JP6483237B2 - How to wash fabric - Google Patents

Description

  The present invention relates to a method of washing fabric.

  Fabric care compositions are often added by the consumer during the rinse phase of the fabric laundering operation. Fabric care compositions provide 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 washing process of a laundry operation. In particular, there is a further need for means to improve cleaning at low cleaning temperatures and short cleaning cycles.

  The present invention alleviates this problem.

International Patent No. 95/05442

The present invention relates to a method for washing a fabric comprising the following steps.
i) contacting the fabric with an aqueous cleaning solution comprising a detergent composition, the detergent composition comprising a surfactant, and the washing solution comprising 0.05 to 4 g / l surfactant, and ii) Contacting the fabric of step (i) with a first rinse in one washing step;
iii) contacting the fabric of step (ii) with a second rinse comprising lipid esterase in a second wash 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 washing solution comprising 0.05 to 4 g / l surfactant.

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

The method of the present invention includes the following steps.
i) contacting the fabric with an aqueous cleaning solution comprising a detergent composition, the detergent composition comprising a surfactant, and the washing solution comprising 0.05 to 4 g / l surfactant, and ii) Contacting the fabric of step (i) with a rinsing liquid in one washing step;
iii) contacting the fabric of step (ii) with a second aqueous rinse comprising lipid esterase in a second wash 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 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 in which an aqueous washing liquid is formed by adding the detergent composition to water. The surfactant concentration in the aqueous cleaning solution is 0.05 to 4 g / l. In step (ii), the fabric undergoes a rinsing stage of the cleaning operation, and the cleaning liquid is substantially removed from the fabric. In step (iii), a further rinsing step is provided wherein the fabric contacts the lipid esterase. The fabric is then dried in step (iv) and is soiled in step (v), i.e. 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 liquid in step (vi). Without being bound by theory, the lipid esterase that contacts the fabric in step (iii) has an “out of the wash” action on the hydrolysis of the soil / stain that contacts the fabric during the soiling step (v). It is considered to be. This results in good soil removal in the subsequent washing step (iv) and effective soil removal from the fabric in step (vi). This allows a reduction in the amount of surfactant used to provide effective cleaning.

Step (i)
The method of the present invention comprises the step (i) of contacting the fabric with an aqueous cleaning liquid. An aqueous cleaning liquid is formed by the addition of laundry detergent compositions to water. The detergent composition added to water to form an aqueous cleaning solution may be in any suitable form including granules, liquids or serving volumes. In the case of a single volume form, the composition is preferably enclosed in a water-soluble film, for example, a polyvinyl alcohol film. The fabric may come into contact with the composition in the hand washing washing process or the washing liquid in the machine washing cycle.

  Laundry detergent compositions typically comprise 1 to 70%, or 2 to 50% or 5 to 40% by weight of surfactant, based on the total weight of the laundry detergent composition. The concentration of the surfactant in the cleaning liquid 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 zwitterionic surfactant, an amphoteric surfactant or a combination thereof. The surfactant composition may comprise one surfactant or typically a mixture of 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, especially those having carbon chain lengths C8-C15, or C _10-13 alkyl benzene sulfonic acids. Suitable alkyl benzene sulfonic acids (LAS) are available by sulphonation of commercially available linear alkyl benzenes (LAB) or are obtained and supplied by Sasol under the trade name Isochem® as a preferred LAB. Low 2-phenyl LAB, such as those sold or sold under the trade name Petrelab (registered trademark) by Petrsa, other suitable LABs are supplied by Sasol as the trade name Hybrene (registered trademark) And high 2-phenyl LAB. Another suitable anionic detersive surfactant is an alkylbenzene sulfonic acid, preferably having 8 to 15 carbon atoms, obtained by the DETAL catalyzed 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 primarily C ₁₂ alkyl sulfates. Alkyl sulfates may be derived from natural sources such as coco and / or tallow. Alternatively, the alkyl sulfate may be derived from a synthetic source such as a C _12-15 alkyl sulfate.

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 0.5-20, or 0.5-10, or 0.5-7, or 0.5-5, or 0.5-3. Examples include dominant sodium C12 lauryl ether sulfate 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 alkylbenzene 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 ethoxycarboxylate.

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 these Any combination is mentioned.

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

Preferable examples of the nonionic surfactants are selected from Shell NEODOL such as a non-ionic surfactant sold under the name (R), from the group consisting of C ₈ -C ₁₈ alkyl ethoxylates 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 alkylphenol condensates (eg Pluronic® sold by BASF), C ₁₄ -C ₂₂ medium chain branched chain alcohols, typically C ₁₄ -C having an average degree of alkoxylation of 1-30 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 nonionic detersive surfactants are also alkylpolyglucosides and / or alkylalkoxylated alcohols.

  Suitable nonionic detersive surfactants include secondary alcohol detersive surfactants having the following 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 straight or branched, substituted or unsubstituted, saturated or unsaturated C _2-8 alkyl, wherein R ² is straight 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 ranges from 7-13. EO / PO is an alkoxy moiety selected from ethoxy, propoxy, or mixtures thereof, optionally the EO / PO alkoxy moiety is a random or block structure, n is the average degree of alkoxylation, The range is 10.

  Other suitable nonionic detersive surfactants include EO / PO block copolymer surfactants such as Plurafac® series of surfactants available from BASF, and sugars such as alkyl N-methylglucosamide. Derived surfactants.

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

  The composition may further comprise an amine oxide, preferably in an amount up to 10% by weight of the surfactant composition. Suitable amine oxides are described in WO 2014/114570, and a particularly preferred amine oxide is lauryl dimethylamine oxide. The composition may further comprise a bipolar surfactant. Preferred bipolar surfactants are betaine surfactants, such as carbobetaines such as Empigen® sold by Harzmann. 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 (EC 3.1.1.1.74)
(4) Sterol esterase (EC 3.1.1.13)
(5) Wax ester hydrolase (EC 3.1.1.1.50)

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

  Suitable carboxylic ester hydrolases are B.I. B. gladioli, P.M. P. fluorescens, P. fluorescens putida, B. et al. acidocaldarius, B.I. subtilis, B.M. Stearothermophilus, Streptomyces chrysomalus, S. et al. It can be selected from wild-type or mutant forms of carboxylic acid ester hydrolase endogenous to diastatochromogenes and Saccharomyces cerevisiae.

  Suitable cutinase, Aspergillus strains, in particular Aspergillus oryzae, Alternaria strain, in particular Alternaria Brassiciola, Fusarium strain, in particular Fusarium solani, Fusarium solani pisi, Fusarium oxysporum, Fusarium oxysporum cepa, Fusarium roseum culmorum, or Fusarium roseum sambucium, Helminthosporum strains, particularly Helminthosporum sativum, Humicola strains, in particular Humicola insolens, Pseudomonas strains, in particular Pseudomonas mendocia, or Pseudomo the as putida, Rhizoctonia strains, in particular Rhizoctonia solani, Streptomyces strain, in particular Streptomyces scabies, Coprinopsis strains, particularly Coprinopsis cinerea, Thermobifida strains, particularly Thermobifida fusca, Magnaporthe strains, particularly Magnaporthe grisea, or Ulocladium strains, cutinase of endogenous particularly Ulocladium consortiale Can be selected from wild-type or mutant types.

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

  In another preferred embodiment, the cutinase is H.264. Kontkanen et al, App Environ. Microbiology, 2009, p2148-2157 is a wild-type or mutant type of six cutinases that are endogenous to Coprinopsis cinerea.

