JP2019073715A - Method of laundering fabrics - Google Patents

Abstract

To provide laundry detergent compositions that improve cleaning at low wash temperatures and also at short wash cycles.SOLUTION: There is provided a method of laundering a fabric, comprising the steps of: (i) contacting a fabric with an aqueous wash liquor comprising a detergent composition, the detergent composition comprising a surfactant and wherein the wash liquor comprises from 0.05 to 4 g/l of a surfactant; and (ii) in a first rinse step, contacting the fabric from step (i) with a first rinse liquor; (iii) in a second rinse step, contacting the fabric from step (ii) with a second rinse liquor comprising a lipid esterase; (iv) drying the fabric; (v) contacting the fabric from step (iv) with a soil; and (vi) contacting the fabric from step (v) with an aqueous wash liquor of a detergent composition wherein the detergent composition comprises a surfactant, the wash liquor comprising from 0.05 to 4 g/l of a surfactant.SELECTED DRAWING: None

Description

  The present invention relates to a method of laundering fabrics.

  Fabric care compositions are often added by consumers at the rinse stage of fabric washing operations. Fabric care compositions impart a number of sensory benefits including flexibility and freshness that consumers can enjoy. Most often, flexibility is provided by etherified cationic surfactants or silicones. It is also known to add cellulase enzymes in such compositions as described in WO 95/05442.

  Laundry detergent compositions are used to provide fabric cleaning benefits in the cleaning process of a laundry operation. In particular, there is a further need for means for improving cleaning with low cleaning temperatures and short cleaning cycles.

  The present invention alleviates this problem.

International Patent Publication No. 95/05442

The present invention relates to a method of laundering a fabric comprising the following steps.
i) contacting the fabric with an aqueous washing solution comprising the detergent composition, the detergent composition comprising a surfactant and the washing solution comprising 0.05 to 4 g / l of surfactant, and ii) Bringing the fabric of step (i) into contact with a first rinse in one washing step;
iii) contacting the fabric of step (ii) with a second rinse comprising lipid esterase in the second washing step;
iv) drying the fabric,
v) contacting the fabric of step (iv) with dirt;
vi) contacting the fabric of step (v) with an aqueous washing solution of the detergent composition, the detergent composition comprising a surfactant and the washing solution comprising 0.05 to 4 g / l surfactant.

  Typically, the first and second rinses are aqueous. Preferably, the rinse, in particular the second rinse, further comprises an antifouling polymer.

The method of the present invention comprises the following steps.
i) contacting the fabric with an aqueous washing solution comprising the detergent composition, the detergent composition comprising a surfactant and the washing solution comprising 0.05 to 4 g / l of surfactant, and ii) Bringing the fabric of step (i) into contact with the rinse solution in one washing step;
iii) contacting the fabric of step (ii) with a second aqueous rinse comprising lipid esterase in a second washing step;
iv) drying the fabric,
v) contacting the fabric of step (iv) with dirt;
vi) contacting the fabric of step (v) with an aqueous washing solution of the detergent composition, the detergent composition comprising a surfactant and the washing solution comprising 0.05 to 4 g / l surfactant.

  In the method of the present invention, the fabric of step (i) may be washed in a conventional washing step where the addition of the detergent composition to water forms an aqueous washing solution. The surfactant concentration in the aqueous cleaning solution is 0.05 to 4 g / l. In step (ii), the fabric is subjected to the rinse step of the washing operation and the cleaning solution is substantially removed from the fabric. In step (iii), an additional rinse step is provided in which the fabric contacts the lipid esterase. The fabric is then dried in step (iv) and soiled in step (v), ie the fabric is then worn by the consumer or otherwise used for the application. Following use of the fabric, the fabric may then be further contacted with an aqueous cleaning solution in step (vi). Without being bound by theory, the lipid esterase which contacts the fabric in step (iii) acts "out of the wash" on the hydrolysis of the soil / stain which contacts the fabric during the soiling step (v) It is believed that. This results in good soil removal in the subsequent washing step (iv) and effective soil removal from the fabric in step (vi). This enables the reduction of the amount of surfactant used to provide effective cleaning.

Process (i)
The method of the present invention comprises the step (i) of contacting the fabric with an aqueous cleaning solution. An aqueous cleaning solution is formed by the addition of the laundry detergent composition to water. The detergent composition added to water to form an aqueous cleaning solution may be in any suitable form including granules, liquids or single dose volumes. In the case of a single dose form, it is desirable for the composition to be enclosed in a water soluble film, for example in a polyvinyl alcohol based film. The fabric may be contacted with the composition in the hand washing process or the cleaning solution in the machine cleaning cycle.

  Laundry detergent compositions typically comprise 1 to 70 wt%, or 2 to 50 wt% or 5 to 40 wt% surfactant based on the total weight of the laundry detergent composition. The concentration of surfactant in the washing solution is 0.05 to 5 g / l, or 0.1 to 4 g / l.

  The detersive surfactant may be an anionic surfactant, a cationic surfactant, a nonionic surfactant, a dipolar surfactant, an amphoteric surfactant or a combination thereof. The surfactant composition may comprise one surfactant or a mixture of typically two or more surfactants.

  Preferred anionic detersive surfactants are alkyl benzene sulfonic acids, alkoxylated anionic surfactants, or combinations thereof. Suitable anionic detersive surfactants include sulfate detersive surfactants and sulfonate detersive surfactants.

Particularly preferred alkylbenzene sulfonic acids are linear alkyl benzene sulfonic acids, in particular those having a carbon chain length C8 to C15, or _C10-13 alkyl benzene sulfonic acids. Suitable alkyl benzene sulfonic acids (LAS) are obtainable or obtained by sulfonation of commercially available linear alkyl benzenes (LAB), supplied by Sasol under the trade name Isochem® as a suitable LAB. Low 2-phenyl LABs such as those being marketed or supplied by Petrsa under the trade name Petrelab®, other suitable LABs supplied by Sasol under the trade name Hyblene® And high 2-phenyl LAB. Another suitable anionic detersive surfactant is an alkyl benzene sulfonic acid, preferably having 8 to 15 carbon atoms, obtained by the DETAL catalytic process. Other synthetic routes such as HF may also be suitable.

Suitable sulfate detersive surfactants include alkyl sulfates such as C _8-18 alkyl sulfates, or predominantly C ₁₂ alkyl sulfates. The alkyl sulfates may be derived from natural sources such as coco and / or tallow. Alternatively, the alkyl sulfates may be derived from synthetic sources such as _C12-15 alkyl sulfates.

It may be preferred that the surfactant composition further comprises an alkyl alkoxylated sulfate, such as an alkyl ethoxylated sulfate, or a C _8-18 alkyl alkoxylated sulfate, or a C _8-18 alkyl ethoxylated sulfate. Preferably, the alkyl chain length may be 12 to 16 carbon atoms. The alkyl alkoxylated sulfate may have an average degree of alkoxylation of 0.5 to 20, or 0.5 to 10, or 0.5 to 7, or 0.5 to 5, or 0.5 to 3. Examples include sodium predominantly C12 lauryl sulfate ether ethoxylated with an average of 3 moles of ethylene oxide per mole.

  The alkyl sulfate, alkyl alkoxylated sulfate, and alkyl benzene sulfonate may be linear or branched, and may be substituted or unsubstituted.

The anionic detersive surfactant may be a medium chain branched anionic detersive surfactant such as a medium chain branched alkyl sulfate and / or a medium chain branched alkyl benzene sulfonate. The medium chain branch is typically a C _1-4 alkyl group such as a methyl group and / or an ethyl group.

  Another suitable anionic detersive surfactant is an alkyl ethoxy carboxylate.

The anionic detersive surfactant is typically present in its salt form and is typically complexed with a suitable cation. Suitable counter ions include Na ⁺ and K ⁺ , substituted ammonium such as C ₁ -C ₆ subalkanol ammonium, such as monoethanolamine (MEA), triethanolamine (TEA), diethanolamine (DEA), and the like. Any combination may be mentioned.

Preferably, the surfactant composition comprises, in addition to the anionic surfactant, a nonionic surfactant. Preferred nonionic surfactants are primary and secondary alcohols, in particular ethoxylates. Suitable non-ionic detersive surfactants include _C8-18 alkyl alkoxylated alcohols or alkyl alkoxylated alcohols such as _C8-18 alkyl ethoxylated alcohols. The alkyl alkoxylated alcohol may have an average degree of alkoxylation of 0.5 to 50, or 1 to 30, or 1 to 20, or 1 to 10. The alkyl alkoxylated alcohol may typically be a C _8-18 alkyl ethoxylated alcohol having an average degree of ethoxylation of 1 to 10, or 1 to 7, or 1 to 5, or 3 to 7. The alkyl alkoxylated alcohol may be linear or branched and may be substituted or unsubstituted.

Preferred examples of non-ionic surfactants are selected from the group consisting of C ₈ -C ₁₈ alkyl ethoxylates, such as the non-ionic surfactants sold under the name NEODOL® by Shell. like, optionally in the alkoxylate units are ethyleneoxy units, propyleneoxy units or a mixture thereof, C ₆ ~ a C ₆ -C ₁₂ alkyl phenol alkoxylates C ₁₂ -C ₁₈ alcohol and ethylene oxide / propylene oxide block copolymer C ₁₂ alkyl phenol condensates (eg Pluronic® sold by BASF), C ₁₄ -C ₂₂ medium-chain branched alcohols, typically C ₁₄ -C with an average degree of alkoxylation of 1 to 30 ₂₂ in the chain branched alkyl alkoxylates, A Alkylpolysaccharides such as kills polyglycosides, polyhydroxy fatty acid amides, ether capped poly (oxyalkylated) alcohol surfactants, and mixtures thereof. Suitable non-ionic detersive surfactants are also alkyl polyglucosides and / or alkyl alkoxylated alcohols.

  Suitable non-ionic detersive surfactants include secondary alcohol-based detersive surfactants having the formula:

式中、Ｒ^１は、直鎖又は分枝鎖、置換又は非置換、飽和又は不飽和のＣ_２〜８アルキルであり、式中、Ｒ^２は、直鎖又は分枝鎖、置換又は非置換、飽和又は不飽和のＣ_２〜８アルキルであり、Ｒ^１＋Ｒ^２部分中に存在する炭素原子の総数は７〜１３の範囲である。ＥＯ／ＰＯは、エトキシ、プロポキシ、又はこれらの混合物から選択されるアルコキシ部分であり、任意で、ＥＯ／ＰＯアルコキシ部分はランダム又はブロック構造であり、ｎは、平均アルコキシル化度であり、４〜１０の範囲である。

Wherein R ¹ is linear or branched, substituted or unsubstituted, saturated or unsaturated C _2-8 alkyl, wherein R ² is linear or branched, substituted or unsubstituted , Saturated or unsaturated C _2-8 alkyl, and the total number of carbon atoms present in the R ¹ + R ² moiety is in the range of 7-13. EO / PO is an alkoxy moiety selected from ethoxy, propoxy, or a mixture thereof, optionally the EO / PO alkoxy moiety is a random or block structure and n is an average degree of alkoxylation, 4 to 4 It is in the range of ten.

  Other suitable nonionic detersive surfactants include EO / PO block copolymer surfactants such as the Plurafac® series of surfactants available from BASF, and sugars such as alkyl N-methyl glucose amides And surfactants of origin.

  The ratio of anionic surfactant to nonionic surfactant may be 2: 1 to 1: 2, alternatively 1: 1 to 1: 3, or 1: 1 to more than 1: 2.

  The composition may further comprise amine oxide, preferably in an amount of up to 10% by weight of the surfactant composition. Suitable amine oxides are described in WO 2014/114570, a particularly preferred amine oxide is lauryl dimethyl amine oxide. The composition may further comprise a dipolar surfactant. A preferred dipolar surfactant is a betaine surfactant, such as a carbobetaine such as Empigen® sold by the company Hartsmann. When an amine oxide and / or betaine surfactant is present, the weight ratio of anionic and / or nonionic surfactant to amine oxide and / or betaine is typically 10: 1 to 20: 1. It is.

  The laundry detergent composition may comprise a lipid esterase. The lipid esterase may be any lipid esterase. The lipid esterase may be a lipase, or a cutinase, or a combination thereof.

The lipid esterase may be selected from:
(1) Triacylglycerol lipase (EC 3.1.1.3)
(2) Carboxylic acid ester hydrolase (EC 3.1.1.1)
(3) Cutinase (E.C. 3.1.1. 74)
(4) Sterol esterase (EC 3.1.1.13)
(5) Wax ester hydrolase (E.C. 3.1.1. 50)

  Suitable triacylglycerol lipases can be selected from the lipase variants of Humicola lanuginosa (Thermomyces lanuginosus, Thermomyces lanuginosus). Other suitable triacylglycerol lipases are e.g. Alkaline Genes (P. alcaligenes) or P. al. P. pseudoalcaligenes (European Patent No. 218, 272), P. p. P. cepacia (European Patent No. 331,376), P.C. P. stutzeri (British Patent No. 1,372, 034), P. st. Fluorescein (P. fluorescens), Pseudomonas sp. Strain SD 705 (WO 95/06720 and WO 96/27002), P.I. Pseudomonas lipases such as P. wisconsinensis (WO 96/12012), for example B. pylori. subtilis (Dartois et al. (1993) Biochemica et Biophysica Acta, 1131, 253-360), B. subtilis. B. stearothermophilus (Japanese Patent No. 64/744992) or B. stearothermophilus (Japanese Patent No. 64/744992). It can be selected from mutant forms of Bacillus lipase such as B. pumilus (WO 91/16422).

