JPH07509526A - detergent composition - Google Patents

Abstract

Granular detergent compositions comprising ethylenediamine-N,N'-disuccinic acid or salts thereof and a crystalline layered sodium silicate of formula LMSixO2xH.yH2O wherein L is an alkali metal, and M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 are provided. The compositions also preferably comprise surfactant and additional non-phosphate detergent builder compounds.

Description

[Detailed description of the invention] detergent composition This invention is based on crystalline layered silicates and ethylenediamine-N,N'-dismber. The present invention relates to detergent compositions containing acids or salts thereof. Contains layered sodium silicate Detergent compositions are known, e.g. DE-A-3742043 and EP-A It is disclosed in No.-0337219. In these disclosures a layer of sodium silicate Crystalline silicates are mineral hardness metals that are superior to their amorphous counterparts. It is taught that it can be advantageously used as a detergent building material because it exhibits ion-sequestering properties. are doing.

Phosphorus-free, chelating agent, ethylenediamine-N,N'-succinic acid (EDDS) The containing laundry detergent compositions are also known in the industry and are described, for example, in EP-A-0267653. There is a description in . In this description, the addition of EDDS to such laundry detergent compositions Helps remove food, beverage and certain other organic stains from fabrics during the washing process. It is taught that Also, EDDS is one of the many products for &4 currently on the market. Alternative materials for all or some of the phosphonate chelators used in It teaches that it can be used as

A known problem associated with the washing process is that an insoluble inorganic salt coating is deposited on the fabric surface during the washing process. and accumulate them. These coatings remain on the fabric even at the end of the washing process. Most of it remains. Over a series of cleaning cycles, such insoluble inorganic salt deposits are further removed. It accumulates in the fabric, giving it a dark, discolored appearance. Most of these inorganic salts are calcium Si or magnesium salts or heavy metals such as zinc, iron, manganese and copper It is a salt of the genus ion. The applicant of this invention has provided the above-mentioned dark and discolored appearance to the fabric. It was confirmed that the main cause of this was the accumulation of insoluble heavy metal ion salts.

The applicant also. The coating of such heavy metal ion salts on the surface of the fabric can be achieved by ) Washing with detergent compositions containing oxygen bleach may cause local damage to fabrics. I also confirmed that. These results indicate that catalytic activation of peroxygen yarn bleach on fabrics This is due to the action of heavy metal ions.

Applicants have now discovered that insoluble inorganic salts, especially heavy metal The above problem of salt accumulation on fabrics can be solved with crystalline layered sodium silicates and It has been found that the use of laundry detergent compositions in combination with EDDS can alleviate this problem.

The combined effect of EDDS and crystalline layered silicate is that these components alone contain The effect was significantly better than that of the composition and was unexpected.

Therefore, an object of the present invention is to prevent the precipitation of an inorganic salt coating on the fabric surface during the washing process. and more specifically to reduce the multi-level accumulation of such coatings. The present invention provides a detergent composition in which a crystalline layered silicate and EDDS are used in combination.

Another object of the invention is to prevent the heavy metal ion-containing inorganic salt coating from being applied to the fabric surface during the washing process. Improve the white color of white fabrics by providing a detergent composition that reduces the amount of deposits on white fabrics. This method improves water retention and reduces discoloration damage to colored fabrics washed in the washing process. It's there.

The problem of surface coating with inorganic salts containing heavy metal ions during the cleaning process can be solved by cleaning. Salt coating problems are particularly important during the washing or cleaning process. This is essentially a problem that can be encountered in both cases. Therefore, the detergent composition of this invention For example, salt in automatic dishwashing processes and any process involving the cleaning of hard surfaces. It is expected that it will be used to soften the coating.

According to this invention, the first-order (a) General formula LMS i! 02 Engineering+,,yH20 [wherein L is an alkali metal 9M is sodium or hydrogen, x (a number from 1.9 to 4, and y from 0 to 20 1 to 80 weight of crystalline layered silicate builder material, expressed by the number of %; (b) Ethylenediamine-N,N'-disuccinic acid or its alkali metal, 0.05 to 10 of alkaline earth metal, ammonium or substituted ammonium salts weight%.

(c) Anionic surfactant, nonionic surfactant, zwitterionic surfactant 2 selected from zwitterionic surfactants, cationic surfactants and mixtures thereof. 0 to 30% by weight of detergent surfactant: and (d) non-phosphate detergent builder. 0 to 50% by weight of the compound; A detergent composition is provided.

The detergent composition of this invention contains two essential components: crystalline layered silicate; Consists of ethylenediamine-N,N'-disuccinic acid or a salt thereof.

Although the physical form of the detergent composition of this invention does not matter, it is preferably a granular composition, especially a granular composition. in the form of concentrated granular laundry compositions, and heavy duty liquid compositions.

Crystalline layered silicate materials have the following general formula % formula % [wherein or alkali metal, preferably sodium, M is sodium or hydrogen] , or a number from 1.9 to 4, and y represents a number from 0 to 20]. child The crystalline layered silicate of the type is disclosed in EP-A-0164514, The manufacturing method is disclosed in DE-A-3417649 and DE-A-3742043. be. For the purpose of this invention, X in the above formula is 2, 3 or 4. Preferably 2 Ru. More preferably, M is sodium, y is 0, and a preferable example of this formula is N The α-1β-1γ- and δ-forms of 251205 are included. These materials are Product name rNaSKS-5J from KIST (Hoechs AG FRG), rNaSKS-7'', rNasK-8-11J and rNaSKS-6J available. The most preferred material is Na2Si2O5°rNaSKS-6J. be. These materials have a particle size of 150 to 1000 micrometers and a low bulk density. Formed into a flowable solid of at least 800 g/L, preferably about 900 g/L . However, the crystals are brittle and easily disintegrate into two particles with a diameter of 100 micrometers or less. .

The content of the crystalline layered silicate builder material used in this invention is 1 part per composition. 80% to 80% by weight, preferably 5 to 40% by weight, most preferably 7 to 20% by weight %.

