JP2002527576A - Laundry detergent compositions having a combination of a cyclic amine based polymer and a hydrophobically modified carboxymethyl cellulose - Google Patents

Abstract

  (57) [Summary] Detergent compositions containing from about 0.01 to about 5.0% by weight of a mixture of a polymer or oligomer based on a cyclic amine based polymer, oligomer or copolymer and a hydrophobically modified cellulosic derivative, and for fabric conditioning Composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] Technical Field The present invention relates to liquid or granular composition for use in laundry applications. Here, the composition comprises a predetermined cyclic amine-based polymer, oligomer or copolymer material in combination with hydrophobically modified carboxymethylcellulose. This combination has a beneficial appearance and integrity effect on fabrics and fabrics washed in a cleaning solution made from such a composition.

[0002] inevitably in the background and worn was using a cloth and fabrics such as clothing and clothing performed alternately cycle of washing, appearance and integrity of the fabric and textile products, which was used as such washing It is, of course, well-known that this is adversely affected. Fabrics and fabrics easily age with time and over time. Washing fabrics and fabrics is necessary to remove dirt and stains that have accumulated in and on them during normal use. However, if the washing operation itself is repeated many times, such deterioration of the integrity and appearance of the fabric or the woven fabric may be noticeable or contribute to the deterioration.

[0003] Deterioration of the integrity and appearance of fabrics is evident in several ways. From the woven or knitted fabric / textile fabric, the mechanical action of washing removes short fibers. These detached fibers are easily visible on the surface of the fabric and can form lint, fluff, or "pills" that can detract from the appearance of the fabric. Also, repeated washing of fabrics and fabrics, especially with laundry products that contain bleach, results in a loss of dye from the fabric or fabric, resulting in reduced color purity and, in many cases, hue and color. Changes can result in a tinted, obscured appearance.

[0004] In view of the above, the fibers of a fabric or fabric washed with a laundry detergent product are combined with the detergent product itself, thereby reducing the tendency of the appearance of the washed fabric / fabric to deteriorate. It is clear that there is still a need to identify substances that could be added to the laundry detergent product, or to a minimum. Of course,
Any additive material for such a detergent product must be capable of having a beneficial effect on the appearance and integrity of the fabric without unduly hindering the ability of the laundry detergent to exhibit fabric cleaning action. No. The present invention is directed to the use of mixtures of certain cyclic amine based polymer, oligomer or copolymer materials and hydrophobically modified carboxymethylcellulose (CMC) in laundry applications made in this desired manner. I have.

DISCLOSURE OF THE INVENTION [0005] The present invention provides: a) a surfactant selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof. From about 1 to about 80% by weight of an activator; and b) about 0.01% by weight of a mixture of a polymer, oligomer or copolymer based on a cyclic amine and a polymer or oligomer based on a hydrophobically modified cellulosic derivative. Or more, preferably about 0.1% or more, most preferably about 0.5% or more, and less than about 50% by weight, preferably about 25.0% by weight.
Less than about 5.0% by weight, most preferably less than about 5.0% by weight.

[0006] Cyclic amine-based polymer, oligomer or copolymer materials which are suitable for use in laundry operations and which provide the desired effect in favor of the appearance and integrity of the fabric are characterized by the following general formula: It is something that can be done.

Embedded image In the formula, each T is H, C ₁ -C ₁₂ alkyl, substituted alkyl, C ₇ -C ₁₂ alkylaryl, — (CH ₂ ) _h COOM, — (CH ₂ ) _h SO ₃ M, CH ₂ CH (OH
_{) SO 3 M, - (CH} 2) h OSO 3 M,

Embedded image And -R ₂ Q are independently selected from the group consisting of Where W is

Embedded image And at least one cyclic component selected from the group consisting of: In addition to the at least one cyclic component, W may also include an aliphatic or substituted aliphatic component having the following general structure .

Embedded image - each B is independently _C 1 _{-C 12 alkylene,} C 1 _{-C 12} substituted _alkylene, C 3 _{-C 12 alkenylene,} C 8 _{-C 12} dialkyl _arylene, C 8 _{-C 1 2} dialkylamino arylene yl, and - ( R ₅ O) _n R ₅ —. - each D is _C 2 -C ₆ alkylene independently. Each Q is a hydroxy group, a C ₁ -C ₁₈ alkoxy group, a C ₂ -C ₁₈ hydroxyalkoxy group, an amino group, a C ₁ -C ₁₈ alkylamino group, a dialkylamino group, a trialkylamino group, a heterocyclic group; It is independently selected from the group consisting of a monoamino group and a diamino group. Each R ₁ is independently selected from the group consisting of H, C ₁ -C ₈ alkyl, and C ₁ -C ₈ hydroxyalkyl. - each _{R 2,} C 1 _{-C 12 alkylene,} C 1 _{-C 12 alkenylene, - (CH 2) -CH (} OR 1) -CH 2, C 8 ~C 12 _{alkarylene, C} 4 _{~C 1 2} dihydroxy alkylene, poly _(C 2 -C ₄ alkyleneoxy) alkylene _{emissions, H 2 CH (OH) CH} 2 oR 2 OCH 2 CH (OH) CH 2 -, and independently from the group consisting of _C 3 _{-C 12} hydrocarbyl moiety Is the choice. However, when R ₂ is C ₃ -C ₁₂ hydrocarbyl moiety, the hydro carbyl component, Ru can contain from about 2 to about 4 branching components of the following general structure.

Embedded image Each R ₃ is H, O, R ₂ , C ₁ -C ₂₀ hydroxyalkyl, C ₁ -C ₂₀ alkyl, substituted alkyl, C ₆ -C ₁₁ aryl, substituted aryl, C ₇ -C ₁₁ alkylaryl, ₁ -C _{20 aminoalkyl, - (CH 2) h CO} OM, - (CH 2) h SO 3 M, CH 2 CH (OH) SO 3 M, - (CH 2) h OSO 3 M,

Embedded image Are independently selected from the group consisting of Each R ₄ is independently selected from the group consisting of H, C ₁ -C ₂₂ alkyl, C ₁ -C ₂₂ hydroxyalkyl, aryl, and C ₇ -C ₂₂ alkylaryl. Each R ₅ is independently selected from the group consisting of C ₂ -C ₈ alkylene, C ₂ -C ₈ alkyl-substituted alkylene; A is a compatible monovalent, divalent, or polyvalent anion, M is a compatible cation, b is the number required to balance the charge, and each x is independently from 3 to about 1000, each c is independently 0 or 1, each h is independently about 1 to about 8, each q is independently 0 to about 6, each n is independently 1 From about 20; each r is independently 0 to about 20; and each t is independently 0 to 1.

[0007] Polymeric or oligomeric substances based on cellulosic derivatives which are suitable for use in laundry operations and which have the desired effect on the appearance and integrity of the fabric are characterized by the following general formula: It can be.

