JP2003514102A - Detergent compositions containing aroma reaction products - Google Patents

Abstract

  (57) [Summary] Aroma reaction product formed by reacting a primary amine compound with a perfume component selected from the group consisting of C6-C14 aliphatic aldehydes, C6-C14 acyclic terpene aldehydes and mixtures thereof A detergent composition comprising: The odor of the amine compound is less than the odor of a 1% solution of methyl anthranilate in dipropylene glycol. The dry surface odor of the aroma reaction product must be above 5.

Description

Detailed Description of the Invention

[0001]

【Technical field】

The present invention relates to detergent compositions containing aroma reaction products. In particular, the present invention relates to detergent compositions containing aroma reaction products obtained by reacting amines with perfume ingredients.

[0002]

[Background technology]

Laundry and cleaning products are well known in the industry. However, consumer acceptance of these products depends not only on their performance, but also on their aesthetics. Therefore, perfume ingredients are an important factor in the successful formulation of such commercial products.

Consumers prefer that the pleasant scent of the washed fabric be maintained over time. When wearing these fabrics, the scent feels comfortable when lasting for a long time.
The perfume additive makes the laundry composition aesthetically pleasing to the consumer,
In some cases, the fragrance imparts a pleasant odor to the treated fabric.

Further, when the fabric is dried in the sun, the fabric has a “sun-dry type” odor. Consumers often prefer it over the standard odor. Also, fabrics with these odors often feel cleaner. Consumers prefer these odors and therefore prefer to dry the fabric in the sun. However, in some countries there are consumers who cannot dry the fabric outside due to unclean air or heavy rain. as a result,
The fabric must be dried indoors and cannot benefit from the "sun-dry" odor imparted to the fabric.

We have discovered a detergent composition containing a perfume capable of imparting a “sun dry type” odor.

[0006]

DISCLOSURE OF THE INVENTION

The present invention includes a primary amine component, a C6 to C12 aliphatic aldehyde, and a C6 to C
A detergent composition comprising an aroma reaction product produced by reacting a perfume ingredient selected from the group consisting of 12 acyclic terpene aldehydes and mixtures thereof, wherein the odor of a primary amine compound is Is less than the odor of a 1% solution of methyl anthranilate in dipropylene glycol and the dry surface odor of the aroma reaction product is greater than 5.

In a second aspect of the invention, from about 1% to about 60% by weight detergent surfactant,
A detergent composition comprising from about 0% to about 60% by weight of a detergent builder and from about 0.0001% to about 10% by weight of a fragrance reaction product produced by reacting a primary amine compound with a perfume ingredient. Detergent composition wherein the odor of the primary amine compound is less than the odor of a 1% solution of methyl anthranilate in dipropylene glycol and the aroma reaction product has a dry surface odor of greater than 5. Will be provided.

In another aspect of the invention, a primary amine compound and a perfume ingredient selected from the group consisting of C6-C14 aliphatic aldehydes, C6-C14 acyclic terpene aldehydes and mixtures thereof. A detergent composition comprising an aroma reaction product produced by a reaction, wherein the odor of a primary amine compound is lower than that of a 1% solution of methyl anthranilate in dipropylene glycol. The dry surface odor of the reaction product exceeds 5, and the detergent composition has a water vapor transmission rate of 50 g / m 2.
Provided is a detergent composition packaged in a sealed packaging system having / 24 hours.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION

While the specification concludes with the claims which clearly identify and claim the invention, it is believed that the present invention will be further understood by the following description.

[0010]   All percentages are by weight of the total composition unless otherwise noted.

[0011]   Unless otherwise noted, all ratios are weight ratios.

Definitions As used herein, “comprising” means that other steps and other ingredients that do not affect the final result can be added. This term includes the terms “consisting of” and “consisting essentially of”.

The contents of all cited references are hereby incorporated by reference. Citation of the references is not an admission as to its availability as prior art to the claimed invention.

As used herein, the term “detergent composition” or “detergent” refers to agents commonly used for soil removal, such as general household detergents or synthetic or soap type laundry detergents.

Aroma Reaction Product The present invention relates to an aroma reaction product that produces a “sun dried odor”. The fragrance reaction product is useful in cleaning compositions for cleaning fabrics and / or hard surfaces. As used herein, the term "cleaning composition" includes both detergent compositions that provide fabric cleaning benefits and hard surface cleaning benefits. Cleaning compositions can be used for laundry of fabrics, dishes, floors, tiles, bathrooms,
Cleaning hard surfaces such as toilets, kitchens and other surfaces is commonly used. The cleaning composition comprises from about 0.0001% to about 10%, preferably from about 0.001% to about 5%, more preferably from about 0.01% to about 2% by weight of the odor of the present invention. Includes reaction products.

The fragrance reaction product comprises a compound containing a primary amine compound and a fragrance component selected from the group consisting of C6-C14 aliphatic aldehydes, C6-C14 acyclic terpene aldehydes and mixtures thereof. It is produced by reacting. Preferably, the perfume ingredient is citral, neral, isocitral, dihydrocitral, cyroneral, octanal, nonanal, decanal, undecanal,
Dodecanal, tridecanal, 2-methyldecanal, methylnonylacetaldehyde, 2-nonane-1-al, 2-decanal, undecenal, undecylene aldehyde, 2,6 dimethyl octanal, 2,6,10-trimethyl-
It is selected from the group consisting of 9-undecen-1-al, trimethylundecanal, dodecenal, melonal, 2-methyloctanal, 3,5,5, trimethylhexanal and mixtures thereof.

When the fabric is washed with the detergent composition containing the present fragrance reaction product, a “sun dried odor” is produced on the fabric even if the fabric is not actually dried by the sun. The reaction mixture is formed by selecting at least one aldehyde naturally present in the cotton fabric after the fabric is dried in the sun, which is a component of the sun dried odor.

The aroma reaction product of the present invention may comprise a mixture of a variety of different products produced by different reactions according to the present invention. These mixtures of aroma reaction products can be made separately and then mixed, or simultaneously produced by reacting one or more primary amines with one or more perfume ingredients. For example, a preferred aroma reaction product is 30% by weight of the reaction product of ethyl 4-aminobenzoate ("EAB") and 2-nonen-1-al, 10% by weight of the reaction product of EAB and methylnonylacetaldehyde, and EAB. It contains 20% by weight of the reaction product of undecylenaldehyde, 10% by weight of the reaction product of EAB and laurylaldehyde and 30% by weight of the reaction product of EAB and citral.

A Primary Amine The primary amine compounds suitable for use in the present invention are characterized by their odor level, preferably less than the odor level of a 1% solution of methyl anthranilate in dipropylene glycol. . Primary amines are non-volatile. That is, the boiling point of the primary amine is at least about 125 ° C, preferably about 150 ° C to about 300 ° C. The molecular weight of the primary amines useful in the present invention is at least about 80 g / mol, preferably about 1
00 g / mol to about 30,000 g / mol, more preferably about 125 g / mol to about 25,000 g / mol. Such boiling point and molecular weight information for primary amines is readily available in standard literature and from primary amine manufacturers.
Primary amines useful in the present invention include primary amines having straight, branched and / or cyclic chains, including saturated, unsaturated, polymeric or aromatic primary amines.
It may be a primary amine. Unsaturated, polymeric and aromatic primary amines are especially preferred in the present invention. Further preferred are unsaturated, polymeric and aromatic primary amines containing both alkoxy and carboxylate ester groups in their structure. Primary amines having multiple reactive amine groups are also useful and preferred in the present invention.

Preferred polymeric primary amines include “Lupasols” from BASF.
Examples of commercially available polyethyleneimine include, for example, Lupasol
FG (MW800), G20wfv (MW1,300), PR8515 (MW
2,000), WF (MW25,000), FC (MW800), G20 (MW
1,300), G35 (MW1,200), G100 (MW2,000), HF
(MW 25,000), P (MW 750,000), PS (MW 750,000)
, SK (MW 2,000,000) and SNA (MW 1,000,000). Particularly preferred primary amines useful in the present invention include meta-, para- and ortho-aminomethylbenzoates, n-ethylaminobenzoate, cumene 55.
7H and cumene 450 (polymer amine from Hercules formed from repeating polyamide and reactive azetidine and epoxide moieties), Lupasol
HF and mixtures thereof. Primary amines useful in the present invention are, for example, BASF AG (Ludwigshafen, Germany), Bushbo Kearen (London, UK), Hermann & Reimer GmbH (Holzminden, Germany) and Hercules (Delaware, USA). (Wilmington, W.).

Without wishing to be bound by theory, the free electron pair of the nitrogen of the primary amine undergoes a nucleophilic attack on the carbonyl carbon of the perfume ingredient in the presence of an acid catalyst to produce a Schiff base. It is believed to form water with the reaction product. The acid catalyst acts as a carbonyl activator and greatly increases the reaction rate. The Schiff base reaction product has a desirable odor and is activated by changes in external conditions such as pH, temperature and humidity to produce a high level of odor when needed, for example when wearing clothing. Emits a level of odor. As a result, the release of perfume from the washed item is controlled. Therefore, such a fragrance has a great advantage as compared with the conventional fragrance in which the fragrance is constantly released until it deteriorates. For example, even a small amount of fragrance can give an odor that is perceived by consumers. Since the fragrance is very expensive, this can significantly reduce the cost.

In addition, due to the physical and chemical properties of the perfume raw materials, conventional perfumes do not allow many desirable odors, such as sun dried odors, to be deposited on the fabric. This controlled release facilitates the attachment of such odors to the dried fabric.

Odor Degree Measurement Method As used herein, the term "odor level" is defined by a test in which the pure chemical substance to be tested is diluted to 1% by weight in the odorless solvent dipropylene glycol. Soak it in a scent, the so-called "blotting paper," and present it to a professional panelist for evaluation. Specialized panelists are panelists trained for at least 6 months to assess odors, and their grades are checked regularly, with continuous reproducibility versus control, to ensure accuracy at all times. For each amine compound, two blotters were given to the panelists, one is the reference (methyl anthranilate, the panelist is unknown) and the other is the sample. Panelists are asked to rank both scents on a scale of 0-5 odor. 0 indicates no odor and 5 indicates a very strong odor.

Below, the odor levels of amine compounds suitable for use in the present invention are shown according to the above procedure. In each case, the numbers are the arithmetic mean by 5 expert panelists and the results are statistically 95% reliable.