This crystalline layered silicate material is a homogeneous particulate mixture with a solid water-soluble ionizable material. As a product, it is preferably used in the granular detergent composition of this invention. This solid water soluble The ionizable materials consist of organic acids, organic and inorganic acid salts, and mixtures thereof. selected from the group. The first requirement is at least one with a pKa of less than 9. The hydroxyl group released by this crystalline layered silicate contains the functional acid groups of It has the ability to at least partially neutralize sil ions. This ion The pH in the solution of the crystalline layered silicate does not need to be <7. supply hydrogen ions in the same stoichiometric amount as the hydroxyl ions produced by the solution. Surprisingly, it was found that it can be contained in an amount as low as 1. In fact, the ions in the storage of this particulate Neutralization of the dyed material causes some loss of fabric damage prevention ability, but does not eliminate the ability to prevent fabric damage. I won't let you lose it.

The particle size of this ionized material is less than 300 micrometers, preferably 100 micrometers. It must be less than or equal to romometer. Thus ionizable materials and crystallinity Uniform dispersion of the layered silicate is facilitated, and localization of fine particles when dissolved in the cleaning solution is facilitated. It is thought that the degree of pH reduction will be increased.

Among the preferred organic acids are ascorbic acid and citric acid.

Glutaric acid, gluconic acid, glycolic acid, malic acid, maleic acid, malonic acid, Oxalic acid, succinic acid and tartaric acid.

1-Hydroxyethane-1,1-diphosphonic acid (EHDP), NTMP, EDT Aminopolymethylenephosphonic acids such as MP and DETPMP, and mixtures thereof compounds are included. Among the suitable acid salts is sodium bicarbonate.

Sodium hydrogen oxalate, sodium hydrogen sulfate, sodium acid pyrophosphate, acid acidic sodium orthophosphate, acidic sodium tartrate, and mixtures thereof. Included.

A fine particle mixture of crystalline layered silicate and solid water-soluble ionizable material was heated to 20°C. The pH of a 1% distilled aqueous solution is at least 10 and usually at least 11. usually is at least 11.5.

When adding other ingredients other than crystalline layered silicates and ionized water-soluble compounds, Particularly advantageous in fine particle treatment and in enhancing the stability of detergent compositions . Particularly in the case of certain types of agglomerates, support for the bonding of silicates and ionized water-soluble materials In order to produce granules with acceptable physical properties, one or more or more binder is required. The amount of binder ranges from 0 to 20% by weight of the particulate matter. Ru. This binder is used by uniformly mixing it with silicates and ionized water-soluble materials. Good. The melting point of this binder is 30 to 70°C, and the melting point of this binder is 1 to 1 It is used in an amount of 0% by weight, preferably 2 to 5% by weight.

Among the preferred binders are Cl0-20 alcohol ethoxylate [ethylene oxy (E, O,) 5 to 100 molar adducts, and more preferably Cl3-2 0-Alcohol ethoxylate [ethylene oxide (E, O,) 20 to 10 0 molar adduct] are included.

Among the preferred binder agents are certain polymeric materials. Kaka Polymer materials with an average molecular weight of 12,000 to 700,000 Vinylpyrrolidone, polyethylene glycol with an average molecular weight of 600 to 10,000 Included. Containing at least 20 mol% maleic anhydride in the polymer Maleic anhydride and ethylene, methyl vinyl ether or methacrylic acid Copolymers are also useful as examples of binder agents. These polymeric materials themselves , or water, propylene glycol and the C10-20 alcohol ethoxy It is used together with a solvent such as Rate [E, O, amount added = 5 to 100 moles]. by Other targets for under-the-counter agents include:

C10-20 mono- and diglycerol ethers and/or C10-20 Includes fatty acids. Inorganic salt solutions containing sodium silicate may also be used for this purpose. Wear.

Methylcellulose, carboxymethylcellulose and hydroxyethylcellulose Cellulose derivatives such as

and homo- or copolymerized polycarboxylic acids or their salts are also suitable. This is another example of a binder agent.

These particles also contain other ingredients that are normally included in detergent compositions and are themselves incompatible with each other. may be included as long as it does not inhibit the granulation function of the crystalline layered silicate. . Thus, the particles contain up to 59% anions and nonions by weight of the particles. surfactants, zwitterionic, or amphoteric surfactants or mixtures thereof, and certain preferred particulate mixed surfactants. Examples of such surfactants will be described in detail later. However, any surfactant agent added to the microparticles Free (unbound) water that can dissolve even a portion of the crystalline layered silicate is collected in fine particles. Do not introduce it inside. For this purpose, the surfactant is solid and has a free water content of approximately 5%. Below, preferably 2% or less, more preferably 1% or less should be used. Ru. Other components can also be added to the fine particles in an amount of 50% or less of the total amount under the above-mentioned addition conditions. child Optional ingredients such as are solid at room temperature and have a free moisture content of 5% or less, preferably 1%. The following should be used:

A non-aqueous liquid component in which the crystalline layered silicate is hardly dissolved is also added at 20% by weight or less. can. This allows the melt to act as an agglomerate/coating agent for fine particles. It can also be applied to ordinary solid components added in a state.

The shape of the particles may be extrudates, ma+umei, agglomerates, flakes or takes various physical shapes such as compact powder. Crystalline layered silicates and A method for preparing compact powders consisting of solid water-soluble ionizable materials is described in PCT Application No. WO9. It is described in No. 2106163.

The composition of this invention contains 0.05 to 10% by weight of the composition as an essential component. , preferably Olo 5 to 1%, more preferably 0.1 to 0.5% ethyl Diamine-N,N'-disuccinic acid (EDDS) or its alkali metal , alkaline earth metal, ammonium, or substituted ammonium salts; Contains a mixture of. Preferable E to be included in this particulate detergent composition The forms of DDS compounds are the free acid and its sodium or magnesium salts . Preferred salt targets for EDDS include MgEDDS and Mg2EDDs. It will be done.

Magnesium complexes are most suitable for the purpose of adding them into the particulate compositions of this invention.

These complexes can be added to the composition as is, or MgCA2 or EDDS compounds added as either acids, salts or complexes are It is formed during the manufacturing process of the composition by using the reaction with active magnesium salt. Good too.