Embedded image Wherein each R is R ₂ , R _C , and

Embedded image Is selected from the group consisting of Wherein: each R ₂ is independently selected from the group consisting of H, and C ₁ -C ₄ alkyl. -Each _RC

Embedded image In this formula, each Z is independently selected from the group consisting of M, R ₂ , R _C , and _RH . - each _{R H is,} C 5 _{-C 20 alkyl,} C 5 -C _{7 cycloalkyl,} C 7 _{-C 2 0 alkylaryl,} C 7 _{-C 20} arylalkyl, substituted alkyl, hydrate _{Rokishiarukiru,} C 1 _{-C 20 alkoxy-2-hydroxyalkyl,} C 7 _{-C 20 alkylaryl-2-hydroxyalkyl,} (R ₄₎ 2 N - _{alkyl, (R 4) 2 N-} 2- _{hydroxy-alkyl,} (R ₄₎ 3 N- al Kill, (R ₄ ) ₃ N-2-hydroxyalkyl, C ₆ -C ₁₂ aryloxy-2-hydroxyalkyl,

Embedded image Independently selected from the group consisting of - each _{R 4 is, H,} C 1 _{-C 20 alkyl,} C 5 -C _{7 cycloalkyl,} C 7 _{~ C 20} alkyl _aryl, C 7 _{-C 20} arylalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, It is independently selected from the group consisting of piperidinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl, and hydroxyalkyl. - each _{R 5 is, H,} C 1 _{-C 20 alkyl,} C 5 -C _{7 cycloalkyl,} C 7 _{~ C 20} alkyl _aryl, C 7 _{-C 20} arylalkyl, substituted alkyl, _{hydroxyalkyl, (R 4) 2} It is independently selected from the group consisting of N-alkyl, and (R ₄ ) ₃ N-alkyl. Wherein M is a suitable cation selected from the group consisting of Na, K, ＣａCa, and ＭｇMg; each x is 0 to about 5; and each y is about 1 to about 5 . However, - a degree of substitution of about 0.0005 to about _{R H} group, more rather preferably about 0.005 to 0.05, and most preferably from about 0.01 to 0.05 The degree of substitution for the _RC groups wherein Z is H or M is about 0.2-2.0, more preferably about 0.3-1.0, most preferably about 0.4-0. a .7, - If any of R _H has a positive charge, it has been combined Ri fishing by suitable anion and - two R ₄ on the same nitrogen are taken together, It may form a cyclic structure selected from the group consisting of piperidine and morpholine.

A polymer, oligomer or copolymer material based on a cyclic amine as defined above is to be used together with a polymer or oligomer based on a hydrophobically modified cellulosic derivative as a granular or liquid additive for a washing solution. Can be. Alternatively, they may be mixed with a particulate detergent, dissolved in a liquid detergent composition, or added to a fabric softening composition.

The ratio of the hydrophobically modified cellulosic derivative to the cyclic amine based polymer, oligomer or copolymer material is from 1000: 1 to 1: 1000, preferably from 100: 1 to 50: 1, more preferably It is from 50: 1 to 1: 1, even more preferably from 10: 1 to 1: 1.

The laundry detergent composition of the present invention comprises from about 1 to 80% by weight of a detersive surfactant, from about 0.01 to 80% by weight of an organic or inorganic detersive builder, a polymer or oligomer based on a cyclic amine. Or about 0.01 to 5% by weight of the fabric treatment material of the present invention based on a mixture of a copolymer or a polymer or an oligomer based on a copolymer and a hydrophobically modified cellulosic derivative. The detersive surfactant material and the detersive builder material can be any of those that can be used in conventional laundry detergent products.

An aqueous solution of a mixture of a polymer, an oligomer or a copolymer based on a cyclic amine, which is a subject of the present invention, and a polymer or an oligomer based on a cellulosic derivative hydrophobically modified is prepared by dissolving the cyclic amine in water. Approximately 0.01 to 80% by weight of a fabric treating substance based on a polymer or oligomer based on a polymer or an oligomer or a mixture of a hydrophobic derivative of a cellulosic derivative and a copolymer, and a stabilizer or a pH adjuster And other components such as

[0012] The present invention relates, in its method aspects, to an aqueous wash or aqueous wash formed using an effective amount of the detergent compositions described herein, or formed using the individual components of such compositions. It relates to washing or treating fabrics or fabrics in a treatment solution. Washing the fabric or fabric in such a washing solution, followed by rinsing and drying has a cosmetically advantageous effect on the fabric or fabric product thus treated. Such effects may include improving overall appearance, reducing pills / fluff, preventing fading, improving abrasion resistance, and / or improving flexibility. Surprisingly, a mixture of a polymer, oligomer or copolymer based on a cyclic amine according to the invention and a polymer or oligomer based on a hydrophobically modified cellulosic derivative may be used in equal amounts of either component. It has been found that it has a greater effect on the appearance and integrity of the fabric than is obtained when the fabric is used.

[0013] invention, as already mentioned best mode for carrying out a cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic-based polymers, or a mixture of oligomers, of the present invention Washing fabrics and fabrics in a cleaning solution comprising a lacquer improves the appearance and integrity of the fabric. Mixtures of polymers, oligomers based on cyclic amine-based polymers, oligomers or copolymers and polymers or oligomers based on hydrophobically modified cellulosic derivatives can be incorporated into detergent solutions or fabric softeners into cleaning solutions. Can be added. Alternatively, they can be added to the cleaning solution separately from the detergent composition and the fabric softener. Mixtures of polymers, oligomers based on cyclic amines, or polymers or oligomers based on hydrophobically modified cellulosic derivatives with copolymers, are described herein primarily as liquid or particulate detergent additives. The invention is not so limited. Polymers based on cyclic amines,
Mixtures of polymers or oligomers based on oligomers or copolymers and hydrophobically modified cellulosic derivatives, components of detergent compositions, optional components for such compositions, and methods of using such compositions. Are described in detail below. All percentages are by weight unless otherwise indicated.

A) Cyclic amine based polymer, oligomer or copolymer material The essential component of the composition according to the invention comprises one or more cyclic amine based polymers, oligomers or copolymers It is. Such materials use detergent compositions containing fabric treatment materials based on cyclic amine-based polymers, oligomers, or copolymers based on hydrophobically modified cellulosic derivatives with copolymers or oligomers. It has been found that fabrics and fabrics washed in an aqueous cleaning solution formed as described above have a number of cosmetically beneficial effects. Advantageous effects on the appearance of such fabrics can include, for example, improving the overall appearance of the washed fabric, reducing the formation of pills and fluff, preventing fading, improving wear resistance, and the like. The fabric treatment materials based on cyclic amines used in the compositions and methods of the present invention can have such an effect on the appearance of the fabric, and the cleaning performance provided by laundry detergent compositions incorporating such materials. It can be brought with little or no loss as permissible.

The polymer, oligomer or copolymer component based on cyclic amine of the composition of the present invention may be composed of a combination of these substances based on cyclic amine. For example, a mixture of condensates of piperazine and epihalohydrin can be combined with a mixture of condensates of morpholine and epihalohydrin to obtain the desired fabric treatment effect. Also, the molecular weight of the cyclic amine-based fabric treatment material can be varied within the range of mixtures as shown in the examples below.

As will be appreciated by those skilled in the art, an oligomer is a molecule consisting of only a small number of monomer units, while a polymer comprises a significantly greater number of monomer units. For purposes of the present invention, an oligomer is defined as a molecule having an average molecular weight of about 1,000 or less, and a polymer is defined as about 1,
A molecule having an average molecular weight greater than 000. Two different types of copolymers,
Or, it is a polymer or oligomer obtained by simultaneously or sequentially polymerizing more monomers. The copolymers of the present invention can include, for example, polymers or oligomers obtained by polymerizing a mixture of a cyclic primary amine based monomer such as piperazine and a cyclic secondary amine monomer such as morpholine.

A polymer based on a cyclic amine-based polymer, oligomer or copolymer and a hydrophobically modified cellulosic derivative of the detergent composition of the present invention;
Alternatively, the mixture of oligomers is usually from about 0.01 to about 5% by weight of the detergent composition. More preferably, the mixture of the polymer, oligomer or copolymer based on the cyclic amine and the polymer or oligomer based on the hydrophobically modified cellulosic derivative is from about 0.1 to about 4% by weight of the detergent composition. , Most preferably from about 0.75 to about 3%. However, as discussed above, when used as an additive for a wash solution, i.e., a polymer, oligomer or copolymer based on a cyclic amine and a polymer or oligomer based on a hydrophobically modified cellulosic derivative, or a mixture of oligomers Is not included in the detergent composition, the concentration of the cyclic amine based polymer, oligomer, or copolymer and the hydrophobically modified cellulosic derivative based polymer, or mixture of oligomers can be adjusted to about It can be from 0.1 to about 80% by weight.