  In another preferred embodiment, the cutinase is a wild type or mutant form of two cutinases that are endogenous to Trichoderma reesei described in WO 2009007510 (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. A preferred commercial cutinase includes Novozym 51032 (available from Novozymes, Bagsvaard, Denmark).

  Suitable sterol esterases are Ophiostoma strains, such as Ophiostoma piceae, Pseudomonas strains, such as Pseudomonas aeruginosa, or Melanocarpus strains, such as Melanocarpus Melanocarpus albomyces).

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

  A suitable wax ester hydrolase may be derived from jojoba (Simmondsia chinensis).

  Lipid esterase is the enzyme E. coli. C. Class 3.1 or 3.2 or a combination thereof may be selected. Lipid esterase is the enzyme E. coli. C. It may be selected from class 3.1.1.1 or 3.1.1.3 or a combination thereof.

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

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

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

Step (iii)
The method of the present invention comprises a second rinsing step (iii), wherein the fabric is contacted with a second rinsing liquid comprising lipid esterase.

  The lipid esterase may be any suitable lipid esterase. The lipid esterase may comprise at least a first and second lipid esterase. 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 (EC 3.1.1.1.74)
(4) Sterol esterase (EC 3.1.1.13)
(5) Wax ester hydrolase (EC 3.1.1.1.50)

  According to the “EC class” which means Enzyme Commission class in this specification. The Enzyme Commission class is an internationally recognized enzyme classification table based on enzyme-catalyzed chemical reactions.

  A suitable trisylglycerol lipase can be selected from a lipase variant of Humicola lanuginosa (Thermomyces lanuginosus). Other suitable triacylglycerol lipases are e.g. P. alcaligenes or P. alcaligenes P. pseudoalcaligenes (European Patent No. 218,272), P.P. P. cepacia (European Patent No. 331,376), P.C. P. stutzeri (UK Patent No. 1,372,034), P. stutzeri. Fluorescens, Pseudomonas sp. Strain SD705 (WO95 / 06720 and WO96 / 27002), p. Pseudomonas lipases such as P. wisconsinensis (International Patent Publication No. 96/12012), for example subtilis (Dartois et al. (1993) Biochemica et Biophysica Acta, 1131, 253-360), B. et al. B. stearothermophilus (Japanese Patent No. 64/744992) or B. It can be selected from mutant forms of Bacillus lipase such as B. pumilus (International Patent Publication No. 91/16422).

  Suitable carboxylic ester hydrolases are B.I. B. gladioli, P.M. P. fluorescens, P. fluorescens. putida, B. et al. acidocaldarius, B.I. subtilis, B.M. Stearothermophilus, Streptomyces chrysomalus, S. et al. It can be selected from wild-type or mutant forms of carboxylic acid ester hydrolase endogenous to diastatochromogenes and Saccharomyces cerevisiae.

  Suitable cutinase, Aspergillus strains, in particular Aspergillus oryzae, Alternaria strain, in particular Alternaria Brassiciola, Fusarium strain, in particular Fusarium solani, Fusarium solani pisi, Fusarium oxysporum, Fusarium oxysporum cepa, Fusarium roseum culmorum, or Fusarium roseum sambucium, Helminthosporum strains, particularly Helminthosporum sativum, Humicola strains, in particular Humicola insolens, Pseudomonas strains, in particular Pseudomonas mendocia, or Pseudomo the as putida, Rhizoctonia strains, in particular Rhizoctonia solani, Streptomyces strain, in particular Streptomyces scabies, Coprinopsis strains, particularly Coprinopsis cinerea, Thermobifida strains, particularly Thermobifida fusca, Magnaporthe strains, particularly Magnaporthe grisea, or Ulocladium strains, cutinase of endogenous particularly Ulocladium consortiale Can be selected from wild-type or mutant types.

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

  In another preferred embodiment, the cutinase is H.264. These are wild-type or mutant types of six cutinases that are endogenous to Coprinopsis cinerea described in Kontkanen et al, App Environ Microbiology, 2009, P2148-2157.

  In another preferred embodiment, the cutinase is a wild type or mutant form of two cutinases that are endogenous to Trichoderma reesei described in WO 2009007510 (VTT).

  In a most preferred embodiment, the cutinase is derived from a Humicola insolens strain, in particular a Humicola insolens DSM1800 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 cutinases include variants, including those described in Example 2 of WO 01/92502.

  Suitable sterol esterases are Ophiostoma strains, such as Ophiostoma piceae, Pseudomonas strains, such as Pseudomonas aeruginosa, or Melanocarpus strains, such as Melanocarpus Melanocarpus albomyces).

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

  A suitable wax ester hydrolase may be derived from jojoba (Simmondsia chinensis).

  Lipid esterase is the enzyme E. coli. C. Class 3.1 or 3.2 or a combination thereof may be selected. Lipid esterases have been described in E.C. C. It may comprise an enzyme selected from class 3.1.1.1 or 3.1.1.3 or 3.1.1.14 or a combination thereof. Preferred lipid esterases are E. coli. An enzyme selected from C class 3.1.1.3 may be included. Lipid esterase has at least 90% sequence identity to wild-type lipase from Thermomyces lanuginosus and has a sequence substitution T231R and N233R, or claim 5, EP1290150 A variant corresponding to part (u) of (B1) or a combination thereof may be included. Lipid esterases may include variants having at least 90% sequence identity to the wild type lipase from Thermomyces lanuginosus and having the sequence substitutions T231R and N233R.

  The fabric may be contacted with lipid esterase at a concentration between 30-55,000 ng enzyme / g fabric. The fabric may be contacted with lipid esterase at a concentration between 30-2000 ng enzyme / g fabric. The fabric may be contacted with 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 lipid esterase at a concentration between 100-3000 ng enzyme / g fabric, or 125-2,500 ng enzyme / g fabric. The fabric may be contacted with lipid esterase at a concentration between 100-35,000 ng enzyme / g fabric, or 500-30,000 ng enzyme / g fabric. Without being bound by theory, these concentrations are believed to be optimal for removing dirt from the fabric.

  In step (ii), the fabric of step (ii) is contacted with lipid esterase in the second rinsing stage. This can be a hand wash rinse step in which the fabric of step (ii) is placed in rinse water that is substantially free of the detergent composition present in step (i), or it can be a rinse step in a washing machine. In the step (iii) where the fabric contacts the lipid esterase, the lipid esterase is thereby attached to the fabric.

  The rinsing liquid of the second rinsing stage includes softener ingredients such as quaternary ammonium surfactants or silicones, and optionally other ingredients useful in the rinsing stage such as perfumes, dyes, polymers, surfactants, etc. Optional additional rinse additive components may be included.

  Preferably, the aqueous rinsing liquid in the second rinsing stage of step (iii) comprises an antifouling polymer. The antifouling polymer may be present in the aqueous rinse in an amount up to about 0.00001-3 g / l, 0.0001-2 g / l, 1 g / l or 0.5 g / l in the rinse. A rinsing liquid may be provided by adding the softener composition to water to form an aqueous rinsing liquid. An antifouling polymer may be added through the softener composition. In such softening compositions, the antifouling polymer is 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 an amount from about 0.1% to about 5%, and in some embodiments from 0.2% to about 3.0%.

  Suitable antifouling polymers are typically deposited on the hydrophilic segments that hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and the hydrophobic fibers, and washed and completed during the completion of the washing and rinsing cycle. It has a hydrophobic segment that remains attached during the completion of the rinse cycle, thereby serving as a tether point for the hydrophilic segment. This may allow stains that occur after treatment with the soil release agent to be more easily cleaned in a subsequent cleaning procedure.

