Liquid bleaching compositions

[Detailed Description of the Invention]

The present invention relates to the water fluid bleaching constituent which may be used in order to bleach textiles, the hard surface, and other substrates effectively. The water bleaching constituent of the present invention contains insoluble in water organicity peroxy acid substantially [ a solid ] as a bleach. Generally, organic peroxy acid is very effective bleaches. The peroxy acid which may be used by the present invention is the compounds of insoluble in water nature substantially [ a solid ]. detailed in the letter -- " -- substantially insoluble in water -- sex" -- a term points out that the degree of aqueous solution in room temperature is less than about 1%. Generally, the peroxy acid which has at least about seven carbon atoms does not dissolve in Almost water, when using it by the present invention. The general formula of these substances,<img file="JPH0360877B2_D0001.tif" />the inside of a formula, and R -- about [ which is not replaced / substitution or / carbon number 6~] -- it is a phenylene group which is not replaced [ the Al Killen machine of 20 substitution, or ] -- Y -- hydrogen, halogen, Alkyl, and Aryl -- or [Formula]

or [Formula]

It comes out. It Have. Then of a fatty series is [ the organic peroxy acid which may be used by the present invention ] also good at an aromatic series including one piece or two peroxy machines. When organic peroxy acid is a fatty series, unreplaced acid has the following general formula.<img file="JPH0360877B2_D0002.tif" />(The inside of a formula and Y are H and CH.)₃CH₂It is Cl, COOH, or COOOH, and when a certain organic peroxy acid of n is an aromatic series for the integer of 6~20, unreplaced acid has the following general formula.<img file="JPH0360877B2_D0003.tif" />(The inside of a formula and Y are hydrogen, Alkyl, Alkyl halogen, halogen, COOH, or COOOH) the typical mono-peroxy acid used by the present invention is Alkyl peroxy acid, Alke nil peroxy acid, and Aryl peroxy acid -- for example () Peroxybenzoic acid and ring-substitution peroxy benzoin fellows (example: peroxy alpha-naphthoic acid), () Substitution and unreplaced fatty series mono-peroxy acid (example: peroxy lauric acid and peroxy stearic acid) , are illustrated. the typical Jiper oxy acid used by the present invention is Alkyl di pen oxy acid, Alkenyl di peroxy acid, and Aryldi peroxy acid -- for example () 1, 12-Diperoxydde can dione acid, () 1, 9-Diperoxy azelaic acid, () Diperoxybrusil acid, Diperoxy sebacic acid and Diperoxy isophthalic acid, () 2-Decylji peroxy butane 1 and 4-dione acid are illustrated. [Description of the Prior Art] The water bleaching constituent in which a solid contains insoluble in water organicity peroxy acid substantially is written in U.S. Pat. No. 3996152 and a U.S. Pat. No. 4017412 specification. These constituents are the consistency or the gel-like products which use the organicity / inorganic consistency agent of starch or non-starch. The greatest fault of the Like consistency indicated to the above-mentioned conventional technology or a gel-like meter (system) is that viscosity becomes very high in order to make solid peroxy acid suspended stably, and it becomes impossible to pour in well. With the hypoviscosity fluid (for example, fluid made to consistency-ize by line polymer like line polyacrylamide) which the quantity of the viscous agent was decreased extremely, was easy to pour in, and was adjusted, It is impossible to make solid peroxy acid suspended, or a front fluid has a fault which lacks in storage stability, in order that the suspension network (polymer suspending network) of polymer may break. Since Mostly of the suspension nature currently used by the above-mentioned conventional technology or consistency polymer (they are not all) does not permit an electrolyte at all, another fault of dissociating immediately also has an electrolyte. Therefore, in the system of the above-mentioned patent, it will be restricted to the constituent which comprises peroxy acid, water, and a viscous agent and very little addition salt. If the suspended state peroxy acid constituent containing temporary very little (namely, less than 1%) polymers or starch consistency agents and which can be poured in is dried, Although this is what may happen when a user spills an incorrect intermediary sample or hangs down an adjustment thing to Edge of several drop bottle, the very dangerous and harmful solid concentration peroxy acid of a dry state will remain. the statement of U.S. Pat. No. 3996152 and a U.S. Pat. No. 4017412 specification -- therefore, the prepared Like manufacture things also have the