JP2002536535A - Laundry detergent composition containing a fabric enhancing component - Google Patents

Abstract

  (57) [Summary] A detergent composition comprising from about 0.01 to about 5.0% by weight of a fabric-enhancing component selected from the group consisting of cyclic amine-based polymers, oligomers or copolymers, hydrophobically modified cellulose-based polymers or oligomers and mixtures thereof; Fabric conditioning composition. Containers for such compositions containing the fabric enhancing composition are also provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

【Technical field】

The present invention relates to compositions in liquid or granular form for the laundry sector, which compositions contain certain fabric-enhancing components, such as, for example, cyclic amine-based polymer, oligomer or copolymer materials, hydrophobically modified carboxymethylcellulose and There is a mixture of In addition, containers for such compositions are provided.

[0002]

BACKGROUND OF THE INVENTION

Of course, it is well known that repeated cycles of using and washing fabrics and textiles, such as worn clothing and apparel, will necessarily adversely affect the appearance and integrity of the thus used and washed fabrics and textiles. ing. Fabrics and textiles simply wear out over time as they are used. Washing of fabrics and textiles is necessary to remove dirt and stains that have accumulated in and on them during normal use. However, the washing operation itself over many cycles can enhance and contribute to the deterioration of the integrity and appearance of such fabrics and textiles.

[0003] Deterioration of fabric integrity and appearance is manifested in several ways. Short fibers are removed from the woven and knitted fabric / textile structures by the mechanical action of washing. These removed fibers may form lint, fluff or "pills" that are visible on the surface of the fabric and impair the new appearance of the fabric. Furthermore, repeated washing of fabrics and textiles, particularly with bleach-containing laundry products, removes dyes from the fabrics and textiles, resulting in reduced color intensity and, in many cases, changes in shades or shades. The result may be a faded and worn appearance.

[0004] Thus, when added to a laundry detergent product, a material that binds to fabrics and textiles that have been laundered with such detergent products and textiles can be identified to provide the laundry fabric / There is a clear continuing need to reduce or minimize the tendency of textiles to degrade in appearance. Any such detergent product additives
Of course, the effect should be imparted to the appearance and integrity of the fabric without unduly hindering the ability of the laundry detergent to perform its fabric cleaning function. Further, there is a need for containers for such products. The container must not only store the composition, but also communicate the benefits of the new product to the consumer.

[0005]

[Summary of the Invention]

The present invention includes: a) about 1 to about 80% by weight of a surfactant selected from the group consisting of nonionic, anionic, cationic, amphoteric, zwitterionic surfactants and mixtures thereof, and b) cyclic amine A fabric enhancing component selected from the group consisting of base polymers, oligomers or copolymers, hydrophobically modified cellulose base polymers or oligomers and mixtures thereof, from about 0.01 to about 5.0% by weight, preferably from about 0.1 to about 4%. 0.03% of a detergent composition.

[0006] Further, the detergent composition is contained within an interior chamber of the container, the container further having an outer surface, the outer surface of which helps to make the garment look more healthy.
Helps to reduce the wear before it starts, keeps the appearance of the garment, helps prevent the garment from appearing worn, cleans and looks good and strengthens the garment at the same time, yarns to make the garment look good Strengthens, helps to prevent clothes from appearing worn, helps prevent clothes from being worn out in a washing machine that makes them look old,
Helps to keep the clothes from aging, helps to show the clothes from the washing machine as well as putting them in, helps to preserve the fabric integrity of the clothes, wraps yarn from inside and outside to make the clothes look good Strengthen, extend the life of clothing, is like clothing vitamins, acts like anti-aging clothing products, is like clothing calcium, is like clothing supplements, After 10 washes, the garment looks better than when washed with other detergents, strengthens the yarn to make the garment appear healthy, helps prevent the garment from looking old before it is needed, A description of a composition characterized by language, selected from the group consisting of: stopping time to remain visible.

[0007] Cyclic amine-based polymer, oligomer or copolymer materials suitable for use in laundry operations and exhibiting desirable fabric appearance and integrity effects are characterized by the following general formula:

Embedded image Wherein each T is independently 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; -W is:

Embedded image Consisting of at least one cyclic component selected from the group consisting of: In addition to at least one cyclic component, W may also include an aliphatic or substituted aliphatic moiety of 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 dialkylarylene, C ₈ -C ₁₂ dialkylarylenediyl and-(R ₅ O) _n R _5- each D is independently C ₂ -C ₆ alkylene; each Q is independently hydroxy, C ₁ -C ₁₈ alkoxy, C ₂ -C ₁₈ hydroxyalkoxy, amino , C ₁ -C ₁₈ alkylamino, dialkylamino, trialkylamino, heterocyclic monoamino and diamino; each R ₁ is independently H, C ₁ -C ₈ alkyl and is selected from the group consisting of C ₁ -C ₈ hydroxyalkyl; - each _{R 2} is independently _C 1 _{-C 12 alkylene,} C 1 _{-C 12} alkenyl Down, -C
H ₂ —CH (OR ₁ ) —CH ₂ , C ₈ —C ₁₂ alkarylene, C ₄ —C ₁₂ dihydroxyalkylene, poly (C ₂ —C ₄ alkyleneoxy) alkylene, H ₂ CH (OH) CH ₂ OR _{2 OCH 2 CH (OH) CH 2} - and _C 3 _{-C 12} is selected from the group consisting of hydrocarbyl moiety, provided that when _{R 2} is _C 3 _{-C 12} hydrocarbyl moiety, the hydrocarbyl moiety is from about 2 to about 4 Can include a branching portion of the general structure:

Embedded image Each R ₃ is independently 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 , C ₁ -C ₂₀ aminoalkyl,-(CH ₂ ) _h COOM
_{, - (CH 2) h SO} 3 M, CH 2 CH (OH) SO 3 M, - (CH 2) h OS
O ₃ M,

Embedded image 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 alkyleryl, C ₂ -C ₈ alkyl-substituted alkylene; A is a compatible monovalent or di- or polyvalent anion; M is compatible B is the number required to balance the charge; each x is independently 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 to about 20; each r is independently 0 to about 20; and each t is independently 0 to 1.

[0008] Cellulose-based polymer or oligomeric materials suitable for use in laundry operations and that exhibit desirable fabric appearance and integrity effects are characterized by the following general formula:

Embedded image In the above formula, each R is R ₂ , R _C and

Embedded image Wherein each R ₂ is independently selected from the group consisting of H and C ₁ -C ₄ alkyl; each R _C is — (CH ₂ ) _y —C ( ＯO) -OZ, wherein each Z is independently selected from the group consisting of M, R ₂ , R _C and R _H. Each R _H is independently C ₅ -C ₂₀ alkyl. , _C 5 -C ₇ cycloalkyl, _{C 7} -
C ₂₀ alkylaryl, C ₇ -C ₂₀ arylalkyl, substituted alkyl, hydroxyalkyl, C ₁ -C ₂₀ alkoxy-2-hydroxyalkyl, C ₇ -C ₂₀ alkylaryloxy-2-hydroxyalkyl, (R ₄ ) ₂ N-alkyl, (R ₄ ) ₂ N-2-hydroxyalkyl, (R ₄ ) ₃ N-alkyl, (R ₄ ) ₃ N-2-hydroxyalkyl, C ₆ -C ₁₂ aryloxy-2-hydroxyalkyl,

Embedded image Wherein each R ₄ is independently H, C ₁ -C ₂₀ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₂₀ alkylaryl, C ₇ -C ₂₀ arylalkyl, amino Alkyl, alkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl,
Each R ₅ is independently H, C ₁ -C ₂₀ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₂₀ alkylaryl, wherein each R ₅ is independently selected from the group consisting of morpholinoalkyl, cycloalkylaminoalkyl and hydroxyalkyl; , C ₇ -C ₂₀ arylalkyl, substituted alkyl,
Selected from the group consisting of hydroxyalkyl, (R ₄ ) ₂ N-alkyl and (R ₄ ) ₃ N-alkyl; wherein M is from the group consisting of Na, K, １ ／ Ca and ＭｇMg. Each x is 0 to about 5; each y is about 1 to about 5; and:-the degree of substitution of the group _RH is about 0.001 to 0.1. , More preferably about 0.005 to 0.5.
05, most preferably about 0.01 to 0.05; the degree of substitution of the group _{RC wherein} -Z is H or M is about 0.2-2.0, more preferably about 0.3-1. 0, most preferably about 0.4 to 0.7; if any _RH has a positive charge, it is balanced with the appropriate anion; and on the same nitrogen two R ₄ together in, may form a ring structure selected from the group consisting of piperidine and morpholine.