The soil release agent may comprise a variety of charged, eg 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 include a cap portion, which is particularly useful 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 tailored as needed for application to different fiber or textile forms and formulation in different detergents or detergent additive products. Suitable 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)
Where
a, b and c are 1 to 200;
d, e, and f are 1-50,
Ar is 1,4-substituted phenylene;
sAr is 1,3-substituted phenylene substituted at the 5-position with SO ₃ Me,
Me is H, Na, Li, K, Mg + 2, Ca + 2, Al + 3, ammonium, mono-, di-, tri- or tetra-alkyl ammonium (the alkyl group is C1-C18 alkyl or C2-C10 hydroxyalkyl) Or a mixture thereof,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently H or C, -C18n- or iso-alkyl, and R7 is linear or branched C1-C18. It is alkyl, or linear or branched C2-C30 alkenyl, or a cycloalkyl group having 5-9 carbon atoms, or a C6-C30 aryl group, or a C6-C30 arylalkyl group.

  Suitable polyester antifouling polymers are terephthalate polymers having the above structure (III) or (IV). Other suitable antifouling polymers may include, for example, end-cap and non-end-cap 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. Other suitable antifouling polymers include TexCare (R) SRA-100, TexCare (R) SRA-300, TexCare (R) SRN-100, TexCare (R) SRN-170 supplied by Clariant. , TexCare (R) SRN-240, TexCare (R) SRN-300, and TexCare (R) SRN-325. A particularly useful antifouling polymer is a sulfonated non-end capped polyester as described in WO 95 / 32997A (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, 8574, 877, 8963, 959, 2303, 893, 9294,000, 0935, 415, 8074, 201, 8244, 240, 9184, 525, 5244, 201, 8244, 579,681 and 4,787,989 European Patent Application No. 0219048 279,134A457,205A and German Patent No. 2,335,044 and International Publication No. 20141419792 International Publication No. 201214156/57/58, International Publication Japanese Patent No. 201419658 International Publication No. 20141965 International Publication No. 2014149479.

Optionally, the second rinse may further comprise a diester quaternary ammonium compound, a dialkyl quaternary ammonium compound, an imidazolinium quaternary compound, a cationic starch, a sucrose ester 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 triester quaternary ammonium fabric softener actives and ion-to-fabric softener actives are selected from the group consisting of: The
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

Where
(I) R ₁ and R ₂ are each independently a C _{5 to} C ₂₃ hydrocarbon,
(Ii) R ₃ and R ₄ are C ₁ -C ₄ hydrocarbon, C ₁ -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— and —OC (O) —.
(Iv) Z is selected from the group consisting of — (CH ₂ ) _n , —CH ₂ C (CH ₃ ) H—, wherein each n is independently an integer of 1 to 4.
(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

Where
(I) R ₅ is a C ₅ -C ₂₃ hydrocarbon,
(Ii) each R ₆ is a group consisting of C ₁ -C ₄ hydrocarbon, C ₁ -C ₄ hydroxy-substituted hydrocarbon, benzyl, and-(C ₂ H ₄ O) _y H where y is an integer from 1 to 10. Selected independently from the
(Iii) L is selected from the group consisting of -C (O) O-, -C- (O) C-,
(Iv) Z is selected from the group consisting of — (CH ₂ ) _n , —CH ₂ C (CH ₃ ) H—, wherein each n is independently an integer of 1 to 4.
(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

Where
(I) R ₅ is a C ₅ -C ₂₃ hydrocarbon,
(Ii) each R ₆ is a group consisting of C ₁ -C ₄ hydrocarbon, C ₁ -C ₄ hydroxy-substituted hydrocarbon, benzyl, and-(C ₂ H ₄ O) _y H where y is an integer from 1 to 10. Selected independently from the
(Iii) L is selected from the group consisting of -C (O) O-, -C- (O) C-,
(Iv) Z is selected from the group consisting of — (CH ₂ ) _n , —CH ₂ C (CH ₃ ) H—, wherein each n is independently an integer of 1 to 4.
(V) X ⁻ is an anionic surfactant containing C _{6 to} C ₂₄ hydrocarbons.
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。

Where
(I) R ₇ , R ₈ and R ₉ are each independently a C _{5 to} C ₂₃ hydrocarbon,
(I) Each R ₁₀ is a group consisting of C ₁ -C ₄ hydrocarbon, C ₁ -C ₄ hydroxy-substituted hydrocarbon, benzyl, and-(C ₂ H ₄ O) _y H where y is an integer from 1 to 10. Selected from the
(Ii) L is selected from the group consisting of -C (O) O-, -O- (O) C-.
(Iii) Z is selected from the group consisting of — (CH ₂ ) _n , —CH ₂ C (CH ₃ ) H—, wherein each n is independently an integer from 1 to 4.
(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

Where
(I) R ₁ and R ₂ are each independently a C _{11 to} C ₁₇ hydrocarbon.
(Ii) R ₃ and R ₄ are each independently selected from the group consisting of C ₁ -C ₂ hydrocarbons, C ₁ -C ₂ hydroxy group substituted hydrocarbons,
(Iii) Z is selected from the group consisting of — (CH ₂ ) _n , —CH ₂ C (CH ₃ ) H—, wherein each n is independently an integer of 1-2.
(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

Where
(I) R ₅ is a C _{11 to} 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 is selected from the group consisting of — (CH ₂ ) _n , —CH ₂ C (CH ₃ ) H—, wherein each n is independently an integer from 1 to 4.
(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.
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。

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

Where
(I) R ₁ and R ₂ are each independently a C _{11 to} C ₁₇ hydrocarbon.
(Ii) R ₃ and R ₄ are each independently selected from the group consisting of C ₁ -C ₂ hydrocarbons, C ₁ -C ₂ hydroxy group substituted hydrocarbons,
(Iii) Z is selected from the group consisting of — (CH ₂ ) _n , —CH ₂ C (CH ₃ ) H—, wherein each n is independently an integer of 1-2.
(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

Where
(I) R ₅ is a C _{11 to} 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 is selected from the group consisting of — (CH ₂ ) _n , —CH ₂ C (CH ₃ ) H—, wherein each n is independently an integer from 1 to 4.
(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 anionic surfactants including chlorine, bromide, methyl sulfate, ethyl sulfate and methyl sulfonate or 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。

Where
(I) R ₅ is a C _{11 to} 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 is selected from the group consisting of — (CH ₂ ) _n , —CH ₂ C (CH ₃ ) H—, wherein each n is independently an integer from 1 to 4.
(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 anionic surfactants including chlorine, bromide, methyl sulfate, ethyl sulfate and methyl sulfonate or 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-dimethylammonium chloride. N, N-di (tallow oil oxyethyl) -N, N-dimethylammonium chloride, N, N-di (hydrogenated tallow oil oxyisopropyl) -N, N-dimethylammonium 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 the cationic nitrogen-containing salts herein, the anion A ⁻ is any anion that is compatible with the softener and provides electrical neutrality. In most cases, the anions used to impart electrical neutrality in these salts are derived from strong acids, particularly those derived from halides such as chloride, bromide, or iodide. . However, other anions such as methyl sulfate, ethyl sulfate, acetic acid, formic acid, sulfuric acid, carbonic acid may be used. The chloride and methyl sulfate are preferably anion A herein. Further, the anion is preferably of somewhat less, A ^- if the representative one half of the group is capable of carrying a doubly charged.

Step (iv)
In step (iv), the fabric is dried. This can be any conventional drying method, such as air drying or mechanical drying in a conventional laundry dryer.

