Liquid laundry detergent composition

Abstract

The purpose of the present invention is to provide a composition that includes a biodegradable additive and exhibits excellent washing performance when used as a liquid laundry detergent. The present invention is a liquid laundry detergent composition that includes a vinyl alcohol polymer and a surfactant. The vinyl alcohol polymer may include a structural unit (a) represented by formula (1), a structural unit (b) represented by formula (2), and other structural units (c) other than the structural unit (a) and the structural unit (b), the structural unit content proportions relative to a total of 100 mol% for all of the structural units being structural unit (a) / structural unit (b) / other structural units (c)=50–100 / 0–50 / 0–20 mol%, and the average degree of polymerization is 50–800. The vinyl alcohol polymer content proportion is 0.3–10 mass% relative to 100 mass% of the liquid laundry detergent composition, the surfactant content proportion is 10–80 mass% relative to 100 mass% of the liquid laundry detergent composition, the cationic surfactant proportion is no more than 20 mass% relative to 100 mass% of the surfactant, and the inorganic builder content proportion is no more than 50 mass% relative to 100 mass% of the liquid laundry detergent composition.

Description

Liquid laundry detergent composition

[0001] The present invention relates to liquid laundry detergent compositions, and more particularly to liquid laundry detergent compositions useful as concentrated liquid laundry detergents and the like.

[0002] Various types of detergents containing surfactants as the main component have been developed for use in laundry, dishwashing, etc. In addition to surfactants, various detergent additives are used in detergents, and polyvinyl alcohol is known as one such additive (see, for example, Patent Documents 1 to 5).

[0003] In recent years, the demand for liquid laundry detergents that dissolve easily in water has been increasing due to the spread of drum-type washing machines that use less water and the need to wash clothes in a shorter time to improve housework efficiency.

[0004] Japanese Patent Laid-Open No. 59-6299 Japanese Patent Laid-Open No. 63-305198 Japanese Patent Laid-Open No. 11-5992 International Publication No. 2002 / 046348 Japanese Patent Laid-Open No. 2022-080076

[0005] In order to meet the above-mentioned demands, various additives for use in liquid laundry detergents have been developed, but there is still room for further improvement in the cleaning performance of liquid laundry detergents. In addition, with consumers becoming increasingly concerned about environmental protection, there is a demand for additives derived from sustainable resources, such as biodegradable compounds.

[0006] The present invention has been made in consideration of the above-mentioned current situation, and aims to provide a composition that contains a biodegradable additive and can exhibit excellent cleaning performance when used as a liquid laundry detergent.

[0007] The present inventors have conducted extensive research into detergent additives and have found that, in a composition containing surfactants in predetermined proportions, by limiting the amount of cationic surfactant and inorganic builder to predetermined amounts or less and adding a biodegradable vinyl alcohol polymer having an average degree of polymerization within a predetermined range in a predetermined proportion, excellent cleaning performance can be achieved when used as a liquid laundry detergent. This has led to the realization that the above-mentioned problems can be successfully solved, and has led to the present invention.