[0009] The cyclic amine-based polymer, oligomer or copolymer material as described above can be used as a detergent additive in granular or liquid form together with a hydrophobically modified cellulose-based polymer or oligomer. On the other hand, they may be mixed into a granular detergent, dissolved in a liquid detergent composition, or added to a fabric softening composition. The laundry detergent composition comprises about 1-80% by weight of a detersive surfactant, about 0.01-80% by weight.
It contains by weight organic or inorganic cleaning builders and from about 0.01 to 5% by weight of the fabric enhancing component of the present invention. The detersive surfactant and detergency builder substance may be any of those useful in conventional laundry detergent products. The aqueous solution of the fabric enhancing component of the present invention comprises a cyclic amine-based polymer, oligomer or copolymer, a hydrophobically modified cellulose-based polymer or oligomer and mixtures thereof dissolved in water and other additives such as stabilizers and pH modifiers. About 0.01 to 80% by weight of the components.

[0010] In its method aspect, the present invention provides an aqueous cleaning or treating solution formed from an effective amount of the detergent compositions described herein, or formed from the individual components of such compositions, for fabrics and textiles. Related to washing or treating styles. Washing of the fabric and textile with such a washing liquid, followed by rinsing and drying, imparts a fabric appearance effect to the thus treated fabric and textile. Such effects include improved overall appearance, reduced pills / fluff, fade resistance, improved abrasion resistance and / or increased flexibility.

[0011]

DETAILED DESCRIPTION OF THE INVENTION

As described above, when the fabric or textile is washed with the washing liquid containing the fabric enhancing component of the present invention, the appearance and maintainability of the fabric are improved. The fabric-enhancing components, i.e., cyclic amine-based polymers, oligomers or copolymers, and hydrophobically modified cellulose-based polymers or oligomers can be formulated by incorporating them into detergent compositions, fabric softeners, or adding them separately to the wash liquor. , Can be added to the cleaning solution.

Although cyclic amine-based polymers, oligomers or copolymers, and hydrophobically modified cellulose-based polymers or oligomers are described herein primarily as liquid or granular detergent additives, the present invention is not intended to be so limited. Absent.
Similarly, the detergent containers of the present invention include any suitable type of detergent composition container.
Non-limiting examples of such containers include boxes, bags and bottles made of paper, plastic, cardboard, laminate, and the like. One skilled in the art will know what types of structural materials and materials are suitable for the detergent compositions of the present invention.

[0013] Cyclic amine-based polymers, oligomers or copolymers, and hydrophobically modified cellulose-based polymers or oligomers, detergent composition components, optional components for such compositions, and methods of using such compositions are described below. In more detail. All percentages are by weight unless otherwise specified.

A) Cyclic amine-based polymer, oligomer or copolymer material The composition of the present invention can contain one or more cyclic amine-based polymer, oligomer or copolymer. Such materials have been found to impart some cosmetic effects to fabrics and textiles washed with aqueous cleaning solutions formed from detergent compositions containing these materials. Such fabric appearance effects include, for example, improving the overall appearance of the washed fabric, reducing pilling and fluff formation, preventing fading, and improving abrasion resistance. The cyclic amine-based fabric treatment materials used in the present compositions and methods can be used to fabricate such fabrics without the disadvantageous loss of cleaning performance provided by laundry detergent compositions incorporating such materials. The appearance effect can be exhibited.

The cyclic amine-based polymer, oligomer or copolymer component of the composition comprises:
A combination of these cyclic amine-based materials may be used. For example, a mixture of piperazine and epihalohydrin condensate can be combined with a mixture of morpholine and epihalohydrin condensate to obtain the desired fabric treatment result.
Further, the molecular weight of the cyclic amine-based fabric treatment material varies within the mixture, as shown in the examples below.

As will be apparent to those skilled in the art, oligomers are molecules consisting of very few monomer units, while polymers are made up of significantly more monomer units. For the purposes of the present invention, an oligomer is defined as a molecule having an average molecular weight of about 1000 or less;
Polymers are molecules having an average molecular weight greater than about 1000. A copolymer is a polymer or oligomer in which two or more different monomers are polymerized simultaneously or sequentially. Copolymers of the present invention include, for example, polymers or oligomers polymerized from a mixture of a primary amine-based monomer, such as piperazine, and a secondary cyclic amine monomer, such as morpholine.

[0017] The fabric-enhancing component comprising the cyclic amine-based polymer, oligomer or copolymer, the hydrophobically modified cellulose-based polymer or oligomer and mixtures thereof of the detergent composition generally comprises from about 0.01 to about 5% by weight of the detergent composition. %. More preferably, the fabric enhancing component 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 noted above, when used as a washing liquid additive, i.e., when the fabric enhancing component is not incorporated into the detergent composition, the concentration of the fabric enhancing component is from about 0.1 to about 80% by weight of the additive.

[0018] Cyclic amine-based polymer, oligomer or copolymer materials that exhibit desirable fabric appearance and integrity effects suitable for laundering operations are characterized by the general formula set forth in the Summary of the Invention.

Preferred compounds belonging to this general structure include: each R ₁ is H; and at least one W is

Embedded image There is a compound selected from the group consisting of:

Even more preferred compounds for fabric appearance and integrity effects are: each R ₁ is H; and at least one W is

Embedded image Is selected from the group consisting of:

The most preferred compounds for fabric appearance and integrity effects are: each R ₁ is H; and at least one W is

Embedded image Is selected from the group consisting of:

Preferred compounds used as the linking group R ₂ include polyepoxide, ethylene carbonate, propylene carbonate, urea, α, β-unsaturated carboxylic acid, 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, chloroacetic acid Esters, derivatives of chloroformate, derivatives of chloroacetate, epihalohydrin, glycerol dichlorohydrin, bis (halohydrin), polyether dihalo compounds, phosgene, polyhalogens, functionalized glycidyl ethers and mixtures thereof. It is not limited to. Further, R ₂ represents one or more polyether diamines, alkylenediamines, polyalkylene polyamines, alcohols, alkylene glycols and polyalkylene glycols as α, β-unsaturated carboxylic acids, α,
esters of β-unsaturated carboxylic acids, amides of α, β-unsaturated carboxylic acids and α
, Β-unsaturated carboxylic acid anhydrides may be used, provided that the reaction product comprises at least two double bonds, two carboxyl groups,
It must have one amide group or two ester groups.

Other preferred cyclic amine based polymer, oligomer or copolymer materials for use herein include piperazine, piperazine, epichlorohydrin, epichlorohydrin benzyl quaternary, epichlorohydrin methyl quaternary, There are adducts of two or more compounds selected from the group consisting of morpholine and mixtures thereof.

[0024] These cyclic amine-based polymers may be linear or branched. Certain types of branches can be introduced using multifunctional crosslinking agents. An example of one such polymer is shown below.

