JPH05502907A - liquid bleaching composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] liquid bleaching composition The present invention also relates to a liquid detergent composition comprising an aqueous phase, a detergent active material and a bleaching material. It is.

EP 294904 (P&G) perborate bleaching materials in liquid detergent compositions discloses the use of bleaching materials having a weight average particle size of G5-2 Quttt. These particles exist in the form of particles that Formed by crystallization. The problem with using these small particles is that they cause troublesome mixing. This process often results in a harsh viscous process that results in a mousse of the product. The problem is that it requires a mixing process. Furthermore, these small particles are often relatively large. They tend to be unstable due to the presence of small surface species. Furthermore, it contains these small particles. Liquid detergent compositions often have the disadvantage of high viscosity.

EP No. 368575 (ICI) describes the use of superimposed borium for incorporation into liquid detergent compositions. It concerns a suspension of an acid salt and a thickener. bleaching material to produce liquid detergent The problem with using suspensions of materials is that the presence of an aqueous phase in the suspension is particularly The problem is that the detergent composition is diluted in the body detergent composition. This kind of dilution process is often undesirable. Additionally, the use of presuspensions of bleaching materials creates suspensions. resulting in extra processing and/or transportation steps to produce and/or transport , which generally results in increased liquid detergent composition costs.

Surprisingly, bleach particles with a weight average particle size greater than 20m have been To solve one or more of the above problems by forming on-site It has been found that a more stable bleach-containing liquid detergent composition can be obtained.

Accordingly, the present invention comprises a bleaching material of an aqueous phase and one or more detergent active materials. The method relates to a method for producing a liquid detergent composition comprising: It is characterized by the in-situ formation of bleach particles having a uniform particle size.

In another aspect of the invention, the bleaching agent has a weight average particle size greater than 20 μs. If the particles are formed in situ, this will result in a relatively small amount of water (i.e. less than 50% by weight). , more preferably less than 40% by weight, particularly preferably 10-35% water). A large amount of detergent active material (i.e. greater than 15% by weight, more preferably greater than 20%, especially (preferably 25-60%) and a relatively large amount of bleaching material (i.e. 1% or more, (more preferably 7% or more, particularly preferably 10 to 50%) enables the production of pharmaceutical compositions.

The invention therefore further provides that less than 50% by weight water and more than 15% bleach active material. and more than 1% by weight of a bleaching material, said bleaching material weighing more than 20% by weight. The present invention relates to liquid detergent compositions having average particle size.

bleaching material The composition according to the invention comprises a bleaching material which is preferably a peroxygen bleach. This drift The white component is present in the system at least partially in undissolved form, but generally in at least a small amount. Part of the peroxygen bleach is solubilized. Generally solid particles are suspended in the system.

Examples of suitable bleaching compounds are perborates, persulfates, peroxydisulfates, and calcium peroxides. Reaction of sium, superphosphate, and hydrogen peroxide with urea or alkali metal carbonates contains crystalline peroxyhydrate produced by encapsulated drift Whitening agents may also be used. Particular preference is given to using perborate or percarbonate bleaches.

Typical amounts of bleaching agents are from 1 to 50% by weight of the aqueous composition, more preferably from 7 to 50% by weight of the aqueous composition. 30%, particularly preferably 10 to 25% by weight, based on the composition.

The weight average size of the bleach particles is greater than 20 F, preferably between 22 and 150 F, more preferably Preferably 25-60m, most preferably 3o-5o or 45m. weight A suitable method for determining the average particle size is a magnification of 50-600 (preferably Make a micrograph of the liquid detergent composition at approximately 150x magnification and then manually remove the visible particles. Alternatively, automatically count and measure the particle size of each particle, then weigh each visible particle. The amount consists of calculating the average particle size.

Bleaching materials are often suspended in systems as agglomerates of bleach particles as small constituents. It becomes cloudy. In general, the size of the aggregates rather than the size of the constituent bleach particles is the Bleach particle size is refers to the weight average particle size of the aggregates. If aggregates of bleach particles are present, the particles When determining child dimensions, care must be taken to ensure that the material being measured is not subjected to unnecessary shear or stress. have to pay. This is because this results in fragmentation of the aggregates.

detergent active materials The compositions of the invention further include detergent active materials. Surprisingly, the weight average particle size It has been found that this can be obtained by forming in situ bleach particles having .

