JP2002513807A - Fabric care compositions containing cellulose binding domains - Google Patents

Abstract

  (57) [Summary] The present invention relates to a fabric care composition containing one or more amino acid sequences comprising a cellulose binding domain for providing fabric care. In another aspect, the invention is directed to a fabric care composition wherein an amino acid sequence comprising one or more cellulose binding domains is linked to a softening protein.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION

The present invention relates to a fabric care composition containing an amino acid sequence containing a cellulose binding domain (CBD).

[0002]

BACKGROUND OF THE INVENTION

Current laundry detergents and / or fabric care compositions contain various detergent components that have one or more purposes in obtaining a fabric that is not only clean, but also looks and integrity. As such, detergent ingredients such as fragrances, soil release agents, fabric brighteners, fabric softeners, chelants, bleaching agents and catalysts, dye fixatives and enzymes have been incorporated into laundry detergents and / or fabric care compositions. One such embodiment is the use of enzymes, especially proteases, lipases, amylases and / or cellulases.

In particular, cellulase enzymes have been used in detergent / fabric care compositions due to their cleaning and fabric care benefits. The activity of cellulases is that the cellulose fiber or substrate is hydrolyzed by the cellulases and depends on the specific function of the cellulases, including endo- or exo-cellulases and the respective hemicellulases. The cellulosic structure is depolymerized or cleaved into smaller, and thus more soluble or dispersible, fractions. This activity, especially on fabrics, results in cleaning, renewal, softening, and generally improved touch characteristics to fabric construction. Cellobiohydrolases, major endoglucanases and bacterial cellulases have bifunctional structures in the form of a catalytic core domain and a smaller cellulose binding domain separated by amino acid linkers or flexible hinge stretches, according to protein analysis. As known in the art.

[0004] In recent years, there has been an increasing desire of consumers for fabric conditioning compositions.
Fabric softening compositions impart some desirable properties to the treated garment, including softness and static control. Fabric flexibility of the washed garment is typically obtained by delivering a quaternary ammonium compound to the surface of the fabric. Consumers' desire for durable press fabric garments, especially cotton fabric garments, has also increased.
Durable press garments include those that resist fabric wrinkles both during wear and during the washing process. Durable press garments can significantly reduce the manual work involved in washing by eliminating ironing, which is sometimes needed to prevent wrinkling of the garments. However, in most commercially available durable press fabrics, the ability of the fabric to resist wrinkles is:
As the garment is worn and washed many times, it gradually decreases. In addition, colored clothing tends to wear out and show a loss of appearance. Part of this fading may be due to abrasion in the washing process, especially in automatic washing machines and automatic washing and drying machines. Moreover, the tensile strength loss of the fabric appears as an unavoidable result of mechanical / chemical action due to use / wear or washing.

[0005] As mentioned above, it provides fabric flexibility, imparts tensile strength, anti-wrinkle, anti-pilling and anti-shrink properties to the fabric, refreshes or restores, as well as suppresses static electricity, color appearance and fabric. There is a continuing need for fabric care compositions that provide abrasion resistance properties and benefits.

[0006] The above objectives have been met by formulating a fabric care composition that includes one or more amino acid sequences that include a cellulose binding domain (CBD).

[0007] Enzymes linked to the cellulose binding domain have been described in the art: WO9
1/10732 discloses that the core region derived from the endoglucanase produced by the strain of Bacillus spp. A novel derivative of the cellulase enzyme is described which combines a core region derived from the cellulase enzyme with CBD derived from the endoglucanase. WO94 / 07998
Describes a cellulase variant of cellulase classified into family 45, comprising a CBD, a catalytically active domain (CAD) and a region connecting the CBD to the CAD, wherein one or more amino acid residues are added or deleted. Or has been substituted and / or another CBD has been added to the opposite end of the CAD. WO9
5/16782 describes a Trichoderm containing different core regions with several CBDs.
Cloning and high-level expression of a novel truncated cellulase protein or its derivative in a longibrachiatum. WO 97/01629 describes cellulolytic enzyme products in which the mobility of the cellulase component has been reduced, for example, by adsorption to insoluble or soluble carriers, via existing or newly introduced CBD. WO97 / 28243 is a modified enzyme comprising a catalytically active amino acid sequence of a non-cellulolytic enzyme selected from amylase, protease, lipase, pectinase and oxidoreductase, which is linked to an amino acid sequence containing a cellulose binding domain and an aqueous medium. A process for removing or bleaching stains or stains from cellulosic fabrics, and detergent compositions containing such modified enzymes and surfactants are described.

[0008] However, none of these references disclose fabric care compositions containing one or more amino acid sequences containing one or more cellulose binding domains for fabric care benefits.

[0009]

[Summary of the Invention]

The present invention relates to fabric care compositions containing one or more amino acid sequences comprising one or more cellulose binding domains for providing fabric care. In another aspect, the invention is directed to a fabric care composition wherein the amino acid sequence comprising the cellulose binding domain is linked to a softening protein. The fabric care composition of the present invention may further contain a softening component selected from a cationic surfactant, a transferase enzyme and / or a clay.

[0010]

DETAILED DESCRIPTION OF THE INVENTION

An essential element of the fabric care compositions of the present invention is an amino acid sequence that includes a cellulose binding domain. This amino acid sequence, including the cellulose binding domain (CBD),
Can be native sequence or modified: cross-linked CBD, ie, an amino acid sequence comprising cellulose binding domains cross-linked to each other and / or CBD further linked to a softening protein, ie, linked to a softening protein An amino acid sequence containing a cellulose binding domain is contemplated.

Indeed, the present invention includes several embodiments. In a first aspect, the invention relates to a fabric care composition comprising one or more amino acid sequences comprising a cellulose binding domain. It has been surprisingly found that such compositions containing one or more CBD provide flexibility, abrasion resistance and pilling protection. In fact, without being bound by theory, it is believed that CBD adsorbs onto the fibers of the fabric. Such adsorbed CBD protects the fabric fibers and prevents the cellulose fibers from becoming smaller. Furthermore, CBD provides flexibility because it is a protein.

[0012] In a second aspect, the invention relates to a fabric care composition containing a crosslinked amino acid sequence comprising a cellulose binding domain. It has been surprisingly found that such cross-linked CBD provides flexibility, prevents cellulosic fiber fibrillation, restores tensile strength, prevents the appearance of wrinkles, and increases the hydrophilicity of synthetic fibers as described above. Was. In fact, without being bound by theory, it is believed that each crosslinked CBD also restores tensile strength by adsorbing to the opposite side of the damaged fiber.

[0013] In a third aspect, the invention relates to a fabric care composition comprising the above aspect linked to a softening protein. Without being bound by theory, the addition of the cellulose binding domain to the softening protein results in a higher concentration of the softening protein on the fabric, ie, closer and / or more persistent contact, resulting in more efficient It is thought that it exerts a great activity. The softened protein thus modified has a high affinity (compared to the unmodified softened protein) in binding to cellulose fibers or textiles.

[0014] The fabric care composition described above may further comprise a softening component selected from a cationic surfactant, a transferase enzyme and / or a clay.

Cellulose Binding Domain (CBD) In this context, the term “amino acid sequence containing CBD, cellulose binding domain or CBD” is meant to indicate an amino acid sequence that can bind cellulase to a cellulose substrate (eg, P .Kraulis et al., Determination of the
three-dimensional structure of the C terminal domain of cellobiohydrolas
e I from Trichoderma reesei.A study using nuclear magnetic resonance and
hybrid distance geometry-dynamically simulated annealing (Trichoderma r
Determination of the three-dimensional structure of the C-terminal domain of cellobiohydrolase I from eesei. Nuclear magnetic resonance and hybrid distance geometry-studies using dynamic simulated annealing). As described in Biochemistry, 28: 7241-7257, 1989).
The classification and properties of the cellulose binding domain are described in P. Tomme et al., The symposium “E.
nzymatic degradation of insoluble polysaccharides "" (ACS Symposium Series 618, edited by JNSaddler and MHPenner, A
CS, 1995).

[0016] Cellulose binding (and other carbohydrate binding) domains are typically composed of a catalytic domain containing an active site for substrate hydrolysis and a carbohydrate binding domain for binding to the carbohydrate substrate in question, especially hydrolysis. In an enzyme (hydrolase), a polypeptide amino acid sequence present as an endogenous portion of a large polypeptide or protein consisting of two or more polypeptide amino acid sequence regions.
Such enzymes include two or more catalytic domains and one or two or three carbohydrate binding domains, which may further include one or more polypeptide amino acid sequence regions linking the carbohydrate binding domain to the catalytic domain; The latter type of region is commonly referred to as a "linker."

Examples of hydrolases having a cellulose binding domain are cellulases, xylanases, mannanases, arabinofuranosidases, acetylesterases and chitinases. "Cellulose binding domain" refers to algae such as the red alga Porphyra purpu
rea in the form of a non-hydrolysable polysaccharide-binding protein [P. Tomme et al.
., Cellulose-binding domains-Classification and Properties in Enzymatic Degradation of Insoluble Carbohydrates , John N. Saddler and Michael H.
Penner (Eds.), ACS Symposium Series, No. 618 (1996)]. However,(
Most of the known CBDs (classified and referred to by P. Tomme et al. (Supra) as "cellulose binding domains") are derived from cellulases and xylanases.

In this context, the term “cellulose binding domain” refers to the latter document (P. To
mme et al., supra). P. Tomme et al. Classify more than 120 “cellulose binding domains” into 10 families (IX), which may have different functions or roles with respect to the mechanism of substrate binding. However, it is anticipated that new family examples and additional families will appear in the future.

In proteins / polypeptides where CBD is present (eg, enzymes, typically hydrolases such as cellulases), the CBD is N- and C-terminal or internal. The portion of the polypeptide or protein (eg, hydrolase) that makes up the CBD itself typically consists of about 30 or more and less than about 250 amino acid residues. For example, the CBD listed and classified in Family I by P. Tomme et al (supra) consists of 33-37 amino acid residues, the one listed and classified in Family IIa consists of 95-108 amino acid residues, One listed and classified in VI consists of 85-92 amino acid residues, whereas one CBD listed and classified in Family VII (derived from cellulase from Clostridium thermocellum) consists of 240 amino acid residues. Therefore, the molecular weight of the amino acid sequence constituting CBD itself is typically in the range of about 4 to about 40 kD, usually about 35 kD or less.

The cellulose binding domain is described in H. Stalbrand et al., Applied and Environmental
Microbiology, Mar. 1995, pp. 1090-1097; E. Brun et al., (1995) Eur. J. Biochem.
231, pp. 142-148; JBCoutinho et al., (1992) Molecular Microbiology, 6 (9), p.
It can be made by recombinant techniques as described on pages 1243-1252.

Several genetic engineering approaches can be used to isolate, for example, the cellulose binding domain of cellulase. In one method, a portion of the gene is removed using restriction enzymes, and the remaining gene-vector fragment is then fused in frame to obtain a mutant gene encoding a protein truncated for a particular gene fragment.
In another method, Ba131 is used to systematically delete nucleotides outside the 5 'and 3' ends of DNA or inside restriction gaps in genes.
With the use of exonucleases such as These gene deficiency methods result in a mutant gene encoding a truncated gene molecule whose expression product binds to a substrate (eg,
Cellulose binding) ability is evaluated. Suitable substrates for assessing binding capacity include cellulosic materials such as Avicel ^™ and cotton fiber. Other substances include CBD, such as terminal CB, from the rest of the polypeptide chain of the protein in question.
There is the use of selective or specific proteases that can cleave D.

Once the nucleotide sequence encoding the substrate binding (carbohydrate binding) region has been identified as cDNA or chromosomal DNA, it can be converted to a D-encoding amino acid sequence of interest.
It is manipulated in various ways to fuse it to the NA sequence. DNA fragment encoding carbohydrate-binding amino acid sequence and DNA encoding target amino acid sequence
The sequences are then ligated with or without a linker. The resulting ligated DNA is then manipulated in various ways to drive expression. Preferred microbial expression hosts include certain Aspergillus species (eg, A.niger or A.oryzae), Bacillus species, and organisms such as Escherichia coli or Saccharomyces cerevisiae.

A preferred CBD for the purposes of the present invention is CBD C from Trichoderma reesei.
BHII, CBD from Cellulomonas fimi CenC, CenA and Cex, T
CBD CBHI from richoderma reesei, CBD Cellulozome from Clostridium cellulovorans, CBD E3 from Thermonospora fusca, Clostridium s
tecorarium (NCIMB11754) CBD dimer from XynA, Bacillus agaradheren
s (NCIMB40482), and / or CBD family 45 from Humicola insolens. More preferred CB for the purpose of the present invention
D is CBD CenC from Cellulomonas fimi, Clostridium cellulovorans
CBD from Cellulozome and / or Novo Nordisk A / S under the trade name “Carezy
CBD from the fungus Humicola insolens cellulase sold under "me". C
arezyme has a molecular weight of about 43 kDa and exhibits cellulolytic activity.
ola insolens A family 45 endoglucanase derived from DSM1800.

[0024] The fabric care composition can contain one or more of the above-mentioned CBDs, any of which is cross-linked and / or further linked to a softening protein, and / or a mixture thereof. The crosslinked CBD of the present invention has 2 to 50, preferably 2
Consists of an amino acid sequence containing 10 to 10 cellulose binding domains. The CBD incorporated into the fabric care compositions of the present invention may be from different sources. The CBD linked to the CBD, cross-linked CBD and / or softening protein is present in the fabric care composition of the present invention in an amount of 0.01 to 10% by weight, preferably 0.1 to 6%, in the concentrated fabric care composition. It is usually blended at a level of 0.2-30%, 2-20%.

For example, M. Linder et al., The Journal of Biological Chemistry, Vol. 271, No.
.35, Issue of August, pp. 21268-21272, 1996, the N-terminal CBD of T. reesei CBHII was replaced with the C-terminal CBD of CBHI with a 24 amino acid linker region.
By fusing to BD, a double CBD can be constructed. The linker region is
It contains three amino acid residues from the natural CBHI linker followed by 21 amino acid residues from the natural CBHI linker. The double CBD was cloned and produced in Escherichia coli. The two domains interact when binding to cellulose, resulting in a higher binding affinity than either of the single domains in the dual CBD.
Bring to.