Step (v)
The method of the present invention comprises the step (v) of contacting the fabric of step (iv) with soil. By “dirt” is meant here any organic or inorganic material deposited on the fabric that the consumer perceives as soiling the fabric. The stain can be a stain, for example a fatty or oily food stain, or a body stain such as sweat or blood. Other common stains include red food stains, mud stains, and grass stains. Alternatively, the soil may be atmospheric soil such as chemical contaminants, dust or smoke. 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. Contact with fabric soils occurs in normal use of fabric articles, for example, by typical use of fabric garments or other fabric articles by consumers.

Step (vi)
In step (vi), the fabric of step (v) is in contact with the aqueous cleaning solution of the detergent composition, the detergent composition comprises a surfactant, and the washing solution comprises 0.05-4 g / l 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 and the respective liquids may be contacted at a temperature of 60 ° C. or lower, or 40 ° C. or lower. In particular, the fabric may be brought into contact with the respective cleaning liquid of step (i) and / or (vi) 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 washing cycle of a domestic washing machine. In particular, the present invention allows for good stain / dirt 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 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 It may be at least 6 minutes, but 30 minutes, 45 minutes, or less than 1 hour.

Other ingredients The laundry detergent composition of step (iii) may further comprise a laundry detergent ingredient. The laundry detergent composition of step (iii) may comprise a hueing agent, a polymer, or a combination thereof. Suitable cleaning surfactants include hueing agents, anionic cleaning surfactants, nonionic cleaning surfactants, cationic cleaning surfactants, zwitterionic cleaning surfactants, cleaning containing amphoteric cleaning surfactants Surfactants, and any combination thereof. Examples of polymers include polyester antifouling polymers such as carboxylate polymers, polyethylene glycol polymers, and terephthalate polymers, amine polymers, cellulosic polymers, dye transfer prevention polymers, and dyes such as condensation oligomers formed by condensation of imidazole and epichlorohydrin. Fixed polymers, optionally in a 1: 4: 1 ratio, include hexamethylenediamine 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, preformed peracids, bleach catalysts, reducing bleaches, and any combination thereof. Chelating agent. Photo bleach. Hue. Brightener. Enzymes include protease, amylase, cellulase, lipase, xyloglucanase, pectate lyase, mannanase, bleaching enzyme, cutinase, and combinations thereof. Softeners include clays, silicones, quaternary ammonium softeners, and any combination thereof. Flocculants such as polyethylene oxide. Perfumes include starch encapsulated perfume accord, perfume microcapsules, perfume loaded zeolites, Schiff base reaction products of ketone perfume raw materials and polyamines, blooming perfumes, and any combination thereof. Aesthetics include soaping, layered aesthetic particles, gelatin beads, carbonate and / or sulfate speckles, color, and any combination thereof.

  Fabric Hue-The composition may include a fabric hueing agent (sometimes referred to as a shading agent, bluing agent, or whitening agent). Typically, the hueing agent provides a blue or purple shade to the fabric. Hue agents can be used alone or in combination to create specific shades and / or tint different types of fabrics. This can be provided, for example, by mixing red and green-blue dyes to produce a blue or purple shade. The hueing agent may be selected from any known chemical class of dyes, which include acridines, anthraquinones (including polycyclic quinones), azines, azos including premetallized azos (eg, Monoazo, diazo, trisazo, tetrakisazo, polyazo), benzodifuran and benzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine, diphenylmethane, formazan, hemicyanine, indigoid, methane, naphthalimide, naphthoquinone, nitro and nitroso, oxazine, phthalocyanine, Including, but not limited to, pyrazole, stilbene, styryl, triarylmethane, triphenylmethane, xanthene, and mixtures thereof.

  Suitable fabric hueing agents include dyes, dye-clay conjugates, and organic and inorganic pigments. Suitable dyes include small molecule dyes and polymer dyes. Suitable small molecule dyes are, for example, blue, purple, red, green, or black, acid dyes, direct dyes, reactive dyes, or hydrolyzed reactions that, alone or in combination, provide the desired shade. And small molecule dyes selected from the group consisting of dyes classified in the color index (CI) class of sexual dyes, solvent dyes, or disperse dyes. In another embodiment, suitable small molecule dyes include color index (Society of Dyers and Colorists, (Bradford, UK)) number direct violet dyes (9, 35, 48, 51, 66, 99, etc.) Direct blue dyes (1, 71, 80, 279, etc.), Acid Red dyes (17, 73, 52, 88, 150, etc.), Acid Violet dyes (15, 17, 24, 43, 49, etc.) , And 50), acid blue dyes (15, 17, 25, 29, 40, 45, 75, 80, 83, 90, and 113), acid black dyes (1), basic violet dyes (1, 3, etc.) 4, 10, and 35), basic blue dyes (such as 3, 16, 22, 47, 66, 75, and 159), dispersed 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 Dye U.S. Patent Application Publication No. 7,208,459 (B2). And small molecule dyes selected from the group consisting of mixtures thereof. In another embodiment, suitable small molecule dyes include C.I. I. Small molecule dyes whose numbers are 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. It is done.

  Preferred dyes include dye polymers in which the dye group is optionally bonded to the polymer group via a linking group. Suitable polymeric groups include (1) alkoxylated polyethyleneimine (eg, disclosed in WO201212119859), (2) polyvinyl alcohol (eg, disclosed in WO20120130492), or (3) A diamine derivative of polyethylene glycol end-capped with an alkylene oxide (for example, disclosed in International Publication No. 20121216665, particularly in FIG. 24), or a polyalkoxylated alcohol (for example, International Publication No. 2011/011799). No., International Publication No. 2012/054058, International Publication No. 2012/166699 or International Publication No. 2012/166768). One preferred class of dye polymers can be obtained by reacting a blue or violet dye containing NH2 groups with the polymer and forming a covalent bond via the NH2 group of the reacted blue or violet dye, And the dye polymer has an average of 0-30, preferably 2-20, most preferably 2-15 similar repeating units. In a preferred embodiment, the monomer units are selected from alkylene oxides, preferably ethylene oxide. Usually, the dye polymer is a mixture of molecules having a large number of monomer group distributions in the polymer chain, such as a mixture produced directly by a suitable organic synthesis route that results in an alkoxylation reaction in the case of alkylene oxide polymers. Are in the form of a dye polymer mixture. Such dye polymers are typically blue or purple and provide the fabric with a hue angle of 230-345, more preferably 250-330, most preferably 270-300. In the synthesis of the dye polymer, a blue or purple unbound organic dye may be present in the 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 NH [2] groups with the polymer or a suitable monomer that forms the polymer in situ. Preferably, NH [2] is covalently bonded to the aromatic ring of the dye. Unbound dye is formed when the dye does not react with the polymer. Preferred dyes containing [2] groups for such reactions are Acid Violet 1, Acid Violet 3, Acid Violet 6 Acid Violet 11, Acid Violet 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 Violet 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 replaced 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 17, 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 -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 bonded to themselves and containing a phenyl group directly bonded to the azo group. For example, a thiophene monoazo dye. The polymer chain may be selected from polyalkylene oxides. The polymer chain and / or the dye chromophore group can carry anionic or cationic groups as desired. Examples of polyoxyalkylene oxide chains include ethylene oxide, propylene oxide, glycidol oxide, butylene oxide, and mixtures thereof.

  Suitable polymer dyes include polymers containing dyes that are covalently bonded (sometimes referred to as conjugated), such as those obtained by copolymerizing a polymer with a chromogen to form the main chain of the polymer (dyes). Polymer conjugates) and polymer dyes selected from the group consisting of mixtures thereof. Examples of the polymer dye include International Publication No. 2011/98355, U.S. Patent Application Publication Nos. 2012/225803 (A1), 2012/090102 (A1), U.S. Pat. No. 7,686,892 (B2), and What is described in international publication 2010/142503 is mentioned.

