as. More preferable alkyl sulfate has a total number of carbon atoms in the alkyl chain of 1
2 is an alkyl sulphate, i.e. sodium 2-butyloctyl sulphate. Such alkyl sulphates are commercially available from Condea under the trade name Isofol 12S.

In a preferred embodiment, the ratio of alkylalkoxylated sulphate surfactant to alkyl sulphate surfactant in the surfactant mixture as described herein is greater than 1: 1 and preferably: The molar ratio of alkylalkoxylated sulphate surfactant to alkyl sulphate surfactant in the surfactant mixture is greater than 1: 1 up to 99: 1, more preferably 6: 4 to 99: 1, more preferably 7. : 3 to 99: 1, most preferably 85:15.

In another embodiment, the surfactant mixture as described herein comprises up to 99% by weight of the total surfactant mixture, preferably up to 95% by weight, more preferably up to 90% by weight. More preferably it comprises up to 85% by weight of alkylalkoxylated sulphate surfactant.

The addition of an alkylsulfate surfactant to a hypohalite bleach-containing composition including an alkylalkoxylated sulfate surfactant increases the chemical stability of the composition upon storage. Also found here. Without being bound by theory, alkyl sulphates prevent or at least reduce the decomposition reaction of hypohalite bleaching agents, such as sodium dichlorite, and alkyl alkoxylated sulphates, and are therefore referred to herein. It is believed to increase the chemical stability of the composition after prolonged storage of the composition as described (eg after storage at room temperature (25 ° C) for 3 months).

The presence of the surfactant mixture as described herein provides excellent stain removal performance for various types of stains, including greasy stains, while achieving excellent chemical stability on storage. provide. Even more beneficially, the present invention allows the formulation of hypohalite bleach-containing compositions with high levels of surfactant while achieving excellent chemical stability on storage. The stain removal performance of the compositions of the present invention can be evaluated by instrument or by visual grading for different types of stains, such as greasy stains.

“Chemical stability” refers to the hypohalite bleaching composition of the present invention at 50 ° C. ± 0.5.
It means not to lose more than 50%, preferably more than 40% of the available chlorine after storage for 5 days at ° C. The% loss of available chlorine is, for example, “La cha
mbre syndicale nationale de L'eau de Javel et des produits connexes ”,
It can be measured using the method described in "Analyses des Eaux et Extraits de Javel" by pages 9-10 (1984). The method described above consists in determining the available chlorine in new compositions, ie immediately after they were made, and in the same composition after 5 days at 50 ° C.

Advantageously, the alkylalkoxylated sulphate used herein is
The compositions herein provide the desired viscosity. The actual alkylalkoxylated sulphate used herein makes the composition relatively thin or thick. Thus, the compositions herein may have viscosities as measured using a Carri-Med CSL2-100 (trade name) rheometer with the following viscosity parameters. That is, angle: 1 ° 58 ′, gap: 60 μm, diameter: 4.0 cm, inner diameter: 63.60 dyne ^* cm ^* s ² , temperature 25 ° C. and shear rate ¹ cp at 30 sec ^−1.
s-2000 cps, preferably 10 cps-1000 cps, more preferably 50 cps-800 cps.

Another aspect of the present invention is the use of a surfactant mixture in a liquid formulation comprising a hypohalite bleach, wherein the surfactant mixture is an alkylalkoxylated sulphate surfactant. And alkyl sulphate surfactants, whereby a good chemical stability on storage of said composition is achieved.

PH The pH of the liquid compositions of the present invention is actually typically 8 when measured at 25 ° C.
-14, preferably 8.5-14, more preferably 9-13.5, still more preferably 9.5-13.5. During the bleaching process, for example 200: 1 (water: composition)
At a dilution level of, the liquid composition of the invention may have a pH of at least 8, preferably at least 8.5, more preferably at least 9.5 for extended periods of time. It is in this alkaline range that the optimum stability and performance of the hypohalite bleach is obtained. The pH range is suitably provided by the pH buffer component, if present, and the alkaline hypohalite bleaching agent described hereinabove. However, in addition to these components, an alkaline source can optionally be used.

Suitable alkaline sources for use herein are caustic, such as sodium hydroxide, potassium hydroxide and / or lithium hydroxide, and / or alkali metal oxides, such as sodium oxide and / or Potassium oxide or a mixture thereof. The preferred alkaline source is caustic, more preferably sodium hydroxide and / or potassium hydroxide. Preferred bleaching compositions herein are up to 10% by weight of the total composition, preferably 0.04% to 5% by weight, more preferably 0.1% to 2% by weight of said alkaline feed. Sources may be included.

Other Optional Ingredients The bleaching composition of the present invention comprises other optional ingredients such as borate or boric acid,
It may further include a pH buffer component, other surfactants, polymers, pigments, dyes, optical brighteners, solvents, stabilizers, enzymes, hydrotropes, fragrances and the like.

Borate or Boric Acid An optional but highly preferred ingredient in the bleaching composition of the present invention is borate, boric acid or mixtures thereof.

Suitable borates include alkali metal borates and mixtures thereof. Suitable alkali metal salts of borates include metaborate, tetraborate, octoborate, pentaborate, dodecaborate, boron trifluoride and alkylboronic acids having 1 to 12 carbon atoms, preferably 1 to 4 carbon atoms. Examples thereof include alkali metal salts of salts. Preferred alkyl borates include methyl borate, ethyl borate and propyl borate. Particularly preferred herein are alkali metal salts of metaborates such as sodium metaborate, potassium metaborate or mixtures thereof.

Borate salts such as sodium metaborate and sodium tetraborate are known as Borax and Societa Ch under the names sodium metaborate and Borax®.
Commercially available from imica Larderello. The bleaching composition of the present invention is 0.01% to 10% by weight of the total composition, preferably 0.1% to 10% by weight, more preferably 0.5% to 5% by weight, further preferably 0.7% to 3% by weight, most preferably 0.7% to 1.5% by weight of the above borate or boric acid or mixtures thereof may be included.

PH Buffer Component The bleaching composition of the present invention, when present, may optionally include a pH buffer component in addition to the pH buffering action that borate may have. Particularly useful are the alkali metal salts of carbonates, polycarbonates, sesquicarbonates, silicates, polysilicates, phosphonates, stannates, aluminates or mixtures thereof.
Preferred alkali metal salts used herein are sodium and potassium salts. Particularly preferred are the alkali metal salts of carbonates. A preferred alkali metal salt of carbonate is sodium carbonate.

The pH buffer component provides a buffering action through the bleach for a long period of time. That is, when compared with the buffering effect obtained with the same composition without the pH buffering component, for example, 200
The pH of the bleaching solution is maintained at a pH of at least 8, preferably at least 8.5, and more preferably at least 9.5 over a long period of time throughout the bleaching process at a dilution level of 1 (water: composition). The bleaching composition of the present invention may include up to 10% by weight of the total composition, preferably 0.01% to 5% by weight, more preferably 0.02% to 3% by weight of a pH buffering component.

Stabilizer Another highly preferred optional component of the present invention is a stabilizer or a mixture thereof, preferably a radical scavenger, a chelating agent or a mixture thereof. Of course, for the purposes of this invention, the stabilizer must be stable to the hypohalite bleach. Highly preferred stabilizers are radical scavengers, alone or in combination with chelating agents.