Construction of Double CBD Peptides—All DNA manipulations were performed using standard protocols. The gene construct was first assembled into the vector pSP73 (Promega). The coding region of the Erwinia carotovora pelB signal sequence was fused in frame with the coding region of the first 41 N-terminal residues of CBHII derived from plasmid pTTc9, followed by the last 57 residues of CBHI derived from plasmid pTTcI. Ligation to the coding region. The construct was inserted into the expression vector pKK223-3 containing the isopropyl-β-D-thiogalactopyranoside inducible tac promoter for expression in E. coli. The nucleotide sequence of the final construct was confirmed by sequencing.

[0027] Fermentation-E. coli culture producing double CBD was prepared using a 1.5 liter working volume
Performed in a CMF experimental fermentor. The pH of 7 was maintained during the fermentation, and the agitation speed was adjusted to maintain a constant dissolved oxygen level. During the exponential growth phase (15-20 h after inoculation
), Isopropyl-β-D-thiogalactopyranoside was added to a final concentration of 0.5 mM to induce gene expression. Fermentation continued until the maximum level of product was reached (20-30 h).

Purification of double CBD-centrifugation of the culture supernatant (10,000 rpm, 45 min)
Mix with an equal volume of 20 mM phosphate buffer pH 8.0 containing 1.5 M ammonium sulfate and keep at 4 ° C. overnight. The sediment was removed by centrifugation as above and the supernatant was
. Filtered through a 45 μm Durapore (Millipore Corp.) membrane. The clarified supernatant was then applied to a butyl-Sepharose 4B column (Pharmacia Biotech Inc.) that had been equilibrated with 10 mM phosphate buffer, pH 8.0, containing 0.75 M ammonium sulfate. The column is then washed with equilibration buffer and the bound proteins are
. Eluted with 10 mM phosphate buffer. Milli-Q elution peak fraction
Source RPC column (Pharmac) equilibrated with water: trichloroacetic acid (1000: 1)
ia). The bound peptide was converted to acetonitrile: trichloroacetic acid (1000
: 1) eluted with increasing linear gradient. The purified peptide was then lyophilized. During all purification steps, double CBD was identified by the monoclonal antibody CI-89 specific for CBHI CBD. All chromatography steps were performed on a high performance protein liquid chromatography (Pharmacia) system.

Proteolytic Cleavage-Lyophilized peptides were prepared using 100 mM Tris pH 8.2.
s buffer (2 mg / ml) and 10 units of immobilized trypsin (Sigma T-401).
9) was added per mg peptide. The suspension was incubated at 37 ° C. overnight, purified by chromatography on Source RPC medium (see above) and then lyophilized. The cleavage products were characterized and identified by amino acid analysis and MALDI-MS.

CBD Peptide Analysis Technique—Purity control and quantification of CBD peptide were performed by RP-HPLC. Pro-PepVydac C18 analytical column with water: trichloroacetic acid (
Used for linear elution from 1000: 1) to acetonitrile: trichloroacetic acid (1000: 1). The absorbance at 225 nm was used for detection. Quantitation of peptides in culture supernatants was also possible with this technique.

Production and Purification of Double CBD—The amino acid sequence of the processed form of double CBD is shown in FIG. 1 (M. Linder et al., The Journal of Biological Chemistry, Vol.
5, Issue of August, pp. 21268-21272, 1996). In fermenter culture of E. coli WCM105 strain, 60-80 mg / liter of peptide was secreted into the medium,
50 mg / l of pure peptide was obtained (see FIG. 2-M. Linder et al., The Jour
nal of Biological Chemistry, Vol.271, No.35, Issue of August, pp.21268-21272
, 1996). Identification and accurate processing of the peptide were performed by amino acid composition analysis. Peptide identification was performed by Western blotting using a monoclonal antibody specific to CBHI CBD.

[0032] The fabric care composition can also include the above amino acid sequences further linked to a softening protein. It has been found that the enzyme protein has unexpectedly high adsorptivity to cellulose fibers (EP687729). The enzyme protein used in the present invention is comprehensively defined as a class of proteins having a specific structure for catalysis. In other words, all proteins that have a structure for catalysis can be used with or without catalysis. However, enzyme proteins suitable for the purposes of the present invention are inactive. Inactivation can occur, for example, by inhibition, for example, by distortion of the three-dimensional structure by thermal or chemical means. Even if a protein other than the enzyme protein is used, the effect of the present invention can be obtained to some extent, but a sufficient effect cannot be obtained. Enzyme proteins have different biological origins: animal, plant and microbial origin. Enzyme proteins of any origin can be used in the present invention.

When classified based on the type of enzyme reaction, such enzyme proteins include hydrolases, lyases, oxidoreductases, ligases, transferases and isomerases, all of which can be used in the present invention. Glucosidases such as hydrolases, cellulases and amylases exemplified by proteases (peptidases) and esterases such as lipases are preferred.

[0034] The molecular weight of the enzyme protein is preferably 10,000 or more, more preferably 2 or more.
It is in the range of 000 to 300,000. When the molecular weight is 10,000 or more,
Some enzyme proteins cannot penetrate cellulosic fibers such as natural cellulose fibers and monofilaments / monofilaments (lamella structure) of rayon. Moreover, they do not penetrate the synthetic fiber monofilaments, because the internal structure of the monofilaments is dense. Therefore, the enzyme adsorption site of the cellulose fiber and the synthetic fiber is limited to the surface of the single fiber / monofilament. Preferably, the softening enzyme protein is selected from inactive enzymes that include CBD in nature, such as cellulase, xylanase, mannanase, arabinofuranosidase, acetylesterase and chitinase.

JP 01280079 describes another type of softening protein that can be used in the fabric care compositions of the present invention. These softening proteins are polyamino acid resin solutions that adhere to synthetic, semi-synthetic or cotton fabrics, and thus exhibit flexibility. These polyamino acids are preferably α-amino acids, such as glutamic acid, glycine, ornithine, mono- or copolymers, such as poly-γ-
L-glutamate.

Suitable for the present invention are C18 alkyl quaternary wheat protein derivatives sold under the trade name Coltide HQS by Croda Colloids Ltd. Usually 0.04-0.
Contained at a level of 2% by weight, these wheat protein derivatives exert a great conditioning effect, i.e. a great feel and flexibility, prevent fiber damage of cotton and wool fabrics, smoothen the wool fibers. It is known to increase.

[0037] comprising one or more CBDs and / or further linked to a softening protein (
(Referred to as CBD hybrids and / or softening protein hybrids)
Such amino acid sequences can be prepared and purified by methods known in the art [eg, WO90 / 00609, WO94 / 24158 and WO95 / 16.
782, and Greenwood et al., Biotechnology and Bioengineering , 44 (1994).
pp.1295-1305]. The preparation of enzyme hybrids is described in WO 91/10732, in which the core region derived from Bacillus NICB 40250 endoglucanase is combined with CBD derived from another cellulase enzyme or derived from another cellulase enzyme. Novel derivatives of cellulase enzymes have been constructed that combine the core region with CBD derived from Bacillus NICB 40250 endoglucanase. WO 95/16782 describes the combination of different core regions with several CBDs in Trichoderma longibrachiatum and the cloning and high-level expression of these novel truncated cellulase proteins or derivatives thereof.

[0038] CBD hybrids and / or softening protein hybrids can be used, for example, for a cellulose binding domain linked with or without a linker to other cellulose binding domains and / or DNA sequences encoding a softening protein of interest. It is produced by introducing a DNA construct at least composed of a fragment of the encoding DNA into a host cell, growing the transformed host cell, and expressing the fusion gene. The result thus obtained-commonly referred to in the art as "fusion protein"-is not limited to one related type of recombinant product (CB
D hybrids and / or softening protein hybrids) are described by one of the following general formulas: A-CBD-MR-XB A-X-MR-CBD-B An amino acid sequence containing the cellulose binding domain (CBD) itself; the MR (intermediate region; connecting region) can be bound or
It may be a linking group consisting of about 100 amino acid residues, especially 2 to 40 amino acid residues, for example 2 to 15 amino acid residues. The MR may in principle be a non-amino acid linker instead (see below). X is an amino acid sequence containing another cellulose binding domain and / or D encoding a softening protein of interest.
An amino acid sequence containing the above-mentioned inactive sequence of the amino acid residue of the polypeptide encoded by the NA sequence. Parts A and B are independently optional. When present, moiety A or B constitutes a terminal extension of the CBD or X moiety,
It usually contains one or more amino acid residues.

Thus, it will be clear from the above, in particular, that the CBD in the softening protein hybrid of the type in question is located C-terminal, N-terminal or inside the softening protein hybrid. Similarly, the X portion of the softening protein hybrid of the type in question is located at the N-terminus, C-terminus or inside of the softening protein hybrid.

The softening protein hybrids of interest in the context of the present invention include, for example, two or more C
Softened protein hybrids with two or more CBDs are either linked directly to each other or separated from each other by a spacer or linker sequence (typically consisting of a sequence of amino acid residues of appropriate length). is there. The two CBDs in a softening protein hybrid of the type in question may be separated from each other, for example by an -MR-X- moiety as described above. One or more cellulose binding domains may be linked to the N-terminal and / or C-terminal portion of the cellulase core region. Any part of the CBD can be selected, modified, trimmed, etc.

Preferably, care is taken in the construction of CBD hybrids and / or softening protein hybrids of the type in question with regard to stability against proteolysis. Two- and multi-domain proteins are particularly susceptible to proteolytic cleavage of the linker region connecting the domains. Proteases that cause such cleavage include, for example, subtilisin, which is well known to exhibit broad substrate specificity [eg, Gron et al., Biochemistry , 31 (1992), pp. 6011-6018; Teplyako
v et al., Protein Engineering , 5 (1992), pp. 413-420]. Glycosylation of linker residues in eukaryotes is one natural way to prevent proteolysis. Another is to use amino acids that are less preferred by peripheral proteases. The length of the linker also plays a role related to accessibility by the protease. Which “solution” is best depends on the environment in which the softening protein hybrid should function. When constructing new CBD hybrid and / or softening protein hybrid molecules, attention is preferably paid to linker stability.

Plasmids Methods for producing plasmids capable of expressing fusion proteins having amino acid sequences derived from fragments of two or more polypeptides are well known in the art (eg, WO
90/00609 and WO 95/16782). The expression cassette may be introduced into a replication system for episomal maintenance in a suitable cellular host, or may be provided without a replication system and integrate it into the host genome. The DNA may be introduced into a host according to known techniques such as transformation, microinjection and the like.

Once the fusion gene has been introduced into a suitable host, the host is propagated to express the fusion gene. Usually, it is further desirable to add a signal sequence that allows secretion of the fusion gene. Typical examples of useful genes are: 1) signal sequence-(propeptide)-carbohydrate binding domain-linker-
CBD and / or softening protein sequence of interest, or 2) signal sequence-(propeptide)-softening protein sequence of CBD and / or interest-linker-carbohydrate binding domain, wherein the propeptide sequence is usually 5 -100, for example, 5-25 amino acid residues. The recombinant product may be glycosylated or non-glycosylated.

The term connecting region "linker", "connecting region" or "intermediate region-MR" refers to CBD
Adjacent to a CBD or a region linking it to the amino acid sequence of another softening protein. When present, this ligation can be performed chemically or by recombinant techniques.

Examples of recombinant techniques describing the expression of enzymes with CBD of different origin include
S. Karita et al., (1996) Journal of Fermentation and Bioengineering, Vol. 81
, No. 6, pp. 553-556. A preferred connecting region is an amino acid connecting region (peptide), some examples of which are described in N, R. Gilkes et al., Microbiol. Rev. 55, 1991, pp.
.303-315. The connecting region is from 1 to about 100 amino acid residues, especially from 2 to
It consists of 40 amino acid residues, for example 2 to 15 amino acid residues. As described above,
It is preferable to use amino acids that are less preferred by peripheral proteases. Suitable amino acid linking regions are Humicola insolens family 45 cellulase linker, Klebs
NifA gene of iella pneumoniae-CiP linker, E. coli OmpA gene-
CiP linker, E3 cellulase Thermonospora fusca linker and CenA
Cellulase linkers, preferably Humicola insolens family 45 cellulase linkers and E3 cellulase Thermonospora fusca linker.

Non-amino acid / protein compounds, also referred to as “non-amino acids”, can also be used to link catalytically active amino acid sequences to CBD: 1) Suitable non-amino acid linking regions can be found in Shearwater polymers, Inc., January 1996.
Polyethylene glycol derivatives described in catalogs such as nucleophilic PEG, carboxyl PEG, electrophilic activated PEG, sulfhydryl selective PEG, heterofunctional PEG, biotin PEG, vinyl derivatives, PEG silane and PEG phospholipid. In particular, suitable non-amino acid linking regions include heterofunctional PEG, Shearw
(X-PEG-Y) polymers from ater, such as PEG (NPC) 2, PEG-
(NH2) 2, t-BOC-NH-PEG-NH2, t-BOC-NH-PEG
-CO2NHS, OH-PEG-NH-tBOC, FMOC-NH-PEG-C
O2NHS or PEG (NPC) ₂ , MW3400 from Sigma, glutardialdehyde in water 50% solution from Aldrich, disuccinimidyl suberate (DSS) from Sigma, γ-maleimidobutyric acid N-hydroxysuccinimide ester from Sigma (GMBS), 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) from Sigma and dimethylsuberimidate hydrochloride (DMS) from Sigma. 2) Other suitable non-amino acid linking regions are 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, N-ethyl-5-phenylisoxazolium-3-
Sulfonate, 1-cyclohexyl-3- (2-morpholinoethyl) carbodidomet-p-toluenesulfonate, N-ethoxycarbonyl-2-ethoxy-1
, 2-dihydroquinoline or glutaraldehyde. 3) Crosslinkers described under the heading "Crosslinking reagents" in the Pierce Company's 1999/2000 Pierce Products Catalog: SMPH, SMCC, LC-SM
Also suitable are CC compounds, preferably Sulfo-KMUS compounds. Preferred chemical linking regions are PEG (NPC) 2, (NH2) from Shearwater
2-PEG, t-BOC-NH-PEG-NH2, MAL-PEG-NHS, V
S-PEG-NHS polymer and / or Sulfo-KMUS compound from Pierce.