[Table 1]

B-Perfume The perfume component of the present invention is selected from the group consisting of C6-C14 aliphatic aldehydes, C6-C14 acyclic terpene aldehydes and mixtures thereof. Preferably, the perfume ingredients of the present invention are selected from C8-C12 aliphatic aldehydes, C8-C12 acyclic terpene aldehydes and mixtures thereof. Most preferably, the perfume ingredients of the present invention are citral, neral, isocitral, dihydrocitral, citronellal, octanal, nonanal, decanal, undecanal, dodecanal, tridecanal, 2-methyldecanal, methylnonylacetaldehyde, 2- Nonen-1-Ar, 2-Decanal, Undecenal,
Undecylene aldehyde, 2,6 dimethyl octanal, 2,6,10-trimethyl-9-undecen-1-al, trimethyl undecaneal, dodecenal, melonal, 2-methyl octanal, 3,5,5, trimethyl hexanal and these Is selected from the group consisting of mixtures of A preferred mixture is, for example,
A mixture comprising 30% by weight 2-nonen-1-al, 40% by weight undecylenaldehyde and 30% by weight citral, or 20% by weight methylnonylacetaldehyde, 25% by weight laurylaldehyde, 35% by weight decanal and It is a mixture containing 20% by weight of 2-nonen-1-al.

[0026]   Isomers of these components are also suitable for use in the present invention.

The cleaning composition of the present invention may further contain other fragrances. Other perfumes can impart additional aroma to the cleaning product and / or aroma at different stages of the cleaning process. Other fragrances are those conventionally added to cleaning compositions as spraying ingredients during the manufacturing process. When adding other perfumes, the ratio of other perfumes to aroma reaction products must be controlled. If the proportion of the aroma reaction product contained in the cleaning composition is too low, the desired "sun-dried odor" may not be sufficient. However, if the cleaning composition contains too little other fragrance, the odor of the cleaning composition may be insufficient. The weight ratio of other perfumes to the aroma reaction products useful in the present invention is from about 100: 1 to about 16: 100. Preferably this ratio is from about 30: 1 to about 1: 5.

C-Process The aroma reaction product is prepared as follows. An "imine" is obtained by reacting a primary amine compound with a perfume ingredient. This imine can be easily prepared by a condensation reaction between the primary amine compound and the carbonyl compound in the perfume ingredient.

[0029]   The general reaction profile is as follows:

[Chemical 1] The α, β-unsaturated ketone not only condenses with an amine to form an imine, but also competing 1,4-adds to form a β-aminoketone.

[Chemical 2]

By this simple method, compounds and compositions containing said compounds can be prepared to delay the release of the active ingredient.

Although not required in the present invention, it is highly preferred that the perfume component is present in an equimolar amount with the reactive amine groups.

D-Release Mechanism The present invention delays the release of perfume ingredients. While not intending to be bound by theory, it is believed that release occurs by the following mechanism.

For imine compounds, the perfume ingredient is released by breaking the imine bond, which leads to the release of the perfume ingredient from the primary amine compound. This is done by either hydrolysis, photochemical cleavage, oxidative cleavage, or enzymatic cleavage on the fabric or hard surface.

The release of perfume ingredients is accelerated, for example by ironing, tumble drying and / or wearing a treated fabric.

E-Dry Surface Odor The dry surface odor of the aroma reaction product from the reaction of the primary amine compound and the perfume component is greater than 5, preferably at least 10.

Dry odor means that the reaction product gives a delta of greater than 5. Here, the delta is the difference between the odor degree of the dry surface treated with the product of the present invention and the odor degree of the dry surface treated only with the perfume raw material.

With respect to the above-mentioned dry surface odor, the products of the present invention suitable for use in the present invention need to be subjected to at least one of the following two tests. Products of the invention suitable for use in the invention are preferably subjected to both tests.

For the test samples, 20 g of the cleaning composition with a total level of aroma reaction products of 0.1% by weight was added to a 30 liter two-tub clothes washing machine. Two 100% cotton pile fabric swatches were placed in the washing machine. The remaining 1.3 kg of laundry was a T-shirt, bath towel and acrylic fabric. This laundry at 30 ℃
Was washed in a normal washing cycle in water.

As a control, a cleaning composition containing the same weight level of unreacted perfume ingredient was used in two control swatches. The cleaning composition dose, the cloth filling amount, the washing cycle and the like for the control and the sample are the same.

Within 45 minutes to 1 hour after the end of the washing cycle, one of the fabric swatches is hung on a string,
Let it dry for 24 hours. Unless otherwise noted, all drying is done indoors. During drying, ambient conditions are a temperature of 18-25 ° C and a humidity of 40-80%.
The other fabric swatch is placed in a tumble dryer, subjected to a 15 minute drying cycle and left for 24 hours.

Odor is evaluated by expert panelists who sniff and grade the fabric. Use a scale of 0-100 for all fabric odor grading. The grading scale is as follows. 100 = Excessively strong perfume odor 75 = Very strong perfume odor 50 = Strong odor 40 = Medium perfume odor 30 = Slight perfume odor 20 = Weak perfume odor 10 = Extreme Has a weak perfume odor 0 = no odor

There is a scale difference of more than 5 after 1 day and / or 7 days between the aroma reaction product (the cleaning composition containing it) and the unreacted perfume component (the cleaning composition containing it). Statistically clear. More than 10 scale differences after 1 and / or 7 days are indicative of graded changes. That is, the aroma reaction products useful in the present invention differ from the unreacted perfume ingredients after 24 hours by at least a scale of 5, preferably at least a scale of 10. Incorporation of the aroma reaction product into the cleaning composition is, if necessary, carried out by conventional means. Aroma reaction products can be sprayed, encapsulated, added to fragranced or unscented product bases,
Dry add or flocculate. The encapsulated aroma reaction product is, for example, GB
It may be encapsulated as described in 1 464 616 or in cyclodextrin. Aggregation is preferably performed with a nonionic surfactant and sodium carbonate. The aroma reaction product is preferably preformed prior to incorporation into the cleaning composition. That is, the fragrance component and the amine compound are first reacted to form a fragrance reaction product and incorporated into the cleaning composition. Pre-formation allows good control of yield, amount, purity, etc. of aroma reaction products and avoids unwanted side reactions.

F Seal Packaging System The detergent of the present invention is preferably packaged in a seal packaging system having a water vapor transmission rate of less than about 40 g / m2 / 24 hours. Water vapor transmission rate is preferably about 30 g / m2 /
It is less than 24 hours, more preferably less than 20 g / m2 / 24 hours.

The sealed packaging system helps to keep the aroma reaction product stable in the cleaning composition. The low water vapor transmission rate reduces possible undesired reverse reactions. These adverse reactions can alter the appearance and / or odor of the cleaning composition and reduce its ability to provide the dried fabric with the best sun dried odor.

Suitable packaging materials can be used in the sealed packaging system. Preferably, the packaging material is polyethylene, polypropylene, polyethylene terephthalate (PET).
), Laminated paper, coated paper, sandwich paper, aluminum and the like.

Detergent Surfactant The detergent composition of the present invention comprises a nonionic and / or anionic and / or cationic and / or zwitterionic and / or amphoteric and / or semipolar surfactant. Included are surfactants that can be selected from the group.

The surfactant is present at a level of about 0.01% to about 60% by weight. More preferred incorporation levels are from about 1% to about 35% by weight of the detergent composition according to the present invention,
Most preferably about 1% to about 30% by weight.

The surfactant is preferably formulated to be compatible with the enzyme components present in the composition. Most preferably, in liquid or gel compositions, the surfactant is formulated so as to not enhance, or at least not degrade, the stability of the enzyme in the composition.

Preferred surfactants for use in the present invention include one or more of the nonionic and / or anionic surfactants described herein as surfactants.

Polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols are suitable for use as the nonionic surfactant of the present invention, with polyethylene oxide condensates being preferred. These compounds are condensation products of alkylphenols in which the alkylene oxide is in a straight or branched chain configuration and has an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms. Including. In a preferred embodiment, ethylene oxide is present in an amount equal to about 2 to about 25 moles, more preferably about 3 to about 15 moles of ethylene oxide per mole of alkylphenol. GAF is a commercially available nonionic surfactant of this type.
Igepal (registered trademark) CO-630, and ROHM &
Triton® X-45, X-114, sold by Haas Company,
Examples include X-100 and X-102. These surfactants are commonly referred to as alkylphenol alkoxylates (eg alkylphenol ethoxylates).

Condensation products of about 1 to about 25 moles of ethylene oxide primary and secondary aliphatic alcohols are suitable for use as the nonionic surfactant of the nonionic surfactants of the present invention. . The alkyl chain of the aliphatic alcohol can be straight or branched, primary or secondary and usually contains from about 8 to about 22 carbon atoms. Preferred is a condensation of an alcohol having an alkyl group containing from about 2 to about 10 moles of ethylene oxide per mole of alcohol with from about 8 to about 20 carbon atoms, more preferably from about 10 to about 18 carbon atoms. It is a product. About 2 to about 7 moles of ethylene oxide per mole of alcohol, most preferably 2 to 5 moles of ethylene oxide are present in the condensation product. Commercially available nonionic surfactants of this type include Tergitol sold by Union Carbide.
(Registered trademark) 15-S-9 (condensation product of C _{11 to} C ₁₅ chain alcohol and 9 mol of ethylene oxide), Tergitol (registered trademark) 24-L-6NM.
W (condensation product of C _{12 to} C ₁₄ primary alcohol and 6 mol of ethylene oxide having a narrow molecular weight distribution), Neodol (sold by Shell Chemical Co.
Trademark) 45-9 (condensation product of C ₁₄ -C ₁₅ chain alcohol and 9 mol of ethylene oxide), Neodol 23-3 (C ₁₂ -C ₁₃ chain alcohol and 3.0). Condensation product with moles of ethylene oxide), Neodo
l _{(R) 45-7} (the condensation product of linear alcohol with 7 moles of ethylene oxide C 14 _{-C 15),} a chain alcohols Neodol _{(TM) 45-5 (C} 14 _{~C 1 5} Condensation product with 5 mol ethylene oxide), proctor &
Kyro® EOB (condensation product of C ₁₃ -C ₁₅ alcohol and 9 moles of ethylene oxide) sold by Gamble, and Genapol LAO3O or O5O (C ₁₂ -C ₁₄ sold by Hoechst. A condensation product of the alcohol with 3 or 5 mol of ethylene oxide). The preferred range of HLB in these products is 8-11, most preferably 8
It is -10.