  Preferred carboxylic acid ester hydrolases are: Gladoli (B. gladioli), P.I. Fluorescence (P. fluorescens), P. fluorescens. putida, B. et al. acidocaldarius, B. subtilis, B. Stearothermophilus, Streptomyces chrysomallus, S. It can be selected from wild type or mutant forms of carboxylic acid ester hydrolase endogenous to D. diastatochromogenes and Saccaromyces cerevisiae.

  Suitable cutinases are Aspergillus strains, in particular Aspergillus oryzae, Alternaria strains, in particular Alternaria brassiciola, Fusarium strains, in particular Fusarium solani, Fusarium solani pisi, Fusarium oxysporum, Fusarium oxyspora, Fusarium roseum culmorum or insulinumium Helminthosporum sativum, Humicola strains, in particular Humicola insolens, Pseudomonas strains, in particular Pseudomonas mendocia, or Pseudomonas as putida, Rhizoctonia strain, especially Rhizoctonia solani, Streptomyces strain, especially Streptomyces scabies, Coprinopsis strain, especially Coprinopsis cinerea, Thermobifida strain, especially Thermobifida fusca, Magnaporthe strain, especially Magnaporthe grisea, or Ulocladium protease, especially Can be selected from wild type or mutant forms of

  In a preferred embodiment, the cutinase is selected from mutants of Pseudomonas mendocia cutinase, such as the three substitution I178M, F180V and S205G mutants described in WO 2003/076580 (Genencor, Genencor).

  In another preferred embodiment, the cutinase is Kontkanen et al, App Environ. It is a wild type or mutant form of six cutinases endogenous to Coprinopsis cinerea described in Microbiology, 2009, p 2148-2157.

  In another preferred embodiment, the cutinase is a wild type or mutant form of two cutinases endogenous to Trichoderma reesei as described in WO2009007510 (VTT).

  In the most preferred embodiment, the cutinase is derived from a Humicola insolens strain, in particular a Humicola insolens DSM 1800 strain. Humicola insolens cutinase is described in WO 96/13580, which is incorporated herein by reference. The cutinase may be a variant such as one of the variants disclosed in WO 00/34450 and WO 01/92502. Preferred cutinase variants include those described in Example 2 of WO 01/92502. Preferred commercial cutinases include Novozym 51032 (available from Novozymes, Bagsvaerd, Denmark).

  Suitable sterol esterases include Ophiostoma strains such as Ophiostoma piceae, Pseudomonas strains such as Pseudomonas aeruginosa, or Melanocarpus strains such as It may be derived from Melanocarpus albomyces).

  In the most preferred embodiment, the sterol esterase is K Kontkanen et al, Enzyme Microb Technol. 39, (2006), 265-273, and is a Melanocarpus albomyces sterol esterase.

  Suitable wax ester hydrolases may be derived from jojoba (Simmondsia chinensis).

  Lipid esterases are enzymes E. coli. C. It may be selected from classes 3.1 or 3.2 or combinations thereof. Lipid esterases are enzymes E. coli. C. It may be selected from classes 3.1.1.1 or 3.1.1.3 or combinations thereof.

  The detergent composition of step (i) optionally contains one or more additional detergent ingredients, as described below.

  The fabric may be any suitable fabric. The fabric may comprise natural or synthetic materials, or a combination thereof. The fabric may comprise cotton, a blend of polyester and cotton, polyester, or combinations thereof. The fabric may comprise cotton.

Step (ii)
In step (ii), the washed fabric of step (i) is typically subjected to a rinse step using an aqueous rinse. This may be a hand wash rinse step in which the fabric of step (i) is placed in a rinse solution substantially free of the detergent composition present in step (i) or a rinse step in a washing machine. Typically, the rinse is then removed from the fabric by conventional means. Step (ii) may comprise two or more separate rinse steps, in each of which a fresh rinse is provided. Removing the laundry detergent composition from the fabric of step (i) at least partially, preferably almost completely, although step (ii) does not remove all the laundry detergent composition, but in the washing step It aims to.

Step (iii)
The method of the invention comprises a second rinse step (iii), wherein the fabric is in contact with a second rinse comprising lipid esterase.

  The lipid esterase may be any suitable lipid esterase. The lipid esterase may comprise at least first and second lipid esterases. The lipid esterase may comprise three or more lipid esterases. The lipid esterase may be a lipase, or a cutinase, or a combination thereof.

The lipid esterase may be selected from:
(1) Triacylglycerol lipase (EC 3.1.1.3)
(2) Carboxylic acid ester hydrolase (EC 3.1.1.1)
(3) Cutinase (E.C. 3.1.1. 74)
(4) Sterol esterase (EC 3.1.1.13)
(5) Wax ester hydrolase (E.C. 3.1.1. 50)

  According to "EC class" which means Enzyme Commission class herein. The Enzyme Commission class is an enzyme classification table recognized internationally based on enzyme-catalyzed chemical reactions.

  Suitable trisylglycerol lipases can be selected from the lipase variants of Humicola lanuginosa (Thermomyces lanuginosus, Thermomyces lanuginosus). Other suitable triacylglycerol lipases are e.g. Alkaline Genes (P. alcaligenes) or P. al. P. pseudoalcaligenes (European Patent No. 218, 272), P. p. P. cepacia (European Patent No. 331,376), P.C. P. stutzeri (British Patent No. 1,372, 034), P. st. Fluorescein (P. fluorescens), Pseudomonas sp. Strain SD 705 (WO 95/06720 and WO 96/27002), P.I. Pseudomonas lipases such as P. wisconsinensis (WO 96/12012), for example B. pylori. subtilis (Dartois et al. (1993) Biochemica et Biophysica Acta, 1131, 253-360), B. subtilis. B. stearothermophilus (Japanese Patent No. 64/744992) or B. stearothermophilus (Japanese Patent No. 64/744992). It can be selected from mutant forms of Bacillus lipase such as B. pumilus (WO 91/16422).

  Preferred carboxylic acid ester hydrolases are: Gladioli (B. gladioli), P.I. Fluorescein (P. fluorescens), P. fluorescens. putida, B. et al. acidocaldarius, B. subtilis, B. Stearothermophilus, Streptomyces chrysomallus, S. It can be selected from wild type or mutant forms of carboxylic acid ester hydrolase endogenous to D. diastatochromogenes and Saccaromyces cerevisiae.

  Suitable cutinases are Aspergillus strains, in particular Aspergillus oryzae, Alternaria strains, in particular Alternaria brassiciola, Fusarium strains, in particular Fusarium solani, Fusarium solani pisi, Fusarium oxysporum, Fusarium oxyspora, Fusarium roseum culmorum or insulinumium Helminthosporum sativum, Humicola strains, in particular Humicola insolens, Pseudomonas strains, in particular Pseudomonas mendocia, or Pseudomonas as putida, Rhizoctonia strain, especially Rhizoctonia solani, Streptomyces strain, especially Streptomyces scabies, Coprinopsis strain, especially Coprinopsis cinerea, Thermobifida strain, especially Thermobifida fusca, Magnaporthe strain, especially Magnaporthe grisea, or Ulocladium protease, especially Can be selected from wild type or mutant forms of

  In a preferred embodiment, the cutinase is selected from mutants of Pseudomonas mendocia cutinase, such as the three substitution I178M, F180V and S205G mutants described in WO 2003/076580 (Genencor, Genencor).

  In another preferred embodiment, the cutinase is It is a wild-type or mutant form of six cutinases endogenous to Coprinopsis cinerea described in Kontkanen et al, App Environ Microbiology, 2009, P 2148-2157.

  In another preferred embodiment, the cutinase is a wild type or mutant form of two cutinases endogenous to Trichoderma reesei as described in WO2009007510 (VTT).

  In the most preferred embodiment, the cutinase is derived from a Humicola insolens strain, in particular a Humicola insolens strain DSM1800. Humicola insolens cutinase is described in WO 96/13580, which is incorporated herein by reference. The cutinase may be a variant such as one of the variants disclosed in WO 00/34450 and WO 01/92502. Preferred cutinases include variants, including the variants described in Example 2 of WO 01/92502.

  Suitable sterol esterases include Ophiostoma strains such as Ophiostoma piceae, Pseudomonas strains such as Pseudomonas aeruginosa, or Melanocarpus strains such as It may be derived from Melanocarpus albomyces).

  In the most preferred embodiment, the sterol esterase is K Kontkanen et al, Enzyme Microb Technol. 39, (2006), 265-273, and is a Melanocarpus albomyces sterol esterase.

  Suitable wax ester hydrolases may be derived from jojoba (Simmondsia chinensis).

  Lipid esterases are enzymes E. coli. C. It may be selected from classes 3.1 or 3.2 or combinations thereof. Lipid esterases are available from E.I. C. An enzyme selected from classes 3.1.1.1 or 3.1.1.3 or 3.1.1.74 or combinations thereof may be included. Preferred lipid esterases are: It may comprise an enzyme selected from C class 3.1.1.3. The lipid esterase is a variant having at least 90% sequence identity to a wild type lipase from Thermomyces lanuginosus and having the sequence substitutions T231R and N233R, or claim 5, EP 1 290 150 A variant corresponding to part (u) of (B1), or a combination thereof may be included. The lipid esterase may comprise variants having at least 90% sequence identity to a wild type lipase from Thermomyces lanuginosus and having the sequence substitutions T231R and N233R.

  The fabric may be contacted with the lipid esterase at a concentration of between 30 and 55,000 ng enzyme / g fabric. The fabric may be contacted with the lipid esterase at a concentration of between 30 and 2000 ng enzyme / g fabric. The fabric may be contacted with the lipid esterase at a concentration between 50-1700 ng enzyme / g fabric, or 80-1600 ng enzyme / g fabric. The fabric may be contacted with the lipid esterase at a concentration of between 100 and 3000 ng enzyme / g fabric, or 125-2500 ng enzyme / g fabric. The fabric may be contacted with the lipid esterase at a concentration of between 100 and 35,000 ng enzyme / g fabric, or between 500 and 30,000 ng enzyme / g fabric. Without being bound by theory, it is believed that these concentrations are optimal for removing soils from fabrics.

  In step (ii), the fabric of step (ii) is contacted with a lipid esterase in a second rinse step. This may be a hand rinse step where the fabric of step (ii) is placed in rinse water substantially free of the detergent composition present in step (i), or it may be a rinse step in a washing machine. In the step (iii) of contacting the fabric with the lipid esterase, the lipid esterase is thereby deposited on the fabric.

  The rinse solution of the second rinse step is a quaternary ammonium surfactant or a softener component such as silicone etc., and optionally other components useful in the rinse step such as perfumes, dyes, polymers, surfactants etc. Optional additional rinse ingredients may be included.

  Preferably, the aqueous rinse in the second rinse step of step (iii) comprises an antifouling polymer. The antifouling polymer may be present in the aqueous rinse in an amount of about 0.00001 to 3 g / l, 0.0001 to 2 g / l, 1 g / l, or 0.5 g / l or less in the rinse. A rinse may be provided by adding the softener composition to water to form an aqueous rinse. The antifouling polymer may be added via the softener composition. In such softening compositions, the antifouling polymer is typically about 0.01% to about 10.0% by weight of the antifouling polymer (also known as a soil release agent or "SRA") composition, typically May be present in amounts of about 0.1% to about 5%, and in some embodiments 0.2% to about 3.0%.

  Suitable antifouling polymers are typically deposited on hydrophilic segments that hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and on hydrophobic fibers, and cleaning and during the completion of the cleaning and rinsing cycles It has a hydrophobic segment that remains attached during the completion of the rinse cycle, thereby acting as an anchor point for the hydrophilic segment. This may allow stains that occur after treatment with the stain release agent to be more easily cleaned in later cleaning procedures.

The soil release agent may comprise various charged, for example anionic or cationic (see, eg, US Pat. No. 4,956,447), as well as uncharged monomer units. The structure of the soil release agent may be linear, branched or star-shaped. The antifouling polymer may comprise a capping moiety, which is particularly effective in controlling the molecular weight of the polymer or modifying the physical or surface active properties of the polymer. The structure and charge distribution of the antifouling polymer may be adjusted as needed for application to different fiber or textile forms and formulation in different detergent or detergent additive products. Preferred polyester antifouling polymers have a structure defined by one of the following structures (III), (IV) or (V):
-[(OCHR ^1- CHR ² )-O-OC-Ar-CO-] _d (III)
_{^{- [(OCHR 3 CHR 4)}} b -O-OC-sAr-CO] e (IV)
-[(OCHR ⁵ -CHR ⁶ ), OR ⁷ ] _f (V)
During the ceremony
a, b and c are 1 to 200,
d, e and f are 1 to 50,
Ar is 1,4-substituted phenylene,
sAr is 1,3-substituted phenylene substituted at position 5 with SO ₃ Me;
Me is H, Na, Li, K, Mg + 2, Ca + 2, Al + 3, ammonium, mono-, di-, tri- or tetra-alkyl ammonium (alkyl group is C1-C18 alkyl or C2-C10 hydroxyalkyl) Or a mixture of these,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently H or C, -C 18 n- or iso-alkyl, R 7 is linear or branched C 1 -C 18 It is alkyl, or linear or branched C2 to C30 alkenyl, or a cycloalkyl group having 5 to 9 carbon atoms, or a C6 to C30 aryl group, or a C6 to C30 arylalkyl group.