Fabric Care and Detergent Ingredients Preferably, the fabric care compositions of the present invention include at least one additional fabric care ingredient. The exact nature of these additional components, and their level of incorporation, will depend on the physical form of the composition and the nature of the cleaning operation in which it is used. The composition may include optional ingredients, such as a dye fixative, a fabric softener compound, and other optional ingredients. The fabric care composition of the present invention preferably further comprises a fabric care component selected from a cationic surfactant, a transferase enzyme and / or a clay. The compositions of the present invention can be used in stand-alone products, including pre- or post-cleaning additives. that is,
Complete formulation compositions, including laundry compositions, as well as fabric softener and dryer additive compositions that provide a rinse and / or antistatic effect (e.g.,
Sheet), and a rinse liquid additive composition.

Cationic Softener The fabric care composition of the present invention preferably further comprises a cationic surfactant.
The fabric care compositions of the present invention, further comprising a cationic surfactant, provide improved fabric flexibility, impart improved tensile strength, anti-wrinkle, anti-pilling and anti-shrink properties to the fabric, refresh or It has been surprisingly found that it recovers and provides improved static control, color appearance and fabric abrasion resistance properties and effects. Typical examples of cationic softening components are quaternary ammonium compounds or their amine precursors as described below.

Quaternary Ammonium Fabric Softening Active Compound (1) Preferred quaternary ammonium fabric softening active compounds have the formula:

Embedded image Or the following formula:

Embedded image Wherein Q is a functional unit having the formula:

Embedded imageEach R unit is independently hydrogen, C₁-C₆Alkyl, C₁-C₆Hydroxyalkyl
And mixtures thereof, preferably methyl or hydroxyalkyl;
R¹The units are independently linear or branched C₁₁-C₂₂Alkyl, straight or branched C ₁₁ -C₂₂Alkenyl, and mixtures thereof;²Is hydrogen, C₁-C ₄ Alkyl, C₁-C₄Hydroxyalkyl and mixtures thereof; X is
Anion compatible with fabric softeners and auxiliary ingredients; index m is 1
The index n is 1-4, preferably 2.

An example of a preferred fabric softener is a mixture of quaternized amines having the formula:

Embedded image Wherein R is preferably methyl; R ¹ is a straight or branched alkyl or alkenyl chain having at least 11 atoms, preferably at least 15 atoms. In the example fabric softener described above, the unit -R ¹ represents a fatty alkyl or alkenyl unit typically derived from a triglyceride source. The triglyceride source is preferably tallow, partially hydrogenated tallow, lard, partially hydrogenated lard, vegetable oil and / or partially hydrogenated vegetable oil such as canola oil, safflower oil, peanut oil, sunflower oil, corn oil, It is derived from soybean oil, tall oil, rice bran oil and the like, and mixtures of these oils.

A preferred fabric softening activator of the present invention is a diester and / or diamide quaternary ammonium (DEQA) compound, wherein the diester and diamide have the formula:

Embedded image Wherein R, R ¹ , X and n are as described above for formulas (1) and (2); Q has the following formula:

Embedded image These preferred fabric softening activators are formed from the reaction of an amine with a fatty acyl unit to form an amine intermediate having the formula: R—N — [(CH ₂ ) _n —Q—R ¹ —] ₂ (where R is preferably methyl, Q and R ¹ are as defined above),
It is then quaternized to the final softener.

[0052] Non-limiting examples of preferred amines used to form the DEQA fabric softening activators according to the present invention include methyl bis (2-hydroxyethyl) amine having the formula:

Embedded image Methyl bis (2-hydroxypropyl) amine having the formula:

Embedded image Methyl (3-aminopropyl) (2-hydroxyethyl) amine having the formula:

Embedded image Methyl bis (2-aminoethyl) amine having the formula:

Embedded image Triethanolamine having the formula:

Embedded image Di (2-aminoethyl) ethanolamine having the formula:

Embedded image There is.

The X ⁽⁻⁾ of the counterion is a softener-compatible anion, preferably a strong acid such as chloride, bromide, methylsulfate, ethylsulfate, sulfuric acid, nitric acid, and more preferably anion of chloride or methylsulfate. The anion is less preferred, but may be divalent, in which case X ^(-) represents half of the group.

Tallow and canola oil are convenient and inexpensive sources of fatty acyl units suitable for use in the present invention as R ¹ units. The following are non-limiting examples of quaternary ammonium compounds suitable for use in the compositions of the present invention. The term "tallowoil" as used below,
R ¹ units are derived from tallow triglyceride source, indicating that a mixture of fatty alkyl or alkenyl units. Similarly, the use of the term canolyl relates to a mixture of fatty alkyl or alkenyl units derived from canola oil.

The table below gives non-limiting examples of suitable fabric softeners according to the above formula. In this list, the term "oxy" refers to -CO- units, while the term "oxo" refers to -O- units. Table II Fabric softeners N, N-di (tallowyloxy-2-oxoethyl) -N-methyl, N- (2
-Hydroxyethyl) ammonium chloride N, N-di (canolyloxy-2-oxoethyl) -N-methyl, N- (2-
(Hydroxyethyl) ammonium chloride N, N-di (tallowyloxy-2-oxoethyl) -N, N-dimethylammonium chloride N, N-di (canolyloxy-2-oxoethyl) -N, N-dimethylammonium chloride N, N , N-Tri (tallowyloxy-2-oxoethyl) -N-methylammonium chloride N, N, N-tri (canolyloxy-2-oxoethyl) -N-methylammonium chloride N- (tallowyloxy-2-oxoethyl) -N- (Taroyl) -N, N
-Dimethylammonium chloride N- (canolyloxy-2-oxoethyl) -N- (canolyl) -N, N-dimethylammonium chloride 1,2-di (tallowyloxyoxo) -3-N, N, N-trimethylammonio Propane chloride 1,2-di (canolyloxyoxo) -3-N, N, N-trimethylammoniopropane chloride and mixtures of the above active agents

Another example of a quaternary ammonium flexible compound is methylbis (tallowamidoethyl) (
2-hydroxyethyl) ammonium methylsulfate and methyl bis (hydrogenated tallow amide ethyl) (a 2-hydroxyethyl) ammonium methylsulfate, each trade name these substances Varisoft ^R 222 and Varisoft ^R 110
And commercially available from Witco Chemical Company. Particularly preferred are N, N-di (tallowyloxy-2-oxoethyl) -N
-Methyl, N- (2-hydroxyethyl) ammonium chloride, the tallow chain of which is at least partially unsaturated.

Transferase Enzyme The fabric care composition of the present invention preferably further comprises a transferase enzyme.
The fabric care composition of the present invention further comprising a transferase enzyme provides improved fabric flexibility, imparts improved tensile strength, anti-wrinkle, anti-pilling and anti-shrink properties to the fabric, refreshes or restores, It has been surprisingly found to provide improved static control, color appearance and fabric abrasion resistance properties and effects.

[0058] Transferase enzymes catalyze the transfer of a functional compound to a substrate. In particular, the transferases of the present invention have the ability to transfer chemical moieties, such as methyl or glycosyl groups, from small substrates to form oligomer molecules or extend polymer compounds. When using small substrates,
The enzymes are methyl, hydroxymethyl, formyl, carboxyl, aldehyde,
Binds to functional groups such as ketone, acyl, amino and phosphorus functions, and / or
Alternatively, the properties of clothing are improved by transferring glycosyl residues to the clothing surface.

Without being bound by theory, aminoacyltransferases of the IUPAC classification EC 2.3.2 bind amino acids of CBD, cross-linked CBD, amino acid connecting regions and / or softening proteins to cotton fibers of the fabric, and It is considered to have added, renewed or restored strength. In addition, glycosyltransferases of IUPAC classification EC2.4 provide glycosyl carbohydrates found in CBDs, cross-linked CBDs, amino acid linking regions and / or softening proteins to fabrics for covalent attachment to impart tensile strength and refresh. Or it is thought to recover.

An aminoacyltransferase (EC 2.3.2) is an enzyme that transfers an amino group, usually an amino acid, from a donor to an acceptor. Even more preferred is protein-glutamine γ-glutamyltransferase (EC 2.3.2.13), also commercially available under the name transglutaminase.

A general property of glycosyltransferases is to transfer a sugar from an oligosaccharide to another carbohydrate as an acceptor. Both hexosyltransferase and pentosyltransferase can be used in the present invention. Examples of suitable glycosyltransferases are galactosyltransferases and fructosyltransferases, such as 1,4-β-galactosyltransferase, 1,3-α-fructosyltransferase, 2,3-sialyltransferase, cyclodextrin glycosyltransferase,
N-acetylglucose or galactosaminyltransferase. Of particular interest are the EC 2.4.4.124 1,4-α-D-glucans: 1,
4-α-D-glucan (D-glucose) 6-α-D-glucosyltransferase. A specific example of this enzyme is commercially available under the name Transglucosidase L-500.

In addition to the glycosyltransferases described above, mutant glycosyltransferases and / or glycosidases (examples include SGWithers Protein Eng.Ne
t. Canada PCT Application Publication No. WO 97/21822) improves the tensile strength and appearance of fabrics, for example, reduces fabric wrinkles, enhances shape retention,
It has been found to reduce shrinkage.

Another enzyme of particular interest is the cyclomaltodextrin glucanotransferase (“CGTase”) (EC 2.4.1.19) commercially available from Amano and Novo Nordisk A / S. Yet another group of enzymes of particular interest is glucansucrase, of which dextransucrase (EC 2.4.1.5) is an example of a glycosyltransferase. Other glucansucrases suitable for use in the compositions described herein include, but are not limited to, various dextransuclases, alternan sucrase and levansucrase. Levansucrase is commercially available from Genencor.

[0064] These transferases are preferably present in 0.0001 to 10% of the total composition.
% By weight, more preferably 0.0005 to 5%, most preferably 0.001 to 1%
At a pure enzyme level in the fabric care composition according to the present invention.

[0065] The enzymes described above may be of any suitable origin, such as plant, animal, bacterial, fungal and yeast sources. The origin may also be mesophilic or extremophilic (cryophilic, eutrophic, thermophilic, barophilic, alkaline, acidophilic, halophilic, etc.). Purified or unpurified forms of these enzymes may also be used. At present, it is customary to modify wild-type enzymes by protein / genetic engineering techniques to maximize performance efficacy with the fabric care compositions of the present invention. For example, variants are designed to increase the compatibility of the enzyme with the common components of such compositions. On the other hand, variants may be designed such that the optimal pH, bleach and / or chelant stability, catalytic activity, etc. of the enzyme variant are adjusted to suit a particular fabric conditioning and / or cleaning application.

In particular, attention should be paid to amino acids that are susceptible to oxidation in terms of bleach stability and surface charge in terms of surfactant compatibility. The isoelectric point of such enzymes may be modified by substitution of some charged amino acids, for example, increasing the isoelectric point helps to improve compatibility with anionic surfactants. Enzyme stability can be further enhanced, for example, by forming additional salt bridges and reinforcing calcium binding sites to increase the stability of the chelants.

Color Care and Fabric Care Effects Technologies that exert a type of color care effect can also be included. Examples of these technologies are metal catalysts for color maintenance. Such metal catalysts are described in co-pending European Patent Application No. 92870181.2. Dye fixing agent, polyolefin dispersant for preventing wrinkles and improving water absorption, fragrance,
Amino-functional polymer for color care treatment and perfume continuation (PCT / US97 /
16546) is another example of a color care / fabric care technology and is described in 1996.
Co-pending patent application No. 96870140.9, filed Nov. 7, 2016.

[0068] Fabric softeners can also be incorporated into the fabric care compositions according to the present invention. These agents may be inorganic or organic in type. The inorganic softener is GB-A-1,400,898
And the smectite clay disclosed in US Pat. No. 5,019,292. Organic fabric softeners include GB-A1,514,276 and EP-B0,0
Water-insoluble tertiary amines such as those disclosed in EP 11,340, EP-B-0,026
527 and mono-C ₁₂ -C ₁₄ quaternary ammonium salts disclosed in EP-B-0,026,528 and combinations thereof, and dilong chains as disclosed in EP-B-0,242,919 There are amides. Other useful organic components of the fabric softening system include high molecular weight polyethylene oxide materials such as those disclosed in EP-A-0,299,575 and 0,313,146.

[0069] Preferably, the fabric care compositions of the present invention comprise a clay. The fabric care composition of the present invention further comprising clay provides improved fabric flexibility, imparts improved tensile strength, anti-wrinkle, anti-pilling and anti-shrink properties to the fabric, refreshes or restores,
It has been surprisingly found to provide improved static control, color appearance and fabric abrasion resistance properties and effects.

The level of smectite clay is usually 2 to 20% by weight, more preferably 5 to 15%.
% Range. Organic fabric softeners such as water-insoluble tertiary amines or dilong chain amide materials are incorporated at levels of 0.5 to 5% by weight, usually 1 to 3% by weight, and include high molecular weight polyethylene oxide materials and water soluble cationic The substance is added at a level of 0.1 to 2% by weight, usually 0.15 to 1.5%.

Dye Fixer The compositions of the present invention may optionally also contain a dye fixer. Dye fixatives or "fixers" are well-known commercial materials and are designed to improve the appearance of colored fabrics by minimizing the release of dye from the fabric upon washing. Components that are fabric softeners, or those described above as amino-functional polymers, are not included within this definition.

Many dye fixatives are cationic and are based on various quaternized or otherwise positively charged organic nitrogen compounds. Cationic fixatives are commercially available from several vendors under various trade names. Representative examples include Crossfield to CROS
COLOR PMF (July 1981, Code No. 7894) and CROSCOLOR NOFF (1988
January, Code No.8544); INDOSOL E-50 from Sandoz (February 27, 1984, Re
f.No. 6008.35.84; polyethylene amine base); SANDOFIX TPS, also commercially available from Sandoz, which are the preferred polycationic fixatives for use herein, and SAND
OFIX SWE (cationic resin compound); CHT-Beitlich GMBH to REWIN SRF, REWIN
SRF-O and REWIN DWR; commercially available from Ciba-Geigy Tinofix ^R ECO, Tinof
ix ^R FRD and Solfin ^R.