fault of lacking the storage stability in high temperature. [Explanation of the present invention] The object of the present invention is to provide the water fluid bleaching constituent which was improved that the above-mentioned fault should be canceled substantially and in which a solid contains insoluble in water organicity peroxy acid substantially. The another object of the present invention is to provide the aqueous suspension of the organic peroxy acid of insoluble in water nature substantially [ the solid which may be poured in stably easily chemically and physically ]. it becomes clear from explanation of these objects and the present invention -- I will come out -- a solid with other specific objects -- it may be attained by making the organic peroxy acid of insoluble in water nature suspended that it is granular and substantially in the acid water fluid containing a surface-active agent. The water fluid containing a surface-active agent has the operation which is what combined one sort, or the surface-active agent and electrolyte beyond it, and may make solid particles Susuki without Then and a viscous agent. The preparing method of the suspension based on a surface-active agent is publicly known to a person skilled in the art, and usually needs nonionic and/or an anionic surface-active agent, and an electrolyte for him. Of course, it is also possible to use other surface-active agents like positive ion nature or both ionic surfactants one sort or more. Although various surface-active agents or the mixture of those is actually used in combination with several sorts of electrolytes, GCC matter salt, the electrolyte, for example, carbonate, which are not compatibility in the electrolyte, for example, the chloride, and bromide which oxidize easily with peroxy acid, an iodide, and desired acid PH range, is excepted from the surface-active agent fluid constituent which made the peroxy acid of the present invention suspended. It is as follows when the combination of the surface-active agent/electrolyte which was suitable in order to prepare the fluid containing the surface-active agent which made peroxy acid suspended is illustrated. (a) The following surface-active agents () Coconut diethanolamide / alkyl bezel sulfonate;() C₉-C₁₆Alcoholic ethoxy Rut / alkyl bezel sulfonate; () Laurylether sulfate / alkyl bezel sulfonate; () Alcoholic ethersulfate; (b) Put together as the following electrolytes. () sodium sulfate -- and/or () Sodium sulfate: Appearance viscosity is comparatively low and the surface-active agent content fluid which the (lamellar) surface-active agent content fluid and appearance viscosity of stratified structure are [ a phase ] higher, for example, is in other phase states like a hexagon phase is contained in the fluid containing the surface-active agent which may make peroxy acid suspended. It is 25degreeC and is 21 sec.^-1The viscosity measured by Disconnection speed which is not carried may be 50~20000cP (0.05~20Pascal seconds). Therefore, although the water liquid products which have the viscosity of a mentioned range are included by the present invention, the product of 0.25PaS~12PaS has especially more preferred viscosity about 0.20 PaS. the first object of the present invention -- viscosity -- a maximum of -- a maximum of [ about 1.5 PaS(s), preferably ] -- although it is in providing the stable peroxy acid suspension system in the form of the thin fluid which about 1.0 PaS(s) may pour in well The present invention is not limited to it but the thick fluid which contains solid insoluble in water organicity peroxy acid by stable suspended state voice may also be prepared. Therefore, the suspension object bleaching constituent based on such a thick surface-active agent is also contained in the concept of the present invention. the water fluid bleaching constituent of the present invention -- an effective amount of solids -- the organic peroxy acid of insoluble in water nature is included that it is granular and substantially in the state where the water fluid containing a surface-active agent and an electrolyte was made suspended stably, and it has acid PH of 1~6.5, preferably 2~5. It is not criticality-like [ particle diameter ] about the peroxy acid used by the present invention, but may be 1~2000 micrometers. Small particle diameter is preferred to wash. The constituent of the present invention contains the peroxy acid of about 1~40 % of the weight, preferably 30 % of the weight of 2.5~abbreviation. Peroxy acid is 1 and 12-Diperoxydde can dione acid (DPDA) preferably. As described above, Then of Then is [ the surface-active agent which may be used by the present invention ] also good