Detergent composition
A nuclease enzyme-based cleaning composition with a balanced surfactant system addresses the challenge of dirt accumulation on fabrics by enhancing enzyme adhesion and cleaning efficacy.
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- PROCTER & GAMBLE CO
- Filing Date
- 2026-02-20
- Publication Date
- 2026-06-09
AI Technical Summary
The accumulation of dirt over time on fabrics, particularly white or light-colored fabrics, leads to unpleasant odors and reduced whiteness, and existing laundry detergents struggle to effectively adhere deoxyribonuclease enzymes to the fabric surface due to the presence of surfactants.
A cleaning composition comprising a nuclease enzyme, preferably deoxyribonuclease or ribonuclease, combined with a surfactant system of anionic and nonionic surfactants in a specific weight ratio, formulated as a water-soluble unit dose pouch.
The composition enhances the adherence of nuclease enzymes to fabrics, effectively removing dirt and reducing odors, thereby improving fabric whiteness and cleanliness.
Smart Images

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Abstract
Description
Technical Field
[0001] The present invention relates to a cleaning composition containing a nuclease enzyme.
Background Art
[0002] The whiteness of fabrics is always a problem for laundry detergent manufacturers. A specific problem can be the accumulation of dirt over time. This is a problem for both colored and white fabrics, but can be particularly noticeable in white or light-colored fabrics, for example around collars and cuffs where washing is incomplete. It can also be a problem as it can cause unpleasant odors. Based on various available washing techniques such as surfactants, bleaches and enzymes, laundry detergent manufacturers can consider many solutions. Many different types of enzymes such as lipase, protease, amylase, cellulase, peroxidase, aryl esterase, cutinase, pectinase, mannanase and deoxyribonuclease are available to detergent formulators for washing various types of dirt. Deoxyribonuclease can be particularly effective in washing this type of dirt, but for it to provide washing, the enzyme needs to adhere to the fabric surface. Since certain surfactants can reduce this adhesion, there is still a need for a washing or treatment composition containing a surfactant that allows the enzyme to adhere.
Summary of the Invention
Means for Solving the Problems
[0003] The present invention relates to a cleaning composition comprising a nuclease enzyme, preferably a deoxyribonuclease or ribonuclease enzyme, and a surfactant system comprising an anionic surfactant and a nonionic surfactant, wherein the weight ratio of the anionic surfactant to the nonionic surfactant is from 1.5:1 to 1:10.
[0004] The cleaning composition containing the nuclease enzyme is in the form of a water-soluble unit dose pouch, preferably a multi-compartment unit dose product.
[0005] The present invention includes a method for washing fabric, which involves contacting the fabric with an aqueous solution containing a washing composition.
[0006] A further aspect of the present invention provides a washing composition comprising a nuclease enzyme as defined herein and a glycosyl hydrolase of the GH20 family, preferably β-N-acetylglucosaminidase of EC3.2.1.52. [Modes for carrying out the invention]
[0007] definition As used herein, the term “alkoxy” is intended to include C1-C8 alkoxys and C1-C8 alkoxy derivatives of polyols having repeating units, such as butylene oxide, glycidol oxide, ethylene oxide, or propylene oxide.
[0008] As used herein, unless otherwise specified, the terms “alkyl” and “alkyl-terminated” are intended to include C1-C18 alkyl groups, or even C1-C6 alkyl groups.
[0009] As used herein, unless otherwise specified, the term "aryl" is intended to include C3-C12 aryl groups.
[0010] As used herein, unless otherwise specified, the terms “arylalkyl” and “alkalil” are equivalent and are intended to include groups that typically have a C1-C18 alkyl group and, in one embodiment, a C1-C6 alkyl group, respectively, comprising an alkyl moiety bonded to an aromatic moiety.
[0011] In this specification, the terms "ethylene oxide," "propylene oxide," and "butylene oxide" may be represented by their typical abbreviations, "EO," "PO," and "BO," respectively.
[0012] As used herein, the term “cleaning and / or treatment composition” includes, unless otherwise specified, cleaning agents and / or fabric treatment compositions in granular, powder, liquid, gel, paste, single-dose, bar, and / or flake form, including, but not limited to, products for washing fabrics, fabric softening compositions, fabric strengthening compositions, fabric freshening compositions, and other products for caring for and maintaining fabrics, as well as combinations thereof. Such compositions may be pre-treatment compositions for use before a washing step, rinse additive compositions, and cleaning aids such as bleaching additives and / or “stain removers,” or products having a base such as a pre-treatment composition or a dryer additive sheet.
[0013] As used herein, “cellulose substrate” is intended to include any substrate containing 100% by weight of cellulose, or at least 20% by weight, or at least 30% by weight, or at least 40% by weight, or at least 50% by weight, or even at least 60% by weight of cellulose. Cellulose can be found in wood, cotton, linen, jute, and hemp cloth. Cellulose substrates may be in the form of powder, fibers, pulp, or articles formed from powder, fibers, and pulp. Examples of cellulose fibers include, but are not limited to, cotton, rayon (regenerated cellulose), acetate (cellulose acetate), triacetate (cellulose triacetate), and mixtures thereof. Typically, cellulose substrates include cotton. Examples of articles formed from cellulose fibers include fabric articles such as cloths. Examples of articles formed from pulp include paper.
[0014] As used herein, the term “maximum extinction coefficient” is intended to represent the molar extinction coefficient at the wavelength of maximum absorbance (also referred to herein as maximum wavelength) in the range of 400 nanometers to 750 nanometers.
[0015] As used herein, "average molecular weight" is recorded as the average molecular weight determined by the molecular weight distribution, and as a result of the manufacturing process, the polymers disclosed herein may have a distribution of repeating units in their polymer portion.
[0016] As used herein, the term “mutant” refers to a polypeptide containing an amino acid sequence different from the wild-type or reference sequence. A mutant polypeptide may differ from the wild-type or reference sequence by deletion, insertion, or substitution of nucleotides relative to the reference or wild-type nucleotide sequence. The reference or wild-type sequence may be a full-length native polypeptide sequence or any other fragment of a full-length polypeptide sequence. Polypeptide variants generally have at least about 70% amino acid sequence identity with the reference sequence, but may also include 75% amino acid sequence identity with the reference sequence, 80% amino acid sequence identity with the reference sequence, 85% amino acid sequence identity with the reference sequence, 86% amino acid sequence identity with the reference sequence, 87% amino acid sequence identity with the reference sequence, 88% amino acid sequence identity with the reference sequence, 89% amino acid sequence identity with the reference sequence, 90% amino acid sequence identity with the reference sequence, 91% amino acid sequence identity with the reference sequence, 92% amino acid sequence identity with the reference sequence, 93% amino acid sequence identity with the reference sequence, 94% amino acid sequence identity with the reference sequence, 95% amino acid sequence identity with the reference sequence, 96% amino acid sequence identity with the reference sequence, 97% amino acid sequence identity with the reference sequence, 98% amino acid sequence identity with the reference sequence, 98.5% amino acid sequence identity with the reference sequence, or 99% amino acid sequence identity with the reference sequence.
[0017] When used herein, articles such as "a" and "an" used in a claim are understood to mean that there is one or more claims or descriptions.
[0018] As used herein, the terms “include / s” and “including” are non-restrictive.
[0019] As used herein, the term “solid” includes product forms such as granules, powders, bars, and tablets.
[0020] As used in this invention, the term "fluid" includes product forms such as liquids, gels, pastes, and gases.
[0021] Unless otherwise specified, all component or composition levels refer to the active portion of the component or composition, excluding impurities that may be present in commercially available sources of such components or compositions, such as residual solvents or by-products.
[0022] All percentages and ratios are calculated by weight unless otherwise specified. All percentages and ratios are calculated based on the total composition unless otherwise specified.
[0023] The washing and / or treatment composition comprises, in addition to the nuclease enzyme, any of the additional auxiliary substances from such washing and / or treatment compositions listed below.
[0024] Nuclease enzyme Nuclease enzymes are enzymes capable of cleaving phosphodiester bonds between nucleotide subunits of nucleic acids. In this specification, nuclease enzymes are preferably deoxyribonucleases or ribonucleases, or functional fragments thereof. A functional fragment or portion means a portion of a nuclease enzyme that catalyzes the cleavage of phosphodiester bonds in the DNA backbone, and therefore a region of the nuclease protein described above that retains catalytic activity. Thus, it includes truncated but functional versions of enzymes and / or variants and / or derivatives and / or homologs whose function is maintained.
[0025] Preferably, the nuclease enzyme is a deoxyribonuclease, and is preferably selected from any of the following classes: EC3.1.21.x (wherein x = 1, 2, 3, 4, 5, 6, 7, 8, or 9), EC3.1.22.y (wherein y = 1, 2, 4, or 5), EC3.1.30.z (wherein z = 1 or 2), EC3.1.31.1, and mixtures thereof.
[0026] Nucleases of class EC3.1.21.x are cleaved at the 3' hydroxyl group, releasing the 5' phosphomonoester as follows.
[0027] [ka]
[0028] Nuclease enzymes of class EC3.1.21.x are preferred, especially when x=1.
[0029] Nucleases of class EC3.1.22.y cleave at the 5' hydroxyl group, releasing the 3' phosphomonoester. Enzymes of class EC3.1.30.z may be preferred because they act on both DNA and RNA to release the 5'-phosphomonoester. A preferred example of class EC3.1.31.2 is described, for example, in U.S. Patent Application Publication 2012 / 0135498(A), specifically in Sequence ID No. 3. Such enzymes are commercially available from c-LECTA as DENARASE® enzymes.
[0030] Nuclease enzymes of class EC3.1.31.1 produce 3'-phosphomonoesters.
[0031] Preferably, the nuclease enzyme includes a microbial enzyme. The nuclease enzyme may be of fungal or bacterial origin. Bacterial nucleases may be most preferred. Fungal nucleases may be most preferred.
[0032] Microbial nucleases can be obtained from bacterial nucleases of the genus Bacillus, such as Bacillus licheniformis or Bacillus subtilis. Preferred nucleases can be obtained from Bacillus licheniformis, preferably strain EI-34-6. Preferred deoxyribonucleases are variants of Bacillus licheniformis derived from the EI-34-6 strain nucB deoxyribonuclease defined in Sequence ID No. 1 herein, i.e., variants that are at least 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, or 100% identical thereto.
[0033] Other suitable nucleases are those specified in SEQ ID NO: 2 herein, or, for example, their variants that are at least 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, or 100% identical thereto. Other suitable nucleases are those specified in SEQ ID NO: 3 herein, or, for example, their variants that are at least 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, or 100% identical thereto.
[0034] Fungal nucleases can be obtained from the genus Aspergillus, for example, Aspergillus oryzae. Preferred nucleases can be obtained from Aspergillus oryzae as defined in Sequence ID No. 5 herein, or from its mutants that are at least 60%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, or 100% identical thereto.
[0035] Another preferred fungal nuclease can be obtained from the genus Trichoderma, for example, Trichoderma harzianum. The preferred nuclease can be obtained from Trichoderma harzianum as defined in Sequence ID No. 6 herein, or from its mutants that are at least 60%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, or 100% identical thereto.
[0036] Other fungal nucleases include Aspergillus oryzae RIB40, Aspergillus oryzae 3.042, Aspergillus flavus NRRL3357, Aspergillus parasiticus SU-1, Aspergillus nomius NRRL13137, Trichoderma reesei QM6a, Trichoderma virens Gv29-8, Oidiodendron maius Zn, Metarhizium guizhouense ARSEF 977, Metarhizium majus ARSEF 297, and Metarhizium robertosii. robertsii)ARSEF 23, Metarhizium acridum CQMa 102, Metarhizium brunneum ARSEF 3297, Metarhizium anisopliae, Colletotrichum fioriniae PJ7, Colletotrichum sublineola, Trichoderma atroviride IMI 206040, Tolypocladium ophioglossoides CBS 100239, Beauveria bassiana ARSEF 2860, Colletotrichum higinsianum Higginsianum), Hirsutella minnesotensis 3608, Sedosporium apiospermum, Phaeomoniella chlamydospora, Fusarium vertisilioidesverticillioides)7600, Fusarium oxysporum special type cuben variety 4, Colletotrichum graminicola M1.001, Fusarium oxysporum FOSC 3-a, Fusarium avenaceum, Fusarium langsethiae, Grosmannia clavigera kw1407, Claviceps purpurea 20.1, Verticillium longisporum, Fusarium oxysporum special type cuben variety 1, Magnaporthe oryzae)70-15, Beauveria bassiana D1-5, Fusarium pseudograminearum CS3096, Neonectria ditissima, Magnaporthiopsis poae ATCC 64411, Cordyceps militaris CM01, Marssonina brunnea special type "multigermtubi" MB_m1, Diaporthe ampelina, Metalhizium album ARSEF 1941, Colletotrichum gloeosporioides Nara gc5, Madurella mycetomatis, Metarhizium brunneum ARSEF 3297, Verticillium alfalfae VaMs.102, Gaeumannomyces graminis variety triticiR3-111a-1, Nectria haematococca mpVI 77-13-4, Verticillium longisporum, Verticillium dahliae VdLs.17, Torrubiella hemipterigena, Verticillium longisporum, Verticillium dahliae VdLs.17, Botrytis cinerea B05.10, Chaetomium globosum CBS 148.51, Metarhizium anisopliae, Stemphylium lycopersici *Lycopersici*, *Sclerotinia borealis* F-4157, *Metallidium robertii* ARSEF 23, *Myceliophthora thermophila* ATCC 42464, *Phaeosphaeria nodorum* SN15, *Phialophora attae*, *Ustilaginoidea virens*, *Diplodia seriata*, *Ophiostoma piceae* UAMH 11346, *Pseudogymnoascus pannorum* VKM F-4515 (FW-2607), *Bipolaris oryzae* oryzae)ATCC 44560, Metarhizium guizhouense ARSEF 977, Chaetomium thermophyllum DSM 1495, Pestalotiopsis fici W106-1, Bipolaris zeicola 26-R-13, Setosphaeria turcica Et28A, Arthroderma otaeExamples include those encoded by the DNA sequence of Pyrenophora tritici-repentis Pt-1C-BFP, as well as CBS 113480.