Similarly useful non-ionic surfactants of the present invention are from about 6 to about 6 disclosed in US Pat. No. 4,565,647 (Llenado) issued Jan. 21, 1986.
An alkyl polysaccharide having a hydrophobic group containing about 30 carbon atoms, preferably about 10 to about 16 carbon atoms, and about 1.3 to about 10, preferably about 1.3 to about 3, most. Polysaccharides having hydrophobic groups, preferably containing from about 1.3 to about 2.7 polysaccharide units, eg polyglycosides. Reduced monosaccharides containing 5 or 6 carbon atoms can be used. For example, glucose, galactose and galactosyl moieties can be substituted for glycosyl moieties (optionally replacing the hydrophobic group with 2-
, 3-, 4-, etc. to give glucose or galactose as opposed to glycoside or galactoside). The intra-monosaccharide bond may be, for example, one position of a plurality of added monosaccharide units and 2-, 3-, 4- and / or the preceding monosaccharide unit.
Or it can be between the 6-position.

Preferred alkyl polyglycosides are represented by the formula R ² O (C _n H _2n O) t (glycosyl) _x , where R ² is from alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof. Selected from the group
Alkyl groups contain 10 to 18, preferably about 12 to about 14 carbon atoms,
n is 2 or 3, preferably 2, t is 0 to 10, preferably 0, x is about 1.3 to.
It is about 10, preferably about 1.3 to about 3, and most preferably about 1.3 to about 2.7. Glycosyl is preferably derived from glucose. To prepare these compounds, an alcohol or alkyl polyethoxy alcohol is first formed and reacted with glucose or a glucose source to form a glycoside (added at the 1-position). The additional glucosyl units are the 1-position and the preceding glycosyl units 2-3.
It is preferentially added between-, 4- and / or 6-position, preferably 2-position.

Condensation products of ethylene oxide with a hydrophobic base formed by the condensation of polypropylene oxide and propylene glycol are also suitable for use as the additional nonionic detergent surfactant of the present invention. The hydrophobic moieties of these compounds preferably have a molecular weight of from about 1500 to about 1800 and are insoluble in water. The addition of a polyoxyethylene moiety to this hydrophobic moiety tends to increase the overall water solubility of the molecule, and the liquid character of this product is that the polyoxyethylene content is about the total weight of the condensation product. Retained up to 50%, which corresponds to condensates of up to about 40 mol of ethylene oxide. Examples of this type of compound include Plur commercially available from BASF.
afac® LF404 and Pluronic® surfactants are exemplified.

Also suitable for use as the nonionic surfactant of the present invention is the condensation product of ethylene oxide with the product obtained from the reaction of propylene oxide and ethylenediamine. The hydrophobic part of these products consists of the aroma reaction product of ethylenediamine and excess polypropylene oxide and has a molecular weight of about 25.
It is from 00 to about 3000. The hydrophobic portion is condensed with ethylene oxide such that the condensation product contains about 40% to about 80% by weight polyoxyethylene and has a molecular weight of about 5,000 to about 11,000. An example of this type of nonionic surfactant is the Tetronic® compound commercially available from BASF.

Suitable for use as the nonionic surfactant of the present invention are polyethylene oxide condensates of alkylphenols, condensation products of primary and secondary aliphatic alcohols with about 1 to about 25 moles of ethylene oxide. , Alkyl polysaccharides and mixtures thereof. Most preferred, _C 8 ~ having 3 to 15 ethoxy groups
C ₁₄ alkylphenol ethoxylates, and C _{8 to} C ₁₈ alcohol ethoxylates having 2 to 10 ethoxy groups (preferably average C ₁₀ ), and mixtures thereof.

Highly preferred nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula:

[Chemical 3] At least in the formula, ^{R 1} is _H, hydrocarbyl of C 1 _{~ 4,} 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, ^{R 2} is a hydrocarbyl of _C 5 _{~ 31,} Z is directly coupled to the chain A polyhydroxyhydrocarbyl having a chain hydrocarbyl chain having 3 hydroxyls, or an alkoxylated derivative thereof. Preferably, ^{R 1} is methyl, ^{R 2} is alkyl or alkenyl difference straight _C 11 _alkyl-15 or _C 16 _{- 18,} for example, coconut alkyl or mixtures thereof, Z is glucose in a reductive amination reaction, fructose, It is derived from reducing sugars such as maltose and lactose.

Suitable anionic cosurfactants for use are C ₈ -C ₂₀ sulfonated with gaseous SO ₃ according to the American Society of Oil and Fat Chemistry Journal 52 (1975) pages 323-329. Are chain alkylbenzene sulfonates including alkyl carboxylic acid (that is, fatty acid) chain esters, alkyl ester sulfonates, branched alkyl sulfonates, and medium chain alkyl sulfonates. Suitable starting materials include natural fatty substances derived from tallow, palm oil and the like.

Particularly preferred alkyl ester sulfonate surfactants for laundry applications are:
Structural formula

[Chemical 4] Alkyl ester sulfonate surfactants. Wherein R ³ is a C _{8 to} C ₂₀ hydrocarbyl, preferably alkyl, or a combination thereof, and R ⁴ is a C _{1 to} C ₆ hydrocarbyl, preferably alkyl, or a combination thereof. , M is a cation that forms a water-soluble salt with an alkyl ester sulfonate. Suitable salt forming cations include metals such as sodium, potassium and lithium, and substituted or unsubstituted ammonium cations such as monomethanolamine, diethanolamine and triethanolamine. Preferably, ^{R 3} is alkyl of _C 10 _{~C 16,} ^{R 4} is methyl, ethyl or isopropyl. Especially preferred are methyl ester sulfonates where R ³ is C ₁₀ -C ₁₆ alkyl.

[0060]   Other suitable anionic surfactants include the formula ROSO_ThreeM water-soluble salt
Or an acid, such as an alkyl sulfate surfactant, in which R is preferably C_{1 0} ~ C₂₄A hydrocarbyl, preferably C₁₀~ C₂₀With an alkyl component of
Alkyl or hydroxyalkyl, more preferably C₁₂~ C₁₈The al
Is alkyl or hydroxyalkyl, M is H or, for example, an alkyl metal cation.
Ions (eg sodium, potassium, lithium), ammonium or substituted
Ammonium (eg methyl-, dimethyl- and trimethylammonium cations)
Of the tetramethyl-ammonium and dimethylpiperidinium cations
Quaternary ammonium cations such as, and ethylamine, diethylamine,
Quaternary ammonium cations derived from lyethylamine and mixtures thereof
Cations). Generally, for low temperature cleaning (below about 50 ° C)
C₁₂~ C₁₆Preferred alkyl chains, and C for hot washing (above about 50 ° C) ₁₆ ~₁₈Is preferred.

Other anionic surfactants useful for laundry purposes can also be included in the detergent compositions of the present invention. These include soap salts (eg sodium,
Potassium, ammonium, and mono-, - di - and substituted ammonium salts such as triethanolamine _salt), primary or secondary alkane sulfonates of C 8 _{-C 22,} olefins C 8 _{-C 24} Sulfonates; sulfonated polycarboxylic acids prepared by sulfonation of the thermal decomposition products of alkaline earth metal citrates, as described, for example, in British Patent Specification 1,082,179. , C ₈ -C ₂₄ alkyl polyglycol ether sulphates (containing up to 10 mol of ethylene oxide), alkyl glycerol sulphonates, fatty acyl glycerol sulphonates, fatty oleyl glycerol sulphates, alkylphenol ethylene oxide ether sulphates, paraffin sulphones Acid salt, alkyl phosphate, acyl Thionating, N- acyl taurates, isethionates, monoesters of sulfosuccinates (especially monoesters of saturated and unsaturated C ₁₂ -C _18), such as alkyl succinamates cinnamate and sulfosuccinates, diesters of sulfosuccinates (especially Saturated and unsaturated C ₆ -C ₁₂ diesters), acyl sarcosinates, sulfates of alkyl polysaccharides such as sulfates of alkyl polyglucosides (nonionic non-sulfated compounds described below), branched primary alkyls sulfates, and wherein _{RO (CH 2 CH 2 O)} k -CH 2 COO-M + ( wherein, R is alkyl of _C 8 _{-C 22,} k is an integer of from 1 to 10, M is a soluble Is a salt-forming cation)
Examples thereof include alkyl polyethoxycarboxylic acid salts. Also suitable are resin acids and hydrogenated resin acids such as rosins, hydrogenated rosins, resin acids and hydrogenated resin acids present in or derived from tall oil.

In addition, “Surfactants and Detergents” (Vol. 1 and 2 Schwartz, Perr
y and Berch). Such various surfactants are also described in U.S. Pat. No. 3,929,678 issued Dec. 30, 1975 (La.
Ughlin et al.) Col. 23, line 58 to Col. 29, line 23 (incorporated herein by reference).

When included, the detergent compositions of the present invention will typically contain from about 1% to about 40%, preferably from about 3% to about 20% by weight of such anionic surfactants. .

Highly preferred anionic surfactants alkylalkoxylated sulphate surfactants are water-soluble salts or acids of the formula RO (A) _m SO3M. Wherein, R is a hydroxy alkyl group having an alkyl component of the alkyl or _C 10 _{-C 24} unsubstituted _C 10 _{-C 24,} preferably an alkyl or hydroxyalkyl of _C 12 _{-C 20,} more preferably _C 12 _{-C 18} Alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, usually between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M Is H or
For example, cations that can be metal cations (eg, sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted ammonium cations. Alkyl ethoxylated sulfates and alkyl propoxylated sulfates are also envisioned in this invention. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium cations, quaternary ammonium cations such as tetramethyl-ammonium, and dimethylpiperidinium cations, and ethylamine, diethylamine, triethylamine. Those derived from alkylamines, mixtures thereof, and the like. Specific co-surfactants are _the alkyl polyethoxylate of C 12 _{-C 18} (
1.0) _{sulfate, (C 12 ~C 18 E (} 1.0) M), alkyl polyethoxylate (2.25) sulfate _{C 12 ~C 18, (C 12} ~C 18 E (2. 25) M
_), C 12 alkyl polyethoxylate (3.0 _{-C 18)} sulfate _{(C 12} ~
C ₁₈ E (3.0) M), and alkyl polyethoxylate of _C 12 _{-C 18} (
4.0) sulfate _{(C 12 ~C 18 E (4.0} ) M) have, where M is suitably selected from sodium and potassium.