Polymeric, oligomeric or copolymeric materials based on cyclic amines which are suitable for use in laundry operations and which provide the desired effect on the appearance and integrity of the fabric are described in the Summary of the Invention. Can be characterized by the following general formula.

Preferred compounds falling within the general structure include the following compounds. Wherein each R ₁ is H; and at least one W is

Embedded image Is selected from the group consisting of

Even more preferred compounds for obtaining advantageous effects on the appearance and integrity of the fabric are: Wherein each R ₁ is H; and at least one W is

Embedded image Selected from the group consisting of

The most preferred compounds for obtaining advantageous effects on the appearance and integrity of the fabric are as follows. Wherein each R ₁ is H; and at least one W is

Embedded image Is selected from the group consisting of

Preferred compounds for use as linking group R ₂ include polyepoxides, ethylene carbonate, propylene carbonate, urea, α, β-unsaturated carboxylic acids, α
Esters of α, β-unsaturated carboxylic acids, amides of α, β-unsaturated carboxylic acids, α,
β-unsaturated carboxylic acid anhydride, di- or polycarboxylic acid, di- or polycarboxylic acid ester, di- or polycarboxylic acid amide, di- or polycarboxylic acid anhydride, glycidyl halogen, chloroformate Ester, chloroacetate, chloroformate derivative, chloroacetate derivative, epihalohydrin, glycerol dichlorohydrin, bis- (halohydrin), polyether dihalo compound, phosgene, polyhalogen, functionalized glycidyl ether,
And mixtures thereof, but are not limited thereto. R ₂ is polyethylenediamine, alkylenediamine, polyalkylenepolyamine,
One or more of alcohols, alkylene glycols, and polyalkylene glycols, and α, β-unsaturated carboxylic acids, esters of α, β-unsaturated carboxylic acids, and α, β-unsaturated carboxylic acids. It can also include amides and reaction products formed by the reaction of α, β-unsaturated carboxylic acids with anhydrides. However,
These reaction products contain two or more double bonds, two carboxyl groups, two amide groups, or two ester groups.

Further preferred cyclic amine based polymer, oligomer or copolymer materials for use in the present invention include piperazine, piperidine, epichlorohydrin, epichlorohydrin benzylated with benzyl, quaternary with methyl. And adducts of two or more compositions selected from the group consisting of activated epichlorohydrin, morpholine, and mixtures thereof.

The polymers based on these cyclic amines can be linear or branched. By using a polyfunctional crosslinking agent, certain special types of branches can be introduced. An example of such a polymer is shown below.

Embedded image

B) Polymers based on hydrophobically modified cellulosic derivatives, or
Gomer The essential component of the composition of the present invention comprises one or more polymers or oligomers based on cellulosic derivatives. Such materials have a number of cosmetically beneficial effects on fabrics and fabrics washed in aqueous washing solutions made from detergent compositions containing such cellulosic-based fabric treatment materials. I understood that. Such advantageous effects on the appearance of the fabric may include, for example, improving the overall appearance of the washed fabric, reducing the formation of pills and fluff, preventing fading, improving wear resistance, and the like. The fabric treating materials based on the cellulosic derivatives used in the compositions and methods of the present invention can provide such benefits that are advantageous to the appearance of the fabric, as well as the cleaning performance provided by laundry detergent compositions incorporating such materials. Can be provided with little or no acceptable loss.

As will be apparent to those skilled in the art, an oligomer is a molecule consisting of only a small number of monomer units, whereas a polymer is a molecule consisting of a much larger number of monomer units. For purposes of the present invention, an oligomer is defined as a molecule having an average molecular weight of about 1,000 or less, and a polymer is defined as about 1,000
A molecule having an average molecular weight greater than zero. Polymeric or oligomeric textile treatment materials based on cellulosic derivatives of a type suitable for use in the present invention have an average molecular weight of about 5,000 to about 2,000,000, preferably about 50,000.
00 to about 1,000,000.

[0027] The fabric treatment component based on the cellulosic derivative of the detergent composition of the present invention is typically from about 0.1 to about 5% by weight of the detergent composition. More preferably, such cellulosic-based fabric treatment materials comprise from about 0.5 to about 4% of the detergent composition.
%, Most preferably from about 0.75 to about 3%. However, as discussed above, when used as an additive for a washing solution, i.e., when a fabric treatment component based on a cellulosic derivative is not included in the detergent composition, the component based on the cellulosic derivative may be used. The concentration can be from about 0.1 to about 80% by weight of the additive material.

One group of cellulosic derivative-based polymer or oligomeric substances suitable for use in the present invention are those characterized by the following formula:

Embedded image Wherein each R is R ₂ , R _C , and

Embedded image Is selected from the group consisting of Wherein: each R ₂ is independently selected from the group consisting of H, and C ₁ -C ₄ alkyl. -Each _RC

Embedded image In this formula, each Z is independently selected from the group consisting of M, R ₂ , R _C , and _RH . - each _{R H is,} C 5 _{-C 20 alkyl,} C 5 -C _{7 cycloalkyl,} C 7 _{-C 2 0 alkylaryl,} C 7 _{-C 20} arylalkyl, substituted alkyl, hydrate _{Rokishiarukiru,} C 1 _{-C 20 alkoxy-2-hydroxyalkyl,} C 7 _{-C 20 alkylaryl-2-hydroxyalkyl,} (R ₄₎ 2 N - _{alkyl, (R 4) 2 N-} 2- _{hydroxy-alkyl,} (R ₄₎ 3 N- al Kill, (R ₄ ) ₃ N-2-hydroxyalkyl, C ₆ -C ₁₂ aryloxy-2-hydroxyalkyl,

Embedded image Independently selected from the group consisting of - each _{R 4 is, H,} C 1 _{-C 20 alkyl,} C 5 -C _{7 cycloalkyl,} C 7 _{~ C 20} alkyl _aryl, C 7 _{-C 20} arylalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, It is independently selected from the group consisting of piperidinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl, and hydroxyalkyl. - each _{R 5 is, H,} C 1 _{-C 20 alkyl,} C 5 -C _{7 cycloalkyl,} C 7 _{~ C 20} alkyl _aryl, C 7 _{-C 20} arylalkyl, substituted alkyl, _{hydroxyalkyl, (R 4) 2} It is independently selected from the group consisting of N-alkyl, and (R ₄ ) ₃ N-alkyl. Wherein M is a suitable cation selected from the group consisting of Na, K, ＣａCa, and ＭｇMg; each x is 0 to about 5; and each y is about 1 to about 5 . However, - the degree of substitution for _{R H} group from about 0.0005 to 0.1, more preferably about 0.005 to 0.05, and most preferably about 0.01 to 0.05, - The degree of substitution for the _RC group where Z is H or M is about 0.2-2.0, more preferably about 0.3-1.0, and most preferably about 0.4-0.7. , and the - If any of R _H has a positive charge, it has been combined Ri fishing by suitable anion and - two R ₄ on the same nitrogen are taken together piperidine, And morpholine may form a cyclic structure selected from the group consisting of:

[0029] The term "degree of substitution" of a for R _H group be abbreviated herein as _"RH DS" is the number of moles of R _H group component as substituents one in anhydrous glucose unit Is what it means. Here, the anhydrous glucose unit is a 6-membered ring shown in the repeating unit having the above general structure.