  Preferred polyester antifouling polymers are terephthalate polymers having the structure (III) or (IV) above. Other suitable antifouling polymers may include, for example, end-capped and non-end-capped sulfonated and non-sulfonated PET / POET polymers. An example of a suitable polyester antifouling polymer is the REPEL-O-TEX® line of polymers supplied by Rhodia, REPEL-O-TEX® SRP6 and REPEL-O-TEX® SF -2 is mentioned. Other suitable antifouling polymers include TexCare® SRA-100, TexCare® SRA-300, TexCare® SRN-100, TexCare® SRN-170 supplied by Clariant. , TexCare® SRN-240, TexCare® SRN-300, and TexCare® SRN-325, including TexCare® polymers. Particularly useful antifouling polymers are the sulfonated non-end capped polyesters described in WO 95/32997 A (Rhodia Chimie). Other suitable antifouling polymers are Marloquest® polymers such as Marloquest® SL supplied by Sasol. Examples of SRAs are described in US Pat. No. 4,968,451. 4, 711, 7304, 721, 5804, 702, 8784, 877, 8963, 959, 2303, 892, 929 4,000, 0935, 415, 201, 8244, 240, 9184, 525, 5244, 201, 8244, 579, 681 and 4, 787, 989 European Patent Applications No. 0 219 048 279, 134 A 457, 205 A and German Patent No. 2, 335, 044 and International Patent Publication No. 2014 19792 International Publication Patent No. 2012 104 156/57/58 Patent No. 201419658 International Publication Patent No. 20141965 International Publication Patent No. 201429479.

Optionally, the second rinse further comprises a diester quaternary ammonium compound, a dialkyl quaternary ammonium compound, an imidazolinium quaternary compound, a cationic starch, a sucrose ester based fabric care substance, and mixtures thereof A fabric softener active selected from In one aspect, such ester quaternary ammonium fabric softener actives, monoesters, diesters, and triesters quaternary ammonium fabric softener actives and ion pair fabric softener actives are selected from the group consisting of: Ru.
a) Substance of the following formula (1)

式中、
（ｉ）Ｒ_１及びＲ_２は、それぞれ独立してＣ_５〜Ｃ_２３炭化水素である、
（ｉｉ）Ｒ_３及びＲ_４は、Ｃ_１〜Ｃ_４炭化水素、Ｃ_１〜Ｃ_４ヒドロキシ基置換炭化水素、ベンジル、ｙが１〜１０の整数である−（Ｃ_２Ｈ_４Ｏ）_ｙＨからなる群からそれぞれ独立して選択される、
（ｉｉｉ）Ｌは、−Ｃ（Ｏ）Ｏ−、−ＯＣ（Ｏ）−からなる群から選択される、
（ｉｖ）Ｚは、各ｎが独立して１〜４の整数である−（ＣＨ_２）_ｎ、−ＣＨ_２Ｃ（ＣＨ_３）Ｈ−からなる群から選択される、
（ｖ）Ｘ⁻は柔軟剤相溶性アニオンである、
ｂ）以下の式（２）の物質

During the ceremony
(I) R ₁ and R ₂ are each independently a C ₅ -C ₂₃ hydrocarbon,
(Ii) R ₃ and R _{4 each} represent a C _{1 to} C ₄ hydrocarbon, a C _{1 to} C ₄ hydroxy group-substituted hydrocarbon, benzyl, and y is an integer of 1 to 10— (C ₂ H ₄ O) _y H Each independently selected from the group consisting of
(Iii) L is selected from the group consisting of -C (O) O-, -OC (O)-,
(Iv) Z, each n is independently an integer of 1 to 4 _{- (CH 2) n,} is selected from the group consisting of _{-CH 2 C (CH 3) H-} ,
(V) X ^- is a softener compatible anion,
b) Substance of the following formula (2)

式中、
（ｉ）Ｒ_５はＣ_５〜Ｃ_２３炭化水素である、
（ｉｉ）各Ｒ_６は、Ｃ_１〜Ｃ_４炭化水素、Ｃ_１〜Ｃ_４ヒドロキシ置換炭化水素、ベンジル、ｙが１〜１０の整数である−（Ｃ_２Ｈ_４Ｏ）_ｙＨからなる群から独立して選択される、
（ｉｉｉ）Ｌは、−Ｃ（Ｏ）Ｏ−、−Ｃ−（Ｏ）Ｃ−からなる群から選択される、
（ｉｖ）Ｚは、各ｎが独立して１〜４の整数である−（ＣＨ_２）_ｎ、−ＣＨ_２Ｃ（ＣＨ_{３）Ｈ−からなる群から選択される、
（ｖ）Ｘ} ⁻は柔軟剤相溶性アニオンである、
ｃ）以下の式（３）の物質

During the ceremony
(I) R ₅ is a C ₅ -C ₂₃ hydrocarbon,
(Ii) each R ₆ is a group consisting of C _{1 to} C ₄ hydrocarbon, C _{1 to} C ₄ hydroxy substituted hydrocarbon, benzyl, and y is an integer of 1 to 10-(C ₂ H ₄ O) _y H Selected independently from
(Iii) L is selected from the group consisting of -C (O) O-, -C- (O) C-,
(Iv) Z, each n is independently an integer of 1 to 4 _{- (CH 2)} n, _{is selected from the group consisting of -CH 2 C (CH 3) H-} ,
_{(V) X} ^- is a softener compatible anion,
c) Substance of the following formula (3)

式中、
（ｉ）Ｒ_５はＣ_５〜Ｃ_２３炭化水素である、
（ｉｉ）各Ｒ_６は、Ｃ_１〜Ｃ_４炭化水素、Ｃ_１〜Ｃ_４ヒドロキシ置換炭化水素、ベンジル、ｙが１〜１０の整数である−（Ｃ_２Ｈ_４Ｏ）_ｙＨからなる群から独立して選択される、
（ｉｉｉ）Ｌは、−Ｃ（Ｏ）Ｏ−、−Ｃ−（Ｏ）Ｃ−からなる群から選択される、
（ｉｖ）Ｚは、各ｎが独立して１〜４の整数である−（ＣＨ_２）_ｎ、−ＣＨ_２Ｃ（ＣＨ_３）Ｈ−からなる群から選択される、
（ｖ）Ｘ⁻は、Ｃ_６〜Ｃ_２４炭化水素を含むアニオン性界面活性剤である。
ｄ）以下の式（４）の物質

During the ceremony
(I) R ₅ is a C ₅ -C ₂₃ hydrocarbon,
(Ii) each R ₆ is a group consisting of C _{1 to} C ₄ hydrocarbon, C _{1 to} C ₄ hydroxy substituted hydrocarbon, benzyl, and y is an integer of 1 to 10-(C ₂ H ₄ O) _y H Selected independently from
(Iii) L is selected from the group consisting of -C (O) O-, -C- (O) C-,
(Iv) Z, each n is independently an integer of 1 to 4 _{- (CH 2) n,} is selected from the group consisting of _{-CH 2 C (CH 3) H-} ,
(V) X ^- is an anionic surfactant comprising a C ₆ -C ₂₄ hydrocarbon.
d) Substance of the following formula (4)

式中、
（ｉ）Ｒ_７、Ｒ_８及びＲ_９は、それぞれ独立してＣ_５〜Ｃ_２３炭化水素である、
（ｉ）各Ｒ_１０は、Ｃ_１〜Ｃ_４炭化水素、Ｃ_１〜Ｃ_４ヒドロキシ置換炭化水素、ベンジル、ｙが１〜１０の整数である−（Ｃ_２Ｈ_４Ｏ）_ｙＨからなる群から選択される、
（ｉｉ）Ｌは、−Ｃ（Ｏ）Ｏ−、−Ｏ−（Ｏ）Ｃ−からなる群から選択される、
（ｉｉｉ）Ｚは、各ｎが独立して１〜４の整数である−（ＣＨ_２）_ｎ、−ＣＨ_２Ｃ（ＣＨ_３）Ｈ−からなる群から選択される、
（ｉｖ）Ｘ⁻が、柔軟剤相溶性アニオンである。

During the ceremony
(I) R ₇ , R ₈ and R ₉ are each independently a C ₅ -C ₂₃ hydrocarbon,
(I) Each R ₁₀ is a group consisting of C _{1 to} C ₄ hydrocarbon, C _{1 to} C ₄ hydroxy substituted hydrocarbon, benzyl, and y is an integer of _{1 to 10-} (C ₂ H ₄ O) _y H Is selected from
(Ii) L is selected from the group consisting of -C (O) O-, -O- (O) C-,
(Iii) Z, each n is independently an integer of 1 to 4 _{- (CH 2) n,} is selected from the group consisting of _{-CH 2 C (CH 3) H-} ,
(Iv) X ^- is a softener compatible anion.

In one aspect, such di-terminal softener actives, mono-terminal softener actives and ion-pair softener actives are selected from the group consisting of:
a) Substance of the following formula (1)

式中、
（ｉ）Ｒ_１及びＲ_２は、それぞれ独立して、Ｃ_１１〜Ｃ_１７炭化水素である、
（ｉｉ）Ｒ_３及びＲ_４は、Ｃ_１〜Ｃ_２炭化水素、Ｃ_１〜Ｃ_２ヒドロキシ基置換炭化水素からなる群からそれぞれ独立して選択される、
（ｉｉｉ）Ｚは、各ｎが独立して１〜２の整数である−（ＣＨ_２）_ｎ、−ＣＨ_２Ｃ（ＣＨ_３）Ｈ−からなる群から選択される、
（ｉｖ）Ｌは、−Ｃ（Ｏ）Ｏ−、−Ｏ−（Ｏ）Ｃ−からなる群から選択される、
（ｖ）Ｘ−は柔軟剤相溶性アニオンであって、ハロゲン化物、スルホン酸塩、硫酸塩、及び硝酸塩からなる群から選択される。
ｂ）以下の式（２）の物質

During the ceremony
(I) R ₁ and R ₂ are each independently a C ₁₁ -C ₁₇ hydrocarbon,
(Ii) R ₃ and R ₄ are each independently selected from the group consisting of C _{1 to} C ₂ hydrocarbons and C _{1 to} C ₂ hydroxy group substituted hydrocarbons;
(Iii) Z is selected from the group consisting of-(CH ₂ ) _n and -CH ₂ C (CH ₃ ) H-, each n is independently an integer of 1 to 2;
(Iv) L is selected from the group consisting of -C (O) O-, -O- (O) C-,
(V) X- is a softener compatible anion selected from the group consisting of halides, sulfonates, sulfates, and nitrates.
b) Substance of the following formula (2)

式中、
（ｉ）Ｒ_５はＣ_１１〜Ｃ_１７炭化水素である、
（ｉｉ）各Ｒ_６は、Ｃ_１〜Ｃ_２炭化水素、Ｃ_１〜Ｃ_２ヒドロキシ基置換炭化水素からなる群から独立して選択される。
（ｉｉｉ）Ｚは、各ｎが独立して１〜４の整数である−（ＣＨ_２）_ｎ、−ＣＨ_２Ｃ（ＣＨ_３）Ｈ−からなる群から選択される、
（ｉｖ）Ｌは、−Ｃ（Ｏ）Ｏ−、−Ｏ−（Ｏ）Ｃ−からなる群から選択される、
（ｖ）Ｘ⁻は柔軟剤相溶性アニオンであって、ハロゲン化物、スルホン酸塩、硫酸塩、及び硝酸塩からなる群から選択される。
ｃ）以下の式（３）の物質

During the ceremony
(I) R ₅ is a C ₁₁ -C ₁₇ hydrocarbon,
(Ii) each R ₆ is independently selected from the group consisting of C ₁ -C ₂ hydrocarbons, C ₁ -C ₂ hydroxy group substituted hydrocarbons.
(Iii) Z, each n is independently an integer of 1 to 4 _{- (CH 2) n,} is selected from the group consisting of _{-CH 2 C (CH 3) H-} ,
(Iv) L is selected from the group consisting of -C (O) O-, -O- (O) C-,
(V) X ^- is a softener compatible anion selected from the group consisting of halide, sulfonate, sulfate and nitrate.
c) Substance of the following formula (3)

式中、
（ｉ）Ｒ_５はＣ_１１〜Ｃ_１７炭化水素である、
（ｉｉ）各Ｒ_６は、Ｃ_１〜Ｃ_４炭化水素、Ｃ_１〜Ｃ_４ヒドロキシ置換炭化水素、ベンジル、ｙが１〜１０の整数である−（Ｃ_２Ｈ_４Ｏ）_ｙＨからなる群から独立して選択される、
（ｉｉｉ）Ｌは、−Ｃ（Ｏ）Ｏ−、−Ｏ−（Ｏ）Ｃ−からなる群から選択される
（ｉｖ）Ｚは、各ｎが独立して１〜４の整数である−（ＣＨ_２）_ｎ、−ＣＨ_２Ｃ（ＣＨ_３）Ｈ−からなる群から選択される、
（ｖ）Ｘ−は、Ｃ_６〜Ｃ_２４炭化水素を含むアニオン性界面活性剤である。

During the ceremony
(I) R ₅ is a C ₁₁ -C ₁₇ hydrocarbon,
(Ii) each R ₆ is a group consisting of C _{1 to} C ₄ hydrocarbon, C _{1 to} C ₄ hydroxy substituted hydrocarbon, benzyl, and y is an integer of 1 to 10-(C ₂ H ₄ O) _y H Selected independently from
(Iii) L is selected from the group consisting of -C (O) O- and -O- (O) C- (iv) Z is-(wherein each n is independently an integer of 1 to 4 It is selected from the group consisting of CH ₂ ) _n and —CH ₂ C (CH ₃ ) H—
(V) X- is an anionic surfactant comprising C ₆ -C ₂₄ hydrocarbons.