The detergent composition of the present invention may also contain cationic, zwitterionic, amphoteric and semipolar surfactants in addition to the nonionic and / or anionic surfactants already mentioned. Good.

[0066]   A suitable cationic detergent surfactant for use in the detergent composition of the present invention is one
Such as having a long chain hydrocarbyl group. Such cationic surfactant
As an ammonium such as an alkyl trimethyl ammonium halide
Surfactants and formulas [R^Two(OR^Three)_y] [R^Four(OR^Three)_y]_TwoR⁵N⁺X⁻ The surfactants of are exemplified. Where R^TwoIs an alkyl of about 8 to about 18 carbon atoms
An alkyl or alkylbenzyl group in the chain, each R^ThreeIs -CH_TwoCH_Two-,
-CH_TwoCH (CH_Three)-, -CH_TwoCH (CH_TwoOH)-,-CH_TwoCH_TwoC
H_Two-And each R selected from the group consisting of^FourIs C₁~ C_FourA
Rukiru, C₁~ C_FourHydroxyalkyl, 2 R^FourBy combining the groups
Formed benzyl ring structure, -CH_TwoCHOH-CHOCOR⁶CHOHCH _Two OH, in the formula, R⁶Is hexose or hexose poly having a molecular weight of less than about 1000
And hydrogen when y is not 0, R⁵Is R^FourSame as or R^TwoPlastic
R⁵An alkyl chain if the total number of carbon atoms in does not exceed about 18, each y is 0 to about 1.
The sum of the values of 0, y is 0 to about 15, and X is a compatible anion.

[0067]   A quaternary ammonium surfactant suitable for the present invention is represented by formula (I).

[Chemical 5] Formula I wherein R1 is a short chain alkyl (C6-C10) or an alkylamidoalkyl of formula (II),

[Chemical 6] Formula II y is 2-4, preferably 3, R2 is H or C1-C3 alkyl, x is 0-4, preferably 0-2, most preferably 0, R3, R4 and R5 are the same or different. , A short chain alkyl (C1-C3) or an alkoxylated alkyl of formula III. Wherein X ⁻ is a counterion, preferably a halide such as chloride or ethyl sulfate.

[Chemical 7] Formula III R6 is C ₁ -C ₄ , z is 1 or.

[0068]   Preferred quaternary ammonium surfactants are as defined in formula I
, In the formula, R₁Is C₈, C₁₀Or a mixture thereof, x = 0, R_Three, R_Four= CH _Three And R₅= CH_TwoCH_TwoIt is OH.

[0069]   Highly preferred cationic surfactants have the formula R₁R_TwoR_ThreeR_FourN⁺X⁻(I)
Is a water-soluble quaternary ammonium compound useful for the composition of the present invention represented by: formula
Medium, R₁Is C₈~ C₁₆Alkyl of each R_Two, R_ThreeAnd R_FourIs independently C₁~ C _Four Alkyl, C₁~ C_FourHydroxyalkyl, benzyl and-(C_TwoH_{Four 0} )_xH and x are values of 2 to 5, and X is an anion. R_Two, R_ThreeOr R_FourOut of
One is benzyl.

Preferred alkyl chain lengths for R ₁ are olefin build-up OX, especially when the alkyl is a mixture of chain lengths derived from coconut or palm kernel fat.
When induced by O alcohol synthesis is _C 12 _{-C 15.} Preferred groups for R ₂ , R ₃ and R ₄ are methyl and hydroxyethyl groups and the anion X is selected from halide, methosulfate, acetate and phosphate ions.

Suitable quaternary ammonium compounds of formula (i) for use in the present invention include coconut trimethyl ammonium chloride or bromide, coconut methyl dihydroxyethyl ammonium chloride or bromide, decyl triethyl ammonium chloride, decyl dimethyl hydroxyethyl ammonium chloride or bromide, C ₁₂ ~ ₁₅ dimethyl hydroxyethyl ammonium chloride or bromide, coconut dimethyl hydroxyethyl ammonium chloride or bromide, myristyl trimethyl ammonium methyl sulphate, lauryl dimethyl benzyl ammonium chloride or bromide, lauryl dimethyl (Etheneoxy) ₄ ammonium chloride or bromide, choline ester (a compound of formula (i), wherein R ¹ is

[Chemical 8] And R ² R ³ R ⁴ is methyl) dialkyl imidazoline [compound of formula (i)].

Other cationic surfactants useful in the present invention are those of October 1, 1980.
U.S. Pat. No. 4,228,044 issued 4 days and European patent application EP 0
No. 00,224.

Representative cationic fabric softening ingredients include water soluble quaternary ammonium fabric softening activators or the corresponding amine precursors, the most commonly used of which are di-long chain alkyls. Ammonium chloride or methyl sulfate.

Preferred cationic softeners include the following: 1) tallow dimethyl ammonium chloride (DTDMAC) 2) tallow dimethyl ammonium chloride dihydride, 3) tallow dimethyl ammonium dihydrogen dimethyl ammonium sulfate, 4) distearyl dimethyl ammonium chloride, 5) dioleyl dimethyl ammonium chloride, 6) di palmityl hydroxyethyl methyl ammonium chloride, 7) stearyl benzyl dimethyl ammonium chloride, 8) tallow trimethylammonium chloride, 9) hydrogenated tallow trimethyl ammonium chloride, ₁₀₎ alkylhydroxyethylammonium dimethyl ammonium chloride _{C 12 ~ 14, 11) C} 12 ~ ₁₈ alkyl dihydroxyethyl methyl ammonium chloride 12) di (stearoyloxyethyl) dimethyl ammonium chloride (DSOED
MAC) 13) Di (tallow-oxy-ethyl) dimethyl ammonium chloride, 14) Ditallow imidazolinium methyl sulfate, 15) 1- (2-Tallow ylamidoethyl) -2-tallow imidazolinium methyl sulfate.

Biodegradable quaternary ammonium compounds have emerged as an alternative to the conventionally used two long chain alkyl ammonium chlorides and methyl sulfate. Such quaternary ammonium compounds contain long chain alkyl (alkenyl) groups interrupted by functional groups such as carboxy groups. Said materials and fabric softening compositions containing them are described in EP-A-No. 0,040,562 and EP-A-No. 0,2.
It is disclosed in numerous documents such as 39,910.

The quaternary amine compound and the amine precursor are represented by the chemical formula (I) or (II).

[Chemical 9] (I) or

[Chemical 10] (II) In formula, Q is -OC (O)-, -C (O) -O-, -OC (O) -O-, -N.
^{R 4 -C (O) -,} - C (O) -NR 4, R 1 is _{(CH 2) n-Q-} T 2 or ^T 3, ^{R 2} is _{(CH 2) m-Q-} T 4 or T ⁵ or R ³ , R ³ is C ₁ -C ₄ alkyl or C ₁ -C ₄ hydroxyalkyl or HR ⁴ is H or C ₁ -C ₄ alkyl or C ₁ -C ₄ hydroxyalkyl,
T ¹ , T ² , T ³ , T ⁴ , and T ⁵ are independently C _{11 to} C ₂₂ alkyl or alkenyl, n and m are integers from 1 to 4, and X ⁻ is an anion compatible with the softener. Is. Anions compatible with softeners include, but are not limited to, chloride or methyl sulfate.

The alkyl or alkenyl chain T ¹ , T ² , T ³ , T ⁴ , T ⁵ is at least 1
It must contain 1 carbon atom, preferably at least 16 carbon atoms. It may be linear or branched. Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl materials. Particularly preferred are compounds in which T ¹ , T ² , T ³ , T ⁴ , T ⁵ are a mixture of long chain materials common in tallow.

Specific examples of the quaternary ammonium compound suitable for use in the aqueous fabric softening composition in the present invention are as follows. 1) N, N-di (tallowyl-oxy-ethyl) -N, N-dimethylammonium chloride, 2) N, N-di (tallowyl-oxy-ethyl) -N-methyl, N- (2-hydroxy) Ethyl) ammonium methyl sulfate, 3) N, N-di (2-tallowyl-oxy-2-oxo-ethyl) -N, N-dimethylammonium chloride, 4) N, N-di (2-tallowyl-oxy) -Ethylcarbonyl-oxy-ethyl)
-N, N-dimethyl ammonium chloride, 5) N- (2-tallow-yl-oxy-2-ethyl) -N- (2-tallow-yl-oxy-2-oxo-ethyl) -N, N-dimethyl ammonium chloride , 6) N, N, N-tri (tallowyl-oxy-ethyl) -N-methylammonium chloride, 7) N- (2-tallowyl-oxy-2-oxo-ethyl) -N- (tallowyl- N
, N-dimethyl-ammonium chloride), and 8) 1,2-ditallow yl-oxy-3-trimethylammonio propane chloride, and mixtures of the above materials.

When included, the detergent compositions of the present invention will typically contain from 0.2% to about 25%, preferably from about 1% to about 8% by weight of such cationic surfactants.

Amphoteric surfactants are also suitable for use in the detergent composition of the present invention. These surfactants are used as an aliphatic derivative of a secondary or tertiary amine and an aliphatic derivative of a heterocyclic secondary and tertiary amine capable of converting an aliphatic radical into a straight chain or a branched chain. It is explained in a broad sense. One of the aliphatic substituents contains at least about 8 carbon atoms, usually about 8 to about 18 carbon atoms, at least one of which is an anionic, water-soluble group such as carboxy, sulfonate, Contains sulfate. For examples of amphoteric surfactants, see US Pat.
, 929,678 (Laughlin et al.) At column 19, lines 18-35.

When included, the detergent compositions of the present invention will typically contain from 0.2% to about 15%, preferably from about 1% to about 10% by weight of such zwitterionic surfactants.

Zwitterionic surfactants are also suitable for use in the detergent composition. These surfactants are used as secondary and tertiary amine derivatives, heterocyclic secondary and tertiary amine derivatives or quaternary ammonium derivatives, quaternary phosphonium or tertiary sulfonium compounds. It is explained in a broad sense. For examples of zwitterionic surfactants, see U.S. Pat. No. 3,929,678, Dec. 30, 1975 (Laughlin et al.), Column 19, line 38 to column 22, line 48. .

When included, the detergent compositions of the present invention will typically include from 0.2% to about 15%, preferably from about 1% to about 10% by weight of such zwitterionic surfactants. .