  In another aspect, suitable polymeric dyes include fabric direct colorants sold under the name Liquidint® (Milliken (Spartanburg, South Carolina, USA)), and at least one reactive dye and a hydroxyl moiety. A polymer selected from the group consisting of polymers comprising a moiety selected from the group consisting of: a primary amine moiety, a secondary amine moiety, a thiol moiety and mixtures thereof, and a dye-polymer conjugate formed from High molecular dyes selected from the group consisting of: In yet another embodiment, suitable polymeric dyes include C.I. sold by Liquidint® Violet CT, Megazyme (Wicklow, Ireland) under the trade name AZO-CM-CELLULOSE, product code S-ACMC. I. Carboxymethylcellulose (CMC), alkoxylated triphenyl-methane polymer colorant, alkoxylated thiophene covalently bonded to reactive blue, reactive violet, or reactive red dyes such as CMC conjugated to Reactive Blue19 And polymeric dyes selected from the group consisting of polymeric colorants and mixtures thereof.

  Preferred hue dyes include the whitening agents found in WO 08/87497 A1, WO 2011/011799 and US 2012/129752 A1. Suitable hueing agents for use in the present invention are suitable dyes disclosed in these references, including dyes selected from Examples 1-42 of Table 5 of International Publication No. WO2011 / 011799. It may be. Other preferred dyes are disclosed in claim 1 of US Pat. No. 8,138,222 (B2), in particular 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 embodiment, 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 1-118, C.I. I. Basic violet 1 to 51, C.I. I. Basic Blue 1-164, C.I. I. Basic green 1-14, C.I. I. One cationic / basic dye selected from the group consisting of Basic Brown 1-23, CI Basic Black 1-11, and selected from the group consisting of montmorillonite clay, hectorite clay, saponite clay, and mixtures thereof And a dye clay complex selected from the group consisting of clays. In yet another embodiment, suitable dye clay composites 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. And dye clay composites selected from the group consisting of basic black 2 composites and mixtures thereof.

  Suitable pigments include flavantrons, indantrons, chlorinated indantrons having 1 to 4 chlorine atoms, pyrantrons, dichloropyrantrons, monobromodichloropyrantrons, dibromodichloropyrantrons, tetrabromopyrantrons, perylene- 3,4,9,10-tetracarboxylic acid diimide (the imide group is unsubstituted or may be substituted with a C1-C3 alkyl or phenyl or heterocyclic radical, the phenyl and heterocyclic radicals Furthermore, it may have a substituent that does not impart water solubility), anthrapyrimidinecarboxylic acid amide, violanthrone, isoviolanthrone, dioxazine pigment, copper phthalocyanine (having 2 or less chlorine atoms per molecule) 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. Can be mentioned.

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

  Polymer: Suitable polymers include polyester antifouling polymers such as carboxylate polymers, polyethylene glycol polymers, terephthalate polymers, amine polymers, cellulosic polymers, dye transfer inhibiting polymers, and optionally 1: 4: 1 ratio of imidazole to epi Examples include dye fixing polymers such as condensation oligomers produced by condensation with chlorohydrin, hexamethylenediamine derivative polymers, and any combination thereof.

  Carboxylate polymers: Suitable carboxylate polymers include maleate / acrylate random copolymers or polyacrylate homopolymers. The carboxylate polymer can 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 in the range of 4,000 Da to 90,000 Da.

  Other suitable carboxylate polymers are copolymers comprising: (I) 50% by weight or more and less than 98% by weight of structural units derived from one or more monomers containing a carboxyl group; and (ii) 1% by weight or more and less than 49% by weight of one or more sulfonate moieties containing sulfonate moieties. 1 wt% to 49 wt% derived from structural units derived from monomers and (iii) one or more monomers selected from monomers containing ether linkages 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 the 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 polymer: Suitable polyethylene glycol polymers include: (i) a hydrophilic backbone containing polyethylene glycol, and (ii) C ₄ -C ₂₅ alkyl groups, polypropylene, polybutylene, saturated C ₁ -C ₆ monocarboxylic acids. Random graft copolymers comprising vinyl esters, C ₁ -C ₆ alkyl esters of acrylic acid or methacrylic acid, and hydrophobic side chains selected from the group consisting of mixtures thereof. Suitable polyethylene glycol polymers have a polyethylene glycol backbone with random grafted polyvinyl acetate side chains. The average molecular weight of the polyethylene glycol backbone can be in the range of 2,000 Da to 20,000 Da, or 4,000 Da to 8,000 Da. The molecular weight ratio of the polyethylene glycol backbone to the polyvinyl acetate side chains may be in the range of 1: 1 to 1: 5, or 1: 1.2 to 1: 2. The average number of graft sites per ethylene oxide unit may be less than 1 or less than 0.8, and the average number of graft sites per ethylene oxide unit may be 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. A suitable polyethylene glycol polymer is Sokalan HP22.

Polyester antifouling polymers: Suitable polyester antifouling polymers have 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
Where
a, b and c are 1 to 200;
d, e, and f are 1-50,
Ar is 1,4-substituted phenylene;
sAr is 1,3-substituted phenylene substituted at the 5-position with SO ₃ Me,
Me is H, Na, Li, K, Mg / 2, Ca / 2, Al / 3, ammonium, mono-, di-, tri- or tetra-alkylammonium, or any mixture thereof, where in the alkyl group _is a 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 -C ₁₈ n- or iso-alkyl, and R ⁷ is linear or branched chain _C 1 _{-C 18} alkyl, or linear or branched _C 2 _{-C 30} alkenyl, or cycloalkyl group having 5-9 carbon atoms, or a _C 8 _{-C 30} aryl group, or a _C 6 ~ C ₃₀ arylalkyl group. Suitable polyester antifouling polymers are terephthalate polymers having the structure of formula (I) or formula (II) above.

  Suitable polyester antifouling polymers include Repel-o-tex series polymers such as Repel-o-tex SF2 (Rhodia) and / or Texcare series polymers such as Texas Care SRA300 (Clariant).

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

  Cellulosic polymer: The composition may comprise a cellulosic polymer, such as a polymer selected from alkylcellulose, alkylalkoxyalkylcellulose, carboxyalkylcellulose, alkylcarboxyalkyl, and any combination thereof. Suitable cellulosic polymers are selected from carboxymethylcellulose, methylcellulose, methylhydroxyethylcellulose, methylcarboxymethylcellulose, and mixtures thereof. Carboxymethylcellulose 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 a hydrophobically modified carboxymethyl cellulose such as Finnfix SH-1 (CP Kelco).

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

  Another suitable substituted cellulosic polymer is cationically 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-vinyl pyrrolidone and N-vinyl imidazole, polyvinyl pyrrolidone polymers, polyvinyl oxazolidone, and polyvinyl imidazole, or mixtures thereof. The aforementioned DTI polymers are well known in the art and are commercially available, for example, PVP-K15 and K30 (Ashland), Sokalan HP165, HP50, HP53, HP59, HP56K, HP56, HP66 (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. Substantially free of zeolite builder is typically 0 wt% to 10 wt% zeolite builder, or 8 wt% or less, or 6 wt% or less, or 4 wt% or less, or 3 wt% or less, 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 “not intentionally added”. Typical zeolite builders include zeolite A, zeolite P, zeolite MAP, zeolite X, and zeolite Y.