Embedded image

B) Hydrophobic Modified Cellulose-Based Polymers or Oligomers The compositions of the present invention can contain one or more cellulose-based polymers or oligomers. Such materials have been found to impart some cosmetic effects to fabrics and textiles washed with aqueous cleaning solutions formed from detergent compositions containing such cellulose-based fabric treatment materials. Such fabric appearance effects include, for example, improving the overall appearance of the washed fabric, reducing pilling and fluff formation, preventing fading, and improving abrasion resistance. The cellulosic-based fabric treatment materials used in the present compositions and methods can be used with such fabric appearance effects with the benefit of little or no cleaning performance provided by laundry detergent compositions incorporating such materials. Can be demonstrated.

As will be apparent to those skilled in the art, oligomers are molecules consisting of very few monomer units, while polymers are made up of significantly more monomer units. For the purposes of the present invention, an oligomer is defined as a molecule having an average molecular weight of about 1000 or less;
Polymers are molecules having an average molecular weight greater than about 1000. One suitable type of cellulose-based polymer or oligomer fabric treatment material for use herein is from about 5000 to about 2,000,000, preferably from about 50,000 to about 1,0,0.
It has an average molecular weight of 00,000.

[0027] The cellulose-based fabric treatment component of the detergent composition typically comprises about 0.1% of the detergent composition.
~ 5% by weight. More preferably, such cellulosic-based fabric treatment components are from about 0.5% to about 4% by weight of the detergent composition, most preferably from about 0.75% to about 3%. However, as noted above, when used as a wash liquor additive, i.e., when the cellulose-based fabric treatment component is not incorporated into the detergent composition, the concentration of the cellulose-based component may range from about 0.1 to about 80% by weight of the additive material. is there.

As used herein, one suitable group of cellulose-based polymer or oligomeric materials is characterized by the formula:

Embedded image In the above formula, each R is R ₂ , R _C and

Embedded image Wherein each R ₂ is independently selected from the group consisting of H and C ₁ -C ₄ alkyl; each R _C is — (CH ₂ ) _y —C ( ＯO) -OZ, wherein each Z is independently selected from the group consisting of M, R ₂ , R _C and R _H. Each R _H is independently C ₅ -C ₂₀ alkyl. , _C 5 -C ₇ cycloalkyl, _{C 7} -
C ₂₀ alkylaryl, C ₇ -C ₂₀ arylalkyl, substituted alkyl, hydroxyalkyl, C ₁ -C ₂₀ alkoxy-2-hydroxyalkyl, C ₇ -C ₂₀ alkylaryloxy-2-hydroxyalkyl, (R ₄ ) ₂ N-alkyl, (R ₄ ) ₂ N-2-hydroxyalkyl, (R ₄ ) ₃ N-alkyl, (R ₄ ) ₃ N-2-hydroxyalkyl, C ₆ -C ₁₂ aryloxy-2-hydroxyalkyl,

Embedded image Wherein each R ₄ is independently H, C ₁ -C ₂₀ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₂₀ alkylaryl, C ₇ -C ₂₀ arylalkyl, amino Alkyl, alkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl,
Each R ₅ is independently H, C ₁ -C ₂₀ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₂₀ alkylaryl, wherein each R ₅ is independently selected from the group consisting of morpholinoalkyl, cycloalkylaminoalkyl and hydroxyalkyl; , C ₇ -C ₂₀ arylalkyl, substituted alkyl,
Selected from the group consisting of hydroxyalkyl, (R ₄ ) ₂ N-alkyl and (R ₄ ) ₃ N-alkyl; wherein M is from the group consisting of Na, K, １ ／ Ca and ＭｇMg. Each x is 0 to about 5; each y is about 1 to about 5; and:-the degree of substitution of the group _RH is about 0.001 to 0.1. , More preferably about 0.005 to 0.5.
05, most preferably about 0.01 to 0.05; the degree of substitution of the group _{RC wherein} -Z is H or M is about 0.2-2.0, more preferably about 0.3-1. 0, most preferably about 0.4 to 0.7; if any _RH has a positive charge, it is balanced with the appropriate anion; and on the same nitrogen two R ₄ together in, may form a ring structure selected from the group consisting of piperidine and morpholine.

[0029] the radicals R _H "degree of substitution" is used herein it is abbreviated "DS _RH" in time, it means a number of moles of group R _H components that are substituted per anhydrous glucose unit, anhydroglucose The unit is a six-membered ring as shown for the repeating unit of the above general structure. The "degree of substitution" of a group R _C , sometimes abbreviated herein as “DS _RC ”, refers to the number of moles of a group R _C component where Z is H or M substituted per anhydroglucose unit. Wherein the anhydroglucose unit is a six-membered ring as shown for the repeating unit of the general structure above. The requirement that Z be H or M is necessary to ensure that there is a sufficient number of carboxymethyl groups that the resulting polymer can be soluble. In addition to the required number of R _C components where Z is H or M, additional R _C components where Z is a group other than H or M may be present, and are most preferably understood to be present. . The preparation of the substance according to the invention is further illustrated in the examples below.

C) Detergent Surfactants The detergent composition contains about 1 to 80% by weight of detersive surfactant. Preferably, such compositions contain about 5 to 50% by weight of a surfactant. The detersive surfactants utilized are of the anionic, nonionic, zwitterionic, amphoteric or cationic type or consist of a compatible mixture of these types. Detergent surfactants useful herein include Norris US Pat. No. 3,664,961, issued May 23, 1972, and Laughlin et al., US Pat.
Cockrell's US patent issued on September 16, 1980, patent 3,919,678.
No. 4,222,905 and Murphy US Pat. No. 4,239,659 issued Dec. 16, 1980. All these patents are incorporated herein by reference. Of all surfactants, anionic and nonionic are preferred.

There are several different types of useful anionic surfactants per se. For example, water-soluble salts of higher fatty acids, or "soaps", are useful anionic surfactants in the present compositions. This includes about 8 to about 24 carbon atoms, preferably about 12 to about 1 carbon atoms.
There are alkali metal soaps of higher fatty acids having 8 carbon atoms, such as sodium, potassium, ammonium and alkylol ammonium salts. Additional non-soap anionic surfactants suitable for use herein include about 10 carbon atoms.
There are water-soluble salts, preferably alkali metal and ammonium salts, of organic sulfuric acid reaction products having from about 20 alkyl groups and sulfonic or sulfate groups in the molecular structure (the term "alkyl" includes acyl groups Also includes the alkyl portion of
. C _11-13 LAS wherein the average number of carbon atoms in the alkyl group is about _11-13.
Particularly useful are linear linear alkyl benzene sulfonates, abbreviated as

A preferred nonionic surfactant is of the formula R ¹ (OC ₂ H ₄ ) _n OH
Here, 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 _are, C 12 _{-C 15} Alcohol 1 condensation product of about 5 to about 20 moles of ethylene oxide per mole, such as an alcohol 1 to about 6.5 mole per mole of ethylene oxide condensed with _C 12 -C ₁₃ alcohols.

Additional suitable surfactants, including polyhydroxyfatty acid amides and amine-based surfactants, include “laundries containing cyclic amine-based polymers to provide appearance and integrity benefits to the washed fabric. Panandik entitled "Detergent Composition"
er et al., filed Sep. 15, 1997, co-pending PCT application WO98 / [P & G Case No. 6834]. The entire disclosure of Panandiker et al. Is incorporated herein by reference.

D) Detergent Builder The detergent composition may also contain about 0.1-80% by weight of a detergent builder. Preferably, such compositions contain about 1-10% by weight of a builder component when in liquid form. Preferably, such compositions contain about 1-50% by weight of the builder component when in granular form. Detergent builders are well known in the art and include, for example, phosphates and various organic and inorganic non-phosphorus builders.