In the broadest sense, detergent-active materials generally include one or more surface-active materials. It can be composed of anionic, cationic, nonionic, and zwitterionic types. and zwitterionic types, and mixtures thereof (if mutually compatible). You can choose. For example, this is the document ['5orfie+ Active Agln mouth'　Yol　1. b7 S+hva+t+ & Ps+B, I+l+ r++i+nce 1949 and’So+txce Achws Agec t+’ Vol It, 5ehv+J+, P! +；7　＆Berch(lale ++ci+nc+ 1985), Co+++nt edilion o! 'M cColcheon’+ Emoliidi:i & DNeBenl+’ Publisher M+Cu1ch son division of Lnot! ctu+in g Coo! e+tions++ Compx*ma or dingen+1d-L++ +hecbo++h', H, S+++h+, 2nd Efln,, Cxtl H xn+e:Ye+lB, Munehe mouth & Lsn, described in 1981 Any particular material of the type can be selected.

Suitable nonionic surfactants are in particular compounds containing hydrophobic groups and reactive hydrogen atoms. reaction products of substances, such as aliphatic alcohols, acids, amides or alkyl phenates. Nor and alkylene oxides, especially ethylene oxide (alone or with propylene oxide) ). Certain nonionic detergent compounds contain ethylene oxide. Alkyl (C-C, ρ first or second linear or branched alcohol, sequence by condensing ethylene oxide with the reaction product of propylene oxide and ethylenediamine. It is a product created by Other so-called non-ionic detergent compounds are long-chain tertiary amino acids. oxides, long-chain tertiary phosphine oxides, and dialkylthrefoxides. .

Furthermore, the salting-out resistant activity as described for example in EP 328177 The use of substances, especially alkyl polymers such as those disclosed in EP 70074. It is also possible to use glycoside surfactants.

Suitable anionic surfactants generally include alkyl surfactants having from about 8 to about 22 carbon atoms. Water-soluble alkali metal salts of organic sulfates and sulfonates with base groups. The term alkyl is used here to include the alkyl portion of higher anru groups. It will be done. Examples of suitable synthetic anionic detergent compounds are sodium alkyl sulfates and carbon dioxide. Lime, especially high grade (Ca~) prepared from e.g. tallow oil or coconut oil Cl8) What is obtained by sulfating alcohol, alkyl (C9-20) benzene Sodium and potassium sulfonates, especially linear tertiary alkyl (C,o-C1 5) Sodium benzenesulfonate: Sodium alkyl glycerether sulfate , especially higher alcohols and petroleum derived from tallow oil or coconut oil. Synthetic alcohol derivatives derived from coconut oil, coconut oil fat monoglyceride sulfate and and sodium sulfonate, higher (C8-Cl8) fatty alcohol-alkyl oxide Sodium and potassium sulfate esters of ethylene (especially ethylene oxide) reaction products salts: esterified with, for example, isethionic acid and neutralized with sodium hydroxide. Fatty acid amide of methyltaurine, a reaction product of fatty acids such as coconut fatty acids sodium and potassium salts; alkane monosulfonates, e.g. Those obtained by reacting fins (Ca to C2o) with sodium bisulfite and Paraffin is reacted with SO and CJ22, and then hydrolyzed with a base to form a random those derived from the production of musulfonates, as well as those derived from olefin sulfonates ( This term refers to olefins, especially C-Cα-olefins, when SO3 is added to Describe the product created by reacting the reaction product, then neutralizing and hydrolyzing the reaction product. ). A suitable anionic detergent compound is (C11-015) Sodium alkylbenzenesulfonate and primary (C,o-Cl8)alkyl Sodium or potassium sulfate.

Furthermore, alkali metal soaps of fatty acids, especially acids with 12 to 18 carbon atoms (such as For example, olefinic acids, lysyllic acid and fatty acids obtained from human oil, alkyl lucuccinic acid), rapeseed oil, groundnut oil, coconut oil, coconut kernel oil or mixtures thereof. Compound soaps can also be included and are often preferred. Na of these acids Thorium or potassium soaps can be used.