  Phosphate builder: The composition may be substantially free of phosphate builder. Substantially free of phosphate builder is typically 0 wt% to 10 wt% phosphate builder, alternatively 8 wt% or less, or 6 wt% or less, or 4 wt% or less, or 3 wt% It means that only 2% by weight or less, or even 1% by weight or less of phosphate builder is contained. Substantially free of zeolite builder preferably means that the phosphate builder is “not intentionally added”. A typical phosphate builder is sodium tripolyphosphate (STPP).

  Citrate: A preferred citrate is sodium citrate. However, citric acid capable of forming a citrate salt in the washing solution may be incorporated into the composition.

  Buffers and alkali sources: Suitable buffers and alkali sources include double salts such as carbonates and / or silicates and / or burkeite.

  Carbonate: A suitable carbonate is sodium carbonate and / or sodium bicarbonate. The carbonate may have a weight average particle size of 100 to 500 micrometers. Alternatively, the carbonate can have a weight average particle size of 10-25 micrometers.

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

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

  Bleach activators: Suitable bleach activators include tetraacetylethylenediamine (TAED), nonanoyloxybenzene sulfonic acid (NOBS), caprylamido nonanoyloxybenzene sulfonic acid (NACA-OBS), 3, 5, 5-Trimethylhexanoyloxybenzenesulfonic acid (Iso-NOBS), oxybenzenesulfonic acid such as 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 available oxygen: A suitable source of available 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 with a coating component such as carbonate, sulfate, silicate, borosilicate, or any mixture thereof including these, or further May be completely coated. Suitable percarbonates can be prepared by a fluid bed process or by a crystallization process. Suitable perborate salts include sodium perborate monohydrate (PB1), sodium perborate tetrahydrate (PB4), and anhydrous sodium perborate, also known as effervescent sodium perborate. 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-phthaloylaminoperoxycaproic acid (PAP).

  Bleach catalyst: Suitable bleach catalysts include oxaziridinium-based bleach catalysts, transition metal bleach catalysts, and bleach enzymes.

  Oxaziridinium-based bleach catalyst: 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, and 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, and optionally R ² is independently N is an integer from 0 to 1;

  Transition metal bleach catalyst: The composition may comprise a transition metal bleach catalyst, typically comprising cations of copper, iron, titanium, ruthenium, tungsten, molybdenum, and / or manganese. A suitable transition metal bleach catalyst is a manganese-based transition metal bleach catalyst.

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

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

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

The co-bleach particles can include a binder. Suitable binders are carboxylate polymers such as polyacrylate polymers, and / or non-ionic detersive surfactant and / or linear C ₁₁ -C ₁₃ surfactant such as anionic detersive surfactants such as alkyl benzene sulfonate It is.

  The co-bleaching particles can include a bleaching catalyst such as an oxaziridinium-based bleaching 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. Suitable 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 enantiomeric form. The composition may comprise disodium salt of 4,5-dihydroxy-m-benzenedisulfonic acid. A suitable chelating agent may be a calcium crystal growth inhibitor.

  Calcium crystal growth inhibitor: The composition comprises 1-hydroxyethanedisulfonic acid (HEDP) and salts thereof, N, N-dicarboxymethyl-2-aminopentane-1,5-dioic acid and salts thereof, 2- 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 may be included.

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

  Brightener: The laundry detergent composition may include a fluorescent brightener. Preferred classes of optical brighteners include, for example, distyryl biphenyl compounds such as Tinopal ™ CBS-X, diaminostilbene disulfonic acids such as Tinopal ™ DMS pure Xtra and Blankophor ™ HRH, and Blankophor ™ SN And 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-2hydroxyethyl) 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 are C.I. I. This is an optical brightener 260. For solid detergent compositions, the brightener may be used in the β or α crystal form or a mixture of these forms.

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

  For the enzyme, the accession number and ID are shown in parentheses to indicate the item number in the Genbank, EMBL and / or Swiss-Prot database. For either mutation, the standard one-letter amino acid code is used with a deletion designation. The accession number preceded by DSM refers to the microorganisms deposited with Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH (Mascherder Weg 1b, 38124 Brunswick) (DSMZ).

Protease: The composition may comprise a protease. Suitable proteases include metalloproteases and / or serine proteases including neutral or alkaline microbial serine proteases such as subtilisin (EC 3.4.21.62). Suitable proteases include those of animal, plant or microbial origin. In one aspect, such suitable protease may be of microbial origin. Suitable proteases include chemically or genetically modified mutants of the aforementioned preferred proteases. In one aspect, a suitable protease may be an alkaline microbial protease or / and a serine protease such as a trypsin-type protease. Examples of suitable neutral or alkaline proteases include the following:
(A) Bacillus lentus, Bacillus alkalophilus (P27963, ELYA_BACAO), Bacillus subtilis, Bacillus amyloliquefaciens (P00782, SUBT_BACAM), Bacillus subtilis (P00782, SUBT_BACAM), Bacillus subtilis 4.21.62).
(B) Trypsin-type or chymotrypsin-type proteases such as trypsin (eg, of 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 DSM5483 (P29599).

  Suitable commercially available protease enzymes include Alcalase (R), Savinase (R), Primease (R), Durazym (R), Polarzyme (R), Kannase (R), and Liquanase (R). Novozymes A / S (Denmark) under the trade names of, Liquanase Ultra (registered trademark), Savinase Ultra (registered trademark), Ovozyme (registered trademark), Neutrase (registered trademark), Everlase (registered trademark), and Esperase (registered trademark). , Maxatase (R), Maxcal (R), Maxapem (R), Properase (R), Purafect ( (Registered trademark), Purefect Prime (registered trademark), Purefect Ox (registered trademark), FN3 (registered trademark), FN4 (registered trademark), Excellase (registered trademark) and Purefect OXP (registered trademark) by Genencor International. Those sold, those sold by Solvay Enzymes under the trade names Optilean® and Optimase®, available from Henkel / Kemira, ie BLAP (with the following mutations S99D + S101R + S103A + V104I + G159S PBL599 (S3T + V4I + V199M + V205I + L21) all available from Henkel / Kemira BLAP with D), BLAP X (BLAP with S3T + V4I + VV205I) and BLAP F49 (S3T + V4I + A194P, BLAP with V199M + V205I + L217D), and KAP available with Kao (A230V + S256G + S259G + S259N Bacillus alcalophilus)).

  Another suitable protease is a fungal serine protease. Suitable enzymes are Trichoderma reesei strain QM9414, Malbranchea cinnamomea strain ALK04122, Fusarium graminearum strain ALK01726, Fusarium equistium 68 Fungal serine protease mutant or wild type endogenous to Fusarium acuminatum strain CBS124084. Examples of commercially available fungal serine proteases are Biotouch ROC and Biotouch Novia, both supplied by AB Enzymes, Darmstadt, Germany.

Amylase: Suitable amylases are α-amylases including those derived from bacteria or fungi. Chemically or genetically modified mutants (variants) are included. Suitable alkaline α-amylases are strains of Bacillus, such as Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, 89, NC, 125 I, Bs , DSM 12368, DSMZ no. Derived from a strain of Bacillus such as 12649, KSM AP1378, 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 are substituted at one or more positions.
(B) AA560 amylase (CBU30457, HD066534) and variants thereof, in particular 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, 283, 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 with substitution, and optionally D183 ^* and G184 ^* Mutants that also contain deletions.
(C) Variants that exhibit at least 90% homology with the wild-type enzyme from Bacillus sp. 722 (CBU30453, HD066526), in particular variants with deletions at positions 183 and 184.

