JPH06502440A - Liquid detergent composition containing suspended peroxygen bleach - 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 detergent composition technology containing suspended peroxygen bleach The present invention provides an aqueous liquid detergent composition containing a suspended solid peroxygen bleach compound and a small amount of bleach. In an attempt to answer the long-standing need for a product, European Patent Application No. 2930 No. 40 and No. 294 904 contain conventional amounts of anionic surfactants. agent and a specific water/solvent vehicle that provides the required chemical stability to the composition. containing a solid peroxygen bleach suspended in describes an aqueous detergent composition having H.

However, in such compositions, the physical stability of the suspended particles in the liquid medium is It is necessary to take certain precautions.

One option is, for example, that solid particles, especially particles of peroxygen compounds, are formed at structured interfaces. Describes a liquid detergent composition suspended by an activator bath (surfactant “Neat Phase J”) Co-pending UK Patent Application No. 8926620.9 Ru. However, it encompasses easier processing compared to structured surfactant baths. There is a need for suspension systems.

The structured surfactant bath is not intended to suspend peroxygen bleach particles. , described in various patent documents (in particular, EP-A No. 79 646) , EP-A No. 86 614, EP-A No. 203 660 and EP-A 295 021, liquid detergent containing suspended builder particles composition (one or more "salting out" electrolytes or "surfactant desolubilizing" electrolytes) (used to prepare structural ratio phases with surfactant materials).

Such electrolytes include, inter alia, silicate power (silicate in suspended form). Other patent documents disclosing use in cleaning/detergent compositions include: , British Patent No. 2031455 and British Patent No. 1342612 (1. Abrasive and water-insoluble phosphate builder salts as solid substances to be suspended) However, there are some examples that include peroxygen bleach particles.

The book specifies that the composition contains a silicate (not a silicate, but instead a carboxylic acid). It is proposed in detail that the number ζf should not contain a gelling inhibitor.

Silicates are also used, for example, in aqueous thixotropic liquid compositions used for automatic dishwashing purposes. It is widely described as an alkalinity-enhancing ingredient in formulations. What represents this technology EP No. 315 discloses silicates in amounts ranging from 2596 to 40%. This is the specification of No. 024.

Small amounts of silicates can be added to EP-A No. 293 04 with only a moderate increase in the viscosity of the composition. peroxygen bleach particles can be efficiently suspended in liquid detergent compositions of the type described in specification no. It has now been surprisingly discovered that it is possible to

The present suspension system does not involve any particular processing difficulties; furthermore, the presence of silicates increases the Provides benefits such as alkalinity, increased washing machine compatibility, etc.

Therefore, the present invention combines solid peroxygen bleach compounds with water and water-miscible organic solvents. Will it be? & phase and a small amount of silicate to suspend the peroxygen bleach particles in the liquid phase. A completely phase-stable aqueous liquid detergent composition containing:

Demonstration of invention The present invention provides a solution for suspending in a liquid phase containing water and at least one water-miscible organic solvent. A compound having a p11 of at least 8 and less than about 11 containing a solid water-soluble peroxygen compound liquid detergent composition, wherein the amount of solid water-soluble peroxygen compound is The amount of available oxygen provided by the peroxygen compound is between 0.5% and 3%. and the composition contains 0.5 to 5% by weight of silicate, preferably 1 to 3% by weight of silicate. ? Contains 0.

BEST MODE FOR CARRYING OUT THE INVENTION water soluble peroxygen compound The water-soluble solid peroxygen compound is present in the composition preferably in an amount of 5 to 50% by weight of the total composition. More preferably 5-40% by weight96, even more preferably 5-30% by weight, most preferably is present in an amount of 10 to 30% by weight.

Examples of suitable water-soluble solid peroxygen compounds include berborate, bersulfate, , peroxydisulfate, perphosphate and hydrogen peroxide with sodium carbonate produced by reacting with urea (which produces bercarbonate) or urea. Examples include crystalline hydrogen peroxide. A preferred peroxygen bleach compound is Belbo rate and bell carbonate.

IJfa average particle size 0.5-20 micrometers, preferably 3-15 micrometers Berborate bleach in the form of particles with m is most preferred in this context. stomach.

The small average particle size is due to in situ crystallization, typically the in situ crystallization of berborate monohydrate. Best achieved by crystallization.

In situ crystallization involves the dissolution of belborate monohydrate and the dissolution of belborate tetrahydrate. Includes methods including dissolution and recrystallization as in post-production. Recrystallization is produced by allowing berborate monohydrate to take up the water of crystallization. may be used, whereby the monohydrate directly recrystallizes to the tetrahydrate without a dissolution step.