Total detergent active materials range from 15 to 70% by weight, such as from 20 to 60% by weight of the total composition. , typically present in an amount of 30 to 50% by weight. Although it may be an isotropic form, a structured form is preferable. Structure of the present invention Structured liquids can be internally structured, in which case the detergent activity in the composition The material can also be structured or externally structured, in which case: Add structure with an external structure-forming agent. Preferably the composition of the invention is internally structured. . Most preferably, the composition of the invention comprises a surface consisting of lamellar droplets of detergent active material. Composed of activator structure.

Some of the different types of possible active structuring materials are described in the literature [11, A, Bz+ne3 'D! tergen+s, Ch, 2°K, Waltv+s (ED).

'Rhcolletl: Indu+1risl Appliexlion +', 1. Wile7 & 5onI.

Le+chvor+h 1980]. In general, this type of system The degree of orientation increases with increasing concentration of surfactant and/or electrolyte. very At very low concentrations, the surfactant is present as a molecular solution or as a solution of spherical micelles. Both of these are isotropic. other surfaces By adding active materials and/or electrolytes, structuring (anisotropic ) system can be generated. These are, for example, rod-micelle and planar lamellar structures, respectively. , referred to by various terms such as lamellar suspension and liquid crystalline phase. often different researchers use different terms to describe structures that are actually the same. .

For example, in European Patent EP-A-151844, Mela droplets are called ``spherulites.'' Surfactant structuring in liquids The existence and identification of the system can be determined by means known to those skilled in the art, such as optical techniques, various flow by chemical measurements, X-ray or neutron diffraction and often by electron microscopy. can be determined.

If the composition has a lamellar droplet structure, the aqueous continuous phase contains dissolved electrolytes. It is preferable to have The term electrolyte as used here refers to any ionic water-soluble means rent. However, in lamellar mats, not all electrolytes It does not necessarily dissolve and may be suspended as solid particles. Because liquid This is because the total electrolyte concentration of is higher than the solubility limit of this electrolyte. electrolyte mixing can also be used, with one or more of the electrolytes present in the dissolved aqueous phase. while one or more of them is present substantially only in a suspended solid phase. If there are two types or more electrolyte may be distributed approximately proportionally between these two phases. can. In part, this depends on the processing method (eg, the order of addition of each component).

On the other hand, the term "salt" refers to surfactants and all organic compounds that may be present outside the water. and inorganic substances, which may or may not be in ionic form; the term sub- The group includes electrolytes (water-soluble monoga).

The type of surfactant and its ratio to obtain a stable liquid with the desired structure. The selection is well within the knowledge of those skilled in the art.

However, an important subgroup of useful compositions differs in detergent active materials. It can be said that it consists of a formulation of surfactants. fabric laundry composition Typical formulations useful for Non-alkoxylated anionic and/or alkoxylated anionic surface activity It includes those consisting of agents.

In the case of surfactant formulations, the precision of each component to provide this type of stability and viscosity The ratio depends on the type and amount of electrolyte as in conventional structured liquids. do.

However, preferably the composition contains 1 to 60%, especially 10 to 45% salting-out electrolyte. Contains quality. Salting-out electrolytes are described in EP-A-796464. ie a salting-out electrolyte has an otropic number of less than 95.

Also included are some salt-soluble electrolytes (as defined in Patent No. 11i1f) as required. but in a type and amount compatible with other organisms, and the composition remains shall be within the scope of the present invention set forth herein.

Some or all of the electrolytes (either salt-soluble or salt-out) that may be present. A substantially water-insoluble salt can have detergent properties. Izu In either case, the composition according to the invention comprises detergent builder materials (some or all of which may be an electrolyte). Bilgoo material is washed with 4 liquids any that can reduce the level of free calcium ions in the or for example the generation of alkaline pH, the suspension of soil removed from the fabric and the fabric softening. It imparts to the composition advantageous properties of ponding, such as dispersion of viscous materials. Preferably, Salting-out electrolytes consist of citrate.

When present, examples of phosphorus-containing inorganic detergents include water-soluble salts, especially alkali metals. Includes the genus pyrophosphates, orthophosphates, polyphosphates and phosphonates. Nothing Specific examples of monophosphates include tripolyphosphate, phosphoric acid and sodium hexametaphosphate. and potassium salts. Phosphonate sequestrant builders may also be used. I can do it.