The “degree of substitution” for the R _C group, which may be abbreviated as “DS _RC ” herein, means that Z as a substituent in one anhydroglucose unit is H or M. It is the number of moles of the _RC group component. Here, the anhydrous glucose unit is a 6-membered ring shown in the repeating unit having the above general structure. The condition that Z is H or M is necessary to ensure that a sufficient number of carboxymethyl groups are present to render the resulting polymer soluble. Number required, Z is in addition to the R _C group component is H or M, Z is there may be additional R _C components is a group other than H or M, and such R _C The best thing to do with the ingredients is, of course, the thing.

The production of the substance according to the invention will be illustrated in more detail in the examples described below.

C) Detersive Surfactant The detergent composition of the present invention comprises about 1 to 80% by weight of a detersive surfactant. Such compositions preferably contain about 5 to 50% by weight of a surfactant. Detergent surfactants used are anionic, nonionic, zwitterionic,
It may be amphoteric or cationic and may consist of a compatible mixture of these types of surfactants. Detergent surfactants that can be used in the present invention are described in Norris U.S. Pat. No. 3,664,9, issued May 23, 1972.
No. 61, Laughlin et al., US Pat. No. 3,91, issued Dec. 30, 1975.
Cockrell, U.S. Pat. No. 4,2,9,678, issued Sep. 16, 1980.
22,905 and Murphy U.S. Pat. No. 4,239,659, issued Dec. 16, 1980. All of these patents are incorporated herein by reference. Of all these surfactants, anionic surfactants and nonionic surfactants are preferred.

Useful anionic surfactants may themselves be of several different types. For example, water-soluble salts of higher fatty acids, or "soaps", are useful anionic surfactants in the compositions of the present invention. This includes alkali metal soaps such as sodium, potassium, ammonium and alkylol ammonium salts of higher fatty acids having about 8 to about 24, preferably about 12 to about 18 carbon atoms. .

Additional non-soap anionic surfactants suitable for use in the present invention include those having about 1 carbon atom.
Water-soluble salts of organic sulfuric acid reaction products having from 0 to about 20 alkyl groups and sulfonic acid or sulfate groups in their molecular structure, preferably alkali metal salts,
And ammonium salts. (Included in the term "alkyl" is the alkyl portion of the acyl group.) Particularly useful is a straight chain, abbreviated as _C11-13 LAS, wherein the alkyl group has an average carbon number of about 11-13. Alkylbenzene sulfonate.

Preferred nonionic surfactants are those having the formula R ₁ (OC ₂ H ₄ ) _n OH. Wherein R ₁ is a C ₁₀ -C ₁₆ alkyl group or a C ₈ -C ₁₂ alkylphenyl group, and n is 3 to about 80. Particularly _preferred, C 12 _{-C 1 5} alcohol and the condensation products of about 5 to about 20 moles of ethylene oxide per mole of alcohol, e.g., _{C 12} condensed with about 6.5 moles of ethylene oxide per mole of alcohol ~C ₁₃ is an alcohol.

Further suitable surfactants, including polyhydroxy fatty acid amides and amine-based surfactants, were filed on September 15, 1997 under the name of Panandiker et al. And filed on March 25, 1999. Published, `` Laundry Detergent Compositions w
ith Cyclic Amine Based Polymers to Provide Appearance and Integrity Bene
Fits to Fabrics Laundered Therewith "is disclosed in co-pending PCT application WO 98/14300. The entire disclosure of Panandiker et al. Is incorporated herein by reference.

D) Detergent Builder The detergent composition of the present invention may also include about 0.1 to 80% by weight of a detergent builder. The liquid detergent composition preferably contains about 1 to 10% by weight of the builder component. The granular detergent composition preferably contains about 1 to 50% by weight of the builder component.
Detergent builders are well known in the art and may consist of, for example, phosphates and various organic and inorganic non-phosphorous builders.

[0038] Water-soluble, non-phosphorus organic builders useful in the present invention include various polyacetic acids, carboxylic acids, polycarboxylic acids, and alkali metals, ammonium, and substituted ammonium polyhydroxysulfonates. Polycarboxylates suitable for use in the present invention are described in U.S. Patent No. 4,144,226 issued March 13, 1979 to Crutchfield et al. And polyacetal carboxylates described in U.S. Pat. No. 4,246,495. Both of these patents are described herein by reference. Particularly preferred polycarboxylate builders are oxydisuccinates and U.S. Pat. No. 4,663,071, issued May 5, 1987 to Bush et al. (The disclosure of which is incorporated herein by reference). An ether carboxylate builder composition comprising a combination of tartrate monosuccinate and tartrate disuccinate as described herein.

[0039] Examples of suitable non-phosphorous inorganic builders include silicates, aluminosilicates, borates, and carbonates. Particularly preferred are sodium and potassium carbonate, sodium and potassium bicarbonate, sodium and potassium sesquicarbonate, sodium and potassium tetraborate decahydrate, and a weight ratio of SiO ₂ to alkali metal oxide of about 0.5. To about 4.0, preferably about 1.0 to about 2.4, sodium and potassium silicate. Aluminosilicates containing zeolites are also preferred. Such substances, and their use as detergent builders, are discussed in more detail in U.S. Pat. No. 4,605,509 to Corkill et al. The disclosure of this patent is incorporated herein by reference. US Patent 4,605
509 discloses a crystalline layered silicate suitable for use in the detergent composition of the present invention.

E) Optional Detergent Components In addition to the above surfactants, builders and mixtures of polymers, oligomers or copolymers based on cyclic amines and polymers or oligomers based on hydrophobically modified cellulosic derivatives. Thus, in the detergent composition of the present invention,
Any number of additional optional ingredients can be included. These include enzymes and enzyme stabilizers, foam enhancers or foam inhibitors, rust and corrosion inhibitors, bleaches, soil suspending agents, soil removers, bactericides, pH regulators, non-builder alkaline sources, Conventional detergent composition components such as chelating agents, organic and inorganic fillers, solvents, hydrotropes, optical brighteners, dyes, and fragrances are included.

Optional ingredients that are preferred for inclusion in the detergent compositions of the present invention include bleaches, such as peroxygen bleaches. Such peroxygen bleaches may be organic or inorganic. Inorganic peroxygen bleaches are often used in combination with bleach activators.

Useful organic peroxygen bleaches include percarboxylic acid bleaches and salts thereof. Examples of suitable bleaching agents of this type include magnesium monoperoxyphthalate pentahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4
-Oxoperoxybutyric acid, and diperoxide decandioic acid. Such bleaches are disclosed in Hartman, U.S. Pat.
No. 83,781, European Patent Application No. A-133,354 by Banks et al. Published on Feb. 20, 1985, and Chun published on Nov. 1, 1983.
g et al. in U.S. Pat. No. 4,412,934. Highly preferred bleaches include 6-nonylamino-6- as described in U.S. Pat. No. 4,634,551, issued Jan. 6, 1987 to Burns et al.
Also included is oxoperoxycaproic acid (NAPAA).

Inorganic peroxygen bleaches, which are generally granular, can also be used in the detergent compositions of the present invention. In fact, inorganic bleaches are preferred. Such inorganic peroxygen compounds include alkali metal perborate and alkali metal percarbonate. For example, sodium perborate (eg, monohydrate or tetrahydrate) can be used. Suitable inorganic bleaches also include sodium or potassium carbonate peroxyhydrate and their corresponding "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, ureaperoxyhydrate, and sodium peroxide be able to. Persulfate bleach (eg, OXO manufactured industrially by DuPont)
NE) can also be used. Inorganic peroxygen bleaches are often coated with silicates, borates, sulfates, or water-soluble surfactants. For example, coated percarbonate particles are available from various vendors, such as FMC, Solvay Interlocks, Tokai Denka, and Degussa.