In one aspect, such di-terminal softener actives, mono-terminal softener actives and ion-pair softener actives are selected from the group consisting of:
b) Substance of the following formula (1)

式中、
（ｉ）Ｒ_１及びＲ_２は、それぞれ独立して、Ｃ_１１〜Ｃ_１７炭化水素である、
（ｉｉ）Ｒ_３及びＲ_４は、Ｃ_１〜Ｃ_２炭化水素、Ｃ_１〜Ｃ_２ヒドロキシ基置換炭化水素からなる群からそれぞれ独立して選択される、
（ｉｉｉ）Ｚは、各ｎが独立して１〜２の整数である−（ＣＨ_２）_ｎ、−ＣＨ_２Ｃ（ＣＨ_３）Ｈ−からなる群から選択される、
（ｉｖ）Ｌは、−Ｃ（Ｏ）Ｏ−、−Ｏ−（Ｏ）Ｃ−からなる群から選択される、
（ｖ）Ｘ⁻は柔軟剤相溶性アニオンであって、塩素、臭化物、硫酸メチル、硫酸エチル及びメチルスルホネートからなる群から選択される。
ｂ）以下の式（２）の物質

During the ceremony
(I) R ₁ and R ₂ are each independently a C ₁₁ -C ₁₇ hydrocarbon,
(Ii) R ₃ and R ₄ are each independently selected from the group consisting of C _{1 to} C ₂ hydrocarbons and C _{1 to} C ₂ hydroxy group substituted hydrocarbons;
(Iii) Z is selected from the group consisting of-(CH ₂ ) _n and -CH ₂ C (CH ₃ ) H-, each n is independently an integer of 1 to 2;
(Iv) L is selected from the group consisting of -C (O) O-, -O- (O) C-,
(V) X ^- is a softener compatible anion selected from the group consisting of chlorine, bromide, methyl sulfate, ethyl sulfate and methyl sulfonate.
b) Substance of the following formula (2)

式中、
（ｉ）Ｒ_５はＣ_１１〜Ｃ_１７炭化水素である、
（ｉｉ）各Ｒ_６は、Ｃ_１〜Ｃ_２炭化水素、Ｃ_１〜Ｃ_２ヒドロキシ基置換炭化水素からなる群から独立して選択される。
（ｉｉｉ）Ｚは、各ｎが独立して１〜４の整数である−（ＣＨ_２）_ｎ、−ＣＨ_２Ｃ（ＣＨ_３）Ｈ−からなる群から選択される、
（ｉｖ）Ｌは、−Ｃ（Ｏ）Ｏ−、−Ｏ−（Ｏ）Ｃ−からなる群から選択される、
（ｖ）Ｘ−柔軟剤相溶性アニオンであって、塩素、臭化物、硫酸メチル、硫酸エチル及びメチルスルホネート又はＣ_６〜Ｃ_１８炭化水素を含むアニオン性界面活性剤からなる群から選択される。
ｃ）以下の式（３）の物質

During the ceremony
(I) R ₅ is a C ₁₁ -C ₁₇ hydrocarbon,
(Ii) each R ₆ is independently selected from the group consisting of C ₁ -C ₂ hydrocarbons, C ₁ -C ₂ hydroxy group substituted hydrocarbons.
(Iii) Z, each n is independently an integer of 1 to 4 _{- (CH 2) n,} is selected from the group consisting of _{-CH 2 C (CH 3) H-} ,
(Iv) L is selected from the group consisting of -C (O) O-, -O- (O) C-,
(V) X-softener compatible anions selected from the group consisting of chlorine, bromide, methyl sulfate, ethyl sulfate and methyl sulfonate or anionic surfactants comprising C ₆ -C ₁₈ hydrocarbons.
c) Substance of the following formula (3)

式中、
（ｉ）Ｒ_５はＣ_１１〜Ｃ_１７炭化水素である、
（ｉｉ）各Ｒ_６は、Ｃ_１〜Ｃ_２炭化水素、Ｃ_１〜Ｃ_２ヒドロキシ基置換炭化水素からなる群から独立して選択される。
（ｉｉｉ）Ｚは、各ｎが独立して１〜４の整数である−（ＣＨ_２）_ｎ、−ＣＨ_２Ｃ（ＣＨ_３）Ｈ−からなる群から選択される、
（ｉｖ）Ｌは、−Ｃ（Ｏ）Ｏ−、−Ｏ−（Ｏ）Ｃ−からなる群から選択される、
（ｖ）Ｘ−柔軟剤相溶性アニオンであって、塩素、臭化物、硫酸メチル、硫酸エチル及びメチルスルホネート又はＣ_６〜Ｃ_１８炭化水素を含むアニオン性界面活性剤からなる群から選択される。

During the ceremony
(I) R ₅ is a C ₁₁ -C ₁₇ hydrocarbon,
(Ii) each R ₆ is independently selected from the group consisting of C ₁ -C ₂ hydrocarbons, C ₁ -C ₂ hydroxy group substituted hydrocarbons.
(Iii) Z, each n is independently an integer of 1 to 4 _{- (CH 2) n,} is selected from the group consisting of _{-CH 2 C (CH 3) H-} ,
(Iv) L is selected from the group consisting of -C (O) O-, -O- (O) C-,
(V) X-softener compatible anions selected from the group consisting of chlorine, bromide, methyl sulfate, ethyl sulfate and methyl sulfonate or anionic surfactants comprising C ₆ -C ₁₈ hydrocarbons.

In one embodiment, for Formula 2, X- is a _C 6 _{-C 24} hydrocarbon is an anionic surfactant.

  In one aspect, such fabric care actives include softener actives selected from the group consisting of N, N-di (hydrogenated tallow oil oxyethyl) -N, N-dimethyl ammonium chloride. N, N-di (tallow oil oxyethyl) -N, N-dimethyl ammonium chloride, N, N-di (hydrogenated tallow oil oxyisopropyl) -N, N-dimethyl ammonium chloride, N, N-di (tallow oil Oxyisopropyl) -N, N-dimethylammonium chloride, N, N-di (stearoyloxyisopropyl) -N, N-dimethylammonium chloride, N, N-di (palmoyloxyisopropyl) -N, N-dimethylammonium chloride, bis- (2-hydroxypropyl) -dimethylammonium chloride stearic acid diester, partially hydrogenated bis- (2-hydroxypropyl) -dimethylammonium chloride palmitic acid diester, and mixtures thereof.

In cationic nitrogen-containing salts hereof, the anion A ^- is any anion which is compatible to the softener provides electrical neutrality. In most cases, the anions used to impart electrical neutrality in these salts are from strong acids, in particular from halides such as chlorides, bromides or iodides . However, other anions such as methyl sulfate, ethyl sulfate, acetic acid, formic acid, sulfuric acid, carbonic acid may be used. Chloride and methyl sulfate are preferred herein for the anion A. Further, the anion is preferably of somewhat less, A ^- if the representative one half of the group is capable of carrying a doubly charged.

Process (iv)
Dry the fabric in step (iv). This can be any conventional drying method, such as air drying or machine drying in a conventional laundry dryer.

Process (v)
The method of the present invention comprises the step (v) of contacting the fabric of step (iv) with the soil. By "dirt" is meant herein any organic or inorganic substance deposited on the fabric that the consumer perceives to stain the fabric. The stain may be a stain, such as a stain of fatty or oily food, or a stain of the body such as sweat or blood. Other common stains include red food stains, mud stains and grass stains. Alternatively, the contamination may be atmospheric contamination such as chemical contaminants, dust or soot. The soil may be water soluble or water insoluble. These are non-limiting examples. Those skilled in the art will know what "dirt" in the context of the present invention means. The contact of the fabric with the soiling occurs in the normal use of fabric articles, for example by the typical use of fabric garments or other fabric articles by the consumer.

Process (vi)
In step (vi), the fabric of step (v) is in contact with the aqueous cleaning solution of the detergent composition, the detergent composition comprising a surfactant, the cleaning solution comprising 0.05 to 4 g / l of surfactant. Step (vi) is independent but as described in step (i) above.

  In any of the steps (i), (ii), (iii) and / or (vi), the fabric may be brought into contact with the respective liquids at a temperature of 60 ° C. or less, or 40 ° C. or less. In particular, the fabric may be brought into contact with the washing solutions of steps (i) and / or (vi), respectively, at a temperature between 5 ° C. and 50 ° C., preferably between 10 ° C. and 30 ° C. The fabric may be contacted at these temperatures in the cleaning cycle of a domestic washing machine. In particular, the invention enables good stain / soil removal in step (vi) even at low wash temperatures between 10-30 ° C.

  In step (i) and / or step (vi), the fabric and the laundry detergent composition may be contacted during the washing cycle of the automatic washing machine, and the length of the washing cycle is at least 30 seconds, at least 3 minutes, or It may be at least 6 minutes, but less than 30 minutes, 45 minutes, or 1 hour.

Other Ingredients The laundry detergent composition of step (iii) may further comprise laundry detergent ingredients. The laundry detergent composition of step (iii) may comprise a hueing agent, a polymer, or a combination thereof. Suitable cleaning surfactants include, but are not limited to, hueing agents, anionic cleaning surfactants, nonionic cleaning surfactants, cationic cleaning surfactants, zwitterionic cleaning surfactants, amphoteric cleaning surfactants. Sex surfactants, and any combination thereof. As the polymer, dyes such as carboxylate polymers, polyester glycol polymers, polyester antifouling polymers such as terephthalate polymers, amine polymers, cellulose polymers, dye transfer polymers, condensation oligomers produced by condensation of imidazole and epichlorohydrin Fixed polymers, optionally in a ratio of 1: 4: 1, include hexamethylene diamine derivative polymers, and any combination thereof. Builders include zeolites, phosphates, citrates, and any combination thereof. Buffers and alkali sources include carbonates and / or silicates. Fillers include sulfate and / or biofiller materials. Bleaching agents include bleach activators, sources of available oxygen, pre-formed peracids, bleach catalysts, reduction bleaches, and any combination thereof. Chelating agent. Light bleach. Hue agent. Brightener. Enzymes include proteases, amylases, cellulases, lipases, xyloglucanases, pectate lyases, mannanases, bleaching enzymes, cutinases, and combinations thereof. Softeners include clays, silicones, quaternary ammonium softeners, and any combination thereof. Flocculant such as polyethylene oxide. Perfumes include starch encapsulated perfume accords, perfume microcapsules, perfume loaded zeolite, Schiff base reaction product of ketone perfume raw materials and polyamines, blooming perfume, and any combination thereof. Aesthetics include soaps, layered aesthetic particles, gelatin beads, speckles of carbonate and / or sulfate, color earth, and any combination thereof.

  Fabric hueing agent-The composition may also include a fabric hueing agent (sometimes referred to as a shading agent, a bluing agent, or a whitening agent). Typically, the hueing agent gives the fabric a blue or purple tint. The hueing agents can be used alone or in combination to create a particular shade and / or to tint different types of fabrics. This may be provided, for example, by mixing red and green-blue dyes to produce a blue or purple tint. The hue agents may be selected from dyes of any known chemical class, such as acridine, anthraquinones (including polycyclic quinones), azines, azos including premetallized azo (eg, Monoazo, diazo, trisazo, tetrakisazo, polyazo), benzodifuranone and benzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine, diphenylmethane, formazan, hemicyanine, indigoid, methane, naphthalimide, naphthoquinone, naphthoquinone, nitro and nitroso, oxazine, phthalocyanine, Nonlimiting examples include pyrazole, stilbene, styryl, triarylmethane, triphenylmethane, xanthene, and mixtures thereof.