Examples of phosphorus-free inorganic detergents, when present, include water-soluble alkali metals. Includes carbonates, bicarbonates, silicates, and crystalline and amorphous aluminosilicates do. Specific examples are sodium carbonate (with or without calcite seeds), potassium carbonate um, sodium and potassium bicarbonate, and zeolites.

Examples of organic detergents, when present, include alkali metals, ammonium and Ammonium polyacetate, carboxylate, polycarboxylate, polyacetyl Includes carboxylates and polyhydroxysulfonates. A specific example is ethylene Diaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, CMO5°TMS, TDS, mellitic acid, benzene polycarboxylic acid and sodium citric acid, potassium lithium, ammonium and substituted ammonium salts.

Preferably, the level of non-soap builder material is from 0 to 50% by weight of the composition, and more. Preferably it is 5 to 40%, particularly preferably 10 to 35%.

In the scope of organic bilgoux, water as described in EP 301.882 It may also be desirable to incorporate polymers that are only partially soluble in the continuous phase. This is the viscosity (based on dissolved polymers) as well as secondary benefits (especially for builders). - properties). Because, Isn't the part that doesn't dissolve causing the same instability that would occur if almost all of it dissolved? It is et al. Typical amounts are 05-45% by weight.

Additionally, the compositions of the present invention may further include, in place of or in addition to the partially dissolved polymer. may contain other polymers, said other polymers being almost completely soluble in the aqueous phase. 5g or more of nitrilotrifluoride per 100ml of 5% by weight aqueous solution of the polymer. The second polymer has an electrolytic resistance of sodium acid, and the second polymer is further dissolved in a 20% aqueous solution. 2% by weight of polyethylene glycol having an average molecular weight of 6000 or less has a vapor pressure equal to or lower than the vapor pressure of the above-mentioned aqueous solution, and The polymer of No. 2 has a molecular weight of at least +000. The use of this type of polymer is Generally described in EP 301.883 of the applicant. Typical level is 0 It is 5 to 45% by weight.

The viscosity of the composition according to the invention is preferably 2500 mP a-s at 21 s-' less than 1,500 mPa-s, especially 30 to 900 mPa-s -5 range.

One way to adjust the viscosity and stability of compositions according to the invention is to use viscosity-adjusting The first step is to include a polymeric material.

Suitable viscosity and/or stability modifying polymers for incorporating into the compositions of the invention include: , a peptizing polymer having a hydrophilic backbone and at least one hydrophobic side chain. . Polymers of this type are described, for example, in co-pending European patent application EP No. 89201530, No. 6 (EP No. 346995). preferred Preferably, the amount of the viscosity regulating polymer is 1 to 5% by weight of the total composition, more preferably It is 0.02 to 2%.

Additionally, the compositions of the invention may also include substances for adjusting the pH. pH It is preferable to use a weak acid to reduce the , more preferably using 01-8 carboxylic acid, most preferably using citric acid do.

The use of these pH lowering agents allows the compositions of the present invention to contain, for example, amylase, protease, etc. It is particularly suitable when containing enzymes such as enzymes such as enzymes and lipolases.

In addition to the components listed above, a number of optional components can also be present, such as alkaline monoetas derived from nolamide, especially coconut kernel fatty acids and coco coconut fatty acids Foam promoters such as nolamide, e.g. clays, amines and amine oxides fabric softeners, suds suppressants, inorganic salts such as sodium sulfate, Fluorescent agents, fragrances, fungicides, colorants, and For example, protease, cellulase, amylase and lipase [+J-polase (registered) Enzymes such as those available from Novo, Inc.) may also be included. proteer Examples of suitable enzymes include Sabinase (Novo), Maxatal (Gistau Procade), ), Obticlean (MKC) or API22 (Showa Denko), Alcalase , maxatase, esperase, octimase, protease and subtilis It is Shin BPN. Suitable lipolases include, for example, Lipolase (Novo), Alka la-se, matelipase, lipozyme, S P225, S P285, to It's Yojozo Lipase.