If the EDDS compound is added together with an inert magnesium salt during the manufacturing process, the magnetic The molar ratio of Si 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 EDDS is as follows: EDDS is a combination of maleic anhydride and ester It can be synthesized from easily available and inexpensive materials such as ethylene diamine as follows: EDDS A detailed method for synthesizing from commercially available starting materials is given by Kezerian and Ramsey (Ke+ U.S. Pat. No. 3,158,635 (1) of e+ian and Rxm+a7) et al. , 964, dated November 24).

The synthesis of EDDS from maleic anhydride and ethylenediamine originates from two asymmetric carbon atoms. Therefore, three optical isomers of [R,R], [S,S], and [3,R] are generated. do. The biodegradation of EDDS is selective to the optical isomer, and the decomposition of the [S,S] isomer [S,S] is the fastest and largest, and therefore it is necessary to Most preferred is the gender form.

[S,S] isomer of EDS S is L-aspartic acid and 1,2-dibromoethane 2C0OHC00H synthesized as follows from [S,S] isomer of EDSS from L-aspartic acid and 1,2-dibromoethane The details of the method for synthesizing are described in Neat and Rose et al. entitled ``Stereoregular ligands and their complexes with ethylenediamine disuccinic acid''. InoBanic Cbemis+rY , Vol. 7 (1968), pp. 2405-2412.

The detergent composition of the present invention also contains ingredients that are commonly included in detergent products. and these ingredients include organic surfactants, other additional detergent builders, and acids. Base bleaching systems and auxiliary materials such as redeposition inhibitors and soil suspending agents, air bubble suppressants, etc. Detergents, other heavy metal ion chelating agents, enzymes, fluorescent bleaches, photoactive bleaches, fragrances and colorants. Fabric softeners and antistatic agents are also present in some products. Contains.

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 laurin (LaBhlin) and ()leu+in g) et al., U.S. Patent No. 3,929,678 (Monday, December 30, 1975) ) is disclosed. For suitable cationic surfactants see Mu+phy ) 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 Surfactant mixtures typically have a sulfonate to sulfate ratio of 5.1 to 1.2. ．． Preferably 3:1 to 2:3. More preferably a mixture of 3.1 to 1.1 used.

Preferred sulfonates include those having 9 to 15 carbon atoms. Especially having 11 to 13 alkylbensulfonates of alkyl groups, and C12-18 fat sources, preferred or α-sulfonated methyl fatty acid esters from fatty acids derived from CI6-18 fat sources. Tel is included. The cation in each case is an alkali metal, preferably nat It is Rium. Preferred sulfates in such sulfonate/sulfate mixtures The surfactant has 12 to 22 carbon atoms in the alkyl group. Preferably 16 to 1 8 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. Consists of a mixture with I6-18 alkyl sulfate in a weight ratio of 3.1 to 1. . This alkyl sulfate has an alkyl group having 10 to 20 carbon atoms. Preferably 1 0 to 16 alkyl ethoxy sulfates (average addition of 1 to 6 moles of E, O, Can be used in combination with The cation in each case is an alkali metal, preferably nat It is Rium.

Other particularly preferred anionic surfactants are CI2-20 alkyl sulfate and water. Soluble C11-18 alkyl ethoxy sulfate (average E, with 0.1 to 7 mol) It consists of a mixture of alkyl sulfate and alkyl ethoxy sulfate. The weight ratio is 2.1 to 19:1. More preferably 3.1 to 12:1. The most preferred ratio is 3.5:1 to 10:1.

Alkyl sulfates are derived from natural or synthetic hydrocarbons. Al A good example of kill sulfate is a C14-15 alkyl chain with a degree of branching of 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 has 1 to 1 C11-1 alcohol. derived from a condensation product condensed with up to seven ethylene oxide (E, O,) groups, Cl2-15 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 CII-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 [5he Commercially available product name: rDobanol 25 from Chemicals (US) Commercially available product name rE+h71244 from Elhyl Camp. , BASF Corporation (formerly BASFGmb, product name r　Lu!en+olJ and ICI From the company under the product name r 5ynpe + onic J, and also from Liqimica (Liqa ichimica l1aliana) as the product name rLial 125J Commercially available. 013 to CI5 is 67 to 33 (% ratio) CI3-15 alcohol mixture compounds are included. Among natural sources are coconut and palm kernel oils and corresponding fatty acids. There is.

The content of C11-18 alkyl ethoxy sulfate is 0, based on the weight of the composition. 5-10%, preferably 0.5-5%, most preferably 1-3%.

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 Cl-4 alkyl group 1M represents an alkali metal] It is an alkali metal sarcosinate shown in Lauro as sodium salt Ile, Cocoyl (CocBl) (CI2-14), Myristyl and Olay A preferred example is methyl sarcosinate.

One group of nonionic surfactants useful for use in this invention is that the lipophilic moiety is Condensed with oxide. Average HL is 8 to 17. Preferably 9.5 to 13.5. difference More preferably, it consists of 10 to 12.5 condensates. This lipophilic part is oily in nature. Polyoxyesters that are aliphatic or aromatic and are fused with any specific lipophilic group. Adjust the length of the Chen group to achieve the desired balance between hydrophilic and lipophilic elements. It is easy to produce water-soluble compounds prepared in the following manner. This kind of nonion world Particularly preferred surfactants are E, 0. C9-15- with an average addition mole of 3 to 5 alcohol ethoxylate. Especially E.

CI 4-15-grade alcohol ethoxylates with an average O1 addition mole of 6 to 8; and E, O, CI 2-15-class alcohol ethoxylate with an average addition mole of 3 to 5. 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. 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 E, where R is H, C1-4hydro Carbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof compound, preferably cl-4 alkyl, more preferably C1 or C2 alkyl , i! Also preferably C1 alkyl (i.e. methyl) and R2 is C5-3 1 hydrocarbyl, preferably straight chain C7-19 alkyl or alkynyl.

More preferably straight chain C9-17 alkyl or alkenyl.