Suitable radical scavengers for use herein include C 3
-20, preferably 3-18, more preferably 5-14, in total 4n + 2 (
Here, n is an integer of 0 to 4, preferably 1 to 3) and aromatic radical scavengers including unsaturated ring systems having a set of double bonds enclosing electrons.
In fact, said aromatic radical scavengers include benzene derivatives, naphthalene derivatives, annulene derivatives, cyclopentadiene derivatives, cyclopropene derivatives, etc., especially arylcarboxylates and / or arylsulfonates.

Particularly suitable radical scavengers (arylcarboxylates, arylsulfonates and their derivatives) for use in the present invention have one of the following formulas:

[0042]

[Chemical 1]

[0043]

[Chemical 2]

In the formula, X, Y and Z are each —H, —COO ⁻ M ⁺ , —Cl, —Br, —SO ₃ ⁻ M ⁺ , —NO ₂ , —OCH ₃ , or C ₁ -C _10. Are primary and secondary alkyl groups and M is H or an alkali metal, or a mixture thereof. Examples of these constituents include pyromellitic acid (ie, X, Y and Z are —COO ⁻ H ⁺ ); hemimellitic acid, trimellitic acid (ie, X and Y are —COOH,
Z is H). Preferred as radical scavengers for use in the present invention are phthalic acid, sulfophthalic acid, other monosubstituted phthalic acids,
Disubstituted benzoic acids, alkyl -, chloro -, bromo -, sulfo -, nitro - and alkoxy - benzoic acid (i.e., Y and Z are each -H, first and X is C ₁ -C _{1 0} two alkyl ^{_{groups, -Cl, -Br, -SO 3 -}} H +, a -NO ₂ or -OCH ₃ (anisic acid)), as well as substituted sulfonic acid. Highly preferred examples of radical scavengers useful in the present invention are benzoic acid, toluic acid, 4
-Toluenesulfonic acid, 3-nitrobenzoic acid, 2n-octylbenzoic acid, 2n-octylsulfonic acid, anisic acid or a mixture thereof. Most preferred herein are n-anisic acid, benzoic acid, methoxybenzoic acid and / or 3-nitrobenzoic acid.

The radical scavengers mentioned above are the acid forms of these species, ie M is H. The present invention is also intended to cover salt derivatives of these species, ie M is an alkali metal, preferably sodium or potassium. In fact, when the pH of the bleaching composition of the present invention is in the alkaline range, the radical scavenger of the present invention is primarily present as an ionized salt in the aqueous compositions herein. Certain anhydrous derivatives described herein, such as pyromellitic dianhydride, phthalic anhydride, sulphthalic anhydride and the like, may also be used in the present invention.

Suitable chelating agents for use herein are any of those known to those skilled in the art, such as phosphonate chelating agents, phosphate chelating agents, polyfunctional substituted aromatic chelating agents, ethylenediamine N. , N'-disuccinic acid or a mixture thereof.

Suitable phosphonate chelating agents used herein include alkali metal ethane 1-hydroxy diphosphonates (HEDP), alkylene poly (alkylene phosphonates), as well as amino phosphonate compounds such as aminoaminotri (methylenephosphones). Acid) (ATMP), nitrilotrimethylene phosphonate (NTP), ethylenediamine tetramethylene phosphonate and diethylene triamine pentamethylene phosphonate (DTPMP). The phosphonate compounds may exist in their acid form or as salts of different cations with respect to some or all of their acid functionality. Preferred phosphonate chelating agents used herein are diethylenetriaminepentamethylenephosphonate (DTPMP) and ethane 1-hydroxydiphosphonate (HEDP).
). Such a phosphonate chelating agent is DEQUEST (trade name)
It is marketed by Monsanto under the brand name of.

Suitable phosphate chelators are as follows: The phosphonic acid can be condensed in the following reaction.

[0049]

[Chemical 3]

The reaction is repeated with either of the reactive OH groups and the phosphate component is obtained as follows: -A linear or branched polyphosphate with the following structure:

[0051]

[Chemical 4]

[0052]   -Where R is represented by M or

[0053]

[Chemical 5]

—M is a counterion, preferably an alkali metal, and −0 ≦ n + m <500 (if n + m = 0, the compound is a phosphonic acid).

A cyclic polyphosphate (also called metaphosphate) of the following structure:

[0056]

[Chemical 6]

[0057]   -Where R is represented by M or

[0058]

[Chemical 7]

[0059]   -If R is

[0060]

[Chemical 8]

Phosphate compounds contain both cyclic and branched chains and may be referred to as superphosphates) -M is a counterion, preferably an alkali metal, -0 <n + m <500.

All such phosphate components are suitable for use herein,
Preferred is a linear phosphate component where n is 1 (pyrophosphate) and n is 2 (tripolyphosphate (STPP)), most preferably n is 2 (ie R is M). Is. Most commercial forms of this phosphate are those where M is sodium.

Phytic acid, a particularly suitable chelating agent for use herein, is hexaphosphoric acid, which occurs naturally in the seeds of many grains, generally in the form of an insoluble calcium-magnesium salt. It is also obtained from corn steep liquor. Commercial grade phytic acid is commercially available from JT Baker Co., for example as a 40% aqueous solution. The present invention is intended to cover the acid form of phytic acid, as well as its alkali metal salt derivatives. Sodium phytate is commercially available from Jonas Chemical Co. (Brookl
yn. NY). In fact, because the typical pH of the bleaching compositions of the present invention is in the alkaline pH range, the phytic acid component, even when added in its acid form, is predominantly ionized salt in the liquid compositions herein. Exists as. Also,
Mixtures of such salts of phytic acid are also covered.

Polyfunctionally substituted aromatic chelating agents may also be useful in the bleaching compositions herein (US Pat. No. 3,812,044 (Connor et al., Issued May 21, 1974). )reference). A preferred compound of this type in the acid form is dihydroxydisulfobenzene, such as 1,2-dihydroxy-3,5-disulfobenzene.

Preferred biodegradable chelating agents for use herein are ethylenediamine N, N′-disuccinic acid or its alkali metal or alkaline earth metal, ammonium or substituted ammonium salts or mixtures thereof. . Ethylenediamine N, N'-disuccinic acid, especially the (S, S) isomer, is described in US Pat.
4,233 (Hartman and Perkins, 3 November 1987). Ethylenediamine N, N'-disuccinic acid is, for example, ssEDDS (trade name)
Marketed by Palmer Research Laboratories under the tradename of.

Particularly preferred chelating agents for use herein are phosphate chelating agents such as sodium tripolyphosphate, sodium pyrophosphate, phytic acid and mixtures thereof. Typically, the bleaching composition of the present invention will comprise from 0.01% to 10% by weight of the total composition.
%, Preferably 0.01% to 8% by weight, more preferably 0.1% to 5% by weight, most preferably 0.2% to 3% by weight.

Other Surfactants The bleaching composition of the present invention may include further surfactants in addition to the alkylalkoxylated sulphate and alkyl sulphate surfactants described above. Said further surfactants are bleaching compositions according to the invention in an amount of up to 30% by weight of the total composition, preferably 0.1% to 20% by weight, more preferably 1% to 10% by weight. Can be present in things.