Another cationic dye fixative is “Aftertreatments for improving the fastness”
of dyes on textile fibres ”, Christopher C. Cook (REV.PROG.COLORATION, Vol.
12,1982). Dye fixatives suitable for use in the present invention include ammonium compounds such as fatty acid-diamine condensates, such as hydrochloric acid, acetic acid, methosulfate and benzyl hydrochloride of oleyldiethylaminoethylamide, oleylmethyldiethylenediaminemethosulfate, monostearyl- Oxidation products of ethylenediaminotrimethylammonium methosulfate and tertiary amines; derivatives of polymeric alkyldiamines, polyamine-cyanuric chloride condensates and aminated glycerol dichlorohydrin.

The typical amount of dye fixative used in the composition of the present invention is preferably 90% of the composition.
% By weight, preferably within 50% by weight, more preferably 0.001 to 10% by weight, most preferably 0.5 to 5% by weight.

Fabric Soft Compounds Typical loading levels of soft compounds in a fabric care composition are from 1 to 8 of the composition.
0% by weight, preferably 5-75%, more preferably 15-70%, even more preferably 19-65%. The fabric softener compound is preferably selected from cationic, nonionic, amphoteric or anionic fabric softening components. Typical examples of cationic softening components are quaternary ammonium compounds or amine precursors thereof as described below.

Quaternary Ammonium Fabric Softening Active Compound As mentioned above, the fabric care compositions of the present invention preferably further comprise a cationic surfactant.

Amine Fabric Softening Active Compounds The amine fabric softening compounds suitable for use herein, which are in amine or cationic form, are selected from: (i) from hydroxyalkylalkylenediamines, dialkylenetriamines and mixtures thereof. A reaction product of a polyamine and a higher fatty acid selected from the group consisting of: These reaction products are mixtures of several compounds in view of the polyfunctional structure of the polyamine. Preferred component (i) is a nitrogen-containing compound selected from the group consisting of reaction product mixtures or partially selected components of the mixture.

One preferred component (i) is a compound selected from the group consisting of substituted imidazoline compounds having the formula:

Embedded image In the above formula, R ⁷ is an acyclic aliphatic C ₁₅ -C ₂₁ hydrocarbon group, and R ⁸ is a divalent C ₁ -C ₃ alkylene group. Component (i) materials of Mazer Chemicals Sales Mazamide ^R 6 or Sandoz Colors
& Chemicals sales of Ceranine ^R HC; Alkaril Chemicals, trade name Alkazi from Inc.
. ne ^R ST or Scher Chemicals, Inc from Schercozolone ^{R S} Stearyl hydroxyethyl sold under imidazoline; N, N "- ditallow alkoyl diethylenetriamine; in 1-tallow amido ethyl-2-tallow imidazoline (previous structure, R ¹ Is an aliphatic C ₁₅ -C ₁₇ hydrocarbon group and R ⁸ is a divalent ethylene group).

Certain component (i) may be initially dispersed in a Bronsted acid dispersing aid having a pKa value of about 4 or less, but the pH of the final composition should be about 6 or less. Some preferred dispersing aids are hydrochloric, phosphoric or methyl sulfonic acids.

N, N ″ -Ditallowalcoyldiethylenetriamine and 1-tallow (amidoethyl) -2-tallowimidazoline are both reaction products of tallow fatty acids and diethylenetriamine and are cationic fabric softeners methyl-1-tallowamide It is a precursor of ethyl-2-tallowimidazolinium methyl sulfate ("Ca
tionic Surface Active Agents as Fabric Softeners ”, RREgan, Journal of t
he American Oil Chemical's Society, January 1978, pages 118-121). N
, N "-ditalycoyldiethylenetriamine and 1-tallowamidoethyl-2-tallowimidazoline are obtained from Witco Chemical Company as experimental compounds. Methyl-1-tallowamidoethyl-2-tallowimidazolinium methyl sulfate is sold by Witco Chemical Company under the trade name Varisoft ^R 475.

(Ii) softener having the formula:

Embedded image Wherein each R ² is a C _1-6 alkylene group, preferably an ethylene group; G is an oxygen atom or a —NR— group; each R, R ¹ , R ² and R ⁵ has the previously defined definition ; a ^- the X ^- has the been defined for. An example of compound (ii) is 1-oleylamidoethyl-2-oleylimidazolinium chloride, R ¹ is an acyclic aliphatic C ₁₅ -C ₁₇ hydrocarbon group, R ² is an ethylene group, G is an NH group, R ⁵ is a methyl group, and A ⁻ is a chloride anion.

(Iii) softener having the formula:

Embedded image In the above formula, R, R ¹ , R ² and A ⁻ are as described above. Examples of compound (iii) are compounds having the formula:

Embedded image In the above formula, R ¹ is derived from oleic acid.

Additional fabric softeners useful herein are described in Toan Trinh, Errol H. Wahl, Donald M. Swart
US Patent 4,661,269 issued April 28, 1987 under the name of ley and Ronald L. Hemingway; Burns US Patent 4,439,335 issued March 27, 1984; Edwards and Diehl US Patent 3,861,870; Cambr
e, 4,308,151; Bernardino, 3,886,075; Davis, 4,233
Verbruggen 4,401,578; Wiersema and Rieke 3,974.
, 076; Rudkin, Clint and Young, 4,237, 016; and Yamamura et al., European Patent Application Publication 472,178, the entire contents of which are incorporated herein by reference.

Of course, the term “softening active” can also include mixed softening actives. Preferred among the classes of softener compounds described above are diester or diamide quaternary ammonium fabric softening active compounds (DEQA). The fully formulated fabric care composition may contain, in addition to the above components, one or more of the following components.

Liquid Carrier Another optional but preferred component is a liquid carrier. The liquid carrier used in the composition is preferably at least predominantly water because of its low cost, relatively easy availability, safety and environmental compatibility. The level of water in the liquid carrier is preferably at least 50% by weight of the carrier, most preferably at least 60%
It is. Mixtures of water with low molecular weight, eg, <200, organic solvents, eg, lower alcohols such as ethanol, propanol, isopropanol or butanol, are also useful as carrier liquids. For low molecular weight alcohols, monohydric and dihydric (
Glycol, etc.), trivalent (glycerol, etc.) and higher polyvalent (polyols)
There is alcohol.

Additional Solvents The compositions of the present invention may include one or more solvents that increase the ease of formulation. All of these formulation facilitating solvents are disclosed in WO 97/03169. This is especially the case when formulating liquid transparent fabric softening compositions. When used, the formulation facilitating solvent system preferably comprises less than about 40% by weight of the composition, preferably about 10 to about 35%, more preferably about 12 to about 25%, even more preferably about 14 to about 25%. 20
%. The formulation facilitating solvent is selected to provide a low viscosity to the final composition with minimal solvent odor impact in the composition. For example, isopropyl alcohol is not very effective and has a strong odor. n-Propyl alcohol is more effective but also has a unique odor. Some butyl alcohols also have an odor, but can be used for effective clarity / stability, especially when used as part of a formulation facilitating solvent system to minimize their odor. The alcohols were also selected for best low temperature stability, i.e., they were about 40 ° F (about 4.
(4 ° C.), a translucent, preferably transparent liquid of low viscosity that is acceptable to form a composition that is recoverable after storage down to about 20 ° F. (about −6.7 ° C.). be able to.

The suitability of a formulation facilitating solvent for the formulation of a liquid, concentrated, preferably transparent fabric softener composition with essential stability is surprisingly selective. Suitable solvents may be selected based on their octanol / water partition coefficient (P) as defined in WO 97/03169. Here, the formulation facilitating solvent is about 0.15 to about 0.64, preferably about 0.25 to about
Selected from those having a ClogP of about 0.62, more preferably about 0.40 to about 0.60, wherein the formulation facilitating solvent is preferably at least somewhat asymmetric,
It preferably has a melting point or freezing point that becomes liquid at or near room temperature. Solvents having a low molecular weight and being biodegradable are also desirable for some purposes. Asymmetric solvents seem to be much more desirable, while 1,1 with a center of symmetry
Highly symmetric solvents such as 7-heptanediol or 1,4-bis (hydroxymethyl) cyclohexane, when used alone, even if their Clos
Even if the gP value falls within the preferred range, it does not seem to be able to provide an essentially transparent composition.

The most preferred formulation facilitating solvent can be identified by the appearance of softener vesicles, as seen from cryogenic electron microscopy of the composition diluted to the concentration used for rinsing. These dilute compositions appear to have more dispersibility of fabric softeners that exhibit a single lamellar appearance than conventional fabric softener compositions. The closer the appearance is to a single lamella, the better the composition will perform. These compositions exhibit surprisingly good fabric softness as compared to similar compositions made in the conventional manner with similar fabric softening activators.

Useful formulation facilitating solvents having ClogP values that fall within the required range are disclosed and listed below. These include monool, C6 diol, C7 diol, octanediol isomer, butanediol derivative, trimethylpentanediol isomer, ethylmethylpentanediol isomer, propylpentanediol isomer, dimethylhexanediol isomer, ethylhexanediol Isomer, methylheptanediol isomer, octanediol isomer, nonanediol isomer,
Alkyl glyceryl ethers, di (hydroxyalkyl) ethers, aryl glyceryl ethers, aromatic glyceryl ethers, alicyclic diols and derivatives,
C ₃ C ₇ diol alkoxylated derivatives, aromatic diols, and unsaturated diols. Particularly preferred formulation facilitating solvents are 1,2-hexanediol and 2
Hexanediols such as -ethyl-1,3-hexanediol, 2,2,4
Pentanediols such as -trimethyl-1,3-pentanediol.

Dispersing Aids A relatively concentrated composition containing both saturated and unsaturated diester quaternary ammonium compounds which is stable without the addition of a concentration aid can be produced. However, the compositions of the present invention may require organic and / or inorganic thickening auxiliaries to achieve higher concentrations and / or meet higher stability standards, depending on the other ingredients. There is. These thickening aids, which are typical viscosity modifiers, are required or preferred to ensure stability under extreme conditions where special soft activator levels are used. Surfactant concentration aids typically include (1) single long chain alkyl cationic surfactants, (2) nonionic surfactants, (3) amine oxides, (4) fatty acids and (5) Are selected from the group consisting of: These auxiliaries are described in WO 94/20597, in particular from page 14, line 12 to page 20, page 1.
It is described in the second line, which is incorporated herein by reference.

When the above dispersing aids are present, their total level is from 2 to 25% by weight of the composition, preferably 3 to 17%, more preferably 4 to 15%, even more preferably 5 to 13%.
%. These materials, such as mono-long chain alkyl cationic surfactants and / or fatty acids, which are the reactants used to form the biodegradable fabric softeners as described above, are used in the active softener raw material (I). Added as part or as a separate component. The total level of dispersing aid also includes the amount present as part of component (I).

Inorganic viscosity / dispersibility control agents that act like or enhance the effect of surfactant concentration aids are water soluble and ionizable, optionally incorporated into the compositions of the present invention. There is salt. Various ionizable salts can be used. Examples of suitable salts are halides of metals of Groups IA and IIA of the Periodic Table of the Elements, such as calcium chloride, magnesium chloride, sodium chloride, potassium bromide and lithium chloride. Ionizable salts are particularly useful during the process of making the composition and then mixing the components to achieve the desired viscosity. The amount of ionizable salt used depends on the amount of active ingredient used in the composition and can be adjusted as desired by the trader. Typical levels of salts used to control the viscosity of the composition are from about 20 to about 20,000 parts per million (ppm) of the composition, preferably about 20 parts per million (ppm).
~ 11,000 ppm.

An alkylene polyammonium salt may also be used in addition to the ionizable water-soluble salt described above.
Alternatively, it can be incorporated into the composition for viscosity control. In addition, these agents can act as scavengers and form ion pairs with the rinse solution and anionic detergent carried over on the fabric from the main wash liquor to improve softness performance. These agents stabilize the viscosity over a wide range of temperatures, especially at low temperatures, compared to inorganic electrolytes. Specific examples of alkylene polyammonium salts include l-lysine monohydrochloride and 1,1
There is 5-diammonium 2-methylpentane dihydrochloride.

Stabilizers Stabilizers can also be present in the compositions of the present invention. As used herein, the term "stabilizer" includes antioxidants and reducing agents. These agents may range from 0 to about 2%, preferably from about 0.01 to about 0.2%, more preferably from about 0.035 to about 0.2% in the case of antioxidants.
It is present at a level of about 0.1%, more preferably about 0.01 to about 0.2% in the case of a reducing agent. These ensure good aroma stability under long-term storage conditions for the compositions and compounds stored in the molten form. The use of stabilizers as antioxidants and reducing agents is particularly important in the case of low perfume products (low perfume).

[0095] Examples of antioxidants that can be added to the compositions of the present invention, trade name Tenox ^R PG and T
A mixture of ascorbic acid, ascorbic acid palmitate, propyl gallate commercially available from Eastman Chemical Products, Inc. as enox S-1; trade name Tenox
. -6 as Eastman Chemical Products, Inc commercially available from BHT (butylated hydroxy toluene), BHA (butylated hydroxy anisole), a mixture of propyl gallate and citric acid; UOP Process D tradename Sustane ^R BHT
Butylated hydroxytoluene commercially available from ivision; Eox as Tenox TBHQ
Tertiary butyl hydroquinone from tman Chemical Products, Inc .; Natural tocopherols from Eastman Chemical Products, Inc. as Tenox GT-1 / GT-2; Ea as BHA
Butylated hydroxyanisole from stman Chemical Products, Inc .; long-chain esters of gallic acid (C ₈ -C ₂₂ ), such as dodecyl gallate; Irganox ^R 1010, Irgan
ox ^R 1035, Irganox ^RB 1171, Irganox ^R 1425, Irganox ^R 3114, Irganox ^R 3125 and mixtures thereof; preferably Irganox ^R 3125, Irganox ^R 1425, Irganox ^R 311
4 and mixtures thereof; more preferably Irganox ^R 3125 alone. The chemical names and CAS numbers of some of the above stabilizers are listed in Table II below.