[0008] The present invention includes the following liquid laundry detergent compositions, etc.: [1] A liquid laundry detergent composition containing a vinyl alcohol-based polymer and a surfactant, wherein the vinyl alcohol-based polymer is represented by the following formula (1): and further having a structural unit (a) represented by the following formula (2): and a structural unit (b) represented by the following formula (I): and a structural unit (c) other than the structural unit (a) and the structural unit (b), wherein the content ratio of each structural unit relative to 100 mol% of the total amount of all structural units is structural unit (a) / structural unit (b) / other structural unit (c) = 50-100 / 0-50 / 0-20 mol%, and the average degree of polymerization is 50-800, the content ratio of the vinyl alcohol-based polymer is 0.3-10 mass% relative to 100 mol% of the liquid laundry detergent composition, the content ratio of the surfactant is 10-80 mass% relative to 100 mol% of the liquid laundry detergent composition, the content ratio of the cationic surfactant is 20 mass% or less relative to 100 mol% of the surfactant, and the content ratio of the inorganic builder is 50 mass% or less relative to 100 mol% of the liquid laundry detergent composition. [2] The liquid laundry detergent composition according to [1] above, wherein the compatibility probability 1 / (1+Exp(-y)), expressed using y as defined in the following formula (I), is 0.5 or more: y=73.7-0.418×α-0.725×β-0.00332×γ (I) (wherein α represents the content (mass%) of the surfactant in the evaluation liquid when evaluating compatibility using the liquid laundry detergent composition, β represents the degree of saponification (mol%) of the vinyl alcohol-based polymer, and γ represents the average degree of polymerization of the vinyl alcohol-based polymer.) [3] The liquid laundry detergent composition according to [1] or [2] above, wherein the content of the surfactant is 45 to 80% by mass, relative to 100% by mass of the liquid laundry detergent composition. [4] The liquid laundry detergent composition according to any of [1] to [3] above, wherein the surfactant includes an anionic surfactant. [5] The liquid laundry detergent composition according to any one of [1] to [4] above, wherein the surfactant comprises an anionic surfactant and a nonionic surfactant. [6] The liquid laundry detergent composition according to any one of [1] to [5] above, wherein the surfactant comprises an anionic surfactant and a nonionic surfactant, and the proportion of the anionic surfactant relative to the total amount of the anionic surfactant and the nonionic surfactant is 30% by mass or more (100% by mass). [7] The liquid laundry detergent composition according to [5] or [6] above, wherein the content of the nonionic surfactant is 5 to 70% by mass relative to the total amount of surfactants (100% by mass).[8] The liquid laundry detergent composition according to any one of [1] to [7] above, which contains a polyalkylene glycol compound. [9] The liquid laundry detergent composition according to [8] above, wherein the content of the polyalkylene glycol compound is 100 to 1,000% by mass relative to 100% by mass of the vinyl alcohol-based polymer.

[10] The liquid laundry detergent composition according to any one of [1] to [9] above, which contains an enzyme.

[11] A composite composition in which a liquid laundry detergent composition is encapsulated in a detergent packaging film, the liquid laundry detergent composition comprising a vinyl alcohol-based polymer and a surfactant, and the vinyl alcohol-based polymer is represented by the following formula (1): and further having a structural unit (a) represented by the following formula (2): and a structural unit (b) represented by the formula: and a structural unit (c) other than the structural unit (a) and the structural unit (b), wherein the content ratio of each structural unit relative to 100 mol% of the total amount of all structural units is structural unit (a) / structural unit (b) / other structural unit (c) = 50 to 100 / 0 to 50 / 0 to 20 mol%, and the average degree of polymerization is 50 to 800.

[12] The composite composition according to

[11] above, wherein the content ratio of the surfactant is 50 to 80 mass% relative to 100 mass% of the liquid laundry detergent composition.

[0009] The liquid laundry detergent composition of the present invention has the above-mentioned configuration, contains biodegradable additives, and exhibits excellent cleaning performance when used as a liquid laundry detergent, and can therefore be suitably used as a concentrated liquid laundry detergent, etc.

[0010] Preferred embodiments of the present invention will be specifically described below, but the present invention is not limited to the following description and can be appropriately modified and applied within the scope of the present invention. Note that a combination of two or more of the individual preferred embodiments of the present invention described below also falls within the scope of the present invention.

[0011] [Liquid Laundry Detergent Composition] The liquid laundry detergent composition of the present invention has a structural unit (a) represented by the above formula (1), and may further have a structural unit (b) represented by the above formula (2), and other structural units (c) other than the structural units (a) and (b). The content ratio of each structural unit relative to the total amount of all structural units (100 mol%) is structural unit (a) / structural unit (b) / other structural units (c) = 50-100 / 0-50 / 0-20 mol%, and the composition comprises a vinyl alcohol polymer having an average degree of polymerization of 50-800, and a surfactant, the content ratio of the surfactant being 10-80% by mass relative to 100% by mass of the liquid laundry detergent composition. Due to the above-described configuration, the liquid laundry detergent composition of the present invention exhibits excellent cleaning performance and is also excellent in biodegradability when used as a liquid laundry detergent. The liquid laundry detergent composition of the present invention is particularly excellent in cleaning performance for muddy stains.