Suitable amylases include, for example, Termamil (registered trademark of Novo) and Maxamyl. It is le. Suitable cellulases include Cellzyme (Novo).

The compositions of the invention preferably contain 5-50% water by weight, more preferably 15-35% water. Contains water.

The liquid detergent composition according to the invention is preferably prepared for 21 days after being made at 25°C. It is physically stable in that it exhibits phase separation of 2% by volume when stored for a long time. Ru.

The liquid detergent composition according to the invention is preferably prepared at a temperature of 20 to 37° C. after making. less than 25%, preferably less than 10%, more preferably less than 10% when stored for several months. is volume stable in that it exhibits a volume increase of less than 5%.

Further preferably, the composition according to the invention also has solid suspension properties, particularly preferably: They do not develop any visible sedimentation after storage for 3 weeks at 21°C.

The compositions of the invention may also include one or more bleach precursors. this A well known example of such a drug is TAED. Preferably the bleach precursor is present in the system at least is also present in partially undissolved form. Ensure that the precursor is present in undissolved form. One method is to increase the amount of electrolyte in the composition to increase the solubility of the precursor in the system. The goal is to reduce the degree of resolution. Electrolytes suitable for this purpose include, for example, at least Partially water soluble carbonates, sulfates and halides.

Advantageously, the composition according to the invention further comprises one or more stabilizers for the bleaching material. It may also contain the above ingredients. Suitable substances include, for example, metaborate electrolytes and magnesi It is um salt.

In use, the detergent composition of the present invention can be used, for example, in a washing liquid for use in a washing machine. The washing should be diluted with water. Wash +1! The concentration of the liquid detergent composition in the liquid is preferably Preferably 0.05 to 10% by weight, more preferably 01 to 3% by weight.

To ensure effective detergent properties, liquid detergent compositions are preferably alkaline. , about 70 to 12, preferably about 8 when the composition is used in aqueous solution at the recommended concentration. It is preferred to provide a pH in the range of from to about 11. To meet this requirement, undiluted The liquid composition preferably has a pH greater than 7, such as about pH 8, Q to about 12.5. Should be. Excessively high pH, for example above about pH 13, Less desirable in terms of safety.

One aspect of the present invention is a method for producing a liquid bleach-containing composition, which method forming in situ bleach particles having a larger weight average particle size. . In situ formation of bleach particles e.g. If the particles are in situ, e.g. by a dissolution/recrystallization process or by hydration of perborate-water salts, Concerning the process formed by. Adopting processing conditions that yield the required particle size It is well known to those skilled in the art to do so. be varied to obtain the desired particle size. The preferred parameters to be considered are the physical form of the bleaching material added to the composition, the stirring conditions, and the order of addition.

If the bleaching material is a perborate bleaching material, preferably the bleaching agent is a perborate-water salt. The perborate bleach is added to form a perborate bleach in the composition. Others containing bleach The preferred method is to use a combination of hydrogen peroxide and borate materials, which Reacts in situ to produce perborate bleach. The preferred borate material is metaboric acid It's salt.

The bleaching material is added to the composition under mild agitation conditions, preferably less than 10 c/s, particularly preferred. More preferably, it is added under conditions of 02 to 3 c/s. Stirrer tip The speed is preferably 0.01 to 1Om/s, more preferably 0.1 to 5m/s. s, most preferably 05 to 2 m/s.

The preferred order of addition is to add the electrolyte non-bleaching material to the water at elevated temperature, then wash. the agent active material, the bleaching material and the remaining ingredients.

The present invention will be further explained below with reference to Examples. In all examples, unless otherwise noted. Unless otherwise specified, all percentages are by weight.

Example D Add citrate/citric acid and polymer to elevated temperature water, then pre-mix Detergent active materials and bleaching materials can be added to make the following compositions: I can do it.

Ingredients Weight% Citrate/citric acid (1) 10 Bleach 15 Polymer (2)l Metaborate 2.6 water remainder jl): Mixture (2)・EP 346995 used to adjust the pH to 85 Polymer A-11 described in No. 2j glass with 6 blade stirrer with diameter 8an Prepare the composition several times on a 1 kg scale in a storage container, and check the type of bleach and stirring materials. was changed as follows: IO,2 perborate-hydrogen ■　10〃 ■　5〃 ■　10 IX t,o Perboric acid tetrahydrate (3) Selected proportions such that diperborate tetrahydrate is generated in situ.