with Then or its mixture at anionic (anionic), nonionic (nonionic), cationic (cationic), or both the ionicity detergent with soap. Desirable surface-active agents are an anionic detergent, a nonionic detergent, and/or Setsuke. A publicly known detergent active substance (detergent-active material) may be used as a surface-active agent. As an anionic detergent, publicly known anionic surface-active agents, such as an alkyl aryl sulfonate type, a Alkyl sulfate type and an alkyl ether sulfate type, Alekan, a Alkene sulfonate type, are contained. A Alkyl machine contains 9~20 carbon atoms in these surface-active agents. The surface-active agent of various kinds of above-mentioned substances and other models is illustrated by Schwartz (Schwartz), perry (Perry), the 2nd volume (1958), and "a detergent and a surface-active agent." As a suitable anionic surface-active agent, it is sodium lauryl sulfate, Especially Dioctyl ester and sodium lauryl sulfonate of the sodium salt of potassium Dodecyl sulfo Nate, sodium Dodecyl benzene sulfonate, and lauryl polyoxy ethylene sulfate and sulfo Succinic acid sodium are illustrated. As non-ion Special detergent, an ethylene oxide and/or propylene oxide, alcohol, Alkyl phenol and fatty acid, or a condensation thing with fatty acid amide is contained. Generally these condensation things contain 5~30 ethylene oxides and/or a propylene oxide machine. Fatty acid Monod and Dialki roll amide, and tertiary amine oxide are also included by the nonionic detergent active substance. As a suitable nonionic detergent, they are nonyl phenol polyoxy ethylene ether, tridecyl Alcohol poly oxyethylene ether, Dodecyl mercaptan polyoxy Ethylene thioether, lauryl acid ester of polyethylene glycols, and C.₁₂--C₁₅The primary alcohol/7 ethylene oxide, the lauryl acid ester of sorbitan polyoxy ethylene ether, the 3rd class alkylamine oxide, and especially its mixture are illustrated. Other nonionic surface-active agents are indicated to Schwartz (Schwartz), perry (Perry), the 2nd volume (1958), "a detergent and a surface-active agent", Sock (Schick), the 1st volume (1967), and a "nonionic surface-active agent." The quarternary ammonium salt which contains at least one Alkyl machine which has 12~20 carbon atoms as a cationic detergent used by the present invention is contained. Although a halogen ion is desirable negative ion, as suitable Is an anion, acetate ion, a phosphate ion, a sulfuric acid ion, nitrate ion, etc. are mentioned. In a suitable cationic detergent, it is distearyldimethyl ammonium chloride, Stearyldimethylbenzylammonium chloride, stearyl trimethylammonium chloride, Cocodimethyl benzylammonium chloride, Dicoco dimethylammoniumchloride, Cetyl pyridinium chloride, a Sept Iles trimethylammonium star's picture, Water-soluble stearyl amine salt, for example, stearyl amine acetate and stearyl amine chloride salt, Stearyl dimethylamine hydrochloride, distearyl amine chloride salt, Alkylphenoxy ethoxyethyl dimethylammoniumchloride, A Decyl pyridinium star's picture, the pyridinium chloride derivative of the acetylamino ethyl ester of lauryl acid, Lauryl trimethylammonium chloride, Decyl amine acetate, The mixture of salt with lauryldimethyl ethyl ammonium chloride, methyl chloride, Benzyl chloride, chloracetic acid, a similar compound and lactic acid of stearyl 1-amide imidazoline, citrate, or other acid or the above-mentioned compound, etc. are contained. As a both sexes ion cleaning agent, Al kill- beta-imino Zypro pinnate, Al kill- beta-amino propionate, fatty series imidazoline, solid in, and its mixture are contained. As the suitable above-mentioned detergent, they are salt in a molecule of 1-Here- 5-hydroxyethyl 5-carboxymethyl imidazoline, Dodecyl- beta-Alanine, and 2-Trimethyl amino lauryl acid, and N. - Dodecyl-N and N-dimethylamino acetic acid are illustrated. Although the surface-active agent total amounts in the fluid bleaching constituent of the present invention differ according to the purpose of use, they are 2~50 % of the weight, preferably 5~35 % of the weight. In the case of the suspension object containing an anionic surface-active agent and a nonionic surface-active agent, the ratio is abbreviation 10:1~1:10. The composition which usually has a carbon atom of 12~20, or the alkaline metal soap of natural long chain fatty acid is contained in the term in this specification "anionic surface-active agent." A total amount of an electrolyte beyond one sort or it which exists in a constituent is 30 % of the weight of abbreviation 1.5~abbreviation. Preferably it is 2.5~25 % of the weight. Since the metal ion impurities (for example, iron and copper) which promote disassembly of peroxy acid