The water-soluble non-phosphorus organic builders useful herein include various alkali metal, ammonium and substituted ammonium polyacetates, carboxylate, polycarboxylate and polyhydroxysulfonate. Polycarboxylates suitable for use herein are described in Crutchfield et al., US Pat.
Patents 4,144,226 and Crutchfiel issued March 27, 1979
d. US Pat. No. 4,246,495 to Polyacetal Carboxylates, both of which are incorporated herein by reference. A particularly preferred polycarboxylate builder is an ether carboxylate comprising a combination of tartrate monosuccinate and tartrate disuccinate described in Bush et al., US Pat. No. 4,663,071, issued May 5, 1987. Builder compositions and oxydisuccinates, the disclosures of which are incorporated herein by reference.

Examples of suitable non-phosphorous inorganic builders include silicates, aluminosilicates, borates and carbonates. Sodium and potassium carbonate, bicarbonate, sesquicarbonate carbonate, tetraborate ten anhydride, and a weight ratio of about 0.5 to about 4.0, preferably from about 1.0 to about 2.4 SiO ₂ to alkali metal oxide Is particularly preferred. Aluminosilicates including zeolites are also preferred. Such substances and their use as detergent builders are described in Cork
It is further described in US Pat. No. 4,605,509 to ill et al., the disclosure of which is incorporated herein by reference. Crystal-laminated silicates suitable for use in the detergent compositions of the present invention are also described in US Pat. No. 4,605,509.

E) Optional Detergent Components In addition to the surfactants, builders and fabric enhancing components described above, the detergent compositions of the present invention may also contain some additional optional components. These include enzymes and enzyme stabilizers, foam enhancers or foam inhibitors, rust and corrosion inhibitors, bleaches, soil suspending agents, soil release agents, bactericides, pH adjusters, non-builder alkaline sources There are conventional detergent composition components such as, chelating agents, organic and inorganic fillers, solvents, hydrotropes, optical brighteners, dyes and fragrances. One preferred additive is
Most preferably, it is carboxymethyl cellulose at a concentration of about 0.01 to about 5% by weight of the detergent composition. Since the fabric integrity effect of the present composition begins to decrease at high pH, a pH adjuster may be required in certain applications where the pH of the cleaning solution is greater than about 10.0. Thus, if the wash liquor is greater than about 10.0 after the addition of the fabric enhancing component of the present invention, the pH adjuster will increase the pH of the wash liquor to about 10.0 or less, preferably to about 9.5 or less, and most preferably to about 7 or less. Should be used to reduce to .5 or less. Suitable pH adjusters are known to those skilled in the art.

Preferred optional ingredients for incorporation into the present detergent compositions include bleaching agents, such as peroxygen bleach. Such peroxygen bleaches can 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. Suitable examples of this type of agent include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of m-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxide decandioic acid. Such bleaches are available from 19
Hartman US Patent No. 4,483,781,1 issued November 20, 1984
European Patent Application EP-A-133, Banks et al., Published on February 20, 985
354, and US Patent No. 4,4,464, issued to Chung et al.
12,934. Highly preferred bleaches include January 6, 1987
6 as described in US Patent No. 4,634,551 issued to Burns et al.
There is also -nonylamino-6-oxoperoxycaproic acid (NAPAA).

[0040] Inorganic peroxygen bleaches may also be used in the present detergent compositions, usually in particulate form. Inorganic bleaches are practically preferred. Such inorganic peroxygen compounds include alkali metal perborate and percarbonate materials. For example, sodium perborate (eg, mono- or tetrahydrate) is used. Suitable inorganic bleaches also include sodium or potassium carbonate peroxyhydrate and the corresponding "percarbonate" bleach, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Persulfate bleach (eg, OXONE from DuPont) may also be used. Often, the inorganic peroxygen bleach is coated with a silicate, borate, sulfate or water-soluble surfactant. For example, coated percarbonate particles are available from FMC, Solvay Int.
Available from various commercial sources such as erox, Tokai Denka and Degussa.

Inorganic peroxygen bleaches, such as perborates, percarbonates, etc., are preferably combined with a bleach activator, which can be prepared by adding the corresponding peroxyacid to the bleach activator in aqueous solution (ie in the case of fabric washing / bleaching). Is formed in situ (during use of the composition). Various non-limiting examples of activators are described in US Pat. No. 4,915,85 issued to Mao et al. On Apr. 10, 1990.
No. 4,412, issued Nov. 1, 1983 to Chung et al.
934. Nonanoyloxybenzenesulfonate (NOBS)
And tetraacetylethylenediamine (TAED) activators are typical and preferred. Mixtures thereof may also be used. See also above-cited US Pat. No. 4,634,551 for other typical bleach and activators useful herein.

Other useful amide-derived bleach activators are of the formula: R ¹ N (R ⁵ ) C (O) R ² C (O) L or R ¹ C (O) N (R ⁵ ) R ² C (O) L wherein R ¹ is an alkyl group having about 6 to about 12 carbon atoms and R ² is 1 to
Alkylene having from about 6 carbon atoms, R ⁵ is alkyl, aryl or alkaryl having a H or from about 1 to about 10 carbon atoms,, L is any suitable leaving group. A leaving group is a group that leaves a bleach activator as a result of a nucleophilic attack on the bleach activator by a perhydrolysis anion. A preferred leaving group is phenolsulfonate. Preferred examples of the bleach activator of the above formula include the aforementioned US Pat.
(6-Octanamidocaproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamidocaproyl) oxybenzenesulfonate and mixtures thereof as described in US Pat. There is.

Another type of useful bleach activator is US Pat. No. 4,966 to Hodge et al., Issued Oct. 30, 1990, which is incorporated herein by reference.
, 723, there is a benzoxazine type activator. See also US Pat. No. 4,545,784, issued to Sanderson on Oct. 8, 1985, which discloses acylcaprolactams, including benzoylcaprolactam adsorbed in sodium perborate, incorporated herein by reference.

If utilized, the peroxygen bleach is usually from about 2 to 30% by weight of the detergent composition. More preferably, the peroxygen bleach is from about 2% to 20% by weight of the composition. Most preferably, the peroxygen bleach is present on the order of about 3 to 15% by weight of the composition. If utilized, the bleach activator is about 2 to 10% by weight of the detergent composition. Most often, the activator is used such that the molar ratio of bleach to activator is from about 1: 1 to 10: 1, more preferably from about 1.5: 1 to 5: 1.

Additional suitable bleaching and bleach activators are Panandiker, entitled “Laundry Detergent Compositions Containing Cyclic Amine-Based Polymers to Provide Appearance and Integrity Effects to Washed Fabrics” Co-pending PCT application WO98 / [P & G case no. 6834]. The entire disclosure of Panandiker et al. Is incorporated herein by reference.

Another highly preferred optional ingredient in the present detergent compositions is a cleaning enzyme component.
Enzymes may be included in the detergent composition for a variety of purposes, including removing protein-based, carbohydrate-based or triglyceride-based stains from the substrate, preventing free dye transfer in fabric washing, and fabric regeneration. Can be. Suitable enzymes include
There are proteases, amylases, lipases, cellulases, peroxidases and mixtures thereof of any suitable origin, such as plant, animal, bacterial, fungal and yeast origins. Preferred choices are pH activity and / or stability, optimal thermal stability,
And stability to active detergents, builders and the like. In this regard, bacterial or fungal enzymes such as bacterial amylase and protease, and fungal cellulase are preferred.