Each of these compositions can be stored for 24 hours at room temperature and Microscopic photographs can be taken at 0x magnification.

The weight average particle size of the bleaching material was determined by counting visible particles.

Citric acid/citric acid determines the physical stability, volumetric stability and solid suspension properties of the composition Add the acid salt to the water, then add sodium metaborate to neutralize the detergent active material. Premixes of detergent active materials in sodium hydroxide, polymeric, acid form, small quantities The following compositions were prepared using Na-dobu by adding hydrogen peroxide or perborate-water salt. 2; 2t 21' Nmberoninoku A7 9 9 9 9 Citrate/citric acid 10 10 15 15 Perborate-Hydroxy acid 1515 Metaborate/H2O2-1515 Polymer 1 l 1 1 Sodium metaborate 2.6 2.6 2.6 2.6 Antifoam/dye 0.5 0.5 G, 5 0.5 Water <up to 95><up to 100> Note: ・Na-Dobbs is sodium dodecylbenzenesulfonate (in NaOH) summed Markov AS3).

・　Amperonic A7 has an average of 7 EO groups per molecule 013-1 5 fatty alcohol (ICI).

- A final pH of the product of 9 was obtained using a citrate/citric acid mixture.

・Metaborate/H202 generates 15 parts of perborate tetrahydrate on the spot. sodium metaborate and H2O2 in such a ratio.

・The polymer is as described in EP 346995 as Polymer A-44. It is a peptizing polymer.

・In addition to the metaborate used to generate perborate, 26 parts of sodium metaborate was added. Added.

Each of the compositions contained 21 glass containers with a 6-blade stirrer of diameter 8a11. It was created on a 1kir scale. Stirring conditions were varied as described below. bleaching The particle size of the agent is determined by applying a thin film of the product onto a microscope glass plate under moderate pressure. , then determined by taking a micrograph at a magnification of approximately 400 times, and then determining the coarseness of the visible particles. By counting the fraction and measuring the particle size, the weight average particle size can be roughly calculated. That was decided. In most samples, the bleach particles were present as small elements. It existed in the form of different aggregates. The table below shows the average particle size of the aggregates.

The table below shows the weight average particle size of the bleach in the composition as a function of agitation speed. : B 60 100 - C6030 D' 120 50 Example■ Electrolytes are added to warmed water along with a small amount of ingredients other than fragrance and enzymes, and then Add the detergent active ingredients as a remix under stirring and then cool the mixture The following composition was created by adding enzymes, fragrances, and bleaching agents: Borate 2.9 2.6 Sodium citrate/citric acid (1) 11.1 9.8 Dequest 2060S As F100%’) Q, 4 0.4 Sodium perborate hydrate 7210 Enzyme, Alcalase G, 8 0.8 Ca C1・2 H20o, 2o, 2 fluorescent agent, Tinopal CBSX O, 10,1 Silicone, Dow Corning DB1tlO0,3G, 3 Fragrance 03 0 3 Peptizing polymer (4) 1.1 1 Water - Qi and the remainder part - 1 ~ - (1) A mixture of two and two was used to adjust the final pH.

(2): Expressed as a % of the analyzed enzyme level in the fresh sample.

(3): Peptizing polymer of formula I of EP 346995, X=50. Y=O, R=t(, R'=-Co-0° R2 and R3 are absent.

R'=-C12H25, MW=7.500.

(4): Total filtrate obtained by removing undissolved bleach particles by mild centrifugation. Approximate weight % of acid salt.

(5): Not measured.

The product obtained had the following properties: A B Volume stability 00 (volume increase%, (3 months at 25℃) No separation of transparent layer (3 weeks at 37℃) No solid sedimentation (3 weeks at 37℃) Viscosity 21s’ 80G 760 Dissolved perborate (5) 86 Bleach activity 9697 (2 months at room temperature) Enzyme activity 76 mouth 1 (5) (2 months at room temperature) (2) Summary book Liquid detergent composition comprising an aqueous phase and one or more detergent active ingredients and bleaching ingredients 1. A method of manufacturing a product, the method having a weight average particle size greater than 20 m. Including forming bleach particles in situ.