  Suitable fabric tinting agents include dyes, dye-clay conjugates, and organic and inorganic pigments. Suitable dyes include small molecule dyes and polymeric dyes. Suitable small molecule dyes, for example, acid dyes, direct dyes, reactive dyes, or hydrolyzed reactions which are classified as blue, purple, red, green or black and which alone or in combination give the desired color shade Mention may be made of small molecule dyes selected from the group consisting of sex dyes, solvent dyes, or dyes classified in the Color Index (CI) classification of disperse dyes. In another embodiment, suitable small molecule dyes include, but are not limited to, Color Index (Society of Dyers and Colourists, (Bradford, UK)) Number Direct Violet Dye (9, 35, 48, 51, 66 and 99) direct blue dyes (such as 1, 71, 80 and 279), acid red dyes (such as 17, 73, 52, 88 and 150), acid violet dyes (15, 17, 24, 43, 49) And 50 etc.), acid blue dyes (15, 17, 25, 29, 40, 45, 75, 80, 83, 90 and 113 etc.), acid black dyes (1 etc.), basic violet dyes (1, 3 etc.) , 4, 10 and 35), basic blue dyes (eg 3, 16, 22, 47, 66, 75 and 159), dispersion or solvent dyes (As described in U.S. Patent Application Publication No. 2008/034511 (A1), or U.S. Patent Application Publication No. 8,268,016 (B2) or the dye U.S. Patent Application Publication No. 7,208,459 (B2) And the like, and small molecule dyes selected from the group consisting of mixtures thereof. In another aspect, suitable small molecule dyes include C.I. I. Listed are small molecule dyes selected from the group consisting of Acid Violet 17, Direct Blue 71, Direct Violet 51, Direct Blue 1, Acid Red 88, Acid Red 150, Acid Blue 29, Acid Blue 113, or a mixture thereof. Be

  Preferred dyes include dye polymers in which the dye group is optionally attached to the polymer group via a linking group. Suitable polymer groups include (1) alkoxylated polyethylenimine (for example as disclosed in WO 2012119859), (2) polyvinyl alcohol (for example as disclosed in WO 2012130492), or (3) Alkylene oxide-capped diamine derivatives of polyethylene glycol (for example, disclosed in WO 2012126665, in particular in FIG. 24), or polyalkoxylated alcohols (for example, WO 2011/011799 No. WO 2012/054058, WO 2012/166699 or WO 2012/166768). One preferred class of dye polymers can be obtained by reacting a blue or purple dye containing an NH2 group with the polymer and forming a covalent bond through the NH2 group of the reacted blue or purple dye, And the dye polymer has an average of 0 to 30, preferably 2 to 20, most preferably 2 to 15 similar repeat units. In a preferred embodiment, the monomer units are selected from alkylene oxides, preferably ethylene oxide. In general, the dye polymer is a mixture of molecules having a large distribution of monomer groups in the polymer chain, for example a mixture directly produced by an appropriate organic synthesis route such that an alkoxylation reaction occurs in the case of an alkylene oxide polymer. Etc. are present, in the form of dye-polymer mixtures. Such dye polymers are typically blue or purple, giving the fabric a hue angle of 230 to 345, more preferably 250 to 330, most preferably 270 to 300. In the synthesis of the dye polymer, the blue or purple non-bonded organic dye may be present in a mixture with the final dye polymer product. The chromophore of the blue or violet dye is preferably selected from the group consisting of azo, anthraquinone, phthalocyanine, triphenodioxazine and triphenylmethane. In one aspect, the dye polymer can be obtained by reaction of a dye containing an NH [2] group with a polymer or a suitable monomer that forms a polymer in situ. Preferably, NH [2] is covalently attached to the aromatic ring of the dye. Unbound dye is formed when the dye does not react with the polymer. Preferred dyes containing a [2] group for such reactions are Acid Violet 1, Acid Violet 3, Acid Violet 6 Acid Violet 11, Acid Bio Red 13, Acid Violet 14, Acid Violet 19, Acid Violet 20, Acid Violet 36, Acid Violet 36: 1, Acid Violet 41, Acid Violet 42, Acid Violet 43, Acid Violet 50, Acid Violet 51, Acid Bio Red 63, Acid Violet 48, Acid Blue 25, Acid Blue 40, Acid Blue 40 : 1 Acid Blue 41, Acid Blue 45, Acid Blue 47, Acid Blue 49, Acid Blue 51, Acid Blue 53, Acid Blue 56, Acid Blue 61, Acid Blue 61: 1, Acid Blue 62, Acid Blue 69, Acid Blue 78, Acid Blue 81: 1, Acid Blue 92, Acid Blue 96, Acid Blue 108, Acid Blue 111 , Acid Blue 215, Acid Blue 230, Acid Blue 277, Acid Blue 344, Acid Blue 117, Acid Blue 124, Acid Blue 129, Acid Blue 129: 1, Acid Blue 138, Acid Blue 145, Direct Violet 99, Direct Violet 5 , Direct Violet 72, Direct Violet 16, Direct Violet 78, Direct Violet 77, Direct Violet 83, Hood Rack 2, Direct Blue 33, Direct Blue 41, Direct Blue 22, Direct Blue 71, Direct Blue 72, Direct Blue 74, Direct Blue 75, Direct Blue 82, Direct Blue 96, Direct Blue 110, Direct Blue 111, Direct Blue 120 , Direct Blue 120: 1, Direct Blue 121, Direct Blue 122, Direct Blue 123, Direct Blue 124, Direct Blue 126, Direct Blue 127, Direct Blue 128, Direct Blue 129, Direct Blue 130, Direct Blue 132, Direct Blue 133 , Direct Blue 135, Direct Blue 138, Direct Blue 140, Direct Blue 145 , Direct Blue 148, Direct Blue 149, Direct Blue 159, Direct Blue 162, Direct Blue 163, Hood Black 2, Hood Black 1 in which the acid amide group is substituted with NH [2], Basic Violet 2, Basic Violet 5 , Basic violet 12, basic violet 14, basic violet 8, basic blue 12, basic blue 16, basic blue 47, basic blue 47, basic blue 99, disperse blue 1, disperse blue 5 , Disperse blue 6, disperse blue 9, disperse blue 11, disperse blue 19, disperse blue 20, disperse blue 28, disperse blue 40, disperse blue 56, disperse blue 60, disperse blue -81, disperse blue 83, disperse blue 87, disperse blue 104, disperse blue 118, disperse violet 1, disperse violet 4, disperse violet 8, disperse violet 17, disperse violet 26, disperse It is selected from Violet 28, Solvent Violet 26, Solvent Blue 12, Solvent Blue 13, Solvent Blue 18, and Solvent Blue 68. Further preferred dyes are selected from monoazo dyes having a NH [2] group covalently linked to itself and containing a phenyl group directly linked to the azo group. For example, thiophene monoazo dyes. The polymer chain may be selected from polyalkylene oxides. The polymer chains and / or dye chromophore groups can optionally carry anionic or cationic groups. Examples of polyoxyalkylene oxide chains include ethylene oxide, propylene oxide, glycidol oxide, butylene oxide, and mixtures thereof.

  Suitable polymer dyes include, for example, polymers containing covalently bonded (sometimes called conjugated) chromogens, such as those obtained by copolymerizing a polymer and a chromogen to form a polymer main chain (dye Polymeric dyes selected from the group consisting of: polymer conjugates), and mixtures thereof. As polymer dyes, WO 2011/98355, U.S. Patent Application Publication 2012/225803 (A1), U.S. 2012/090102 (A1), U.S. Patent 7,686,892 (B2), and Those described in WO 2010/142503 are mentioned.

  In another aspect, suitable polymeric dyes include the fabric direct colorant sold under the name Liquitint® (Milliken (Spartanburg, South Carolina, USA)), and at least one reactive dye, and a hydroxyl moiety. A polymer selected from the group consisting of: a polymer selected from the group consisting of: a primary amine moiety, a secondary amine moiety, a thiol moiety and a moiety selected from the group consisting of mixtures thereof And polymeric dyes selected from the group consisting of In yet another embodiment, suitable polymeric dyes include Liquitint® Violet CT, C.I., sold by Megazyme (Wicklow, Ireland) under the tradename AZO-CM-CELLULOSE, product code S-ACMC. I. Carboxymethyl cellulose (CMC), alkoxylated triphenyl-methane polymeric colorant, covalently bonded to a reactive blue, reactive violet, or reactive red dye such as CMC conjugated to Reactive Blue 19, alkoxylated thiophene Polymeric colorants, and polymeric dyes selected from the group consisting of mixtures thereof.

  Preferred color dyes include the whitening agents found in WO 08/87497 A1, WO 2011/011799 and U.S. Patent Application Publication 2012/129752 A1. Preferred hueing agents for use in the present invention are the preferred dyes disclosed in these references, including the dyes selected from Examples 1 to 42 of Table 5 of WO 05/2011799. May be there. Other preferred dyes are disclosed in US Pat. No. 8,138,222 (B2), especially in claim 1 of US Pat. No. 8,138,222 (B2). Other suitable dyes are disclosed in US Pat. No. 7,909,890 B2.

  Suitable dye clay conjugates include dye clay conjugates selected from the group comprising at least one cationic / basic dye and smectite clay, and mixtures thereof. In another aspect, suitable dye-clay complexes include C.I. I. Basic Yellow 1 to 108, C.I. I. Basic orange 1 to 69, C.I. I. Basic red 1 to 118, C.I. I. Basic violet 1 to 51, C.I. I. Basic Blue 1 to 164, C.I. I. Basic green 1 to 14, C.I. I. It is selected from the group consisting of montmorillonite clay, hectorite clay, saponite clay, and mixtures thereof, with one cationic / basic dye selected from the group consisting of Basic Brown 1-23, CI Basic Black 1-11. And dye clay complexes selected from the group consisting of clays. In yet another aspect, suitable dye clay complexes include montmorillonite basic blue B7 C.I. I. 42595 complex, Montmorillonite Basic Blue B9 C.I. I. 52015 complex, Montmorillonite Basic Violet V3 C.I. I. 42555 complex, Montmorillonite Basic Green G1 C.I. I. 42040 complex, Montmorillonite Basic Red R1 C.I. I. 45160 complex, montmorillonite C.I. I. Basic Black 2 complex, Hectorite Basic Blue B7 C.I. I. 42595 conjugate, Hectorite Basic Blue B9 C.I. I. 52015 complex, Hectorite Basic Violet V3 C.I. I. 42555 complex, hectorite basic green G1 C.I. I. 42040 complex, hectorite basic red R1 C.I. I. 45160 complex, hectorite C.I. I. Basic Black 2 complex, Saponite Basic Blue B7 C.I. I. 42595 complex, Saponite Basic Blue B9 C.I. I. 52015 complex, Saponite Basic Violet V3 C.I. I. 42555 complex, Saponite Basic Green G1 C.I. I. 42040 complex, Saponite Basic Red R1 C.I. I. 45160 complex, Saponite C.I. I. Included are dye clay complexes selected from the group consisting of Basic Black 2 complexes, and mixtures thereof.

  Preferred pigments include flavanthrone, indanthrone, chlorinated indanthrone having 1 to 4 chlorine atoms, pyranthrone, dichloropyranthrone, monobromodichloropyranthrone, dibromodichloropyranthrone, tetrabromopyranthrone, perylene- 3,4,9,10-tetracarboxylic acid diimide (the imide group is not substituted or may be substituted by C1 to C3 alkyl or phenyl or heterocyclic radical, this phenyl and heterocyclic radical Furthermore, it may have a substituent that does not impart water solubility), anthrapyrimidine carboxylic acid amide, biolanthrone, isobiolanthrone, dioxazine pigment, copper phthalocyanine (having 2 or less chlorine atoms per molecule) (Optional), polychloro-copper phthalocyanine Emissions, or polybrominated chloro - (having per molecule more than 14 bromine atoms) copper phthalocyanine, and include pigments selected from the group consisting of mixtures.

  In another aspect, suitable pigments include pigments selected from the group consisting of Ultramarine Blue (CI Pigment Blue 29), Ultramarine Violet (CI Pigment Violet 15), and mixtures thereof. It can be mentioned.

  The aforementioned fabric hueing agents can be used in combination (any mixture of fabric hueing agents can be used).

  Polymers: Preferred polymers include: carboxylate polymers, polyester glycol polymers, polyester antifouling polymers such as terephthalate polymers, amine polymers, cellulosic polymers, migration inhibiting polymers, optionally with a ratio of 1: 4: 1 imidazole and epi Dye fixing polymers such as condensation oligomers produced by condensation with chlorohydrin, hexamethylene diamine derivative polymers, and any combination thereof.

  Carboxylate Polymers: Suitable carboxylate polymers include maleate / acrylate random copolymers, or polyacrylate homopolymers. The carboxylate polymer may be a polyacrylate homopolymer having a molecular weight of 4,000 Da to 9,000 Da, or 6,000 Da to 9,000 Da. Another suitable carboxylate polymer is a copolymer of maleic acid and acrylic acid and may have a molecular weight within the range of 4,000 Da to 90,000 Da.

  Other suitable carboxylate polymers are copolymers comprising: (I) from 50% by weight to less than 98% by weight of structural units derived from one or more monomers containing a carboxyl group, and (ii) from 1% by weight to less than 49% by weight of one or more containing sulfonate moieties 1% by weight to 49% by weight derived from a structural unit derived from a monomer and (iii) one or more monomers selected from monomers containing an ether bond represented by formulas (I) and (II) % Structural unit.

式（Ｉ）中、Ｒ_０は、水素原子又はＣＨ_３基を表し、Ｒは、ＣＨ_２基、ＣＨ_２ＣＨ_２基、又は単結合を表し、Ｘは、０〜５の数を表すが、Ｒが単結合であるとき、Ｘは、１〜５の数を表し、Ｒ_１は、水素原子又はＣ_１〜Ｃ_２０有機基である。

In formula (I), R ₀ represents a hydrogen atom or a CH ₃ group, R represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and X represents a number of 0 to 5, When R is a single bond, X represents a number of 1 to 5 and R ₁ is a hydrogen atom or a C _{1 to} C ₂₀ organic group.

式（ＩＩ）中、Ｒ_０は、水素原子又はＣＨ_３を表し、Ｒは、ＣＨ_２、ＣＨ_２ＣＨ_２、又は単結合を表し、Ｘは、０〜５の数を表し、Ｒ_１は、水素原子又はＣ_１〜Ｃ_２０有機基である。

In formula (II), R ₀ represents a hydrogen atom or CH ₃ , R represents CH ₂ , CH ₂ CH ₂ or a single bond, X represents a number of 0 to 5, and R ₁ represents is a hydrogen atom or a _C 1 _{-C 20} organic group.

Polyethylene glycol polymers: Suitable polyethylene glycol polymers, (i) hydrophilic backbone comprising polyethylene glycol, and _{(ii) C} 4 ~C ₂₅ alkyl group, polypropylene, polybutylene, saturated _C 1 -C ₆ monocarboxylic acid And random graft copolymers comprising a hydrophobic side chain selected from the group consisting of vinyl esters, C ₁ -C ₆ alkyl esters of acrylic acid or methacrylic acid, and mixtures thereof. Preferred polyethylene glycol polymers have a polyethylene glycol backbone with randomly grafted polyvinyl acetate side chains. The average molecular weight of the polyethylene glycol backbone may range from 2,000 Da to 20,000 Da, or from 4,000 Da to 8,000 Da. The molecular weight ratio of polyethylene glycol backbone to polyvinyl acetate side chain may be in the range of 1: 1 to 1: 5, or 1: 1.2 to 1: 2. The average number of grafting sites per ethylene oxide unit may be less than 1 or less than 0.8, even though the average number of grafting sites per ethylene oxide unit is in the range of 0.5 to 0.9. Alternatively, the average number of graft sites per ethylene oxide unit may be in the range of 0.1 to 0.5, or 0.2 to 0.4. The preferred polyethylene glycol polymer is Sokalan HP22.