Table II Antioxidants CAS No. Chemical name Irganox ^R 1010 6683-19-8 Tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] used in the regulations of the Federal Regulations. Methane Irganox ^R 1035 41484-35-9 Thiodiethylenebis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)
Irganox ^R 1098 23128-74-7 N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxyhydrocinnamamide) Irganox ^R B 1171 31570-04-4 Irganox ^R 1098 and Irgafos ^R 168 of 23128-74-7 1: 1 blend Irganox ^R 1425 65140-91-2 bis [monoethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate] Calcium Irganox ^R 3114 65140-91-2 bis [Monoethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate] Calcium Irganox ^R 3125 34137-09-2 1,3,5-Tris (2-hydroxyethyl) -S-triazine-2,4 3,5-Di-tert-butyl-4-hydroxyhydrocinnamic acid triester with 2,6- (1H, 3H, 5H) trione Irgafos ^R 168 31570-04-4 Tris (2,4-di-tert -Butylphenyl) phosphite of reducing agent The sodium borohydride, hypophosphorous acid, Irgafos ^R 168 and mixtures thereof.

Soil Release Agents Soil release agents are also desirably used in the fabric care compositions of the present invention. Any polymeric soil release agent known to those skilled in the art can optionally be used in the compositions of the present invention. The polymeric soil release agent will adhere to the hydrophilic segment, which renders the surface of hydrophobic fibers such as polyester and nylon hydrophilic, and on the hydrophobic fibers, until the end of the wash and rinse cycle, and thus the hydrophilic segments. It is characterized by having both a hydrophobic segment that acts as an anchor.
In this way, the soil generated after treatment with the soil release agent can be more easily washed off in a subsequent washing operation. If utilized, the soil release agent will typically comprise from about 0.01 to about 10 of the present fabric care composition.
. 0% by weight, typically from about 0.1 to about 5%, preferably from about 0.2 to about 3.0%.

The following are all incorporated herein by reference and describe soil release polymers suitable for use in the present invention. Hays US issued May 25, 1976
3,959,230; Basadur US 3,8, issued July 8, 1975.
93,929; Nicol et al., US 4,004, issued December 28, 1976.
Gosselink U.S. Pat. No. 4,009,093; issued Oct. 27, 1987;
Scheibel et al., US Pat. No. 4,968,45, issued Nov. 6, 702;
1: US 4,702,85 of Gosselink issued October 27, 1987
7; Gosselink et al., US Pat. No. 4,711,73, issued Dec. 8, 1987.
0; Gosselink US Pat. No. 4,721,580 issued Jan. 26, 1988.
Maldonado et al., US Pat. No. 4,877,89, issued Oct. 31, 1989;
6; Gosselink et al., US Pat. No. 4,956,44, issued Sep. 11, 1990.
7; Gosselink et al., US Pat. No. 5,415,80, issued May 16, 1995.
7; European Patent Application 0,219, published April 22, 1987 by Kud et al.
, 048.

Another suitable soil release agent is US Pat. No. 4,201,824 to Violland et al .; US Pat. No. 4,240,918 to Lagasse et al .; US Pat. No. 4,525,524 to Tung et al.
S4,579,681; US4,240,918; US4,787,989; U
S4,525,524; 1988, Rhone-Poulenc Chemie, EP 279,134.
A; BA457, EP 457, 205A (1991); and 1974 Unilever.
It is described in NV DE 2,335,044, which is incorporated herein by reference in its entirety.

Commercially available soil release agents include METOLOSE SM100 and METOLOSE SM2 manufactured by Shin-Etsu Chemical KK.
00, a substance of the SOKALAN type commercially available from BASF (Germany), such as SOKALAN HP-22, ZE
There are LCON 5126 (Dupont) and MILEASE T (ICI).

[0102] Philadel Examples of fungicides fungicides used in the composition of the present invention, the dosage of 1~1000ppm by weight, glutaraldehyde, formaldehyde, trade name Bronopol ^R
2-Bromo-2-nitropropane-1,3-diol, sold by Inolex Chemicals of Pennsylvania, phia, Rohm and Haas Company under the trade name Kathon
There is a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one sold by the company.

Fragrance In the present invention, a fragrance can be contained. Suitable fragrances are US Patent 5,500,
138, which patent is incorporated herein by reference. As used herein, perfumes include natural (ie, obtained by extraction of flowers, herbs, leaves, roots, bark, trees, flowers, or plants), artificial (ie, mixtures of different natural oils or oil components) and synthetic ( That is, there are fragrances including fragrances (made synthetically) or mixtures thereof. Such substances are often accompanied by auxiliary substances such as fixing agents, extenders, stabilizers and solvents. These adjuvants are also included within the meaning of "perfume" as used herein. Typically, a fragrance is a complex mixture of a plurality of organic compounds.

The range of natural raw materials includes not only volatile components but also moderately volatile components and slightly volatile components. In the case of synthetic compounds, as is apparent from the following examples, practically all classes are used. Representative examples of aromatic substances: natural products such as tree moss absolut (
tree moss absolute), basil oil, citrus fruit oil (eg bergamot oil, mandarin oil, etc.), mastic oil (mastix absolute), myrte oil, palmarosa oil, patchouli oil, petitgren oil Paraguay, bittersweet oil, alcohols such as farnesol Geraniol, linalool, nerol, phenylethyl alcohol, rosinol, cinnamyl alcohol, aldehydes such as citral, Helional ^™ , α-hexylcinnamaldehyde, hydroxycitronellal, Lilial ^™ (p-tert-butyl-α-methyldihydro Cinnamaldehyde), methylnonylacetaldehyde, ketones such as allylyonone, α-yonone, β-yonone, isorardine (isomethyl-α-yonone), methylyonone, esters such as phenoxy Allyl acid, benzyl salicylate, cinnamyl propionate, citronellyl acetate, citronellyl ethoxylate, decyl acetate, dimethyl benzyl carbyl acetate, dimethyl benzyl carbyl butyrate, ethyl acetoacetate, ethyl acetyl acetate, hexenyl isobutyrate, linalyl acetate, methyl Lactones such as dihydrojasmonate, styralyl acetate, vetiveryl acetate, etc., for example γ-undecalactone, various components commonly used in perfumes, for example, musk ketone, indole, p-menthan-8-thiol-3-one and methyleugenol including. Similarly, any conventional fragrance acetal or ketal known in the art may be added to the composition as an optional ingredient of perfume (c) formulated in a conventional manner. Such conventional aromatic acetals and ketals include the well-known methyl and ethyl acetals and ketals, as well as acetal or ketals based on benzaldehyde, those containing a phenylethyl moiety, or "Acetals and Ketals of Oxo-Tetralins and Oxo -Indanes "(see US Pat. No. 5,084,440, issued Jan. 28, 1992, assigned to Givaudan Corp.), a recently developed specialty. is there. Of course, other recent synthetic specialties can also be included in perfume compositions for fully formulated fabric softening compositions. These include the U transferred to Givaudan
Enol ethers of alkyl-substituted oxotetralins and oxoindanes as described in S Patent 5,332,725, or 1991 assigned to Givaudan
There are Schiff bases as described in US Pat. No. 5,264,615 dated Dec. 9, 2012.

The perfumes useful in the compositions of the present invention are substantially free of halogenated substances and nitromsk. The perfume may be present at a level of 0 to 10%, preferably 0.1 to 5%, more preferably 0.2 to 3% by weight of the final composition. The fabric care compositions of the present invention exhibit improved fabric perfume adhesion.

[0105]Crystal growth inhibitor component The fabric care composition of the present invention comprises a crystal growth inhibitor component, preferably an organic diphosphonic acid.
Ingredients can be further included, preferably 0.01 to 5% by weight of the composition, more preferably
It is formulated at a level of 0.1-2%. Organic diphosphonic acids are organic diphosphonic acids that do not contain nitrogen as part of their chemical structure.
Means sulphonic acid. Therefore, this definition excludes organic aminophosphonates.
However, it is present in the compositions of the present invention as a heavy metal sequestrant component.
May be contained. The organic diphosphonic acid is preferably C₁-C₄Diphosphonic acid, more preferably C ₂ Diphosphonic acids, such as ethylene diphosphonic acid, most preferably ethane 1-hydrido
Roxy-1,1-diphosphonic acid (HEDP), especially as a salt or complex
It may be present in a partially or fully ionized form.

Enzymes In the present compositions and processes, one or more enzymes such as lipases, proteases, cellulases, amylases and peroxidases can optionally be used. A preferred enzyme for use herein is a cellulase enzyme. In fact, this type of enzyme further imparts a color care effect to the treated fabric. Cellulases that can be used here include:
There are both bacterial and fungal types, preferably having an optimum pH of 5 to 9.5. In US 4,435,307, Humicola insolens or Humicola strain DS
Suitable fungal cellulases from M1800, or cellulase 212 producing fungi belonging to the genus Aeromonas, and cellulases extracted from the hepatopancreas of the marine mollusc Dolabella Auricula Solander are disclosed. A suitable cellulase is GB-A
-2,075,028, GB-A-2,095,275 and DE-OS-2
247, 832. CAREZYME ^R and CELLUZYME ^R (Novo) is especially useful. Other suitable cellulases are Novo's WO 91/17243, WO
96/34092, WO 96/34945 and EP-A-0,739,982
But it is also disclosed. For current commercial products, typical amounts are within 5 mg of active enzyme per gram of detergent composition, more typically 0.0001 to 3 mg. In other words, the composition is typically 0.001-5% by weight, preferably 0.01-1%.
% Of commercial enzyme products. In certain cases where the activity of the enzyme product can be defined, for example, by cellulase, the corresponding activity unit (eg, CEVU or cellulase equivalent viscosity unit) is preferred. For example, the composition of the present invention is 0.5 to 1000 CEVU / g of composition.
Cellulase enzyme at a level corresponding to the activity of Cellulase enzyme products used to formulate compositions of the present invention typically have an activity in liquid or solid form of 1000 to 10,000 CEVU / g.

Other Optional Components In the present invention, optional components commonly used in textile treatment compositions, for example, whitening agents,
Contains colorants, surfactants, anti-shrink agents, fabric crisping agents, stain removers, fungicides, fungicides, antioxidants such as butylated hydroxytoluene, corrosion inhibitors, defoamers, etc. be able to. In the present invention, WO 96/02625, WO 96/21714 and WO 96/21714
Other compatible components, including those disclosed in US Pat. No. 21715, and dispersible polyolefins such as Vellustol ^R disclosed in co-pending application PCT / US97 / 01644, and the like can also be included. In the present invention, any chelating agent can be contained.

Application The compositions of the present invention are applied at any step of the domestic treatment, ie, as a pretreatment composition, as a cleaning additive, for use in the rinse cycle of a wash cycle or on a dryer sheet. Suitable for use as a composition. Obviously, for the purposes of the present invention, such as treating a fabric with a pretreatment composition of the present invention followed by a composition of the present invention suitable for use in a rinse cycle and / or for use as a dryer sheet, Many applications are possible. The composition of the invention may take the form of a spray, foam or aerosol, for example, which is suitable for use in ironing or applied to the surface of a tumble dryer.

The surfactant-based fabric care compositions may be used in accordance with the present invention for laundering softening through the wash.
-the-wash) when formulated as a composition, the surfactant can be selected from nonionic and / or anionic and / or cationic and / or amphoteric and / or zwitterionic and / or semipolar surfactants , A surfactant system.

The surfactant is typically present at a level of from 0.1 to 60% by weight. Further preferred loading levels are 1 to 35%, most preferably 1 to 30% by weight of the fabric care composition according to the invention.

[0111] Surfactants are preferably formulated to be compatible with the enzyme components present in the composition. In liquid or gel compositions, the surfactant may be formulated to promote the stability of the enzyme in these compositions or to not degrade it at least.
Most preferred.

The preferred surfactant systems used according to the invention comprise, as surfactants, one or more of the nonionic and / or anionic surfactants described herein.

Polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols are suitable for use as the nonionic surfactant of the surfactant system of the present invention, with polyethylene oxide condensates being preferred. These compounds include condensation products of alkyl phenols with alkyl phenols having an alkyl group of from about 6 to about 14, preferably from about 8 to about 14, carbon atoms in a straight or branched configuration. In a preferred embodiment, the ethylene oxide is present in an amount corresponding to about 2 to about 25 moles, more preferably about 3 to about 15 moles of ethylene oxide per mole of alkylphenol. Commercially available nonionic surfactants of this type include GAF Cor
There are Igepal ^™ CO-630 sold by poration, all Triton ^™ X-45, X-114, X-100 and X-102 sold by Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (eg, alkylphenol ethoxylates).

The condensation products of primary and secondary aliphatic alcohols with about 1 to about 25 moles of ethylene oxide are suitable for use as nonionic surfactants in the nonionic surfactant systems of the present invention. The alkyl chain of the aliphatic alcohol is straight or branched, primary or secondary, and usually has about 8 to about 22 carbon atoms. About 8 to about 20 carbon atoms
And more preferably an alcohol having an alkyl group of about 10 to about 18 carbon atoms;
Condensation products with from about 2 to about 10 moles of ethylene oxide per mole of alcohol are preferred. About 2 to about 7 moles, most preferably 2 to 5 moles, of ethylene oxide are present in the above condensation product per mole of alcohol. Examples of commercially available nonionic surfactants of this type include both Union Carbide Corporation
Tergitol ^™ 15-S-9 (condensation product of C ₁₁ -C ₁₅ linear alcohol and 9 moles of ethylene oxide) and Tergitol ^™ 24-L-6 NMW (C ₁₂ -C ₁₄ primary alcohol and ethylene oxide 6 Condensation product of narrow molecular weight distribution with mol); Shel
l Chemical Company Neodol sold by ^TM 45-9 _(C 14 _{-C 15} condensation product of linear alcohol with 9 moles ethylene _{^{oxide), Neodol TM 23-3 (C 12}} -C 1 3 linear alcohols with ethylene oxide 3 Condensation product with 2.0 mol), Neodol ^TM 45-7
(Condensation product of C ₁₄ -C ₁₅ linear alcohol and 7 mol of ethylene oxide), Ne
odol ^TM 45-5 _(C 14 _{-C 15} linear alcohol with condensation product of 5 moles of ethylene oxide); The Procter & Gamble Company, sold by _{^{Kyro TM EOB (C 1 3 -C}} 15 alcohol with 9 moles ethylene oxide and there are Genapol sold by Hoechst LA O3O or O50 (C ₁₂ -C ₁₄ alcohols with ethylene oxide 3 or 5 moles and condensation products of); condensation products of). HLB in these products
Is preferably from 8 to 11, and most preferably from 8 to 10.