Copy of amendment and submission of translation ability (Article 184-8 of the Patent Law) Commissioner of the Patent Office Aso Watari August 1992 783, Patent Applicant Address: P., N.L.-3000 Day Car Rotterdam, Netherlands ・O Box 137 Name: Unilever Namrose Pen Note Sharp 4, Agent: Tokyo Yamada Building, 1-1-14 Shinjuku, Shinjuku-ku, Miyako (3 others) 5. Date of submission of written amendment: January 21, 1992 6. List of attached documents (1) One translation of the written amendment as well as fluorescent agents, fragrances, fungicides, coloring agents, which are generally present in extremely small amounts, and For example, protease, cellulase, amylase and River Zero lipolase ( Enzymes such as those available from Novo, Inc.) may also be included. protea -ase enzyme [F] Suitable examples include Sabinase (Novo), Maxatal [F] (Gistopro ), Obticlean [F] (MKC) or AP■ -■ 122 (Showa Denkosha), Alka7-ase, Maxatase ■, Engineering [F] Sperase, octimese■, proteinase and subtilisin BPN be. Suitable lipolases include, for example, lipolase (Novo), Amano lipase, Mate Lipase, Lipozyme ■, S P225, S P285, Toyoji -It is sea lipase. Suitable amylases are, for example, Termamil (Novo ) and Maxamil ■. A suitable cellulase is Cellzyme ( Novo Inc.).

The compositions of the invention preferably contain 5-50% water by weight, more preferably 15-35% water. Contains water.

The liquid detergent composition according to the invention is preferably prepared for 21 days after being made at 25°C. It is physically stable in that it exhibits phase separation of 2% by volume when stored for a long time. Ru.

The liquid detergent composition according to the invention is preferably prepared at a temperature of 20 to 37° C. after making. less than 25%, preferably less than 10%, more preferably less than 10% when stored for several months. is volume stable in that it exhibits a volume increase of less than 5%.

Example I Add citrate/citric acid and polymer to elevated temperature water, then pre-mix Detergent active materials and bleaching materials can be added to make the following compositions: I can do it.

Ingredients Weight% ABS 21 Numperonik ■ A7 9 Citrate/citric acid (1)jO Bleach 15 Polymer (2ゝ　l Metaborate 2.6 water remainder (1): Mixture used to adjust pH to 85 (2): E P34699 Polymer A-11 described in No. 5 21 having a six-blade agitator with a diameter of 80 Create the composition several times on a 1 kg scale in a glass container, and check the type of bleach and stirring. The materials were changed as follows. Experiment Stirring speed Type of bleach IO,2 perborate-hydrogen ■ O, 2H202/ml a f’rN Mu IX 1.0 Perboric acid tetrahydrate (3): The proportion selected so that perborate tetrahydrate is generated in situ.

Example■ Add citric acid/citrate to water, then sodium metaborate, detergent active ingredient Preparation of detergent active materials in sodium hydroxide, polymeric, acid form to neutralize mix, add minor ingredients and hydrogen peroxide or perborate-water salt to the next set. created a product.

Citrate/Citric acid 10 1Q 15 15 Perborate-Hydrogen 15-1 5 - Metaborate/H2O2-15-1,5 Polymer 1 1 1 l Sodium metaborate 2.6 2.6 2.6 2.6 Antifoam/dye 0.5 0.5 0.5 0.5 water <up to 95><up to 100> Note: ・Na-Dobbs is sodium dodecylbenzenesulfonate (in NaOH) summed Markov AS3).

・　Amperonik■A7 is a C13~ having an average of 7 EO groups per molecule. 15 fatty alcohol (IC1 Company).

- A final pH of the product of 9 was obtained using a citrate/citric acid mixture.

・Metaborate/H202 can generate 15 parts of perborate tetrasalt on the spot sodium metaborate and H2O2 in such a ratio.

・The polymer is as described in EP 346995 as Polymer A-44. It is a peptizing polymer.

・In addition to the metaborate used to generate perborate, 26 parts of sodium metaborate was added. Added.