[0037] Preferably, the nuclease is an isolated nuclease.
[0038] Preferably, the nuclease enzyme is present in the laundry aqueous solution in an amount of 0.01 ppm to 1000 ppm, or 0.05 or 0.1 ppm to 750 or 500 ppm.
[0039] Nucleases can also produce a biofilm-disrupting effect.
[0040] A preferred composition further comprises the β-N-acetylglucosaminidase enzyme of EC3.2.1.52, preferably an enzyme having at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or at least 100% identity with SEQ ID NO: 4.
[0041] Surfactant-based The surfactant system includes an anionic surfactant and a nonionic surfactant, and the weight ratio of the anionic surfactant to the nonionic surfactant is 1.5:1 to 1:10, preferably 1.2:1 to 1:5, and more preferably 1:1 to 1:4.
[0042] The total surfactant level in the cleaning composition is preferably 5-80% by weight or 10-50% by weight, more preferably 15-45% by weight.
[0043] Anionic surfactants Anionic surfactants may consist of one surfactant or, typically, a mixture of one or more surfactants. Preferred anionic detergents are alkylbenzene sulfonates, alkoxylated anionic surfactants, or combinations thereof. Suitable anionic detergents include sulfate detergents and sulfonate detergents.
[0044] Particularly preferred alkylbenzene sulfonates are linear alkylbenzene sulfonates, especially those having a carbon chain length of C8 to C15, or C 10~13 These are alkylbenzene sulfonates. Suitable alkylbenzene sulfonates (LAS) can be obtained, or are even obtained, by sulfonating commercially available linear alkylbenzenes (LABs). Suitable LABs include low 2-phenyl LABs such as those supplied by Sasol under the trademark name Isochem® or by Petresa under the trademark name Petrelab®, while other suitable LABs include high 2-phenyl LABs such as those supplied by Sasol under the trademark name Hyblene®. Another suitable anionic detergent surfactant is an alkylbenzene sulfonate obtained by a DETAL catalytic process, preferably having a carbon chain length of 8 to 15. Other synthetic routes, such as HF, may also be suitable.
[0045] Suitable sulfate-based cleaning surfactants include alkyl sulfates, for example, C 8~18 Alkyl sulfates, or mainly C 12 Alkyl sulfates are an example. Alkyl sulfates may be derived from natural sources such as cocoa and / or taloupe. Alternatively, alkyl sulfates may be C 12~15 It may be derived from synthetic sources such as alkyl sulfates.
[0046] The surfactant composition may also preferably further contain an alkylalkoxylylated sulfate, such as alkylethoxylylated sulfate, or C8-18 alkylalkoxylylated sulfate, or C8-18 alkylethoxylylated sulfate, as an additional anionic surfactant. Preferably, the alkyl chain length may be 12-16 carbon atoms. The alkylalkoxylylated 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 mainly include C12 sodium lauryl ether sulfate ethoxylyzed with an average of 3 moles of ethylene oxide per mole.
[0047] Alkyl sulfates, alkylalkoxylated sulfates, and alkylbenzene sulfonates may be linear or branched, and may be substituted or unsubstituted.
[0048] The anionic cleansing surfactant may be a medium-chain branched anionic cleansing surfactant such as a medium-chain branched alkyl sulfate and / or a medium-chain branched alkylbenzene sulfonate. The medium-chain branching is typically a C group such as a methyl group and / or an ethyl group. 1~4 It is an alkyl group.
[0049] Another suitable anionic cleaning surfactant is alkylethoxycarboxylate.
[0050] Anionic surfactants typically exist in salt form and are typically complexed with a suitable cation. A suitable counterion is Na. + and K + Examples include substituted ammonium compounds such as C1-C6 alkanolammonium compounds, such as monoethanolamine (MEA), triethanolamine (TEA), diethanolamine (DEA), and any mixture thereof.
[0051] In the cleaning composition, when an alkyl (optionally ethoxylated) sulfate is present, preferably, the weight ratio of linear alkylbenzene sulfonate to alkyl sulfate and / or alkyl alkoxylated sulfate is from 20:1 to 1:2, more preferably from 5:1 to 1:1. Typically, the anionic surfactant is present in the cleaning composition in an amount of 5 to 30% by weight of anionic surfactant, or at least 8 or at least 10% by weight of anionic surfactant.
[0052] In this specification, fatty acids are not regarded as surfactants.
[0053] Nonionic surfactant Examples of suitable nonionic surfactants are C8-C 18 alkyl ethoxylates (e.g., NEODOL® nonionic surfactants from Shell); C6-C 12 alkylphenol alkoxylates (the alkoxylate units may be ethyleneoxy units, propyleneoxy units, or mixtures thereof); C 12 -C 18 alcohols and C6-C 12 alkylphenol condensates (e.g., Pluronic® from BASF); C 14 -C 22 medium-chain branched alcohols; C 14 -C 22 medium-chain branched alkyl alkoxylates (typically having an average degree of alkoxylation of 1 to 30); alkyl polysaccharides (in one aspect, alkyl polyglycosides); polyhydroxy fatty acid amides, ether-terminally protected poly(oxyalkylated) alcohol surfactants, and mixtures thereof.
[0054] Suitable nonionic cleaning surfactants include alkyl polyglycosides and / or alkyl alkoxylated alcohols.
[0055] When alkylalkoxylated alcohols are present, preferably C 8~18 Alkylalkoxylated alcohols, for example, C 8~18 Selected from alkylethoxylated alcohols. Preferably, the alkylalkoxylated alcohol has an average degree of alkoxylation of 1 to 80, preferably 1 to 50, most preferably 1 to 30, 1 to 20, or 1 to 10. Preferred nonionic surfactants have an average degree of alkoxylation (preferably ethoxylation) of 1 to 10, 1 to 7, more preferably 1 to 5, or 3 to 7, or even more preferably 3 or less than 2. 8~18 The alcohol may be an alkylalkoxylated (preferably ethoxylated) alcohol. The alkylalkoxylated alcohol may be linear or branched, and may be substituted or unsubstituted.
[0056] A suitable nonionic surfactant is Lutensol® (BASF).
[0057] Typically, nonionic surfactants are present in the cleaning composition in amounts of 4-40% by weight of anionic surfactants, or at least 8 or at least 10% by weight of nonionic surfactants, or 12-10% by weight of nonionic surfactants.
[0058] The preferred composition of the present invention is in liquid or unit dose form. The liquid is preferably an externally structured aqueous isotropic liquid laundry detergent composition.
[0059] Cleaning and / or treatment aids The cleaning composition of the present invention comprises a nuclease enzyme and a surfactant system, in addition to any cleaning and / or processing aid. Preferably, the composition further comprises the β-N-acetylglucosaminidase enzyme of EC3.2.1.52, preferably an enzyme having at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or at least 100% identity with SEQ ID NO: 4. When present, the β-N-acetylglucosaminidase enzyme is typically present in an amount of enzyme protein of about 0.00001% to about 2% by weight, about 0.0001% to about 1% by weight, or even about 0.001% to about 0.5% by weight of the composition.
[0060] Further preferred auxiliary agents may include, for example, those that support or enhance cleaning performance, those that treat the substrate to be cleaned, such as by softening or freshening, or those that alter the aesthetics of the detergent composition, such as fragrances, colorants, non-fabric shading dyes, etc. Suitable auxiliary substances include, but are not limited to, surfactants, builders, chelating agents, dispersants, enzymes and enzyme stabilizers, catalysts, bleach activators, hydrogen peroxide, hydrogen peroxide sources, preforming peracids, polymer dispersants, clay stain removers / anti-redeposition agents, additional whitening agents, antifoaming agents, dyes, color dyes, fragrances, fragrance delivery systems, structural elastochemicals, fabric softeners, carriers, hydrotropes, processing aids, solvents, additional dyes and / or pigments (some of which will be discussed in more detail below). In addition to the following disclosures, preferred examples and levels of use of such other excipients can be found in U.S. Patents No. 5,576,282, No. 6,306,812(B1) and No. 6,326,348(B1), which are incorporated herein by reference.
[0061] Particularly preferred additional auxiliary substances may be further enzymes.
[0062] Enzymes. Preferably, the composition comprises one or more additional enzymes. Preferred enzymes provide cleaning performance and / or fabric care effects. Examples of preferred enzymes include, but are not limited to, hemicellulase, peroxidase, protease, cellulase, xylanase, lipase, phospholipase, esterase, cutinase, pectinase, mannanase, pectinate lyase, keratinase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, maranase, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, and amylase, or mixtures thereof. Preferred combinations of additional enzymes preferably include protease and lipase together with amylase. If present in the composition, the above additional enzymes may be present at enzyme protein levels of approximately 0.00001% to approximately 2% by weight, approximately 0.0001% to approximately 1% by weight, or even approximately 0.001% to approximately 0.5% by weight, respectively.
[0063] Protease. Preferably, the composition contains one or more proteases. Suitable proteases include metalloproteases and serine proteases, and include neutral or alkaline microbial serine proteases such as subtilisin (EC 3.4.21.62). Suitable proteases may be of animal, plant, or microbial origin. In one embodiment, such suitable proteases may be of microbial origin. Suitable proteases may be chemically or genetically modified mutants of the aforementioned suitable proteases. In one embodiment, suitable proteases may be alkaline microbial proteases and / or serine proteases such as trypsin-type proteases. Examples of suitable neutral or alkaline proteases include the following: (a) Subtilisins (EC 3.4.21.62) including those derived from the genus Bacillus, such as Bacillus lentus, Bacillus alkalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus, and Bacillus gibsonii, as described in U.S. Patent No. 6,312,936(B1), No. 5,679,630, No. 4,760,025, No. 7,262,042, and International Publication No. WO09 / 021867. (b) Trypsin-type or chymotrypsin-type proteases such as trypsin (e.g., of porcine or bovine origin), including Fusarium proteases described in International Publication No. 89 / 06270, and chymotrypsin proteases derived from the genus Cerulomonas described in International Publication Nos. 05 / 052161 and 05 / 052146. (c) Metalloproteinases, including those derived from Bacillus amyloricephasiensis, as described in International Publication No. 07 / 044993(A2).
[0064] Preferred proteases include those derived from Bacillus gibsonii or Bacillus lentus.
[0065] Suitable commercially available protease enzymes include those sold by Novozymes A / S (Denmark) under the trademark names Alcalase(registered trademark), Savinase(registered trademark), Primase(registered trademark), Durazym(registered trademark), Polarzyme(registered trademark), Kannase(registered trademark), Liquanase(registered trademark), Liquanase Ultra(registered trademark), Savinase Ultra(registered trademark), Ovozyme(registered trademark), Neutrase(registered trademark), Everlase(registered trademark), and Esperase(registered trademark); those sold by Genencor International under the trademark names Maxatase(registered trademark), Maxacal(registered trademark), Maxapem(registered trademark), Properase(registered trademark), Purafect(registered trademark), Purafect Prime(registered trademark), Purafect Ox(registered trademark), FN3(registered trademark), FN4(registered trademark), Excellase(registered trademark), and Purafect OXP(registered trademark); and Solvay Products sold by Enzymes under the trademark names Opticlean® and Optimase®, and those available from Henkel / Kemira, namely BLAP (the sequence shown in Figure 29 of U.S. Patent No. 5,352,604, with the following mutation: S99D+S101R+S103A+V104I+G159S, hereinafter referred to as BLAP), BLAP R (BLAP with S3T+V4I+V199M+V205I+L217D), BLAP X (BLAP with S3T+V4I+V205I), and BLAP F49 (BLAP with S3T+V4I+A194P+V199M+V205I+L217D) (all manufactured by Henkel / Kemira);Examples include Kao's KAP (subtilisin of Bacillus alkarophilus having mutation A230V+S256G+S259N), or as disclosed in International Publications 2009 / 149144, 2009 / 149145, 2010 / 56653, 2010 / 56640, 2011 / 072117, U.S. Patent Application Publication 2011 / 0237487, International Publications 2011 / 140316, 2012 / 151480, European Patents 2510092, 2566960, or 2705145.