[0044] Inorganic peroxygen bleaches, such as perborates, percarbonates, etc., are preferably combined with a bleach activator. This produces an aqueous solution of the peroxyacid corresponding to the bleach activator in situ (ie, during use of the inventive composition for fabric laundering / bleaching). Various non-limiting examples of activators are described in U.S. Patent No. 4,915,854 issued to Mao et al. On April 10, 1990, and Chun on November 1, 1983.
g et al. in U.S. Patent No. 4,412,934. Nonanoyloxybenzenesulfonate (NOBS) activators and tetraacetylethylenediamine (TAED) activators are typical and preferred. Mixtures of these can also be used. See also the previously cited U.S. Patent No. 4,634,551 for other typical bleaches and activators useful in the present invention.

Other useful amide-derived bleach activators are of the formula R¹N (R⁵) C (O) R²C (O) L or R¹C (O) N (R⁵) R²C (O) L. Where R¹Is an alkyl group having about 6 to about 12 carbon atoms; ² Is alkylene having 1 to about 6 carbon atoms;⁵Is H or about 1 to about 1 carbon atoms
0 alkyl, aryl, or alkaryl, wherein L is any suitable
A leaving group. Leaving group means that bleach activator is nucleophilic attack by hydrogen peroxide decomposition anion.
Any group that leaves the bleach activator as a result of being shot. Preferred leaving groups are
, Phenol sulfonate.

Examples of preferred bleach activators of the above formula include US Pat.
(6-Octanamidocaproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamidocaproyl) oxybenzenesulfonate, and the like, described in 634,551. A mixture is included.

Another class of useful bleach activators is the benzoxazine-type activator disclosed by Hodge et al. In US Pat. No. 4,966,723 issued Oct. 30, 1990. Is included. This patent is incorporated herein by reference. U.S. Pat. No. 4, issued to Sanderson on Oct. 8, 1985
No., 545,784, which is hereby incorporated by reference. This patent discloses acylcaprolactam, including benzoylcaprolactam adsorbed on sodium perborate.

The peroxygen bleaches, if used, generally comprise about 2 to 30% by weight of the detergent composition of the present invention. More preferably, the peroxygen bleach is from about 2 to 20% by weight of the composition. Most preferably, the peroxygen bleach is present in the range of about 3 to 15% by weight of the composition of the present invention. The bleach activator, if used, can be from about 2 to 10% by weight of the detergent composition of the present invention. The activator is used in a molar ratio of bleach to activator of about 1: 1 to 10: 1, more preferably about 1.5: 1 to 5: 1.
Often used to be.

Further suitable bleaching agents and bleaching activators are described in the name of Panandiker et al.
"Laundry Detergen, filed on March 15 and published on March 25, 1999
t Compositions with Cyclic Amine Based Polymers to Provide Appearance an
d Integrity Benefits to Fabrics Laundered Therewith, which is disclosed in co-pending PCT application WO 98/14300. Panandiker
All disclosures of such documents are incorporated herein by reference.

Another highly preferred optional ingredient in the detergent composition of the present invention is a detersive enzyme component. Enzymes can be used to remove protein-based, carbohydrate-based, or triglyceride-based soils from the substrate, prevent migration of dyes that fall off while washing the fabric, and restore the fabric. For any purpose, it can be included in the present detergent composition. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof obtained from any suitable enzyme source, such as plants, animals, bacteria, fungi, and yeast. Factors such as pH activity and / or solubility, optimal thermal stability, and stability to effective detergents, builders, and the like must be considered in making a preferred choice. From this point, bacterial enzymes and fungal enzymes such as bacterial amylase and protease, and fungal cellulase are preferable.

[0051] As used herein, "detergent enzyme" means any enzyme that exhibits a cleaning, soil removal, or other beneficial effect in a laundry detergent composition. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases, amylases, and peroxidases.

[0052] The enzyme is usually incorporated into the detergent composition at a level sufficient to achieve a "cleaning effective amount". The term "cleaning effective amount" refers to any amount capable of providing a cleaning, stain removal, stain removal, bleaching, deodorizing, or freshening effect to a substrate such as a fabric. Practical conditions for currently marketed formulations are typically about 5 mg or less by weight of effective enzyme per gram of detergent composition, more typically 0.01 to 3 mg. is there. Stated another way, the compositions of the present invention typically comprise 0.001-5%, preferably 0.01-1%, by weight of a commercially available enzyme formulation. Protease enzymes typically provide an activity of 1 gram of composition in such a commercially available enzyme formulation as 0.00 g.
It is present at a level sufficient to be between 5 and 0.1 Anson units (AU). In highly concentrated detergent formulations, higher activity levels may be desirable.

Cellulases that can be used in the present invention include Barbesgoard et al., US Pat. No. 4,435,307, issued Mar. 6, 1984, and British Patent Application A
-2.075.028, British Patent Application No. A-2.095.275, and German Patent Publication No. 2.247.832. Karezaimu ^R, and Seruzaimu ^R (Novo) is especially useful. See also Novo International Patent No. 9117243.

The enzyme-containing composition of the present invention may contain an enzyme stabilizing system of about 0.001 to about 10
%, Preferably from about 0.005 to about 8%, most preferably from about 0.01 to about 6% by weight. The enzyme stabilization system may be any stabilization system compatible with the detersive enzyme. Such systems may be those originally provided by other active ingredients of the formulation, or may be added separately, for example by the formulator or the manufacturer of the ready-to-use enzyme in detergents. Such stabilizing systems may include, for example, calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boric acids, and mixtures thereof, and vary depending on the type of detergent composition and physical form. It is intended to deal with the problem of stabilization.

The compositions of the present invention may also include a dye transfer inhibitor such as a polyvinylpyrrolidone polymer, a polyamine N-oxide polymer, a copolymer of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidase, and mixtures thereof. it can. These inhibitors typically comprise from about 0.01 to about 10% by weight of the composition, preferably from about 0.01 to about 5% by weight, more preferably from about 0.05 to about 2%. % By weight.

[0056] More specifically, preferred polyamine N- oxide polymers for use in the present invention, the following structural formula: are those containing units with R-A X _-P. In the formula, P is a polymerizable unit to which an N—O group may be attached, or the N—O group may form a part of the polymerizable unit, or The unit may be attached. A is one of the following structures: -NC (O)-, -C (O) O-, -S-, -O-, -N =. x is 0 or 1. R is an aliphatic group which may be attached to the nitrogen of the NO group, an ethoxylated aliphatic group, an aromatic group, a heterocyclic group, an alicyclic group, or any combination thereof; Or the NO group forms part of these groups. Preferred polyamine N-oxides are those in which R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, and derivatives thereof.

The NO group can be represented by the following general structure:

Embedded image In the formula, R ₁ , R ₂ , and R ₃ are an aliphatic group, an aromatic group, a heterocyclic group, an alicyclic group, or a combination thereof, and x, y, and z are 0 or 1. And N
The nitrogen of the -O group may be attached to any of the above groups or may be part of any of the groups. The amine oxide units of the polyamine N-oxide have a pKa <10, preferably a pKa <7, more preferably a pKa <6.

Any polymer backbone can be used so long as the amine oxide polymer formed is water-soluble and has anti-migration properties. Examples of suitable polymer backbones are polyvinyl, polyalkylene, polyester, polyether, polyamide, polyimide, polyacrylate, and mixtures thereof. These polymers include:
Random or block copolymers are included, wherein one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
The amine to amine N-oxide ratio of the amine N-oxide polymer is typically from 10: 1 to 1: 1,000,000. However, the number of amine oxide groups in the polyamine oxide polymer can be varied by appropriate copolymerization or by a suitable degree of N-oxidation. Polyamine oxides are obtained with almost any degree of polymerization. The average molecular weight is typically between 500 and 1,0.
00,000, more preferably 1,000 to 500,000, and most preferably 5,000 to 100,000.