Example■ Electrolytes are added to warmed water along with a small amount of ingredients other than fragrance and enzymes, and then Add the detergent active ingredients as a remix under stirring and then cool the mixture The following composition was created by adding enzymes, fragrances, and bleaching agents: Borate 2.9 2.6 Sodium citrate/citric acid (1) 11.1 9. ! 1 Dequest’2060 3F 100% r), 0.4G, 4 Sodium perborate hydrate 721 0 Enzyme, Alcalase ■ 0.8 0.8 Fluorescent agent, Tinopal ■ CBSX O,1 0,1 Silicone, Dow Corning DB100 O,30,3 Fragrance Oj O, 3 Peptizing polymer (411,11 Water - Qi Ichi Part - Qi Ichi (1) This mixture was used to adjust the final pH.

(2): Expressed as a % of the analyzed enzyme level in the fresh sample.

(3): Peptizing polymer of formula 1 of EP 346995, X=50. Y=O, R5=H, R1=-Co-0°R and R3 are absent.

R' = -C12H25, MW = 7.500° (4): By mild centrifugation Approximate weight percent of total perborate obtained by removing undissolved bleach particles.

(5): Not measured.

Submission of revised copy (Article 184-8 of the Patent Law) Commissioner of the Patent Office Aso Watari August 7, 1992 1. Indication of patent application PCT/EP 91100259 Country 2. Title of the invention: Liquid bleaching composition 3. Patent applicant Address: P., N.L.-3000 Day Car Rotterdam, Netherlands ・O 4, Director, Yamada Building, 1-1-14 Shinjuku, Shinjuku-ku, Tokyo (and 3 others) given name) 5. Date of submission of written amendment: March 20, 1992 6. List of attached documents (1) One translation of the written amendment The scope of the claims 1. Less than 50% water and more than 15% detergent active materials and more than 1% bleach by weight 1. A method for producing a liquid composition comprising: weight average particles larger than 20 particles; Liquid detergent composition comprising forming in situ perborate bleach particles having dimensions How things are manufactured.

2. According to claim 1, the perborate bleach is added to the composition as a perborate-water salt. Method described.

3. Perborate bleach is produced in situ by the reaction of hydrogen peroxide with borate materials. 2. The method according to claim 1, wherein:

4. A claim comprising incorporating a bleaching agent into the composition at a stirring speed of less than 10 c/s. The method described in 1.2 or 3.

5. Contains lamellar droplets of detergent active material with less than 50% water and more than 15% wash A liquid detergent composition comprising an agent-active material and more than 1% by weight of a bleaching material, said A liquid detergent composition, wherein the bleaching material has a weight average particle size greater than 20m.

6, with a viscosity of less than 2.500 mP at 213', 70~ It has a pH of 12.0, is physically stable and volumetrically stable, and is a solid suspension. The liquid detergent composition according to claim 5 or 6, which has the following properties.

international search report international search report EP 9100259 S^　44035

Claims (1)

[Claims] 1. A liquid composition consisting of an aqueous phase and one or more detergent active ingredients and bleaching ingredients A method for producing bleach granules having a weight average particle size greater than 20 μm, the method comprising: CLAIMS 1. A method of making a liquid detergent composition comprising forming a filtrate in situ. 2. The bleaching material is preferably a perborate salt added to the composition as perborate monohydrate. 2. The method of claim 1, wherein the agent is a bleaching agent. 3. The bleaching material is preferably produced in situ by reaction of hydrogen peroxide with the borate material. 2. The method of claim 1, wherein the perboric acid bleach is a perboric acid bleaching agent. 4. Claims comprising incorporating a bleaching agent into the composition at a stirring speed of less than 10 c/s 1, 2 or 3. 5. Less than 50% water and more than 15% detergent active materials and more than 1% bleach by weight and wherein the bleaching material has a weight average particle size of greater than 20 μm. , liquid detergent composition. 6. Claim 5 comprising a surfactant structure consisting of lamellar droplets of detergent active material. The liquid detergent composition described. with a viscosity of less than 2,500 mPas at 7.21 s-1 and between 7.0 and 1 It has a pH of 2.0, is physically stable and volumetrically stable, and has solid suspension properties. The liquid detergent composition according to claim 5 or 6.