[0066] Amylase. Preferably, the composition may contain amylase. Preferred α-amylases include those of bacterial or fungal origin. Chemically or genetically modified mutants (mutants) are included. Preferred alkaline α-amylases are derived from strains of the genus Bacillus, e.g., Bacillus licheniformis, Bacillus amyloricephasiens, Bacillus sterothermophilus, Bacillus subtilis, or other species of the genus Bacillus, e.g., Bacillus species NCIB 12289, NCIB 12512, NCIB 12513, DSM 9375 (U.S. Patent No. 7,153,818), DSM 12368, DSMZ No. 12649, KSM AP1378 (International Publication No. 97 / 00324), KSM K36, or KSM K38 (European Patent No. 1,022,334). Preferred amylases include the following: (a) Mutants described in International Publication Nos. 94 / 02597, 94 / 18314, 96 / 23874 and 97 / 43424, in particular mutants in which one or more of the following positions are substituted for the enzyme listed as Sequence ID No. 2 in International Publication No. 96 / 23874: 15, 23, 105, 106, 124, 128, 133, 154, 156, 181, 188, 190, 197, 202, 208, 209, 243, 264, 304, 305, 391, 408 and 444. (b) For the variants described in U.S. Patent No. 5,856,164, and International Publication Nos. 99 / 23211, 96 / 23873, 00 / 60060 and 06 / 002643, in particular for the AA560 enzyme listed as Sequence ID No. 12 in International Publication No. 06 / 002643, at the following positions: A variant in which one or more of the following are substituted, preferably D183: 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. * and G184 * A variant that also contains a deletion. (c) Variants exhibiting at least 90% identity with the wild-type enzyme from Bacillus SP722, as described in International Publication No. 06 / 002643, particularly those having deletions at positions 183 and 184, and the variants described in International Publication No. 00 / 60060 incorporated herein by reference. (d) A mutant showing at least 95% identity with the wild-type enzyme from Bacillus species 707 (US Patent No. 6,093,562, Sequence ID No. 7), particularly containing one or more of the following mutations: M202, M208, S255, R172 and / or M261. Preferably, the above amylase contains one or more of M202L, M202V, M202S, M202T, M202I, M202Q, M202W, S255N and / or R172Q. Particularly preferred is one containing the M202L or M202T mutation. (e) A variant described in International Publication No. 09 / 149130, preferably a variant showing at least 90% identity with Sequence ID No. 1 or Sequence ID No. 2 of International Publication No. 09 / 149130, a wild-type enzyme derived from Geobacillus Stearophermophiluss, or a cleaved version thereof. (f) Variants described in European Patent Nos. 2540825, 2357220, and 2534233. (g) Variants described in International Publication Nos. 2009100102 and 2010115028.
[0067] Suitable commercially available α-amylases include DURAMYL®, LIQUEZYME®, TERMAMYL®, TERMAMYL ULTRA®, NATALASE®, SUPRAMYL®, STAINZYME®, STAINZYME PLUS®, FUNGAMYL®, and BAN® (Novozymes A / S (Bagsvaerd, Denmark)), KEMZYM® AT 9000 (Biozym Biotech Trading GmbH (Wehlistrasse 27b A-1200 Wien Austria)), RAPIDASE®, PURASTAR®, ENZYSIZE®, OPTISIZE HT PLUS®, POWERASE®, and PURASTAR OXAM® (Genencor International Inc., (Palo) Examples include Alto, California; and KAM® (Kao Corporation (Japan, 103-8210, 1-14-10 Nihonbashi Kayabacho, Chuo-ku, Tokyo)). In one embodiment, preferred amylases include NATALASE®, STAINZYME®, STAINZYME PLUS®, and mixtures thereof.
[0068] Lipase. Preferably, the composition comprises one or more lipases, including a “first-cycle lipase,” such as those described in U.S. Patent No. 6,939,702(B1) and U.S. Patent Application Publication No. 2009 / 0217464. A preferred lipase is a first-wash lipase. In one embodiment of the present invention, the composition comprises a first-wash lipase. The first washing lipase is a polypeptide lipase having an amino acid sequence that satisfies the following constraints: (a) having at least 90% identity with the wild-type lipase derived from Humicola lanuginosa strain DSM4109; (b) being substituted with positively charged amino acids on the surface of the three-dimensional structure within 15A of E1 or Q249 compared to the wild-type lipase; (c) including a peptide addition at the C-terminus and / or (d) including a peptide addition at the N-terminus and / or (e) the following constraints: i) containing a negative amino acid at position E210 of the wild-type lipase; ii) containing a negatively charged amino acid in the region corresponding to positions 90-101 of the wild-type lipase; and iii) containing a neutral or negative amino acid at the position corresponding to N94 of the wild-type lipase and / or having a negative or neutral net charge in the region corresponding to positions 90-101 of the wild-type lipase. A variant of wild-type lipase derived from Thermomyces lanuginosus containing one or more T231R and N233R mutations is preferred. The wild-type sequence is the 269 amino acids (amino acids 23-291) of Swissprot accession number Swiss-Prot O59952 (Thermomyces lanuginosus (derived from Humicola lanuginosa)). Preferred lipases include those sold under the trademark names Lipex®, Lipolex®, and Lipoclean®. Other preferred lipases include those described in European Patent Application No. 12001034.3 or European Patent No. 2623586.
[0069] Endoglucanase. Other preferred enzymes include endoglucanases derived from microorganisms exhibiting endo-β-1,4-glucanase activity (EC 3.2.1.4), including bacterial polypeptides endogenous to members of the genus Bacillus and mixtures thereof, having sequences with at least 90%, 94%, 97%, and even 99% identity to the amino acid sequence of Sequence ID No. 2 in U.S. Patent No. 7,141,403(B2). Preferred endoglucanases are marketed under the trademark names Celluclean® and Whitezyme® (Novozymes A / S (Bagsvaerd, Denmark)).
[0070] Pectin lyase. Other preferred enzymes include pectin lyase sold under the trademark names Pectawash®, Pectaway®, and Xpect®, as well as mannase sold under the trademark names Mannaway® (all manufactured by Novozymes A / S (Bagsvaerd, Denmark)) and Purabrite® (Genencor International Inc. (Palo Alto, California)).
[0071] Antimicrobial agents. Preferably, this composition further contains one compound or a mixture of more than one compound capable of producing an antimicrobial effect. These may be standard components of treatment compositions added for cleaning or malodor effects, such as bleaching agents, but may also be added to have some antimicrobial effect or specifically to provide an antimicrobial effect. Suitable examples include aldehydes (formaldehyde, glutaraldehyde, orthophthalaldehyde), sulfur dioxide, sulfites, bisulfites, vanillic acid esters), chlorine and oxygen-based oxidizing agents (hypochlorous acid or calcium and sodium hypobromite, chloramine and chloramine-T, chlorine dioxide, hydrogen peroxide, iodine, ozone, peracetic acid, performic acid, potassium permanganate, potassium peroxymonosulfate), phenols (phenol, o-phenylphenol, chloroxylenol, hexachlorophene, thymol, amylmetacresol, 2,4-Dichlorobenzyl alcohol, polycresylen, fenticol, 4-allylcatechol, p-hydroxybenzoic acid esters (including benzylparaben, butylparaben, ethylparaben, methylparaben and propylparaben), butylated hydroxyanisole, butylated hydroxytoluene, capsaicin, carvacrol, creosol, eugenol, guaiacol), halogenated (hydroxy)diphenyl ether (di Closan, triclosan, hexachlorophene and bromochlorophene, 4-hexylresorcinol, 8-hydroxyquinoline, and salts thereof), quaternary ammonium compounds (benzalkonium chloride derivatives, benzethonium chloride derivatives, cetrimonium chloride / bromide, cetylpyridinium, cetrimide, benzooxonium chloride, didecyldimethylammonium chloride), acridine derivatives (ethacrylidine lactate, 9-aminoacrylidine, euflavin), biguanides including polymeric biguanides, and amidine (polya Minopropyl biguanide, dibronpropamidine, chlorhexidine, alexidine, propamidine, hexamidine, polyhexanide), nitrofuran derivatives (nitrofurazone), quinoline derivatives (decalinium, chlorquinaldol, oxyquinoline, cryoquinol), iodine products, essential oils (bay leaf, cinnamon, clove, thyme, eucalyptus, peppermint, lemon, tea tree, magnolia extract, menthol, geraniol), cations, anilides (saclicylanilide, di Phenylurea), salicylate esters (including menthyl salicylate, methyl salicylate, and phenyl salicylate), pyrocatechol, phthalates and their salts, hexetidine, octenidine, sanguinalin, domiphene bromide, alkylpyridinium chloride (e.g., cetylpyridinium chloride, tetradecylpyridinium chloride, and N-tetradecyl-4-ethylpyridinium chloride), iodine, sulfonamides, piperidino derivatives (e.g., dermopinol and octapinol), and mixtures thereof, various preservatives (1,Examples include, but are not limited to, derivatives of 3-dioxane, imidazole, isothiazolone, hexamine, triazine, oxazolo-oxazole, sodium hydroxymethylglycinate, methylene bisthiocyanate, and captan.
[0072] Preferred antimicrobial systems include halogenated benzyl alcohol derivatives such as chlorooxylenol (PCMX), halogenated hydroxydiphenyl ethers, preferably diclosan, quaternary ammonium salts, preferably alkylbenzalkonium and alkylbenzethonium chloride, and their derivatives, essential oils, bleaching agents, preferably peroxide bleaches, and mixtures thereof. The most preferred antimicrobial system is benzalkonium chloride, diclosan, and PCMX.
[0073] Encapsulating agent. The composition may include an encapsulating agent, for example, an encapsulating agent containing a core, and a shell having an inner surface and an outer surface, the shell enclosing the core. The core may contain any laundry care aids, but typically the core may contain substances selected from the group consisting of fragrances, whitening agents, dyes, insecticides, silicones, waxes, scenting agents, vitamins, fabric softeners, skincare agents (in one embodiment, paraffin), enzymes, antimicrobial agents, bleaching agents, sensory agents, and mixtures thereof, and the shell may contain substances selected from the group consisting of polyethylene, polyamides, polyvinyl alcohols optionally containing other comonomers, polystyrene, polyisoprene, polycarbonate, polyester, polyacrylate, aminoplast (in one embodiment, the aminoplast may include polyurea, polyurethane and / or polyurea urethane, and in one embodiment, the polyurea may include polyoxymethylene urea and / or melamine formaldehyde), polyolefins, polysaccharides (in one embodiment, the polysaccharide may include alginates and / or chitosan), gelatin, shellac, epoxy resins, vinyl polymers, water-insoluble inorganic substances, silicones, and mixtures thereof. A preferred encapsulant comprises a fragrance. A preferred encapsulant comprises a shell which may contain melamineformaldehyde and / or cross-linked melamineformaldehyde. A preferred encapsulant comprises a core material and a shell which is disclosed to at least partially surround the core material. At least 75%, 85%, or even 90% of the above encapsulant may have a breaking strength of 0.2 MPa to 10 MPa, and the beneficial agent leakage rate may be 0% to 20%, or even less than 10% or 5%, based on the initial total amount of the encapsulated beneficial agent. Preferably, at least 75%, 85%, or even more than 90% of the above-mentioned mounting agent may (i) have particle sizes of 1 to 80 micrometers, 5 to 60 micrometers, 10 to 50 micrometers, or even 15 to 40 micrometers, and / or (ii) at least 75%, 85%, or even more than 90% of the above-mentioned mounting agent may have particle wall thicknesses of 30 nm to 250 nm, 80 nm to 180 nm, or even 100 nm to 160 nm.The formaldehyde scavenger may be used together with the encapsulant, for example, in a capsule slurry, and / or added to the composition before, during, or after the addition of the encapsulant. Suitable capsules can be prepared according to the teachings in U.S. Patent Application Publication No. 2008 / 0305982(A1) and / or U.S. Patent Application Publication No. 2009 / 0247449(A1). Alternatively, suitable capsules can be purchased from Appleton Papers Inc. (Appleton, Wisconsin, USA).
[0074] In a preferred embodiment, the composition may preferably include an adhesion aid in addition to the encapsulant. The preferred adhesion aid is selected from the group consisting of cationic and nonionic polymers. Suitable polymers include polymers containing dimethylaminoethyl methacrylate together with one or more monomers selected from the group consisting of cationic starch, cationic hydroxyethyl cellulose, polyvinyl formaldehyde, locust bean gum, mannan, xyloglucan, tamarind gum, polyethylene terephthalate, and optionally acrylic acid and acrylamide.
[0075] Fragrances. Preferred compositions of the present invention include fragrances. Typically, the compositions include fragrances comprising one or more fragrance raw materials selected from the group described in International Publication No. 08 / 87497. However, any fragrance useful in detergents may be used. A preferred method of incorporating fragrances into compositions of the present invention is via encapsulated fragrance particles comprising either a water-soluble hydroxy compound, melamine-formaldehyde, or modified polyvinyl alcohol. In one embodiment, the encapsulant comprises (a) a solid matrix that is at least partially water-soluble and comprises one or more water-soluble hydroxy compounds, preferably starch, and (b) a fragrance oil encapsulated by this solid matrix. In further embodiments, the fragrance may be pre-compounded with a polyamine, preferably polyethyleneimine, to form a Schiff base.
[0076] Polymers. The detergent composition may contain one or more polymers in addition to DTI, which may be polymers. Examples include optionally modified carboxymethylcellulose, poly(ethylene glycol), poly(vinyl alcohol), polycarboxylates such as polyacrylate, maleic acid / acrylic acid copolymers and lauryl methacrylate / acrylic acid copolymers, and carboxylate polymers.
[0077] Suitable carboxylate polymers include maleate / acrylate random copolymers or polyacrylate homopolymers. The carboxylate polymer may be a polyacrylate homopolymer having a molecular weight of 4,000 Da to 9,000 Da or 6,000 Da to 9,000 Da. Another suitable carboxylate polymer is a copolymer of maleic acid and acrylic acid, which may have a molecular weight in the range of 4,000 Da to 90,000 Da.
[0078] Other suitable carboxylate polymers are copolymers comprising (i) 50 to less than 98% by weight of structural units derived from one or more monomers containing a carboxyl group, (ii) 1 to less than 49% by weight of structural units derived from one or more monomers containing a sulfonate moiety, and (iii) 1 to 49% by weight of structural units derived from one or more monomers selected from ether-bonded monomers represented by formulas (I) and (II):
[0079] [ka] (In formula (I), R0 represents a hydrogen atom or a CH3 group, R represents a CH2 group, a CH2CH2 group or a single bond, and X represents a number from 0 to 5, however, if R is a single bond, X represents a number from 1 to 5, and R1 represents a hydrogen atom or C1 to C 20 (It is an organic group.)
[0080] [ka] (In formula (II), R0 represents a hydrogen atom or a CH3 group, R represents a CH2 group, a CH2CH2 group or a single bond, X represents a number from 0 to 5, and R1 represents a hydrogen atom or C1 to C 20 (It is an organic group.)