Still other suitable surfactants for use herein include other anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, Included are zwitterionic surfactants and mixtures thereof. Naturally, for the purposes of the present invention, the surfactant must be stable to the bleach used.

Particularly preferred nonionic surfactants are alkoxylated nonionic surfactants. Suitable alkoxylated nonionic surfactants for use herein include endcapped and non-endcapped alkoxylated nonionic surfactants. Alkoxylated nonionic surfactant which is not suitable endcap formula _{RO- (C 2 H 4 O)} n H ( wherein, R is a C ₆ -C _22, preferably an alkyl chain of C ₈ -C ₂₂ Or a C _{6 to} C ₂₈ alkylbenzene chain, and n is 0 to 20, preferably 1 to 15, more preferably 2 to 15, and most preferably 2
~ 12) non-endcapped ethoxylated nonionic surfactants. Preferred R chains for use herein are alkyl chains of C ₈ -C _22. The propoxylated, butoxylated, ethoxy / butoxylated, ethoxy / propoxylated, butoxy / propoxylated and ethoxy / butoxy / propoxylated nonionic surfactants are also non-ethoxylated non-ionic agents described herein. It can be used herein in place of or together with the ionic surfactants.

[0070]   Preferred non-endcapped ethoxylated nonionic surfactants have the formulas above.
Less than 16, preferably less than 15, more preferably 14
It has a lower HLB (hydrophilic-lipophilic balance). Those ethoxylated non-io
It has been found that cationic surfactants give good degreasing properties. According to
Suitable for use herein, non-endcapped ethoxylated nonionic
The functional surfactant is Dobanol (trade name) 91-2.5 (HLB = 8.1; R is C₉And C ₁₁ Mixture of alkyl chains, n is 2.5), or Lutensol (trade name) TO3
(HLB = 8; R is C₁₃Alkyl chain, n is 3, or Lutensol (commodity
Name) AO3 (HLB = 8; R is C₁₃And C₁₅Alkyl chain, n is 3)
Or Tergitol (trade name) 25L3 (HLB = 7.7; R is C₁₂~ C₁₅Alkyl chain length of
, And n is 3, or Dobanol (trade name) 23-3 (HLB = 8.
1; R is C₁₂And C₁₃Is a mixture of alkyl chains of n, and n is 3), or
Dobanol (trade name) 23-2 (HLB = 6.2; R is C₁₂And C₁₃Of the alkyl chain
A mixture, n is 2), or Dobanol 45-7 HLB = 11.
6; R is C₁₄And C₁₅Is a mixture of alkyl chains of, n is 7), or
Dobanol (trade name) 23-6.5 (HLB = 11.9; R is C₁₂And C₁₃The alkyl
A mixture of chains, n is 6.5), or Dobanol 25-7 (trade name)
HLB = 12; R is C₁₂And C₁₅Is a mixture of alkyl chains of and n is 7.
), Or Dobanol (trade name) 91-5 (HLB = 11.6; R is C₉And C₁₁A
It is a mixture of rutile chains, n is 5, or Dobanol (trade name) 91-6 (H
LB = 12.5; R is C₉And C₁₁A mixture of alkyl chains of
, Or Dobanol (trade name) 91-8 (HLB = 13.7; R is C)₉And C₁₁of
A mixture of alkyl chains, n is 8), or Dobanol (trade name) 91-10 (
HLB = 14.2; R is C₉And C₁₁Is a mixture of alkyl chains of
, Or Dobanol (trade name) 91-12 (HLB = 14.5; R is C)₉and
C₁₁Is a mixture of alkyl chains, n is 12), or a mixture thereof.
is there. Preferred herein is Lutensol (trade name) TO3 or Lutensol (trade name).
Product name) AO3 or Tergitol (product name) 25L3 or Dobanol (product name) 23-3 or Do
banol 23-6.5 or Dobanol 45-7 or Dobanol 9
1-8 or Dobanol 91-10 or Dobanol 91-12 or those
Is a mixture of. These Dobanol ™ surfactants are commercially available from SHELL.
ing. These Lutensol (trade name) surfactants are commercially available from BASF,
These Tergitol ™ surfactants are commercially available from UNION CARBIDE.

[0071]   Suitable end-capped alkoxylated nonionic with a terminal hydroxyl group
The surfactant has the formula R (A)_n-O-R1 (wherein R and R1 are independently C₆~ C _{twenty two} , Preferably C₈~ C_{twenty two}Alkyl chain of C or₆~ C₂₈Alkylbenzene chain
Where A is an ethoxy or propoxy or butoxy unit and n is 0-2
0, preferably 1-15, more preferably 2-15, most preferably 2-12
It is).

Suitable chemical methods for the preparation of alkoxylated nonionic surfactants for use herein include condensation of the corresponding alcohols with alkylene oxides in the desired proportions. Such methods are well known to those of skill in the art and have been extensively described in the art.

In a preferred embodiment of the present invention, the bleaching compositions herein comprise one of their ethoxylated nonionic surfactants or their ethoxyls with different HLB (hydrophilic-lipophilic balance). A mixture of modified nonionic surfactants may be included. In a preferred embodiment, the bleaching compositions herein are HLB according to the above formula and up to 10 (ie so-called hydrophobic ethoxylated nonionic surfactants), preferably less than 10, more preferably Is an ethoxylated nonionic surfactant having an HLB less than 9, and an HLB according to the above formula and up to 10 (ie, so-called hydrophilic ethoxylated nonionic surfactants), preferably 11 to Includes ethoxylated nonionic surfactants having an HLB of 14. In fact, in this preferred embodiment, the bleaching composition of the invention typically comprises from 0.01% to 15% by weight of the total composition, preferably from 0.5%.
10% by weight of said hydrophobic ethoxylated nonionic surfactant, and 0.01
% To 15% by weight, preferably 0.5 to 10% by weight of the abovementioned hydrophilic ethoxylated nonionic surfactants are included. Such a mixture of ethoxylated nonionic surfactants with different HLBs enables optimum greasy soil scrubbing performance for a wide range of greasy soils where they have different hydrophobic / hydrophilic character Therefore, it may be desired.

Other suitable anionic surfactants for use herein include alkyl sulfonates, alkylaryl sulfonates, C _{6 to} C ₂₀ alkyl alkoxylate linear or branched diphenyl oxide disulfonates. Alternatively, a mixture thereof can be used.

Suitable alkyl sulfonates for use herein include those of the formula RSO ₃
M (wherein R is a C _{6 to} C ₂₀ linear or branched chain, saturated or unsaturated alkyl group,
Preferably an alkyl group of C ₈ -C _18, more preferably an alkyl group of C ₁₀ -C _16, M is H or a cation, such as alkali metal cations (e.g., sodium, potassium, lithium), or ammonium or Substituted ammonium (
For example, methyl-, dimethyl- and trimethylammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethylpiperdinium cations, and quaternary ammonium derived from alkylamines such as ethylamine, diethylamine, triethylamine. Cations, as well as water-soluble salts or acids)) which are).