The nonionic surfactants of the surfactant system of the present invention include hydrophobic groups having about 6 to about 30 carbon atoms, preferably about 10 to about 16 carbon atoms, and about 1.3 to about 10 carbon atoms. ,
Llenado published January 21, 1986, having a polysaccharide having preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units, such as the hydrophilic group of a polyglycoside. Also useful are the alkyl polysaccharides disclosed in US Pat. No. 4,565,647. Reducing sugars having 5 or 6 carbon atoms can also be used, for example, glucose, galactose and galactosyl moieties can be used in place of the glucosyl moiety (optionally a hydrophobic group is attached at the 2, 3, 4 position, etc. Give glucose or galactose instead of galactoside). For example, an intersugar linkage may be present between one position of the additional sugar unit and positions 2, 3, 4, and / or 6 of the preceding sugar unit.

Preferred alkyl polyglycosides have the formula: R ² O (C _n H _2n O) _t (glycosyl) _{x wherein} R ² is alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and (Alkyl groups have about 10 to about 18, preferably about 12 to about 14 carbon atoms); n is 2 or 3, preferably 2; t is 0 to about 10, preferably 0; x is about 1
. 3 to about 10, preferably about 1.3 to about 3, most preferably about 1.3 to about 2.7.
It is. Glycosyl is preferably derived from glucose. To make these compounds, an alcohol or alkyl polyethoxy alcohol is first formed and then reacted with glucose or a source of glucose to form glucoside (1).
Bond). Additional glycosyl units may also be linked between their 1-position and the preceding glycosyl unit at positions 2, 3, 4, and / or 6, preferably predominantly at position 2.

The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant system of the present invention. The hydrophobic portion of these compounds is preferably about 1500
It has a molecular weight of ~ 1800 and is water-insoluble. The addition of a polyoxyethylene moiety to this hydrophobic moiety tends to increase the overall water solubility of the molecule, and the liquidity of the product is such that the polyoxyethylene content is up to about 50% of the total weight of the condensation product. Again, this corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain commercial Plurafac ^™ LF404 and Pluronic ^™ surfactants, sold by BASF.

As the nonionic surfactant of the nonionic surfactant system of the present invention, a product obtained from the reaction of propylene oxide with ethylenediamine and a condensation product of ethylene oxide are also suitable for use. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide, usually from about 2500 to about 300
It has a molecular weight of 0. The hydrophobic moiety is condensed with ethylene oxide to an extent that the condensation product contains about 40 to about 80% by weight polyoxyethylene and has a molecular weight of about 5000 to about 11,000. Examples of this type of nonionic surfactant include certain commercially available Tetronic ^™ compounds sold by BASF.

The nonionic surfactants of the surfactant system of the present invention include polyethylene oxide condensates of alkylphenols, primary and secondary aliphatic alcohols and about 1 to about 25.
Condensation products with moles of ethylene oxide, alkyl polysaccharides, and mixtures thereof are preferred for use. _C 8 _{-C 14} alkyl phenol ethoxylates having from 3 to 15 ethoxy groups, _C 8 _{-C 18} alcohol ethoxylates having from 2 to 10 ethoxy groups (preferably _{C 10} average), and mixtures thereof are most preferred.

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

Embedded image Or the formula ^{R 1} is H, or ^{R 1} is C _1-4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, ^{R 2} is C _5-31 hydrocarbyl, Z is A polyhydroxyhydrocarbyl having a linear hydrocarbyl chain and at least three hydroxyls directly attached to the chain, or an alkoxylated derivative thereof. Preferably, R ¹ is methyl, R ² is a linear C _11-15 alkyl or C _16-18 alkyl or alkenyl chain, such as coconut alkyl, or mixtures thereof, and Z is glucose,
It is derived from reducing sugars such as fructose, maltose and lactose.

Suitable anionic surfactants used are described in “The Journal of the American O.
il Chemists Society ", 52 (1975 ), C 8 -C 20 carboxylic acids which are sulfonated with gaseous SO ₃ according Pp.323-329 (i.e., fatty acids), including straight-chain esters of, linear alkylbenzene sulfonates, alkyl Ester sulfonate surfactants Suitable starting materials include natural fatty substances such as those derived from tallow, palm oil and the like.

Preferred alkyl ester sulfonate surfactants, especially for laundry applications, include:
There are alkyl ester sulfonate surfactants of the following structural formula:

Embedded image Wherein R ³ is C ₈ -C ₂₀ hydrocarbyl, preferably alkyl, or a combination thereof, R ⁴ is C ₁ -C ₆ hydrocarbyl, preferably alkyl, or a combination thereof, and M is an alkyl ester sulfonate. Is a cation that forms a water-soluble salt with the cation. Suitable salt-forming cations include metals such as sodium, potassium and lithium, substituted or unsubstituted ammonium cations, for example, monoethanolamine, diethanolamine and triethanolamine. Preferably, R ³ is C ₁₀ -C ₁₆ alkyl and R ⁴ is methyl, ethyl or isopropyl. Methyl ester sulfonates where R ³ is C ₁₀ -C ₁₆ alkyl are particularly preferred.

Other suitable anionic surfactants include those of the formula ROSO₃With a water-soluble salt or acid of M
There are certain alkyl sulphate surfactants, where R is preferably C₁₀-C ₂₄ Hydrocarbyl, preferably C₁₀-C₂₀Alkyl with alkyl moiety
Or hydroxyalkyl, more preferably C₁₂-C₁₈Alkyl or hydrid
M is H or a cation, such as an alkali metal cation (
Eg sodium, potassium, lithium), ammonium or substituted ammonium
(Eg, methyl-, dimethyl- and trimethyl-ammonium cations,
And like tetramethylammonium and dimethylpiperidinium cations
Quaternary ammonium cations and ethylamine, diethylamine, triethyl
Quaternary ammonium cations derived from alkylamines such as
And mixtures thereof). Typically, C₁₂-C₁₆Alkyl chains are low
Low washing temperature (for example, below about 50 ° C.)₁₆-C₁₈Alkyl chains are high
A low cleaning temperature (eg, about 50 ° C. or higher) is preferred.

Other anionic surfactants useful for cleaning purposes are also present in the fabric care compositions of the present invention.
It can be contained. These include soap salts (eg, sodium, potassium)
, Ammonium and substituted ammonium salts such as mono, di and trietano
Oleamine salts), C₈-C₂₂Primary or secondary alkane sulfonate, C ₈ -C₂₄Olefin sulphonates, for example British Patent Specification 1,082,17
As described in No. 9, the sulfone of the pyrolysis product of alkaline earth metal citrate
Sulfonated polycarboxylic acid produced by₈-C₂₄Alkyl polygly
Coal ether sulfate (containing up to 10 moles of ethylene oxide);
Kill glycerol sulfonate, fatty acyl glycerol sulfonate, fatty acid
Rail glycerol sulfate, alkyl phenol ethylene oxide ether
Rusulfate, paraffin sulfonate, alkyl phosphate, acylise
Isethionate such as thionate, N-acyl taurate, alkyl succina
Mate and sulfosuccinate, monoesters of sulfosuccinate (especially saturated
Sum and unsaturated C₁₂-C₁₈Monoester) and sulfosuccinate
Stell (especially saturated and unsaturated C₆-C₁₂Diester), acyl sarcocine
Alkyl polysaccharide sulfates, such as alkyl polyglucoside sulfates
(Nonionic non-sulfate compounds are described below), branched primary
Kill sulfate, and the formula RO (CH₂CH₂O)_k-CH₂COO⁻M⁺(
R is C₈-C₂₂Alkyl, k is an integer from 1 to 10, and M is a soluble salt form.
Alkyl ethoxy carboxylate). G
Rosin, hydrogenated rosin, present in or derived from oleoresin,
Resin acids and hydrogenated resin acids, such as resin acids and hydrogenated resin acids, are also suitable.
You.

Another example is “Surface Active Agents and Detergents” (Vol. I and II, Schwar
tz, Perry and Berch). Various such surfactants include 19
US Pat. No. 3,929,678 to Laughlin et al., Issued Dec. 30, 75, also commonly discloses at column 23, line 58 to column 29, line 23 (herein incorporated by reference). Incorporated).

When included herein, the laundry detergent compositions of the present invention typically contain from about 1 to about 40% by weight, preferably from about 3 to about 20%, of such anionic surfactant. I have.

Highly preferred anionic surfactants include alkylalkoxylated sulfate surfactants that are water-soluble salts or acids of the formula RO (A) _m SO ₃ M, where R is an unsubstituted C ₁₀ − C ₂₄ alkyl or _C 10 _{-C 24} hydroxyalkyl group having an alkyl moiety, preferably a _C 12 _{-C 20} alkyl or hydroxyalkyl, more preferably _C 12 _{-C 18} alkyl or hydroxyalkyl, a is an ethoxy or propoxy unit And m is greater than zero, typically from about 0.5 to about 6, more preferably from about 0.5 to about 3, and M is H or a cation, such as a metal cation (eg, sodium, potassium, lithium , Calcium, magnesium, etc.), ammonium or substituted ammonium cations .
Alkyl ethoxylated sulfates and alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations are derived from methyl, dimethyl, trimethyl-ammonium cations, and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, and alkylamines such as ethylamine, diethylamine, triethylamine. And mixtures thereof. An exemplary surfactant is C _12-
C ₁₈ alkyl polyethoxylate (1.0) sulfate (C ₁₂ -C ₁₈ E
(1.0) M), C ₁₂ -C ₁₈ alkyl polyethoxylate (2.25) sulfate (C ₁₂ -C ₁₈ E (2.25) M), C ₁₂ -C ₁₈ alkyl polyethoxylate (3. 0) sulfate _{(C 12 -C 18 E (3.0} ) M) , and _C 12 _{-C 18} alkyl polyethoxylate (4.0) sulfate _{(C 12} -
C ₁₈ E (4.0) M), where M is conveniently selected from sodium and potassium.

The fabric care compositions of the present invention also contain cationic, amphoteric, zwitterionic and semipolar surfactants, as well as nonionic and / or anionic surfactants other than those already described herein. Good.

[0129] Cationic detersive surfactants suitable for use in the fabric care compositions of the present invention include one
It has a long-chain hydrocarbyl group. Such cationic surfactants
Examples include ammonium surfactants such as alkyltrimethylammonium halo
There are genoides, and surfactants having the formula: [R²(OR³)_y] [R⁴(OR³)_y]₂R⁵N⁺X⁻ R in the above formula²Is an alkyl having about 8 to about 18 carbon atoms in the alkyl chain or
An alkylbenzyl group; each R³Is -CH₂CH₂-, -CH₂CH (CH₃ )-, -CH₂CH (CH₂OH)-, -CH₂CH₂CH₂-And their
Selected from the group consisting of mixtures; each R⁴Is C₁-C₄Alkyl, C₁-C₄Hi
Droxyalkyl, two R⁴A benzyl ring structure formed by linking groups, -C
H₂CHOH-CHOHCOR⁶CHOHCH₂OH (R⁶Is less than about 1000
A hexose or hexose polymer having a molecular weight), and y is 0.
If not selected from the group consisting of hydrogen; R⁵Is R⁴Is the same as R ² + R⁵Is an alkyl chain having no more than about 18 carbon atoms; each y is from 0 to about
10, the sum of the y values is from 0 to about 15; X is any suitable anio
It is.

A quaternary ammonium surfactant suitable for the present invention has the following formula (I):

Embedded image Formula I wherein R ₁ is a short chain alkyl (C ₆ -C ₁₀ ) or an alkylamidoalkyl of formula (II):

Embedded image Wherein R ₂ is H or C ₁ -C ₃ alkyl; wherein x is 0-4, preferably 0-2, most preferably Wherein R ₃ , R ₄ and R ₅ are the same or different and are a short-chain alkyl (C ₁ -C ₃ ) or an alkoxylated alkyl of the following formula III:

Embedded image Formula III (where R ⁶ is C ₁ -C ₄ and z is 1 or 2) wherein X ⁻ is a counter ion, preferably a halide such as chloride or methyl sulfate.

Preferred quaternary ammonium surfactants are those of the formula wherein R ₁ is C ₈ , C ₁₀ or a mixture thereof, x = 0, R ₃ , R ₄ ＣＨCH ₃ and R ₅ ＣＨCH ₂ CH ₂ OH. It is as defined in I.

Highly preferred cationic surfactants are water-soluble quaternary ammonium compounds useful in the present compositions having the formula: R ₁ R ₂ R ₃ R ₄ N ⁺ X ⁻ (i) Wherein R ₁ is C ₈ -C ₁₆ alkyl, and each of R ₂ , R ₃ and R ₄ is independently C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, benzyl and-
A _{(C 2 H 40) x H} (x has a value of 2 to 5), X is an anion.
No more than one of R ₂ , R ₃ or R ₄ must be benzyl. The preferred alkyl chain length for R ₁ is C ₁₂ -C ₁₅ , especially where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat, or synthetically derived by olefin build-up or oxo alcohol synthesis. Is done. Preferred groups for R ₂ , R ₃ and R ₄ are methyl and hydroxyethyl groups, and the anion X is selected from halide, methosulfate, acetate and phosphate ions.

Examples of quaternary ammonium compounds of the formula (i) suitable for use herein are: coconut trimethylammonium chloride or bromide coconut methyldihydroxyethylammonium chloride or bromide decyltriethylammonium chloride decyldimethylhydroxyethylammonium chloride or bromide C _12-15 dimethyl hydroxyethyl ammonium chloride or bromide coconut dimethyl hydroxyethyl ammonium chloride or bromide myristyl trimethyl ammonium methyl sulphate lauryl dimethyl benzyl ammonium chloride or bromide lauryl dimethyl (ethenoxy) ₄ ammonium chloride or bromide choline esters (R ₁ is CH _{2 -CH 2 -O-C (= O} ) A C _{12-14 alkyl, R 2, R 3, R} 4 is methyl, the compound of formula (i)) compounds of dialkyl imidazoline (Formula (i))

Other cationic surfactants useful herein include Cambre US Pat. No. 4,228,044, issued Oct. 14, 1980, and European Patent Application EP000,20.2.
24.

When included herein, the fabric care compositions of the present invention typically comprise 0.2 to about 25.
% By weight, preferably from about 1 to about 8% of such a cationic surfactant.