[0081] This composition has the following general structure: bis((C2H5O)(C2H4O)n)(CH3)-N + -C x H 2x -N + The present invention may contain one or more amphiphilic cleaning polymers, such as a compound having -(CH3)-bis((C2H5O)(C2H4O)n) (wherein n=20 to 30 and x=3 to 8), or a sulfated or sulfonated variant thereof. In one embodiment, this polymer is sulfated or sulfonated to obtain a bipolar fouling suspension polymer.
[0082] The composition preferably comprises an amphiphilic alkoxylylated grease-cleaning polymer whose hydrophilicity and properties are balanced to remove grease particles from fabrics and surfaces. A preferred amphiphilic alkoxylylated grease-cleaning polymer comprises a core structure and a plurality of alkoxylate groups bonded to the core structure. These may preferably include alkoxylylated polyalkylene imines having an inner polyethylene oxide block and an outer polypropylene oxide block. Typically, these can be incorporated into the composition of the present invention in an amount of 0.005 to 10% by weight, generally 0.5 to 8% by weight.
[0083] Alkoxylated polycarboxylates, such as those prepared from polyacrylates, are useful herein for providing additional grease removal performance. Such materials are described in International Publication No. 91 / 08281 and International Application PCT90 / 01815. Chemically, these substances comprise polyacrylates having one ethoxy side chain for every 7-8 acrylate units. The side chains are of the formula -(CH2CH2O) m (CH2) nThe compound is CH3 (wherein m is 2-3 and n is 6-12). The side chains are ester-bonded to the polyacrylate "main chain" to provide a "comb-shaped" polymer structure. The molecular weight can vary, but is typically in the range of about 2,000 to about 50,000. Such alkoxylated polycarboxylates may be present in the compositions herein in amounts of about 0.05% to about 10% by weight.
[0084] This composition may contain polyethylene glycol polymers, which may be particularly preferred in compositions containing mixed surfactant systems. Suitable polyethylene glycol polymers include random graft copolymers comprising (i) a hydrophilic main chain containing polyethylene glycol, and (ii) side chains selected from the group consisting of C4-C25 alkyl groups, polypropylene, polybutylene, vinyl esters of saturated C1-C6 monocarboxylic acids, C1-C6 alkyl esters of acrylic acid or methacrylic acid, and mixtures thereof. A suitable polyethylene glycol polymer has a polyethylene glycol main chain with random grafted polyvinyl acetate side chains. The average molecular weight of the polyethylene glycol main chain may 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 main chain to the polyvinyl acetate side chain may be in the range of 1:1 to 1:5 or 1:1.2 to 1:2. The average number of graft sites per ethylene oxide unit may be less than 1 or less than 0.8, or it may be in the range of 0.5 to 0.9, or it 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.
[0085] Typically, these are incorporated into the composition of the present invention in an amount of 0.005 to 10% by weight, more typically 0.05 to 8% by weight.
[0086] Preferably, the composition comprises one or more carboxylate polymers, such as maleate / acrylate random copolymers or polyacrylate homopolymers. In one embodiment, the carboxylate polymer is a polyacrylate homopolymer having a molecular weight of 4,000 Da to 9,000 Da or 6,000 Da to 9,000 Da. Typically, these are incorporated into the composition of the present invention in an amount of 0.005 to 10% by weight or 0.05 to 8% by weight.
[0087] Preferably, the composition comprises one or more fouling-releasing polymers. Examples include fouling-releasing polymers having a structure defined by one of the following formulas (VI), (VII), or (VIII). (VI)-[(OCHR 1 -CHR 2 ) a -O-OC- Ar-CO-] d (VII)-[(OCHR 3 -CHR 4 ) b -O-OC-s Ar-CO-] e (VIII)-[(OCHR 5 -CHR 6 ) c -OR 7 ] f (In the formula, a, b, and c are between 1 and 200. d, e, and f are between 1 and 50. Ar is a 1,4-substituted phenylene, sAr is a 1,3-substituted phenylene with SO3Me substituted at position 5. Me is Li, K, Mg / 2, Ca / 2, Al / 3, ammonium, mono-, di-, tri-, or tetraalkylammonium (alkyl groups are C1-C) 18 Alkyl or C2-C 10 It is a hydroxyalkyl group, or a mixture thereof; R 1 , R 2 , R 3 , R 4 , R 5 and R 6These are independently H or C1~C 18 n- or iso-alkyl R 7 This refers to a linear or branched chain C1-C 18 Alkyl, or linear or branched C2-C 30 Alkenyl, or cycloalkyl group having 5-9 carbon atoms, or C8-C 30 Aryl group or C6~C 30 (It is an arylalkyl group.)
[0088] Suitable fouling-releasing polymers are polyester fouling-releasing polymers such as Repel-o-tex polymers, including Repel-o-tex SF, SF-2, and SRP6 supplied by Rhodia. Other suitable fouling-releasing polymers include Texcare polymers, including Texcare SRA100, SRA300, SRN100, SRN170, SRN240, SRN300, and SRN325 supplied by Clariant. Other suitable fouling-releasing polymers are Marloquest polymers, such as Marloquest SL supplied by Sasol.
[0089] Preferably, the composition comprises one or more cellulosic polymers selected from alkylcellulose, alkylalkoxyalkylcellulose, carboxyalkylcellulose, and alkylcarboxyalkylcellulose. Preferred cellulosic polymers are selected from the group comprising carboxymethylcellulose, methylcellulose, methylhydroxyethylcellulose, methylcarboxymethylcellulose, and mixtures thereof. In one embodiment, the carboxymethylcellulose has a carboxymethyl substitution degree of 0.5 to 0.9 and a molecular weight of 100,000 Da to 300,000 Da.
[0090] Bleaching agents. The composition may preferably contain one or more bleaching agents. Suitable bleaching agents other than bleaching catalysts include photobleaching agents, bleaching activators, hydrogen peroxide, hydrogen peroxide sources, preformed peracids, and mixtures thereof. Generally, when using bleaching agents, the composition of the present invention may contain about 0.1% to about 50% by weight of the bleaching agent or a mixture of bleaching agents, or even more, about 0.1% to about 25% by weight of the target composition. Examples of suitable bleaching agents are as follows:
[0091] (1) Photobleaching agents, such as zinc phthalocyanine sulfonate, aluminum phthalocyanine sulfonate, xanthene dyes, and mixtures thereof.
[0092] (2) Preforming peracids: Suitable preforming peracids include, but are not limited to, compounds selected from the group consisting of preforming peroxy acids or salts thereof, typically percarboxylic acids and salts, percarbonates and salts, perimide acids and salts, peroxymonosulfuric acids and salts, e.g., Oxone®, and mixtures thereof. Suitable examples include peroxycarboxylic acids or salts thereof, or peroxysulfonic acids or salts thereof. Typical peroxycarboxylic acid salts suitable for use herein have chemical structures corresponding to the following chemical formulas:
[0093] [ka] (In the formula, R 14 R is selected from alkyl, aralkyl, cycloalkyl, aryl, or heterocyclic groups. 14 The group may be linear or branched, substituted or unsubstituted, and when the peracid is, it has 6 to 14 carbon atoms or 8 to 12 carbon atoms, and when the peracid is hydrophilic, it has fewer than 6 carbon atoms or even fewer than 4 carbon atoms, and Y is any suitable counterion that results in charge neutrality, preferably Y is selected from hydrogen, sodium, or potassium). Preferably, R 14 C is a linear or branched chain, substituted or unsubstituted. 6~9It is alkyl. Preferably, the peroxy acid or its salt is selected from peroxyhexanoic acid, peroxyheptanoic acid, peroxyoctanoic acid, peroxynonanoic acid, peroxydecanoic acid, any salt thereof, or any combination thereof. Particularly preferred peroxy acids are phthalimide-peroxy-alkanoic acids, in particular ε-phthalimideperoxyhexanoic acid (PAP). Preferably, the peroxy acid or its salt has a melting point in the range of 30°C to 60°C.
[0094] The preformed peroxy acid or its salt may also be a peroxysulfonic acid or its salt having a chemical structure typically corresponding to the following chemical formula:
[0095] [ka] (In the formula, R 15 R is selected from alkyl, aralkyl, cycloalkyl, aryl, or heterocyclic groups. 15 The group may be linear or branched, substituted or unsubstituted, and Z is any suitable counterion that results in charge neutrality, preferably Z is selected from hydrogen, sodium or potassium). Preferably R 15 C is a linear or branched chain, substituted or unsubstituted. 4~14 Preferably C 6~14 It is alkyl. Preferably, such a bleaching agent composition may be present in the composition of the present invention in an amount of 0.01 to 50%, most preferably 0.1% to 20%.
[0096] (3) A source of hydrogen peroxide, for example, an alkali metal salt such as perborate (usually monohydrate or tetrahydrate), percarbonate, persulfate, superphosphate, persilicate, and sodium salts of mixtures thereof, or an inorganic perhydrate salt. In one aspect of the present invention, the inorganic perhydrate salt is selected from the group consisting of sodium perborate, sodium percarbonate, and mixtures thereof. When used, the inorganic perhydrate salt is typically present in an amount of 0.05 to 40% by weight or 1 to 30% by weight of the total fabric care and home care product, and is typically incorporated into such fabric care and home care products as a crystalline solid that can be coated. Suitable coatings include alkali metal salts such as inorganic salts, for example silicates, carbonates or borates, or mixtures thereof, or organic substances such as water-soluble or dispersible polymers, waxes, oils or fatty soaps.
[0097] (4) Bleaching activators having R-(C=O)-L (wherein R is an alkyl group, optionally branched, having 6 to 14 carbon atoms or 8 to 12 carbon atoms when the bleaching activator is hydrophilic, having less than 6 carbon atoms or even less than 4 carbon atoms, and L is a leaving group). Examples of suitable leaving groups are benzoic acid and its derivatives, particularly benzenesulfonates. Suitable bleaching activators include dodecanoyloxybenzenesulfonate, decanoyloxybenzenesulfonate, decanoyloxybenzoic acid or its salts, 3,5,5-trimethylhexanoyloxybenzenesulfonate, tetraacetylethylenediamine (TAED), and nonanoyloxybenzenesulfonate (NOBS). Further suitable bleaching activators are disclosed in International Publication No. 98 / 17767. Any suitable bleach activator may be used, but in one aspect of the invention, the composition in question may contain NOBS, TAED, or a mixture thereof.
[0098] (5) Bleaching catalyst. The compositions of the present invention may contain one or more bleaching catalysts capable of receiving an oxygen atom from a peroxy acid and / or a salt thereof and transferring the oxygen atom to an oxidizable substrate. Suitable bleaching catalysts include, but are not limited to, iminium cations and polyions, iminium dipolar ions, modified amines, modified amine oxides, N-sulfonylimines, N-phosphonylimines, N-acylumines, thiadiazole dioxides, perfluoroimines, cyclic sugar ketones and alpha-amino-ketones, and mixtures thereof. Suitable alpha-amino-ketones are, for example, described in International Publication Nos. 2012 / 000846(A1), 2008 / 015443(A1), and 2008 / 014965(A1). Suitable mixtures are described in U.S. Patent Application Publication No. 2007 / 0173430(A1).
[0099] In one embodiment, the bleaching catalyst has a structure corresponding to the following general formula:
[0100] [ka] (In the formula, R 13 (Selected from the group consisting of 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, iso-nonyl, iso-decyl, iso-tridecyl, and iso-pentadecyl).
[0101] (6) The composition may preferably contain a catalytic metal complex. One preferred type of metal-containing bleaching catalyst is a catalyst system comprising a transition metal cation with a predetermined bleaching catalytic activity (e.g., copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cation), an auxiliary metal cation with little or no bleaching catalytic activity (e.g., zinc or aluminum cation), and a metal ion chelating agent having a predetermined stability constant with respect to the catalytic metal cation and auxiliary metal cation, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid), and water-soluble salts thereof. Such catalysts are disclosed in U.S. Patent No. 4,430,243.
[0102] If necessary, the compositions herein may be catalyzed with manganese compounds. Such compounds and levels of use are well known in the art, and include, for example, the manganese catalysts disclosed in U.S. Patent No. 5,576,282.
[0103] Cobalt bleaching catalysts useful in this specification are known and are described, for example, in U.S. Patent Nos. 5,597,936 and 5,595,967. Such cobalt catalysts can be readily prepared by known procedures, for example, as taught in U.S. Patent Nos. 5,597,936 and 5,595,967.
[0104] Furthermore, the compositions herein may preferably contain transition metal complexes of ligands such as bispidone (International Publication No. 05 / 042532(A1)) and / or macropolycyclic rigid ligands (abbreviated as "MRL"). In practice, but not limited to, the compositions and methods herein can be prepared to provide active MRL species on the order of at least parts per hundred million in an aqueous washing medium, typically providing about 0.005 ppm to about 25 ppm, about 0.05 ppm to about 10 ppm, or even about 0.1 ppm to about 5 ppm of MRL in the washing solution.
[0105] Suitable transition metals in this transition metal bleaching catalyst include, for example, manganese, iron, and chromium. A suitable MRL is 5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane.
[0106] Suitable transition metal MRLs can be readily prepared by known procedures, such as those taught in International Publication No. 00 / 32601 and U.S. Patent No. 6,225,464.
[0107] Where present, sources of hydrogen peroxide / peracids and / or bleach activators are generally present in the composition in amounts of about 0.1 to about 60% by weight, about 0.5 to about 40% by weight, or even about 0.6 to about 10% by weight, based on fabric care and home care products. One or more peracids or their precursors may be used in combination with one or more hydrophilic peracids or their precursors.