Semi-polar nonionic surfactants are a special class of nonionic surfactants,
A water-soluble amine oxide containing one alkyl moiety of about 10 to about 18 carbon atoms and two moieties selected from the group consisting of alkyl groups of about 1 to about 3 carbon atoms and hydroxyalkyl groups; A water-soluble phosphine containing one alkyl moiety of about 10 to about 18 carbon atoms and two moieties selected from the group consisting of alkyl groups containing about 1 to about 3 carbon atoms and hydroxyalkyl groups. An oxide; and one alkyl moiety of about 10 to about 18 carbon atoms and two moieties selected from the group consisting of an alkyl group containing about 1 to about 3 carbon atoms and a hydroxyalkyl group. Water-soluble sulfoxides may be mentioned.

Semi-polar detergent surfactants include amine oxide surfactants of the formula:

[Chemical 11] Wherein R ³ is an alkyl, hydroxyalkyl or alkylphenyl group containing about 8 to about 22 carbon atoms, or mixtures thereof, R ⁴ is an alkylene or hydroxy containing about 2 to about 3 carbon atoms. An alkylene group or mixtures thereof, where x is 0 to about 3, each R ⁵ is an alkyl or hydroxyalkyl group containing about 1 to about 3 carbon atoms, or a poly containing about 1 to about 3 ethylene oxide groups. It is an ethylene oxide group. The R ⁵ groups can be added to each other, for example via an oxygen or nitrogen atom, to form a ring structure.

In particular, these amine oxide surfactants include C ₁₀ -C ₁₈ alkyldimethylamine oxides and C ₈ -C ₁₂ alkoxyethyldihydroxyethylamine oxides.

When included, the detergent compositions of the present invention will typically include from 0.2% to about 15%, preferably from about 1% to about 10% by weight of such semipolar nonionic surfactants. Including.

The detergent composition of the present invention may further comprise a cosurfactant selected from the group of primary or tertiary amines. Suitable primary amines for use in the present invention include amines of the formula R ₁ NH ₂ , where R ₁ is a C _{6 to} C ₁₂ , preferably a C _{6 to} C ₁₀ alkyl chain, or _{R 4 X (CH 2) n} , X is -O
-, - C (O) NH- or -NH-, alkyl chain of _{R 4} is _C 6 _{-C 12,} n is 1-5, preferably 3. The R ₁ alkyl chain may be linear or branched, and
Up to, preferably less than 5, ethylene oxide moieties.
The preferred amine according to the above formula is an n-alkyl amine. Suitable amines for use in the present invention are selected from 1-hexylamine, 1-octylamine, 1-decylamine and laurylamine. Other preferable primary amines include C8-C10 oxypropylamine, octyloxypropylamine, and 2
-Ethylhexyl-oxypropylamine, laurylamidopropylamine and amidopropylamine.

Suitable tertiary amines for use in the present invention include tertiary amines of formula R ₁ R ₂ R ₃ N, where R ₁ and R ₂ are C ₁ -C ₈ Alkyl chain, or chemical formula

[Chemical 12] And R^ThreeIs C₆~ C₁₂, Preferably C₆~ C₁₀Alkyl chain of R, or R _Three Is R_FourX (CH_Two)_n, X is -O-, -C (O) NH- or -NH-, R_Four Is C_Four~ C₁₂, N is 1 to 5, preferably 2 to 3, R₅Is H or C₁~ C_Twoof
Alkyl, x is 1-6. R_ThreeAnd R_FourMay be straight or branched and R_Three The alkyl chain has up to 12 and preferably less than 5 ethylene oxide moieties.
It may be suspended.

A preferred tertiary amine is R ₁ R ₂ R ₃ N, wherein R ₁ is C 6 -C 12.
An alkyl chain of R2 and R3 is C1-C3 alkyl, or

[Chemical 13] And R5 is H or CH3, and x = 1 to 2.

[0091]   Also preferred are amidoamines of the formula:

[Chemical 14] In the formula, R ₁ is C ₆ -C ₁₂ alkyl, n is 2-4, preferably n is 3, R ₂ and R ₃ are C ₁ -C ₄ .

The most preferred amines of the present invention include 1-octylamine, 1-hexylamine, 1-decylamine, 1-dodecylamine, C8-C10 oxypropylamine, N coco 1-3 diaminopropane, coco alkyl dimethyl. Amine, lauryl dimethyl amine, lauryl bis (hydroxyethyl) amine, coconut bis (hydroxy ethyl) amine, lauryl amine 2 mol propoxylation, octyl amine 2 mol propoxylation, lauryl amido propyl dimethyl amine, C8-C10
And C10 amidopropyldimethylamine.

Most preferred for use in the compositions of the present invention are 1-hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine. Particularly desirable are n-dodecyldimethylamine, bishydroxyethylcocoalkylamine, oleylamine 7-fold ethoxylated, laurylamidopropylamine and palmamidopropylamine.

[0094]   Additional ingredients builder   The detergent composition of the present invention can optionally include a builder.

The level of builders varies greatly depending on the end use of the composition and its desired physical form. The composition, if present, is generally at least 1%, preferably 1%.
Includes ~ 80% builder. Liquid formulations generally contain from 5% to 50% by weight, more preferably from 5% to 30% by weight of detergent builder. Granule formulations generally contain from 1% to 80% by weight, more usually from 5% to 50% by weight of detergent builder. However, less or more builders are not excluded.

Inorganic or P-containing detergent builders include pyrophosphate (tripolyphosphate,
Of pyrophosphate and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and tricarbonates), sulfates and aluminosilicates Examples include, but are not limited to, alkali metal, ammonium and alkanol ammonium salts. However, some areas require non-phosphate builders. Importantly, so-called "weak" builders such as citrate (compared to phosphates) are present, or so-called "unpotency enhancement" that can occur with zeolites or layered silicate builders.
It is surprising that the composition also works well in the "der built)" state.

[0097]   As silicate builders, alkali metal silicates, especially SiO_Two: Na_TwoO
Ratios of 1.6: 1 to 3.2: 1 and US Pat. No. 4,664,839
Illustrative are layered silicates such as the layered sodium silicates described in the text.
. NaSKS-6 is a trademark of crystalline layered silicate commercially available from Hoechst.
(Here, abbreviated as “SKS-6”). Unlike zeolite builder, N
The aSKS-6 silicate builder does not contain aluminum. NaSKS-
6 is layered silicate delta-Na_TwoSiO₅Have the morphological morphology of
. This is described in DE-A-3,417,649 and DE-A-3,742.
, 043 specification. S
KS-6 is a highly preferred layered silicate for use in the present invention. Was
However, general formula NaMSi_xO_2x+₁・ YH_TwoO (where M is sodium or
Hydrogen, x is a number from 1.9 to 4, preferably 2, and y is 0 to 20, preferably
Other such layered silicates, such as those having a number of
It can be used in As various other layered silicates from Hoechst
Is NaSKS-5, NaSKS- as the alpha, beta and gamma forms.
7 and NaSKS-11. As mentioned above, Delta-Na_TwoSiO ₅ (NaSKS-6 form) is most preferred for use in the present invention. Silicate
Other silicates, such as gnesium, are also useful and may be useful in granular formulations.
As a relishing agent, as a stabilizer of oxygen bleach, and as a component of foam control system.
To use.

Examples of carbonate builders include the alkaline earth and alkali metal carbonates disclosed in DE 2,321,001.

Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are very important for the most popular heavy duty detergent compositions today and may also be an important builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula Mz / n [(AlO ₂ ) z (SiO ₂ ) y] .xH ₂ O. In the formula, z and y are usually integers of at least 6, the molar ratio of z to y is in the range of 1.0 to 0, x is an integer of 0 to 264, M is a group IA or group IIA element. , For example, n-valent Na, K, Mg, and Ca.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure, can be aluminosilicates found in nature, or can be synthetically derived. A method of making an aluminosilicate ion exchange material is described in US Pat. No. 3,985.
, 669. Preferred synthetic crystalline aluminosilicate ion exchange materials useful in the present invention are zeolite A, zeolite P (B), zeolite M.
It is available under the trade names AP and Zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula _{Na 12 [(AlO 2) 1} 2 (SiO 2) 12] · xH 2 O. In the formula, x is 20 to 30, especially 2
7 This material is known as Zeolite A. Dehydrated zeolite (x =
0-10) may also be used in the present invention. Preferably the aluminosilicate has a particle size of 0.1-10 microns in diameter.

Suitable organic detergent builders for the purposes of the present invention include, but are not limited to, various polycarboxylic acid salt compounds. As used herein, "polycarboxylate" refers to a compound having multiple carboxylate groups, preferably at least 3 carboxylates. The polycarboxylate builder is usually added to the composition in the acid form, but it can also be added in the neutralized salt form.
When utilized in salt form, alkali metal or alkanol ammonium salts such as sodium, potassium and lithium are preferred.

Polycarboxylate builders include various classes of useful materials. One important class of polycarboxylate builders includes oxydisuccinates, as disclosed in US Pat. No. 3,128,287 and US Pat. No. 3,635,830. It is an ether polycarboxylic acid salt. See also the "TMS / TDS" builder in U.S. Pat. No. 4,663,071. Suitable ether polycarboxylic acid salts also include U.S. Pat. No. 3,923,67.
No. 9, No. 3,835,163, No. 4,158,635,
Mention may be made of cyclic compounds, in particular alicyclic compounds, as described in 4,120,874 and 4,102,903.

Other similar detergent builders include ether hydroxypolycarboxylates, copolymers of maleic anhydride and ethylene or vinyl methyl ether, 1,
Various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as 3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, ethylenediaminetetraacetic acid and nitrilotriacetic acid, and melitto Acids, pyromellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, polymeric acids, polycarboxylic acid salts such as benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, such as citric acid and its soluble salts (particularly the sodium salt), are particularly important for heavy duty liquid detergent formulations due to their availability and biodegradability from renewable sources. Polycarboxylate builder. Citrates can also be used in granular compositions, especially in combination with zeolites and / or layered silicate builders. Oxydisuccinates are also particularly useful in such compositions and combinations.

Similarly, suitable in the detergent composition of the present invention is 3,3-dicarboxy-4.
-Oxa-1,6-hexanedioate and related compounds disclosed in U.S. Pat. No. 4,566,984. Useful succinic acid builders include alkyl and alkenyl succinic acids and salts thereof C ₅ -C _20. A particularly preferred compound of this type is dodecenyl succinic acid. Specific examples of the succinate builder include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), and 2-pentadecenyl succinate. . Lauryl succinate is a preferred builder of this group and is described in EP 0,200,263.