Suitable alkylaryl sulfonates for use herein include those of the formula RSO ₃ M, where R is aryl, preferably C ₆ -C ₂₀ linear or branched, saturated or unsaturated. alkyl group, preferably a benzyl group of C ₈ -C _18, more preferably substituted by an alkyl group of C ₁₀ -C _16, M is H or a cation, such as alkali metal cations (e.g., sodium, Potassium, lithium, calcium, magnesium, etc.) or ammonium or substituted ammonium (eg, methyl-, dimethyl- and trimethylammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethylpiperdinium cations, and Alkylamines such as ethylamine, di Butylamine, quaternary ammonium cations derived from triethylamine, as well as water-soluble salts or acids of the a) mixtures thereof, and the like) and the like.

The term “secondary C ₆ -C ₂₀ alkyl or C ₆ -C ₂₀ alkylaryl sulfonate” as used herein refers to a group of SO ₃ M or aryl-SO ₃ M group in the above formula. , Is attached to the other carbon atom (second carbon atom) of the alkyl group located between the two carbons of the alkyl chain.

An example of a C ₁₄ -C ₁₆ alkyl sulfonate is the Hostapu available from Hoechst
r (trade name) SAS. One example of a commercially available alkylaryl sulfonate is lauryl aryl sulfonate from Su.Ma. A particularly preferred alkylaryl sulfonate is the alkylbenzene sulfonate available from Albright & Wilson under the Nansa brand name.

The term “linear alkyl sulfonate” as used herein means that the alkyl chain has 6 to 20, preferably 8 to 18 and more preferably 10 to 16 carbon atoms, and the alkyl chain has one terminal. Means an unsubstituted alkyl sulfonate that is sulfonated with. The term “branched-chain sulfonate” as used herein has a total carbon number of 6 to 20, preferably 8 to 18, more preferably 10 to 16, and the main alkyl chain is substituted with at least another alkyl chain. And the alkyl chain is sulfonated at one end.

Suitable C _{6 to} C ₂₀ alkylalkoxylated linear or branched diphenyloxide disulfonate surfactants for use herein are according to the formula:

[0081]

[Chemical 9]

R is a C _{6 to} C ₂₀ linear or branched chain, saturated or unsaturated alkyl group, preferably a C _{12 to} C ₁₈ alkyl group, and more preferably a C _{14 to} C ₁₆ alkyl group. And X ⁺ is H or a cation, such as an alkali metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.). Alkyl alkoxylated linear or branched chain diphenyl oxide disulphonate surfactants particularly suitable C ₆ -C ₂₀ used herein is a linear branched diphenyl oxide disulfonic acid and C ₁₆ to C ₁₂ Diphenyl oxide disulfonate sodium salt, Dowfax 2A1 (trade name) and Dowfax 8390 (trade name), respectively
It is marketed by DOW under the brand name of.

Other anionic surfactants useful herein include soap salts (eg, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts), C ₈ -C olefin sulfonate _24, for example, British Patent sulfonated polycarboxylic acids prepared by sulfonation of the pyrrole substances of alkaline earth metal citrates, as described in No. 1,082,179, alkyl polyglycol ether sulfates of C ₈ -C ₂₄ (
Containing up to 10 moles of ethylene oxide); alkyl ester sulfonates, eg C ₁₄ -C ₁₆ methyl ester sulfonates; acyl glycerol sulfonates, alkyl phosphates, isethionates such as acyl isethionates, N
- acyl taurates, alkyl succinamates and sulfosuccinates, (monoester especially saturated and unsaturated C ₁₂ -C ₁₈₎ sulfosulfuron monoesters of succinate, diesters of sulfosuccinate (especially saturated and unsaturated C ₆ -C ₁₄ diesters), acyl sarcosinates, alkyl polyethoxy carboxylates,
For example in the formula _{RO (CH 2 CH 2 O)} k CH 2 COO-M + ( wherein, R is alkyl of C ₈ -C _22, k is an integer of 0, and M is a soluble salt-forming cation (Which are ions). Also suitable are resin acids and hydrogenated resin acids, such as rosins, hydrogenated rosins, and resin acids and hydrogenated resin acids present in or obtained from tall oil. Yet another example is Surface Active Agents
and Detergents ”(Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are described in US Pat. No. 3,929,678 (La
Ullin et al., published December 30, 1975, column 23 line 58 to column 29 line 23).

[0084]   Suitable amphoteric surfactants used herein include those of the formula R₁R₂R₃NO
(In the formula, R₁, R₂And R₃Are each independently a saturated substitution of 1 to 30 carbon atoms or
Amine oxides having an unsubstituted, linear or branched hydrocarbon chain)
To be Preferred amine oxide surfactants used in accordance with the present invention have the formula R ₁ R₂R₃NO (in the formula, R₁Has 1 to 30 carbon atoms, preferably 6 to 20 carbon atoms, and more preferably
Preferably 8-16, most preferably 8-12 hydrocarbon chains, and R₂And
And R₃Are independently a substituted or unsubstituted linear group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms.
Or a branched hydrocarbon chain, and more preferably a methyl group).
It is minoxide. R₁Is a saturated substituted or unsubstituted linear or branched hydrocarbon
It can be a bare chain. Suitable amine oxides for use herein are, for example,
Natural mixture C₈~ C_TenAmine oxides and C commercially available from Hoechst₁₂ ~ C₁₆Is an amine oxide.

Suitable zwitterionic surfactants for use herein form internal salts to form cationic and anionic hydrophilic groups on the same molecule over a relatively wide range of pH. It contains both basic and acidic groups which occur together. Typical cationic groups are quaternary ammonium groups, but other positively charged groups such as phosphonium, imidazolium and sulfonium groups can be used. Typical anionic hydrophilic groups are carboxylates and sulfonates, but other groups such as sulphates, phosphonates and the like can be used.

[0086]   Preferred zwitterionic surfactants (ie, betaines and betaines) for use herein.
And / or sulfobetaine)         R₁-N⁺(R₂) (R₃) R_FourX^- Where R₁Is a hydrophobic group; R₂Is hydrogen, C₁~ C₆The alkyl of hydroxya
Luquil or other substitution C₁~ C₆Is an alkyl group of R;₃Is C₁~ C₆The al
Kill, hydroxyalkyl or R₂To form a ring structure with N
Other substitution C₁~ C₆Alkyl or C₁~ C₆Carboxylic acid group of, or C ₁ ~ C₆A sulfonate group of R;_FourBinds a cationic nitrogen atom to a hydrophilic group
A moiety, typically an alkylene having 1 to 10 carbon atoms, hydroxyalkylene
Or a polyalkoxy group; and X is a carboxylate or sulphonate
Hydrophilic group, which is a sulfonate group, preferably a sulfonate group.

Preferred hydrophobic groups R ₁ are aliphatic or aromatic saturated or unsaturated, substituted or unsubstituted hydrocarbon chains which may contain linking groups such as amide groups, ester groups. More preferable R ₁ is an alkyl group having 1 to 24 carbon atoms, preferably 8 to 18 carbon atoms, and more preferably 10 to 16 carbon atoms. These simple alkyl groups are preferred for cost and stability reasons. However, the hydrophobic group R ₁ can obtain also the amide group of the _{formula: R a -C (O) -NR} b - in _{(C (R c) 2)} m formula, R _a is up to 8 to 20 carbon atoms An aliphatic or aromatic alkyl group having 8 to 20 carbon atoms, preferably 18 carbon atoms, more preferably 16 carbon atoms,
A saturated or unsaturated, substituted or unsubstituted hydrocarbon; R _b is hydrogen, carbon number 1
~ 4 short-chain alkyl or substituted alkyl, preferably a group selected from the group consisting of methyl, ethyl, propyl, hydroxy-substituted ethyl or propyl and mixtures thereof, more preferably methyl or hydrogen; R _c Is selected from the group consisting of hydrogen and hydroxy groups, and m is 1-4, preferably 2-.
3, more preferably 3, having no more than one hydroxy group on any (C (R _c ) ₂ ) moiety.