[0108] Typically, the hydrogen peroxide source and the bleach activator are combined. The amounts of the hydrogen peroxide source and the peracid or bleach activator may be selected so that the molar ratio of available oxygen (from the peroxide source) to the peracid is 1:1 to 35:1 or even 2:1 to 10:1.
[0109] Surfactants. In addition to anionic and nonionic surfactants, the compositions of the present invention may include additional surfactants, such as cationic, amphoteric, amphoteric electrolyte, amphiphilic, and bipolar surfactants, and mixtures thereof, selected from among them. Preferably, these surfactants are included in an amount of less than 50% by weight, more preferably less than 30% by weight, and more preferably less than 10% by weight of the total surfactant system.
[0110] Suitable cationic cleaning surfactants include alkylpyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl tertiary sulfonium compounds, and mixtures thereof.
[0111] Suitable cationic cleansing surfactants are quaternary ammonium compounds having the following general formula. (R)(R1)(R2)(R3)N + X - (In the formula, R is a linear or branched, substituted or unsubstituted C) 6~18 The alkyl or alkenyl moiety is selected from R1 and R2 independently from the methyl or ethyl moiety, R3 is the hydroxyl, hydroxymethyl, or hydroxyethyl moiety, and X is an anion that provides electrical neutrality. Suitable anions include, for example, halides such as chlorides, sulfuric acid, and sulfonic acid. A suitable cationic cleaning surfactant is mono-C 6~18 Alkyl monohydroxyethyldimethylquaternary ammonium chloride. A very suitable cationic cleaning surfactant is mono-C 8~10 Alkyl monohydroxyethyldimethyl quaternary ammonium chloride, mono-C 10~12 Alkyl monohydroxyethyldimethyl quaternary ammonium chloride, and mono-C 10 It is an alkyl monohydroxyethyldimethyl quaternary ammonium chloride.
[0112] Suitable amphoteric / bipolar surfactants include amine oxides and betaines.
[0113] Amine-Neutralized Anionic Surfactants - The anionic surfactants and auxiliary anionic auxiliary surfactants of the present invention may exist in acidic form, and this acidic form may be neutralized to form surfactant salts desirable for use in the detergent composition. Typical neutralizing agents include metal counterionic bases such as hydroxides (e.g., NaOH or KOH). More preferred agents for neutralizing the anionic surfactants and auxiliary anionic surfactants or auxiliary surfactants of the present invention in acidic form include ammonia, amines, or alkanolamines. Alkanolamines are preferred. Preferred non-limiting examples include monoethanolamine, diethanolamine, triethanolamine, and other linear or branched alkanolamines known in the art. For example, very preferred alkanolamines include 2-amino-1-propanol, 1-aminopropanol, monoisopropanolamine, or 1-amino-3-propanol. Amine neutralization may be carried out completely or partially. For example, a portion of the anionic surfactant mixture may be neutralized with sodium or potassium, or a portion of the anionic surfactant mixture may be neutralized with an amine or alkanolamine.
[0114] Builder. Preferably, the composition comprises one or more builders or builder systems. When a builder is used, the composition of the present invention typically comprises at least 1% or at least 2% to 60% of the builder. Suitable builders include, for example, zeolites, phosphates, and citrates. The composition may preferably contain low levels, for example, 1 to 10 or 5% by weight of phosphates and / or zeolites. The composition may also substantially not contain strong builders. Substantially not containing strong builders means that zeolites and / or phosphates are "intentionally not added". Typical zeolite builders include zeolite A, zeolite P, and zeolite MAP. A typical phosphate builder is sodium tripolyphosphate.
[0115] Chelating agent. Preferably, the composition contains a chelating agent and / or a crystal growth inhibitor. Suitable molecules include copper, iron, and / or manganese chelating agents, and mixtures thereof. Suitable molecules include aminocarboxylates, aminophosphonates, succinates, salts thereof, and mixtures thereof. Non-limiting examples of chelating agents suitable for use herein include ethylenediaminetetraacetate, N-(hydroxyethyl)ethylenediamine triacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetraamine hexaacetate, diethylenetriamine pentaacetate, ethanol diglycine, ethylenediaminetetrakis(methylenephosphonate), diethylenetriaminepenta(methylenephosphonic acid) (DTPMP), ethylenediamine disuccinate (EDDS), hydroxyethanedimethylenephosphonic acid (HEDP), methylglycine diacetic acid (MGDA), diethylenetriamine pentaacetic acid (DTPA), salts thereof, and mixtures thereof. Other non-limiting examples of chelating agents used in the present invention can be found in U.S. Patent No. 7,445,644, U.S. Patent No. 7,585,376, and U.S. Patent Application Publication No. 2009 / 0176684(A1). Other chelating agents suitable for use in this specification include the commercially available DEQUEST series, as well as chelating agents manufactured by Monsanto, DuPont, and Nalco, Inc.
[0116] pH adjuster. A pH adjuster may be added to obtain the desired pH. Any alkali or acid known to those skilled in the art of detergent manufacturing, such as hydroxide, carbonic acid, sodium silicate, potassium silicate, citric acid, or strong acids such as hydrochloric acid, may be added. A pH adjuster that adds buffering capacity may be particularly preferred.
[0117] Silicate. This composition may preferably contain a silicate such as sodium silicate or potassium silicate. This composition may contain 0% to less than 10% by weight, 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 4% by weight or less, 3% by weight or less, or even 2% by weight or less of silicate, preferably more than 0% by weight, or 0.5% by weight or more, or even 1% by weight or more of silicate. A suitable silicate is sodium silicate.
[0118] Dispersant. This composition may preferably contain a dispersant. Suitable water-soluble organic substances include acids of homopolymers or copolymers or salts thereof, in which case the polycarboxylic acid contains at least two carboxyl radicals separated from each other by two or fewer carbon atoms.
[0119] Enzyme stabilizers. The composition may preferably contain enzyme stabilizers. Any conventional enzyme stabilizers may be used, for example, by providing a water-soluble source of calcium and / or magnesium ions in the final fabric care and home care product that supplies calcium and / or magnesium ions to the enzyme. In the case of aqueous compositions containing proteases, reversible protease inhibitors may be added to further improve stability, for example, boron compounds containing borates, or preferably 4-formylphenylboronic acid, phenylboronic acid, and their derivatives, or compounds such as calcium formate, sodium formate, and 1,2-propanediol, diethylene glycol, etc.
[0120] Fabric shades and dyes This composition may contain fabric shading dyes. Suitable fabric shading dyes (sometimes called colorants, bluers, or whitening agents) typically bring shades of blue or purple to fabrics. Fabric shading dyes can be used alone or in combination to produce shades of a specific hue and / or to shade different types of fabrics. This can be provided, for example, by mixing red and green-blue dyes to produce shades of blue or purple. Fabric dyes include, but are not limited to, acridines, anthraquinones (including polycyclic quinones), azines, azos (e.g., monoazo, diazo, trisazo, tetrakisazo, polyazo) including premetallized azos, benzodifurans and benzodifuranones, carotenoids, coumarins, cyanines, diazahemicyanines, diphenylmethane, formazan, hemicyanines, indigoids, methane, naphthalimide, naphthoquinones, nitros and nitroso, oxazines, phthalocyanines, pyrazoles, stilbenes, styryls, triarylmethanes, triphenylmethanes, xanthenes, and mixtures thereof, and may be selected from any known chemical classification of dyes.
[0121] Suitable fabric shading dyes include dyes and dye-clay conjugates. Preferred fabric shading dyes are selected from small molecule dyes and polymer dyes. Suitable small molecule dyes include, for example, small molecule dyes selected from the group consisting of acid dyes, direct dyes, basic dyes, reactive dyes, solvent dyes, or disperse dyes classified by color index (CI) classification, which are classified as blue, purple, red, green, or black, and which produce the desired shade alone or in combination with other dyes or auxiliary components. Dyes described as hydrolyzed reactive dyes, as described in European Patent Application Publication No. 1794274(A), may also be included. In another embodiment, suitable small molecule dyes include color index (CI) dyes (Society of Dyers and Colourists (Bradford, UK) numbers: Direct violet dyes (5, 7, 9, 11, 31, 35, 48, 51, 66 and 99, etc.), Direct blue dyes (1, 71, 80 and 279, etc.), Acid red dyes (17, 73, 52, 88 and 150, etc.), Acid violet dyes (15, 17, 24, 43, 49 and 50, etc.), Acid blue dyes (15, 17, 25, 29, 40, 45, 48, 75, 80, 83, 90 and 113, etc.), Acid black dye (1, etc.), Basic violet dyes (1, 3, 4, 10 and 35, etc.), Basic blue dyes (3, 16, 22, 47, 66, 75 and 159, etc.), Dispersion or solvent dyes (e.g., USA) Examples of suitable low molecular weight dyes include those described in U.S. Patent Publication No. 2008 / 034511(A1) or U.S. Patent No. 8,268,016(B2), or those disclosed in U.S. Patent No. 7,208,459(B2), such as solvent violet 13, and small molecular weight dyes selected from the group consisting of mixtures thereof. In another embodiment, suitable low molecular weight dyes include those selected from the group consisting of CI numbers acid violet 17, acid blue 80, acid violet 50, direct blue 71, direct violet 51, direct blue 1, acid red 88, acid red 150, acid blue 29, acid blue 113, or mixtures thereof.
[0122] Suitable polymer dyes include polymers containing covalently bonded (sometimes referred to as complexed) colorants (dye-polymer conjugates), such as polymers having colorants copolymerized to the polymer's main chain, and polymer dyes selected from the group consisting of mixtures thereof. Examples of polymer dyes include those described in International Publication 2011 / 98355, U.S. Patent Application Publications 2012 / 225803(A1), 2012 / 090102(A1), International Publication 2012 / 166768, U.S. Patent No. 7,686,892B2, and International Publication 2010 / 142503.
[0123] Other suitable polymer dyes include direct fabric colorants sold under the name Liquitint® (Milliken, Spartanburg, South Carolina, USA), and polymer dyes selected from the group consisting of dye-polymer conjugates formed from at least one reactive dye and a polymer selected from the group consisting of a polymer comprising a hydroxyl moiety, a primary amine moiety, a secondary amine moiety, a thiol moiety, and mixtures thereof. In yet another embodiment, preferred polymer dyes include polymer dyes selected from the group consisting of one or more reactive blue, reactive violet, or reactive red dyes, such as carboxymethylcellulose (CMC) bonded to CI Reactive Blue 19, sold by Megazyme (Wicklow, Ireland) under the trade name AZO-CM-CELLULOSE and trade code S-ACMC, alkoxylated triphenyl-methane polymer colorants, alkoxylated thiophene polymer colorants, alkoxylated carbocyclic and alkoxylated heterocyclic azo colorants, and mixtures thereof. Preferred polymer dyes include Liquitint dyes and optionally substituted alkoxylated dyes such as alkoxylated triphenyl-methane polymer colorants, alkoxylated thiophene polymer colorants, alkoxylated carbocyclic and alkoxylated heterocyclic azo colorants, and mixtures thereof.
[0124] Preferred colorants include whitening agents found in International Publication No. 08 / 87497(A1), International Publication No. 2011 / 011799, and U.S. Patent Application Publication No. 2012 / 129752(A1). Preferred colorants for use in the present invention may be preferred dyes disclosed in these references, including those selected from Examples 1 to 42 in Table 5 of International Publication No. 2011 / 011799. Other preferred dyes are disclosed in U.S. Patent No. 8,138,222. Other preferred dyes are disclosed in U.S. Patent No. 7,909,890(B2).
[0125] Suitable dye-clay conjugates include those selected from the group comprising at least one cationic / basic dye and smectite clay, as well as mixtures thereof. In another embodiment, suitable dye-clay conjugates include those selected from the group comprising one cationic / basic dye and clay selected from the group comprising montmorillonite clay, hectorite clay, saponite clay, and mixtures thereof. Examples of suitable cationic / basic dyes include CI Basic Yellow 1-108, CI Basic Orange 1-69, CI Basic Red 1-118, CI Basic Violet 1-51, CI Basic Blue 1-164, CI Basic Green 1-14, CI Basic Brown 1-23, and CI Basic Black 1-11. In yet another embodiment, suitable dye-clay conjugates include: montmorillonite basic blue B7 C.I.42595 conjugate, montmorillonite basic blue B9 C.I.52015 conjugate, montmorillonite basic violet V3 C.I.42555 conjugate, montmorillonite basic green G1 C.I.42040 conjugate, montmorillonite basic red R1 C.I.45160 conjugate, montmorillonite CI basic black 2 conjugate, hectorite basic blue B7 CI42595 conjugate, hectorite basic blue B9 CI52015 conjugate, hectorite basic violet V3 CI42555 conjugate, hectorite basic green G1 CI42040 conjugate, hectorite basic red R1 CI45160 conjugate, hectorite CI basic black 2 conjugate, saponite basic blue B7 CI42595 conjugate, saponite basic blue B9 Examples include dye-clay conjugates selected from the group consisting of CI52015 conjugate, Saponite Basic Violet V3 CI42555 conjugate, Saponite Basic Green G1 CI42040 conjugate, Saponite Basic Red R1 CI45160 conjugate, Saponite CI Basic Black 2 conjugate, and mixtures thereof.
[0126] Fabric dyes, or in practice other auxiliaries produced by organic synthesis routes such as pigments, fluorescent whitening agents, and polymers, may be incorporated into the detergent composition as part of a reaction mixture obtained as a result of the organic synthesis of the auxiliary using any purification step. Such a reaction mixture generally contains the auxiliary itself and may also contain unreacted starting materials and / or by-products of the organic synthesis route.
[0127] Suitable polymer fabric dyes are listed below. As with all such alkoxylated compounds, mixtures of molecules having varying degrees of alkoxylation can be produced by organic synthesis. Such mixtures may be used directly to provide fabric dyes or may undergo a purification process.