[0136] Amphoteric surfactants are also suitable for use in the fabric care compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines, wherein the aliphatic group is linear or It may be branched. One of the aliphatic substituents has at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one has an anionic water-soluble group, such as carboxy, sulfonic acid, sulfuric acid. Group. For examples of amphoteric surfactants, see Laughlin et al., US Pat.
See Patent No. 3,929,678, column 19, lines 18-35. As contained herein, the fabric care compositions of the present invention typically comprise from 0.2 to about 15
% By weight, preferably from about 1 to about 10% of such amphoteric surfactants.

[0137] Zwitterionic surfactants are also suitable for use in the fabric care compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. . For examples of zwitterionic surfactants, see
US Patent No. 3,929,67 to Laughlin et al., Issued December 30, 1975.
8, column 19, line 38 to column 22, line 48. As contained herein, the fabric care compositions of the present invention typically comprise from 0.2 to about 15
% By weight, preferably from about 1 to about 10% of such a zwitterionic surfactant.

Semipolar nonionic surfactants comprise two alkyl moieties selected from the group consisting of one alkyl moiety having about 10 to about 18 carbon atoms, an alkyl group having about 1 to about 3 carbon atoms, and a hydroxyalkyl group. Water-soluble amine oxide having about 10 to about 1 carbon atoms
Water-soluble phosphine oxide having one alkyl moiety of eight, two moieties selected from the group consisting of an alkyl group of about 1 to about 3 carbon atoms and a hydroxyalkyl group; one alkyl of about 10 to about 18 carbon atoms Particular categories of nonionic surfactants, including water-soluble sulfoxides having a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of about 1 to about 3 carbon atoms.

Semipolar nonionic detergent surfactants include amine oxide surfactants having the formula:

Embedded image Wherein R ³ is an alkyl, hydroxyalkyl, alkylphenyl group having about 8 to about 22 carbon atoms or a mixture thereof; R ⁴ is an alkylene, hydroxyalkylene group having about 2 to about 3 carbon atoms or Mixtures thereof;
x is 0 to about 3; each R ⁵ is an alkyl or hydroxyalkyl group having about 1 to about 3 carbon atoms, or a polyethylene oxide group having about 1 to about 3 ethylene oxide groups. The R ⁵ groups may be linked together, for example, via an oxygen or nitrogen atom to form a ring structure. Among these amine oxide surfactants are, in particular, C ₁₀ -C ₁₈ alkyldimethylamine oxide and C ₈ -C ₁₂ alkoxyethyldihydroxyethylamine oxide. When included herein, the cleaning compositions of the present invention typically comprise from 0.2 to about 15% by weight, preferably from about 1 to about 10%, of such a semi-polar nonionic surfactant.

The fabric care compositions of the present invention may further comprise a cosurfactant selected from the group of primary or tertiary amines. Primary amines suitable for use herein include amines according to the formula R ₁ NH ₂ , where R ₁ is a C ₆ -C ₁₂ , preferably C ₆ -C ₁₀ alkyl chain, or R ₄ X (C
H ₂₎ is _n, X is -O -, - C (O) NH- or a -NH-, _{R 4} is a _C 6 _{-C 12} alkyl chains, n represents 1-5, preferably 3 is there. The R ₁ alkyl chain may be straight or branched and may have up to 12 and preferably less than 5 ethylene oxide moieties. Preferred amines according to the above formula are n-alkylamines. Amines suitable for use herein are selected from 1-hexylamine, 1-octylamine, 1-decylamine and laurylamine. Other preferred primary amines include C ₈ -C ₁₀ oxypropylamine, octyloxypropylamine, 2-ethylhexyloxypropylamine, laurylamidopropylamine and amidopropylamine.

Tertiary amines suitable for use herein include tertiary amines having the formula R ₁ R ₂ R ₃ N, where R ₁ and R ₂ are a C ₁ -C ₈ alkyl chain or

Embedded image And R ₃ is a C ₆ -C ₁₂ , preferably a C ₆ -C ₁₀ alkyl chain, or R ₃ is R ₄ X (CH ₂ ) _n (X is —O—, —C (O) NH -Or -NH-
Wherein R ₄ is C ₄ -C ₁₂ and n is 1-5, preferably 2-3. R ₅ is H or C ₁ -C ₂ alkyl, and x is 1-6. R ₃ and R ₄ may be linear or branched, and the R ₃ alkyl chain may have up to 12, preferably less than 5, ethylene oxide moieties.

Preferred tertiary amines are those in which R ₁ is a C ₆ -C ₁₂ alkyl chain and R ₂ and R ₃ are C ₁ -C ₃ alkyl or

Embedded image (Wherein R ₅ is H or CH ₃ and x = 1 to 2), and is R ₁ R ₂ R ₃ N. Amidoamines of the following formula are also preferred:

Embedded image In the above formula, R ₁ is C ₆ -C ₁₂ alkyl, n is 2 to 4, preferably n is 3, and R ₂ and R ₃ are C ₁ -C ₄ .

The most preferred amines of the present invention include 1-octylamine, 1-hexylamine, 1-decylamine, 1-dodecylamine, C _8-10 oxypropylamine, N-
Coco-1,3-diaminopropane, coconut alkyldimethylamine, lauryldimethylamine, laurylbis (hydroxyethyl) amine, cocobis (hydroxyethyl) amine, 2 mol propoxylated laurylamine, 2 mol propoxylated octylamine, laurylamide dimethylamine, there is C _8-10 dimethylamine and C ₁₀ amidopropyl dimethylamine. The most preferred amines for use in the composition are 1-hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine. Particularly desirable are:
n-dodecyldimethylamine, bishydroxyethyl coconut alkylamine,
7-ethoxylated oleylamine, laurylamidopropylamine and cocoamidopropylamine.

Bleaching Agents When formulated as the laundry softening through-the-wash composition of the present invention, additional optional detergent components that may be included in the fabric care composition include hydrogen peroxide, PB1,
There are bleaching agents such as PB4, and percarbonates having a particle size of 400-800 microns. These bleach components can include one or more oxygen bleaches and, depending on the bleach selected, one or more bleach activators. When present, the oxygen bleaching compound is typically present at a level of about 1 to about 25%. The bleach component used herein can be any bleach useful in fabric care compositions, including oxygen bleaches and others known in the art. Bleaches suitable for the present invention are activated or deactivated bleaches.

One category of oxygen bleaches that can be used is polycarboxylic acid bleaches and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, magnesium salt of m-chloroperbenzoic acid, 4-nonylamino-4
-Oxoperoxybutyric acid and diperoxidedecanedioic acid. Such bleaching agents are disclosed in U.S. Pat. No. 4,483,781, U.S. Pat. No. 740,446, European Patent Application 0,133,354 and U.S. Pat.
Highly preferred bleaches include 6 as described in US Pat. No. 4,634,551.
There is also -nonylamino-6-oxoperoxycaproic acid.

Another category of bleaches that can be used is the halogen bleaches. Examples of hypohalous acid bleaches include, for example, trichloroisocyanuric acid, sodium and potassium dichloroisocyanurates, N-chloro and N-bromoalkanesulfonamides. Such substances are usually added at 0.5 to 10% by weight, preferably 1 to 5% by weight of the final product.

Hydrogen peroxide releasing agents are perhydrolyzed to form peracids as active bleaching species, resulting in improved bleaching effects, tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate ( NOBS, US
4,412,934), 3,5-trimethylhexanoloxybenzenesulfonate (described in ISONOBS, EP120,591), pentaacetylglucose (PAG) or phenolsulfonate ester of N-nonanoyl-6-aminocaproic acid (NACA- OBS, described in WO 94/28106). Co-pending European Patent Application No. 91
Acylated citrate esters as disclosed in US Pat. No. 870207.7, as well as Procter & Gamble co-pending patent application US Ser. No. 60 / 022,786 (
Asymmetrical acyclic imido bleach activators of the following formulas, such as those disclosed in US Patent Application Serial No. 60 / 028,122 (filed October 30, 1996) and 60 / 028,122 (filed October 15, 1996) are also suitable activators. Beta is:

Embedded imageR in the above formula₁Is C₇-C₁₃A linear or branched saturated or unsaturated alkyl group;
R₂Is C₁-C₈A linear or branched saturated or unsaturated alkyl group; ₃ Is C₁-C₄It is a linear or branched saturated or unsaturated alkyl group.

Useful bleaching agents, including bleach activators and peroxygen bleaching compounds, and peroxy acids, for use in detergent compositions according to the present invention, are described in our co-pending application USSN 08 / 136,626. , PCT / US95 /
07823, WO95 / 27772, WO95 / 27773, WO95 / 277
74 and WO 95/27775.

Hydrogen peroxide may also be present at the beginning or during the washing and / or rinsing process by adding an enzyme system capable of generating hydrogen peroxide (ie, the enzyme and its substrate). Such an enzyme system is described in EP-A-Oct.
It is disclosed in patent application 91202655.6.

The metal-containing catalyst used in the bleach composition includes a cobalt-containing catalyst such as a pentaaminecobalt (III) acetate salt, and a manganese-containing catalyst such as EPA549271,
EPA 549272, EPA 458 397, US 5,246,621, EPA 4
58398, US 5,194,416 and US 5,114,611. Bleach compositions comprising a peroxy compound, a manganese-containing bleach catalyst and a chelating agent are described in patent application 94870206.3.

Bleaches other than oxygen bleaches are known in the art and may be utilized herein. One type of non-oxygen bleach of particular interest is a light activated bleach such as sulfonated zinc and / or aluminum phthalocyanine. These substances can adhere to the substrate during the cleaning process. Light irradiation in the presence of oxygen, such as hanging and drying clothes under sunlight, activates the sulfonated zinc phthalocyanine, thereby bleaching the substrate. A preferred zinc phthalocyanine and light activated bleaching process is described in US Pat. No. 4,033,718. Typically,
The detergent composition contains about 0.025 to about 1.25% by weight of the sulfonated zinc phthalocyanine.

Builder System When formulated as a laundry softening through-the-wash composition of the present invention, the fabric care composition may further include a builder system. Aluminosilicate materials, silicates, polycarboxylates, alkyl or alkenyl succinic acids, and fatty acids, materials such as ethylenediaminetetraacetic acid, diethylenetriaminepentamethyleneacetic acid, sequestering agents such as aminopolyphosphonates, especially ethylenediaminetetramethylenephosphonic acid and diethylenetriamine Any conventional builder system is suitable for use herein, including pentamethylenephosphonic acid.
A phosphate builder may also be used here.

Suitable builders include inorganic ion exchange materials, usually inorganic hydrated aluminosilicate materials, and more specifically hydrated synthetic zeolites, such as hydrated zeolites A, X
, B, HS or MAP. Another suitable inorganic builder material is a laminated silicate, such as SKS-6 (
Hoechst). SKS-6 is a crystal laminated silicate made of sodium silicate (Na ₂ Si ₂ O ₅ ).

Suitable polycarboxylates having one carboxy group include lactic acid, glycolic acid and their ether derivatives as disclosed in Belgian patents 831,368, 821,369 and 821,370. Polycarboxylates having two carboxy groups include succinic acid, malonic acid, (ethylenedioxy)
Water-soluble salts of diacetate, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid and the ethers described in DE-A 2,446,686, 2,446,687 and US Pat. No. 3,935,257 Carboxylates and the sulfinylcarboxylates described in Belgian Patent 840,623. Polycarboxylates having three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates, and British Patent 1,379,241.
Carboxymethyl oxysuccinate, Dutch application 720587
3, and oxypolycarboxylate materials such as 2-oxa-1,1,3-propanetricarboxylate described in British Patent 1,387,447. is there.

The polycarboxylates having four carboxy groups are described in GB 1,261
Oxydisuccinate, 1,1,2,2-ethanetetracarboxylate, 1,1,3,3-propanetetracarboxylate and 1,1
There is 1,2,3-propanetetracarboxylate. Polycarboxylates with sulfo substituents include the sulfosuccinate derivatives disclosed in British Patents 1,398,421, 1,398,422 and US Pat. No. 3,936,448, and in British Patent 1,082,179. Among the sulfonated pyrolytic citrates described, polycarboxylates having a phosphon substituent are known from British Patent 1,439,000.
Are disclosed.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,
Cis, cis-tetracarboxylate, cyclopentadienidepentacarboxylate, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylate, 2,5-tetrahydrofuran-cis-dicarboxylate, 2,
2,5,5-tetrahydrofuran-tetracarboxylate, 1,2,3,4
There are 5,6-hexane-hexacarboxylate and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include melitic acid, pyromellitic acid, and the phthalic acid derivatives disclosed in British Patent 1,425,343. Among the above preferred polycarboxylates are hydroxycarboxylates having up to 3 carboxy groups per molecule, more particularly citrates.

Preferred builder systems for use in the present compositions include a water-insoluble aluminosilicate builder or laminated silicate (SKS-6) such as zeolite A and a water-soluble carboxylate chelating agent such as citric acid. There is a mixture. Other preferred builder systems include water-insoluble aluminosilicate builders such as zeolite A;
There are mixtures with water-soluble carboxylate chelators such as citric acid. Preferred builder systems for use in the liquid detergent compositions of the present invention are soaps and polycarboxylates.

Other builder substances which can form part of the builder system on use in the granular composition include inorganic substances such as carbonates, bicarbonates, alkali metal silicates, and organic phosphonates.
There are organic substances such as aminopolyalkylene phosphonates and aminopolycarboxylates. Other suitable water-soluble organic salts are homo- or copolymeric acids or salts thereof, wherein the polycarboxylic acid has at least two carboxyl groups separated from each other by no more than 2 carbon atoms. This type of polymer is GB-
A-1,596,756. Examples of such salts are MW2000
-5000 polyacrylates and their copolymers with maleic anhydride, such copolymers having a molecular weight of 20,000-70,000, especially about 40,000.
It has a molecular weight of 00.

The washing builder salt is usually present in an amount of from 5 to 80%, preferably from 10 to 70%, most usually from 30 to 60% by weight of the composition.

Chelating Agents When formulated herein as a laundry softening through-the-wash composition, the fabric care composition may also optionally include one or more iron and / or manganese chelators. Such chelators can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelators and mixtures thereof, all as described below. Without being bound by theory, it is believed that the effects of these materials are due in part to their exceptional ability to remove iron and manganese ions from the wash liquor by the formation of soluble chelates.

Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid,
There are ethylene diamine tetrapropionic acid, triethylene tetraamine hexaacetic acid, diethylene triamine pentaacetic acid and ethanol diglycine, their alkali metal, ammonium and substituted ammonium salts, and mixtures thereof. Aminophosphonates are also suitable for use as chelating agents in the compositions of the present invention when at least low levels of total phosphorus are acceptable in the detergent composition, including DEQUES
There is ethylenediaminetetrakis (methylene phosphonate) such as T. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups of about 7 or more carbon atoms. Polyfunctionally substituted aromatic chelators are also useful in the present compositions. May 2, 1974
See Connor et al., U.S. Pat. A preferred compound of this type is a dihydroxydisulfobenzene, such as 1,2-dihydroxy-3,5-disulfobenzene, in the acid form.

[0162] Preferred biodegradable chelators for use herein are Hartma, Nov. 3, 1987.
n and ethylenediaminedisuccinic acid ("EDDS") as described in Perkins US Patent 4,704,233, especially the [S, S] isomer. The composition may also contain a water-soluble methylglycine diacetate (MGDA) salt (or acid form) as a cobuilder useful as an insoluble builder, such as zeolites, laminated silicates, and the like, or as a chelant.

[0163] If utilized, these chelating agents are usually from about 0.1 to about 15% by weight of the detergent composition. More preferably, if utilized, the chelating agent will be from about 0.1 to about 3.0% by weight of such a composition.

[0164] Another optional component foam control agents, silicone and silica - a foam control agent which is exemplified by silicone mixture. Silicones are typically represented by alkylated polysiloxane materials, and silica is commonly used in finely divided form, exemplified by silica airgels, xerogels and various types of hydrophobic silica. These materials can be formulated as particles, and the suds suppressor is advantageously formulated to be released in a water-soluble or water-dispersible, substantially non-surfactant, detergent-impermeable carrier. . Alternatively, the foam control agent may be applied by dissolving or dispersing in a liquid carrier and spraying on one or more other components.

Preferred silicone suds suppressors are described in US Pat. No. 3,933,67 to Bartollota et al.
2 is disclosed. Another particularly useful suds suppressor is a self-emulsifying silicone suds suppressor, which is a German patent application DTOS 2,6 published April 28, 1977.
46, 126. An example of such a compound is DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer. A particularly preferred suds suppressor is a suds suppressor system consisting of a mixture of silicone oil and a 2-alkyl-alkanol. A suitable 2-alkyl-alkanol is 2-butyloctanol, sold under the trade name Isofol 12R. Such a suds suppressor system is described in co-pending European Patent Application N 92870174.7, filed November 10, 1992. Particularly preferred silicone suds suppressors are described in co-pending European Patent Application N 92022
649.8. The compositions may comprise silicone / silica mixture in combination with a molten nonporous silica such as Aerosil ^R.

[0166] The above-mentioned suds suppressor is used in an amount of 0.001 to 2% by weight of the composition, preferably 0.02%
Usually used at a level of 1 to 1% by weight.

Method In another aspect of the present invention, there is provided a method for providing fabric care to a fabric in a domestic treatment comprising the step of contacting the fabric with an aqueous medium containing a composition as described above. Preferably, the aqueous medium is 2 to 40C, more preferably 5 to 25C.
Temperature.

In another aspect of the invention, the compositions of the invention may be applied on a substrate such as a dryer sheet. Accordingly, there is also provided a method for providing fabric care to a treated fabric in a domestic treatment comprising the step of contacting the fabric with a composition as described above, wherein the composition is applied to a substrate, preferably a dryer sheet. Provided. Preferably, when the composition of the present invention is applied on a dryer sheet, the composition is used in a tumble drying process.

The compositions of the present invention can be used in any step of domestic treatment, ie, as a pre-treatment composition, as a cleaning additive, suitable for use in the rinse cycle of a wash cycle or applied on a dryer sheet. Suitable for use as an object. Obviously, for the purposes of the present invention, such as treating a fabric with a pretreatment composition of the present invention followed by a composition of the present invention suitable for use in a rinse cycle and / or for use as a dryer sheet, Many applications are possible. The composition of the invention may take the form of a spray, foam or aerosol, for example, which is suitable for use in ironing or applied to the surface of a tumble dryer.

“Softening throuth the wash”
When formulated as a composition, the process described herein consists of contacting the fabric with a wash liquor in a conventional manner, and is exemplified below. Conventional laundering methods consist of treating a soiled fabric with an aqueous liquid in which an effective amount of a laundry detergent and / or a fabric care composition has been dissolved or dispensed. The process of the present invention is conveniently performed during the cleaning process. The cleaning method is preferably performed at 5 to 95 ° C, particularly 10 to 60 ° C. The pH of the treatment solution is preferably 7-12.

[0171] Examples The following examples are meant to exemplify compositions of the present invention, not necessarily mean that limit or or limit the scope of the present invention. In fabric care compositions, enzyme levels are expressed as pure enzyme by weight of total composition, and detergent components are expressed by weight of total composition unless otherwise noted. Therefore abbreviated ingredients displayed have the following meanings: LAS: Sodium linear C _11-13 alkyl benzene sulphonate CxyAS: Sodium C _1x -C _1Y alkyl sulfate CxyEz: Mean z moles of ethylene oxide condensed with C _1X - C _1Y primarily straight chain primary alcohol DEQA: di (tallow oxyethyl) dimethylammonium chloride DEQA (2): di (soft tallow-yl oxy) hydroxyethyl methylation ammonium methylsulfate DTDMAMS: ditallow dimethyl ammonium methyl sulfate SDASA 1: 2 ratio stearyl dimethylamine: triple pressed stearic acid zeolite A: water of the formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ · 27H ₂ O with a main particle size in the range of 0.1 to 10 μm Na-SKS-6: Crystal-laminated silicate citrate of formula δ-Na ₂ Si ₂ O ₅ : 86.4% active citric acid with a particle size distribution of 425-850 μm Trisodium dihydrate carbonate: anhydrous sodium carbonate having a particle size of 200 to 900 μm MA / AA: random copolymer of 4: 1 acrylate / maleate Average molecular weight of about 70,000 to 80,000 PB1: empirical formula NaBO ₂ .H ₂ O ₂ anhydrous sodium perborate monohydrate Percarbonate: empirical formula 2 Na ₂ CO ₃ .3H ₂ O ₂ anhydrous sodium percarbonate TAED: tetraacetylethylenediamine DETPMP: diethyl sold under the trade name Dequest 2060 from Monsanto Triamine penta (methylene) phosphonate protease: Novo Nordis k Proteolytic enzymes sold by A / S under the trade names Savinase, Alcalase, Durazym; Maxacal, Maxapem sold by Gist-Brocades; and protease amylases described in patents WO 91/06637 and / or WO 95/10591. Amylolytic enzymes described in WO 94/18314, WO 96/05295 sold by Genencor under the trade name Purafact Ox Am ^R ; Termamyl ^R , Fungamyl ^R and Duramyl ^R , all commercially available from Novo Nordisk A / S; and Description of WO95 / 26397 Lipase: Lipoase, trade name from Novo Nordisk A / S, lipolytic enzyme sold under Lipolase Ultra, and Lipomax cellulase by Gist-Brocades: Carezyme, Celluzyme, trade name from Novo Nordisk A / S And / or cellulolytic enzyme CBD1 sold by Endolase: 24 amino A double CBD consisting of the N-terminal CBD of Trichoderma reesei CBHII linked to the C-terminal CBD of CBHI at the acid-linking region (M. Linder et al-The Journal of Biological Chemistry, Vol.271, No.35, Issue of August, pp. 21268-21272, 1996) CBD2: linked to a C18 alkyl quaternary wheat protein derivative sold under the trade name Coltide HQS by Croda Colloids Ltd., sold under the trade name Cellulose Binding Domain by Sigma. CBD from Clostridium cellulovorans Cellulozome CMC: Sodium carboxymethylcellulose Silicone defoamer: Polydimethylsiloxane foam preparation with siloxane oxyalkylene copolymer as dispersant in a ratio of 10: 1 to 100: 1 foam modifier to dispersant. Agent Foaming Inhibitor: Granular, 12% silicone / silica, 18% stearyl alcohol, 70% Starch HMWPEO: High molecular weight polyethylene oxide

Example 1 The following granular fabric detergent composition exhibiting "softening through the wash" capability was prepared in accordance with the present invention: I II C45AS 10.0 LAS 7.6-C68AS 1.3- C45E7 4.0-C25E3-5.0 Cocoalkyldimethylhydroxy 1.4 1.0 Ethyl ammonium chloride citrate 5.0 3.0 Na-SKS-6-11.0 Zeolite A 15.0 15.0 MA / AA 4.0 4.0 DETPMP 0.4 0.4 PB1 15.0-Percarbonate-15.0 TAED 5.0 5.0 Smectite clay 10.0 10.0 HMWPEO-0.1 Protease 0.02 0.0 01 lipase 0.002 0.01 amylase 0.03 0.005 cellulase 0.001 0.00 5 CBD1 - until silicate 3.0 5.0 Carbonate 10.0 10.0 suds suppressor 1.0 4.0 CMC 0.2 0.1 Water / Other 100% - 2.0 CBD2 0.2

Example 2 The following rinse aided fabric softener composition was prepared in accordance with the present invention: I II III
CBD1-2.0 0.5 CBD2 0.2-0.05 DEQA (2) 20.0 20.0 20.0 Cellulase 0.001 0.001 0.001
HCl 0.03 0.03 0.03 Defoamer 0.01 0.01 0.01 Blue pigment 25 ppm 25 ppm 25 ppm CaCl ₂ 0.20 0.20 0.20 Fragrance 0.90 0.90 0.90 Water and Others up to 100%

Example 3 The following fabric softener and dryer-added fabric conditioner composition was prepared in accordance with the present invention: I II III IV V
DEQA 2.6 19.0---DEQA (2)----51.8 DTMAMS---26.0-SDASA--70.0 42.0 40.2 Stearic acid with IV = 0 0.3----Neodol 45-13--13.0--Hydrochloric acid 0.02 0.02 ---Ethanol--1.0--Cellulase 0.0001 0.001 0.0005 0.005 0.0003 CBD1-1.0 1.0-5.0 CBD2 0.2--0.2-Fragrance 1.0 1.0 0.75 1.0 1.5 Glycoperse S-20----15.4 Glycerol monostearate---26.0 -Digeranyl succinate--0.38--Silicone defoamer 0.01 0.01---Electrolyte-0.1---Clay---3.0-Dye 10ppm 25ppm 0.01--Water and other 100% 100%---

Example 4 The following pre- or post-treatment compositions were prepared according to the present invention: I II III CBD1 2.0 1.0-CBD2--0.4 DEQA (2)-20.0 20.0 Cellulase 0 .002 0.001 0.001 HCl - 0.03 0.03 antifoam - 0.01 0.01 blue dye 25ppm 25ppm 25ppm CaCl ₂ - 0.20 0.20 perfume 0.90 0.90 0.90 Water / others up to 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, 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, CU, CZ, DE, DK, 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 (71) CINCINNATI, OHIO, UNITED STATES OF AMERICA (72) Inventor Joan, Smetz Belt-3210, Belgium, Rubeik, Bohlenberg, 79 (72) Inventor Stanton, Rein, Boyer Ohio, Fairfield, Fall, River, United States Coat, 12

Claims (14)

[Claims] 1. A softening protein hybrid comprising an amino acid sequence comprising a cellulose binding domain linked to a softening protein. 2. A fabric care composition comprising one or more amino acid sequences comprising a cellulose binding domain and / or a softening protein hybrid according to claim 1. 3. Cellulose binding domain is CBD CenC, C from Cellulomonas fimi
enA, Cex, CBD CBHI, Clostridium ce from Trichoderma reesei
CBD from Cellulozome from C. llulovorans, CBD E from Thermonospora fusca
3. CBD dimer from Clostridium stecorarium XynA, Bacillus agara
dherens, CBD family 45 from Humicola insolens and / or
Or a softening protein hybrid or fabric care composition according to claim 1 or 2 selected from the group consisting of or a mixture thereof. 4. The method according to claim 1, wherein the amino acid sequence containing the cellulose binding domain comprises a C
4. The softening protein hybrid or fabric care composition of claim 3, wherein the softening protein hybrid or fabric care composition is selected from the group consisting of BD Family 45, CBD CenC from Cellulomonas fimi and / or CBD Cellulozome from Clostridium cellulovorans. 5. The softening protein hybrid or fabric care composition according to claim 1, wherein some amino acid sequences comprising the cellulose binding domain are cross-linked. 6. The softened protein hybrid or fabric care composition according to claim 5, wherein 2 to 50, preferably 2 to 10, amino acid sequences comprising the cellulose binding domain are crosslinked. 7. The amino acid sequence containing the N-terminal CBD of Trichoderma reesei CBHII is
The softening protein hybrid or fabric care composition of claim 5 or 6, wherein the softening protein hybrid or fabric care composition is linked to an amino acid sequence comprising the C-terminal CBD of erma reesei CBHI. 8. The softening protein hybrid or fabric care composition according to any one of claims 2 to 7, wherein the softening protein is an inactive enzyme and / or a C18 alkyl quaternary wheat protein derivative. 9. A softening protein hybrid or fabric care composition according to any one of claims 2 to 8, wherein the softening protein is linked via a linking region to an amino acid sequence comprising a cellulose binding domain. object. 10. The connecting region is a non-amino acid connecting region, preferably PEG (NPC) 2, (NH2).
10. The softened protein hybrid or fabric care composition according to claim 9, which is a polymer selected from 2-PEG, t-BOC-NH-PEG-NH2, MAL-PEG-NHS and / or VS-PEG-NHS polymer. object. 11. The softening protein hybrid or fabric care composition of claim 9, wherein the connecting region is an amino acid connecting region. 12. The fabric care composition according to any one of claims 2 to 11, further comprising another fabric care component. 13. The fabric according to any one of claims 2 to 12, wherein the other fabric care component is selected from cationic surfactants having two long alkyl chain lengths, clays and / or transferases. Care composition. 14. A method for imparting, renewing or restoring tensile strength by providing fabric flexibility, anti-wrinkle property, anti-pilling property, anti-shrinkage property, static electricity control, color appearance and fabric wear resistance. 14. A method comprising contacting a fabric with a fabric care composition according to any one of 2 to 13.