Most preferred among the polyamine N-oxides useful in the detergent compositions of the present invention are those having an average molecular weight of about 50,000 and a ratio of amine to amine N-oxide of about 1: 4. (4-vinylpyridine-N-oxide). This preferred type of material can be referred to as "PVNO".

Further suitable dye transfer inhibitors can be found in US Pat. No. 5,466,802 issued Nov. 14, 1995 to Panandiker et al.
This patent is incorporated herein by reference.

F) Preparation of the Detergent Composition The detergent composition according to the invention may be liquid, paste-like or granular. Such compositions may be prepared by combining the required concentrations of the essential and optional ingredients in any suitable order and by any conventional means. The previous description of the use of mixtures of polymers, oligomers or copolymers based on cyclic amines and polymers or oligomers based on hydrophobically modified cellulosic derivatives, as set forth herein, has been given by way of example. And other uses will be apparent to those skilled in the art,
They also fall within the scope of the present invention.

For example, particulate compositions generally combine the base fine-grained components, eg, surfactant, builder, water, etc., as a slurry and spray-dry the resulting slurry to reduce the level of residual moisture ( 5-12%). Fine particles of an essential mixture of the remaining dry components, for example polymers or oligomers based on cyclic amine-based polymers, oligomers or copolymers and hydrophobically modified cellulosic derivatives, and fine particles spray-dried, It can be mixed in a rotary mixing drum in the form of a granular powder. Liquid components, such as polymers, oligomers or copolymers based on cyclic amines and polymers or oligomers based on hydrophobically modified cellulosic derivatives, an essential mixture of oligomers, enzymes, binders,
The resulting detergent composition can be sprayed onto the resulting fine granules to obtain a finished detergent composition. The particulate composition according to the invention may be "compact". That is, they have a relatively higher density than conventional granular detergents, ie, 550-950 g.
/ L. In such a case, the granular detergent composition according to the present invention will contain a smaller amount of "inorganic filler salt" than conventional granular detergents. A typical filler salt is an alkaline earth metal salt of sulfuric acid or chlorine, typically sodium sulfate. "Compact" detergents are those that comprise typically less than 10% filler salt.

The liquid detergent composition is obtained by mixing essential and optional components in any desired order,
It can be prepared by making a composition containing the components in the required concentration. The liquid composition according to the invention may be "compact". In such a case, the liquid composition according to the present invention will contain less water than conventional liquid detergents. Addition of a mixture of a polymer or oligomer based on a cellulosic derivative hydrophobically modified with a polymer, oligomer or copolymer based on a cyclic amine to the liquid detergent composition of the present invention, or other aqueous composition, In a liquid solution, a cyclic amine-based polymer, an oligomer, or a copolymer and a polymer based on a hydrophobically modified cellulosic derivative,
Alternatively, this can be done by simply mixing in the desired mixture of oligomers.

The methods and compositions disclosed so far can also be applied to the production of particles that can be used as one of the detergent granules that are a component of the granular detergent composition.

G) Method for Washing Fabrics The present invention also provides a mixture of a polymer, oligomer or copolymer based on a cyclic amine and a polymer or oligomer based on a hydrophobically modified cellulosic derivative for use in the present invention. The present invention provides a method for laundering a fabric in such a way as to have a beneficial effect on the appearance of the fabric to be produced. Such methods are by contacting these fabrics with an aqueous cleaning solution formed using an effective amount of the aforementioned detergent composition, or formed using the individual components of such a composition. is there. Although contact between the fabric and the cleaning solution generally occurs under agitation conditions, the compositions of the present invention may be used to make non-agitated aqueous immersion solutions for fabric cleaning and treatment. .

For sufficient washing, it is preferable to stir in a washing machine. After washing, the wet fabric is preferably dried in a conventional clothes dryer. An effective amount of the dense liquid or granular detergent composition in the aqueous washing solution to be placed in the washing machine is preferably about 5
0.00 to about 7000 ppm, more preferably about 1000 to about 3000 pp
m.

H) Fabric Conditioning and Softening Based on the cyclic amine-based polymers, oligomers or copolymers and the hydrophobically modified cellulosic derivatives mentioned above as components of the laundry detergent compositions of the present invention. The mixture of polymers or oligomers is used to treat fabrics and fabrics in the absence of the surfactant component and the builder component of the detergent composition of the present invention,
It may be used for conditioning. Thus, for example, polymers, oligomers or copolymers based on cyclic amines and polymers based on cellulosic derivatives hydrophobically modified, or comprising only mixtures of oligomers, or polymers, oligomers based on cyclic amines, Alternatively, a fabric conditioning composition comprising an aqueous solution of a mixture of a polymer or an oligomer based on a copolymer and a hydrophobically modified cellulosic derivative provides the desired effects described above in terms of fabric appearance and integrity. For this purpose, it may be added to the rinsing cycle of a conventional home laundry operation.

A further suitable fabric softener is “Laundry Detergent Composite,” filed September 15, 1997 under the name of Panandiker et al. And published on March 25, 1999.
ions with Cyclic Amine Based Polymers to Provide Appearance and Integrit
y Benefits to Fabrics Laundered Therewith ”co-pending PCT
It is disclosed in application WO 98/14300. The entire disclosure of Panandiker et al. Is incorporated herein by reference.

The compositions of the present invention may comprise one or more fabric softening actives of at least about 1%, preferably about 10%, more preferably about 20% by weight of the composition.
% By weight up to about 80% by weight, more preferably up to about 60% by weight.

[0070] illustrate the compositions and methods of the present invention by the following examples examples, these examples are either to limit the scope of the present invention necessarily, otherwise not limiting.

Example 1 Synthesis of an adduct of imidazole and epichlorohydrin (ratio of imidazole to epichlorohydrin 1: 1) A polycation condensate is prepared by reacting imidazole and epichlorohydrin. To a round bottom flask equipped with a magnetic stirrer, condenser, and thermometer, add imidazole (0.68 mol) and 95 ml of water. The solution is heated to 50 ° C., after which epichlorohydrin (0.68 mol) is added dropwise. After all the epichlorohydrin has been added, the temperature is raised to 80 ° C. until all the alkylating agent has been consumed.
The molecular weight of the produced condensate was about 12,500.

Example 2 Synthesis of an adduct of imidazole and epichlorohydrin (ratio of imidazole to epichlorohydrin 1.4: 1) In a round bottom flask equipped with a magnetic stirrer, a condenser and a thermometer, imidazole ( (0.68 mol) and 95 ml of water. The solution is heated to 50 ° C., after which epichlorohydrin (0.50 mol) is added dropwise. After all the epichlorohydrin has been added, the temperature is raised to 80 ° C. until all the alkylating agent has been consumed. The molecular weight of the produced condensate was about 2,000.

Example 3 Adducts of piperazine, morpholine and epichlorohydrin (ratio 1.8 / 0
. 8 / 2.0) Synthesis In a round bottom flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 154.8 g (1.8 mol) of piperazine, 69.6 g (0.8 mol) of morpholine.
And 220 ml of water are added. When a clear solution at 40 ° C. is obtained, the solution is heated to 55-65 ° C. and, with vigorous stirring, 185 g (2 mol) of epichlorohydrin are added at a rate not exceeding 80 ° C. . After all of the epichlorohydrin has been added, the reaction mixture is heated to 85 ° C. until all of the alkylating agent has been consumed (Prussman test after 4 hours is negative). 25% Na
108.8 g (0.68 mol) of OH and 40 g of water are added and the reaction mixture is stirred at 85 ° C. for another hour. Thereafter, a further 47 g of water are added and the mixture is cooled to room temperature.