in the fluid bleaching constituent of the present invention are contained in the commercial surface-active agent, it is preferred to use the surface-active agent as for which the least amount contains these metal ion impurities. The result reacted to the metal ion which peroxy acid dissolved in the suspension object base slightly as peroxy acid is unstable, and this dissolved peroxy acid dissolved is caused. Since it is possible to remove a metal ion contaminant from the constituent of the present invention using a certain kind of metal ion complexing agent and the above-mentioned complexing agent bars disassembly of peroxy acid, the knowledge of the To prolong is carried out [ constituent ] in the life. Improvement may be further carried out by giving the safeguard like coating to the particle that the chemical stability of peroxy acid should protect solid peroxy acid particles from the surrounding medium. In this case, it can be used without a risk of oxidizing with peroxy acid during storage, other incompatible electrolytes, for example, halogenation thing. Dipicolinic acid is illustrated as a useful metal ion complexing agent, and it is a water-soluble phosphate of this and the amount of multiplication, Dipicolinic acid N-oxide, picolinic acid, ethylene-diamine-tetraacetic acid (EDTA), its salt, various organic phosphonic acid or phosphonate salt (methylene phosphonic acid), for example, ethylene diamine tetra, and diethylene triamine Penta (methylene phosphonic acid) may be combined. Other publicly known metal complexing agents are used for a person skilled in the art, and the validity is greatly dependent on PH of the last manufacture things. Generally, in the case of many purposes of use, it is effective in the metal ion complexing agent of about ten to 1000 ppm removing a metal ion contaminant. Arbitrary ingredient The fluid bleaching constituent of the present invention may contain a little arbitrary ingredient of a certain kind other than the above-mentioned ingredient according to the purpose of use. As a typical arbitrary ingredient, a bubble modifier (sud-controlling agent), a Fluorescence substance, spice, colorant, abrasive soap, and a positive hydrotropism substance and an antioxidant are illustrated. However, which ingredient may be added unless chemical and the physical stability of the peroxy acid in a suspension system are spoiled by making an arbitrary ingredient exist in a constituent. In contrast with the conventional thick gel-like constituent, a present invention constituent is dealt with, it is upper safety, and even when it is made to dry temporarily, the safe peroxy acid diluted with a lot of surface-active agents and the hydration salt of high moisture content only remains. The constituent of the present invention is chemically stable, and this will be a surprising thing if it takes into consideration making peroxy acid suspended in the medium containing a lot of organic substances (namely, usually organic surfactant beyond about 10 % of the weight or it). The use of the constituent of the present invention reaches far and wide extremely. For example, (a) The bleaching additive agent for wash, (b) Light duty fluid, (c) The hard surface cleaner of health facilities (hygienic) including toilet bathroom cleaning, (d) A cleaner for home use, (e) Low PH fluid polish cleaner, It is used for etc. The following can be considered as a form of a product. () For example, a light duty fluid or the single component liquid products as a bleaching additive agent at the time of washing work; () the perfect heavy-duty fluid detergent for low-temperature bleaching -- it should provide In order to use it without the manufacture things together with the fluid detergent manufacture things in the manufacture thing;() small bag (sachet) combined with the heavy-duty Built fluid detergent stored in 2 division bottle, Form which is combined with the fluid detergent which is bleaching manufacture thing;() independent [ which was Pat(ed) by the small bag ], or is supplied from wipe (wipe), and is supplied from wipe; () Form which it is combined with the form;() heavy-duty powder cleanser which makes the fluid detergent constituent from a 2 Bat- 1 box system, and a pair, and is supplied, and Pat in a small bag, and is supplied from a small bag; () It Pat separately from enzyme manufacture things, and below form; together put at the time of use explains the present invention, while referring to an example. Example 1 In the fluid constituent containing a surface-active agent, 1 of various quantity and 12-Diperoxydde can dione acid (DPDA) were made suspended, and the following fluid bleaching constituent was prepared.