Polyester Antifouling Polymer: A suitable polyester antifouling polymer has a structure defined by one of the following structures (I), (II), or (III).
(I)-[(OCHR ¹ -CHR ² ) _a -O-OC-Ar-CO-] _d
(II)-[(OCHR ³ -CHR ⁴ ) _b -O-OC-sAr-CO-] _e
(III)-[(OCHR ⁵ -CHR ⁶ ) _c -OR ⁷ ] _f
During the ceremony
a, b and c are 1 to 200,
d, e and f are 1 to 50,
Ar is 1,4-substituted phenylene,
sAr is 1,3-substituted phenylene substituted at position 5 with SO ₃ Me;
Me is H, Na, Li, K, Mg / 2, Ca / 2, Al / 3, ammonium, mono-, di-, tri- or tetra-alkyl ammonium, or a mixture of any of these, In which the alkyl group is C ₁ -C ₁₈ alkyl or C ₂ -C ₁₀ hydroxyalkyl,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently selected from H or C _{1 to} C ₁₈ n- or iso-alkyl, and R ⁷ is linear or branched A linear C _{1 to} C ₁₈ alkyl, or a linear or branched C _{2 to} C ₃₀ alkenyl, or a cycloalkyl group having 5 to 9 carbon atoms, or a C _{8 to} C ₃₀ aryl group, or C ₆ to It is a _C30 arylalkyl group. Suitable polyester antifouling polymers are terephthalate polymers having the structure of formula (I) or formula (II) above.

  Suitable polyester antifouling polymers include polymers of the Repel-o-tex series, such as Repel-o-tex SF2 (Rhodia), and / or polymers of the Texcare series, such as Texcare SRA 300 (Clariant).

  Amine Polymer: Suitable amine polymers include polyethyleneimine polymers such as alkoxylated polyalkyleneimines, optionally including polyethylene and / or polypropylene oxide blocks.

  Cellulosic Polymer: The composition may comprise a cellulosic polymer such as a polymer selected from alkylcelluloses, alkylalkoxyalkylcelluloses, carboxyalkylcelluloses, alkylcarboxyalkyls, and any combination thereof. Suitable cellulosic polymers are selected from carboxymethylcellulose, methylcellulose, methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose, and mixtures thereof. Carboxymethyl cellulose may have a degree of carboxymethyl substitution of 0.5 to 0.9, and a molecular weight of 100,000 Da to 300,000 Da. Another suitable cellulosic polymer is hydrophobically modified carboxymethylcellulose such as Finnfix SH-1 (CP Kelco).

Other suitable cellulosic polymers have a degree of substitution (DS) of 0.01 to 0.99 and either DS + DB is at least 1.00, or DB + 2 DS-DS ² is at least 1.20. And the degree of block (DB). The substituted cellulosic polymers can have a degree of substitution (DS) of at least 0.55. The substituted cellulosic polymer can have a degree of block (DB) of at least 0.35. The substituted cellulosic polymer can have a DS + DB of 1.05 to 2.00. The preferred substituted cellulosic polymer is carboxymethylcellulose.

  Another suitable substituted cellulosic polymer is cation modified hydroxyethyl cellulose.

  Dye Transfer Inhibitor (DTI) Polymer: The laundry detergent composition may comprise a DTI polymer. Suitable DTIs include polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidone, and polyvinylimidazole, or mixtures thereof. The above mentioned DTI polymers are well known in the art and are commercially available, eg PVP-K15 and K30 (Ashland), Sokalan HP 165, HP 50, HP 53, HP 59, HP 56 K, HP 56, HP 66 (BASF), Chromabond S-400. , S403E, and S-100 (Ashland), and Polyquart FDI (Cognis).

  Builders: Suitable builders include zeolites, phosphates, citrates, and any combination thereof.

  Zeolite builder: The composition may be substantially free of zeolite builder. 0 wt% to 10 wt% of the zeolite builder, or 8 wt% or less, or 6 wt% or less, or 4 wt% or less, or 3 wt% or less, substantially free of zeolite builder Or, it means that it contains only 2 wt% or less, or even 1 wt% or less of zeolite builder. Substantially free of zeolite builder preferably means that the zeolite builder is "intentionally not added". Exemplary zeolite builders include Zeolite A, Zeolite P, Zeolite MAP, Zeolite X, and Zeolite Y.

  Phosphoric acid builder: The composition may be substantially free of phosphoric acid builder. Typically, 0 wt% to 10 wt% of the phosphate builder, or 8 wt% or less, or 6 wt% or less, or 4 wt% or less, or substantially 3 wt% Below, or 2% by weight or less, or even 1% by weight or less of phosphoric acid builder is included. Substantially free of zeolite builder preferably means that the phosphate builder is "intentionally not added". An exemplary phosphate builder is sodium tripolyphosphate (STPP).

  Citrate: The preferred citrate is sodium citrate. However, citric acid which can form citrate in the wash solution may be incorporated into the composition.

  Buffering agents and alkali sources: Suitable buffering agents and alkali sources include carbonates and / or silicates and / or double salts such as burkite.

  Carbonate: Preferred carbonates are sodium carbonate and / or sodium bicarbonate. The carbonate may have a weight average particle size of 100 to 500 micrometers. Alternatively, the carbonate may have a weight average particle size of 10 to 25 micrometers.

  Silicate: The silicate may be crystalline or amorphous. Suitable crystalline silicates include crystalline layered silicates such as SKS-6. Other suitable silicates include 1.6R silicates and / or 2.0R silicates. The preferred silicate is sodium silicate. Another suitable silicate is sodium metasilicate.

  Sulfate: The preferred sulfate is sodium sulfate. The sulfate may have a weight average particle size of 100 to 500 micrometers, or the sulfate may have a weight average particle size of 10 to 45 micrometers.

  Bleaching Activator: Suitable bleach activators include tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonic acid (NOBS), caprylamidononanoyloxybenzenesulfonic acid (NACA-OBS), 3,5, Oxybenzenesulfonic acid such as 5-trimethylhexanoyloxybenzenesulfonic acid (Iso-NOBS), dodecyloxybenzenesulfonic acid (LOBS) and mixtures thereof, caprolactam, pentaacetate glucose (PAG), nitrile quaternary ammonium, N- Imide bleach activators such as nonanoyl-N-methylacetamide and mixtures thereof.

  Source of effective oxygen: A suitable source of effective oxygen (AvOx) is a source of hydrogen peroxide such as percarbonate and / or perborate, for example sodium percarbonate. The source of peroxygen may be at least partially coated by coating components such as carbonates, sulfates, silicates, borosilicates, or any mixtures thereof including mixtures thereof, or even May be completely coated. Suitable percarbonates can be prepared by a fluid bed process or by a crystallization process. Preferred perborates include sodium perborate monohydrate (PB1), sodium perborate tetrahydrate (PB4), and anhydrous sodium perborate, also known as effervescent sodium perborate It can be mentioned. Other suitable sources of AvOx include persulfates such as oxone. Another suitable source of AvOx is hydrogen peroxide.

  Pre-formed peracid: A preferred pre-formed peracid is N, N-phthaloylamino peroxy caproic acid (PAP).

  Bleaching Catalyst: Suitable bleaching catalysts include oxaziridinium based bleaching catalysts, transition metal bleaching catalysts, and bleaching enzymes.

  Oxaziridinium-based bleach catalysts: Suitable oxaziridinium-based bleach catalysts have the following formula:

式中、Ｒ_１は、Ｈ、３〜２４個の炭素原子を含む分枝状アルキル基、及び１〜２４個の炭素原子を含む直鎖アルキル基からなる群から選択される。Ｒ^１は６〜１８個の炭素原子を含む分枝状のアルキル基、又は５〜１８個の炭素原子を含む直鎖アルキル基であり、Ｒ^１は、２−プロピルヘプチル、２−ブチルオクチル、２−ペンチルノニル、２−ヘキシルデシル、ｎ−へキシル、ｎ−オクチル、ｎ−デシル、ｎ−ドデシル、ｎ−テトラデシル、ｎ−ヘキサデシル、ｎ−オクタデシル、イソ−ノニル、イソ−デシル、イソ−トリデシル、及びイソ−ペンタデシルからなる群から選択される。Ｒ^２は独立してＨ、３〜１２個の炭素を含む分枝状アルキル基、及び１〜１２個の炭素を含む直鎖アルキル基からなる群から選択され、任意に、Ｒ^２は独立してＨ及びメチル基から選択され、かつｎは０〜１の整数である。

Wherein R ₁ is selected from the group consisting of H, a branched alkyl group containing 3 to 24 carbon atoms, and a linear alkyl group containing 1 to 24 carbon atoms. R ¹ is a branched alkyl group containing 6 to 18 carbon atoms, or a linear alkyl group containing 5 to 18 carbon atoms, R ¹ is 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, iso-nonyl, iso-decyl, iso-tridecyl And iso-pentadecyl. R ² is independently selected from the group consisting of H, a branched alkyl group containing 3 to 12 carbons, and a linear alkyl group containing 1 to 12 carbons; optionally, R ² is independently And H is selected from H and methyl, and n is an integer from 0 to 1.

  Transition Metal Bleaching Catalyst: The composition may comprise a transition metal bleaching catalyst, typically comprising a cation of copper, iron, titanium, ruthenium, tungsten, molybdenum and / or manganese. The preferred transition metal bleach catalyst is a manganese based transition metal bleach catalyst.

  Reduction bleach: The composition may comprise a reduction bleach. However, the composition may be substantially free of reducing bleach. Substantially not included means "not intentionally added." Suitable reducing bleaches include sodium sulfite and / or thiourea dioxide (TDO).

  Co-bleach agent particles: The composition may comprise co-bleach agent particles. Typically, the co-bleach agent particles comprise a bleach activator and a source of peroxide. It may be highly preferred that a large amount of bleach activator is present in the co-bleach particles relative to the source of hydrogen peroxide. The weight ratio of bleach activator to hydrogen peroxide source in the bleach particles is at least 0.3: 1, at least 0.6: 1, at least 0.7: 1, at least 0.8: 1, at least 0. It may be 9: 1, or at least 1.0: 1.0 or at least 1.2: 1.

  The bleach particles may comprise (i) a bleach activator such as TAED, and (ii) a hydrogen peroxide source such as sodium percarbonate. The bleach activator can at least partially or even completely encapsulate the source of hydrogen peroxide.

The co-bleach agent particles may comprise a binder. Suitable binders are carboxylate polymers such as polyacrylate polymers and / or surfactants such as non-ionic detersive surfactants and / or anionic detersive surfactants such as linear C ₁₁ -C ₁₃ alkyl benzene sulfonates It is.

  The co-bleach agent particles may comprise a bleach catalyst, such as an oxaziridinium based bleach catalyst.

  Chelating agents: Suitable chelating agents are diethylenetriaminepentaacetic acid, diethylenetriaminepenta (methylphosphonic acid), ethylenediamine-N'N'-disuccinic acid, ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid), hydroxyethanedi (methylenephosphonic acid) And any combination thereof. Preferred chelating agents are ethylenediamine-N'N'-disuccinic acid (EDDS) and / or hydroxyethane diphosphonic acid (HEDP). The laundry detergent composition may comprise ethylenediamine-N'N'-disuccinic acid, or a salt thereof. Ethylenediamine-N'N'-disuccinic acid may be in the S, S enantiomer form. The composition may comprise 4,5-dihydroxy-m-benzenedisulfonic acid disodium salt. Suitable chelating agents may also be calcium crystal growth inhibitors.

  Calcium crystal growth inhibitor: The composition comprises 1-hydroxyethanedisulfonic acid (HEDP) and salts thereof, N, N-dicarboxymethyl-2-aminopentane-1,5-diacid and salts thereof, 2- It may include one calcium carbonate crystal growth inhibitor selected from the group consisting of phosphonobutane-1,2,4-tricarboxylic acid and salts thereof, and any combination thereof.

  Photobleaching agents: Suitable photobleaching agents are sulfonated phthalocyanine zinc and / or aluminum.

  Brightener: The laundry detergent composition may comprise a fluorescent brightener. Preferred classes of optical brighteners are, for example, distyrylbiphenyl compounds such as Tinopal (TM) CBS-X, diaminostilbezysulfonic acids such as Tinopal (TM) DMS pure Xtra and Blancophor (TM) HRH, and Blancophor (TM) SN. And other pyrazoline compounds. Preferred fluorescent agents are sodium 2 (4-styryl-3-sulfophenyl) -2H-naphthol [1,2-d] triazole, disodium 4,4'-bis {[(4-anilino-6- (N methyl) -N-2 hydroxyethyl) amino 1,3,5-triazin-2-yl)]; amino} stilbene-2-2'-disulfonate, sodium 4,4'-bis {[(4-anilino-6-morpholino) -1,3,5-Triazin-2-yl)] amino} stilbene-2-2 ′ disulfonate and disodium 4,4′-bis (2-sulfostyryl) biphenyl.

  Particularly preferred optical brighteners include C.I. I. It is a fluorescent whitening agent 260. For solid detergent compositions, this brightener may be used in beta or alpha crystal forms or mixtures of these forms.