[0012] The surfactant content in the liquid laundry detergent composition may be 10 to 80% by mass, preferably 15 to 80% by mass, based on 100% by mass of the liquid laundry detergent composition. In this case, it is believed that the interaction between the surfactant and the vinyl alcohol polymer is greater, thereby further enhancing the effect of the surfactant. The surfactant content is more preferably 15 to 75% by mass, even more preferably 20 to 75% by mass, and particularly preferably 20 to 70% by mass. In one aspect, the surfactant content is 30 to 80% by mass, 40 to 80% by mass, or 45 to 80% by mass, based on 100% by mass of the liquid laundry detergent composition, which is also a preferred embodiment.

[0013] The surfactant preferably contains an anionic surfactant, and although the proportion is not particularly limited, it is preferably 30% by mass or more relative to 100% by mass of the total surfactant amount in the liquid laundry detergent composition. It is more preferably 40 to 100% by mass, even more preferably 40 to 90% by mass, and particularly preferably 50 to 90% by mass. In one embodiment, the content of the anionic surfactant is preferably 5% by mass or more relative to 100% by mass of the total surfactant amount. It is more preferably 10 to 90% by mass, and even more preferably 20 to 80% by mass.

[0014] The surfactant preferably includes a nonionic surfactant, and although the proportion is not particularly limited, it is preferably 0 to 70% by mass relative to 100% by mass of the total surfactant amount in the liquid laundry detergent composition. It is more preferably 0 to 60% by mass, even more preferably 10 to 60% by mass, and particularly preferably 10 to 50% by mass. In one embodiment, the proportion of the nonionic surfactant relative to 100% by mass of the total surfactant amount is also preferably 5 to 50% by mass. It is more preferably 7.5 to 40% by mass, and even more preferably 10 to 30% by mass.

[0015] The surfactant preferably contains an anionic surfactant and a nonionic surfactant, and the total proportion of the anionic surfactant and the nonionic surfactant is not particularly limited, but is preferably 15 to 80% by mass, more preferably 15 to 75% by mass, even more preferably 20 to 75% by mass, and particularly preferably 20 to 70% by mass, relative to 100% by mass of the total surfactant amount in the liquid laundry detergent composition.

[0016] The surfactant may contain a cationic surfactant, but the proportion thereof is 20% by mass or less relative to the total surfactant amount (100% by mass) in the liquid laundry detergent composition. This can sufficiently prevent the anionic surfactant from impairing the cleaning performance. The proportion of the cationic surfactant is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and most preferably 0% by mass.

[0017] The proportion of the anionic surfactant relative to the total of the anionic surfactant and the nonionic surfactant (100% by mass) is not particularly limited, but is preferably 30% by mass or more, more preferably 40 to 100% by mass, even more preferably 40 to 90% by mass, and particularly preferably 50 to 90% by mass.

[0018] The content of the vinyl alcohol polymer in the liquid laundry detergent composition is not particularly limited, but is preferably 0.5 to 10% by mass, more preferably 1 to 9% by mass, and even more preferably 2 to 8% by mass, based on 100% by mass of the liquid laundry detergent composition. In one embodiment, the content of the vinyl alcohol polymer is also preferably 0.3 to 10% by mass, based on 100% by mass of the liquid laundry detergent composition. More preferably, it is 0.5 to 8% by mass, and even more preferably 0.8 to 6% by mass.

[0019] The content of the vinyl alcohol polymer in the liquid laundry detergent composition is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, even more preferably 2 to 15% by mass, and particularly preferably 3 to 10% by mass, based on 100% by mass of the surfactant.

[0020] The liquid laundry detergent composition may contain other components in addition to the vinyl alcohol polymer and the surfactant, and the content of the other components is not particularly limited, but is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, and even more preferably 30 to 80% by mass.