[Table]

[Table]

From the above-mentioned storage stability data, peroxy acid was Confirm(ed) as it is quite stable in the fluid of the present invention. Example 2 In the fluid constituent containing another surface-active agent, 1 of various quantity and 12-Diperoxydde can dione acid (DPDA) were made suspended, and the following fluid bleaching constituent was prepared.

[Table]

[Table]

It is stability, and can pour in easily except for (f), and all of these fluids are Oh. [Table]

[Table]

Example 3 The following fluid bleaching constituent was prepared and it stored by 20degreeC, 30degreeC, and 40 degreeC.

[Table]

Separation was not accepted during storage.

[Table]

[Table]

From the above-mentioned storage stability data, it was checked that the fluid constituent is chemically excellent in stability. Example 4 and 5 The following fluid bleaching constituent was prepared and it stored for 30 days by 40 degreeC. DPDA which remains was measured periodically. Example 4 Ingredient Weight % sodium alkylbenzene sulfonate 6.305C₁₂-C₁₅The primary alcohol/7 ethylene oxide 3.395 tri-citrate sodium 2 hydrate 7.76DPDA 3.0 water +H₂SO₄(It adjusts to PH4.5) Remaining Part viscosity (PaS) 0.361 example 5 Ingredient Weight % sodium lauryl sulfate The 7.76 3rd class alkylamine oxide 1.94 Anhydrous sodium sulfate 12. 61DPDA 3.0 Water (it Adjusts to PH+4.5) Remaining Part Viscosity (PaS) 0.137 With both stable constituents, it is a thin fluid which can be poured in easily and is Oh.

[Table]

From the above-mentioned storage stability data, it was checked that peroxy acid DPDA is chemically stable in the fluid constituent of the present invention. Example 6 and 7 The following fluid bleaching constituent was prepared. As peroxy acid, Diperoxy azelaic acid (DPAA) was used in Example 6, and P-nitroglycerine peroxybenzoic acid was used in Example 7. The constituent of Example 6 [Table]

The constituent of Example 7 [Table]

All of these constituents are stability, and they are the thin fluids which can be poured in easily, and are Oh. Storage stability The constituent of Example 6 [Table]

The constituent of Example 7 [Table]

Example 8 It is Elrepho about the reflectance of 460 nm before and after To wash in the bleaching performance to the examination cloth of the class product, of Example 1~8 dyed with tea. It measured and investigated using the reflective meter. the display frequency of all the reflectance -- a Fluorescence substance (fluorescer) -- it received calmly and amended. Bleaching is △R to the following table.₄₆₀* It is the degree of increase of the reflectance displayed, and was shown.

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