Preferred R ₂ is hydrogen or a group selected from the group consisting of alkyl or substituted alkyl having 1 to 4 carbon atoms, preferably methyl, ethyl, propyl, hydroxy, substituted ethyl or propyl and mixtures thereof. Yes, and more preferably methyl. Preferred R ₃ is C ₁ -C ₄ carboxylic acid group, C ₁ -C ₄ sulfonate group, or C ₁ -C ₄ alkyl or substituted alkyl group, preferably methyl, ethyl, propyl, hydroxy-substituted ethyl or A group selected from the group consisting of propyl and mixtures thereof, more preferably methyl. Preferred R ₄ is (CH ₂ ) _n (wherein n is 1 to 10, preferably 1 to 6, and more preferably 1 to 3). Some common examples of betaines / sulfobetaines are described in US Pat. No. 2,082,
275, 2,702,279 and 2,255,082, the contents of which are incorporated herein by reference.

Examples of particularly suitable alkyl dimethyl betaines include coconut-dimethyl betaine, lauryl dimethyl betaine, decyl dimethyl betaine, 2- (N-decyl-N, N-dimethyl-ammonia) acetate, 2- (N-coco N, N-dimethylammonio) acetate, myristyl dimethyl betaine, palmityl dimethyl betaine, cetyl dimethyl betaine, stearyl dimethyl betaine. Coconut dimethyl betaine, for example, is Seppic under the trade name of Amonyl 265 (trade name).
Is commercially available from. Lauryl betaine is the trade name of Empigen BB / L (trade name)
Commercially available from Albright & Wilson.

Yet another example of betaine is lauryl-imino-dipropionate,
It is commercially available from Rhone-Poulenc under the trade name of Mirataine H ₂ C-HA (trade name). Particularly preferred zwitterionic surfactants for use in the bleaching composition of the present invention are:
It is a sulfobetaine surfactant because it gives optimum soap scum cleaning effect. Examples of particularly suitable sulfobetaine surfactants include tallow bis (hydroxyethyl) sulfobetaine, cocoamidopropyl hydroxysulfobetaine. These are Mirataine CBS (trade name) and Rewoteric AM CAS15, respectively.
It is marketed by Rhone Poulenc and Witco under the brand name (brand name).

Further examples of amidobetaine / amidosulfobetaine include cocoamidoethyl betaine, cocoamidopropyl betaine or C ₁₀ -C ₁₄ fatty acylamido propylene (hydropropylene) sulfobetaines. For example, a C ₁₀ -C ₁₄ fatty acyl amide propylene (hydropropylene) sulfobetaine is
Sherex Company under the product name of "Varion CAS (trade name) sulfobetaine"
Is commercially available from.

Suitable amines for use herein have the formula RR′R ″ N.
Wherein R is a saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl group having 1 to 30, preferably 1 to 20 carbon atoms, and R ′ and R ″ are independently It is a saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl group having 1 to 30 carbon atoms, or hydrogen, and a particularly preferred amine used according to the present invention has the following formula: RR'R " It is an amine having N. (In the formula, R has 1 to 30 carbon atoms, preferably 8 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, and most preferably 8 carbon atoms.
-14 saturated or unsaturated, linear or branched alkyl groups and R '
And R "are independently a substituted or unsubstituted C1 to C4, preferably C1 to C3,
It is a linear or branched alkyl group, more preferably a methyl group or a mixture thereof. )

Suitable amines for use herein are, for example, C ₁₂ dimethylamine, coconut dimethylamine, C ₁₂ -C ₁₆ dimethylamine. The amine is Ge
It is marketed by Hoechst under the trade name of namine (trade name), AKZO under the trade name of Aromox (trade name), or Fina under the trade name of Radiamine (trade name).

Suitable quaternary ammonium surfactants for use herein are of the formula R ₁ R ₂ R ₃ R ₄ N ⁺ X ⁻ . Wherein X is a counterion such as halogen, methylsulfate, methylsulphonate or hydroxide; R ₁ is C ₁ -C 1
30, preferably 12-20, more preferably 8-20 saturated or unsaturated,
A substituted or unsubstituted, linear or branched alkyl group; and R ₂ , R ₃ and R ₄ are independently hydrogen, or a saturated or unsaturated group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms. It is a saturated, substituted or unsubstituted, linear or branched alkyl group, more preferably methyl. In the highly preferred quaternary ammonium surfactants herein, R ₁ is a C _{10 to} C ₁₈ , most preferably C ₁₂ , C ₁₄ or C ₁₆ hydrocarbon, and R ₂ , R ₃ and All three of R ₄ are methyl, and X is halogen, preferably bromide or chloride, most preferably bromide.

Examples of quaternary ammonium surfactants are myristyl trimethyl ammonium methyl sulfate, cetyl trimethyl ammonium methyl sulfate, lauryl trimethyl ammonium bromide, stearyl trimethyl ammonium bromide (STAB), cetyl trimethyl ammonium bromide (CTAB) and myristyl. Trimethylammonium bromide (MTAB). Highly preferred herein is the lauryl trimethyl ammonium salt. Such trimethyl quaternary ammonium surfactants are commercially available from Hoechst, or Empigen C
It is commercially available from Albright & Wilson under the trade name M (trade name).

Suitable cationic surfactants for use in the bleaching compositions of the present invention are those with long chain hydrocarbyl groups. Examples of such cationic surfactants include ammonium surfactants such as alkyldimethylammonium halides, and surfactants having the formula: [R ² (OR ³ ) _y ] [R ⁴ (OR ³ ) _y ] ₂ R ⁵ N ⁺ X ⁻ (In the formula, R ² is an alkyl or alkylbenzyl group having 8 to 18 carbon atoms in the alkyl chain, and each R ³ is —CH ₂ CH ₂ —. _{, -CH 2 CH (CH 3)} -, - CH 2 CH (CH 2 OH) -, - CH 2 CH 2 CH 2 - and it is selected from the group consisting of mixtures thereof; each R ⁴ is, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, a benzyl ring structure formed by linking two R ⁴ groups, —CH ₂ CHO
H-CHOCHOR ⁶ CHOHCH ₂ OH (where R ⁶ is any hexose or hexose polymer having a molecular weight of less than 1000) and hydrogen (when y is not zero); R ⁵ is selected from R ⁴ Is the same as or R ²
+ R ⁵ is an alkyl chain having a total number of carbon atoms of 18 or less; y is 0 to 10 respectively.
And the sum of y values is 0-15; and X is any compatible anion). Other cationic surfactants useful herein are those disclosed in US Pat. No. 4,228.
, 044 (Cambre, published October 14, 1980), the contents of which are incorporated herein by reference.