[0128] Fabric dyes can have the following structures:
[0129] [ka] (In the formula, R1 and R2 are independently selected from the group consisting of H, alkyl, alkoxy, alkylene oxy, alkyl-terminated alkylene oxy, urea, and amide. R3 is a substituted aryl group, X is a substituent comprising a sulfonamide moiety and optionally an alkyl and / or aryl moiety, wherein the substituent comprises at least one alkylene oxy chain). The color dye may be a thiophene dye, such as a thiophene azo dye, which is preferably alkoxylated. Optionally, the dye may be substituted with at least one solubilizing group selected from a sulfonic acid group, a carboxylic acid group, or a quaternary ammonium group. Particularly preferred dyes are Liquitint dyes from Milliken Company, in particular Violet DD.
[0130] Pigments. Suitable pigments include those selected from the group consisting of flavantron, indantron, chlorinated indantron containing 1 to 4 chlorine atoms, pyrantron, dichloropyrantron, monobromodichloropyrantron, dibromodichloropyrantron, tetrabromopyrantron, perylene-3,4,9,10-tetracarboxylic acid diimide (the imide group may be unsubstituted or substituted with C1-C3 alkyl, phenyl, or heterocyclic radicals, and the phenyl and heterocyclic radicals may further have substituents that do not impart water solubility), anthrapyrimidine carboxylic acid amide, biolantron, isobiolantron, dioxazine pigments, copper phthalocyanines that may contain up to 2 chlorine atoms per molecule, polychloro-copper phthalocyanines or polybromochloro-copper phthalocyanines containing up to 14 bromine atoms per molecule, and mixtures thereof. Other suitable pigments are described in International Publication No. 2008 / 090091. In another embodiment, preferred pigments include those selected from the group consisting of ultramarine blue (CI Pigment Blue 29), ultramarine violet (CI Pigment Violet 15), monastrahl blue, and mixtures thereof. Particularly preferred are Pigment Blue 15-20, especially Pigment Blue 15 and / or 16. Other preferred pigments include those selected from the group consisting of ultramarine blue (CI Pigment Blue 29), ultramarine violet (CI Pigment Violet 15), monastrahl blue, and mixtures thereof. Preferred colorants are described in detail in U.S. Patent No. 7,208,459(B2).
[0131] The above-mentioned fabric colorants can be used in mixtures of colorants and / or mixtures with any pigment.
[0132] Fluorescent whitening agents. Preferred examples of fluorescent whitening agents include, for example, stilbene whitening agents, coumarin whitening agents, benzoxazole whitening agents, and mixtures thereof. Diaminostilbenisulfonic acid type whitening agents (hereinafter referred to as "DAS") are classified as hydrophilic in International Publication No. 98 / 52907(A). An example of a commercially available DAS is Tinopal DMS (ex CIBA). Another type of low ClogP whitening agent is distyrylbiphenyl whitening agent (hereinafter referred to as "DSBP"). An example of a commercially available whitening agent of this type is Tinopal CBS-X (similarly ex CIBA). Commercially available fluorescent whitening agents that may be useful in the present invention can be classified into subgroups, which include, but are not limited to, stilbenes, pyrazolines, carboxylic acids, methyncyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered heterocyclic compounds, and derivatives of various other agents. Particularly preferred whitening agents are selected from sodium 2(4-styryl-3-sulfophenyl)-2H-naphtho[1,2-d]triazole, disodium 4,4'-bis([4-anilino-6-(N-methyl-2-hydroxyethylamino)-1,3,5-triazine-2-yl]amino)stilbene-2,2'-disulfonate, disodium 4,4'-bis[(4-anilino-6-morpholino-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonate, and disodium 4,4'-bis(2-sulfostyryl)biphenyl. Other examples of such whitening agents are disclosed in "The Production and Application of Fluorescent Brightening Agents" (M. Zahradnik, John Wiley & Sons, New York (1982)).
[0133] A preferred whitening agent has the following structure:
[0134] [ka]
[0135] Suitable levels of whitening agent range from approximately 0.01, 0.05, 0.1, or even 0.2% by weight to an upper limit of 0.5, 0.75, or even 1.0% by weight.
[0136] A highly preferred optical whitening agent is one comprising a CI fluorescent whitening agent 260 (preferably having the following structure).
[0137] [ka]
[0138] The method for preparing CI fluorescent whitening agent 260 is described in Belgian Patent No. 680847.
[0139] Aesthetic dyes. This composition may contain aesthetic dyes and / or pigments. Suitable dyes include any conventional dyes used to color washing and / or treatment compositions, typically small molecule dyes or high molecular weight dyes. These are generally non-fabric dyes.
[0140] Solvent system. The composition may contain a solvent system, for example, water alone, or a mixture of organic solvents that do not contain water or contain water. Suitable organic solvents include 1,2-propanediol, ethanol, glycerol, dipropylene glycol, methylpropanediol, and mixtures thereof. Other lower alcohols, C1-C4 alkanolamines, such as monoethanolamine and triethanolamine, may also be used. The solvent system may not be present in the anhydrous solid embodiment of the present invention, for example, but is more typically present at a level in the range of about 0.1% to 98%, preferably at least about 1% to about 50%, and more generally about 5% to about 25%. Such a solvent system may be particularly useful for pre-mixing with the whitening agent before mixing the whitening agent with other components in the detergent composition. Alternatively, a surfactant may be further pre-mixed with the whitening agent. In such a preferred embodiment, the surfactant pre-mixed with the whitening agent contains at least 25% by weight or at least 50% by weight of a nonionic surfactant (based on the total weight of the surfactant).
[0141] In some embodiments of the present invention, the composition is in the form of a structured liquid. Such a structured liquid may be internally structured by a primary component (e.g., a surfactant) to form a structure, and / or externally structured by a secondary component (e.g., a polymer, clay, and / or silicate) to give a three-dimensional matrix structure for use as a thickener, for example. The composition may contain a structuring agent, preferably 0.01% to 5% by weight, or 0.1% to 2.0% by weight of a structuring agent. Examples of suitable structuring agents are shown in U.S. Patent Applications Publication Nos. 2006 / 0205631(A1), 2005 / 0203213(A1), U.S. Patent Nos. 7,294611, and 6855680. Structuring agents are typically selected from the group consisting of diglycerides and triglycerides, ethylene glycol distearate, microcrystalline cellulose, cellulosic substances, microfiber cellulose, ally-modified alkali-swelling emulsions such as Polygel W30 (3VSigma), biopolymers, xanthan gum, gellan gum, hydrogenated castor oil, derivatives of hydrogenated castor oil (e.g., non-ethoxylated derivatives of hydrogenated castor oil), and mixtures thereof, and in particular, selected from the group consisting of hydrogenated castor oil, derivatives of hydrogenated castor oil, microfiber cellulose, hydroxy-functional crystalline substances, long-chain aliphatic alcohols, 12-hydroxystearic acid, clay, and mixtures thereof. Preferred structuring agents are described in detail in U.S. Patent No. 6,855,680, which defines preferred hydroxy-functional crystalline substances. Hydrogenated castor oil is preferred. Non-limiting examples of useful structuring agents include [examples omitted]. Such structuring agents have a filamentous structure system with a certain range of aspect ratios. Other suitable structuring agents and methods for preparing them are described in International Publication No. 2010 / 034736.
[0142] The compositions of the present invention may contain high-melting-point aliphatic compounds. High-melting-point aliphatic compounds useful herein have a melting point of 25°C or higher and are selected from the group consisting of aliphatic alcohols, fatty acids, aliphatic alcohol derivatives, fatty acid derivatives, and mixtures thereof. Compounds with such low melting points are not intended to be included in this section. Non-limiting examples of high-melting-point aliphatic compounds can be found in the International Cosmetic Ingredient Dictionary, 5th edition (1993) and the CTFA Cosmetic Ingredient Handbook, 2nd edition (1992). Where present, high-melting-point aliphatic compounds are preferably included in the composition at levels of 0.1% to 40% by weight, preferably 1% to 30% by weight, more preferably 1.5% to 16% by weight, or 1.5% to 8% by weight, from the viewpoint of improving conditioning effects such as a smooth feel while applied to wet hair and a soft and moist feel on dry hair.
[0143] Cationic polymer. The compositions of the present invention may contain a cationic polymer. The concentration of the cationic polymer in the composition is typically in the range of 0.05% to 3%, in another embodiment 0.075% to 2.0%, and in yet another embodiment 0.1% to 1.0%. A suitable cationic polymer has a cationic charge density of at least 0.5 meq / gm, in another embodiment at least 0.9 meq / gm, in another embodiment at least 1.2 meq / gm, and in yet another embodiment at least 1.5 meq / gm at the pH of the intended use of the composition (generally in the range of pH 3 to pH 9, and in one embodiment pH 4 to pH 8), but less than 7 meq / gm in one embodiment and less than 5 meq / gm in another embodiment. In this specification, “positive charge density” of a polymer refers to the ratio of the number of positive charges on the polymer to the molecular weight of the polymer. The average molecular weight of such suitable cationic polymers is generally 10,000 to 10,000,000, 50,000 to 5,000,000 in one embodiment, and 100,000 to 3,000,000 in another embodiment.
[0144] Cationic polymers suitable for use in the compositions of the present invention contain a cationic nitrogen-containing moiety such as a quaternary ammonium compound, or a protonated cationic amino compound. Any anionic counterion may be used in combination with the cationic polymer, provided that the polymer remains soluble in water, in the composition, or in the coacervate phase of the composition, and the counterion is physically and chemically compatible with the essential components of the composition, or otherwise does not excessively impair the performance, stability, or aesthetics of the product. Non-limiting examples of such counterions include halides (e.g., chlorides, fluorides, bromides, iodides), sulfates, and methyl sulfates.
[0145] Non-exclusive examples of such polymers are listed in the CTFA Cosmetic Ingredient Dictionary, 3rd edition, edited by Estrin, Crosley, and Haynes (The Cosmetic, Toiletry, and Fragrance Association, Inc. (Washington, DC) (1982)).
[0146] Other cationic polymers suitable for use in this composition include polysaccharide polymers, cationic guar gum derivatives, quaternary nitrogen-containing cellulose ethers, synthetic polymers, copolymers of etherified cellulose, guar, and starch. When used, the cationic polymers herein are soluble in the composition or soluble in the composite coacervate phase in the composition formed by the cationic polymers described above, as well as anionic, amphoteric, and / or bipolar surfactant components. The composite coacervate of the cationic polymer may also be formed with other charged substances in the composition.
[0147] Suitable cationic polymers are described in U.S. Patent No. 3,962,418, U.S. Patent No. 3,958,581, and U.S. Patent Application Publication No. 2007 / 0207109(A1).
[0148] Nonionic polymers. The compositions of the present invention may contain nonionic polymers as conditioning agents. Polyalkylene glycols having a molecular weight greater than 1000 are useful herein. Those having the following general formulas are useful:
[0149] [ka] (wherein R95 is selected from the group consisting of H, methyl, and mixtures thereof). Conditioning agents, particularly silicones, may be included in the composition. Conditioning agents useful in the compositions of the present invention typically include water-insoluble, water-dispersible, non-volatile liquids that form emulsified liquid particles. Conditioning agents suitable for use in the compositions are generally characterized as silicones (e.g., silicone oils, cationic silicones, silicone gums, high refractive index silicones, and silicone resins), organic conditioning oils (e.g., hydrocarbon oils, polyolefins, and fatty acid esters), or combinations thereof, or conditioning agents that otherwise form liquid dispersion particles in the aqueous surfactant matrix herein. Such conditioning agents must be physically and chemically compatible with the essential components of the composition and must not unduly impair the stability, aesthetics, or performance of the product.
[0150] The concentration of the conditioning agent in this composition should be sufficient to produce the desired conditioning effect. Such a concentration may vary depending on the conditioning agent, the desired conditioning performance, the average size of the conditioning agent particles, the types and concentrations of other components, and other similar factors.
[0151] The concentration of silicone conditioning agents is typically in the range of about 0.01% to about 10%. Non-limiting examples of suitable silicone conditioning agents and any suspensions for silicones are U.S. Reissue Patent No. 34,584, U.S. Patent No. 5,104,646; U.S. Patent No. 5,106,609, U.S. Patent No. 4,152,416, U.S. Patent No. 2,826,551, U.S. Patent No. 3,964,500, U.S. Patent No. 4,364,837, U.S. Patent No. 6,607,717, U.S. Patent No. 6,482,969, U.S. Patent No. 5,807,956, U.S. Patent No. 5,981, Patent Nos. 681, 6,207,782, 7,465,439, 7,041,767, 7,217,777, U.S. Patent Application Publication No. 2007 / 0286837(A1); 2005 / 0048549(A1); 2007 / 0041929(A1); UK Patent No. 849,433; German Patent No. 10036533; (all incorporated herein by reference); Chemistry This information is found in *and Technology of Silicones* (New York: Academic Press (1968)); General Electric Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54, and SE 76; *Silicon Compounds* (Petrarch Systems, Inc. (1984)); and *Encyclopedia of Polymer Science and Engineering*, Vol. 15, 2nd edition, pp. 204-308, John Wiley & Sons, Inc. (1989).
[0152] Discoloration inhibitors (DTIs). Washing and / or treatment compositions preferably comprise a mixture of one or more discoloration inhibitors. Suitable discoloration inhibitors are selected from the group consisting of polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidone, polyvinylimidazole, and mixtures thereof. Other suitable DTIs are triazines described in International Publication No. 2012 / 095354, polymerized benzoxazines described in International Publication No. 2010 / 130624, polyvinyltetrazole described in German Patent Application No. 102009001144(A), porous polyamide particles described in International Publication No. 2009 / 127587, and insoluble polymer particles described in International Publication No. 2009 / 124908. Other suitable DTIs are those described in International Publication No. 2012 / 004134, or polymers selected from the group consisting of (a) amphiphilic alkoxylated polyamines, amphiphilic graft copolymers, bipolar fouling suspension polymers, manganese phthalocyanines, peroxidases, and mixtures thereof.