[0021] From the viewpoint of improving cleaning performance and stability of the composition, the liquid laundry detergent composition preferably has a pH of 5 to 11 at 25°C. It is more preferably 5.5 to 10.5, even more preferably 6 to 10, even more preferably 6 to 9.5, and particularly preferably 6 to 9. The pH is measured at 25°C using a glass electrode. Specifically, it is measured by the following method. (pH Measurement Method) A pH electrode (Model 6367) mounted on a Horiba, Ltd. pH meter D-52 is pre-calibrated with a phthalate buffer solution (pH 4.01), a phosphate standard solution (pH 6.84), and a borate standard solution (pH 9.18), and then thoroughly rinsed with ion-exchanged water. The pH electrode calibrated and washed as described above is placed in the liquid laundry detergent composition whose temperature has been adjusted to 25°C, and the pH is measured using the AUTO HOLD mode of the pH meter until a constant value is obtained.

[0022] The liquid laundry detergent composition preferably has a compatibility probability 1 / (1+Exp(-y)), expressed using y as defined in the following formula (I), of 0.5 or greater: y=73.7-0.418×α-0.725×β-0.00332×γ (I) (wherein α represents the surfactant content (mass%) in the evaluation liquid when evaluating compatibility using the liquid laundry detergent composition, β represents the degree of saponification (mol%) of the vinyl alcohol polymer, and γ represents the average degree of polymerization of the vinyl alcohol polymer.) Formula (I) above was calculated by varying the surfactant concentration, the degree of saponification and the average degree of polymerization of the vinyl alcohol polymer in the compatibility evaluation liquid, binarizing whether the composition is compatible or not, and parameterizing the result using logistic regression.

[0023] The liquid laundry detergent composition preferably contains a polyalkylene glycol compound. This improves the compatibility of the composition with surfactants. The content of the polyalkylene glycol compound in the liquid laundry detergent composition is not particularly limited, but is preferably 100 to 1,000% by mass relative to 100% by mass of the vinyl alcohol polymer. It is more preferably 100 to 900% by mass, and even more preferably 100 to 800% by mass.

[0024] The liquid laundry detergent composition of the present invention may contain an inorganic builder, but the amount is 50% by mass or less relative to 100% by mass of the liquid laundry detergent composition. This prevents the inorganic components from separating in the composition and destabilizing the composition. The content of the inorganic builder is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, and most preferably 0% by mass. The inorganic builder is not particularly limited, but examples thereof include sodium carbonate, sodium triborate, potassium pyrophosphate, sodium silicate, sodium sulfate, and zeolite.

[0025] The liquid laundry detergent composition of the present invention preferably contains water. Examples of water that can be used include ion-exchanged water, distilled water, tap water, and water containing 1 mg / kg or more and 5 mg / kg or less of sodium hypochlorite. In terms of physical properties such as viscosity of the composition and workability during laundry washing, the liquid laundry detergent composition of the present invention preferably contains 5 to 90% by mass, more preferably 5 to 85% by mass, even more preferably 5 to 80% by mass, and particularly preferably 5 to 75% by mass, based on 100% by mass of the composition. In one aspect, a preferred embodiment is one in which the water content is 10 to 70% by mass, 20 to 65% by mass, or 30 to 60% by mass, based on 100% by mass of the liquid laundry detergent composition.

[0026] The essential and optional ingredients included in the liquid laundry detergent compositions of the present invention are further described below.

[0027] <Vinyl Alcohol-Based Polymer> The vinyl alcohol-based polymer contained in the liquid laundry detergent composition of the present invention has a structural unit (a) represented by the above formula (1), and may further have a structural unit (b) represented by the above formula (2) and another structural unit (c) other than the above structural unit (a) and the above structural unit (b), wherein the content ratio of each structural unit relative to 100 mol % of the total amount of all structural units is structural unit (a) / structural unit (b) / other structural unit (c) = 50 to 100 / 0 to 50 / 0 to 20 mol %, and the average degree of polymerization is 50 to 800.