Other suitable polycarboxylic acid salts are disclosed in US Pat. No. 4,144,226 and US Pat. No. 3,308,067. See also U.S. Pat. No. 3,723,322.

Fatty acids, such as C _{12 to} C ₁₈ monocarboxylic acids, may also be incorporated into the composition, either alone or in combination with the aforementioned builders, especially the citrate and / or succinate builders, to provide additional activity to the builders. You can also give. When a fatty acid is used in this manner, bubbling cleaning is usually suppressed. This should be considered by the prescriber.

When using phosphorus-based builders, various alkali metal phosphates such as the well known sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate can be used, especially in the formulation of bars for hand washing. .
Ethane-1-hydroxy-1,1-diphosphate and other known phosphates (
For example, U.S. Pat. Nos. 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3
, 422,137) may also be used.

Bleach Compounds-Bleaches and Bleach Activators The detergent compositions may optionally contain a bleach, or a bleach composition containing a bleach and one or more bleach activators. The bleach, if present, is
Generally, levels of 1% to 30%, more commonly 5% to 20% of detergent compositions (especially for laundry laundry). When present, the amount of bleach activator will generally be from 0.1% to 60% of the bleaching composition containing bleach plus bleach activator, more typically from 0.5% to 40%. is there.

The bleaching agent used in the present invention can be any bleaching agent useful in detergent compositions for the purposes of washing fabrics, or any other presently known washing purpose. This includes oxygen bleaches and other bleaches such as hypochlorous acid bleach. Perborate bleaches such as sodium perborate (eg, mono- or tetra-hydrate) can be used in the present invention. When using hypochlorite, a highly preferred hypochlorite bleaching component is an alkali metal hypochlorite. Although alkali metal hypochlorites are preferred, other hypochlorite compounds may also be used in the present invention and can be selected from calcium and magnesium hypochlorite. The preferred alkali metal hypochlorite salt for use in the present invention is sodium hypochlorite.

Other classes of bleaching agents that can be used without limitation include percarboxylic acid bleaching agents and salts thereof. Suitable solvents of this type include magnesium monoperoxyphthalate hexahydrate, magnesium salt of metachloroperbenzoic acid, 4
Examples include -nonylamino-4-oxoperoxybutyric acid and diperoxide decanedioic acid. Such bleaching agents are described in U.S. Pat. No. 4,483,781, U.S. Patent Application No. 740,446, EP 0,133,354 and U.S. Pat. No. 4,412,934. Is disclosed in. Highly preferred bleaches also include 6-nonylamino-6-oxoperoxycaproic acid as described in US Pat. No. 4,634,551.

Peroxygen bleaches can also be used. Suitable peroxygen bleaching compounds include
Included are sodium carbonate peroxyhydrate, equivalent "percarbonate" bleach, sodium pyrosulfate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Persulfate bleach (eg, OXONE, commercially manufactured by DuPont) can also be used.

A preferred percarbonate bleach comprises dry particles having an average particle size in the range of 500 micrometers to 1,000 micrometers, 10% by weight of said particles.
The following are smaller than 200 micrometers, and 10% by weight or less of the particles are 1, 2
Greater than 50 micrometers. Optionally, the percarbonate can be coated with silicates, borates or water-soluble surfactants. Percarbonate is FMC, So
It is available from various commercial sources such as lvay and Tokai Denka.

[0114]   Mixtures of bleaching agents can also be used.

Peroxygen bleaches, perborates, percarbonates and the like are preferably mixed with the bleach activator. This leads to in situ production of peracid corresponding to the bleach activator in an aqueous solution (eg during the washing process). Examples of various activators are given in US Pat.
, 915,854 and U.S. Pat. No. 4,412,934, but are not limited thereto. Nonanonyloxybenzene sulfonate (NOBS), 3,5,5-tri-methylhexanoyloxybenzene sulfonate (ISONOBS) and tetraacetylethylenediamine (TAED)
) Activators are a typical example, and mixtures thereof can also be used. For other representative bleaches and activators useful in the present invention, see US Pat. No. 4,634,55.
See also No. 1.

A highly preferred amide-derived bleach activator is of the formula R ¹ N (R ⁵ ) C (O) R ² C (
O) O or R ¹ C (O) N (R ⁵ ) R ² C (O) L. In the formula, R ¹ is an alkyl group containing 6 to 12 carbon atoms, R ² is alkylene containing 1 to 6 carbon atoms, and R ⁵ is H or 1 to 10 carbon atoms. Is an alkyl, aryl or alkaryl containing L and L is a suitable residue. A residue is a group that displaces a bleach activator as a result of a nucleophilic attack on the bleach activator by a perhydrolytic anion. A preferred residue is phenyl sulfonate.

Preferred examples of the bleach activator of the above formula include (6-octanamido-caproyl) oxybenzene sulfonate, (6-nonanamidocaproyl) oxybenzene sulfonate, (6-decanamido-caproyl) oxybenzene sulfonate and Mention may be made of those mixtures described in US Pat. No. 4,634,551, which is hereby incorporated by reference.

Other species of bleach activators include the benzoxazine type activators disclosed in US Pat. No. 4,966,723. A highly preferred activator of the benzoxazine type is

[Chemical 15] Is.

Yet another class of preferred bleach activators includes acyl lactam activators, especially acyl caprolactam and acyl valerolactam of the formula:

[Chemical 16] In the formula, R ⁶ is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing 1 to 12 carbon atoms. Highly preferred lactam activators include benzoylcaprolactam, octanoylcaprolactam, 3,5,5.
5-trimethylhexanoylcaprolactam, nonanoylcaprolactam, decanoylcaprolactam, undecenoylcaprolactam, benzoylvalerolactam, octanoylvalerolactam, decanoylvalerolactam, undecenoylvalerolactam, nonanoylvalerolactam, 3,5,5 -Trimethylhexanoyl valerolactam and mixtures thereof. U.S. Pat. No. 4,545,784 (Sa, issued Oct. 8, 1985, incorporated herein by reference).
See also the specification. It discloses acylcaprolactams, including benzoylcaprolactam adsorbed on sodium perborate.

Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized in the present invention. One class of non-oxygen bleaching agents of particular interest includes photoactive bleaching agents such as zinc sulfonate and / or aluminum phthalocyanines. See also U.S. Pat. No. 4,033,718. When used, the detergent compositions usually contain 0.025% to 1.25% by weight of such bleaching agents, especially zinc phthalocyanine sulfonate.

[0121]   If desired, the bleaching compound should be catalyzed by manganese compounds.
You can Such compounds are well known in the art and are described, for example, in US Pat.
No. 5,246,621, US Pat. No. 5,244,594, fifth
, 194,416, US Pat. No. 5,114,606, European patent
Application Publication No. 549,271A1, Specification No. 549,272A1, Specification No. 5,
44,440A2 and 544,490A1.
Examples include gangan-based catalysts. Preferred examples of these catalysts include Mn^IV _Two (U-O)_Three(1,4,7-Trimethyl-1,4,7-triazacyclononane
)_Two-(PF₆)_Two, Mn^III _Two(U-O)₁(U-OAc)_Two(1, 4, 7
-Trimethyl-1,4,7-triazacyclononane)_Two-(ClO_Four)_Four, Mn ^IV _Four (U-O)₆(1,4,7-triazacyclononane)_Four(ClO_Four)_Four,
Mn^IIIMn^IV _Four(U-O)₁(U-OAc)_Two-(1,4,7-Trimethy
Ru-1,4,7-triazacyclononane)_Two(ClO_Four)_Three, Mn^IV(1,4
, 7-Trimethyl-1,4,7-triazacyclononane)-(OCH_Three)_Three(P
F₆) And mixtures thereof. Other metal-based bleach catalysts
U.S. Pat. No. 4,430,243 and U.S. Pat. No. 5,114,611.
As disclosed in the specification. To improve bleaching,
The use of manganese with various complexing ligands is also described in US Pat. No. 4,728,455.
No. 5,284,944, No. 5,246,612,
5,256,779, 5,280,117, 5,274,
No. 147, No. 5,153,161 and No. 5,227,084
Reported in the specification.

In practice, the compositions and processes of the present invention can be adjusted to provide an active bleaching species in the wash liquor on the order of at least 1 ppt, with the catalytic species in the wash liquor preferably 0.1 ppm to 700 ppm. , More preferably 1 ppm to 50
It is 0 ppm.

Brighteners The compositions of the present invention may also optionally contain from about 0.005% to 5% by weight of a specific type of hydrophilic optical brightener that provides a dye transfer inhibiting effect. When used, the compositions of the present invention preferably contain from 0.001% to 1% by weight of such optical brighteners. The hydrophilic optical brighteners useful in the present invention have the following structural formula.

[Chemical 17] Wherein R ₁ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R ₂ is N-2-bis-hydroxyethyl, N-2
Selected from -hydroxyethyl-N-methylamino, morpholino, chloro and amino; M is a salt forming cation such as sodium or potassium.

In the above formula, when R ₁ is anilino, R ₂ is N-2-bis-hydroxyethyl, and M is a cation such as sodium, the brightener is 4,4′-bis [( 4-
Anilino-6- (N-2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is Tinopal-UNPA-GX from Ciba Geigy.
(Registered trademark). Tinopal-UNPA-GX
Is a preferred hydrophilic optical brightener useful in rinses added to the compositions of the present invention.

In the above formula, R ₁ is anilino and R ₂ is N-2-hydroxyethyl-N-2.
-Methylamino, when M is a cation such as sodium, the whitening agent is 4,4
'-Bis [(4-anilino-6- (N-2-bis-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbene disulfonic acid sodium salt. . This particular brightener species is available from Ciba Geigy
It is commercially available under the trade name of nopal 5BM-GX (registered trademark).

In the above formula, when R ₁ is anilino, R ₂ is morpholino and M is a cation such as sodium, the whitening agent is 4,4′-bis [(4-anilino-6-morpholino -S-triazin-2-yl) amino] -2,2'-stilbene disulfonic acid and disodium salt. This particular brightener species is available from Ciba Geigy
It is commercially available under the trade name of inoper AMS-GX (registered trademark).