Optional Polymer The optional component of the bleaching composition herein is a polymer. Naturally, for the purposes of this invention, the polymer must be stable in the presence of the hypohalite bleach.

Suitable polymers for use are unsaturated carboxylic acids, polycarboxylic acids, sulphonic acids,
Polymers containing monomeric units selected from the group consisting of phosphonic acids and mixtures thereof. Of the above-mentioned monomer units between them, or comonomers,
Copolymerization with, for example, styrene sulphonic acid is also suitable.

Preferred examples of such polymers are polymers and copolymers of monomeric units selected from the group consisting of acrylic acid, maleic acid, vinylsulphonic acid and mixtures thereof. Further suitable for use herein are the aforementioned polymers and copolymers modified to contain other functional groups such as aminophosphonic acid and / or phosphonic acid units. Further preferred polymers are selected from the group consisting of polyacrylate polymers, copolymers of acrylic acid and maleic acid, copolymers of styrene sulphonic acid and maleic acid, and mixtures thereof, preferably with aminophosphonic acid and / or phosphonic acid groups. Be qualified.

The molecular weight of these polymers and copolymers is preferably 100,000.
It is smaller, most preferably 500 to 50,000. The most suitable polymers and copolymers for use herein are in aqueous bleaching compositions containing 5% by weight sodium chloride adjusted to pH 13 with sodium hydroxide in amounts up to 0.1% by weight. Dissolve.

Commercial polymers suitable for use herein are from BF Goodrich under the Good-Rite tradename, Rohm & Haas under the Acrysol tradename, and Sokal.
It is a polyacrylate polymer sold by BASF under the trade name an (trade name) and Norso Haas under the trade name Norasol (trade name). Further suitable for use herein are copolymers of styrene sulfonic acid and maleic acid,
This is a Versaflex brand name like Versaflex 157 National Starc
from hohm under the name of Acumer (trade name) terpolymer, especially as Acumer (trade name) 3100 from Rohm & Haas. Preferred commercially available polymers are polyacrylate polymers, especially Norasol® 410N (molecular weight 10,000), and polyacrylate polymers modified with phosphonic acid groups Norasol® 440N (molecular weight 4000) and its corresponding acid form. Norasol (trade name) QR784 (molecular weight 4
000).

A preferred polymer for use herein is a polyacrylate polymer modified with phosphonic acid groups, which is Norasol® 440N (molecular weight 400).
0) and its corresponding acid form, Norasol (trade name) QR784 (molecular weight 4000), is commercially available from Norso-Haas. Mixtures of the polymers described herein can also be used in the present invention.

Typically, the bleaching compositions of the present invention are up to 10% by weight of the total composition, preferably up to 1% by weight, more preferably 0.001% to 0.5% by weight and most preferably 0.005% to 0.2% by weight of polymer may be included.

Optional Brightening Agent The bleaching composition of the present invention may also include a brightening agent as an optional component. Naturally, for the purposes of the present invention, the brightener must be stable in the presence of the bleach used. A whitening agent is used to further enhance the bleaching performance of the bleaching compositions herein.
It may be desired herein.

Whitening agents are compounds that have the ability to absorb the ultraviolet wavelengths of light and emit fluorescence by re-emitting visible light. Whitening agents are also called fluorescent whitening agents (FWA) and are widely used in the art, for example EP-A-0265041, EP-A-0322564,
EP-A-0317979 or "Fluorescent whitening agents" by AK
. Sarkar, published by MERROW (especially PP71-72).

Commercially available optical brighteners that may be useful in the present invention are divided into subgroups, examples of which are stilbene, pyrazoline, coumarin, carboxylic acids, methinecyanine, dibenzothiophene-5,5-dioxide, azoles. , 5- and 6-
Examples include, but are not limited to, derivatives of membered heterocycles, as well as other agents. An example of such a brightener is "The Production and Application of Fl
uorescent Brightening Agents '' M. Zahradnik, Published by John Wiley & S
ons, New York (1982). Further optical brighteners that may be used in the present invention include naphthylimide, benzoxazole, benzofuran, benzimidazole and any mixtures thereof.

Examples of optical brighteners useful in the bleaching compositions of this invention are found in US Pat. No. 4,790,8.
It was identified in No. 56. These whitening agents include PHORWH from Verona.
Whitening agents from the ITE (trade name) series can be mentioned. Other brighteners disclosed in this reference include Tinopal-UNPA Tinopal-UNPA (trade name), Tinopal CB.
S (trade name) and Tinopal 5BM (trade name) (Ciba-Geigy); Artic-White CC (trade name) and Artic-White CWD (trade name); 2- (4-styryl-phenyl)-
2H-naphtho [1,2-d] triazole, 4,4′-bis (1,2,3-triazol-2-yl) -stilbene; 4,4′-bis (styryl) bisphenyl; and aminocoumarin Can be mentioned.

Specific examples of whitening agents useful herein include 4-methyl-7-diethyl-
Aminocoumarin; 1,2-bis (-benzimidazol-2-yl) ethylene;
1,3-diphenyl-pyrazoline; 2,5-bis (benzoxazol-2-yl) thiophene; 2-styryl-naphtho- [1,2-d] oxazole; 2- (stilben-4-yl) -2H -Naphtho [1,2-d] triazole, 3-phenyl-7- (isoindolinyl) coumarin; 3-methyl-7- (isoindolinyl) coumarin; 3-chloro-7- (isoindolinyl) coumarin; 4- (isoindolinyl)- 4- (isoindolinyl) -4'-methoxystilbene; sodium 4- (isoindolinyl) -4'-stilbene sulfonate; 4- (isoindolinyl) -4'-phenylstilbene; 4- (isoindolinyl) -3 -Methoxy-4'-methylstilbene; 4- (2-chloroisoindolinyl) -4 '-( -Methylisoindolinyl) 2,2'-stilbenedisulfonic acid; disodium 4,4'-diisoindolinyl-2,2'-stilbenedisulfonate, 4,4'-diisoindolinyl-2,2 ' -Stilbene disulfonamide; disodium 4,4 '-(7,8-dichloro-1-isoindolinyl) 2,2-stilbene disulfonate; disodium 4,4'-(7-
Chloro-1-isoindolinyl) 2,2-stilbene disulfonate; disodium 4,4 '-(6-isopropoxy-1-isoindolinyl) 2,2-stilbene disulfonate; disodium 4,4'-(7,8) -Diisopropyl-1-
Isoindolinyl) 2,2-stilbene disulfonate; disodium 4,4 ′
-(7-Butoxy-1-isoindolinyl) 2,2-stilbene disulfonate; disodium 4,4 '-(6-trifluoromethyl-1-isoindolinyl)
2,2-stilbene disulfonate; disodium 4,4 ′-[6- (1,4
7-trioxanonyl) -1-isoindolinyl] 2,2-stilbene disulfonate; disodium 4,4 ′-(7-methoxymethyl-1-isoindolinyl) 2,2-stilbene disulfonate; disodium 4,4 ′ -(6-Phenyl-1-isoindolinyl) 2,2-stilbene disulfonate; disodium 4
, 4 '-(6-naphthyl-1-isoindolinyl) 2,2-stilbene disulfonate; disodium 4,4'-(6-Methylsulfonyl-1-isoindolinyl) 2,2-stilbene disulfonate; disodium 4, 4 '-(7-cyano-1-isoindolinyl) 2,2-stilbene disulfonate; and disodium 4,4'-[7- (1,2,3-trihydroxypropyl) -1-isoindolinyl] 2,2 -Stilbene disulfonate; disodium 4-isoindolinyl-4'-ethoxy 2,2'-stilbene disulfonate; disodium 4-
Isoindolinyl-4'-methoxy 2,2'-stilbene disulfonate; disodium 4-isoindolinyl-4'-ethoxy-2,2'-stilbene disulfonamide; disodium 4-isoindolinyl-4'-methyl-2,2 ' -Stilbene disulfonamide; 4,4'-bis (4-phenyl-2H-1,2,3
-Triazol-2-yl) -2,2'-stilbene disulfonic acid and mixtures thereof. For additional examples useful herein, see US Pat. No. 3,646,015, US Pat. No. 3,346,502 and US Pat.
, 393, 153.