Most preferably straight chain C11-17 alkyl or alkenyl.

or a mixture thereof; and Z has at least 3 hydroxyls directly attached to the chain. polyhydroxyhydrocarbyl having a linear hydrocarpyl chain, or its derivatives Rukoxylated derivatives (preferably ethoxylated or propoxylated) , Z is derived from a reducing sugar obtained by a reductive amination reaction; more preferably Z is a group derived from a reducing sugar obtained by a reductive amination reaction; This is a polyhydroxy fatty acid amide surfactant indicated by the symbol lysyl. good Suitable reducing sugars include glucose, fructose, maltose, lactose, and Includes lactose, mannose, and xylose. As a raw material, high-density kistose corn syrup, high fructose corn syrup, and high maltose Scone syrup can be used as well as the individual sugars mentioned above. These cones The lop yields a sugar component mix for Z. However, excluding other suitable raw materials That was never my intention. Z is -CH2-(CHOH) n-CH20H, -CH(CH20H) -(CHOH) n-lCH20H, -CH2-(CH OH) 2 (CHOR’) (CHOH)-CH20H.

[Wherein, n is an integer from 3 to 5 (including 5), Ro is H or cyclic or aliphatic monosaccharides and their alkoxylated derivatives] Preferably, it is selected from the group consisting of: Most preferred is glycityl (n is 4 ),especially -CH2-(C)(OH) 4-CH20Ht'.

In formula (I), Ro is, for example, N-methyl, N-ethyl, N-propyl, N- Isopropyl, N-butyl.

N-2-hydroxyethyl or N-2-hydroxypropyl.

R-Co-N< is 1, for example cocamide.

stearamide, oleamide, lauramide, myristamide, caprinamide, These include lumitamide and tallowamide.

Z is 1-deoxygludityl, 2-deoxyfructityl, 1-deoxymulti Chil, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymane Nityl, 1-deoxymaltotriothytyl, and the like. Preferred compounds are 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 C8-18 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-alkyl surfactants. or alkenyl ammonium surfactants (where the remaining N positions are methyl, hydrogen, (substituted with a droxyel or hydroxypropyl group).

The detergent composition contains O 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 0 to 10% by weight of the composition, preferably 0.5 to 10% by weight of the composition. It contains 10% by weight of surfactant, more preferably 1 to 5% by weight. child Surfactants include anionic, cationic, nonionic, zwitterionic, and amphoteric surfactants. You can choose from. The most preferred surfactants are low foaming. automatic dishwasher Typical surfactants for detergent compositions are described in EP-A-0414549. There is a list. Most preferred are low foaming nonionic surfactants, especially water-soluble ethoxylate surfactants. Sylated C6-16 fatty alcohols and C6-16 mixed ethoxylated/propokyl sylated fatty alcohols and mixtures thereof. This ethoxylated fatty acid Cole is a C1G-16 ethoxylated fatty alcohol (E, with 0.5 to 50 mol) additives) most preferably CI2-16 ethoxylated fatty alcohols (E, O.

(8 to 40 mole adducts) are preferred. Mixed ethoxylated/propoxylated fats The alkyl chain length of the alcohol is 10 to 16 carbon atoms, and the degree of ethoxylation is 3 to 30, and the degree of propoxylation is preferably 1 to 1o.

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 Although surfactants can be incorporated into the composition as a mixture, they 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 are discussed below. Detergent composition of this invention What are the most preferred ingredients?

This is another non-phosphate building goo, hereinafter referred to as additional non-phosphate building goo. these targets It contains alkali metal aminosilicates, polycarboxylate monomers, and polycarbonate. Homo- or copolymers or salts of carboxylic acid (where polycarboxylic acid is consisting of at least two carboxyl groups separated from each other by a number of carbon atoms ), carbonate.

Silicates, and mixtures thereof are included.

Although a range of aluminosilicate ion exchange materials can be used, the preferred materials are: unit cell system %formula%] [wherein 2 and y are small (both 6; the molar ratio of z to y is 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 Licate materials are hydrated.

Preferably 10 to 28% by weight, more preferably 18 to 22% by weight of bound water. It is a crystal containing.

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. Measure 9 Measurement under a microscope, for example 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 Ca CO based on cardiomium ion hardness. 3/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 is available under the trade name "Zeolite AJ". , rzeolite B,” “zeolite P,” “zeolite X,” “zeolite H3. J, r zeolite MAp, 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% [In the formula, X is 20 to 30. In particular, "zeolite AJ (Product name). formula% formula% Also "zeolite X" designated as 276H20.

Formula Na6 [(AlO2)6], 7.5H20 [Similar to zeolite H3J Useful.

Are water-soluble carboxylate builder monomers or oligomers a wide range of compounds? However, the -order carboxyl log acidity constant pK is 9 or less, preferably 2. and 8.5, more preferably between 4 and 7.5.

This I) K, (logarithmic acidity constant) is the following equilibrium H+ +A-;: HA [where A is the fully ionized carboxylate anion of this builder salt] It is defined as follows with reference to: The equilibrium constant of a dilute solution is Therefore, p　K　　=l　o　g　1oK For the purposes of this invention, acidity determination Numbers are defined at 25°C and zero ionic strength. Adopt from literature values when possible. Ru. [“Stability Constants of Metal Ion Complexes” Special Issue No. 25, Chemical Society of London’5ta bility Con+ant of Metal-Ion Complexes ', 5special Publication No. 25. TheChem ical 5ociety, London)]: If in doubt, please contact Gala. Determined by potentiometric titration using a gas electrode.

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

Monomer and oligomer builders have the following general formula or (c) [wherein R1 is R2 or a hydroxy, carboxy, sulfo or phosphono group] Optionally replace with, or E, ○.

C l-30 alkyl optionally bonded to a polyethyleneoxy moiety containing up to 20 groups or alkenyl; R2 is H1C14 alkyl, alkenyl or hydroxy Sialkyl, or alkaryl, sulfo, or phosphono group; X is a single bond; O; S; So; or NR'.

Y is H, carboxy: hydroxy; carboxymethyloxy; or also hydroxy 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, where p+q is 1 to 6; 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, ring ring, heterocyclic and aromatic carboxylates.