Soil Release Agent In the present invention, any soil release agent can be added. Typical levels of incorporation into the composition are 0% to 10%, preferably 0.2% to 5% soil release agent. Preferably, such soil release agent is a polymer.

Soil release agents are desirably used in the fabric softening compositions of the present invention. Any polymeric soil release agent known to those skilled in the art may optionally be used in the compositions of the present invention. The polymeric soil release agent is deposited on the hydrophobic fibers, with hydrophilic moieties to hydrophilize the surface of the hydrophobic fibers, such as polyester and nylon, and remains bonded to it at the completion of the wash and rinse cycle. It is characterized by having both a hydrophilic portion and a hydrophobic portion that acts as an anchor. This makes it possible to more easily wash the stains generated after the treatment with the stain release agent in the subsequent water washing procedure.

If used, the soil release agent will typically be from about 0.01 to about 10.0 of the detergent composition.
% By weight, preferably about 0.1 to about 5% by weight, more preferably about 0.2 to about 3% by weight.

The following references, incorporated herein by reference, describe stain release polymers suitable for the present invention. US Pat. No. 3,959,230 issued May 25, 1976 (Hays), US Pat. No. 3,893,929 issued July 8, 1975 (Basadur), December 1976. U.S. Pat. No. 4,000,093 issued 28th (Nicol et al.), 198
U.S. Pat. No. 4,702,857 issued October 27, 1995 (Gossei)
nk), US Pat. No. 4,968,451, issued Nov. 6, Schei.
Bel et al.), U.S. Pat. No. 4,702,857 issued Oct. 27, 1987 (Gosselink et al.) U.S. Pat. No. 4,7 issued Dec. 8, 1987.
11,730 (Gosselink et al.), U.S. Pat. No. 4,721,580 (Gosselink), issued January 26, 1988, 1989
U.S. Pat. No. 4,877,896 issued 31st March (Maldonado)
Et al., US Pat. No. 4,956,447, issued Sep. 11, 1990 (G.
Osselink et al.), US Pat. No. 5,415,8, issued May 16, 1995.
07 (Gosselink et al.) And European Patent Application 0 219 048 (Kud et al.) Published Apr. 22, 1987.

Further suitable soil release agents are US Pat. No. 4,201,824 (Voilland et al.), US Pat. No. 4,240, all incorporated herein by reference.
, 918 (Lagasse et al.), U.S. Pat. No. 4,525,524 (Tung et al.), U.S. Pat. No. 4,579,681 (Ruppert et al.), U.S. Pat. No. 4,240,918. , U.S. Pat. No. 4,787,989, 1988 EP 279,134A (Rhone Poulin Chemie).
, EP 457,205A (BASF) (1991) and DE2.
No. 335,044 (Unilever NV,) (1974).

As a commercially available stain release agent, METOLOSE SM1 manufactured by Shin-Etsu Chemical Co., Ltd.
00, METOLOSE SM200, SO available from BASF (Germany)
KALAN type material, eg SOKALAN HP-22, ZELCON
5126 (manufactured by DuPont) and MILEASE T (manufactured by ICI).

Enzymes The compositions and processes of the present invention can optionally use one or more enzymes such as lipases, proteases, cellulases, amylases and peroxidases. The preferred enzyme for use in the present invention is the cellulase enzyme. That is, this type of enzyme further confers the benefit of color care to the treated fabric.
Cellulases that can be used in the present invention preferably include both bacterial and fungal cellulases having a pH optimum of 5 to 9.5. U.S. Pat. No. 4,435,307 describes suitable fungal cellulases from Humicola insolens or Humicola strain DSM1800 or cellulase 212 producing fungi belonging to the genus Aeromonas, and marine molluscs (Dolab).
Disclosed is a cellulase extracted from the hepatopancreas of ella Auricula Solander). Also, a suitable cellulase is GB-A-2.075.
No. 028, GB-A-2.095.275 and DE-OS 2.247.832. CAREZYME® and CELLUZYME® (Novo) are particularly useful. Other suitable cellulases are also WO 91/17243 (Novo),
WO 96/34092, WO 96/34945 and EP
-A-No. 0,739,982. Practical amounts for the currently marketed formulations are up to 5 mg of active enzyme per gram of detergent composition, more commonly 0.01 mg to 3 mg of active enzyme. Unless otherwise specified, the composition is
It contains 0.001% to 5% by weight, preferably 0.01% to 1% by weight of a commercial enzyme formulation. In the particular case where the activity of the enzyme formulation is defined, such as cellulase, the corresponding activity unit is preferred (eg CEVU, cellulase equivalent viscosity unit). For example, a composition of the invention may contain cellulase enzyme at a level equal to 0.5 to 1000 CEVU / gram composition. The activity of the cellulase enzyme formulation used to formulate the compositions of the present invention is 1,000 to 1 in liquid form.
10,000 CEVU / gram, about 1,000 CEVU / gram in solid form.

Other preferred optional ingredients include enzyme stabilizers, polymeric soil release agents,
Materials effective in inhibiting the transfer of dye from one fabric to another during the cleaning process (ie, dye transfer inhibitors), polymeric dispersants, defoamers, optical brighteners or other whitening and bleaching agents. , Chelating agents, fabric softening clays, antistatic agents, other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, and solid fillers for bar compositions.

The liquid detergent composition may contain water and other solvents as carriers.
Low molecular weight primary or secondary alcohols demonstrated with methanol, ethanol, propanol and isopropanol are suitable. Monohydric alcohols are preferred for dissolving the surfactant, but polyols having 2-6 carbon atoms and 2-6 hydroxyl groups (eg 1,3-propanediol, ethylene glycol, glycerin. And 1,2-propanediol) can also be used. The composition may contain from 5% to 90%, generally from 10% to 50% of such carrier.

Granule detergents include, for example, spray drying the base granules (final product density 52
0 g / l) or by agglomeration (final product density above 600 g / l). The remaining dry ingredients can be mixed in granules or powder form with the base granules, eg in a rotary mixing drum, and the liquid ingredients (eg nonionic surfactants and perfumes) can be sprayed on. .

The detergent composition has a pH of the wash water of 6.
It is preferably formulated to be 5 to 11, preferably 7.5 to 10.5.
Laundry products generally have a pH of 9-11. Techniques for controlling pH at recommended use levels are well known to those of skill in the art, such as with buffers, alkalis, acids and the like.

Methods of Use: Contacting the surface to be treated with a compound or composition of the invention, and facilitating release of the perfume from the material, preferably an aqueous medium such as steam or an amine aroma reaction product. Also provided is a method of providing a delayed release of an active aldehyde comprising contacting with other means.

“Surface” is a surface to which a compound is attached. Representative examples of such materials include hard surfaces such as fabrics, dishes, floors, bathrooms, toilets, kitchens and other surfaces where a delayed release of perfume aldehyde is required such as animal toilets. Preferably the surface is selected from fabrics, tiles and ceramics. More preferably, it is a cloth.

“Delayed release” refers to the release of the active ingredient (eg, perfume) over a longer period than using the active agent (eg, perfume) itself.

Examples The following examples describe and illustrate preferred embodiments within the scope of the present invention. The examples are intended to be illustrative only and are not intended to limit the invention as many variations are possible without departing from the spirit and scope of the invention.

Abbreviations used in the following laundry and cleaning composition examples In the laundry and cleaning compositions, the meanings of the abbreviated components are as follows. In the detergent composition, the meanings of the abbreviated components are as follows.