  Suitable commercially available α-amylases are Duramyl®, Liquizyme®, Termamy®, Termamyl Ultra®, Natalase®, Supramyl®, Stainzyme® ), Stainzyme Plus (registered trademark), Fungamyl (registered trademark), and BAN (registered trademark) (Novozymes A / S), Bioamylase (registered trademark) and its variants (Biocon India Ltd.), Kemzym (registered trademark) AT9000. (Biozym Ges.mbH, 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 (R), Stainzyme (R), and Stainzyme Plus (R).

  Cellulase: The composition may comprise cellulase. Suitable cellulases include bacterial or fungal cellulases. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genus Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, and Acremonium, such as those produced from Humicola insolens, Mycelophorum thermophila, and fungus

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

  Cellulases exhibit endo-β-1,4-glucanase activity (EC 3.2.1.4), including bacterial polypeptides endogenous to members of Bacillus sp. AA349 and mixtures thereof. A microorganism-derived endoglucanase can be mentioned. Suitable endoglucanases are sold under the trade names Celluclean® and Whitezyme® (Novozymes A / S, Bagsvaard, Denmark).

  The composition is sold under the trade name of a washed cellulase 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.

  Suitable cellulases such as Whitezyme® may also exhibit xyloglucanase activity.

  Xyloglucanase: A suitable xyloglucanase enzyme can have enzymatic activity on both xyloglucan and amorphous cellulose substrates. The enzyme may be a glycoside hydrolase selected from glycoside hydrolase (GH) family 5, 12, 44, or family 74. A glycosyl hydrolase selected from GH family 44 is 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 (R), Pectaway (R), and X-Pect (R) (Novazymes A / S (Bagsvaard, Denmark)) , Either a wild-type or a mutant form of pectate lyase derived from Bacillus (CAF05441, AAU25568).

  Mannanase: Suitable mannanases are sold under the trade name Mannaway (R) (Novozymes A / S (Bagsvaerd, Denmark)) and the trade name Purabrite (R) (available from Genencor International Inc. (Palo Alto, Calif.)). Yes.

  Bleaching enzymes: Suitable bleaching enzymes include oxidoreductases such as oxidases such as glucose oxidase, choline oxidase or carbohydrate oxidase, oxygenases, catalases, peroxidases (haloperoxidase, chloroperoxidase, bromoperoxidase, lignin peroxidase, glucose peroxidase, Or manganese peroxidase), dioxygenase, or laccase (phenol oxidase, polyphenol oxidase). Suitable commercial products are sold under the trade names Guardzyme® and Denilite® by Novozymes. It may be advantageous to formulate additional organic compounds, in particular aromatic compounds, together with the bleaching enzyme, these compounds interact with the bleaching enzyme to enhance the activity of the oxidoreductase (enhancing agent) or It promotes electron flow between the oxidase and the soil, typically across very different redox potentials (mediator).

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

  Homology: The correlation between two amino acid sequences is represented by the parameter “homology”. For purposes of the present invention, the alignment of the two amino acid sequences is determined by using the Needle program of the EMBOSS package (http://emboss.org) version 2.8.0. The Needle program is available from Needleman, S .; B. and Wunsch, C.I. D. (1970) J. Org. Mol. Biol. 48, 443 to 453 is executed. The substitution matrix used is BLOSUM62, 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 clay, hectorite clay, and / or laponite clay. A suitable clay is montmorillonite clay. Suitable silicones include aminosilicones and / or polydimethylsiloxane (PDMS). Suitable softening agents are particles comprising clay and silicone, such as particles comprising montmorillonite clay and PDMS.

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

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

  Perfume: Suitable perfumes include perfume microcapsules, polymer assisted perfume delivery systems including Schiff base perfume / polymer composites, perfume accord encapsulated in starch, perfume-filled zeolite, blooming perfume accord, and any combination thereof Is mentioned. Suitable perfume microcapsules are melamine formaldehyde-based and typically include a perfume encapsulated by a shell containing melamine formaldehyde. Such perfume microcapsules may very well include a cationic material and / or a cationic precursor material such as polyvinylformamide (PVF) and / or cationically modified hydroxyethyl cellulose (catHEC) in the shell.

  Aesthetics: Suitable esthetic particles include soaping, layered aesthetic particles, gelatin beads, carbonate and / or sulfate speckles, color earth particles, and any combination thereof.

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

  A composition containing a Western liquid detergent, described in detail in Table 1, was prepared. This composition was labeled as antecedent composition 1.

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

  A variant that is identical to the antecedent composition 2 but has at least 90% sequence identity to the wild type lipase from Thermomyces lanuginosus and has the sequence substitutions T231R and N233R. A third antecedent composition was also prepared.

  A fourth antecedent composition was prepared that was identical to antecedent composition 2, but was also used with an antifouling polymer (SRP).

  A variant that is identical to the antecedent composition 4 but has at least 90% sequence identity to the wild type lipase from Thermomyces lanuginosus and has the sequence substitutions T231R and N233R. A fifth antecedent composition was also prepared, including

Summary,
1. Only the antecedent composition 2. only antecedent compositions combined with cleaning additives 3. Only antecedent compositions containing Lipex® in combination with cleaning additives. 4. only antecedent compositions containing SRP in combination with cleaning additives Only antecedent compositions containing SRP and Lipex® in combination with cleaning additives

  Standard fabric samples, TF7436-M polycotton (polyester and cotton blend, 25 x 20 cm) and Dacron 64 polyester were obtained from Westrails. Two each of these were added to the washing machine along with 2.5 kg of cotton fabric and a cotton towel supplied from the test fabric as an additional ballast.

  The sample is then washed with the detergent composition detailed in Table 1 so that 13 liters of wash solution contains 2692 ppm of detergent at 1600 rpm at 30 ° C. short cotton cycle. did. An application amount of 30 g of the cleaning additive detailed in Table 2 was added to the rinse compartment of the washing machine drawer to be added during the rinse phase of the washing machine cycle. Lipid esterase was added to the rinsing compartment of the washing machine drawer so that an active enzyme protein concentration of 1 ppm was provided during the rinsing phase of the washing machine 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 cleaning additive, then lipid esterase, then antifouling polymer. After the wash cycle was completed, the fabric was then dried in a row. This was repeated so that all samples were washed four times with the same preconditioning treatment composition during washing, and washing additives, lipid esterase and antifouling polymer were added over the rinse.

  Prepare 5 × 5 cm samples of TF7436-M and Dacron 64 for each preconditioning treatment and color with 200 L of SV13-stained lard (Asda lard batch 130R7, SV13%, batch SPt001013) overnight at 32 ° C./80%. saved.

  The colored swatch was then washed in a Thermometer (0.8 L pot) in the presence of a Western liquid detergent (total concentration 2692 ppm) detailed in Table 1. A ballast fabric composed of knitted cotton fabric was also added with a total fabric load of 26.7 g. The cleaning conditions in the Thermometer are 200 rpm, 30 ° C., a cleaning time of 20 minutes, and a rinsing time of 5 minutes. The fabric was then dried overnight on a metal shelf.

  Lipid esterase was added to the rinse at a concentration of 1 ppm (active enzyme protein). Antifouling polymer Texcare® SRA300 was added at 0.2% w / w.

Stain removal was quantified using commercially available Digieye software and the stain removal rate was 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 + ( _ac −a _b ) ² + b _c −b _b ) ² )
ΔE _a = √ ((L _c −L _a ) ² + ( _ac −a _a ) ² + b _c −b _a ) ² )
Subscript “b” means stain data before washing Subscript “a” means stain data after washing Subscript “c” means fabric data without stain

Therefore, L ^* a ^* b values are taken from unstained fabrics, fabrics with stains before washing, and fabrics with stains after washing.