[0153] Preferred DTIs include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidone, polyvinylimidazole, and mixtures thereof. More specifically, preferred polyamine N-oxide polymers for use herein contain units having the following structural formula: R-AX-P (wherein P is a polymerizable unit to which an NO group can be bonded, or an NO group can form part of a polymerizable unit, or an NO group can be bonded to both units; A is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1; and R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group, or any combination thereof, to which the nitrogen of an NO group can be bonded, or the NO group is part of these groups). Preferred polyamine N-oxides are those in which R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, and derivatives thereof.
[0154] The NO group can be represented by the following general structure.
[0155] [ka] (In the formula, R1, R2, and R3 are aliphatic, aromatic, heterocyclic, or alicyclic groups, or combinations thereof; x, y, and z are 0 or 1; and the nitrogen of the NO group can be bonded to any of the above groups or form part thereof). The amine oxide unit of the polyamine N-oxide has a pKa < 10, preferably pKa < 7, and more preferably pKa < 6.
[0156] Any polymer backbone can be used, as long as the formed amine oxide polymer is water-soluble and has transfer-inhibiting properties. Suitable polymer backbone examples include polyvinyl, polyalkylene, polyester, polyether, polyamide, polyimide, polyacrylate, and mixtures thereof. These polymers include random or block copolymers in which one monomer species is an amine N-oxide and the other monomer species is an N-oxide. Amine N-oxide polymers typically have an amine-to-amine N-oxide ratio of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can vary depending on the appropriate copolymerization or degree of N-oxidation. Polyamine oxides can be obtained at almost all degrees of polymerization.
[0157] Typically, their average molecular weight is in the range of 500 to 1,000,000, more preferably 1,000 to 500,000, and most preferably 5,000 to 100,000. This preferred class of substances is sometimes referred to as "PVNO".
[0158] The most preferred polyamine N-oxide useful in the detergent compositions described herein is poly(4-vinylpyridine-N-oxide) having an average molecular weight of about 50,000 and a ratio of amine to amine N-oxide of about 1:4.
[0159] Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as the "PVPVI" class) are also preferred for use herein. Preferably, PVPVI has an average molecular weight in the range of 5,000 to 1,000,000, more preferably 5,000 to 200,000, and most preferably 10,000 to 20,000. (This average molecular weight range is determined by light scattering as described in Barth et al., Chemical Analysis, Vol. 113, "Modem Methods of Polymer Characterization," which disclosure is incorporated herein by reference.) PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of 1:1 to 0.2:1, more preferably 0.8:1 to 0.3:1, and most preferably 0.6:1 to 0.4:1.
[0160] These copolymers may be linear or branched.
[0161] Furthermore, the compositions of the present invention may also use polyvinylpyrrolidone ("PVP") having an average molecular weight of about 5,000 to about 400,000, preferably about 5,000 to about 200,000, and more preferably about 5,000 to about 50,000. PVP is known to those skilled in the field of detergents; see, for example, European Patent Application Publications No. 262,897(A) and No. 256,696(A), which are incorporated herein by reference.
[0162] The composition containing PVP may also contain polyethylene glycol ("PEG") having an average molecular weight of about 500 to about 100,000, preferably about 1,000 to about 10,000. Preferably, the ratio (in ppm) of PEG to PVP delivered into the washing solution is about 2:1 to about 50:1, more preferably about 3:1 to about 10:1.
[0163] A particularly preferred DTI system is a mixed polymer system comprising (a) N-vinylpyrrolidone and N-vinylimidazole and (b) a copolymer of a polyamine N-oxide polymer, particularly poly-4-vinylpyridine N-oxide, with a particularly preferred weight ratio of (a):(b) being 5:1 to 1:5. The preferred molecular weight of DTI, which is essential to the present invention, is 1,000 to 250,000 daltons, more preferably 2,000 to 150,000, or even more preferably 8,000 to 100,000 daltons.
[0164] Suitable examples include PVP-K15, PVP-K30, ChromaBond S-400, ChromaBond S-403E and Chromabond S-100 from Ashland Aqualon, and Sokalan® HP165, Sokalan® HP50, Sokalan® HP53, Sokalan® HP59, Sokalan® HP56K and Sokalan® HP66 from BASF.
[0165] The inventors have found that a composition containing a fluorescent whitening agent and DTI significantly increases whiteness, which is surprising because DTI typically reduces the effectiveness of fluorescent whitening agents.
[0166] The color transfer inhibitor may be present in the composition at a level of about 0.0001% to about 15% by weight, about 0.01% to about 10% by weight, preferably about 0.01% to about 5% by weight.
[0167] Organic conditioning oils. The compositions of the present invention may also contain, as a conditioning agent, at least one organic conditioning oil in an amount of about 0.05 to about 3%, either alone or in combination with other conditioning agents such as silicones (as described herein). Suitable conditioning oils include hydrocarbon oils, polyolefins, and aliphatic esters. The conditioning agents described by Procter & Gamble Company in U.S. Patents No. 5,674,478 and No. 5,750,122 are also suitable for use in the compositions of this specification. Similarly, the conditioning agents described in U.S. Patents No. 4,529,586, No. 4,507,280, No. 4,663,158, No. 4,197,865, No. 4,217,914, No. 4,381,919 and No. 4,422,853 are also suitable for use in this specification.
[0168] Sanitary agent. The composition of the present invention may contain components for providing sanitary and / or deodorizing effects, such as zinc ricinoleate, thymol, quaternary ammonium salts such as Bardac®, polyethyleneimine (such as Lupasol® from BASF), and one or more of these zinc complexes, silver and silver compounds, in particular those designed to release Ag+ or nanosilver dispersions.
[0169] Probiotics. This composition may contain probiotics such as those described in International Publication No. 2009 / 043709.
[0170] Foam extenders. When high foaming ability is desired, the composition may preferably contain foam extenders. Suitable examples are C10-C16 alkanolamides or C10-C14 alkyl sulfates, which are preferably included at a level of 1%-10%. C10-C14 monoethanols and diethanolamides represent a typical classification of such foam extenders. It is also beneficial to use such foam extenders together with high-foaming auxiliary surfactants such as the amine oxides, betaines, and sultaines mentioned above. If necessary, water-soluble magnesium and / or calcium salts such as MgCl2, MgSO4, CaCl2, and CaSO4 may be added, typically at a level of 0.1%-2%, to provide additional foam and enhance grease removal performance.
[0171] Foam inhibitors. Compounds that reduce or suppress foam formation may be incorporated into the compositions of the present invention. Foam suppression may be particularly important in so-called "high-concentration washing processes" as described in U.S. Patents 4,489,455 and 4,489,574, as well as in front-loading washing machines. A wide range of materials may be used as foam inhibitors, and foam inhibitors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, 3rd edition, Vol. 7, pp. 430-447 (John Wiley & Sons, Inc., 1979). Examples of foam inhibitors include monocarbonate fatty acids and their soluble salts, high molecular weight hydrocarbons such as paraffins, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monohydric alcohols, aliphatic C18-C40 ketones (e.g., stearone), N-alkylated aminotriazines, waxy hydrocarbons preferably having a melting point of less than about 100°C, silicone foam inhibitors, and secondary alcohols. Foam inhibitors are described in U.S. Patent Nos. 2,954,347, 4,265,779, 4,265,779, 3,455,839, 3,933,672, 4,652,392, 4,978,471, 4,983,316, 5,288,431, 4,639,489, 4,749,740, and 4,798,679, 4,075,118, European Patent Application Publication No. 89307851.9, European Patent No. 150,872, and DOS 2,124,526.
[0172] For any detergent composition used in an automatic washing machine, foam should not be formed to the extent that it overflows from the washing machine. When used, the antifoaming agent is preferably present in an "antifoaming amount." "Antifoaming amount" means that the compounder of the composition can select the amount of this antifoaming agent that sufficiently controls foaming so that the detergent becomes a low-foaming laundry detergent when used in an automatic washing machine. The compositions herein generally contain 0% to 10% antifoaming agent. When used as an antifoaming agent, monocarbonate fatty acids and their salts are typically present in an amount of 5% by weight or less of the detergent composition. Preferably, 0.5% to 3% of an aliphatic monocarboxylate antifoaming agent is used. Silicone antifoaming agents are typically used in an amount of 2.0% by weight or less of the detergent composition, but higher amounts may be used. Monostearyl phosphate antifoaming agents are generally used in an amount ranging from 0.1% to 2% by weight of the composition. Hydrocarbon antifoaming agents are typically used in an amount ranging from 0.01% to 5.0%, but higher levels may be used. Alcohol-based foam inhibitors are typically used in an amount of 0.2% to 3% by weight of the final composition.
[0173] Pearlescent agent. The pearlescent agent described in International Publication No. 2011 / 163457 may be incorporated into the composition of the present invention.
[0174] Fragrance. Preferably, this composition contains fragrance in an amount of 0.001 to 3% by weight, most preferably 0.1 to 1% by weight. (CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide (CFTA Publications) and OPD 1993 Chemicals Buyers Directory 80) thThe Annual Edition (published by Schnell Publishing Co.) provides many suitable examples of fragrances. Typically, the compositions of the present invention contain multiple fragrance components, for example, four, five, six, seven, or more. In the fragrance mixture, preferably 15-25% by weight is the top note. The top note is defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80
[1995] ). Preferred top notes include rose oxide, citrus oil, linalyl acetate, lavender, linalool, dihydromyrcenol, and cis-3-hexanol.
[0175] Packaging. Any conventional packaging may be used, and the packaging may be entirely or partially transparent so that consumers can see the color of the product that may be brought about by, or to which the color of the dye essential to the present invention may contribute. Part or all of the packaging may contain an ultraviolet-absorbing compound.
[0176] Method for preparing a composition The compositions of the present invention may be in solid form (e.g., granules or tablets) or in liquid form. Preferably, the compositions are in liquid form. The compositions may be prepared by any method selected by the compounder, non-limiting examples of which are given in the Examples and U.S. Patent Publication No. 4,990,280, U.S. Patent Application Publication No. 20030087791(A1), No. 20030087790(A1), No. 20050003983(A1), No. 20040048764(A1), U.S. Patent No. 4,762,636, This is described in Patent No. 6,291,412, U.S. Patent Application Publication No. 20050227891(A1), European Patent No. 1070115(A2), U.S. Patents No. 5,879,584, No. 5,691,297, No. 5,574,005, No. 5,569,645, No. 5,565,422, No. 5,516,448, No. 5,489,392, and No. 5,486.
[0177] When in liquid form, the composition of the present invention may be aqueous (typically with a total water content of more than 2% by weight, or more than 5 or 10% by weight, up to 90% or up to 80% or 70% by weight) or non-aqueous (typically with a total water content of less than 2% by weight). Typically, the composition of the present invention is in the form of an aqueous solution or homogeneous dispersion or suspension of an optical whitening agent, DTI, and any further auxiliary substances, some of which may be in solid form and are combined with the typically liquid components of the composition (e.g., an alcohol ethoxylate nonionic liquid, an aqueous liquid carrier, and any other optional component that is a typically liquid). Such solutions, dispersions, or suspensions have acceptable phase stability. When in liquid form, the detergent of the present invention is preferably 1 to 1500 centipoise (1 to 1500 mPa) at 20s⁻¹ and 21°C. * s), more preferably 100-1000 cmpoise (100-1000 mPa) * s), most preferably 200-500 centipoise (200-500 mPa) * It has a viscosity of s). Viscosity can be measured by conventional methods. Viscosity may be measured using a TA Instruments AR550 rheometer with a plate steel spindle of 40 mm diameter and a gap size of 500 μm. The high shear viscosity at 20 s⁻¹ and the low shear viscosity at 0.05 s⁻¹ can be obtained from a logarithmic shear rate sweep of 0.1 s⁻¹ to 25 s⁻¹ over 3 minutes at 21C. The preferred rheology described herein can be obtained by using an internal structural agent together with the detergent component, or by using an external rheology modifier. More preferably, detergents such as detergent liquid compositions have a high shear rate viscosity of about 100 centipoise to 1500 centipoise, more preferably 100 to 1000 cps. A unit dose detergent such as a detergent liquid composition has a high shear rate viscosity of 400 to 1000 cps. Detergents such as laundry softening compositions typically have a high shear rate viscosity of 10 to 1000, more preferably 10 to 800 cps, and most preferably 10 to 500 cps. Dishwashing hand-washing compositions have a high shear rate viscosity of 300 to 4000 cps, more preferably 300 to 1000 cps.
[0178] The liquid cleaning and / or treatment compositions described herein can be prepared by combining their components in any convenient order and mixing, for example, stirring the resulting combination of components to form a phase-stable liquid detergent composition. In a method for preparing such a composition, a liquid matrix is formed containing at least the majority, or even substantially all, of the liquid components, such as a nonionic surfactant, a non-surfactant liquid carrier, and any other liquid components, and these liquid components are thoroughly mixed by applying shear stirring to this combination of liquids. For example, high-speed stirring with a mechanical stirrer can be commonly used. While maintaining shear stirring, any anionic surfactant and substantially all of the components in solid form can be added. The stirring of the mixture is continued and increased as necessary to form a solution or homogeneous dispersion of insoluble solid phase particles in the liquid phase. After some or all of the solid-form material is added to this stirred mixture, particles of any enzymatic material to be included, such as enzyme prills, are incorporated. As a variation of the composition preparation procedure described above, one or more solid components may be added to the stirred mixture as a solution or slurry of particles pre-mixed with trace amounts of one or more liquid components. After all the composition components have been added, the mixture is stirred for a sufficient amount of time to form a composition with the required viscosity and phase stability. In most cases, this involves stirring for about 30 to 60 minutes.