As used herein, “wash enzyme” refers to an enzyme that has the ability to clean, stain, or otherwise effect a laundry detergent composition. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases, amylases and peroxidases. Enzymes are usually incorporated into detergent compositions at a level sufficient to provide a "cleaning effective amount". The term "cleaning effective amount" relates to an amount capable of producing a cleaning, stain, stain removal, whitening, deodorizing or freshness improving effect on a substrate such as a fabric. For practical use of current products, a typical amount is 1 g of detergent composition
Within about 5 mg, more typically 0.01 to 3 mg of active enzyme per weight. In other words, the composition is typically 0.001-5% by weight, preferably 0.0
Contains 1-1% commercial enzyme products. Protease enzymes are present in 0.0 g / g of composition.
It is usually present in such products at a level sufficient to provide from 0.5 to 0.1 Anson units (AU) of activity. Even higher activity levels may be desirable in highly concentrated detergent formulations.

[0048] Cellulases that can be used herein include those described by Barbesgoard et al.
Patent 4,435,307, GB-A-2,075,028, GB-A-2,09
No. 5,275 and DE-OS-2,247,832. CA
REZYME ^R and CELLUZYME ^R (Novo) is especially useful. Novo's WO91172
See also 43.

The present enzyme-containing composition comprises about 0.001 to about 10% by weight, preferably about 0.005 to about 10% by weight.
From about 8%, most preferably from about 0.01 to about 6%, may optionally be included. The enzyme stabilization system can be any stabilization system compatible with the wash enzyme. Such systems may be provided together with other formulated actives or added separately, for example by a formulator or a manufacturer of ready-to-use enzymes. Such stabilizing systems can include, for example, calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boronic acids and mixtures thereof, depending on the type and physical form of the detergent composition. Designed to handle problems.

F) Preparation of the Detergent Composition The detergent composition according to the invention can be in liquid, paste or granular form. Such compositions may be prepared by mixing the essential and optional ingredients in the required concentrations in any suitable order and by any convenient means. The foregoing description of uses for the fabric enhancing component is exemplary and other uses will be apparent to those skilled in the art and are within the scope of the present invention.

The granule composition is prepared, for example, by mixing a base granule component such as a surfactant, a builder, water and the like as a slurry, and mixing the obtained slurry with a low level of residual moisture (5 to 12).
%) By spray-drying until it becomes%. The remaining dry ingredients, for example granules of the essential fabric enhancing ingredient, can be mixed in a rotary mixing drum with the spray-dried granules in the form of a granulated powder. Liquid components, such as solutions of the essential fabric enhancing components, enzymes, binders and perfumes, may be sprayed onto the resulting granules to form the final detergent composition. Granular compositions according to the invention may be in "compact form", ie they have a relatively higher density than conventional granular detergents, i.e. 550-950 g / L. In such a case, the granular detergent composition according to the invention contains a lower amount of "inorganic filler salts" compared to conventional granular detergents; typical filler salts are the alkaline earth metal salts of sulfates and chlorides, Typically, it is sodium sulfate; "compact" detergents typically contain up to 10% filler salt.

Liquid detergent compositions can be prepared by mixing the essential and optional ingredients in any desired order to provide a composition containing the ingredients at the required concentrations. The liquid composition according to the invention may be in "compact form", in which case the liquid detergent composition according to the invention contains a small amount of water compared to conventional liquid detergents. Addition of the fabric enhancing component to the liquid detergents or other aqueous compositions of the present invention may be accomplished by simply mixing the desired fabric enhancing component into the liquid solution.

G) Fabric Washing Method The present invention also provides a method for washing a fabric so as to impart a fabric appearance effect by the fabric enhancing component used herein. In such a method, the fabrics are contacted with an aqueous wash solution formed from an effective amount of the detergent composition described above, or formed from individual components of such a composition. Although the contact between the fabric and the cleaning solution is usually performed under stirring conditions, the compositions of the present invention may be used to form a non-stirring immersion aqueous solution for fabric cleaning and treatment. As described above, the washing solution is about 10.
Preferably it has a pH of less than 0, preferably it has a pH of about 9.5, and most preferably it has a pH of about 7.5. Agitation is preferably performed in a washing machine for good cleaning. After washing, the wet fabric is dried, preferably in a conventional clothes dryer. The effective amount of the high density liquid or granular detergent composition in the aqueous washing solution in the washing machine is preferably from about 500 to about 7
000 ppm, more preferably about 1000 to about 3000 ppm.

H) Fabric Conditioning and Softening The fabric enhancing component described above as a component of the present laundry detergent composition can be used for fabric and textile in the absence of the surfactant and builder components of the detergent composition embodiment of the present invention. It may be used for processing and conditioning. Thus, for example, a fabric conditioning composition containing only the fabric-enhancing component, or containing an aqueous solution of the fabric-enhancing component, may be used in conventional household laundry operations to impart the desired fabric appearance and maintainability benefits described above. May be added during the rinse cycle.

An additional suitable fabric softener is the name of Panandiker et al., Entitled “Laundry Detergent Composition Containing Cyclic Amine-Based Polymers to Bring Appearance and Integrity Effects to Washed Fabrics”. Co-pending PCT application WO98 / [P & G case no. 6834]. The entire disclosure of Panandiker et al. Is incorporated herein by reference.

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

EXAMPLES The following examples illustrate the compositions and methods of the present invention, but do not necessarily limit or limit the scope of the present invention. Example 1 Imidazole and adducts of epichlorohydrin to produce a polycationic condensate by a synthetic imidazole and epichlorohydrin (imidazole: Epikurorohi Dorin 1 1 ratio) to react. To a round bottom flask equipped with a magnetic stirrer, condenser and thermometer is added imidazole (0.68 mol) and 95 ml of water. After heating the solution to 50 ° C., epichlorohydrin (0.68 mol) is added dropwise. After all epichlorohydrin has been added, the temperature is raised to 80 ° C. until all the alkylating agent is consumed. The resulting condensate had a molecular weight of about 12,500.

[0058] Example 2 Imidazole and adducts of epichlorohydrin (imidazole: Epikurorohi Dorin 1.4: 1 ratio) Synthesis magnetic stirrer, imidazole (0.68 mol) to a round bottom flask equipped with a condenser and thermometer And 95 ml of water. After heating the solution to 50 ° C., epichlorohydrin (0.50 mol) is added dropwise. After all epichlorohydrin has been added, the temperature is raised to 80 ° C. until all the alkylating agent is consumed. The condensate formed had a molecular weight of about 2000.

Example 3 Synthesis of adducts of piperazine, morpholine and epichlorohydrin (ratio 1.8 / 0.8 / 2.0) Piperazine to round bottom flask equipped with stirrer, thermometer, dropping funnel and reflux condenser 154.8 g (1.8 mol), 69.6 g (0.8 mol) of morpholine and 220 ml of water are added. After obtaining a clear solution at 40 ° C., the solution was
185 g (2 mol) of epichlorohydrin while heating to ~ 65 ° C and stirring vigorously
At a rate such that the temperature does not exceed 80 ° C. After all epichlorohydrin has been added, the reaction mixture is heated to 85 ° C. until all the alkylating agent is consumed (negative Preussmann test after 4 hours). 108.8 g of 25% NaOH (0
. 68 mol) and 40 g of water are added and the reaction mixture is stirred at 85 ° C. for a further hour. Then add 47 g of water and cool the mixture to room temperature.

Example 4 Synthesis of piperazine / morpholine / epichlorohydrin adduct in a ratio of 1.8 / 0.8 / 2.0 Piperazine to a round bottom flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser. 154.8 g (1.8 mol), 69.6 g (0.8 mol) of morpholine and 220 ml of water are added. After obtaining a clear solution at 40 ° C., the solution was
185 g (2 mol) of epichlorohydrin while heating to ~ 65 ° C and stirring vigorously
At a rate such that the temperature does not exceed 80 ° C. After all epichlorohydrin has been added, the reaction mixture is heated to 85 ° C. until all the alkylating agent is consumed (negative Preussmann test after 4 hours). 108.8 g of 25% NaOH (0
. 68 mol) and 40 g of water are added and the reaction mixture is stirred at 85 ° C. for a further hour. Then add 47 g of water and cool the mixture to room temperature.