  Enzymes: Suitable enzymes include proteases, amylases, cellulases, lipases, xyloglucanases, pectate lyases, mannanases, bleaching enzymes, cutinases, and mixtures thereof.

  The accession number and ID are shown in parentheses to indicate the item number in the Genbank, EMBL and / or Swiss-Prot database for the enzyme. For any mutation, the standard single-letter amino acid code is used with a defect indicator. The accession number preceded by DSM refers to the microorganism deposited at Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH (Mascheroder Weg 1b, 38124 Brunswick) (DSMZ).

Protease: The composition may comprise a protease. Suitable proteases include metalloproteases including neutral or alkaline microbial serine proteases such as subtilisin (EC 3.4.21.62) and / or serine proteases. Suitable proteases include those of animal, vegetable or microbial origin. In one aspect, such suitable proteases may be of microbial origin. Suitable proteases include chemically or genetically modified mutants of the aforementioned suitable proteases. In one aspect, suitable proteases may be alkaline microbial proteases and / or serine proteases such as trypsin-type proteases. Examples of suitable neutral or alkaline proteases include:
(A) Subtilisins including those derived from Bacillus such as Bacillus lentus, Bacillus alkalophilus (P27963, ELYA_BACAO), Bacillus subtilis, Bacillus amyloliquefaciens (P00782, SUBT_BACAM), Bacillus pumilus (P07518), and Bacillus gibsonii (DSM 14391) (EC3. 4.21.62).
(B) Trypsin-type or chymotrypsin-type proteases, such as trypsin (for example from porcine or bovine origin), including fusarium protease and chymotrypsin protease derived from Cellumonas (A2RQE2).
(C) Metalloproteases including those derived from Bacillus amyloliquefaciens (P06832, NPRE_BACAM).

  Suitable proteases include those derived from Bacillus gibson or Bacillus lentus, such as subtilisin 309 (P29600) and / or DSM 5483 (P29599).

  Suitable commercial protease enzymes include Alcalase®, Savinase®, Primase®, Durazym®, Polarzyme®, Kannase®, Liquanase®. Novozymes A / S (Denmark) under the trade names Liquanase Ultra (R), Savinase Ultra (R), Ovozyme (R), Neutrase (R), Everlase (R) and Esperase (R). Marketed by: Maxatase®, Maxacal®, Maxapem®, Properase®, Purafect , Purafect Prime®, Purafect Ox®, FN 3®, FN 4®, Excellase®, and Purafect OXP® by Genencor International under the trade names Those sold by Solvay Enzymes under the brand names Opticlean® and Optimase®, available from Henkel / Kemira, ie having the following mutations SAP D (S99D + S101R + S103A + V104I + G159S) P29599) as well as BLAP R (S3T + V4I + V199M + V205I + L21) all available from Henkel / Kemira With the mutants of KAP (A230V + S256G + S259N) available from Kao and their variants including BLAP with D, BLAP X (BLAP with S3T + V4I + VV205I) and BLAP F49 (S3T + V4I + A194P, V199M + V205I + L217D with BLAP) and available by Kao Bacillus alcalophilus)).

  Another suitable protease is a fungal serine protease. Preferred enzymes are Lycoderma reesei (Trichoderma reesei) strain QM9414, Marblanca cinnamomea strain ALK04122, Fusarium graminearum strain Fusarium graminearum strain ALK01726, Fusarium equiceti (Fusarium equiseti C.sub.C). It is a fungal serine protease mutant or wild type that is endogenous to F. acuminatum strain CBS 124084. Examples of commercially available fungal serine proteases are Biotouch ROC and Biotouch Novia, both supplied by AB Enzymes, Darmstadt, Germany.

Amylases: Suitable amylases are alpha-amylases, including those of bacterial or fungal origin. Chemically or genetically modified mutants (mutants) are included. Suitable alkaline alpha-amylases are strains of Bacillus, such as Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, Bacillus subtilis, or other Bacillus species, such as Bacillus species, NCIB 12289, NCIB 12512, NCIB 12513, sp 707, DSM 9375 , DSM 12368, DSMZ no. It is derived from a strain of Bacillus, such as 12649, KSM AP 1378, KSM K36, or KSM K38. Suitable amylases include the following.
(A) α-Amylase derived from Bacillus licheniformis (P06278, AMY_BACLI), and variants thereof, in particular 15, 23, 105, 106, 124, 128, 133, 154, 156, 181, 188, 190, 197, 202 , 208, 209, 243, 264, 304, 305, 391, 408, and 444, which are substituted at one or more positions.
(B) AA 560 amylase (CBU 30457, HD 066 534), and variants thereof, in particular at positions 26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186, 193 , 203, 214, 231, 256, 257, 258, 269, 270, 272, 295, 296, 298, 299, 303, 304, 305, 311, 314, 315, 318, 319, 339, 345, 361 , 378, 383, 419, 421, 437, 441, 444, 445, 446, 447, 450, 461, 471, 482, 484, having a substitution, and optionally D183 ^* and G184 ^* A mutant that also contains a deletion of
(C) A variant exhibiting at least 90% homology with a wild-type enzyme from Bacillus sp. 722 (CBU 30453, HD066526), in particular a variant having a deletion at positions 183 and 184.

  Suitable commercially available α-amylases are: Duramyl®, Liquezyme®, Termamy®, Termamyl Ultra®, Natalase®, Supramyl®, Stainzyme® ), Stainzyme Plus (R), Fungamyl (R), and BAN (R) (Novozymes A / S), Bioamylase (R) and its variants (Biocon India Ltd.), Kemzym (R) AT 9000 (Biozym Ges. M. B. H, Austria), Rapidase (R), Purastar (R), Optisize HT Plus (R), Enzysi e (TM), is a Powerase (registered trademark), and Purastar Oxam (registered trademark), Maxamyl (registered trademark) (Genencor International Inc.) and KAM (registered trademark) (Kao, Japan). Suitable amylases are NATALASE®, Stainzyme®, and Stainzyme Plus®.

  Cellulase: The composition may comprise cellulase. Suitable cellulases include cellulases of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, such as fungal cellulases produced from Humicola insolens, Myceliophthora thermophila, and Fusarium oxysporum.

  Commercially available cellulases include Celluzyme® and Carezyme® (Novozymes A / S), Clazinase® and Puradax HA® (Genencor International Inc.), and KAC-500 (B). (Registered trademark) (Kao).

  Cellulases exhibit endo-.beta.-1,4-glucanase activity (E.C. 3.2.1.4), including bacterial polypeptides endogenous to members of Bacillus sp. Genus AA 349 and mixtures thereof Examples include endoglucanases of microbial origin. Suitable endoglucanases are sold under the trade names Celluclean® and Whitezyme® (Novozymes A / S, Bagsvaerd, Denmark).

  The composition is marketed under the tradenames of washed cellulases belonging to family 45 of glycosyl hydrolases, having a molecular weight of 17 kDa to 30 kDa, such as Biotouch® NCD, DCC, and DCL (AB Enzymes, Darmstadt, Germany) Endoglucanase may be included.

  In addition, suitable cellulases such as Whitezyme® may also exhibit xyloglucanase activity.

  Xyloglucanase: Suitable xyloglucanase enzymes may have enzymatic activity on both xyloglucan substrates and amorphous cellulose substrates. The enzyme may be a glycoside hydrolase selected from glycoside hydrolase (GH) family 5, 12, 44, or family 74. Glycosyl hydrolases selected from the GH family 44 are particularly preferred. A preferred glycosyl hydrolase selected from GH family 44 is XYG1006 glycosyl hydrolase from Paenibacillus polyxyma (ATCC 832), and variants thereof.

  Pectate lyase: Suitable pectate lyases are sold under the trade names Pectawash®, Pectaway®, and X-Pect® (Novozymes A / S (Bagsvaerd, Denmark)) Or pectate lyase from Bacillus, either wild type or mutant (CAF05441, AAU 25568).

  Mannanase: A suitable mannanase is sold under the tradename Mannaway (R) (Novozymes A / S (Bagsvaerd, Denmark)) and trade name Purabrite (R) (Genencor International Inc. (Palo Alto, California)) There is.

  Bleaching enzymes: Suitable bleaching enzymes include oxidoreductases, for example, oxidases such as glucose oxidase, choline oxidase, or carbohydrate oxidase, oxygenase, catalase, peroxidase (haloperoxidase, chloroperoxidase, bromoperoxidase, lignin peroxidase, glucose peroxidase, Or manganese peroxidase, etc., dioxygenase, or laccase (phenol oxidase, polyphenol oxidase). Suitable commercial products are marketed by Novozymes under the tradenames Guardzyme® and Denilite®. It may be advantageous to formulate additional organic compounds, in particular aromatic compounds, together with the bleaching enzymes, which interact with the bleaching enzymes to enhance the activity of the oxidoreductases (enhancers), or Promotes electron flow between the oxidative enzyme and the soil, typically across widely different redox potentials (mediator).

  Other suitable bleaching enzymes include perhydrolases which catalyze the formation of peracids from ester substrates and peroxygen sources. Suitable perhydrolases include variants of Mycobacterium smegmatis perhydrolase, variants of the so-called CE-7 perhydrolase, and variants of the wild-type subtilisin Carlsberg, which possesses perhydrolase activity. .

  Homology: The correlation of two amino acid sequences is represented by the parameter "homology". For the purpose of the present invention, the alignment of the two amino acid sequences is determined by using the Needle program of the Embossed (EMBOSS) package (http://emboss.org) version 2.8.0. The Needle program is described by Needleman, S., et al. B. and Wunsch, C .; D. (1970) J.L. Mol. Biol. The global alignment algorithm described in 48, 443-453 is performed. The substitution matrix used is BLOSUM 62, the gap opening penalty is 10, and the gap extension penalty is 0.5.

  Softeners: Suitable fabric softeners include clays, silicones, and / or quaternary ammonium compounds. Suitable clays include montmorillonite clays, hectorite clays, and / or laponite clays. The preferred clay is montmorillonite clay. Suitable silicones include aminosilicone and / or polydimethylsiloxane (PDMS). Suitable softeners are particles comprising clay and silicone, such as particles comprising montmorillonite clay and PDMS.

  Flocculants: Suitable flocculants include, for example, polyethylene oxide having an average molecular weight of 300,000 Da to 900,000 Da.

  Antifoam agents: Suitable antifoam agents include silicone and / or fatty acids such as stearic acid.

  Perfumes: As suitable perfumes, perfume microcapsules, polymer-assisted perfume delivery system including Schiff base perfume / polymer complex, perfume encapsulated in starch, perfume filled zeolite, blooming perfume accord, and any combination thereof Can be mentioned. Suitable perfume microcapsules are melamine formaldehyde based and typically comprise perfume encapsulated by a shell comprising melamine formaldehyde. Such perfume microcapsules may be very suitable to include in the shell a cationic material and / or a cationic precursor material such as polyvinyl formamide (PVF) and / or cation modified hydroxyethyl cellulose (catHEC).

  Cosmetics: Suitable cosmetic particles include soaps, layered cosmetic particles, gelatin beads, speckles of carbonate and / or sulfate, colored earth particles, and any combination thereof.

Example 1
The improved soil removal effect of the method of the invention is demonstrated in the following experiments.

  A composition comprising a Western liquid detergent, which is described in detail in Table 1, was prepared. This composition was labeled as an antecedent composition 1.

  A second antecedent composition was prepared which is identical to the antecedent composition 1 but which is also used with the detergent additives detailed in Table 2.

  A variant identical to the antecedent composition 2 but having at least 90% sequence identity to a wild-type lipase from Thermomyces lanuginosus and having the sequence substitutions T231R and N233R A third annex composition was also prepared, including:

  A fourth annex composition was prepared which is identical to the antecedent composition 2 but is also used with the antifouling polymer (SRP).

  A variant identical to the preceding composition 4 but having at least 90% sequence identity to a wild type lipase from Thermomyces lanuginosus and having the sequence substitutions T231R and N233R A fifth antecedent composition was also prepared, including:

Summary,
1. Antecedent composition only 2. 2. An adjunct composition only in combination with a cleaning additive. 3. Only adjunctive compositions comprising Lipex® combined with a cleaning additive. Only an anclyte composition containing SRP combined with a cleaning additive. Only an accompaniment composition comprising SRP and Lipex® combined with a cleaning additive

  Standard fabric swatches TF7436-M polycotton (a polyester and cotton blend, 25 × 20 cm) and Dacron 64 polyester were obtained from Westlairds. Each of these two was added to the washing machine, with 2.5 kg of cotton fabric and a cotton towel supplied by the test fabric as an additional ballast.

  The swatches are then washed with a detergent composition as detailed in Table 1, such that 13 liters of wash liquor contains 2692 ppm detergent at short cotton cycle (30 ° C.), 1600 rpm. did. An application of 30 g of the wash additive as detailed in Table 2 was added to the rinse compartment of the washer drawer as added during the rinse phase of the wash cycle. The lipid esterase was added to the rinse compartment of the washer drawer so as to provide an active enzyme protein concentration of 1 ppm during the rinse phase of the washer cycle. The antifouling polymer was added to the rinse compartment of the washer drawer at a concentration of 0.2% w / w to be delivered during the rinse phase of the washer cycle. The order of addition to the rinse compartment is the detergent additive, then the lipid esterase, then the antifouling polymer. After the wash cycle was complete, the fabric was then dried in a line. This was repeated so that all swatches were washed four times with the same preconditioning composition during the wash, and wash additives, lipid esterase and antifouling polymer were added over the rinse time.