Suitable carboxylate steels 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). 31°368, 821,369 and 821,370). two pieces Polycarboxylate steel containing carboxyl groups contains 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. 687 and U.S. Pat. No. 3,935,257. 840.623; including vinyl carboxylates. Polycapoxylene containing three carboxyl groups 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-propanetricarboxylate (UK Patent No. 1 , 387, 447).

Oxydisuccinate ( British Patent No. 1,261.829), 1,1,2,2-ethanetetracarbo xy L/-1-,1,1,3,3-propane tetracarboxylate and 1, 1,2,3-propane tetracarboxylate is included. Has a sulfo substituent The polycarboxylates used are sulfosuccinate derivatives (UK Patent No. 1,398.4). ．． No. 21, No. 1,398.422 and U.S. Pat. No. 3,936,448. ), and sulfonated pyrolytic citrate (UK Patent No. 1,439.000). information) is included.

Cyclopentadiene boron is present in alicyclic and heterocyclic polycarboxylate steels. Ricarboxylate, 2,3°4,5-tetrahydrofuran-cis, 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.

Mellitic acid in aromatic polycarboxylate steel.

Pyromellitic acid and phthalic acid derivatives (British Patent No. 1゜425.343) is included.

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 1 such as citric acid or citrate/citric acid mixtures may also be used. Used as a builder component 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.

Polyacrylate with a weight average molecular weight of 2,000 to 5,000 is contained in the steel of such salts. and its maleic acid copolymers, the molecular weight of such copolymers being 20, 000 to 70,000. In particular, 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.

A chelating agent is included as an optional ingredient in the composition of this invention. Optional chelate As a curing agent, aminoalkylene poly(alkylene phosphonate), alkali gold Genus ethane 1-hydroxy diphosphonate, nitrilotrimethylene phosphonate, Ethylenediaminetetramethylenephosphonate, and diethylenetriaminepe Organic phosphonates include tamethylene phosphonate. This ho Sulfonates are present in the free acid form or in complexes with alkali or alkaline earth metal ions. The molar ratio of metal ion to phosphonate is small. It is at least 1.1. A preferred organic phosphonate compound is a magnesium salt. Ru. The amount of phosphorus-containing chelating agent should be kept to a minimum and preferably not added. stomach.

Soluble silicates in known formulations are used for various purposes; is not necessary in the compositions of this invention. However, it forms part of the builder 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 are free of aluminosilicate builders.

And it is particularly useful when it is made of only organic materials. The preferred silicate is S1 0:Na20 ratio is in the range of 2.0 to 2.8.

For the purpose of detergent compositions containing crystalline layered silicates as builder component, The amount of the non-phosphorus salt-based additional building block added is preferably 0 to 50% by weight based on the composition. Preferably, it is 10 to 40% by weight. ``Zeolite AJ (product name) etc. The amount of aluminum silicate added is 20 to 60% by weight of the total amount of bilge, and the amount of monomer or oligomeric carboxylates from 5 to 30% by weight based on total builders, crystalline The amount of layered silicates is from 10 to 65% by weight, based on the total builder. Such a group The builder system in the composition is sodium carbonate, maleic anhydride/acrylic acid copolymer. Combinations of auxiliary organic and inorganic building blocks such as It is preferable to contain it at a concentration.

The detergent composition of the present invention comprises an inorganic perhydrate bleach, usually in the form of a sodium salt. . The perhydrate generally comprises 3-40% by weight of the composition, more preferably 5-30%. , most preferably in an amount of 10 to 25% by weight.

Perhydrates are inorganic salts such as perborate, percarbonate, perphosphate and persilicate. can be either a perborate or an alkali metal, typically a sodium perborate. or percarbonate. Sodium perborate is monohydrate with the nominal formula NaBO2H2O2 It may be in the form of hydrate or tetrahydrate NaBOH0, 3H20.

Sodium percarbonate, which is a preferred perhydrate, is is an adduct compound with the corresponding formula and is commercially available as a crystalline solid. percarbonate Although salts can be incorporated into detergent compositions without special protection, the preferred implementation of such compositions Embodiments use the material in coated form. The most preferred coating material is alkali metal sulfates and carbonates. Such coatings and coating methods have previously been GB-1,466,799 recognized by Inte+ox on March 9, 1977 Are listed.

The weight ratio of mixed salt coating material to percarbonate is from 1:200 to 1:4, more preferably The ratio is preferably 1:99 to 1:9, most preferably 1:49 to 119. Preferably, The mixed salt has the general formula Na S○, n, Na Co3 (where n is 0.1 to 3, Preferably n is 0.3 to 1. O1 most preferably n is 0.2-0.5. ) It consists of sodium sulfate and sodium carbonate.

Another suitable coating material has an S10:Na20 ratio of 1.6:1 to 3.4:1; Preferably 2.8:1 sodium silicate, 2 to 1 by weight to percarbonate. It is applied as an aqueous solution giving an amount of silicate solids of 10% (usually 3-5%).

The coating may also include magnesium silicate. Other suitable coating materials Includes alkali and alkaline earth metal sulfates and carbonates.

Heavy metals present in the sodium carbonate used in the production of percarbonate are present in the reaction mixture Percarbonates can be suppressed by including chelates in the product, but percarbonates can be suppressed by including chelates in the product. Further protection must be provided from heavy metals present as impurities. therefore, In detergent compositions that use percarbonate as the perhydrate salt, the stability of percarbonate is adversely affected. The total amount of iron, copper, and manganese ions in the product must be 25 ppm to prevent It should not be more than 20 ppm, preferably less than 20 ppm. alkali metal Detergent compositions with enhanced stability of percarbonate bleaches are being developed in the PC T application W092106163.