In fact, 4,4′-bis (4-phenyl-2H-1,2,3-triazole-2
-Yl) -2,2'-stilbene disulfonic acid, a functionally equivalent derivative salt, namely its sodium salt, is named Phorwhite (trade name) CAN and is a subsidiary of Bayer AG, Mo.
Available from bay Chemical Corporation. The amine salt is available from Molay under the name Phorwhite CL solution. Potassium salt is available under the name Phorwhite (trade name) BHC766.

Other particular examples of optical brighteners useful in the present invention are those having the following structural formula:

[0111]

[Chemical 10]

Wherein R ₁ is selected from N-2-bis-hydroxyethyl and NH-2-hydroxyethyl, R ₂ is N-2-bis-hydroxyethyl, N-2-hydroxyethyl- Selected from N-methylamino, morpholino, chloro and amino, and M is a salt-forming cation such as sodium or potassium).

When R ₁ is anilino, R ₂ is N-2-bis-hydroxyethyl, and M is a cation, eg sodium, in the above formula, the brightener is 4,4
'-Bis [(4-anilino-6- (N-2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is Ciba-Ge under the tradename Tinopal-UNPA-GX.
Commercially available from igy Corporation. Tinopal-UNPA-GX is a preferred hydrophilic optical brightener useful in the detergent compositions herein.

In the above formula, R ₁ is anilino and R ₂ is N-2-hydroxyethyl-N-
2-methylamino, and when M is a cation, for example sodium,
The whitening agent is 4,4′-bis [(4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2′-stilbene. It is disulfonic acid disodium salt. This particular brightener species is Tinopal-5B
It is commercially available from Ciba-Geigy Corporation under the trade name of M-GX. Where R ₁ is anilino, R ₂ is morpholino and M is a cation, eg sodium, in the above formula, the whitening agent is 4,4′-bis [(4-anilino-6 -Morpholino-s-triazin-2-yl) amino] -2,2'-
Stilbene disulfonic acid, sodium salt. This particular brightener species is Tinopa
It is commercially available from Ciba-Geigy Corporation under the trade name of l-AMS-GX.

Other substituted stilbene 2,2′-disulfonic acid derivatives also include 4-4′-bis (2-2′styryl sulfonate) biphenyl, which is available from Brightner 49 (trade name).
From Ciba-Geigy, or other hydrophilic brighteners such as Brightner 3 (trade name) or Brightner 47 (trade name) are also available from Ciba-Geigy.

Yet another specific example of whitening agents useful in the present invention includes polycyclic oxazole derivatives, such as benzo-oxazole derivatives or mixtures thereof.
Particularly preferred herein are benzo-oxazole derivatives. An example of such a brightener is benzoxazole 2,2 ′ having the formula C ₁₈ H ₁₀ N ₂ O ₂ S.
-(Thiophenaldyl) bis, Ciba under the trade name of Tinoal SOP (trade name)
-Commercially available from Geigy. This brightener is almost insoluble in water, ie it has a solubility of less than 1 gram / liter. Another example of such a brightener is bis (sulfobenzofuranyl) biphenyl, Tinopal PLC (trade name).
It is commercially available from Ciba-Geigy under the brand name of.

Typically, the bleaching composition of the present invention comprises up to 1.0% by weight of the total composition, preferably 0.005% to 0.5%, more preferably 0.005%. 0.
3% by weight, most preferably 0.008% to 0.1% by weight, may be included.

Surface Treatment Method In the present invention, the bleaching composition of the present invention is used by applying a liquid composition to the surface to be treated. By "liquid" is meant a liquid composition that can be used per se, or in diluted form. By "diluted form" is meant herein that the composition for bleaching fabrics according to the present invention can be diluted with solvent by the user, the preferred solvent being water. Such dilutions can occur, for example, in hand-washing laundry applications, as well as by other means, such as in washing machines. The composition is up to 500: 1 (solvent: composition), preferably 5: 1 to 20.
It may be used at a dilution level of 0: 1, more preferably 10: 1 to 80: 1 (solvent: composition).

By “surface” is meant herein any inanimate surface. These inanimate surfaces include hard surfaces typically found in homes, such as kitchens, bathrooms, or in cars, such as tiles, walls, floors, chrome compounds, glass, smooth vinyl, any plastic, plasticized wood, Table tops, sinks, cooker tops, dishes, sanitary items such as sinks, showers, shower curtains, washbasins, WC, etc., as well as fabrics such as clothing, curtains, comforters, sheets, bath towels, tablecloths, pillows, tents , Upholstered furniture, and carpets, but are not limited to these. Inanimate surfaces include, but are not limited to, household items such as refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers, and the like.

By “treating a surface” is meant herein bleaching and / or disinfecting the surface, as the compositions of the present invention include a bleaching agent. Accordingly, the present invention also includes methods of treating (eg, bleaching) fabrics as an inanimate surface. In such a method, the composition of the present invention is contacted with the fabric to be treated.

This is the so-called “pretreatment mode” in which a liquid bleaching composition as described herein is applied as such to the above fabrics, followed by rinsing or washing and then rinsing.
Alternatively, the bleaching composition as described herein may first be diluted in an aqueous bath, then the fabrics may be dipped, soaked in the bath, and then rinsed,
A bleaching composition which may be made "in a dip mode" or as set forth herein,
Add to the top of the wash liquor produced by dissolving or dispersing a typical laundry detergent.
It can be done in a continuous washing mode. In each case, it is also essential that the fabrics be rinsed after they are contacted with the composition and before the composition has dried out.

In particular, the method of bleaching a fabric according to the invention comprises first contacting said fabric with a bleaching composition of this invention in its diluted form, and then for a period of time sufficient to bleach said fabric. Typically, the fabric is left in contact with the composition for 1 to 60 minutes, preferably 5 to 30 minutes, after which the fabric is rinsed with water. When said fabric is laundered, i.e. with a conventional composition comprising at least one surfactant, said laundering comprises washing said fabric simultaneously with the bleaching composition according to the invention and said detergent composition. It can be carried out by contact, or the washing is carried out before or after the fabric is bleached. Accordingly, said method comprises prior to the step of bleaching the fabric and contacting said fabric with said bleaching composition and / or during the step of contacting said fabric with said bleaching composition and / or Or washing the fabric with a detergent composition, optionally after the step of contacting the fabric with the bleaching composition and before the rinsing step and / or after the rinsing step, optionally comprising at least one surfactant. To enable.