[0179] Pouch. In preferred embodiments of the present invention, the composition is provided in the form of unit doses, tablets, or, preferably, in the form of a liquid / solid (optionally granules) / gel / paste held in a water-soluble film (known as a pouch or pod). The composition may be enclosed in a single-compartment or multi-compartment pouch. Multi-compartment pouches are described in detail in European Patent Application Publication No. 2133410(A). Dyes or pigments of varying or non-dyes, or other aesthetic agents, may also be used in one or more compartments.
[0180] A suitable film for forming a pouch is water-soluble or water-dispersible, and preferably has a water solubility / dispersibility of at least 50%, preferably at least 75%, or even more than 95%, when measured using a glass filter with a maximum pore size of 20 micrometers and then measured by the method described below.
[0181] Add 50 grams ± 0.1 grams of pouch material to a pre-weighed 400 mL beaker, and add 245 mL ± 1 mL of distilled water. Stir vigorously for 30 minutes using an electromagnetic stirrer set to 600 rpm. Then filter the mixture through a folded sintered glass filter for qualitative analysis with the pore size defined above (maximum 20 micrometers). Dry the water from the recovered filtrate by any conventional method and weigh the remaining material (this is the dissolved or dispersed fraction). Then the percentage of solubility or dispersion can be calculated. Preferred film materials are polymer materials. Film materials can be obtained, for example, by casting, blow molding, extrusion molding or blow extrusion molding of polymer materials as is well known in the art. Preferred polymers, copolymers, or derivatives thereof suitable for use as pouch materials are selected from polyvinyl alcohol, polyvinylpyrrolidone, polyalkylene oxide, acrylamide, acrylic acid, cellulose, cellulose ether, cellulose ester, celluloseamide, polyvinyl acetate, polycarboxylic acids and salts, polyamino acids or peptides, polyamides, polyacrylamide, maleic acid / acrylic acid copolymers, polysaccharides including starch and gelatin, and natural rubbers such as xanthan gum and kara rubber. More preferred polymers are selected from polyacrylate and water-soluble acrylate copolymers, methylcellulose, sodium carboxymethylcellulose, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, maltodextrin, and polymethacrylate, and most preferably from polyvinyl alcohol, polyvinyl alcohol copolymer and hydroxypropyl methylcellulose (HPMC), and combinations thereof. Preferably, the level of polymer in the pouch material, for example, PVA polymer, is at least 60%. The polymer may have any weight-average molecular weight, preferably about 1,000 to 1,000,000, more preferably about 10,000 to 300,000, and even more preferably about 20,000 to 150,000. Polymer mixtures can also be used as pouch materials.This may be useful for controlling the mechanical and / or solubility properties of the compartment or pouch, depending on its application and required needs. Suitable mixtures include, for example, mixtures in which one polymer has higher water solubility than another polymer, and / or one polymer has higher mechanical strength than another polymer. Mixtures of polymers having different weight-average molecular weights are also suitable, for example, mixtures of PVA or its copolymers with a weight-average molecular weight of about 10,000 to 40,000, preferably around 20,000, and PVA or its copolymers with a weight-average molecular weight of about 100,000 to 300,000, preferably around 150,000. Polymer blend compositions, for example, polymer blends that are hydrolyzable and water-soluble (such as polylactide and polyvinyl alcohol, obtained by mixing polylactide and polyvinyl alcohol, typically containing about 1 to 35% by weight of polylactide and about 65% to 99% by weight of polyvinyl alcohol) are also suitable herein. Preferred for use in this specification are polymers that have been hydrolyzed by about 60% to about 98%, preferably about 80% to about 90%, in order to improve the solubility of the material.
[0182] Naturally, different film materials and / or films of different thicknesses may be used to create the compartments of the present invention. The advantage of selecting different films is that the resulting compartments may exhibit different solubility, i.e., release characteristics.
[0183] The most preferred film materials are PVA films known as MonoSol commodity codes M8630, M8900, and H8779 (as described in concurrent pending applications 44528 and 11599 by the applicants), as well as those described in U.S. Patent Nos. 6,166117 and 6,787512, and PVA films with corresponding solubility and deformation properties.
[0184] Furthermore, the film materials of this specification may contain one or more additive components. For example, it may be beneficial to add plasticizers such as glycerol, ethylene glycol, diethylene glycol, propylene glycol, sorbitol, and mixtures thereof. Other additives include functional detergent additives delivered to the washing water, such as organic polymer dispersants.
[0185] The bittering agent may be incorporated into the pouch or pod by being mixed into the composition inside the pouch and / or by being coated onto the film.
[0186] Method of Use. Typically, an aqueous washing / treatment solution for use in washing / treating fabrics can be formed using the composition of the present invention, prepared as described above. Generally, an effective amount of such composition is added to water (for example, in a conventional automatic washing machine for fabrics) to form such an aqueous washing solution. The aqueous washing solution thus formed is then brought into contact with the fabric to be washed / treated with the solution, typically under agitation. The effective amount of the detergent composition of this specification to produce an aqueous washing solution when added to water may be sufficient to produce about 500 to 25,000 ppm or 500 to 15,000 ppm of the composition in the aqueous washing solution, or about 1,000 to 3,000 ppm of the detergent composition of this specification may be supplied to the aqueous washing solution.
[0187] Typically, the washing solution is formed by contacting detergent with washing water in such an amount that the concentration of detergent in the washing solution is greater than 0 g / L and up to 5 g / L, or between 1 g / L and 4.5 g / L, or 4.0 g / L or less, or 3.5 g / L or less, or 3.0 g / L or less, or 2.5 g / L or less, or even 2.0 g / L or less, or even 1.5 g / L or less. The method of washing fabrics or textiles may be carried out in a top-loading or front-loading automatic washing machine, or it may be used for hand washing. In these applications, the washing solution formed and the concentration of the laundry detergent composition in the washing solution are those of the main wash cycle. When determining the volume of the washing solution, the amount of water added during any optional additional rinsing steps is not included.
[0188] The cleaning solution may contain 40 liters or less of water, or 30 liters or less, or 20 liters or less, or 10 liters or less, or 8 liters or less, or even 6 liters or less. The cleaning solution may contain more than 0 liters but up to 15 liters, or more than 2 liters but 12 liters or less, or even 8 liters or less of water. Typically, 0.01 kg to 2 kg of fabric per liter of cleaning solution is added to the cleaning solution. Typically, 0.01 kg or more, or more than 0.05 kg or more, or more than 0.07 kg or more, or more than 0.10 kg or more, or more than 0.15 kg or more, or more than 0.20 kg or more, or more than 0.25 kg of fabric per liter of cleaning solution is added to the cleaning solution. Optionally, a cleaning solution is formed by contacting water with a composition of 50 g or less, or 45 g or less, or 40 g or less, or 35 g or less, or 30 g or less, or 25 g or less, or 20 g or less, or even 15 g or less, or even 10 g or less. Such compositions are typically used at concentrations of about 500 ppm to about 15,000 ppm in the solution. When the cleaning solvent is water, the water temperature is usually in the range of about 5°C to about 90°C, and when the area includes fabric, the water-to-fabric ratio is usually about 1:1 to about 30:1. Typically, the pH of the cleaning solution containing the detergent of the present invention is 3 to 11.5.
[0189] In one embodiment, a method is disclosed, along with an optional drying step, which includes optionally washing and / or rinsing the surface or fabric, bringing the surface or fabric into contact with any composition disclosed herein, and then optionally washing and / or rinsing the surface or fabric.
[0190] Drying of such surfaces or fabrics can be carried out by any one of the common means used in either a home or industrial environment, whether by machine drying or outdoor drying. The fabrics may include any fabrics that can be washed under general consumer use conditions or commercial conditions, and the present invention is particularly suitable for synthetic fabrics such as polyester and nylon, and especially for the treatment of blended fabrics and / or fibers including synthetic and cellulosic fabrics and / or fibers. Examples of synthetic fabrics are polyester and nylon, which may be present in blended fabrics with cellulosic fibers, such as polycotton fabrics. The pH of the solution is typically 7 to 11, more commonly 8 to 10.5. The composition is typically used at a concentration of 500 ppm to 5,000 ppm in solution. The water temperature is usually in the range of about 5°C to about 90°C. The water-to-fabric ratio is usually about 1:1 to about 30:1.
[0191] The auxiliary components in the composition of the present invention can be incorporated into the composition as synthetic products that produce such components, with or without an intermediate purification step. If a purification step is absent, the mixture used generally includes the desired component or a mixture thereof (the proportions shown herein relate to the weight percentage of the component itself unless otherwise specified), as well as unreacted starting materials and impurities formed by side reactions and / or incomplete reactions. For example, with respect to ethoxylated or substituted components, the mixture may contain varying degrees of ethoxylation / substitution. [Examples]
[0192] The following are examples of the cleaning composition of the present invention.
[0193] Examples 1-7 Heavy liquid laundry detergent compositions
[0194] [Table 1] Based on the total weight of the washing and / or treatment composition. Enzyme levels are reported as raw materials.
[0195] Examples 8-16 Unit Dose Compositions These examples provide various formulations for unit-dose laundry detergents. Compositions 8-12 each contain one unit-dose compartment. The film used to enclose the composition is PVA.
[0196] [Table 2] Based on the total weight of the washing and / or treatment composition. Enzyme levels are reported as raw materials.
[0197] In the following embodiments, the unit dose has three compartments, but similar compositions can also be prepared with two, four, or five compartments. The film used to enclose the compartments is polyvinyl alcohol.
[0198] [Table 3]
[0199] [Table 4] Based on the total weight of the washing and / or treatment composition, the enzyme level is reported as a raw material.
[0200] Examples 19-24: Granular laundry detergent compositions for hand washing or washing machines, typically top-loading washing machines.
[0201] [Table 5]
[0202] Examples 25-37 A granular laundry detergent composition typically for front-loading automatic washing machines.
[0203] [Table 6]
[0204] [Table 7]
[0205] The dimensions and values disclosed herein should not be understood as being strictly limited to the exact numerical values stated. Rather, unless otherwise specified, such dimensions are intended to mean both the stated value and a functionally equivalent range around that value. For example, a dimension disclosed as "40 mm" is intended to mean "approximately 40 mm".
Claims
1. A cleaning composition comprising a nuclease enzyme, preferably deoxyribonuclease and / or ribonuclease enzyme, and a surfactant system comprising an anionic surfactant and a nonionic surfactant, wherein the weight ratio of the anionic surfactant to the nonionic surfactant is 1.5:1 to 1:
10.
2. The cleaning composition according to claim 1, comprising a total surfactant level of 5 to 80% by weight or 10 to 50% by weight, more preferably 15 to 45% by weight.
3. The cleaning composition according to claim 1 or 2, wherein the weight ratio of the anionic surfactant to the nonionic surfactant is 1.2:1 to 1:4, or more preferably 1:1 to 1:
2.
4. The cleaning composition according to any one of claims 1 to 3, wherein the anionic surfactant comprises an alkylalkoxylylated sulfate surfactant, is preferably ethoxylated, and preferably has an average degree of alkoxylation of 0.5 to 2.
5.
5. The cleaning composition according to any one of claims 1 to 4, wherein the surfactant system comprises an additional surfactant selected from cationic, bipolar, and amphoteric surfactants, and preferably the additional surfactant is present in an amount of less than 20% by weight of the total surfactant system.
6. The washing composition according to any one of claims 1 to 5, wherein the nuclease enzyme is selected from any one of E. C. class E. C. 3.1.
21. x (wherein x = 1, 2, 3, 4, 5, 6, 7, 8, 9), 3.1.
22. y (wherein y = 1, 2, 4, 5), E. C. 3.1.
30. z (wherein z = 1, 2), or E. C. 3.1.31.1, or a mixture thereof, preferably E. C. 3.1.21, and preferably E. C. 3.1.21.
1.
7. The washing composition according to any one of claims 1 to 6, wherein the nuclease enzyme comprises deoxyribonuclease.
8. The washing composition according to claim 6, wherein the enzyme comprises an enzyme having both RNase activity and DNase activity, preferably an enzyme of E.C. 3.1.30.
2.
9. The cleaning composition according to any one of claims 1 to 8, wherein the enzyme is a microbial enzyme, preferably a bacterial enzyme.
10. The washing composition according to any one of claims 1 to 9, wherein the enzyme has an amino acid sequence that is at least 85%, at least 90%, at least 95%, or even 100% identical to the amino acid sequence shown in SEQ ID NO: 1, SEQ ID NO: 2, or SEQ ID NO:
3.
11. A washing composition according to any one of claims 1 to 10, comprising the β-N-acetylglucosaminidase enzyme of E.C. 3.2.1.52, preferably an enzyme having at least 70% identity with SEQ ID NO:
4.
12. The washing composition according to any one of claims 1 to 11, wherein the composition further comprises a fabric color dye and / or an additional enzyme selected from lipases such as a first washing lipase, amylase, protease, mannanase, pectinate lyase, cellulase and cutinase.
13. A method for washing fabric, comprising the steps of: mixing a washing composition according to any one of claims 1 to 12 with water to form an aqueous solution; and bringing the fabric into contact with the aqueous solution during a washing process.
14. The use of a surfactant system containing an anionic surfactant and a nonionic surfactant, wherein the weight ratio of the anionic surfactant to the nonionic surfactant is 1.5:1 to 1:10, and the use is for promoting the washing of fabric by nuclease enzymes.