Example 4 Synthesis of piperazine / morpholine / epichlorohydrin adduct in the ratio 1.8 / 0.8 / 2.0 In a round bottom flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser. , Piperazine 154.8 g (1.8 mol), morpholine 69.6 g (0.8 mol)
And 220 ml of water are added. When a clear solution at 40 ° C. is obtained, the solution is heated to 55-65 ° C. and, with vigorous stirring, 185 g (2 mol) of epichlorohydrin are added at a rate not exceeding 80 ° C. . After all of the epichlorohydrin has been added, the reaction mixture is heated to 85 ° C. until all of the alkylating agent has been consumed (Prussman test after 4 hours is negative). 25% Na
108.8 g (0.68 mol) of OH and 40 g of water are added and the reaction mixture is stirred at 85 ° C. for another hour. Thereafter, a further 47 g of water are added and the mixture is cooled to room temperature.

[0075]Example 5 100% oxidized piperazine / morpholine / epichlorohydrid obtained in Example 4
233.6 g of the substance obtained in Example 4 above (corresponding to 1,292 moles of oxidizable nitrogen atoms)
) Is mixed with 22.1 g (0.276 mol) of 50% NaOH and then
Heat to ° C. At this temperature for 3.5 hours, H₂O₂(47.2%) to 102
. 4 g (1.421 mol) are added dropwise. After the addition is complete, the reaction mixture is further brought to this temperature.
Hold for 3 hours, then stir at room temperature overnight. Pt / C was added, and unreacted H₂O ₂ Was decomposed and the solution was filtered. The characteristics of the reaction product are as follows. Water content 58% pH 5.6 Chloride content 1.593 mmol / g

Example 6 Synthesis of imidazole / piperazine / epichlorohydrin adduct in a ratio of 1.0 / 3.0 / 4.0 68.8 g (1.0 mol) of imidazole and 260.6 g (3.0 mol) of piperazine ) Is dissolved in 700.2 g of water, and epichlorohydrin is added at a temperature of 50 to 60 ° C.
70 g (4.0 mol) are added dropwise. After the addition is complete, the reaction mixture is stirred at 80 ° C. for another 5 hours.

Example 7 Imidazole / piperazine / epichlorohydrin adduct from Example 6 oxidized 100% 237 g of the product from Example 6 above (corresponding to 1,022 moles of oxidizable nitrogen atoms)
Is added to 80.7 g (1.12 mol) of a 47.2% aqueous solution of H ₂ O ₂ at 40 ° C. over 5 hours. Thereafter, the reaction mixture is stirred for 5 hours until the theoretical amount of H ₂ O ₂ is consumed.
Heat to 0-60 ° C. After decomposing unreacted H ₂ O ₂ using Pt / C, the solution is filtered. The characteristics of the reaction product are as follows. Water 58.6% pH 2.86 Chloride content 3.694 mmol / g Mn (GPC) 340 Mw (GPC) 940 Mn / Mw 2.8 +/- 0.1

Example 8 Synthesis of Hydrophobically Modified CMC Material Carboxylation of cellulose to produce CMC is a method well known to those skilled in the art. One method for producing the modified CMC material of the present invention is to use CMC
In the step of manufacturing the compound, a substance to be replaced is added. An example of such a method is described below. This method can be used for other substituents described herein (replace hexyl chloride with those of interest, eg, cetyl chloride). The amount of material to be added to the CMC manufacturing process to obtain the desired degree of substitution will be easily calculated by one skilled in the art from the following examples.

Example 9 Synthesis of hexyl ether of CMC This example illustrates the preparation of a hydrophobically modified carboxymethylcellulose and is representative of the preparation of all cellulose ether derivatives of the present invention. Cellulose (20 g), sodium hydroxide (10 g), water (30 g), and ethanol (150 g) are charged to a 500 ml glass reactor. The resulting alkali cellulose is stirred at 25 ° C. for 45 minutes. Then, monochloroacetic acid (15
g) and hexyl chloride (1 g) are added and the temperature is raised to 95 ° C. over time,
Hold at 95 ° C for 150 minutes. After cooling the reaction mixture to 70 ° C, it is cooled to 25 ° C. Neutralize by adding a sufficient amount of nitric acid / acetic acid to bring the pH of the slurry to 8-9. The slurry is filtered to obtain the hexyl ether of CMC.

Example 10 Cellulosic Derivative Polymers Used in Test Detergent Compositions The properties of the representative modified cellulosic derivative polymers used in the liquid and granular detergent compositions described below are shown in Tables 10A and 10B. "General polymer parameters" are common to all polymers, while the unique chemical structures of the tested substances are described under "Unique polymer parameters".

[Table 1]

[Table 2]

Example 11 The following is the idealized chemical structure of a particular cyclic amine-based polymer, oligomer, or copolymer of the present invention. Side reactions that would occur during the condensation are not shown.

[Table 3]

Example 12 Preparation of a particulate detergent test composition A heavy particulate detergent composition containing a mixture of a polymer, oligomer or copolymer based on a cyclic amine and a polymer or oligomer based on a hydrophobically modified cellulosic derivative. Are prepared. All of these granular detergent compositions have the following basic formula.

[Table 4]

Example 13 Preparation of a Liquid Detergent Test Composition A heavy liquid detergent composition containing a mixture of a polymer, oligomer or copolymer based on a cyclic amine and a polymer or oligomer based on a hydrophobically modified cellulosic derivative. Are prepared. All of these liquid detergent compositions have the following basic formula:

[Table 5]

Example 14 Preparation of a particulate detergent test composition A number of particulate detergent compositions containing a mixture of a polymer, oligomer or copolymer based on a cyclic amine and a polymer or oligomer based on a hydrophobically modified cellulosic derivative. Is prepared. All such granular detergent compositions have the following basic formula:

[Table 6]

Example 15 A detergent agglomerate that can be used as a particulate component in a detergent composition is prepared according to the following recipe and range. The granules can be made by agglomeration methods known to those skilled in the art. Some of such methods are described herein.

[Table 7]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C11D 3/39 C11D 3/39 3/395 3/395 10/02 10/02 D06L 1/12 D06L 1 / 12 (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, 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, CR, CU, CZ, DE, DK, DM, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP , KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Jennifer, Ann, Leupin Ohio, Cincinnati, Phone Creek, Drive, 7974 (72) Inventor William, Conrad Waelz United States Indiana, Wes door, Harrison, Morgan, load, 1273 F-term (reference) 4H003 AB19 AB31 AC08 BA10 BA12 DA01 EA16 EA20 EA28 EB22 EB28 EB36 EB42 EC03 EE05 FA15 FA21 FA43 4J043 QB47 QB51 QB53 RA41 RA51 SA31 TA37 TA41 TA42 UA381

Claims (10)