In another embodiment of the present invention, a method of bleaching a fabric comprises contacting the fabric of the present invention with a liquid bleaching composition in its net form, for a time sufficient to bleach said fabric, typically Includes allowing the fabric to remain in contact with the composition for 5 seconds to 30 minutes, preferably 1 to 10 minutes, after which the fabric is rinsed with water. If the fabric is laundered, i.e. with a conventional composition comprising at least one surfactant, the laundering can be carried out before or after the fabric is bleached. In one embodiment of the invention, where the liquid bleaching composition of the invention is contacted with the fabric in its net form, the level of hypohalite bleach is 0.01% to 5% by weight, preferably 0. 1% by weight to 3.5% by weight, more preferably 0.2% by weight
It is preferably 2% by weight, most preferably 0.2% to 1% by weight. Beneficially, the present invention provides a liquid hypohalite bleach that can be applied as is to fabrics for bleaching, despite many years of prejudice to using hypochlorite-containing compositions as such on fabrics. An agent-containing composition is provided.

It is preferred herein to carry out the bleaching method before the fabric is washed. Before washing the fabric with the detergent composition, prior to washing the fabric with the detergent composition, bleaching the fabric with the composition of the invention (dilution and / or net bleaching method), the fabric is first washed. It was then observed that less energy and detergent were used to provide superior whiteness and stain removal than if bleached.

Alternatively, instead of using a net bleaching method (pretreatment application) as described above, with a rinsing step and / or a conventional washing step with a liquid or powder conventional detergent,
The bleaching pretreatment operation may also be carried out in a bucket (hand wash) or in a washing machine, such as the diluted bleaching method described above. In another embodiment, the invention also includes a method of treating a hard surface, such as an inanimate surface. In such a method, the compositions described herein are contacted with the hard surface to be treated. The method of treating a hard surface with the compositions described herein comprises:
Applying the composition to the hard surface and optionally rinsing the hard surface.

In the method of treating a hard surface according to the invention, the composition as described herein can be applied to the surface to be treated in its neat form, or, preferably, using water as the solvent. , 200: 1 (solvent: composition), preferably 2: 1 to 8
It may be applied at a dilution level of 0: 1, more preferably 2: 1 to 60: 1 (solvent: composition). When used as a hard surface bleaching / disinfecting composition, the compositions of the present invention are easy to rinse and provide the treated surface with good gloss characteristics.

[0127] By mixing the ingredients listed in the proportions listed examples were prepared the following composition to further illustrate the present invention.

[0128]

[Table 1]

[0129]

[Table 2]

Tinopal PLC ™ whitening agent is bis (sulfobenzofuranyl) biphenyl, commercially available from Ciba-Geigy. E3S of NaC ₁₂ -C ₁₄ is an alkyl C _12/14 (ethoxy) ₃ sulphate is commercially available from Rhone Poulenc and Albright & Wilson. NaC _12/14 S is sodium C _12/14 alkyl sulfates.

All of the above compositions are chemically stable, ie they do not suffer more than 35% loss of available chlorine after storage at 50 ° C. for 5 days. Furthermore, these compositions may be stored for long periods of time, eg after manufacture, after storage for 3 months at room temperature (25 ° C.), neat or in diluted form, eg 200% by weight.
Achieves excellent stain removal performance when diluted with twice the water and used in laundry applications. These compositions achieve effective cleaning performance when used in any household cleaning application.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) D06L 3/08 D06L 3/08 3/16 3/16 (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG) , KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CR, CU, CZ, DE, D , DM, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR , TT, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Briatore, Andrea Italy, 00155 Rome, Viale, Sacco, E, Vanzetti 163 (72) Inventor Grande, Giovanni Italy , 00136 Rome, Via, Fridgeri 131 (72) Inventor Moss, Michael Allan John Italy, 00123 Rome, Isola, Enne 91 Chi, Largo, Olgiata, Enne 15 (72) Inventor Todini Oreste Italy, 00060 Rome, Kasuterunu Vo, di, Porto, Via, Garibaru di 26 A F-term (reference) 4H003 AB27 AB31 BA12 BA15 DA01 DA04 DA05 DA06 DA07 DA08 DA17 EA15 EA16 EA21 ED02 EE08 FA44

Claims (14)

[Claims] 1. A liquid composition comprising a hypohalite bleach and greater than 1.5% surfactant mixture, wherein the surfactant mixture is an alkylalkoxylated sulphate surfactant and an alkylsulfate. A composition comprising a surfactant. 2. The composition according to claim 1, wherein the hypohalite bleaching agent is an alkali metal or alkaline earth metal hypohalite. 3. The any of the preceding claims, wherein the hypohalite bleach is present in an amount of 0.01% to 20% by weight of the total composition, based on active halide. The composition according to. 4. A composition according to any of the preceding claims comprising greater than 0.5% by weight of the total composition of an alkylalkoxylated sulphate surfactant. 5. The alkylalkoxylated sulphate surfactant is of the formula RO (A) _m SO ₃ M, where R is a substituted or unsubstituted, linear or branched C ₆ -C _{2 4} alkyl group. A is an ethoxy or propoxy or butoxy unit; m is greater than 0; and M is H or a cation). 6. The composition of any of the preceding claims, wherein the alkylalkoxylated sulfate surfactant is an alkylethoxylated surfactant. 7. The alkyl sulfate surfactant is represented by the formula R ₁ SO ₄ M (wherein R ₁ is a substituted or unsubstituted, linear or branched chain alkyl group having 6 to 24 carbon atoms in the alkyl group). And a hydrocarbon group selected from the group consisting of alkylphenyl groups having 6 to 18 carbon atoms; and M is H or a cation). 8. A composition according to any of the preceding claims wherein the ratio of alkylalkoxylated sulphate surfactant to alkyl sulphate surfactant in the surfactant is greater than 1: 1. 9. The surfactant mixture comprises 99% by weight of the total surfactant mixture.
10. A composition according to any of the preceding claims, consisting of up to 8 alkylalkoxylated sulphate surfactants. 10. A composition according to any of the preceding claims, wherein the composition actually has a pH of 8-14 and optionally comprises an alkalinity source. 11. A fabric comprising the step of contacting a fabric with a composition according to any of the preceding claims in diluted form at a dilution level with water up to 500: 1 (water: composition). Processing method. 12. The fabric before the step of contacting the fabric with the composition, and / or during the step of contacting the fabric with the composition, and / or after the composition is removed. The method according to claim 11, which is washed with a detergent composition including at least one surfactant after the rinsing step. 13. A method of treating a fabric, wherein the fabric is contacted with the composition of any one of claims 1 to 10 in its net form for a time sufficient to treat the fabric. A method of treating a fabric comprising leaving the fabric in contact with the composition and then rinsing the fabric in water to remove the composition. 14. Use of a surfactant mixture in a liquid bleaching composition comprising a hypohalite bleach, wherein the surfactant mixture is an alkylalkoxylated sulfate surfactant and an alkylsulfate surfactant. Use of a surfactant mixture which consists of an agent, whereby a good chemical stability of the composition on storage is achieved.