[0143]   LAS: straight chain C₁₁~_ThirteenSodium alkylbenzene sulfonate TAS: tallow sodium alkyl sulfate C_xyAS: C_1x~ C_1ySodium alkylsulfate C46SAS: C₁₄~ C₁₆Secondary (2,3) alkyl sulfate C_xyE_zS: C condensed with z mol ethylene oxide_1x~ C_1yAlkyl
Sodium sulfate C_xyE_z: C condensed with an average z mole of ethylene oxide_1x~ C_1yMainly
Chain primary alcohol QAS: R_Two． N⁺(CH_Three)_Two(C_TwoH_FourOH), R_Two= C₁₂~ C₁₄ QAS1: R_Two． N⁺(CH_Three)_Two(C_TwoH_FourOH), R_Two= C₈~ C₁₁ APA: C₈~ C₁₀Amidopropyl dimethylamine Soap: Chain alkyl carvone derived from a mixture of tallow and coconut fatty acid 80/20
Sodium acid STS: Sodium toluene sulfonate CFAA: C₁₂~ C₁₄(Palm) alkyl N-methylglucamide TFAA: C₁₆~ C₁₈Alkyl N-methyl glucamide TPKFA: C₁₂~ C₁₄Extracted fatty acid STPP: anhydrous sodium tripolyphosphate TSPP: Tetrasodium pyrophosphate Zeolite A: Formula Na whose main particle size is 0.1 to 10 micrometers₁₂(
AlO_TwoSiO_Two)₁₂． 27H_TwoO hydrated sodium aluminosilicate (anhydrous group
(Weight expressed in quasi) NaSKS-6: Formula δ-Na_TwoSi_TwoO₅Crystalline layered silicate Citric acid: anhydrous citric acid Borate: Sodium borate Carbonate: Anhydrous sodium carbonate with a particle size of 200 μm to 900 μm Bicarbonate: Anhydrous sodium bicarbonate with a particle size distribution of 400 μm to 1200 μm Silicate: Amorphous sodium silicate (SiO_Two: Na_TwoO = 2.0: 1)
Sulfate: anhydrous sodium sulfate Mg sulfate: anhydrous magnesium sulfate Citrate: 86.4% active particles with a particle size distribution of 425 μm to 850 μm.
Trisodium enoate dihydrate MA / AA: 1: 4 maleic / acrylic acid copolymer having an average molecular weight of about 70,000.
- MA / AA (1): 4: 6 malein / acrylic acid co-polymer having an average molecular weight of about 10,000
polymer AA: Sodium polyacrylate polymer having an average molecular weight of 4,500 CMC: sodium carboxymethyl cellulose Cellulose ether: Methyl cellulose having a polymerization degree of 650 available from Shin-Etsu Chemical
ether Protease: NOVO Industries A / under the trade name Savinase
3.3% by weight proteolytic enzyme sold by S. Protease I: Genencor Int. WO 95 sold by the company
/ 10591 active enzyme 4% by weight proteolytic enzyme Alcalase: Active enzyme 5 sold by NOVO Industries A / S
． 3% by weight of proteolytic enzyme Cellulase: NOVO Industries A / S under the product name Carezyme
0.23% by weight of cellulase degrading enzyme Amylase: NOVO industry under the trade name of Termamyl 120T
1.6% by weight amylase degrading enzyme sold by A / S Lipase: NOVO Industries A / S under the product name Lipolase
2.0% by weight lipase degrading enzyme for sale Lipase (1): NOVO Indah under the trade name Lipolase Ultra
2.0% by weight lipase degrading enzyme of active enzyme sold by Streez A / S
Endolase: Active enzyme 1 sold by NOVO Industries A / S
． 5% by weight of endoglucanase PB4: general formula NaBO_Two． 3H_TwoOH_TwoO_TwoSodium perborate tetrahydrate PB1: general formula NaBO_Two． H_TwoO_TwoAnhydrous sodium perborate bleach Percarbonate: General formula 2Na_TwoCO_Three． 3H_TwoO_TwoOf sodium percarbonate NOBS: Nonanoyloxybenzenesulfonate in the form of sodium salt NAC-OBS: (6-nonamidocaproyl) oxybenzene sulfonate TAED: Tetraacetylethylenediamine DTPA: diethylenetriaminepentaacetic acid Commercially available from Monsanto under the trade name DTPMP: Dequest 2060
Diethylenetriamine penta (methylenephosphonate) EDDS: ethylenediamine-N, N'-disuccinic acid (S
, S) Isomer Photoactive bleaching agent (1): sulfonated zinc fluoride encapsulated in dextrin-soluble polymer
Tarocyanine Photoactive bleach (2): Sulfonated aluminum encapsulated in dextrin soluble polymer
Nophthalocyanine Bleach 1: 4,4'-bis (2-sulfostyryl) biphenyl disodium Bleach 2: 4,4'-bis (4-anilino-6-morpholino-1,3,5-tri
Azin-2-yl) aminostilbene-2,2'-disulfonic acid disodium salt HEDP: 1,1-hydroxyethanediphosphonic acid PEGx: polyethylene glycol of molecular weight x (generally 4,000) PEO: polyethylene oxide having an average molecular weight of 50,000 TAPAE: Tetraethylene pentamine ethoxylate PVI: Polyvinylimidazole having an average molecular weight of 20,000 PVP: Polyvinylpyrrolidone polymer having an average molecular weight of 60,000 PVNO: polyvinyl pyridine N-oxide polymer having an average molecular weight of 50,000 PVPVI: polyvinylpyrrolidone and vinylimidazo having an average molecular weight of 20,000
Copolymer QEA: Screw ((C_TwoH₅O) (C_TwoH_FourO)_n) (CH_Three) -N⁺-C₆H_{1 Two} -N⁺-(CH_Three) Bis ((C_TwoH₅O)-(C_TwoH_FourO))_n, Where n = 2
0-30 SRP1: Anionic end-capped polyester SRP2: Diethoxylated poly (1,2 polypropylene terephthalate) short block
Polymer PEI: average molecular weight 1800, average of 7 ethyleneoxy residues per nitrogen
Polyethyleneimine with a degree of ethoxylation Silicone defoamer: Polydimethylsiloxane Foam suppressor Siloxane as dispersant
The oxyalkylene copolymer has a suds suppressor to dispersant ratio of 10: 1 to 100: 1.
Added Opacifier: A product called Lytron 621 from BASF Actien Gezelshaft
Water-based monostyrene latex mixture sold under the name Wax: paraffin wax PA30: Polyacrylic acid having an average molecular weight of about 4,500 to 8,000 480N: Lath of 7: 3 acrylate / methacrylate having an average molecular weight of about 3,500
Undam copolymer Polygel / Carbopol: High molecular weight crosslinked polyacrylate Metasilicate: Sodium metasilicate (SiO_Two: Na_TwoO ratio = 1.0) Nonionic: C with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5 _Thirteen ~ C₁₅Mixed ethoxylated / propoxylated fatty alcohol Neodol 45-13: C14 to C15 sold by Shell Chemical Company
Chain primary alcohol ethoxylates MnTACN: Manganese 1,4,7-trimethyl-1,4,7-triazacyclo
Nonan PAAC: pentamine cobalt acetate (III) salt Paraffin: Sold under the trade name Winog70 from Wintershall
Paraffin oil NaBz: sodium benzoate BzP: Benzoyl peroxide SCS: Sodium cumene sulfonate BTA: Benzotriazole PH: measured as a 1% solution in distilled water at 20 ° C FRP1: Ethyl 4-aminobenzoate and citral prepared from Synthesis Example I
Aroma reaction product (FRP) FRP2: Aroma reaction product (FRP) of para-aminobenzoic acid and undecanal
FRP3: Aroma reaction of D-glucamine and 2-nonenal prepared from Synthesis Example II Product (FRP)

[0144]   The following are synthetic examples of the compounds defined in the present invention.

Synthesis of I-Ethyl 4-Aminobenzoate and Citral (FRP1) 1 eq of ethyl 4-amino was added to an ice-cooled stirred solution of 10 g (0.07 mol) of citral in 35 mL of EtOH and molecular sieves (4Å, 20 g). Benzoate was added through the addition funnel. The reaction mixture was stirred under a nitrogen atmosphere and protected from light. After 6 days, the mixture was filtered and the solvent was removed. Imine formation yield is about 90
%.

Synthesis of II-D-Glucamine and trans-2-nonenal (FRP-3) 1 eq of trans-in a ice-cold solution of 1 mmol D-glucamine in about 30 mL EtOH and molecular sieves (4Å, 5 g). 2-Nonenal was added.
The reaction mixture was stirred under a nitrogen atmosphere and protected from light. After 3-4 days the molecular sieves and solvent were removed by filtration and each evaporated. 85 to solid imine
Obtained in a yield of 90%.

[0147]   Example 1   The following high density granular laundry detergent compositions AF were prepared according to the present invention.

[Table 2]

Example 2 The following bleach-free detergent formulation according to the invention, dedicated to the washing of pigmented clothing, was prepared.

[Table 3]

[0149]   Example 3   The following granular detergent formulations were prepared according to the present invention.

[Table 4]

Example 4 The following liquid detergent formulation was prepared according to the present invention (levels given in parts by weight).

[Table 5]

Example 5 The following laundry bar detergent composition was prepared according to the present invention (levels given in parts by weight).

[Table 6]

The examples and embodiments described herein are for illustration only, and various modifications or alterations that take these into account will occur to those skilled in the art without departing from the scope of the invention. Is believed to be suggested.

─────────────────────────────────────────────────── ─── Continued front page    (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE), OA (BF, BJ , CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, K E, LS, MW, SD, SL, SZ, TZ, UG, ZW ), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, C R, CU, CZ, DE, DK, DM, EE, ES, FI , GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, K Z, LC, LK, LR, LS, LT, LU, LV, MA , MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, S K, SL, TJ, TM, TR, TT, UA, UG, US , UZ, VN, YU, ZA, ZW (72) Inventor Gauraf, Saini             1-4-127 Naka, Koyo-cho, Higashinada-ku, Kobe-shi, Hyogo             −506 (72) Inventor Kimihiro Nakano             2-30- Nishimaiko 6-chome, Tarumi-ku, Kobe City, Hyogo Prefecture             407 F-term (reference) 4H003 AB19 AB27 AC08 AE04 DA01                       EA08 EA09 EA10 EA11 EA12                       EA15 EA16 EA18 EA28 EB03                       EB08 EB12 EB13 EB32 EB37                       EB42 EC01 EC02 EC03 EE05                       FA19 FA26                 4H059 BA19 BA42 BB55 BB60 CA31                       EA32

Claims (10)

[Claims] 1. A detergent composition comprising a fragrance reaction product produced by reacting a primary amine component and a fragrance component, wherein the fragrance component is a C6 to C14 aliphatic aldehyde. , A C6-C14 acyclic terpene aldehyde and mixtures thereof, wherein the odor of the primary amine compound is that of a 1% solution of methyl anthranilate in dipropylene glycol. A detergent composition having a odor degree lower than that of the odor reaction product, wherein the odor reaction product has a dry surface odor degree of more than 5. 2. A spray dried perfume, wherein the ratio of said spray dried perfume to said aroma reaction product is about 1.
The detergent composition of claim 1, further comprising 00:00 to about 16: 100. 3. The detergent composition according to claim 1, wherein the primary amine compound has a boiling point of at least about 125 ° C. 4. The detergent composition of claim 1, wherein the primary amine compound has a molecular weight of at least about 80 g / mol. 5. The fragrance component is citral, neral, isocitral, dihydrocitral, cyroneral, octanal, nonanal, decanal, undecanal, dodecanal, tridecanal, 2-methyldecanal, methylnonylacetaldehyde, 2-nonene-. 1-ar, 2-decanal, undecenal, undecylene aldehyde, 2,6 dimethyl octanal, 2,6,10-trimethyl-9
Detergent composition according to claim 1, which is selected from the group consisting of: undecen-1-al, trimethylundecanal, dodecenal, melonal, 2-methyloctanal, 3,5,5, trimethylhexanal and mixtures thereof. . 6. A. About 1% to about 60% by weight of detergent surfactant, b. About 0% to about 60% by weight of detergent builder, c. A detergent composition comprising a primary amine component and an aroma reaction product produced by reacting a perfume component with about 0.0001% to about 10% by weight, wherein the perfume component comprises: It is selected from the group consisting of C6-C14 aliphatic aldehydes, C6-C14 acyclic terpene aldehydes and mixtures thereof, wherein the odor of the primary amine compound is methyl anthra in dipropylene glycol. A detergent composition having a odor degree lower than that of a 1% solution of nilate, and having a dry surface odor degree of the aroma reaction product of more than 5. 7. The surfactant is selected from the group consisting of anionic, cationic, amphoteric, nonionic surfactants and mixtures thereof, and the detergent builder is a phosphate salt. , Pyrophosphates, orthophosphates, tripolyphosphates, higher phosphates, alkali metal carbonates and bicarbonates, alkali silicates, aluminosilicates, polycarboxylates, citrates and mixtures thereof The detergent composition according to claim 6, which is selected from the group. 8.   7. The detergent composition according to claim 6, further comprising a bleaching agent. 9.   The detergent composition according to claim 6, further comprising an enzyme. 10. The detergent composition according to claim 1, wherein the detergent composition is packaged in a sealed packaging system having a water vapor transmission rate of less than 50 g / m3 / 24 hours.