[Claims] 1. a) a surfactant selected from the group consisting of a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a zwitterionic surfactant, and a mixture thereof; 80% by weight, b) 0.01% by weight or more, preferably 0.1% by weight of a mixture of a polymer or an oligomer based on a cyclic amine and a polymer or an oligomer based on a cellulose derivative hydrophobically modified with a copolymer. % Or more, most preferably 0.5% or more and less than 50% by weight, preferably less than 25.0% by weight, and most preferably less than 5.0% by weight. 2. The detergent composition according to claim 1, wherein the polymer or oligomer based on the hydrophobically modified cellulosic derivative has the following general formula: Wherein each R is R ₂ , R _C , and Wherein each R ₂ is independently selected from the group consisting of H and C ₁ -C ₄ alkyl; and each R _C is , And the In this formula, each Z, which are independently selected _M, R 2, _{R C,} and from the group consisting of _{R H,} - each _{R H is} C 5 _{-C 20} alkyl, _{C 5} -C _{7 cycloalkyl,} C 7 _{-C 2 0 alkylaryl,} C 7 _{-C 20} arylalkyl, substituted alkyl, hydrate _{Rokishiarukiru,} C 1 _{-C 20 alkoxy-2-hydroxyalkyl,} C 7 _{-C 20} alkyl aryloxy _{2-hydroxyalkyl,} (R ₄₎ 2 N - _{alkyl, (R 4) 2 N-} 2- _{hydroxy-alkyl,} (R ₄₎ 3 N- al _{kills, (R 4) 3 N-} 2- hydroxy alkyl, C ₆ -C ₁₂ Ariruoki Shi-2-hydroxyalkyl, embedded image Independently from the group consisting of those selected, - each _{R 4 is, H,} C 1 _{-C 20 alkyl,} C 5 -C _{7 cycloalkyl,} C 7 _{~ C 20} alkyl _aryl, C 7 _{-C 20} aryl alkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, those selected independently Piperijinoaruki Le, morpholinoethyl alkyl, cycloalkyl amino alkyl, and the group consisting of hydroxy Shiarukiru, - each R ₅ is, H, C ₁ -C _{20 alkyl,} C 5 -C _{7 cycloalkyl,} C 7 _{~ C 20} alkyl _aryl, C 7 _{-C 20} arylalkyl, substituted alkyl, _{hydroxyalkyl,} (R ₄₎ 2 N- alkyl and, _(R 4) ₃ are those independently selected from the group consisting of N- alkyl le, in the formula, M, Na K, 1 / 2Ca, and is a suitable cation selected from the group consisting of 1 / 2Mg, each x is 0-5, each y is 1-5, provided that - the degree of substitution for _{R H} group Is from 0.0005 to 0.1, more preferably from 0.005 to 0.05, most preferably from 0.01 to 0.05;-substitution for the _RC group wherein Z is H or M The degree is from 0.2 to 2.0, more preferably from 0.3 to 1.0, most preferably from 0.4 to 0.7,
- If any of R _H has a positive charge, it has been combined Ri fishing by suitable anion and - two R ₄ on the same nitrogen are taken together piperidine, and morpholine And a cyclic structure selected from the group consisting of: 3. The detergent composition according to claim 1, wherein the cyclic amine-based polymer, oligomer or copolymer has the following general formula: 5] In the formula, each T is H, C ₁ -C ₁₂ alkyl, substituted alkyl, C ₇ -C ₁₂ alkylaryl, — (CH ₂ ) _h COOM, — (CH ₂ ) _h SO ₃ M, CH ₂ CH (OH
_{) SO 3 M, - (CH} 2) h OSO 3 M, embedded image And -R ₂ Q is independently selected from the group consisting of:-wherein W is W is characterized by being at least one cyclic component selected from the group consisting of: In addition to the at least one cyclic component, W may also include an aliphatic or substituted aliphatic component having the following general structure. Embedded image - each B is independently _C 1 _{-C 12 alkylene,} C 1 _{-C 12} substituted _alkylene, C 3 _{-C 12 alkenylene,} C 8 _{-C 12} dialkyl _arylene, C 8 _{-C 1 2} dialkylamino arylene yl, and - ( R ₅ O) _n R ₅ —, each D is independently C ₂ -C ₆ alkylene, each Q is a hydroxy group, a C ₁ -C ₁₈ alkoxy group, a C ₂ -C ₁₈ hydroxy. alkoxy group, amino group, C ₁ -C ₁₈ alkylamino group, Jiarukirua amino group, which are independently selected trialkyl amino groups, heterocyclic monoamino groups, and diamino groups or Ranaru group, - each R ₁ is independently selected from the group consisting of H, C ₁ -C ₈ alkyl, and C ₁ -C ₈ hydroxyalkyl; each R ₂ is a C ₁ -C ₁₂ alkyl; _Killen, C 1 _{-C 12 alkenylene, - (CH 2) -CH (} OR 1) -CH 2, C 8 ~C 12 _alkarylene, C 4 _{-C 1 2-dihydroxy} alkylene, poly _(C 2 -C ₄ alkyleneoxy ) alkylene _{down, H 2 CH (OH) CH} 2 oR 2 OCH 2 CH (OH) CH 2 -, and _C 3 are in _{-C 12} those selected independently from the group consisting of hydrocarbyl moiety, provided that, _{R 2} is If a C ₃ -C ₁₂ hydrocarbyl moiety, the hydrate Rokarubiru components as possible out to contain from about 2 to about 4 branching components of the following general structure. Embedded image Each R ₃ is H, O, R ₂ , C ₁ -C ₂₀ hydroxyalkyl, C ₁ -C ₂₀ alkyl, substituted alkyl, C ₆ -C ₁₁ aryl, substituted aryl, C ₇ -C ₁₁ alkylaryl, ₁ -C _{20 aminoalkyl, - (CH 2) h CO} OM, - (CH 2) h SO 3 M, CH 2 CH (OH) SO 3 M, - (CH 2) h OSO 3 M, embedded image And each R ₄ is selected from the group consisting of H, C ₁ -C ₂₂ alkyl, C ₁ -C ₂₂ hydroxyalkyl, aryl, and C ₇ -C ₂₂ alkylaryl. Each R ₅ is independently selected from the group consisting of C ₂ -C ₈ alkylene, C ₂ -C ₈ alkyl-substituted alkylene; Or a divalent or polyvalent anion, M is a compatible cation, b is the number required to balance charge, each x is independently 3-1000, each c is independent Each h is independently 1-8, each q is independently 0-6, each n is independently 1-20, and each r is independently 0 to 20 and each t is independently 0 to 1 It is. 4. Each R ₁ is H, and at least one W is: The detergent composition according to any one of claims 1 to 3, which is selected from the group consisting of: 5. Each R ₁ is H, and at least one W is: The detergent composition according to any one of claims 1 to 4, which is selected from the group consisting of: 6. Each R ₁ is H, and at least one W is: The detergent composition according to any one of claims 1 to 5, which is selected from the group consisting of: 7. Each R _H is a C ₅ -C ₂₀ alkyl, a C ₅ -C ₇ cycloalkyl, a C ₇ -C ₂₀ alkylaryl, a C ₇ -C ₂₀ arylalkyl, a substituted alkyl, a hydroxyalkyl, a C ₁ -C ₂₀ alkyl. C _{20 alkoxy-2-hydroxyalkyl,} C 7 _{-C 20 alkylaryl-2-hydroxyalkyl,} (R ₄₎ 2 N-alkyl, (
R ₄ ) ₂ N-2-hydroxyalkyl, (R ₄ ) ₃ N-alkyl, (R ₄ ) ₃ N
2-hydroxyalkyl, and C ₆ is -C ₁₂ those selected independently from the group consisting of aryloxy-2-hydroxyalkyl, the detergent composition according to any one of claims 1 to 6. 8. A mixture of a) 1-80% by weight of water and b) a polymer or oligomer based on a cyclic amine or a polymer or oligomer based on a hydrophobically modified cellulosic derivative with a copolymer. A laundry additive composition comprising from 0.01 to 5.0% by weight, preferably from 0.1 to 4.0% by weight. 9. The composition comprising an inorganic peroxygen bleaching compound, preferably selected from the group consisting of alkali metal perborates, alkali metal percarbonates, and mixtures thereof, and preferably nonanoyloxybenzenesulfonate. 9. The detergent composition according to claim 1, further comprising a bleach activator. 10. The detergent composition according to claim 1, wherein the composition further comprises a cellulase enzyme.