Example 5 100% oxidized piperazine / morpholine / epichlorohydrin adduct of Example 4 233.6 g of the material from Example 4 above (corresponding to 1292 moles of oxidizable nitrogen atoms) 22.1 g of 50% NaOH (0.276), then 55-65 ° C
Heat to At that temperature 102.4 g (1421 mol) of H ₂ O ₂ (47.2%)
Is added dropwise over 3.5 hours. After the addition is complete, the reaction mixture is kept at the same temperature for a further 3 hours and then stirred at room temperature overnight. Pt / C is added to decompose unreacted H ₂ O ₂ ,
Then the solution was filtered. The reaction product is characterized as follows: water 58% pH 5.6 chlorine content 1.593 mmol / g

[0062] Example 6 1.0 / 3.0 / 4.0 Synthesis imidazole 68.8 g (1.0 mol) of imidazole / piperazine / epichlorohydrin emissions adduct in a ratio of and piperazine 260.6g (3.
0 mol) is dissolved in 700.2 g of water at a temperature of 50 to 60 ° C., and 370 g (4.0 mol) of epichlorohydrin is added dropwise. After the addition is complete, the reaction mixture is stirred at 80 ° C. for a further 5 hours.

Example 7 100% Oxidized Imidazole / Piperazine / Epichlorohydrin Adduct of Example 6 237 g of the product from Example 6 above (corresponding to 1022 mol of oxidizable nitrogen atoms) were treated with H ₂ O ₂ in water. 80.7 g (1.12 mol) of a 47.2% solution are added at 40 ° C. over 5 hours. Thereafter, the mixture is added to 50-6 until the theoretical amount of H ₂ O ₂ is consumed.
Heat to 0 ° C. Unreacted H ₂ O ₂ is decomposed by using Pt / C, after which the solution is filtered. The reaction product is characterized as follows: water: 58.6% pH: 2.86 chlorine: 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 procedure well known to those skilled in the art. One way to make the modified CMC material of the present invention is to add the material to be replaced during the CMC manufacturing process. Examples of such operations are set forth below. The same procedure can be used with the other substitution materials described herein by replacing hexyl chloride with the substitution material of interest, for example cetyl chloride.
The amount of material that must be added to the CMC manufacturing process to obtain the desired degree of substitution is
Those skilled in the art can easily calculate from the following examples.

Example 9 Synthesis of hexyl ether of CMC This example illustrates the preparation of a hydrophobically modified carboxymethyl cellulose 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 into a 500 ml glass reactor. The obtained 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 gradually raised to 95 ° C. and kept at 95 ° C. for 150 minutes. Cool the reaction to 70 ° C. and then to 25 ° C. 8-9
Neutralization is performed by adding a sufficient amount of nitric acid / acetic acid to obtain a slurry pH. Filter the slurry to obtain the hexyl ether of CMC.

Example 10 Cellulose Polymers Used in Test Detergent Compositions Modified cellulosic polymers representative for use in the liquid and granular detergent compositions described below are characterized in Tables 10A and 10B. Although general polymer parameters are common to all polymers, the specific chemical structure of the tested material is listed for a particular polymer parameter.

[0067] Table 10A General Polymer Parameters Molecular Parameters Description Polymer backbone carboxymethylcellulose carboxymethylation degree DS _RC = 0.3-2.0; preferably DS _RC = 0.5-0.70 carboxymethyl along the distribution backbone of methyl carboxymethyl uniform and methyl Random distribution Molecular weight Mw: 5000-2,000,000; Preferred: Intermediate (approximately 250,000 g / mol) Type of modification (in addition to carboxymethylation) Ether modification Mixed cellulose ether Level of modification DS _RH = about 0.001 to about 0.1

Table 10B Table ID of Specific Polymer Parameters Polymer Modification Type ^*** Chemical Type ^* A Hexyl CMC Hexyl Ether Addition of Chlorohexane to CMC Production Process ^* B Decyl CMC Decyl Ether Addition of Chlorodecane to CMC Production Process ^** C C12-C13 alkoxy C12-C13 alkoxy To the CMC production process Add 2-hydroxy-2-hydroxy C12-C13 alkyl propyl CMC propyl ether glycidyl ether ^* D Hexadecyl CMC hexadecyl ether To the CMC production process Add chlorohexadecane ^* E CMC3 -Trimethyl 3-trimethylammonium To CMC production process Ammonio-2-hydroo-2-hydroxypro 2,3-epoxypropyl xypropyl ether Chloride salt of trimethylammonium chloride Salts chloride added ^* F CMC of [-C (O) -CH (C16H33 ) - CMC to the manufacturing process C (O) CH2 (C16H33) ] ester, or cetyl ketene dimer CMC 1,3-dioxo-2-hexadecyl added octadecyl Ester CMC = carboxymethylcellulose ^* manufactured by Metsa Specialty Chemicals ^** manufactured by Akzo ^*** The DS _RH of these materials ranged from about 0.001 to about 0.1.

Example 11 The following is the ideal chemical structure of certain cyclic amine based polymers, oligomers or copolymers of the present invention. No side reactions expected to occur during the condensation are indicated. Table 11 Example Substance 1 imidazole - adduct of epichlorohydrin (imidazole: epichlorohydrin 1: 1 ratio, of Example 1 Polymer)

Embedded image (Ideal structure) 2 Adduct of imidazole-epichlorohydrin (ratio of imidazole: epichlorohydrin 1.36: 1, polymer of Example 2)

Embedded image (Ideal structure) 3. Adduct of imidazole-epichlorohydrin (ratio of imidazole: epichlorohydrin 1.75: 1)

Embedded image (Ideal structure) 4 Adduct of trisglycidyl ether from imidazole-epichlorohydrin-glycerin (ratio of imidazole: epichlorohydrin: tris glycidyl ether 2.0: 1.76: 0.26)

Embedded image Ideal structure 5. Trisglycidyl ether adduct from imidazole-epichlorohydrin-glycerin (trisglycidyl ether 2.0: 1.9: 0.1 ratio from imidazole: epichlorohydrin: glycerin)

Embedded image 6. Adducts of piperazine and epichlorohydrin (ratio 1: 1)

Embedded image 7 adducts of piperazine and epichlorohydrin (ratio 1: 1), benzyl quaternary

Embedded image 8 Piperazine and epichlorohydrin (ratio 1: 1), methyl quaternary

Embedded image 9. Adducts of piperazine, morpholine and epichlorohydrin (ratio 0.9: 0.4: 1.0)

Embedded image 10 Adducts of piperazine, piperidine and epichlorohydrin (ratio 0.9: 0.4: 1.0)

Embedded image 11 Piperazine, adduct of morpholine and epichlorohydrin (ratio 0.9: 0.4: 1.0), methyl quaternary

Embedded image 12 Piperazine, piperidine and epichlorohydrin (ratio 0.9: 0.4: 1.0) adduct, methyl quaternary

Embedded image 13 Piperazine, adduct of morpholine and epichlorohydrin (ratio 0.9: 0.4: 1.0), benzyl quaternary

Embedded image 14 Piperazine, adduct of piperidine and epichlorohydrin (ratio 0.9: 0.4: 1.0), benzyl quaternary

Embedded image 15 Adducts of imidazole, piperazine and epichlorohydrin (ratio 2: 1: 3)

Embedded image 16 Adducts of imidazole, piperazine and epichlorohydrin (ratio 1: 1: 2)

Embedded image 17 Adduct of imidazole, 1,6-diaminohexane and epichlorohydrin (ratio 1: 1: 2)

Embedded image 18 Adducts of imidazole, dimethylaminopropylamine and epichlorohydrin (ratio 1.02: 0.34: 1.0)