  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。）

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

  The data clearly shows that the addition of cleaning additives or antifouling polymers, ie antecedent compositions 2 and 4, respectively, significantly improves the soil removal rate. Further to this, the addition of a lipid esterase combined with either a cleaning additive or an antifouling polymer, ie, each of the antecedent compositions 3 and 5, provides a high soil removal rate. Thus, during the precondition rinsing stage according to the present invention, the inclusion of lipid esterase in combination with either a detergent additive or an antifouling polymer is compared to a fabric having a precondition without lipid esterase. And showed a surprising improvement in the soil reduction rate.

(Examples 3 to 8)
The following examples are for cleaning 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)
Granular laundry detergent compositions designed for hand-washing or top-loading washing machines are added to enough water to form a paste for direct contact with the surface to be treated to form a concentrated cleaning composition You can do it.

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

  Wash the fabric with any of the above compositions at a water concentration of 7000-10000 ppm, 20-90 ° C. and a water to fabric ratio of 5: 1. A 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 fabric is dried in line so that it is exposed to air and optionally sunlight.

  Examples 21-26 Heavy Liquid Laundry Detergent Composition

(Example 27)
The composition may be encapsulated 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 treatment 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 40-60, not exceeding one graft point per 50 ethylene oxide units.
Polyethyleneimine with 20 ethoxylate groups per ^2- NH (MW = 600).
^* Note: All enzyme concentrations are expressed as a percentage of the enzyme material.

Ingredients and Notes for Compositions of Examples 3-8 Silicone HC306 supplied by Wacker Chemical Corporation, Adrian, Michigan, USA
Poly (acrylamide-methacrylamidepropyltrimethylammonium chloride) (PAMMAPTAC)
Butyl carbitol Tallow alkyl ethoxylated alcohol with an average degree of ethoxylation of 80 Proxel ™ GXL
Fragrance 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 a C _12-15 alkyl ethoxy (3) sulfate supplied by Stepan (Northfield, Illinois, USA).
AE7 is a C _12-15 ethoxylate alcohol with an average degree of ethoxylation of 7 supplied by Huntsman (Salt Lake City, Utah, USA).
AE9 is a C _12-13 ethoxylate alcohol with an average degree of ethoxylation of 9 supplied by Huntsman (Salt Lake City, Utah, USA).
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, Nestica, Czech, and Public.
Sodium carbonate is supplied by Solvay, Houston, Texas, USA.
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 diphosphonate (HEDP supplied by Solutia, St Louis, Missouri, USA Bagsvaard, Denmark). ).
Savinase (registered trademark), Natalase (registered trademark), Stainzyme (registered trademark), Lipex (registered trademark), Celluclean (registered trademark), Mannaway (registered trademark), and Whitezyme (registered trademark) are all Novozymes (Bagsvarad, ) Product.
Biotouch® ROC is a product of AB Enzymes (Darmstadt, Germany).
Bacterial proteases described in US Pat. No. 6,312,936 (B1) (Examples 8-13) were supplied by Genencor International (Palo Alto, California, USA).
Bacterial protease described in US Pat. No. 4,760,025 (Examples 14-20) was supplied by Genencor International (Palo Alto, California, USA).
The optical brightener 1 is Tinopal (registered trademark) AMS, the fluorescent brightener 2 is Tinopal (registered trademark) CBS-X, sulfonated zinc phthalocyanine and direct violet 9 are Pergasol (registered trademark) violet BN-Z. All of these are supplied by Ciba Specialty Chemicals (Basel, Switzerland).
Sodium carbonate is that supplied by Solvay, Houston, Texas, USA.
Sodium perborate is supplied by Degussa, Hanau, Germany.
NOBS is sodium nonanoyloxybenzenesulfonate supplied by Future Fuels, Batesville, Arkansas, USA.
TAED is tetraacetylethylenediamine supplied by Clariant GmbH, Sulzbach, Germany under the trade name Peractive®.
S-ACMC is commercially available from Megazyme (Wicklow, Ireland) under the product name (product code S-ACMC), azo-CM-cellulose (AZO-CM-CELLULOSE). I. Carboxymethylcellulose conjugated with Reactive Blue 19.
The soil release agent is Repel-o-tex® 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 and is supplied by BASF, Ludwigshafen, Germany.
Ethylenediamine-N, N'-disuccinic acid, Na salt of (S, S) isomer (EDDS) is supplied by Octel, Ellesmere Port, UK.
Hydroxyethane diphosphonate (HEDP) is supplied by Dow Chemical, Midland, Michigan, USA.
The suspected foam suppressor is 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.
Liquidint (R) 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, a dimension disclosed as “40 mm” is intended to mean “about 40 mm”.

  All references cited herein, including any cross-reference patents or related patents, are hereby incorporated by reference in their entirety, except where expressly excluded or otherwise limited. Incorporated. Citation of any document is not considered prior art to any invention disclosed or claimed herein, or it is combined alone or with any other reference (s) Sometimes it is not considered to teach, suggest or disclose all such inventions. In addition, 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 a document incorporated by reference, the meaning or definition given to that term in this document applies. Shall be.

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

Claims (13)

A method for laundering a fabric comprising the following steps.
i) bringing the fabric into contact with an aqueous cleaning liquid comprising a detergent composition, the detergent composition comprising a surfactant and the washing liquid comprising 0.05 to 4 g / l surfactant; and ii) Contacting the fabric of step (i) with a rinsing liquid in a first rinsing step;
iii) contacting the fabric of step (ii) in a second rinsing step with a second aqueous rinsing solution comprising a lipid esterase and a terephthalate antifouling polymer ;
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, wherein the detergent composition comprises a surfactant and the cleaning solution comprises 0.05 to 4 g / l of surfactant. Including.   2. 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 in contact with the laundry detergent composition in a washing cycle of an 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, wherein the time is 30 minutes, 45 minutes, or 1 hour or less.   The fabric of step (i) and / or step (vi) is in contact with the laundry detergent composition in a 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 claim 1, which is continued between ˜30 ° C.   The lipid esterase is E. coli. C. Selected from classification 3.1, preferably E. C. Classification 3.1.1.1, E.I. C. Classification 3.1.1.3, E.I. C. The method according to claim 1, which is selected from the classification 3.1.1.74 or a combination thereof.   The lipid esterase is classified as E.I. C. 3.1.1.3 or E.I. C. 3.1.1.1 or combinations thereof, preferably E.I. C. 6. The method of claim 5, selected from 3.1.1.3.   Claim 5; European Patent No. 1290150, wherein said lipid esterase has at least 90% sequence identity to wild-type lipase from Thermomyces lanuginosus and has sequence substitutions T231R and N233R. The method according to claim 1, comprising a variant corresponding to part (u) of (B1) or a combination thereof.   8. In step (iii), the fabric is contacted with a lipid esterase and the lipid esterase is present in the aqueous rinse at a concentration between 30-55,000 ng enzyme / g fabric. Method.   9. A method according to claim 1-8, wherein in step (i) and / or step (vi) the ratio of surfactant to fabric on a weight to weight basis is from 1: 150 to 1: 500. Second rinsing step, the final rinsing step before the fabric is dried in step (iv), Method according to claim 1-9. Detersive surfactants, anionic surfactants, preferably linear alkyl benzene sulfonic acid, alkoxylated anionic surfactant, or an anionic surfactant selected from these combinations, claim 1-10 The method described in 1. The method according to claims 1 to 11 , 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 0 wt% to 10 wt% anhydrous base zeolite builder, 0 wt% to 10 wt% phosphate builder, or combinations thereof. 12. The method according to 12 .