The bleach system incorporated into the detergent compositions of the present invention is preferably a solid peracid bleach solution. Contains bleach activator (bleach activator). The solid peracid bleach precursor typically comprises 1 part of the composition. ~20% by weight, more preferably 1-15% by weight, most preferably 1-10% by weight Mix in the amount of

These precursors probably contain one or more N- or O-acyl groups and have a wide range of selected from various types. Suitable materials include acid anhydrides, esters, imides and imides. There are acylated derivatives of dazoles and oximes, among which the effective substances An example is described in GB-A-1586789. The most preferred substance is GB -A-836988, 864, 798, 1147871 and 2143231 Esters and GB-A-855735 and 124633 as described It is an imide as described in 8.

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

An example is tetraacetylmethylenediamine (T A M D ), x = 2, tetraacetylethylenediamine (TAED), and There is tetraacetylhexylene diamine (TAHD) where x=6. these , and similar compounds are described in GB-A-907356. additional drift The most preferred peracid bleach precursor as a whitening agent compound 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 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. R' 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.

or R’-N-C-R2-C-00H where R, R2 and R5 are the corresponding amide-substituted peracid bleach activator compounds 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- Peroxyphthalic acid, perbenzoic acid, and their salts.

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 vinyl Maleic anhydride is a copolymer of ether or methacrylic acid. It makes up at least 20 mol% of the body. Compounds derived from aspartic acid Such polyamino compounds are described in EP-A-305282, EP-A-305283 and and EP-A-351629. These materials generally have a composition of 0.5-10% by weight, more preferably 0.75-8%, most preferably 1-8% by weight It is 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 maintain whiteness, improve fabric build-up, and 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 4.41-bi su-(2-jetanolamino-4-anilino-8-triazin-6-ylami ) Stilbene-2:21-disulfonic acid disodium, 4.41-bis-(2 -morpholino-4-anilino-5-triazin-6-ylamihastilbene-2 = 21-disulfonic acid disodium, 4.4'-bis-(2゜4-dianilino- s-triazin-6-ylamino)stilbene-2,21-disulfonic acid dinato 41゜411-bis-(2,4-dianilino-8-triazin-6-y sodium stilbene-2-sulfonate, 4.41-bis-(2- Anilino-4-(N-methyl-N-2-hydroxyethylamino)-S-)ria Zin-6-ylamino)stilbene-2,21-disulfonic acid disodium, 4 ．． 4'-bis-(4-phenyl-2,1,3-triazol-2-yl)styl Ben-2,21-disulfonic acid disodium, 4.4'-bis=(2-anili No-4-(1-methyl-2-hydroxyethylamino)-s-triazine-6- ylamino) stilbene-2,21-disulfonic acid disodium and "+4 ．． 5) 2(stilbyl-4-(naphtho-1,2-1,2,3-triazole-211- There is sodium 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% (In the formula, PEG is -(OC2H4)〇-, PO is (QCHO), 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. Preferably 1 silicone bubble tone The preparation has a particle size of 10 nanometers to 20 nanometers and a specific surface area of 50 m2. More than 7g of hydrophobically silanized (most preferably trimethylsilanized) Silica is mixed with a dimethyl silicone liquid having a molecular weight of about 500 to about 200,000. Thoroughly mix the silicone to silanized silica at a weight ratio of 1:1 to about 1.2. Manufactured by

A preferred silicone cell control agent is Bartollo N et al., U.S. Pat. No. 3,93 No. 3.672. Other particularly useful foam control agents include German Patent Application No. DTO 52,646,126+, published on the 28th, It is a self-emulsifying silicone foam control agent.

Examples of such compounds include siloxane/glycosiloxanes available from DOW Corning. 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 of the major components of the composition. by spraying or by forming the bubble suppressant into separate particles, which can be applied to Mix with the solid components of the pond. By blending the bubble control agent as a separate particle. , C20=024 fatty acids, which may have a negative effect on the dispersibility of the matrix. , microcrystalline wax and ethylene oxide and propylene oxide Other cell control agents such as high molecular weight copolymers may also be included. bubbles like that The technology for manufacturing modified particles is described in the above-mentioned U.S. Pat. No. 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 Nowo lndηsl+iei A/ Alcilise and 5xvinase from S (Denmark), and Int ernational Blo-3ynlhelics, Inc. (Netherlands) There is an enzyme sold under the trade name Maxa+ahe from ).

Preferred amylases include, for example, those produced by GB-1,296°839 (Novo). Obtained from a special variety of B1ichenilOImI, which is described in detail in There is amylase that can be Preferred commercially available amylases include, for example, Infe+na R sold by lional Blo-3ynlh+fic+, Inc. Sold by apida+e and Novo IndusHie+ A/S There is Te + mamyl.

A particularly preferred lipase enzyme is Novo Induslrie+ A/S (Denma from Lipo1i+e (BioleehnoloB Nev+vztch) .

Manufactured and sold under the product name (March 1988, p. 6), EP-A-025 8068 (Noto), along with other suitable lipases.

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

These softeners may be of inorganic or organic type. The inorganic softener is GB-A, -1, 400,898. organic woven Material softeners include those described in GB-A-1514276 and EP-B-0011340. There are tertiary amines listed that are insoluble in water.

The combination of softener and C12-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 dilong chain amide materials, can be used with 0. It is blended in an amount of 5 to 5% by weight, usually 1 to 3% by weight, but high molecular weight polyethylene 0.1-2% by weight of oxide materials and water-soluble cationic materials, typically 0.15% Add in an amount of ~1.5% by weight. When spray drying part of the composition, these materials can be added to the aqueous slurry fed to the spray-drying tower, but not with the dry mixed particles. 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. Measure using a simple funnel and force/spill device into which the contents can be poured. . The funnel is 130 mm and 40 mm at the top and bottom ends, respectively. The funnel is Install it so that its lower end is 140mm higher than the upper surface of the foundation. Power and pump are all It has a height of 90 mm, an internal height of 87+++n and an internal diameter of 84 mm.

Its nominal volume is 500 m1.

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 or slow to store) There is a tendency for particles to become caked and have poor fluidity.

A preferred granular detergent composition of the present invention comprises at least two particulate multi-ingredient ingredients. include. The first component is at least 15%, typically 25-50% by weight of the composition. , more preferably 35% by weight or less, 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 include granules, flakes, prills, ma+umes, etc. 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. The alkyl groups in both types of surfactants are derived from natural fats such as tallow. It is preferable to

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 014-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 present as a by-product, e.g. 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. can be done. 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 C14-CI5 alkyl sulfur ates, linear C11-C15 alkylbenzene sulfonates and aliphatic C14 ~C18 methyl ester sulfonate.