Embedded image 19 Adduct of imidazole-epichlorohydrin and chloroacetic acid (ratio 1.36: 0.97: 0.07)

Embedded image 20 Adducts of imidazole-epichlorohydrin and chloroacetic acid (ratio 1.36: 0.93: 0.14)

Embedded image 21 Adducts of imidazole-epichlorohydrin and chloroacetic acid (ratio 1.36: 0.83: 0.34)

Embedded image 22 Adducts of imidazole-epichlorohydrin and 3-chlorohydroxypropyl sulfonic acid (ratio 1.0: 0.83: 0.34)

Embedded image 23 Adducts of imidazole-epichlorohydrin and 3-chlorohydroxypropyl sulfonic acid (ratio 1.0: 0.75: 0.5)

Embedded image 24 Additives of imidazole, piperazine and epichlorohydrin (ratio 1.0: 1.0: 2.0), quaternary with 0.22 mol of chloroacetate

Embedded image 25 Imidazole, adduct of piperazine and epichlorohydrin (ratio 1.0: 3.0: 4.0), quaternary with 0.32 mol of chloroacetate

Embedded image 26 Imidazole, adduct of piperazine and epichlorohydrin (ratio 1.0: 1.0: 2.0), quaternary with 0.45 mol of chloroacetate

Embedded image 27 Adducts of oxidized imidazole and epichlorohydrin (ratio 1.75: 1)

Embedded image 28 100% oxidized adduct of piperazine and epichlorohydrin (ratio 1: 1)

Embedded image 29 50% oxidized adduct of piperazine and epichlorohydrin (ratio 1: 1)

Embedded image 30 100% oxidized adduct of piperazine, morpholine and epichlorohydrin (ratio 1: 0.2: 1)

Embedded image 31 Oxidized piperazine, adduct of morpholine and epichlorohydrin (ratio 1: 0.2: 1), 25% methyl quaternary

Embedded image 32 100% oxidized adduct of imidazole, piperazine and epichlorohydrin (ratio 1: 3: 4)

Embedded image 33 Adduct of 50% oxidized imidazole, piperazine and epichlorohydrin (ratio 1: 3: 4)

Embedded image 34 100% oxidized adduct of imidazole, piperazine and epichlorohydrin (ratio 1: 1: 2)

Embedded image 35 100% oxidized adduct of imidazole, piperazine and epichlorohydrin (ratio 1: 5: 6)

Embedded image 36 100% oxidized adduct of imidazole, piperazine and epichlorohydrin (ratio 1:10:11)

Embedded image 37 Quaternary product of adduct of oxidized imidazole, piperazine and epichlorohydrin (ratio 1.0: 3.0: 4.0), 0.32 mol of chloroacetate

Embedded image 38 Quaternary product of adduct of oxidized imidazole, piperazine and epichlorohydrin (ratio 1.0: 1.0: 2.0), 0.45 mol of chloroacetate

Embedded image 39 Quaternary product of adduct of oxidized imidazole, piperazine and epichlorohydrin (ratio 1.0: 5.0: 6.0), 0.32 mol of chloroacetate

Embedded image 40 Additives of oxidized imidazole, piperazine and epichlorohydrin (ratio 1.0: 1.0: 2.0), quaternary with dimethylsulfate 0.45 mol

Embedded image 41 Adducts of oxidized imidazole, dimethylaminopropylamine and epichlorohydrin (ratio 1.02: 0.34: 1.0)

Embedded image

Example 12 Preparation of a Granular Detergent Test Composition Several heavy granular detergent compositions containing fabric enhancing ingredients are prepared. All of these granular detergent compositions have a basic following formulation: TABLE 12 Ingredient Wt% C ₁₂ linear alkyl benzene sulfonate 9.31 C _14-15 alkyl ether (0.35EO) sulfate 12.74 Zeolite Builder 27 .79 sodium carbonate 27.31 PEG 4000 1.60 dispersant 2.26 C _12-13 alcohol ethoxylate (9EO) 1.5 sodium perborate 1.03 soil release polymer 0.41 enzyme 0.59 cyclic amine base Polymer or oligomer 3.0 Hydrophobic modified cellulose-based polymer or oligomer 1.0 Fragrance, whitening agent, foam inhibitor, other, water, sulfate balance 100%

EXAMPLE 13 Preparation of Liquid Detergent Test Compositions Several heavy liquid detergent compositions containing the fabric enhancing ingredients of the present invention are prepared.
All of these liquid detergent compositions have a basic formulation of the following: Table 13 Ingredient Wt% C _12-15 alkyl ether (2.5) sulfate 38 C ₁₂ glucose amide 6.86 Citric Acid 4.75 C _12-14 fatty acid 2.00 enzyme 1.02 MEA 1.0 propanediol 0.36 borax 6.58 dispersant 1.48 Na toluenesulfonate 6.25 cyclic amine base polymer or oligomer 1.0 hydrophobic modification Cellulose base polymer or oligomer 0.1 Dye, fragrance, whitening agent, preservative, antifoaming agent, others, water balance 100%

Example 14 Preparation of a Granular Detergent Test Composition Several granular detergent compositions containing a fabric enhancing component are prepared. Such granular detergent compositions all have the basic formulation of the following: Table 14 Example Comparative Example Ingredient Wt% Wt% C ₁₂ linear alkyl benzene sulfonate Na 9.40 9.40 C _14-15 alkyl Na sulfonate 11.26 11.26 Zeolite builder 27.79 27.79 Sodium carbonate 27.31 27.31 PEG4000 1.60 1.60 Dispersant, Na polyacrylate 2.26 2.26 C _12-13 alkyl ethoxy Rate (E9) 1.5 1.5 Sodium perborate 1.03 1.03 Cyclic amine-based polymer or oligomer 0.80 Hydrophobic modified cellulose-based polymer or oligomer 0.30 Other added components Remaining Remaining Part 100% 100%

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country 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, MA, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW (72 Inventor Rajan, Keshav, Pananda Daiker Ohio, USA, West, Chester, Oregon, Pass, 6484 (72) Inventor Jennifer, Ann, Lupine, Ohio, U.S.A., Cincinnati, Phone Creek, Drive, 7974 (72) Inventor William , Conrad, Weltz, Indiana, USA, West, Harrison, Morgan, Rd, 1273 F-term (reference) 4H003 AB19 AB31 AC08 BA10 BA12 BA21 BA28 DA01 EA12 EA16 EA20 EA28 EB22 EB28 EB36 EB38 EB42 EC01 ED02 EE05 4L033 AC15 CA03 CA57

Claims (11)