In-situ crystallization also shows that sodium perborate is mixed with stoichiometric amounts of hydrogen peroxide and metaphosphatide. such as when produced by reacting with sodium borate or borax. Includes methods involving chemical reactions.

water miscible organic solvent The suspension system for solid peroxygen components of the present invention consists of a liquid phase containing water and a water-miscible organic solvent. Ru. This reduces the amount of available oxygen in the solution to less than 0.5% by weight of the liquid phase, preferably A large amount of solid water-soluble peroxygen is present in the liquid detergent composition of the present invention, while keeping it below 0.1%. Allows compounds to be formulated. Less than 1/10 of the total amount of peroxygen compounds is dissolve in the phase. The small amount of available oxygen in the solution is in fact critical to the stability of the system.

Standard iodometric titration methods (e.g. Methoden der Organischen Che+sle, Houben-Uniil, 1953, Volume 2, No. 562N. (as described above) is suitable for determining the available oxygen (AVO) content of a composition.

To ensure complete equilibrium between liquid and solid phases, the composition should be prepared before AVO titration. It should be kept after mixing for 3 days at room temperature. Accurate sampling of the product before measurement Shake thoroughly to insure.

For the determination of available oxygen (AVO) in the liquid phase, a sample of the composition was Centrifuge at rp- for 10 minutes.

The liquid is then separated from the solid and titrated for available oxygen.

In said method, sufficient solvent is mixed with the water of the composition to affect the solubility of the peroxygen compound. If so, the organic solvent need not be completely miscible with water. completely Water-soluble solvents are preferred for use herein.

The water-miscible organic solvent must, of course, be compatible with the peroxygen bleach compound in the p)l used. Must be. Therefore, polyalcohols with via hydroxy groups (e.g. For example, 1,2-brobanediol and glycerol) are peroxygen bleach compounds. Examples of suitable water-miscible organic solvents, which are less desirable when berborate are , lower aliphatic monoalcohols; diethylene glycol and lower monoaliphatic monoalcohols; Ethers of alcohols; in particular ethanol, n-propanol; isopropanol Tool; butanol; polyethylene glycol (e.g. PEG150.200 ．． 300.400); dipropylene glycol; hexylene glycol; methoxy Diethanol; Ethoxyethanol; Butoxyethanol: Ethyldiglycol Ether; Benzyl alcohol: Butoxypropanol; Butoxybropoxib and mixtures thereof. A preferred solvent is ethyl Nols: isopropanol, 1-methoxy-2-propanol and butylzig Examples include recall ether. A preferred solvent system is ethanol. Etano The alcohol may preferably be present in a water to ethanol ratio of 8:1 to 1:3. .

Although the presence or absence of other components plays a role, the amount of available oxygen in the solution It is largely determined by the proportion of organic solvent. However, the amount of available oxygen in the solution organic solvent in an amount greater than necessary to keep the It is not necessary to use a medium.

In practice, the ratio of water to organic solvent is preferably from 5:1 to 1:3 for most systems. The ratio is within the range of 4:1 to 1:2.

silicate Silicates are present in the composition in an amount of 0.5% to 5%, preferably 1% to 3%. Ru. The addition of such small amounts of silicate can promote the formation of structured surfactant baths. Surprisingly, peroxygen bleach particles with only a moderate increase in the viscosity of the composition allows efficient stable suspension of.

The silicate material for use here is a 1:1 ratio of 5102 to Ng20. to 4:1, preferably 1:1 (metasilicate), 1.621 or 2:1 It can be a natural silicate with

Sodium silicate is preferred, although potassium silicate can also be used.

Synthetic silicates, e.g. cide with a ratio of SiO2 to MgO of 3.5:1 Sydexe 120 can be used for purposes of the present invention.

The liquid detergent composition of the present invention with a bleaching agent has a pH (1% solution in distilled water) of less than 8 and less than about 11, preferably at least 9, more preferably at least 9. 5 is shown. Alkaline pH reduces hyperoxygenation, especially when the peroxygen is berborate. Enables good bleaching action of the compound.

surfactant The composition preferably comprises a total amount of 1% to 20%, most preferably 3% to 10%. of nonionic or cationic surfactants, or mixtures thereof. do.

Nonionic surfactants usually contain reactive hydrogen atoms, e.g. hydroxyl, carboxyl A hydrocarbon having a xyl or amide group and ethylene oxide are combined with an acid catalyst or It is produced by condensation in the presence of a base catalyst and has the general formula RA (CH2CH2 0), H (wherein R represents a hydrophobic moiety and A represents a group supporting a reactive hydrogen atom) and n represents the average number of ethylene oxide moieties). Ru. R typically has about 8 to 22 carbon atoms. They are propylene It can also be produced by condensation of carbon oxide with a low molecular weight compound.

n typically varies from about 2 to about 24.

The hydrophobic portion of the nonionic compound preferably has about 8 to about 24 carbon atoms, preferably about 12 to about 20 primary or secondary straight or branched aliphatic alcohols. good A more complete disclosure of suitable nonionic surfactants is found in U.S. Pat. No. 4,111,855. can be found in the specification. Mixtures of nonionic surfactants may be desirable be.

A preferred class of nonionic ethoxylates are fatty alcohols containing 12 to 15 carbon atoms. and about 4 to 10 moles of ethylene oxide per mole of fatty alcohol. Therefore, it is expressed as

Suitable ethoxylates of this type include C12-C15 oxoalcohols. condensate of alcohol and 7 moles of ethylene oxide per mole of alcohol; narrow cut 014-C15 oxo alcohol and fatty (oxo) alcohol 7 per mole or condensate with 9 moles of ethylene oxide; narrow cut 012-013 fat 6.5 moles of ethylene oxide per mole of (oxo)alcohol and fatty alcohol Condensate with Sid: and degree of ethoxylation (mol EO/mol fatty alcohol) 5-8 C1o-014 coconut fatty alcohol condensate having fat Oxoalcohols are mainly linear, but depending on processing conditions and raw olefins. It can have a corresponding degree of branching, especially short chains such as methyl branches.

A degree of branching of 15% to 50% (wt%) is often found in commercial oxo alcohols. It will be done.

In addition, the preferred nonionic ethoxylation component is two types having different degrees of ethoxylation. Can be represented by a mixture of separately ethoxylated nonionic surfactants Ru.

For example, a nonionic with 3 to 7 moles of ethylene oxide per mole of hydrophobic moiety 8 to 14 moles of ethylene per mole of ethoxylate surfactant and hydrophobic moiety Secondary ethoxylate that grows oxide. Preferred nonionic ethoxylation mixtures are about 3 to 7 moles of ethylene oxide with up to 50% (by weight) lower ethoxylates that are condensates of and with branching higher than 50% (by weight) CI6-019 oxo alcohol and about 8-1 per mole of branched oxo alcohol Contains a higher ethoxylate which is a condensation product with 4 moles of ethylene oxide.

Semipolar nonionic surfactants include alkaline or hydrocarbons having about 8 to about 28 carbon atoms. one loxyalkyl moiety and an alkyl group having from 1 to about 3 carbon atoms and a hydroxyalkyl moiety; two moieties selected from the group consisting of alkyl groups (these may optionally be combined to form a ring Examples include water-soluble amine oxides that contain

The liquid detergent compositions of the present invention optionally contain a cationic surfactant (preferably a surfactant). 0.1 to 10% by weight, more preferably 0.1 to 5% by weight of the composition.

Examples of suitable cationic surfactants include formula R1R2R3R4N''X- (wherein , R1 is CI2-c2o alkyl or hydroxyalkyl; R2 is C1 ~C4 alkyl or hydroxyalkyl or C12-C2o alkyl or hydroxyalkyl or C1-C4 hydroxyalkyl: R3 and R 4 is each C-C alkyl or hydroxyalkyl, or C6-C8 aryl or alkylaryl; X- is halogen) Examples include compounds. Mono-long chain quaternary ammonium compounds (i.e. R2 is C1- Compounds of the above formula which are C4 alkyl or hydroxyalkyl are preferred.

Zwitterionic surfactants that can be used in the compositions of the invention include those in which the aliphatic moiety is linear or can be branched, with one of the aliphatic substituents having about 8 to about 24 carbon atoms; and another substituent contains at least one anionic water-solubilizing group Includes derivatives of ammonium, phosphonium, and sulfonium compounds . A particularly preferred zwitterionic material is the U.S. patent of Rollin et al., issued December 9, 1975 No. 3,925,262 and Rollin et al., issued December 30, 1975. Ethoxylated ammonium sulfur as disclosed in U.S. Pat. No. 3,929,678 phonates and ethoxylated ammonium sulfates.

The composition may also contain anionic surfactants.

Anionic detergents are well known in detergent technology and have found widespread application in commercial detergents. It's out. Suitable anionic synthetic surfactant salts include sulfonates and sulfates. selected from a group of Preferred anionic synthetic water-soluble sulfonates or sulfates are , an alkyl group having about 8 to about 22 carbon atoms is present in the molecular structure.

Therefore, anionic surfactants, if used, preferably up to 40% by weight. It is present in an amount of 1 to 30% by weight, more preferably 5 to 20% by weight.

The synthetic anionic surfactant has the general formula R1S03M (RL is about 8 to about 24 carbon atoms). straight chain or branched alkyl groups and about 9 to about 15 m carbon atoms in the alkyl group; represents a hydrocarbon group selected from the group consisting of alkylphenyl groups having It can be expressed as M is typically sodium, potassium, ammonium , and mixtures thereof.

Preferred synthetic anionic surfactants have 9 to 15 carbon atoms in the alkyl group. It is a water-soluble salt of alkylbenzenesulfonic acid. Another preferred synthetic anion The surfactant has an alkyl sulfate or alkyl group of about 8 to about 24, preferably about 10 to about 20 carbon atoms and preferably about 1 to about 12 g of ethoxy groups. It is a water-soluble salt of an alkyl polyethylate ether sulfuric acid. other suitable Anionic surfactants are described in the U.S. patent of Frelascher et al., issued October 9, 1979. No. 4,170°565.

Examples of such preferred anionic surfactant salts are those derived from tallow and coconut oil. Reaction product obtained by sulfating 08-C18 fatty alcohol alkylbenzene sulfone in which the alkyl group has about 9 to 15 carbon atoms; Sodium alkyl glyceryl ether sulfonate; Tallow and coconut oil ether sulfates of fatty alcohols derived from coconut fatty acid monologues; Lyceride sulfate and coconut fatty acid monoglyceride sulfonate; and paraffin sulfonic acids having about 8 to about 22 carbon atoms in the alkyl chain. It is a water-soluble salt. For example, as detailed in U.S. Pat. No. 3,332°880, Sulfonated olefin surfactants can also be used. Anionic synthetic sulfonate Neutralizing cations for and/or sulfates are widely used in detergent technology. It is represented by common cations such as sodium and potassium.

Particularly preferred anionic synthetic surfactant components here include alkylbenzene sulfone Water-soluble salts of acids, preferably those having about 10 to 13 carbon atoms in the alkyl group. It is represented by sodium alkylbenzene sulfonate.

builder The composition contains a builder (preferably 50% or less of the total composition, more preferably 5% ~40% it).

If present, such builders may be of the inorganic or organic type already mentioned in the art. can become.

The liquid detergent composition of the present invention optionally contains a fatty acid component as a builder. You may. However, preferably the amount of fatty acids is less than 10% by weight of the composition. more preferably less than 4% by weight.

Preferred saturated fatty acids have 10 to 16 carbon atoms, more preferably 12 to 14 carbon atoms. has. Preferred unsaturated fatty acids are oleic acid and palmitoleic acid .

Examples of inorganic builders include phosphorus-based builders, e.g. Sodium phosphate, sodium birophosphate, and aluminosilicate (zeolite) ).

Examples of organic virgoos are polyacids such as citric acid, nitrilotriacetic acid, and tar Expressed by a mixture of trate monosuccinate and tartrate disuccinate I will be forgotten. Preferred builders for use here are citric acid and alkyl or or an alkyl or alkenyl group in which alkenyl has 10 to 16 carbon atoms; It is a succinic acid compound. An example of this group of compounds is dodecenylsuccinic acid . Polyacrylate, polyhydroxyacrylate and polyacrylate/polyacrylate Polymeric carboxylate builders, including limalate copolymers, are also preferably used. Preferred builders as described above, namely citric acid and alkyl or alkenyl substitutions Can be used in combination with succinic acid compounds.

Other ingredients/additives The composition preferably contains less than about 5% of other ingredients and/or additives. You may. Non-limiting examples of such additives (more preferably 0.05% to 2% Polyaminocarboxylate additives, such as ethyl diaminotetraacetic acid, diethylenetriaminopentaacetic acid, ethylenediaminodisuccinic acid Examples include acids or their water-soluble alkali metals. Any other additives available in these amounts. Examples of additives include organophosphonic acids. Ethylene diamino tetramethylene Renphosphonic acid, diethylenetriaminopentamethylenephosphonic acid and amino Particularly preferred are trimethylenephosphonic acid and hydroxyethylidene diphosphonic acid. . Ascorbic acid, dipicolinic acid, sodium stannate, 8-hydroxyquinoline , hydroethylene ethylene diphosphone IIF: (HEDP), diethylenetri Bleach stabilizers such as amine penta(methylene phosphonic acid) can also be used in amounts greater than It can be incorporated into these compositions preferably in an amount of 0.01 to 1%.

The compositions contain a series of further additives which are often used in additive amounts, usually less than about 5%. It can contain meaningful ingredients. Examples of such are polyacids, enzymes and enzyme Fixing agents, foam regulators, emulsifying agents, agents that improve mechanical compatibility in connection with enamel-coated surfaces. agents, bactericides, dyes, fragrances, brighteners, softeners, etc.

As mentioned above, detergent enzymes can be used in the liquid detergent compositions of the present invention. In fact, the main group One of the desirable characteristics of the composition is that it is compatible with such detergent enzymes.

Suitable enzymes include detergent proteases, amylases, lipases and cellular Examples include ze. Enzyme stabilizers for use in liquid detergents are well known. Enzyme stabilizer , if used, is preferably within the range of about 0.5% to 5%. used here Preferred enzyme stabilizers are formic acid, acetic acid, and their salts, such as sodium formate. Thorium and sodium acetate. A more preferred stabilizer is sodium formate and acetic acid.

Uses of the composition The composition is primarily intended for use in washing machine wash cycles. however , other uses, e.g. pre-treatment products for heavily soiled fabrics, or soaking products. , can be intended. Applications are not necessarily limited to the washing machine context and the compositions of the present invention may be used in Can be used alone or in combination with compatible hand wash compositions.

, some exemplary liquid detergent compositions of the present invention include the following formulation III [IrVVVI Linear alkylbenzene sulfonate 10 12 10 8 10 12 dodecenyl Lucuccinic acid 8.5 7 8.5 1 (1 g, 5 8 polymer carboxylate vinyl) Ruder 1.5 1.5 2 1.5 1.5 1 tallow fatty acid -1,52- -1 Diethylene triaminopenta 0.5 0.5 0.4 0.5 0.5 0. 4 (methylene phosphone button Hydroxyethylidene diphosphonic acid 0.2 0.2 0.3 0.2 04 O,4 Sodium formate 1.5 1 1.5 1.5 1 2 Acetic acid 1.4 1 ．． 5 1.4 1.4 2 - Ethanol 8 10 12 10 14 14 Sodium perborate monohydrate 14 - 14 - - 14 Sodium perborate Mu tetrahydrate -20-2220-Silicate SiO to NaO ratio 1.613- --- SiO to NaO ratio 2.0 --- 1.5 3-- Synde ■120 - - - - 1 4 Sodium hydroxide Water raised to pH 9.5 +Minor ingredients (fragrances, brighteners, enzymes, etc.) Remaining portion (100) International investigation report i1″″A groan 5″””’ ffl/I Confucian Ql 107 quotientContinuation of front page (81) Designated countries EP (AT, BE, CH, DE.

DK, ES, FR, GB, GR, IT, LU, NL, SE), 0A (B F, BJ, CF, CG, CI, CM, GA, GN, ML, MR, SN, TD, T G), AT, AU, BB, BG, BR, CA, CH, C8, DE, D K.

ES, FI, GB, HU, JP, KP, KR, LK, LU, MC, MG, MN, MW, NL, NO, PL, RO, SD, SE, SU, U S

Claims (8)

[Claims] 1. A solid suspended in a liquid phase containing water and at least one water-miscible organic solvent a water-soluble peroxygen compound, the amount of said solid water-soluble peroxygen compound being equal to said peroxygen compound; an amount such that the amount of available oxygen provided by the substance is 0.5% to 3%, pH at least 8 and characterized in that it contains 0.5-5% by weight of silicates. A stable liquid detergent composition having a molecular weight of less than about 11. 2. A detergent composition according to claim 1, wherein the silicate is present in an amount of 1% to 3%. 3. Claims 1 and 2, wherein the water-miscible organic solvent is an aliphatic monoalcohol. liquid detergent compositions. 4. the water-miscible organic solvent is ethanol and the water to ethanol ratio is 8:1 3. The liquid detergent set according to claim 2, wherein the ratio is from 5:1 to 1:2. A product. 5. The solid water-soluble peroxygen compound is perborate tetrahydrate and accounts for 5% of the total composition. 4. A liquid detergent composition according to claim 1, 2 or 3, present in an amount of ~30% by weight. 6. The perborate tetrahydrate bleach has a weight average particle size of 0.5 micrometers to 2 micrometers. 6. A composition according to claim 5, in the form of particles having a diameter of 0 micrometers. 7. Perborate tetrahydrate particles are produced by recrystallization of perborate monohydrate The composition according to claim 5, comprising: 8. Claim 1, 2 or 3, wherein the solid water-soluble peroxygen compound is a percarbonate. 3. The composition according to 3.