The second component may have any suitable physical form, i.e. arc, needle-like (p+1lls), marmes (ma+umes), noodles, agglomerated by ribbon or spray dryer-C 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 1.4mm , and on the other hand, 10% by weight or less is less than 0.15 mm in the maximum range. It is a good place to go.

The bulk density of the first component is a function of the mode of preparation. However, for some reason, the second component is preferable. 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 Schug i (Netherlands) BY, 29Cb+oom+t+xxt8211 AS, Le lystad, Ne+he+Ixnd+ and Geb+ude+Lodige Ma+hinenban GmbH, D-4790P! de+bo+n 1 ゜El+ene++t+a++e 7-9. Po5llach 2G50F 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 should contain 650 g/liter to 1190 g/liter, more preferably or give a bulk density in the range of 750 g/liter to 850 g/liter. I can do it.

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 filed under PCT Application No. wo921061, assigned to the same person. 63+: Disclosed.

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 a flexible item 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 bag or container type variations, 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. Can also be used as a laminated sheet product. Layers remain joined during use May be sealed together or coated to facilitate release of impregnated substances. May separate on 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 expected number of pouch-like containers per unit area is selected However, it will typically vary from 500 to 25,000 per d.

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 is then passed 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.

Lnnlzctu+ing Chemist (1989, November, 41-46 Published on page) 1. Also in the article by Bland, "g"xnulelje" A particularly preferred dispensing device for use with granular products of the type commonly known as 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 5EY C-based linear chain enriched with an average of Y moles of ethylene oxide Primary alcohol +2-15 TAED: Tetraacetylethylenediamine silicate: Amorphous sodium silicate (SiO2:Na20 ratio follows normal case) NaSKS-6+crystalline layer coated, δ-Na2SiO5 Carbonate/Anhydrous Sodium Carbonate CMC: Sodium carboxymethyl cellulose zeolite A: Formula Na (AI OSiO)・212 22+2 7H20 hydrated sodium aluminosilicate with a major particle size of 1 to 1 0 μm range Polyacrylate: Mwl 4ooo homopolymer of acrylic acid rimmer Citrate nitri-sodium anhydrous citrate MA/AA: 1: 4 Male A copolymer of inic acid/acrylic acid with an average molecular weight of approximately 5oooo Berborate/Anhydrous Sodium Perbore Monohydrate Bleach, Empirical Formula NaB○2. H 2o2 Enzyme: Mixed enzyme for proteolytic and starch decomposition DETPMP: 1Aon Diethylene thoria sold under the Sanl beam product name Deque+t2Q60 Minpenta (methylene phosphonic acid) foam suppressor/25% paraffin wax M pf 50'C117% hydrophobic silica 58% paraffin oil EDDS: Tilene diamine-N, N-disuccinic acid, [S, S] isomer, sodium Salt form Example 1 The following detergent compositions were prepared (parts by weight). Compositions A-D are prior art compositions. Composition E is a composition according to the invention.

^　BCDE LAS 7.7 7.7- 7.7 7.7? , 7T A S 2.4 2. 4 2.4 2.4 2.4 TAE11 1.1 1.1 1.1 1.1 + , 125E3 3.3 3.3 3J i, 3 3J Zeolite A 19,5 19.5 19.5 13. fl 13.0 citrate 6.5 6.5 6. 5 MA/AA 4.3 4J 4.3 4.3. 4.3NaSKS-6” 10 ．． 0 10.0 Citric acid” 2.7 2.7 TAE5Q” (1, 3θ, 3 Carbonate 11.1 11.1 11.1 9.8 9.8 Belporate 1 6,0 16.0 16.0 16.0 +6.0TAED 5.0 5. Q 5.0 5.0 5.0EDDS O, 2-G CMC8, 5tl, 5 1), 5 0.5 it.

Foam suppressant 0.5 0.5 0.5 G, 5 0.5M 1.4 1.4 +, 4 1.4 1.4 Silicate (2,0 ratio) 4.4 4.4 4.4 -Mg SO40, 40, 40, 40, 4G, 4DETPMP 0.4 - The remainder is water and minor components Present as a component of zero-crystalline layered (coated) silicate particles.

Full scale 25 cycle washing machine test using Miele 701 washing machine The effects of the three compositions were compared. Each full wash cycle includes a pre-wash and and main wash cycle. The boiling cleaning setting (temperature 95℃) is determined by each cleaning cycle. Washed in Kuru, and water with German hardness of 25 degrees (Ca: Mg = 3: 1) was used. Each washing load consists of 15an x 30an pieces of clean white tissue. - Consisting of towels, knitted cotton and cotton cloth. Before starting the first full wash cycle , granules containing laundry and 100 g of detergent product along with 20 g of artificial soil ( A dispersing means of the grxnule+te) type was placed in the drum of the washing machine. Continued 24 The same amount of artificial soil and laundry was used for each full wash cycle.

The artificial stain was sifted with 5g of palmitic acid, 5g of stearic acid, and 4g of sieve. soil, 3g glycerol/triolate and 3g dirty car oil. Ru. At the end of 25 full wash cycles, the laundry is removed from the machine, dried and Furthermore, evaluation of whiteness/soiling and heavy metal ion content of 4 pieces of each of the 3 types of fabric was performed. I did the price.

maintain whiteness The whiteness/dirt of each month of the fabric is evaluated using the 5-level chef scale (Scbeffe +c). Ale　) was used for evaluation by an expert judge. The overall average result is for each of the three The comparison set is as follows. Prior art composition A is a crystalline layer coated silicate. Or, it does not contain chelanl, and is a common reference. It was used as

B/A C/A D/A E/A O,890,040,391,75s Statistical significance comparison B/A at s = 95% confidence level 1 shows the advantageous effects obtained due to the inclusion of sphate chelate. Comparison C/A is Similarly, EDDS is in composition A (NB: 0.2 wt% EDDS is approximately 0.4 wt% E The extremely molar amount obtained when EDDS is added to DTPMP (in equimolar amounts) Showing the effect of inus. Comparison D/A is the amount of zeolite A added and the amount of zeolite A added to the composition. All citric acid and silicates, 5KS-6, citric acid and TAE50 It shows a small effect when replaced with crystalline layered silicate particles. comparison E/A shows the important advantages obtained by using composition E according to the invention. show.

The heavy metal ion content of the inorganic salt clusters attached to each fabric was determined using the following method. It was measured using From each fabric obtained from the 25 cycle test process described above. Samples weighing at least 2 grams were cut out. The sample is then placed in a clean magnetic field. Place the fabric in a crucible and heat using a Bunsen burner until it ignites. The crucible was heated to complete combustion, leaving an inorganic salt residue in the crucible. inorganic salt residue Measure the weight using an accurate chemical balance and add a known volume of 1M sulfuric acid solution. It was dissolved in The iron, copper, zinc, and manganese ion content of this solution was Measured using an optical analyzer to determine the content of iron, copper, zinc, and manganese ions in inorganic residues. Get quantity.

Inorganic residue iron, copper for tested fabrics using compositions C, D and E , zinc, and manganese ion total averages are as follows:

CD E 2400ppm 950ppm 690ppm Hand continuation amendment 1M April 2, 1995 Director General of the Patent Office ■ Incident display PCT/US 93106876 1994 Patent Application No. 505359 2 Name of the invention detergent composition 3 Person making the amendment Relationship to the incident: Patent applicant 5. Weight of amendment order Shipping date: Month, Day, Heisei 6 Target of correction 7 Contents of amendment Continuation of front page (51) Int, C1,6 identification symbol Internal office reference number C11D 3108 9 546-4H 3/30 9546-4H 3/39 9546-4H (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, NO, NZ, PL, RO, RU, SD, SK, UA, 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 (15)

[Claims] 1. (a) Formula LMSixO2x+1・yH2O (where L is an alkali metal, M is sodium or hydrogen, x is a number from 1.9 to 4, and y is a number from 0 to 20. (a) 1 to 80% by weight of crystalline layered silicate builder material; Amine-N,N-disuccinic acid, or these alkali metals, alkaline earths, ammonium or substituted ammonium salts, or mixtures thereof 0.05 to 10 amount%, (c) Anionic surfactant, nonionic surfactant, amphoteric surfactant , zwitterionic surfactants, cationic surfactants and mixtures thereof. Detergent surfactant 0-30% by weight, (d) 0-50% by weight of additional non-phosphate detergent builder compounds; A detergent composition comprising: 2. Ethylenediamine-N,N'-disuccinic acid component has its [S,S] isomer A detergent composition according to claim 1 in the form of a detergent composition. 3. The ethylenediamine-N,N'-disuccinic acid component is in the form of a magnesium composition. 3. A detergent composition according to claim 1 or 2. 4. The crystalline layered silicate material is δ-Na2SiO5 (NaSKS-6 ) The detergent composition according to any one of claims 1 to 3. 5. The anionic surfactant is a C12-C20 alkyl sulfate and a water-soluble C11- C19 alkyl ethoxy sulfate (with an average of 1 to 7 ethoxy sulfates per mole) the alkyl ethoxy group of the alkyl sulfate; Claim consisting of a weight ratio to sulfate ranging from 2:1 to 19:1. 5. The detergent composition according to any one of 1 to 4. 6. the alkyl sulfate is a C14-C15 alkyl sulfate; C12-C15 alkyl ethoxy sulfate (however, per mol) or containing on average 3 ethoxy groups), and the alkyl sulfate The weight ratio of the salt to the alkyl ethoxy sulfate ranges from 3.5:1 to 10:1. 6. A detergent composition according to claim 5, comprising: 7. The nonionic surfactant has the formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (Here, R1 is H, C1-C4 hydrocarbon group, 2-hydroxyethyl, 2-hydrocarbon group, roxypropyl or a mixture thereof, R2 is a C5-C31 hydrocarbon group, and Z is a polyhydroxy hydrocarbon group having a straight hydrocarbon chain and having at least 3 hydroxyl groups directly attached to the chain, or their alkoxylated derivatives. Any one of claims 1 to 6, which is a polyhydroxy fatty acid amide (which is a conductor) The detergent composition described in Section. 8. The nonionic surfactant is a C9-C15 primary alcohol ethoxylate. and containing an average of 3 to 8 ethylene oxides per mole of alcohol. The detergent composition according to any one of claims 1 to 7, wherein the detergent composition is 9. The primary alcohol ethoxylate is a C12-C15 primary alcohol ethoxylate. toxylate, with an average of 3 to 5 ethyleneoxylates per mole of alcohol. 9. The detergent composition according to claim 8, wherein the detergent composition comprises: 10. The additional non-phosphate builder compound is sodium aluminum silane. Licate zeolites, alkali metal carbonates and bicarbonates, carboxy esters and polycarboxylates, and maleic anhydride/acrylic acid copolymers Detergent composition according to any one of claims 1 to 9, which is selected from the body . 11. 7-20% by weight of crystalline layered silicate builder material and additional non-phosphorous Any one of claims 1 to 10, containing 10 to 40% by weight of a phase builder compound. The detergent composition according to item 1. 12. 3-40% by weight of inorganic perhydrated bleach and solid peroxyacid bleach precursor The detergent composition according to any one of claims 1 to 11, containing 1 to 20% by weight of thing. 13. The inorganic perhydrate salt is sodium percarbonate present at a level of 5 to 30% by weight. and a solid peroxyacid bleach precursor is present at a level of 1 to 10% by weight. 13. The detergent composition of claim 12, which is TAED. 14. Any one of claims 1 to 13, containing 1 to 10% by weight of an organic peroxy acid. The detergent composition according to item 1. 15. Detergent enzymes, stain dispersants and anti-redeposition agents, optical brighteners, foam suppressants, fragrances and and a mixture thereof. The detergent composition according to any one of the above.