[Claims] 1. a) 1 to 80% by weight of a surfactant selected from the group consisting of nonionic, anionic, cationic, amphoteric, zwitterionic and mixtures thereof, and b) a cyclic amine base. 0.01-5.0% by weight, preferably 0.1-4.0% by weight of a fabric enhancing component selected from the group consisting of polymers, oligomers or copolymers, hydrophobically modified cellulose-based polymers or oligomers, and mixtures thereof.
% By weight of the detergent composition, wherein the detergent composition is contained in an interior chamber of the container, the container further having an outer surface, the outer surface further comprising a garment. Helping to look healthy, helping to reduce the abrasion before it begins, maintaining the appearance of the garment, helping to prevent the garment from appearing worn, making the garment look good and enhancing at the same time, Reinforce the yarn to make the clothes look good, help prevent the clothes from appearing worn, help prevent the clothes from being worn out in the washing machine that makes the clothes old, help keep the clothes from getting old, leave the washing machine Helping to make the garment look as good as it was in, helping to preserve the fabric's integrity, strengthening the yarn from inside and outside to make the garment look better, extending the life of the garment, Kinds of vitamins, act like anti-aging products for clothing, are like calcium in clothing, are like supplements for clothing, after 10 washes, other detergents Looks better than when washed in clothes, strengthens the yarn to make the clothes look healthy, helps prevent the clothes from looking old before needed, like stopping the time to keep the clothes looking good A detergent composition, comprising a description of a composition characterized by a language selected from the group consisting of: 2. The hydrophobically modified cellulose-based polymer or oligomer is of the general formula: In the above formula, 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; each R _C is — (CH ₂ ) _y —C ( ＯO) -OZ, wherein each Z is independently selected from the group consisting of M, R ₂ , R _C and R _H. Each R _H is independently C ₅ -C ₂₀ alkyl. , _C 5 -C ₇ cycloalkyl, _{C 7} -
C ₂₀ alkylaryl, C ₇ -C ₂₀ arylalkyl, substituted alkyl, hydroxyalkyl, C ₁ -C ₂₀ alkoxy-2-hydroxyalkyl, C ₇ -C ₂₀ alkylaryloxy-2-hydroxyalkyl, (R ₄ ) ₂ N-alkyl, (R ₄ ) ₂ N-2-hydroxyalkyl, (R ₄ ) ₃ N-alkyl, (R ₄ ) ₃ N-2-hydroxyalkyl, C ₆ -C ₁₂ aryloxy-2-hydroxyalkyl, Embedded image Wherein each R ₄ is independently H, C ₁ -C ₂₀ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₂₀ alkylaryl, C ₇ -C ₂₀ arylalkyl, amino Alkyl, alkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl,
Each R ₅ is independently H, C ₁ -C ₂₀ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₂₀ alkylaryl, wherein each R ₅ is independently selected from the group consisting of morpholinoalkyl, cycloalkylaminoalkyl and hydroxyalkyl; , C ₇ -C ₂₀ arylalkyl, substituted alkyl,
Selected from the group consisting of hydroxyalkyl, (R ₄ ) ₂ N-alkyl and (R ₄ ) ₃ N-alkyl; wherein M is from the group consisting of Na, K, １ ／ Ca and ＭｇMg. Each x is 0-5; each y is 1-5; and:-the degree of substitution of the group _RH is 0.001-0.1, more preferably 0.005-0.05
, Most preferably from 0.01 to 0.05; the degree of substitution of the group _{RC wherein} -Z is H or M is from 0.2 to 2.0, more preferably from 0.
3 to 1.0, most preferably 0.4 to 0.7; if any _RH has a positive charge, it is balanced with the appropriate anion; and two R ₄ on the same nitrogen are taken together, may form a ring structure selected from the group consisting of piperidine and morpholine, the detergent composition according to claim 1. 3. The cyclic amine-based polymer, oligomer or copolymer is of the general formula: Wherein each T is independently 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, And -R ₂ Q; -W is: Characterized by at least one cyclic moiety selected from the group consisting of: In addition to at least one cyclic moiety, W may also include an aliphatic or substituted aliphatic moiety of the general structure: 7] Each B is independently C ₁ -C ₁₂ alkylene, C ₁ -C ₁₂ substituted alkylene, C ₃ -C ₁₂ alkenylene, C ₈ -C ₁₂ dialkylarylene, C ₈ -C ₁₂ dialkylarylenediyl and-(R ₅ O) _n R _5- each D is independently C ₂ -C ₆ alkylene; each Q is independently hydroxy, C ₁ -C ₁₈ alkoxy, C ₂ -C ₁₈ hydroxyalkoxy, amino , C ₁ -C ₁₈ alkylamino, dialkylamino, trialkylamino, heterocyclic monoamino and diamino; each R ₁ is independently H, C ₁ -C ₈ alkyl and is selected from the group consisting of C ₁ -C ₈ hydroxyalkyl; - each _{R 2} is independently _C 1 _{-C 12 alkylene,} C 1 _{-C 12} alkenyl Down, -C
H ₂ —CH (OR ₁ ) —CH ₂ , C ₈ —C ₁₂ alkarylene, C ₄ —C ₁₂ dihydroxyalkylene, poly (C ₂ —C ₄ alkyleneoxy) alkylene, H ₂ CH (OH) CH ₂ OR _{2 OCH 2 CH (OH) CH 2} - and _C 3 _{-C 12} is selected from the group consisting of hydrocarbyl moiety, provided that when _{R 2} is _C 3 _{-C 12} hydrocarbyl moiety, the hydrocarbyl moiety is from about 2 to about 4 Can include a branching moiety of the following general structure: Each R ₃ is independently 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 , C ₁ -C ₂₀ aminoalkyl,-(CH ₂ ) _h COOM
_{, - (CH 2) h SO} 3 M, CH 2 CH (OH) SO 3 M, - (CH 2) h OS
O ₃ M, 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 or di- or polyvalent anion; M is compatible B is the number required to balance charge; each x is independently 3-1000; each c is independently 0 or 1; each h is independently 1-8 Each q is independently 0-6; each n is independently 1-20; each r is independently 0-20; and each t is independently 0-1; The detergent composition according to claim 1. 4. The cyclic amine-based polymer, oligomer or copolymer comprises piperazine, piperazine, epichlorohydrin, epichlorohydrin benzyl quaternary, epichlorohydrin methyl quaternary, morpholine and mixtures thereof. The detergent composition according to any one of claims 1 to 3, which is an additive selected from the group. 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 ₁ is H, and at least one W is The detergent composition according to any one of claims 1 to 6, which is selected from the group consisting of: 8. Each _{R H} is independently _C 5 _{-C 20 alkyl,} C 5 -C ₇ cycloalkyl, _{C 7} -
C ₂₀ alkylaryl, C ₇ -C ₂₀ arylalkyl, substituted alkyl, hydroxyalkyl, C ₁ -C ₂₀ alkoxy-2-hydroxyalkyl, C ₇ -C ₂₀ alkylaryloxy-2-hydroxyalkyl, (R ₄ ) ₂ From N-alkyl, (R ₄ ) ₂ N-2-hydroxyalkyl, (R ₄ ) ₃ N-alkyl, (R ₄ ) ₃ N-2-hydroxyalkyl and C ₆ -C ₁₂ aryloxy-2-hydroxyalkyl The detergent composition according to any one of claims 1 to 7, which is selected from the group consisting of: 9. Each _RH is independently embedded image The detergent composition according to any one of claims 1 to 8, which is selected from the group consisting of: 10. The cellulose-based polymer or oligomer of 5,000 to 2,000,000.
The detergent composition according to any one of claims 1 to 9, having an average molecular weight of: 11. A fabric-enhancing component selected from the group consisting of: a) 1-80% by weight of water, and b) a cyclic amine-based polymer, oligomer or copolymer, a hydrophobically modified cellulose-based polymer or oligomer, and mixtures thereof. 0.01-5.0% by weight, preferably 0.1-4.0%
A laundry additive composition characterized in that the laundry additive composition is contained within an interior chamber of a container, the container further having an outer surface, the outer surface comprising a garment. Helps to look healthier, helps to control the abrasion before it begins, maintains the appearance of the clothing, helps prevent the clothing from appearing worn, makes the clothing look good and strengthens at the same time From the washing machine, to strengthen the thread so that the clothes look good, to help prevent the clothes from appearing worn, to help prevent the clothes from being worn out in a washing machine that makes the clothes old, to help keep the clothes old Helps to show the garment as good as when you put it in, helps to maintain the fabric integrity of the garment, strengthens the yarn from inside and outside to make the garment look better, extends the life of the garment It is like a clothing vitamin, works like a clothing anti-aging product, is like clothing calcium, is like a clothing supplement, after 10 washes, etc. Appears better than when washed with detergent, strengthens the yarn to make the apparel sounder, helps prevent the apparel from looking old before it's needed, stops time so the apparel stays visible A laundry additive composition having a description of a composition characterized by a language selected from the group consisting of: