JPH07509523A - Peroxy bleach composition stabilized with ethylenediamine-N,N-disuccinic acid - 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] Peroxy bleach composition stabilized with ethylenediamine-N,N-disuccinic acid Background of the invention The present invention provides that the stabilizer has a bleaching effect when the composition is used as an aqueous solution in a bleaching process. Active oxygen releasing (peroxy) compounds and phosphorus-free bleaching that can control A bleaching composition comprising: Bleaching compositions may also be used as a component of detergent compositions. It is also useful.

The use of peroxy compounds for bleaching purposes is well known in the art. Peroki Hydrogen peroxide or inorganic perhydrate salts such as perborate or any of its adduct compounds containing percarbonates or organic peroxy acids . Perborate is an ingredient in detergent compositions for applications such as laundry, automatic dishwashing, etc. It is well known as Hydrogen peroxide can be used, for example, in textile and paper valve bleaching processes. Commonly used as a whitening agent.

In processes involving bleaching, the bleaching agent is released in a controlled manner throughout the process. It is desirable that Use of stabilizers to minimize rapid decomposition of peroxy compounds The peroxy bleaching technology is well established. The reason is that other things Incidentally, the oxygen released by such rapid decomposition of peroxy compounds is In general, bleaching It has no effect. In fact, the rapid decomposition of peroxy compounds can be harmful. example For example, cellulosic materials in strongly alkaline peroxy solutions are attacked by oxygen from rapid decomposition. This results in the material losing its strength. In today's laundry and dishwashing conditions, Stabilizers can be used in alkaline solutions and under relatively high temperature conditions that may be encountered in practice. It should preferably be valid under the conditions. Stabilizers can also be used in detergents or It must be compatible with other components that may be present in the oxybleach solution.

The presence of heavy metal ions can cause catalytic effects on peroxy bleach compositions. is also well known. Such heavy metal ions are present in many food and/or body contaminants. component, its presence in cleaning fluids during laundry and dishwashing processes is unavoidable. . Heavy metal ions are also commonly present in the liquid components of the wood pulp bleaching process. do. Wood pulp removes these ions from the process of crushing wood chips and pulp. Easy to incorporate from machines used in

Heavy metal sequestering or chelating agents are present in aqueous peroxy solutions used in the bleaching process. It has been used to control the amount of free heavy metal ions. In this way, The above chemicals prevent the decomposition of peroxy bleach due to heavy metal ion catalytic action. Therefore, it acts as a bleach stabilizer.

For example, one type of bleach was once widely used as a bleach stabilizer in detergent products. The agent (Chelai) is ethylenediaminetetraacetate (EDTA). there were. However, there are concerns about the environmental sustainability of this chelating agent, which is non-biodegradable. However, the current reduction in its use has been eased.

Organic phosphonates and aminoalkylene poly(alkylene phosphonates) Agents are also described, for example, in U.S. Pat. Nos. 3,860,391 and 4,239,643. It is known as a bleach stabilizer as described in No. Phosphonate chelators Their use in paper pulp and fiber bleaching processes and detergent compositions is also known.

Although the phosphonate chelators commonly used today in such processes It is a biodegradable system.

Phosphorus-containing compounds have also been linked to undesirable eutrophication effects in lakes and rivers. This makes the use of phosphorus-containing builder compositions, for example, in detergent compositions difficult. has brought about a reduction in

Phosphorus-free chelating agent, ethylenediamine-N,N'-disuccinic acid (EDDS), A laundry detergent composition comprising is disclosed in European Patent Application No. 0267635. this The disclosure discloses that when EDDS is incorporated into detergent compositions such as those described above, during the washing process. Teach to aid in the removal of food, beverage and certain organic stains from textiles There is. The disclosure also states that EDDS is currently used in many existing detergent products. , as a replacement for all or some of the phosphate chelators used. It also teaches you that you can stay. Applicant claims that when used as a component of detergent compositions, It was recently discovered that EDDS aids in the removal of grease stains. EDDS molecule has two chiral (Chi order 1) centers. European patent application 026765 No. 3 states that EDDS biodegrades most rapidly and extensively [3. S] What appears to be optical isospecificity with isomers is disclosed.

The applicant is now convinced of the optical specificity of the biodegradation of EDDS. [S,S ] The isomer is the only completely biodegradable optical isomer, and is a stumbling block in normal sewage treatment methods. It is essentially completely decomposed during the residence time.

Applicant discloses the use of low amounts of EDDS in certain EDDS, i.e. peroxy Some weight proportions of the compounds are peroxide in aqueous solutions containing certain heavy metal ions. We also made the unexpected discovery that the compound is excellent in stabilizing the use of xyl compounds. This stability is particularly important at high solution temperatures (>60°C). Surprisingly, EDDS , gives significantly better bleach stability than the same chemical isomer of EDTA under the same conditions. I can do it. Applicants also believe that the incorporation of EDDS into bleaching compositions improves the composition. It has also been discovered that it confers excellent storage stability.

European Patent Application No. 0267653 describes the EDDS-containing laundry detergents described therein. The composition may be included as an optical composition, bleach, bleach activator, bleach stabilizer, etc. It also teaches that. Peroxy compounds are not specifically disclosed in this document. not present. European Patent Application No. 0267653 is filed under Chem, 2vesji, 20(6 ), 414-422 (19661 (CA S Abstract 65: 11738f J, Majer, V, Sp+inge+ and B, Kop published in ) Refers to an article by ecka. This article focuses on heavy metal ions, namely Fe, C u　, Nl　, Co　, Zn　, Pb2+O3+　2+　, 2+　2+　2+ gives a stability constant to the complexes of EDDS with Cd2+ and Cd2+, and Comparisons are made with the corresponding stability constants of the complexes. of these metal ions except Cu2+ For each, the stability constant of the EDDS complex is lower than that of the EDTA complex.

For Cu2+ the stability constants are practically the same. EDDS becomes EDT at high temperatures Applicant's finding that it has better bleach stability than A It is even surprising in its presentation.

Disclosure of invention A bleaching composition containing a peroxy compound and a phosphorus-free chelating agent, EDDS. Bleach compositions exhibit good bleaching stability in aqueous solutions, especially solutions at temperatures of 60° C. or higher. It is an object of the present invention to provide a white composition.

According to one aspect of the invention, there is provided a bleaching composition comprising: That is, (a) Hydrogen peroxide, hydrogen peroxide, organic peroxy acids, and mixtures thereof peroxy compounds selected from addition compounds of (b) Ethylenediamine-N,N'-disuccinic acid or alkali metal, alkaline earth metals, their ammonium or substituted ammonium salts, or 0.05 to 2% by weight of the mixture of The weight ratio to diamine-N,N'-disuccinic acid is soo: i to 10 :1 range).

Weight of the peroxy compound relative to ethylenediamine-N,N'-disuccinic acid The ratio is preferably 400:1 to 20:1, more preferably 200:1. 1 to 40:1, and most preferably 150:1 to 50:1.

The peroxy compound preferably comprises 0.5 to 60% by weight of the bleaching composition, more preferably Preferably it is present from 1 to 40% by weight, most preferably from 2 to 25% by weight.

The bleaching compositions of the present invention can be used in essentially any bleaching process. Part of the invention According to aspects, the bleaching process will use an aqueous alkaline solution of the bleaching composition. Said The preferred pH range of the solution is 7.5 to 12.5, more preferably 9 to 12, Most preferably, it is between 9.5 and 11.5. According to a further aspect of the invention, This bleaching process will use a solution of acidic peroxy compounds containing a bleaching formulation. child Formulations such as are commonly used in bleach additive or household hard surface cleaning applications. I'm tired. Such acid bleaching formulations typically have a pH of 0.5 to 6; Preferably it is 1 to 5.

Preferably, the bleaching process according to the invention is carried out at least in part at a temperature above 60°C. It will be.

The first essential component of the bleaching composition of the present invention is a peroxy compound. Peroki The compound is hydrogen peroxide, or hydrogen peroxide or an organic peroxy acid, or It can be an adduct of any mixture thereof. Addition compounds of hydrogen peroxide and is a second chemical compound which may be, for example, an inorganic salt, urea or an organic carboxylate salt. A compound that is formed by the addition of hydrogen peroxide to an adduct. means. Examples of addition compounds of hydrogen peroxide include organic perhydrate salts, hydrogen peroxide Contains compounds formed with organic carboxylic acid salts, urea, and compounds in which hydrogen peroxide is included. be caught.

Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and Contains persilicate salts.

Salts in which hydrogen peroxide is included are described in British Patent Application No. 1494953.

Sodium percarbonate is a preferred inorganic to be included in the granular bleaching composition according to the invention. It is a perhydrate. These are the empirical formula NaBO-HO゛゛゛　・3H20 monohydrate and It will be blended even if you do it.

The bleaching compositions of the present invention, and any compositions with which they can be formulated, are essentially in any physical form, including solids, including powders, bars and granules, or liquids It can be a fluid, gel, or paste. However, peroxy compounds When neat, bleaching compositions generally include a concentrated solution of hydrogen peroxide with EDDS. include. When the peroxy compound is an inorganic perhydrate, the bleaching composition generally has a solid body, preferably granular in nature. Inorganic perhydrate salts provide no additional protection. contained in granular compositions such as crystalline solids. However, certain perhydrates In salts, the preferred use of such granular compositions allows for superhydration in granular products. For salts, a coated form of material is utilized which provides better storage stability.

Percarbonate, a highly preferred perhydrate included in the granular bleaching composition according to the invention Sodium is an addition compound with the formula corresponding to 2NaCO#3H202. It is commercially available as a crystalline solid. Percarbonate in coated form are most preferably incorporated into such compositions. The most preferred coating materials include Contains mixed salts of alkali metal sulfates and carbonates. Such coatings and coating methods No. 1, issued to Interox on March 9, 1977. No. 466.799. Weight of mixed salt coating material relative to percarbonate The quantity ratio is 1:200 to 1:4, more preferably 1:99 to 1:9, most preferably It is also preferably in the range of 1:49 to 1:19. Preferably, the mixed salt is Formula Na2SO4・n-Na2C03 (n is 0.1 to 3, preferably 0.3 to to 1.0, most preferably 0.2 to 0.5) and charcoal. It is a mixed salt of sodium acid.

Another suitable coating material has a SiO:Na20 ratio of 1.6:1 to 3. 4:1, preferably 2.8:1, by weight of percarbonate. water soluble to give an amount of silicate solids of 2% to 10% (usually 3% to 5%) Used as a liquid. Magnesium silicate may also be included in the coating. Other suitable Typical coating materials include alkali and alkaline earth metal sulfates and carbonates. It will be done.

Potassium peroxymonopersulfate is another inorganic perhydrate salt that is particularly useful in compositions. be. Also useful are the corresponding organic peroxy acids, namely peroxymonopersulfuric acid.

The bleaching process utilizing the bleaching compositions of the present invention is performed at least partially at a temperature below about 60°C. Where bleaching is carried out, the bleaching compositions of the present invention are also preferably further suitable for low temperature bleaching. Contains additional bleach. These include, for example, peroxy acid bleach precursors (bleach actives) (sex drugs). The main advantage of the presence of EDDS in the bleaching compositions of the present invention is that the high temperature ( 〉60℃) One of the main reasons for the stabilization of peroxy compounds used in the bleaching process is On the other hand, EDDS also acts as an effective chelating agent at low solution temperatures. Therefore, E The heavy metal ion chelation provided by DDS can be achieved at such low solution temperatures. Can stabilize any organic peroxy acid bleach component present as an active bleach. Ru.

EDDS provides good storage stability when incorporated into bleach-containing compositions . Such good storage stability properties are due to the fact that bleach-containing compositions are superior to alkaline detergent compositions. Especially when formulated as an acidic formulation with a pH of 0.5 to 6. be noticed. Achieving good storage stability properties for acidic bleach formulations is not possible in the prior art. This is known to be a special problem.

This peroxy bleach precursor probably contains one or more N- or O-acyl groups. selected from a wide range of varieties. Suitable materials include acid anhydrides, esters, imides and acylated derivatives of imidazoles and oximes, among which the effects Examples of such substances are described in GB-A-1586789. most preferred thing The quality is GB-A-836988, 864, 798, 1147871 and 214 3231 and GB-A-855735 and 1 246338.

Particularly preferred precursor compounds have the formula (wherein, X may be 0 or an integer from 1 to 6) It is a cetyl compound.

Examples include tetraacetylmethylenediamine (TAMD) where X=1, x =2, and tetraacetylethylenediamine (TAED), and x=6. There is tetraacetylhexylene diamine (TAHD). These and similar The compound is described in GB-A-907356. with additional bleach compounds The most preferred peracid bleach precursor is TAED.

Another preferred class of peracid bleach activator compounds are amide-substituted peracid bleach activators of the general formula: It is a compound that

or R1-N -C-R2-C-L where R1 is an aryl or alkaryl group having about 1 to about 14 carbon atoms. and R2 is alkylene containing about 1 to 14 carbon atoms, arylene, and an alkaryl group, R5 is H or alkyl containing 1 to 10 carbon atoms, It is an aryl or alkaryl group, and L can be virtually any residue.

R1 preferably contains about 6 to about 12 carbon atoms. R2 is preferably about 4-8 Contains carbon atoms. R1 is straight chain or branched alkyl, substituted aryl or alkylaryl containing branched chains, substituents, or both, synthetic sources or may be derived from natural sources including tallow fat. Similar structural changes are , R2 is also possible.

Substituents include alkyl, aryl, halogen, nitrogen, sulfur and other typical substituents can include groups or organic compounds. R5 is preferably H or methyl be.

R and R5 should not contain more than 18 carbon atoms in total. This kind of a Mido-substituted bleach activator compounds are described in EP-A-0170386 .

Other peracid bleach precursor compounds include, for example, those described in EP-A-0341947. Sodium nonanoyloxybenzenesulfonate, trimethyl as listed Sodium hexanoyloxybenzenesulfonate, acetoxybenzenesulfonate sodium chloride and sodium benzoyloxybenzenesulfonate.

The compounds of the present invention contain organic peracids in an amount of 1 to 15% by weight of the composition, more preferably 1 to 1% by weight of the composition. It can also be included in an amount of 0% by weight. Particularly preferred types are amides of the following general formula: It is a substituted peracid.

where R, R and R5 represent the corresponding amide-substituted peracid bleach activator compound. As defined above.

Other organic peracids include, for example, those described in EP-A-0341947. Peroxide dodecanoic acid, diperoxytetradecanoic acid, diperoxyhexadeca acid, mono- and diberazelaic acid, mono- and diberbrasyl acid, mono- These include peroxyphthalic acid, perbenzoic acid, and their salts.

Peroxy as a liquid component, especially when formulating bleaching compositions as acidic liquids. Dissolve or disperse compounds, and especially organic peroxyacids, or form emulsions. It can be formulated as a gel or suspension.

The bleaching compositions of this invention contain as a second essential component 0.05% of the total weight of the composition by weight of the composition. 10% to 10%, preferably 0.05 to 1%, more preferably 0.1 to 0.5 % of ethylenediamine-N,N'-disuccinic acid (EDDS) or its alkali Potash metal, alkaline earth metal, ammonium, or substituted ammonium salts, or contains a mixture of these. suitable for inclusion in this particulate detergent composition. The preferred EDDS compound form is the free acid and its sodium or magnesium form. It's salt. Among the preferred salts of EDDS are MgEDDS and Mg2EDDS. is included.

Magnesium complexes are most suitable for the purpose of adding them to the particulate composition of this invention. Ru. These complexes can be added neat into the composition or added to MgCl2 or The EDDS compound added as either an acid, a salt or a complex is an inert compound such as MgSO4. Even if it is formed during the manufacturing process of the composition by taking advantage of its reaction with magnesium salt, good. If the EDDS compound is added together with an inert magnesium salt during the manufacturing process, The molar ratio of magnesium to EDDS is preferably 1:1 or more, preferably 3:1 or more. This ensures the formation of the desired magnesium complex.

The structural formula of the acid form of EDD S is as follows.

EDDS is an easily available and inexpensive material such as maleic anhydride and ethylenediamine. The detailed method for synthesizing EDDS from commercially available starting materials is as follows: Rice from Kezerian and Ramsay (Ke!e+ign ind Rxm5a7) et al. Described in National Patent No. 3,158,635 (dated November 24, 1964) .

The synthesis of EDDS from maleic anhydride and ethylenediamine originates from two asymmetric carbon atoms. Therefore, [R,R], [S.

Three optical isomers of S co and [S, R] are produced.

The biodegradation of EDDS is selective for the optical isomer; [S.

S] The isomer that decomposes the fastest and is the largest and is therefore added in the composition of this invention. The [S,S] isomer is most preferred.

Are the [S,S] isomers of EDSS L-aspartic acid and 1,2-dibromoethane? are synthesized as follows: C0OHC0OH aOH CS, Sco EDDS Δ [S,S] isomer of EDSS from L-aspartic acid and 1,2-dibromoethane Details of the method for synthesizing entitled ``Stereoregular ligands and their complexes with ethylenediamine disuccinic acid''. Inorganic Chemistry (InoBxnic Chem tB), No. It is described in Volume 7 (+968), pages 2405-2412.

The bleach composition of the present invention is useful for bleaching cellulosic fiber materials. used here The term cellulose fibrous material includes wood, cotton, linen, jute and cellulose It also means other materials of the nature of the or cotton fibers, as well as yarns, tows, fabrics (woven or non-woven) and other Contains collections of these. The bleaching agent of the present invention can also be applied to polyamides, viscose rayons, etc. , useful for synthetic fiber fabrics including polyester.

Bleach compositions of the present invention are also useful in cleaning compositions. These cubes Leaning compositions are essentially suitable for any cleaning method where bleaching is required. It can be used in cleaning methods and cleaning methods.

That is, the cleaning composition can be used in domestic or industrial laundry or In automatic dishwashing affirmations, laundry add-on compositions, stain pretreatment compositions, carpet and and furniture cleaners, as well as bottle washing, such as cleaning toilet bowls. cleaning and manufacturing of hard surfaces such as kitchen and bathroom cleaning processes. It can be used in any way.

In the process of bleaching cellulose fibers or synthetic fiber fabrics, the bleaching agent of the present invention The composition is used in aqueous solution.

The most preferred peroxy compounds used in such processes are peracid It is hydrogen chloride. The peroxide aqueous solution pi-1 is often an inorganic alkyl metal base. chemical substances such as sodium hydroxide, sodium carbonate, sodium silicate and regulated by substances such as mixtures of these. The optimal pH is 7.5-12 ．． The value is between 5 and 5. Normally, if the pH exceeds <12.5, peroxy compounds The material breaks down quickly and can be bleached at an appropriate bleaching rate without damaging the fabric. becomes difficult to control. Also, if the pH value is less than about 7.5, the bleaching rate will decrease. In many cases, the bleaching rate is slowed to such an extent that it becomes uneconomical.

Silicates, particularly sodium silicate, are used in pels for cellulose fiber bleaching applications. Can be used to impart alkalinity in oxy solutions, bleaching Its use is preferably minimized as it tends to form deposits on fibers that are Can be kept to a minimum. Most preferably, the bleaching composition of the present invention is used to bleach cellulose. Peroxy solutions for bleaching textiles and synthetics contain sodium silicate. No.

In bleaching solutions for cellulosic or synthetic fibers, the concentration of EDDS stabilizer are determined, inter alia, by the concentration of the peroxy solution, the type of peroxy compound used, the pH, It is highly dependent on temperature, etc., and also usually the concentration of ordinary peroxy solutions and In the method for bleaching cellulose fibers/synthetic fibers, EDDS is preferably o , ooos to 0.5% by weight, more preferably 0.001 to 0.1% by weight. % by weight.

Bleaching methods using peroxy solutions containing the bleaching compositions of the present invention are very widely used. For example, at a temperature of about 0°C to about 100°C for about 30 minutes. It can be used for about 6-8 hours, and in continuous bleaching method, it can be used at normal temperature. , i.e. should be used at about 25°C, and in contact with the cellulose material at saturation to remove excess moisture and heat the cellulose material to a temperature of about 100°C to about 135°C. temperature for a few seconds (approximately 20) to about an hour (or in some cases longer). long) exposure to saturated steam. U.S. Patent No. 2,839,353, 2.96 0.383 and 2,983.568, representative of continuous peroxy bleaching methods. The law is illustrated.

- The bleaching compositions of the invention are also useful for essentially any laundry, cleaning or cleaning process. It can be blended into a composition used in a leaning method. The bleaching composition of the present invention The compounded laundry composition can be formulated as a granular composition and also It can also be formulated as a duty-liquid composition.

The composition additionally contains common ingredients normally found in detergent compositions. For example, organic surfactants, detergent virgoos, anti-redeposition agents and stains Dispersants, foam suppressants, enzymes, optical brighteners, photoactive bleaches, fragrances, filler salts, antiseptics May contain food and coloring agents.

Laundry detergent compositions may also contain fabric softeners and antistatic agents. .

A wide variety of surfactants can be used in the detergent composition. Typical anion, no ionic, zwitterionic, or amphoteric surfactants and compounds belonging to these Representative examples of the types include Lrughlin and Heavin. g) et al., U.S. Patent No. 3,929,678 (dated December 30, 1975) ) is disclosed. For suitable cationic surfactants see Murpbt. ) is described in US Pat. No. 4,259,217.

Mixtures of anionic surfactants, especially sulfates, sulfonates and/or Mixtures of carboxylate surfactants are preferred. Sulfonate/sulfate The surfactant mixture usually has a sulfonate to sulfate ratio of 5:1 to 1:2; Preferably a mixture of 3:1 to 2:3, more preferably 3:1 to 1:1 is used. used.

Preferred sulfonates have 9 to 15 carbon atoms, especially 11 to 13 carbon atoms. Alkylbensulfonates of alkyl groups and CI2-18 fat sources, preferred α-sulfonated methyl fatty acid ester from fatty acids derived from C16-18 fat source files are included. The cation in each case is an alkali metal, preferably sodium It is um. Preferred sulfates in such sulfonate/sulfate mixtures The surfactant has 12 to 22 carbon atoms in the alkyl group, preferably 16 to 18 carbon atoms. is an alkyl sulfate.

Other useful surfactant systems include two alkyl sulfates with different backbone lengths. consisting of a mixture of One such system is a C14-15 alkyl sulfate and a C14-15 alkyl sulfate. 16-18 alkyl sulfate in a weight ratio of 3:1 to 1:1. Ru. This alkyl sulfate has an alkyl group having 10 to 20 carbon atoms, preferably 10 to 16 alkyl ethoxy sulfates) (average of 1 to 6 moles of E, Oo) can be used in combination with adducts). The cation in each case is an alkali metal, preferably It is sodium.

Other particularly preferred anionic surfactants are CI2-20 alkyl sulfates and Water-soluble C11-18 alkyl ethoxy sulfate (average E, 0.1 to 7 mol) (addition) and consists of a mixture of alkyl sulfates and alkyl ethoxy sulfates. The weight ratio with Most preferably 3.5=1 to 10:1.

Alkyl sulfates are derived from natural or synthetic hydrocarbons. Al A good example of a kill sulfate is one in which the degree of branching of the Cl4-15 alkyl chain is about 20%. The above-mentioned substantially branched CI4-15 alkyl sulfates can be mentioned. It takes Substantially branched CI4-15 alkyl sulfates are commonly synthesized. beef tallow fat Also preferred are CI6-20 alkyl sulfates derived from common natural sources such as and marine oils. Can be hired in a suitable manner.

This C11-18 alkyl ethoxy sulfate is CI! -1 alcohol is 1 derived from a condensation product condensed with up to seven ethylene oxide (E, O,) groups, CI2-15 alkyl ethoxy sulfate (1 to 5 mole adduct of E, O,) , most preferably one with 1 to 3 ethoxy groups (E, O,) added per mole. be.

The CI+-18 alcohol itself can be obtained from natural or synthetic sources. natural fat , or C1 obtained from Ziegler method olefin or by oxo synthesis method 1-18 alcohols are suitable sources for this alkyl group. synthetically derived Among the materials used were Shell's [5he Commercially available product name: rDobanol 25 Commercially available product name: rElhyl 24J from Elhyl Co+p, l. , BASF Corporation (formerly BASFGmb, product name r Lu1ensolJ and IC From Company I under the product name r 5ynperonic J, and also from Liquiquimica (Liq Product name from uichi-micx 1lalixnx) Li5t 125J C13-Is alcohol with a CI3 to C15 ratio of 67 to 33 (% ratio), commercially available as mixtures of alcohols are included. Among natural sources are coconut oil and palm kernel oil and their corresponding Contains fatty acids. The content of Cll-18 alkyl ethoxy sulfate is 0.5 to 10%, preferably 0.5 to 5%, most preferably 1 to 10% by weight. It is up to 3%.

Other preferred anionic surfactants have the following general formula: [Wherein, R is a C5-17 straight chain or branched alkyl or alkenyl group, R1 is C1-4 alkyl group, M represents an alkali metal] It is an alkali metal sarcosinate shown in Lauro as sodium salt Ile, Coco71 (CI2-14), Myristyl and Ole ylmethyl sarcosinate is a preferred example.

One group of nonionic surfactants useful for use in this invention is that the lipophilic moiety is Condensed with oxide, the average -HL is from 8 to 17, preferably from 9.5 to 13.5; More preferably, it consists of 10 to 12.5 condensates. This lipophilic site is characterized by A polyoxy that is aliphatic or aromatic and is fused with any specific lipophilic group. Adjust the length of the ethene group to achieve the desired balance between hydrophilic and lipophilic elements. It is easy to produce water-soluble compounds prepared at the same time. This kind of nonion Particularly preferred surfactants are E, 0. C9-15 with an average addition mole of 3 to 5 - alcohol ethoxylate. Especially E.

0, CI 4-15-grade alcohol ethoxylate with an average addition mole of 6 to 8; and E, 0. CI 2-15-grade alcohol ethoxylate with an average addition mole of 3 to 5 is preferred.

In other groups of nonionic surfactants the general formula % formula %) [In the formula, Z is a glucose-derived moiety, R is a saturated lipophilic alkyl group having 6 to 18 carbon atoms] t is 0 to 10, n is 2 or 3, and X is 1.1 to 4; It is an alkyl polyglucoside compound represented by the following formula.

These compounds contain up to 10% unreacted fatty alcohols and up to 50% short chain Contains alkyl polyglucosides. This type of compound and its preparation method is EP-B No. 0070074, No. 0070077, No. 0075996 and No. No. 0094118 discloses this.

Other preferred nonionic surfactants have the following structural formula [wherein R1 is H, Cl-4 locarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or these mixture, preferably C14 alkyl, more preferably C1 or C2 alkyl , most preferably C1 alkyl (i.e. methyl); and R2 is C5-31 Drocarbyl, preferably straight chain C7-19 alkyl or alkynyl, more preferably preferably straight chain C9-17 alkyl or alkenyl, most preferably straight chain C11 -17 alkyl or alkenyl, or mixtures thereof; and 2 is directly attached to the chain Polyhydrocarbons with linear hydrocarpyl chains having at least 3 hydroxyls oxyhydrocarbyl, or an alkoxylated derivative thereof (preferably ethoxylated) z is derived from reducing sugar obtained by reductive amination reaction more preferably 2 represents glycyl] It is a fatty acid amide surfactant. Suitable reducing sugars include glucose and fructose. maltose, lactose, galactose, mannose, and xylose is included. Ingredients: high dextose corn syrup, high fructose Corn syrup and high maltose corn syrup are similar to the individual sugars listed above. is available. These corn syrups create a sugar component mix for Z. Ru. However, it is in no way intended to exclude other suitable raw materials. 2 is -CH 2-(CHOH)n-CH20H.

-CH(CHOH)-(CHOH) CH20H.

-CH-(CHOH) 2(CHOR')(CHOH)-CH20H [in the formula, n is an integer from 3 to 5 (including 5), and R' is H or a cyclic or aliphatic monomer. charlide and its alkoxylated derivative] Preferably, it is selected from the group consisting of: Most preferred is glycityl (n is 4 ),especially -CH-(CHOH) -CH20H.

In formula (1), R1 is, for example, N-methyl, N-ethyl, N-propyl, N- Isopropyl, N-butyl, N-2-hydroxyethyl, or N-2-hydro It is xypropyl.

R2-Co-N< is 1, such as cocamide, stearamide, or Reamide, lauramide, myristamide, caprinamide, palmitamide, Rouamide etc.

Z is 1-deoxygludityl, 2-deoxyfructityl, 1-deoxymulti Chill, 1-deoxyglutyl, 1-deoxygalactityl, 1-deoxyglutyl and 1-deoxymaltotriothytyl. A preferred compound is N-methyl N-1-deoxygludityl Cl4-18 fatty acid amide.

Another group of surfactants are the semipolar surfactants such as amine oxides. Appropriate a Mine oxides are mono C6-01 preferably Cl0-14 N-alkyl or alkenylamine oxide and propylene-1,3-diamine dioxide (this where the remaining N positions are substituted with methyl, hydroxyl or hydroxypropyl groups. selected from).

Cationic surfactants can also be used in the detergent compositions described herein, with suitable quaternary Ammonium surfactants are mono-C8-16, preferably Cl0-14N-alky or alkenyl ammonium surfactants (where the remaining N positions are methyl, hydrogen, (substituted with a droxyel or hydroxypropyl group).

This detergent composition contains 3 to 30% by weight surfactant. laundry detergent composition Usually 5 to 20% by weight of the composition, more preferably 7 to 15% by weight of surface activity. Contains an agent.

Automatic dishwashing detergent compositions usually contain between 0 and 10% by weight of the composition, preferably 0. -5no The surfactant content is preferably 1 to 10% by weight, more preferably 1 to 5% by weight.

This surfactant has anionic, cationic, nonionic, zwitterionic, and amphoteric surfactants. You can choose from several agents. The most preferred surfactants are low foaming. automatic dishwasher Typical surfactants for detergent compositions are described in EP-A-0414549. There is a description. Most preferred are low foaming nonionic surfactants, especially water-soluble ethyl surfactants. Xylated C6-16 fatty alcohols and C6-16 mixed ethoxylated/propo xylated fatty alcohols and mixtures thereof. This ethoxylated fatty acid Alcohol is a C10-16 ethoxylated fatty alcohol (E, 0.5 to 50 mol adducts) most preferably CI2-16 ethoxylated fatty alcohols (E, O, 8 to 40 molar adducts) are preferred. Mixed ethoxylated/propoxylated fatty acids The alkyl chain length of alcohol is 10 to 16 carbon atoms, and the degree of ethoxylation is 3 The degree of propoxylation is preferably 1 to 30, and the degree of propoxylation is preferably 1 to 10.

The surfactant is a combination type, more preferably an anionic/nonionic and/or anionic surfactant. A mixed ion/cation type is preferred. Regarding particularly preferred combination types, G It is described in B-A-2040987 and EP-A-0087914. world Surfactants can be incorporated into the composition as a mixture, but should be used to optimize the physical properties of the composition. , it is preferable to control the addition point of each surfactant to avoid processing problems. Delicious.

Preferred modes and order of surfactant addition will be described later.

Another highly preferred component of the detergent compositions of the present invention is one or more other non-phosphate detergent compounds. It is a detergent builder type containing detergent. These are crystalline layered sodium silicate, carbonate borates, alkali metal aluminosilicates, monomeric polycarboxylates, Homo- or copolymeric polycarboxylic acids or their salts (where polycarboxylic phosphoric acids contain at least two carboxylic acids separated from each other by not more than two carbon atoms. (containing sil groups), carbonates, silicates and mixtures of any of the above. It is not limited to.

A preferred non-phosphate virgoux salt is a crystalline layered sodium silicate of the general formula:

NaMSixO2□1-yH20 (where M is sodium or hydrogen, X is a number from 1.9 to 4, and y is 0 ~20). This type of crystalline layered sodium silicate is EP-A-01 64514 and its preparation method is disclosed in DE-A-3417649 and It is disclosed in DE-A-3742043. For the purpose of the present invention, the above general formula X has a numerical value of 2.3 or 4, preferably 2.

More preferably, M is sodium and y is 0, and preferred embodiments of this formula Examples are the α-1β-1γ- and δ-forms of Na2S1205. these The substances are Na5KS-5 and Na5KS-7 from AG FRG, respectively. , Na5KS-11 and Na5KS-6. most preferred The substance is δ-form NaSiONa5KS-6.

2 25ゝ These substances have a particle size of 150-1000 μm and a particle size of at least 800 g/ liter, preferably with a bulk density of approximately 900 g/'J liter. Prepared as a movable solid. However, the crystals as produced are brittle; Easily breaks down into particles with a size smaller than 100 μm.

Laundry detergent compositions formulated with the bleaching compositions of the present invention preferably have a Crystals in an amount of 1-80%, more preferably 5-40%, most preferably 7-20% Contains layered sodium silicate.

The crystalline layered sodium silicate is preferably intimately mixed with a solid water-soluble ionizable substance. It exists as a particle. This solid, water-soluble ionizable substance contains organic acids and selected from organic acid salts as well as mixtures thereof. The first requirement is that this substance: Ability to at least partially neutralize hydroxy ions dissociated by crystalline phyllosilicates should contain at least one acidic functional group with a pKa of 9 or less that provides This means that Surprisingly, according to the invention, this ionizable substance is It is not necessary to have a pH of 7 or the substance is formed by dissolution of crystalline silicates. hydroxyl ions and stoichiometric amounts of hydrogen atoms are present. It was found that there are

In fact, the neutralization of ionizable substances during particle storage causes losses in the fabric foil damage effect. but never loses its effect.

In addition, the ionizing substance has an average particle size of 300 μm or less, preferably 100 μm or less. should have a

This facilitates a uniform distribution of ionizable substances and crystalline silicates, ensuring that the particles are free from the washing water. It is believed that when dissolved in water it promotes localized pH lowering.

Suitable organic acids include ascorbic acid, citric acid, glutaric acid, gluconic acid, glycosyl malic acid, malic acid, maleic acid, malonic acid, oxalic acid, succinic acid, tartaric acid, 1- Hydroxyethane, 1,1-diphosphonic acid (EHDP), NTMP, EDTMP and aminopolymethylenephosphonic acids such as DETPMP, and the aforementioned Contains a mixture of deviations. Suitable acid salts are sodium hydrogen carbonate and sodium hydrogen oxalate. um, sodium hydrogen sulfate, sodium pyrophosphate, sodium orthophosphate, alcohol including sodium hydrogen phosphate, or mixtures of any of the foregoing.

The granular mixture of crystalline layered silicic acid and solid water-soluble ionizable substance has a pH of at least 10. (measured in a 1% solution in 20°C distilled water), more typically at least pH 11, Usually it will have a pH of at least 11.5.

The blending of crystalline layered silicic acid and other additional components to the solid water-soluble ionizable substance is the process of particle preparation. and are particularly effective in increasing the stability of detergent compositions containing the particles. especially, Some types of agglomerates are made of silicon to produce particles with acceptable physical properties. Requires the addition of one or more binders to assist in binding the acid salt and the ionizable water-soluble substance It may be. The binder is present in an amount of 0 to 20% by weight of the composition. can be done. Preferably, the binder is intimately mixed with the silicate and the ionizable water-soluble substance. It will be combined.

Preferred binders have melting points of 30-70°C. Preferably, the binder is included in the composition. It is present in an amount of 1 to 10% by weight of the composition, most preferably 2 to 5% by weight of the composition.

A preferred binder contains 5 to 100 moles of ethylene oxide per mole of alcohol. CIO to C20 alcohol ethoxylate containing, preferably 1 mole of alcohol Alcohols from CI5 to C2Q containing 20 to 100 moles of ethylene oxide per Contains ethoxylates.

Other preferred binders include certain polymeric materials.

polyvinylpyrrolidone having an average molecular weight of 12.000 to 700.000; Polyethylene glycol having an average molecular weight of 600 to 10,000 is used as such. This is a specific example of a polymeric substance. Maleic anhydride and ethylene, methyl vinyl ether or or methacrylic acid (at least 20% of the polymer is maleic anhydride) ) are further examples of polymeric materials useful as binders. These polymerizations Substances can be used neat or in water, propylene glycol, 5 to 100 moles per mole. of the above-mentioned CIO to C20 alcohol ethoxylates containing ethylene oxide. It is used in combination with such solvents. Further examples of binders according to the invention are: CIO-C20 mono- and diglycerol ethers and 010-020 fatty acids Contains. Certain organic salts, including sodium silicates, are also used for this purpose.

Methylcellulose, carboxymethylcellulose, hydroxymethylcellulose cellulose derivatives such as, and mono or copolymerizable polycarboxylic acids or These salts are other embodiments of binders according to the invention.

If they are not incompatible per se and interfere with the virgoo function of the crystalline phyllosilicate, Provided that the particles do not harm other compositions commonly used in detergent compositions, It is also possible to include. Therefore, the particles contain up to 50% by weight of anionic particles. surfactants, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof; And some preferred particle embodiments include a surfactant. Such surface activity Specific examples of agents are described in more detail below. However, if the particles are mixed with Any surface-active substance capable of dissolving crystalline phyllosilicates, even partially, is It is important not to create any significant amount of free (unbound) water. for that purpose , the surfactant is solid and preferably has less than about 5% free moisture, more preferably There should be less than 2% free moisture, most preferably less than 1% free moisture.

Other ingredients may be present in a total amount up to 50% by weight of the particles. Regarding surfactant content The same conditions as mentioned above apply. Therefore, such optional ingredients are preferred. Preferably, it is solid at normal temperature (room temperature) and has a free content of less than 5% by weight, preferably less than 1%. It should be (unbound) water.

If crystalline phyllosilicates have no appreciable solubility in such components, If present, non-aqueous liquid components may be present in amounts up to 20% by weight of the particles. This is grain A normally solid component applied in molten form that acts as a massing/coating agent It can also be applied to

Particles can be extrudates, malta (mxrume+), lumps, flakes, or can be in various physical forms, such as compressed granules. crystalline layered silicon Preferred preparation of compacted granules comprising an acid salt and a solid, ionizable, water-soluble substance The method is described in co-assigned UK Application No. 9108 filed April 23, 1991. No. 639.7.

Although a range of aluminosilicate ion exchange materials can be used, the preferred materials are: unit cell system %formula% [wherein 2 and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5; , X is at least 5, preferably 7.5 to 276, more preferably 10 to 276 264] It is a sodium aluminosilicate zeolite shown in This aluminium The silicate material is in hydrated form, preferably 10 to 28% by weight, more preferably is a crystal containing 18 to 22% by weight of bound water.

The aluminosilicate ion exchange material has a particle diameter of 0.1 to 10 micrometers. further characterized by having a diameter of 0.2 to 4 micrometers, preferably 0.2 to 4 micrometers. It will be done. The term “particle diameter” as used herein refers to the average particle diameter of the ion exchange material. measurement under a microscope, e.g. using a scanning electron microscope or a laser viscometer Refers to the particle size measured by known analytical techniques such as This amino silicate toy Further characteristics of on-exchange materials are generally between 300 mg eq./g and 352 mg Calcium ion exchange capacity showing the range of eq, /g, calculated value on anhydrous basis is at least 200 mg equivalent Ca CO3 water hardness (per g aluminosilicate) It is to show that. A further feature of this aluminosilicate material is the calcium ion content. The on-exchange rate is at least 130 mg equivalent CaC○3 based on cardioid ion hardness. /L/min/(g/L) to 390 mg equivalent Ca CO3/L/min/(g/ L).

Calcium ion exchange rate of the highest quality aluminosilicate used for bilgoo purposes The degree is at least 260 mg equivalent Ca CO3/L/min/(g/L).

Aluminosilicate ion exchange materials useful in this invention are commercially available. Although natural products can be used, synthetic products are preferred if possible. aluminosilicate The method for synthesizing the ion exchange material is disclosed in U.S. Patent No. 3,985,669. . A preferred crystalline aluminosilicate ion exchange material has the trade name "Zeolite A" , "zeolite B", "zeolite P", "zeolite X", "zeolite H8" ”, “zeolite MAPJ, r zeolite MABJ, and mixtures thereof It can be obtained from the market. Crystalline aluminosilicate in preferred embodiments The on-exchange material is given by the following formula: %formula% Zeolite AJ represented by [wherein X is 20 to 30, especially 27] (Product name).

Zeolite with the formula Na [(AIO) (StO) 1.276H2o X” is also the formula % formula % It is useful in the same way as "H8".

Is the monomer or oligomer of water-soluble carboxylate virgo a widespread compound? However, the -order carboxyl logarithmic acidity constant pK1 is 9 or less, preferably is preferably between 2 and 8.5, more preferably between 4 and 7.5. .

This pKt (logarithmic acidity constant) is the following equilibrium H++A, HA [where A is the fully ionized carboxylate anion of this bilgoux salt] It is defined as follows with reference to: The equilibrium constant of a dilute solution is Therefore, pK, = 1oglOK For purposes of this invention, acidity constants are defined at 25° C. and zero ionic strength.

Where possible, values are adopted from literature. [Special feature on “Stability constants of metal ion complexes” No. 25, Chemical Society of London “5tabilif7 Con5anj of Met al-fan Complexe+’, 5special Publication No, 25. TheChemicxl 5ocict7. (London) Reference]: If in doubt, determine by potentiometric titration using a glass electrode.

This carboxylate or polycarboxylate can be a monomer or oligomer However, from the viewpoint of price and performance, the use of monomeric polycarboxylates is recommended. Generally preferred.

The monomers and oligomer builders have the following general formula [wherein R1 is Hl or hydrogen] Optionally substituted with Roxy, carboxy, sulfo or phosphono groups, or E, O.

C l-30 alkyl optionally bonded to a polyethyleneoxy moiety containing up to 20 groups or alkenyl; R2 is HlCl-4 alkyl, alkenyl or hydro Xyalkyl, alkaryl, sulfo, or phosphono group: X is a single bond;○ ;S;So, or NR'.

Y is H: carboxy; hydroxy; carboxymethyloxy: or hydroxy as well or a Cl-30 alkyl or alkenyl group optionally substituted with a carboxy group ;Z is H: or carboxy.

m is an integer from 1 to 10; n is an integer from 3 to 6; p, q are integers from 0 to 6, provided that p+q is 1 to 6; and each of X5YSZ is one When repeated in a constant molecular formula, they are the same or different, and the At least one Y or Z is a non-containing group containing one carboxyl group. Select from cyclic, cycloaliphatic, heterocyclic and aromatic carboxylates.

Suitable carboxylates containing one carboxy group include lactic acid, glycol Mention may be made of water-soluble salts of acids and their ether derivatives (Belgium Patent No. 8). No. 31.368, No. 821,369 and No. 821.370). two pieces Examples of polycarboxylates containing carboxyl groups include succinic acid, malonic acid, (ethyl dioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, curtonic acid and and fumaric acid, and West German Publication No. 2.446.686 and West German Publication No. 2.446, 687 and U.S. Pat. No. 3,935,257. Sylates are included, as well as the sulfur compounds described in Belgian Patent No. 840,623. including vinyl carboxylates. Polycarbonate containing three carboxy groups Among the targets are water-soluble citrate, aconitate and citraconate, and carboxymethyloxysuccinate (British Patent No. 1,379,241), Lactoxysuccinate (British Patent No. 1,389.732), Aminosuccinate (Dutch Patent Application No. 7205873) and 2-oxa-1,1,3-propylene Ropantricarboxylate (UK Patent No. 1.387,447) is included. It will be done.

Among the four carboxy group-containing polycarboxylates are oxydisuccinates ( UK patent no. 1.261,829), 1,1.2.2-ethanetetracarboxylate , 1,1,3,3-propane tetracarboxylate and 1,1,2,3-propane Included are lopantetracarboxylate. Polycarbohydrates with sulfo substituents Xylate is a sulfosuccinate derivative (UK Patent No. 1,398,421; ．． 398°422 and U.S. Pat. No. 3,936,448), and Includes phonated pyrolytic citrate (UK Patent No. 1.439,000) .

Among the cycloaliphatic and heterocyclic polycarboxylates are cyclopentadiene molecules. recarboxylate, 2.3°4.5-tetrahydrofuran-cts, cis, cis-tetracarboxylate, 2,5-tetrahydrofuran-cis-cal boxylate, 2,2,5,5-tetrahydrofuran tetracarboxylate, 1,2,3°4.5-hexanehexacarboxylate, and sorbitol, Carboxymethyl derivatives of polyhydric alcohols such as mannitol and xylitol is included. Among the aromatic polycarboxylates are mellitic acid and pyromellitic acid. and phthalic acid derivatives (UK Patent No. 1.425,343). It will be done.

Among these, preferred polycarboxylates contain up to three carboxy groups per molecule. locarboxylates, especially citrate.

Starting Acids for Monomeric or Oligomeric Polycarboxylate Chelating Agents or Mixtures of their salts, such as citric acid or citrate/citric acid mixtures, may also be used. Used as a bilgoo ingredient in detergent compositions of the invention.

Other useful water-soluble organic salts are homo- or copolymeric polycarboxylic acids or salts. and this polycarboxylic acid is separated from each other by no more than two carbon atoms. Consists of at least two carboxyl groups. The latter type of polymer is GB-A- It is described in No. 1,596,756.

Among these salts are polyacrylates with a weight average molecular weight of 2,000 to 5,000. and its maleic acid copolymers, the molecular weight of such copolymers being 20. 000 to 70,000, especially about 40.00. Typical concentrations of these materials is 0.5 to 10% by weight, preferably 0.75 to 8% by weight, more preferably It is 1 to 6% by weight.

Detergent compositions containing the bleaching compositions of the present invention contain non-phosphate detergent builder compounds. at a level of 1 to 80% by weight of the composition, more preferably 10 to 60% by weight of the composition. % by weight, most preferably at a level of 20-50% by weight.

In preferred laundry detergent compositions, sodium aluminosilicate, For example, 20 to 60% by weight of something like zeolite A based on the total amount of builder. The builder can contain monomeric or oligomeric carboxylates. It can contain 5 to 30% by weight based on the body weight, and further includes a crystalline layer coating silicate. It can be contained in an amount of 10 to 65% by weight based on the total amount of the builder. Such a composition , the builder system preferably further comprises supplementary inorganic and organic compounds. compound, such as sodium carbonate and maleic anhydride/acrylic acid copolymer. It can be contained in an amount of 35% by weight or less based on the total amount of the builder.

The detergent composition of the present invention contains a chelating agent (chelan+) as an optional ingredient. or included. Optional chelating agents include aminoalkylene poly(alkylene fluoride) sulfonate), alkali metal ethane 1-hydroxydiphosphonate, nitriloto rimethylene phosphonate, ethylenediaminetetramethylene phosphonate, and organic phosphonates, including diethylenetriamine pentamethylene phosphonate; Examples include the following. The phosphonate may be present in the free acid form or in the alkali or alkali form. present in either the form of a complex with a potassium earth metal ion and The molar ratio of metal ions used is at least 1:1. Preferred organic phosphonates The compound is a magnesium salt. The amount of phosphorus-containing chelating agent should be kept to a minimum and If so, it is preferable not to add it.

Silicates are useful in automatic dishwashing detergent compositions containing the bleaching compositions of the present invention. It is an ingredient. A suitable silicate is water-soluble sodium silicate, S Including those with an iO2:NaO ratio of 1.0 to 2.8. S　iO2+N　a　20 Silicates with a ratio of 2 are most preferred. Silicates are present in the machine of dishwashing detergent compositions. present at a level of 5-50%, more preferably 10-40% by weight of the composition. Exists.

Soluble silicates in known formulations are used for various purposes; is not necessary in the composition of this invention. However, it forms part of the virgoo family of detergents. Crystalline layered silicates must be added as a dry mix, so detergents Still useful as a component in the spray-dried granules that normally make up the composition part It is. Spray-dried particles contain no aluminosilicate builders and are organic materials This is particularly useful when it consists only of ingredients. A suitable silicate is S iO:N a.20 ratio is in the range of 1.6 to 3.4, more preferably 2.0 to 2.8 It is.

Detergent compositions containing the bleaching compositions of the present invention are generally prepared in the form of sodium salts. This includes the inorganic overhydration term. Suitable inorganic perhydration terms are as described above. bleaching composition Usually, the amount is 3 to 40% by weight, more preferably 5 to 30% by weight based on the detergent composition. , most preferably formulated to provide a level of perhydrate of 10-25% by weight. Ru.

Detergent compositions containing the bleaching compositions of the present invention generally include peroxyacid bleach precursors ( It further contains a bleach activator). Suitable peroxy acid bleach precursors typically have the composition 1 to 20% by weight, more preferably 1 to 15% by weight, most preferably Contains at a level of 3-10% by weight.

The detergent composition further contains an organic peroxy acid in an amount of 1 to 15% by weight based on the composition. More preferably, it can be contained at a level of 1 to 10% by weight.

Solid peroxy bleach precursors are acid-coated to minimize fabric discoloration. The protected detergent composition composition is a patent application filed in February 1991, under co-examination with the applicant. It is described in British Patent Application No. 9102507.2 filed on the 6th.

Suitable anti-redeposition and soil suspending agents herein include methylcellulose, carboxylic cellulose derivatives, such as methylcellulose and hydroxyethylcellulose, Homopolymer or copolymer polycarboxylic acids or their salts and polyamino There are compounds. Polymers of this type include polyacrylic esters and EP-A- 137669-, maleic anhydride and ethylene, methyl bicarbonate. There are copolymers of nyl ether or methacrylic acid, and maleic anhydride is a copolymer of It constitutes at least 20 mol% of the total mass. Compounds derived from aspartic acid Polyamino compounds such as EP-A-305282, EP-A-305283 and and EP-A-351629. These materials are generally composed of 0.5 to 10% by weight, more preferably 0.75 to 8% by weight, most preferably 1 Used in an amount of ~6% by weight.

Other useful polymeric materials are polyethylene glycols, especially those with molecular weights between 1000 and 10 000, more preferably from 2000 to 8000, most preferably about 4000. It is ethylene glycol. These materials are preferably 0.20 to 5% by weight, more preferably is used in an amount of 0.25 to 2.5% by weight. These polymers and the previously mentioned monomers Homopolymeric or copolymeric polycarboxylate salts can help with whiteness maintenance, fabric ash build-up, cleaning of viscous, proteinaceous and oxidative soils in the presence of and transition metal impurities. It is useful for improving cleaning performance.

Preferred optical brighteners are anionic in nature, examples include 4,4'-bi su-(2-jetanolamino-4-anilino-8-triazin-6-ylami ) Stilbene-2:21-disulfonic acid disodium, 4.41-bis-(2 -morpholino-4-anilino-8-triazin-6-ylamino)stilbene- 2=21-disulfonic acid disodium, 4.4'-bis-(2゜4-dianilino -5-triazin-6-ylamino)stilbene-2,21-disulfonic acid dina Thorium, 41゜411-bis-(2,4-dianilino-s-triazine-6- ylamino)stilbene-2-sulfonic acid-sodium, 4.41-bis=(2 -anilino-4-(N-methyl-N-2-hydroxyethylamino)-S-tri azin-6-ylamino)stilbene-2,21-disulfonic acid disodium, 4.4'-bis-(4-phenyl-2,1,3-triazol-2-yl)styrene Rubene-2,21-disulfonic acid disodium, 4.4'-bis-(2-ani Lino-4-(1-methyl-2-hydroxyethylamino)-s-triazine-6 -ylamino)stilbene-2,21-disulfonic acid disodium and -1, There is sodium 2,3-4 lyazole-211-sulfonate.

Soil release agents useful in the compositions of the present invention typically include terephthalic acid and ethylene glycol. copolymers or tars of various arrangements of glycol and/or propylene glycol units. -It is a polymer. Examples of such polymers include commonly assigned U.S. Pat. No. 4,116. 885 and 4711730 and published European patent application no. 02720 It is described in No. 33. Particularly preferred polymers according to EP-A-0272033 is the expression %formula% (wherein, PEG is -(OC2H4)0-, PO is (QCHO), and T (pCOC6H4CO) generally has a molecular weight of 5000 to 20000, preferably 10,000-15,000, some polymeric materials such as polyvinylpyrrolidone , is an effective additive that prevents transfer of sensitive dyes between fabrics during washing.

Another optional component is silicone and silica-silicone blends. It is a bubble suppressant represented by a compound. Silicones are generally alkylated polysilicone typified by xane materials, whereas silica is represented by silica aerogels and xane materials. Used in finely divided form, such as rogels and various hydrophobic silicas.

Although these materials can be formulated as particulates, air bubble suppressants are water-soluble or water-dispersible. Formulated for release in a transparent, substantially non-surface-active, detergent-impermeable carrier It is advantageous to do so. Alternatively, the bubble suppressant can be dissolved or It can also be dispersed and applied by spraying onto one or more other ingredients.

As noted above, useful silicone cell control agents include alkylated siloxanes of the types listed above. and solid silica. Such a mixture can be applied to the surface of solid silica. It is manufactured by attaching silicone to. Preferred silicone bubble control The agent has a particle size of 10 nanometers to 20 nanometers and a specific surface area of 50 m2/ hydrophobic silanized (most preferably trimethylsilanated) dimethyl silicone liquid with a molecular weight of about 500 to about 200,000 and silicone. Thoroughly mix the cone to silanized silica in a weight ratio of 1 to about 1:2. Manufactured by.

A preferred silicone foam control agent is disclosed in U.S. Patent No. 3,93 to Biollojx et al. No. 3.672. Other particularly useful foam control agents include It is described in German patent application No. DTO 32,646,126 published on the 28th. It is a self-emulsifying silicone foam control agent.

An example of such a compound is the siloxane/glycosiloxane commercially available from Dot CCo1n1n. This is a copolymer DCO544.

The bubble suppressants mentioned above generally range from 0.001 to 5% by weight of the composition, preferably 0.001% to 5% by weight of the composition. It is used in amounts of 1 to 3% by weight.

In a preferred method of formulation, the foam suppressant in liquid form is added to one or more major components of the composition. by spraying or by forming the bubble suppressant into separate particles, which can be applied to Mix with other solid components of a substance. By blending the bubble control agent as a separate particle. , C2G””C24 fats, which can have a negative effect on the dispersibility of the matrix. Acid, microcrystalline wax and ethylene oxide and propylene oxide Other cell control agents may also be included, such as high molecular weight copolymers of. I feel like that The manufacturing technology for foam regulating particles is the above-mentioned Bt+jollol! U.S. Patent No. 3,93 of et al. No. 3.672.

Other optional components useful in the present invention are one or more enzymes.

Preferred enzyme materials include commercially available amylases conventionally incorporated into detergent compositions, alkaline and alkaline proteases, lipases, esterases and cellulases There is. Suitable enzymes are described in U.S. Pat. Nos. 3,519,570 and 3,533,1. It is described in No. 39.

Preferred commercially available protease enzymes include N (1 mao 1 ndu-sj+ies A/S (Denmark) to ^1c11xse and S! Tfn! ! es and In1ernxlionil Bio-SBlo-S7n1h, Inc. There are enzymes sold under the trade names from Randa) to khxx (*Ie).

Preferred amylases include, e.g., by GB-1, 296,839 (Novo) Obtained from a special variety of Saretail described in detail, B1ichenilo+ms There is amylase. Preferred commercially available amylases include, for example, InHr-n*t ionil Ri sold by Blo-3ynlhelics, Inc. Sold by pidast and Novo Indosfries A/S There is Te+mam71.

A particularly preferred lipase enzyme is Novo Industries A/S (Denma from Lipolase (Biolechnolog7 Nevsvxt cb.

Manufactured and sold under the product name (March 1988, p. 6), EP-A-0 258068 (Novo), along with other suitable lipases.

Further additional ingredients useful in detergent compositions are corrosion inhibitors and 14-C2o fatty acids are preferred.

A fabric softener may also be incorporated into the detergent composition of the present invention.

These softeners may be of inorganic or organic type. Inorganic softener is GB-A-1,4 It is typified by the smectite clays described in No. 00,898. organic textiles Softeners include those described in GB-A-1514276 and EP-B-0011340. There are tertiary amines that are insoluble in water.

The combination of softener and 012-C14 quaternary ammonium salt is EP-B-00265 27 and 528. Other useful organic fabric softeners are EP=B-0 dilong chain amide as described in No. 24919. Textile softening system and others The organic components include those described in EP-A-0299575 and 0313146. There are high molecular weight polyethylene oxide materials such as

The amount of smectite clay is generally 5-15% by weight, more preferably 8-12% by weight. % and is added as a dry mix component to the other ingredients of the formulation. insoluble in water Organic fabric softeners, such as tertiary amines or dilo B-chain amide materials, can be ~5% by weight, usually 1~3% by weight, but high molecular weight polyethylene Oxide materials and water-soluble cationic materials are 0.1-2% by weight, usually 0.15-2% by weight. Add in an amount of 1.5% by weight. When spray drying parts of the composition, these materials Can be added to the aqueous slurry fed to the spray drying tower, but as dry mixed particles. It can be added as a molten liquid or sprayed as a molten liquid onto the other solid components of the composition. Sometimes it is advantageous.

Generally, the granular detergent compositions of the present invention can be prepared by dry mixing, spray drying, agglomeration and granulation. can be manufactured by a variety of methods including Use combinations. Preferred methods of manufacturing the composition include spray drying, high speed mixer combinations of agglomeration and dry mixing.

The bulk density of the granular detergent composition of the present invention is similar to that of conventional cleaning detergent compositions. Generally speaking, it may be 400 to 600 g/liter. Alternatively, the granular detergent composition is , which is characterized by a relatively high density compared to conventional cleaning detergent compositions. It may also be a reduced granular detergent composition. Such dense compositions have a bulk density of at least 650 g/l, more typically at least 700 g/l , more preferably 800 g/liter to 1100 g/liter.

Bulk density is determined by a solidly molded conical funnel on the base with a butterfly valve at its lower end. The inside of the funnel is placed in a cylindrical cup placed in axial alignment below the funnel. It is measured using a simple funnel and cup device into which the contents can be poured.

The funnel is 13 (1+a+ and 40mm) at the top and bottom ends respectively.The funnel is , installed so that its lower end is 140mm higher than the upper surface of the foundation. Cup is full height 90mm, internal height 87mm and internal diameter 84mm.

Its nominal volume is 5001.

To make a measurement, fill the funnel with powder by hand, open the butterfly valve, and remove the cup. flood with powder. Remove the filled cup from the frame and make sure the edges are straight. Remove any excess powder by passing a knife, such as a knife, across the top edge of the cup. Remove the body from the cup. The filled cup is then weighed and the result obtained in terms of powder weight. The obtained value is then doubled to express the bulk density in g/liter. Measure as necessary repeat.

Concentrated detergent compositions generally include at least one multi-ingredient ingredient, i.e. The composition does not include a composition formed by mere dry mixing of the individual components. . Compositions in which the individual components are dry mixed are generally dusty, dissolve slowly, and are difficult to store. There is a tendency for particles to form a cake and have poor fluidity.

- Preferred granular detergent compositions of the present invention contain at least two particulate strip ingredients. including. The first component is at least 15% by weight of the composition, typically 25-50% by weight of the composition. %, more preferably up to 35% by weight, and the second component accounts for 1 to 50% by weight of the composition. %, more preferably 10 to 40% by weight.

The first component is an anionic surfactant in an amount of 0.75 to 40% by weight of the powder. and one or more inorganic and/or organic salts in an amount of 99.25 to 60% by weight of the powder. Contains particles formed by blending. Particles can be granules, flakes, prills, mxrumes or They can have any suitable shape, such as or noodles, but granules are preferred. granules Formed by pan or drum agglomeration or by in-line mixer Although it may be agglomerated, it is usually an aqueous slurry of the raw material, with most of the water removed. Spray-dried particles produced by spraying into a stream of hot air. Then, spray dried The granules are subjected to a densification step, e.g. by a high speed cutter mixer and/or a compression mill. to increase density and then reagglomerate. For illustrative purposes, below the first component is described as a spray-dried powder.

Anionic surfactants suitable for the purpose of the first component include slowly dissolving, alkyl-based surfactants. has an average of 16 to 22 carbon atoms and the alkyl group is It was found to be a straight chain alkyl carboxylate having an average of 16 to 24 carbon atoms. won. In both types, the alkyl groups of the surfactants are derived from natural fats such as tallow. It is preferable to do so.

The amount of anionic surfactant in the spray-dried powder forming the first component ranges from 0.75 to 40% by weight, more typically 2.5-25% by weight, preferably 3-20% by weight, Most preferably it is 5-15% by weight. The spray-dried powder is then coated with a linear alkali. Water-soluble interfaces such as rubenzene sulfonate or CI4-C15 alkyl sulfate The active agent can be added or applied by spraying.

The other main component of the spray-dried powder is one or more inorganic or is an organic salt. Inorganic and/or organic salts may be water-soluble or water-insoluble. However, the latter consists of, or consists largely of, a builder that is insoluble in water; These salts here form part of the builder component. Suitable water-soluble inorganic salts include: There are alkali metal carbonates and bicarbonates. Alkali other than crystalline layered silicates Metal silicates are spray-dried unless aluminosilicates form part of the spray-drying component. It may also be present in mist-dried granules.

However, in concentrated detergent compositions, it is best not to add sodium sulfate as a separate ingredient. Preferably, sodium sulfate is used as a by-product, e.g. at the sulfuric acid (sulfonic acid) interface. Incorporation with the active agent should be minimized.

If the aluminosilicate zeolite forms the builder component, or part thereof, Aluminosilicate zeolite can be used in multi-material compositions by dry mixing without being added directly to other components. It is preferable to mix it within minutes.

The first component contains up to 15% by weight of brighteners, anti-redeposition agents, photoactivated bleaches (tetra sulfonated zinc phthalocyanine) and chelating agents. I can do it. When the first component is a spray-dried powder, the powder typically has a water content of Dried to 7 to 11% by weight, more preferably 8 to 10% by weight of the mist-dried powder. let The moisture content of powders produced by other methods such as agglomeration may be lower; It may be 1 to 10% by weight.

The particle size of the first component is conventional, preferably 5% by weight or less is 1. Should be greater than 4 mm, while not more than 10% by weight should be less than 0.15 mm in the maximum range. It should be full. Preferably at least 60% by weight of the powder, most preferably at least 80% by weight is in the range 0.7 mm to 0.25 mm. sprayed For dried powders, the bulk density of the particles from the spray drying tower is usually 5 ranges from 40 to 600 g/liter, and this is due to the high speed cup following compression. increased by further processing steps such as size reduction in the mixer/mixer. I can do it. Or, as another method, use a method other than spray drying. It can be used to directly form dense particles.

The second component of the preferred composition according to the invention is another component containing a water-soluble surfactant. It is a multi-component granule.

Is it anionic, nonionic, cationic or semipolar? or a mixture of any of these. Suitable surfactants are listed below. As mentioned above, preferred surfactants include CI4-CI5 alkyl sulfurs. ates, linear C11-C15 alkylbenzene sulfonates and aliphatic C14 ~C18 methyl ester sulfonate.

The second component may have any suitable physical form, i.e. ark, prills, mxromes, noodles , ribbon or agglomerated by spray drying or non-spray drying Can be granular. This second component is theoretically the water-soluble surfactant itself. In practice, at least one to expedite the process can be may contain organic or inorganic salts. This is the particle and perhaps the first degree of crystallinity relative to - or more of the organic or inorganic salts present in the and thus provide acceptable flow properties.

The particle size range of the second component is such that it will not separate from the particles of the first component when blended. The range should be such that it can be prevented. In other words, 5% by weight or less is 1.4■ on the other hand, 10% by weight or less is less than 0.15 mm at the maximum range. Should.

The bulk density of the first component is a function of the mode of preparation. However, the preference of the second component A preferable form of the second component is one in which the second component is mechanically mixed and agglomerated. , this can be a pan agglomerate, a two-blade mixer or more preferably a Schag i (Netherlands) B V, 29 Chromesjrzs1g211 AS, Le17slzd, Nefberlxnds and Gebrude+Lodi ge Mrshincnbln GmbH, D -4790P1de+botn LElsenerttrxsse 7-9. Po5llich 205OF The component materials are placed in a dry state in an in-line mixer manufactured by R.G. Alternatively, it can be produced by adding it together with a flocculant. By this means Therefore, the second component contains 650 g/liter to 1190 g/liter, more preferably or provide a bulk density in the range of 750 g/liter to 850 g/liter Can be done.

Preferred laundry compositions contain from 3 to 15% by weight of the composition in the second component, such as some level of alkali metal carbonate, preferably corresponding to an amount of 5 to 12% by weight. It can contain. This results in a concentration of 20 to 40% by weight of the second component. carbonate level is given.

A particularly preferable second component is also a synthetic zeolite-type water-insoluble aluminium oxide, which will be described later. The silicate ion exchange material may be contained in a range of 10 to 35% by weight of the second component. is preferable. The amount of water-insoluble aluminosilicate material added in this case is It is 1 to 10% by weight of the composition, more preferably 2 to 8%.

In one method of preparing the second component, the surfactant salt is mixed in an in-line mixer. It is formed on the spot inside. Granular anhydrous carbon with liquid acid to form a surfactant For acid sodium salts and hydrated sodium aluminosilicate, Lodige in a continuous high speed blender such as a C6 mixer and neutralize. , a surfactant salt is formed while maintaining the particulate character of the mixture.

The resulting agglomerated mixture forms the second component and is added to the other components of the product.

In a variation of this process, the surfactant salt is pre-neutralized and viscous. As a paste, it is added to other ingredients. In a variant, the mixer mixes the ingredients used only to aggregate to form the second component.

In a particularly preferred process for producing the granular detergent composition of the invention, the A portion of the spray-dried product consisting of one particulate ingredient is converted and recycled with the remainder. Subjected to a low level nonionic surfactant spray before being blended. Second The particulate component is manufactured using the preferred method described above. This first and second component is a silicate granular composition with a crystalline layer formed, a superhydrated bleach and a peroxidase. phosphoric acid bleach precursor particles, carboxylate chelating agents, stain removal polymers and fermentation It is fed to a conveyor belt along with other dry mixed ingredients such as the raw material and rotates horizontally. The product is then transferred to a drum where fragrances and silicone foam suppressants are sprayed onto the product. - will be done. In particularly preferred compositions, an additional drum mixing step is employed. , at which time a low level (approximately 2% by weight) of microcrystalline material is introduced to increase the density. Granular flow properties are improved.

In preferred concentrated detergents with the addition of alkali metal percarbonates as a superhydration component, There is a need to control several aspects of the product such as heavy metal ion content and equilibrium relative humidity. It has been found that there is a need. This type of percarbonate with improved stability The sodium-containing composition is incorporated by reference to British Application No. 9021761.3, assigned to the same person. (filed October 6, 1990).

The laundry composition according to the invention also provides automatic washing at the start of the laundry cycle. A distribution system that provides a temporarily localized high concentration of product in the drum of a washing machine. This reduces product losses associated with machine piping and drainage. problems can be prevented.

Distribution to the drum involves placing the composition in a bag or container and then stirring and raising the temperature. It is rapidly released at the beginning of the wash cycle in response to rise in temperature and immersion in the wash water. This can be easily achieved by. In yet another aspect, a washing machine itself dispenses the composition into the drum, for example by dispensing means provided in the access door. It can also be configured so that it can be added directly.

Products consisting of detergent compositions stored in bags or containers usually have no odor in the dry state. Although the integrity of the container is maintained and the contents are prevented from spilling, the cleaning ring the contents of the container are released, usually by immersion in an aqueous solution. It can be designed in any way.

Typically, the container is something flexible, such as a bag or pouch. The bag is from Europe. 0018678 as disclosed in State Patent Application No. 0018678. It may consist of a fibrous structure coated with a water-impermeable protective material. Wear. Alternatively, European Patent Application No. 0011500.0011501.00115 02 and 0011968. A water-insoluble synthetic polymer with an end seal or closure designed to It may be made of any material. The usual forms of water-disintegrating occlusion bodies are: Parts made from water-impermeable polymer films such as polyethylene and polypropylene. Consisting of a water-soluble adhesive that is placed along one edge of the door and seals.

In a bag or container variant, the central flexible layer is impregnated with the composition and/or or coat the central flexible layer with the composition and then apply one or more outer layers to create a fabric-like aesthetic effect. A laminated sheet product can be used. Layers remain joined during use May be sealed together to facilitate release of coated or impregnated substances may separate upon contact with water.

Another laminate form is a series of pouch-like containers, each containing a predetermined amount of detergent ingredients. pouch-like when the second layer is on top of the first layer and the two layers are in contact. embossed or deformed to give it a seal) in the area between the containers It has one layer. The ingredients may be applied in granular, paste or molten form and The laminate layer should prevent extraction of the contents of the pouch-like container before addition to water . The layers may separate upon contact with water or remain bound together. Well, the only requirement is that the structure allows rapid release of the contents of the pouch-like container into solution. This is what should be done. The number of pouch-like containers per unit area of the substrate is selected However, it will usually vary from 500 to 25,000 per m2.

Suitable materials that can be used for the flexible laminate layer in this aspect of the invention include: , inter alia sponges, paper and woven and non-woven fabrics.

However, preferred implementation means of the method of the invention are permeable to liquids. by a reusable dispensing device having walls that are impermeable to the solid composition. , introducing the composition into the liquid surrounding the fabric located within the drum.

Devices of this kind are described in European Patent Applications Nos. 0343069 and 0343 It is disclosed in the specification of No. 070. The latter application includes a support line defining an orifice. A device comprising a flexible sheath in the form of a bag extending from the orifice (the orifice is Suitable for bagging enough product for one wash cycle) is disclosed. A portion of the cleaning medium flows into the bag through the orifice and The solution then passes outward through the orifice to reach the cleaning medium. Ru. The support ring has a masking device to prevent the extraction of wet undissolved product. This device typically has a spoked wheel shape with a diameter extending from a central boss. Consisting of directionally extending walls or similar structures in which the walls have a helical shape.

Minulxctu+ing Chemmouth+ (November 1989, 41-46 An article by I.Blacd published on page) also includes the words “GranuleHe” and “GranuleHe”. A particularly preferred dispensing device for use with granular products of the type commonly known as It is listed.

The invention is illustrated by the following non-limiting examples. All percentages here are weighted unless otherwise noted. It is based on quantity.

In the detergent composition, the abbreviated components have the following meanings.

LAS: Sodium linear C12 alkylbenzene sulfonate TAS: Sodium tallow alkyl sulfate TAE: per mole of alcohol Tallow alcohol 2 ethoxylated with n moles of ethylene oxide 3EY: ZC-based alco enriched with an average of Y moles of ethylene oxide rule 25EY: C-based linear chain enriched with an average of Y moles of ethylene oxide Primary alcohol +2-15 45EY: C-branch 1 enriched with an average of Y moles of ethylene oxide alcohol TAED: Tetraacetylethylenediamine silicate: Amorphous sodium silicate (SiO2:Na20 ratio follows normal case) NaSKS-6: Crystal logging coated, δ-Na2S105 Carbonate: Anhydrous sodium carbonate CMC: Sodium carboxymethyl cellulose zeolite A: Formula Na (A 1OS 1o2) B”27H20 hydrated sodium aluminosilicate, Polyacrylate with main particle size ranging from 1 to 10 μm: MW, 4000 homopolymer of acrylic acid Citrate, trisodium anhydrous citrate M A / A A: 1.4 Copolymer of maleic acid/acrylic acid with an average molecular weight of about 5oooo Perboreto dianhydrous sodium perbore monohydrate bleach, empirical formula NaBOH0 2゛　22 PH1: Anhydrous sodium percarbonate tetrahydrate bleach, empirical formula% formula% Enzyme: Mixed enzyme for proteolytic and starch decomposition (Noyo 1nduuri) Sold by es AS) D E T P M P: MOIII Diethylene trichloride sold under the trade name Deqaesl 206G by IIIO Toaminepenta(methylenephosphonic acid) Foam suppressant = 25% paraffin wax Mpt 50”C117% hydrophobic silica , 58% paraffin oil EDDS: Ethylenediamine-N,N'-dicoha Citric acid, [S,S] isomer in the form of sodium salt Sulfate: Anhydrous sulfur acid sodium EDTA: Ethylenediaminetetraacetate amylase: Noyo In dusl+ies A device sold under the product name Tetmim71 by A/S. Pumpkinase protease: From Noyo Industries A/S Proteolytic enzyme NaC1 sold under the trade name S1ma1nxsc: Anhydrous sodium chloride Nonionic: 013-CI with degree of ethoxylation 3.8 and degree of propoxylation 4.5 5-ethoxylated/propoxylated fatty acid alcohol Montmorillonite: Smectite type resin softener Hectorite 2 Same as above CAS: Sodium Coconut Alkyl Sulfate PEPA: Polyethyl Pro Poxyalcohol sulfuric acid: sulfuric acid (Sulpbu+ic tci) d) Example 1 The following peroxy bleach containing laundry detergent products were prepared (parts by weight). Product A and B are conventional compositions and products C and D are of the invention.

B.C.D. LAS 7.8 7.8 7.8 7.8 TAS 2.4 2.4 2.4 2 ．． 4TAEII 1.1 1.1 1.1 1.125E3 3.3 3.3 3.3 3.3 Zeolite A 19.5 19.5 19.5 19.5 Citre 6.5 6.5 6.5 6.5MA/AA 4.3 4.3 4.3 4.3 Carbonate 11.1 11.1 11.1 11.1 Berborate 16.0 16.0 16.0 16.0TAED 5.0 5.0 5.0 5.0EDTA O, 4--- DETPMP 0.4 - - EDDS O, 40, 2 CMCO,50,50,50,5 Foam suppressant 0.5 0.5 0.5 0.5 Enzyme 1.4 1.4 1.4 1.4 silicate (ratio 2.0) 4.4 4.4 4.4 4.4Mg5O4 0, 40, 40, 40, 4 Sulfate 4.1 4.1 4.1 4.1 The rest is water and others 100 ml of water with a hardness of 17 degrees (Ca COa of 243 ppm) The containing beaker was placed in a constant temperature bath set at 90°C and heated to bath temperature.

Add heavy metal ions in the form of soluble inert organic salts to this beaker, and The weight concentration of 1. lppm Cu, 2ppm Fe, 2.3ppm Zn and and 0.12 ppm of Mn. These concentrations of Cu, FeZn and Mn The standard is the concentration found in the washing liquid of automatic washing machines when washing regular dirty laundry. It is considered to be comparable to the degree level. Wash this beaker with 0.7% detergent solution by weight. One of the agent products was added. Take an aliquot of the solution from the beaker at predetermined time intervals. percentage of the amount present in the detergent product before adding it to the solution. The percent HO remaining (from the velborate bleach) was determined as follows. Residue The percentage of H2O2 present is reduced by aliquots to prevent further decomposition of H2O2. was added to a 20% sulfuric acid solution, then 0. Standard permanganese with KMnO4 in IN It was determined by acid titration. The same method is used for products A, B, C and D. were carried out for each. Repeated testing is performed until consistent results are obtained. It was done.

From the time the detergent product was added to each beaker of products ASB, C and D. The percent H2O2 remaining at each given time is shown below.

Time (minutes) Remaining H202% A B CD o 100 100 100 100 5 92.6 98.9 96.3 91.710 82.6 98.9 94 ．． 2 92.120 67.4 94.4 93.2 91.730 47.4 87.6 85.8 84.450 29.0 78.7' 77.4 78 ．． Comparing the three results, the EDTA-containing composition, the present sulfonate-containing composition, and the present sulfonate-containing composition. B or EDDS-containing compositions C and D are considerably less bleach stable. E.D.D. S in equal amounts (0.4%) and equimolar amounts relative to the phosphonate chelator When used at (0.2%) DETPMP imparts significant bleach stability. A detergent composition for machine dishwashing was produced which solved the following problems (parts by weight).

Products E and F are conventional compositions and product G is according to the invention.

A B C Citrate 42.4 42.4 42.4MA/AA 4.0 4.0 4. 0 Silicate (ratio 2.0) 33.0 33.0 33.0 Nonionic surfactant Agent 1.5 1.5 1.5 Verborate 10.4 10.4 10.4TA ED 2.6 2.6 2.6 Amylase 1.5 1.5 1.5 Protease 2.2 2.2 2.2 Sulfate 0.7 0.7 0.7 NaCI 1. 3 1. 3 1. 3EDTA O, 3-- DETPMP -0,6- EDDS --0,3 The rest is water and other A similar test method was used as described in Example 1, but this test was performed using a domestic automatic dishwasher. Adjustments were made to suit process conditions. 17°Jaman hardness (243ppm C a. A beaker containing 100ml of CO3) water was initially heated to a constant temperature of 20°C. I took a bath. Heavy metal ions are added to this beaker in the form of soluble inert organic salts. The weight concentration of heavy metal ions was set to 1.5 ppm Cu and 0.67 ppm Fe. And so. These concentration levels of Cu and Fe are It is believed that the concentration level is comparable to that found in the washing liquid of household automatic dishwashers during cleaning. It will be done. Add one of the detergent products to this beaker and add 0.4% detergent solution by weight. A liquid was prepared. Pour the solution at a constant rate so that the solution temperature reaches 65°C after 15 minutes. Heat and remove an aliquot of the solution at this time to determine the percent H2O2 remaining. was measured using the method described above.

The solution was then held at a temperature of 65°C for a further 10 minutes, during which time an aliquot of the solution The sample was removed and the remaining 8202% was determined in the same manner. No variation Repeated tests were performed until a satisfactory result was obtained. Each of the products E1F and G The residual H202 percentage is shown below.

Residual H2O2 percent Time (minutes) E F G o 100 100 100 15 56.8 7 81.3 25 42.6 69.7 71.0 Example 3 The following peroxy bleaches contain laundry detergent products containing smectite clay-type softeners: Manufactured according to the invention.

45E7 1.3 1.3 Zeolite A 19.5 19.5 Citrate 5. 0 5. 0 - MA/AA 3.2 3.2 Carbonate 12.0 12.0 Belborate 5. 8 5・8 PB4 7. 8 7. 8 TAED 5. 0 5. 0 EDDS 0.2 0.2 CMCO, 480, 48 Foaming inhibitor 0. 5 0. 5 Enzyme 1. 4 1. 4 Silicate (ratio 2.0) 3.0 3.0 Mg504 0.43 0.43 Sulfate 4. 1 4. 1 Montmorillonite 12.5 - Hectorite 12.5 The rest is water, minor ingredients and other Example 4 The following liquid pels containing ingredients suitable as household cleaners or as bleach additives: An oxy bleach was prepared according to the present invention.

JK Hydrogen peroxide 8.50 3.5 CAS 0. 8 12. 0 PEPA 1.1 - Solphunic (up to pH 4) - Manoethanolamine - EDDS up to pH 2.5 0.1 0.1 Water and minor ingredients less than 100 Minor ingredients less than 100 include fragrances, brighteners and dyes. Includes fees.

Handbook Supplementary Book April 1995 Female 6th grade Continuation of front page (51) Int, C1,6 identification symbol Internal office reference number C11D 3/33 9 546-4H D O6L 3102 7199-3B // C09K 15/20 9049 -48 (81) Designated countries EP (AT, BE, CH, DE.

DK, ES, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE) , 0A (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, NE, SN.

TD, TG), AU, BB, BG, BR, BY, CA.

CZ, FI, HU, JP, KP, KR, KZ, LK, MG, MN, MW, NL, NO, NZ, PL, RO, RU, SD, SK, DA, US, VN FI (72) Inventor: Tree, Graham Alexander, Northumburgh, UK Ndo, Morpeth, Nillington, Premitush, 1 (72) Inventor: Ursolmaz, Semi-Sem, Tyne, & Wear, United Kingdom , Tynemouth, Pursey, Park, 49

Claims (27)

[Claims] 1. (a) Hydrogen peroxide, addition compounds of hydrogen peroxide, organic peroxy acids and the like a peroxy compound selected from a mixture of (b) 0.05 to 2% by weight of ethylenediamine-N,N'-disuccinic acid, or Alkali metal salts, alkaline earth metal salts, ammonium salts, substituted ammonium salts of or a mixture thereof, the ethylenediamine-N,N'-disuccinic acid The weight ratio of the peroxy compound to bleaching composition. 2. the ethylenediamine-N,N'-disuccinic acid in the form of its [S,S] isomer; 2. A bleaching composition according to claim 1. 3. The ethylenediamine-N,N'-disuccinic acid component accounts for 0.05 to 1% of the composition. % by weight and said weight ratio is within the range of 400:1 to 20:1. A bleaching composition according to claim 1 or 2. 4. The ethylenediamine-N,N'disuccinic acid component accounts for 0.1 to 0.5 of the composition. % by weight, and the weight ratio is in the range of 200:1 to 40:1; A bleaching composition according to any one of claims 1 to 3. 5. Bleach according to any one of claims 1 to 4, comprising a peroxyacid bleach precursor. Composition. 6. According to any one of claims 1 to 5, the peroxy compound is hydrogen peroxide. A bleaching composition useful for bleaching cellulosic and synthetic fibers. 7. 7. The bleaching composition of claim 6, wherein the bleaching composition is free of sodium silicate. 8. The peroxy compound is an inorganic perhydrate salt and contains 3 to 40% of the cleaning composition. % and the cleaning composition comprises from 1 to 80% by weight of a non-phosphoric cleaning constituent compound. and a mixture thereof. A cleaning composition comprising a bleaching composition. 9. The ethylenediamine-N,N'-disuccinic acid component is a magnesium salt. 9. The cleaning composition of claim 8. 10. Anionic, cationic, nonionic, amphoteric and zwitterionic surfactants 0.5 to 10% by weight of a low foaming surfactant selected from agents and mixtures thereof. A cleaning composition for machine dishwashing according to claim 8 or 9, comprising: 11. amylolytic, proteolytic and lipolytic enzymes and mixtures thereof 11. The cleaning composition for machine dishwashing according to claim 10, comprising an enzyme selected from the following. 12. Anionic, cationic, nonionic, amphoteric and zwitterionic surfactants 3 to 30% by weight of a surfactant selected from surfactants and mixtures thereof. 10. The laundry cleaning composition according to 8 or 9. 13. Non-phosphoric acid cleaning constituent compounds include crystalline layered sodium silicate and sodium aluminosilicate. Thorium zeolites, alkali metal carbonates and bicarbonates, carboxylates, poly The claim is selected from carboxylic acid salts, maleic anhydride and acrylic acid copolymers. 13. The laundry cleaning composition according to 12. 14. The crystalline sodium layered silicate cleaning component has the formula NaMSixO2x+1 °yH2O (where M is sodium or hydrogen, x is a number from 1.9 to 4, and y The laundry detergent according to claim 13, which is a compound represented by a number from 0 to 20). cleansing composition. 15. The crystalline layered silicate compound is Any one of claims 12 to 14, which is δ-Na2Si2O5 (NaSKS-6). The laundry cleaning composition according to item 1. 16. Anionic surfactant with C12-C20 alkyl sulfate per molecule water-soluble Cl1-C19 alkyl ethoxy having an average of 1 to 7 ethoxy groups; the alkyl ethoxy sulfate to the alkyl ethoxy sulfate; Any of claims 12 to 15, wherein the weight ratio of sulfate is in the range 2:1 to 19:1. The laundry cleaning composition according to item 1. 17. The alkyl sulfate is a C14-C15 alkyl sulfate; C12-C15 acetic acid in which the oxysulfate has an average of 3 ethoxy groups per molecule. alkyl ethoxy sulfate, and the above alkyl ethoxy sulfate is 17. The weight ratio of sulfate is in the range of 3.5:1 to 10:1. Laundry cleaning composition. 18. Nonionic surfactants have the formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R1 is H, C1 to C4 hydrocarbyl, 2-hydroxyethyl, 2- hydroxypropyl or a mixture thereof, R2 is C5-C31 hydro carbyl, and Z has at least three directly bonded hydroxyl groups. Polyhydroxyhydrocarbyl having a straight hydrogen chain or its alkoxylated derivative The laundry cleaning composition according to any one of claims 12 to 17, which is a conductor. 19. On average, 3 to 8 moles of nonionic surfactant per mole of alcohol is a C9 to C15 primary alcohol ethoxylate containing ethylene oxide, The laundry cleaning composition according to any one of claims 12 to 18. 20. The primary alcohol ethoxylate is on average from 3 to 1 mole of alcohol. Claimed to be a C12-C15 primary alcohol containing 5 moles of ethylene oxide. 20. The laundry cleaning composition according to 19. Claims 12-20 comprising from 21.1 to 20% by weight of solid peroxy acid bleach precursor. The laundry cleaning composition according to any one of the above. 22. Sodium peroxycarbonate in which the inorganic perhydrate salt is present in an amount of 5 to 30% by weight and the solid peroxy acid bleach precursor is present in an amount of 1 to 10% by weight of the composition. 22. The laundry cleaning composition of claim 21, wherein the laundry cleaning composition is TAED present in 23. Detergent enzymes, soil suspensions, anli-redeposition agents (anli-rede position agent), optical brightener, foam suppressant, fragrance and these 23. Any one of claims 12 to 22 comprising an additional cleaning component selected from a mixture of The laundry cleaning composition described in . 24. The above composition is a liquid, and the peroxy compound is hydrogen peroxide, organic peroxide, etc. selected from sialic acid and mixtures thereof, and the composition has a pH of 0.5 to 6. A composition comprising a bleaching composition according to any one of claims 1 to 5. 25. The peroxy compound is dissolved or dispersed in a liquid composition or emulsion. 25. The composition of claim 24, wherein the composition is contained as a liquid or a suspension. 26. Dissolved or dispersed in a liquid, or as an emulsion or suspension, 26. A composition according to claim 24 or 25, comprising a bleaching precursor. 27. The above compositions may be used as hard surface cleaners, laundry additives, stain pretreatment compositions, car washes, etc. Claims 24 to 26, which are formulated as a pet or upholstery cleaning agent. The composition according to any one of the preceding items.