  Prepare 5 x 5 cm samples of TF7436-M and Dacron 64 with each preconditioning treatment, stain with 200 L of SV13-stained lard (Asd alard batch 130R7, SV 13%, batch SPt001013), overnight at 32 ° C / 80% saved.

  The colored swatches were then washed in a Tergotometer (0.8 L pot) in the presence of a Western liquid detergent (total concentration 2692 ppm), which is described in detail in Table 1. A ballast fabric composed of knitted cotton fabric (Ballast fabric) was also added at a total fabric load of 26.7 g. The washing conditions in the Tergotometer are 200 rpm, 30 ° C. washing time 20 minutes and rinsing time 5 minutes. The fabric was then allowed to dry overnight on a metal shelf.

  Lipid esterase was added to the rinse at a concentration of 1 ppm (active enzyme protein). Antifouling polymer Texcare (R) SRA 300 was added at 0.2% w / w.

Stain removal was quantified using commercially available Digieye software and stain removal rates were calculated from the L ^* a ^* b values. The software generated L, a and b values and calculated the stain removal rate using the following equation:
% SR (stain removal) = 100 ^* ((E _b −E _a ) / E _b )
ΔE _b = √ ((L _c −L _b ) ² + (a _c −a _b ) ² + b _c −b _b ) ² )
ΔE _a = (((L _c- L _a ) ² + (a _c- a _a ) ² + b _c- b _a ) ² )
Subscript "b" means stain data before cleaning Index "a" means stain data after cleaning Index "c" means no stain fabric data

Thus, L ^* a ^* b values are taken from unstained fabrics, pre-washed, and post-washed fabrics.

  The results can be seen in Table 3.

（標準誤差をＳＥ＝ＳＤ／√ｎ、ＳＤ＝標準偏差、及びｎ＝外部反復として計算した。）

(The standard error was calculated as SE = SD / √n, SD = standard deviation, and n = external iteration.)

  The data clearly show that the addition of detergent additives or antifouling polymers, that is to say the antecedents 2 and 4 respectively, significantly improve the soil removal rate. Furthermore, to this, the addition of a lipid esterase in combination with either a detergent additive or an antifoulant polymer, i.e. each of the preceding compositions 3 and 5 results in a high soil removal rate. Thus, during the preconditioning rinse step according to the invention, the inclusion of the lipid esterase in combination with either the detergent additive or the antifouling polymer is compared to the fabric having the precondition without the lipidesterase. Showed a surprising improvement in the soil reduction rate.

(Examples 3 to 8)
The following examples are of detergent additive compositions suitable for step (i).

(Examples 9 to 27)
The following examples are of laundry detergent compositions suitable for steps (i) and (iii).

(Examples 9 to 14)
Granule laundry detergent compositions designed for hand-washing or top-loading washing machines are added to water sufficient to form a paste for direct contact with the surface to be treated to form a concentrated cleaning composition You may

(Examples 15 to 20)
Granular laundry detergent compositions designed for front-loading washing machines are added to sufficient water to form a paste for direct contact with the surface to be treated to form a concentrated cleaning composition Good.

  The fabric is laundered at a concentration of 700-10,000 ppm in water, 20-90 ° C. and a water-to-cloth ratio, 5: 1, using any of the compositions described above. Typical pH is about 10. Subsequently, the fabric is dried. In one aspect, the fabric is actively dried using a dryer. In one aspect, the fabric is actively dried using an iron. In another aspect, the fabrics are aligned and dried to be exposed to air and optionally sunlight.

  Examples 21 to 26 Heavy Liquid Laundry Detergent Compositions

(Example 27)
The composition may be enclosed in a polyvinyl alcohol pouch.

^＊ 洗浄及び／又は処理組成物の総重量に基づいて、合計７％以下の水
^１ ランダムグラフトコポリマーは、ポリエチレンオキシド主鎖と複数のポリ酢酸ビニル側鎖とを有する、ポリ酢酸ビニルグラフト化ポリエチレンオキシドコポリマーである。ポリエチレンオキシド骨格の分子量は、約６０００であり、ポリエチレンオキシドのポリ酢酸ビニルに対する重量比は、約４０〜６０であり、５０エチレンオキシド単位当たり１グラフト点を超えない。
^２ −ＮＨにつき、２０個のエトキシレート基を有するポリエチレンイミン（ＭＷ＝６００）。
^＊ 注：いずれの酵素濃度も、酵素原料の割合（％）として表されている。

^* 7% or less total water, based on the total weight of the cleaning and / or treating composition
^One random graft copolymer is a polyvinyl acetate grafted polyethylene oxide copolymer having a polyethylene oxide backbone and a plurality of polyvinyl acetate side chains. The molecular weight of the polyethylene oxide backbone is about 6000, and the weight ratio of polyethylene oxide to polyvinyl acetate is about 40 to 60 and does not exceed 1 graft point per 50 ethylene oxide units.
Polyethyleneimine having 20 ethoxylate groups per ² NH (MW = 600).
^* Note: All enzyme concentrations are expressed as percentage of enzyme material.

Ingredients and Notes for the Compositions of Examples 3-8 Silicone HC 306 supplied by Wacker Chemical Corporation, Adrian, Michigan, USA
Poly (acrylamide-methacrylamidopropyl trimethyl ammonium chloride (PAMAPPTAC)
Butyl carbitol Tallow alkyl ethoxylated alcohol with average degree of ethoxylation 80 ProxelTM GXL
Perfume Best B

Material and notes Stepan compositions of Examples 9~27, Northfield, Illinois, linear alkyl benzene sulfonates C _{12 to 14} dimethylsilyl hydroxy having an average aliphatic carbon chain length _C 11 _{-C 12} supplied by USA Ethylammonium is supplied by Clariant GmbH, Sulzbach (Germany).
AE3S is, Stepan (Northfield, Illinois, USA ) C 12~15 alkyl ethoxy (3) which is supplied from a sulfate.
AE7 is, Huntsman (Salt Lake City, Utah , USA) is supplied from an average ethoxylation degree of _{C 12 to 15} ethoxylate alcohol 7.
AE9 is, Huntsman (Salt Lake City, Utah , USA) is supplied from an average ethoxylation degree of _{C 12 to 13} ethoxylate alcohol 9.
HSAS is a medium chain branched primary alkyl sulfate having a carbon chain length of about 16-17.
Sodium tripolyphosphate is supplied by Rhodia (Paris, France).
Zeolite A is supplied by Industrial Zeolite (UK) Ltd, Grays, Essex, UK.
1.6 RSilicate is supplied by Koma, Nestemica, Czech, Republic.
Sodium carbonate is supplied by Solvay, Houston, Texas, USA.
The polyacrylate MW4500 is supplied by BASF, Ludwigshafen, Germany.
Carboxymethylcellulose is Finnfix® V supplied by CP Kelco, Arnhem, Netherlands.
Suitable chelating agents are, for example, diethylenetetraaminepentaacetic acid (DTPA) supplied by Dow Chemical, Midland, Michigan, USA or hydroxyethane diphosphonates (HEDP supplied by Solutia, St Louis, Missouri, USA Bagsvaerd, Denmark) ).
Savinase (R), Natalase (R), Stainzyme (R), Lipex (R), Celluclean (TM), Mannaway (R), and Whitezyme (R) are all Novovozymes (Bagsvaerd, Denmark) ) Products.
Biotouch® ROC is a product of AB Enzymes (Darmstadt, Germany).
The bacterial protease described in US Pat. No. 6,312,936 (B1) (Examples 8 to 13) was supplied by Genencor International (Palo Alto, California, USA).
The bacterial protease described in US Pat. No. 4,760,025 (Examples 14-20) was supplied by Genencor International (Palo Alto, California, USA).
Fluorescent Brightener 1 is Tinopal (R) AMS, Optical Brightener 2 is Tinopal (R) CBS-X, Sulfonated Zinc Phthalocyanine and Direct Violet 9 are Pergasol (R) Violet BN-Z All of which are supplied by Ciba Specialty Chemicals (Basel, Switzerland).
Sodium carbonate is supplied by Solvay, Houston, Texas, USA.
Sodium perborate is supplied by Degussa, Hanau, Germany.
NOBS is sodium nonanoyloxy benzene sulfonate supplied by Future Fuels, Batesville, Arkansas, USA.
TAED is tetraacetylethylenediamine supplied by Clariant Gmbh, Sulzbach, Germany under the trade name Peractive®.
S-ACMC is sold by Megazyme (Wicklow, Ireland) under the product name AZO-CM-CELLULOSE (AZO-CM-CELLULOSE) (product code S-ACMC); I. It is carboxymethylcellulose conjugated with Reactive Blue 19.
The soil release agent is Repel-o-tex.RTM. PF supplied by Rhodia, Paris, France.
The acrylic acid / maleic acid copolymer has a molecular weight of 70,000 and an acrylate: maleate ratio of 70:30, supplied by BASF, Ludwigshafen, Germany.
Ethylenediamine-N, N'-disuccinic acid, the Na salt of the (S, S) isomer (EDDS) is that supplied by Octel, Ellesmere Port, UK.
Hydroxyethane diphosphonate (HEDP) is supplied by Dow Chemical, Midland, Michigan, USA.
Antifoam suger aggregates are supplied by Dow Corning, Midland, MIchigan, USA.
HSAS is a medium chain branched alkyl sulfate as disclosed in US Pat. Nos. 6,020,303 and 6,060,443.
_C12-14 dimethylamine oxide is supplied by Procter & Gamble Chemicals, Cincinnati, Ohio, USA.
Liquitint® violet CT is supplied by Milliken, Spartanburg, South Carolina, USA.

  The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Rather, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, the dimensions disclosed as "40 mm" are intended to mean "about 40 mm".

  All documents cited herein, including any cross-referenced patent or related patent, are herein incorporated by reference in their entirety, unless expressly excluded or otherwise limited. Be incorporated. The citation of any document is not considered prior art to any invention disclosed or claimed herein, or that alone or in combination with any other reference (s) At times, it is not considered to teach, suggest, or disclose all such inventions. Furthermore, to the extent that any meaning or definition of a term in this document conflicts with the meaning or definition of the same term in the document incorporated by reference, the meaning or definition given to that term in this document applies Shall be

  While specific embodiments of the present invention have been illustrated and described, it will be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the present invention. Accordingly, all such changes and modifications that are included within the scope of the present invention are intended to be covered by the appended claims.

Claims (14)

A method of laundering a fabric comprising the following steps.
i) contacting the fabric with an aqueous cleaning solution comprising the detergent composition, the detergent composition comprising a surfactant, and the cleaning solution comprising 0.05 to 4 g / l of surfactant, and ii) Contacting the fabric of step (i) with a rinse solution in a first rinse step;
iii) contacting the fabric of step (ii) with a second aqueous rinse comprising lipid esterase and antifouling polymer in a second rinse step;
iv) drying the fabric,
v) contacting the fabric of step (iv) with dirt;
vi) contacting the fabric of step (v) with an aqueous cleaning solution of a detergent composition, the detergent composition comprising a surfactant, and the cleaning solution comprising 0.05 to 4 g / l of surfactant To include.   The method of claim 1, wherein the lipid esterase comprises at least first and second lipid esterases.   The fabric of step (i) and / or step (vi) is contacted with the laundry detergent composition in the washing cycle of the automatic washing machine, and the length of the washing cycle is at least 30 seconds, at least 3 minutes, or at least 6 The method according to claim 1 or 2, which is a minute but not more than 30 minutes, 45 minutes or 1 hour.   The fabric of step (i) and / or step (vi) is in contact with the laundry detergent composition in the washing cycle of an automatic washing machine, and the washing cycle is at a temperature between 5 ° C and 50 ° C, preferably 10 ° C. The method according to claims 1 to 3, which is continued between -30 ° C.   The lipid esterase is selected from E. coli. C. Selected from category 3.1, preferably E.I. C. Classification 3.1.1.1, E.I. C. Classification 3.1.1.3, E.I. C. 5. The method according to claims 1 to 4 selected from the classes 3.1.1.74 or combinations thereof.   Said lipid esterase is classified under classification E.1. C. 3.1.1.3 or E.I. C. 3.1.1.1 or a combination thereof, preferably E.I. C. The method according to claim 5, selected from 3.1.1.3.   Said lipid esterase is a mutant having at least 90% sequence identity to a wild type lipase from Thermomyces lanuginosus and having the sequence substitutions T231R and N233R, or claim 5, European Patent 1290150. The method according to any one of claims 1 to 6, comprising a mutant corresponding to part (u) of (B1), or a combination thereof.   The process according to claims 1 to 7, wherein in step (iii) the fabric is contacted with a lipid esterase, said lipid esterase being present in the aqueous rinse at a concentration between 30 and 55,000 ng enzyme / g fabric. Method.   The method according to claims 1 to 8, wherein the ratio of surfactant to fabric on a weight to weight basis in step (i) and / or step (vi) is from 1: 150 to 1: 500.   The method of claim 1, wherein the antifouling polymer comprises a terephthalate antifouling polymer.   11. The method according to claims 1 to 10, wherein the second rinsing step is a final rinsing step before the fabric is dried in step (iv).   12. The detergent surfactant comprises an anionic surfactant, preferably an anionic surfactant selected from linear alkyl benzene sulfonic acid, alkoxylated anionic surfactant, or a combination thereof. The method described in.   13. The method according to claims 1-12, wherein the laundry detergent composition of step (i) and / or step (vi) comprises a hueing agent, a polymer or a combination thereof.   The laundry detergent composition of step (i) and / or step (vi) comprises from 0 wt% to 10 wt% anhydrous zeolite builder, 0 wt% to 10 wt% phosphate builder, or a combination thereof. The method of 13.