[0028] The proportion of the structural unit (a) in the vinyl alcohol polymer may be 50 to 100 mol% relative to the total amount of all structural units (100 mol%), but is preferably 55 to 100 mol%, more preferably 60 to 100 mol%, even more preferably 65 to 99 mol%, and particularly preferably 70 to 98 mol%. In one aspect, a proportion of the structural unit (a) of 5 to 100 mol% or 80 to 100 mol% relative to the total amount of all structural units (100 mol%) is also a preferred embodiment. In one aspect, the proportion of the structural unit (a) is preferably 50 to 95 mol% relative to the total amount of all structural units (100 mol%). This results in superior detergency against hydrophobic soils such as sebum, and complex soils composed of a combination of hydrophilic and hydrophobic soils. It is more preferably 60 to 90 mol%, even more preferably 70 to 90 mol%.

[0029] The proportion of the structural unit (b) in the vinyl alcohol polymer may be 0 to 50 mol%, preferably 0 to 45 mol%, more preferably 0 to 40 mol%, even more preferably 0 to 35 mol%, and particularly preferably 0 to 30 mol%, relative to 100 mol% of the total amount of all structural units. In one aspect, the proportion of the structural unit (b) is 0.1 to 25 mol%, or 1 to 20 mol%, relative to 100 mol% of the total amount of all structural units, which is also one of the preferred embodiments.

[0030] The proportion of the structural unit (c) in the vinyl alcohol polymer may be 0 to 20 mol %, preferably 0 to 15 mol %, more preferably 0 to 10 mol %, even more preferably 0 to 5 mol %, and particularly preferably 0 to 1 mol %, relative to the total amount of all structural units (100 mol %). An embodiment in which the proportion of the structural unit (c) is 0 mol % is also one of the preferred embodiments of the present invention.

[0031] The vinyl alcohol polymer may have, as the structural unit (c), a structural unit derived from a hydrophobic monomer, which will be described later, and the proportion thereof is not particularly limited, but is preferably 10 mol % or less, more preferably 10 mol % or less, even more preferably 5 mol % or less, particularly preferably 1 mol % or less, and most preferably 0 mol % relative to 100 mol % of the total amount of all structural units.

[0032] The vinyl alcohol polymer may have a structural unit derived from an alkyl group-substituted 1-ene monomer described below, but the amount thereof is preferably less than 0.25 mol %, more preferably 0 mol %, relative to 100 mol % of the total amount of all structural units.

[0033] The vinyl alcohol polymer has an average degree of polymerization of 50 to 800. This allows the liquid laundry detergent composition of the present invention to exhibit excellent cleaning performance. The average degree of polymerization is preferably 50 to 700, more preferably 100 to 600, even more preferably 100 to 500, and particularly preferably 100 to 450. The average degree of polymerization can be measured by the method described in the Examples.

[0034] The vinyl alcohol polymer may have a structural unit (c), and the structural unit (c) is not particularly limited as long as it is a structural unit other than the structural unit (a) and the structural unit (b). The monomer forming the structural unit (c) may be any monomer that can be copolymerized with vinyl acetate, which is the raw material for the structural units (a) and (b), and examples thereof include unsaturated alcohols having 3 to 8 carbon atoms, such as (meth)allyl alcohol and 3-methyl-3-buten-1-ol (isoprenol), and esters of these with carboxylic acids having 2 to 8 carbon atoms; unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, and citraconic acid, and esters of these with alkoxypolyalkylene glycols, such as methoxypolyethylene glycol; adducts of alkylene oxides, such as ethylene oxide and propylene oxide, to unsaturated alcohols, such as allyl alcohol and isoprenol; acrylamide, sodium acrylamidopropanesulfonate, sodium 2-hydroxy-3-allyloxypropanesulfonate, hydroxyethyl acrylate, hydroxyethyl methacrylate, ethylene glycol monoesters, and the like. vinyl ether, diethylene glycol monovinyl ether, hydroxybutyl vinyl ether and other vinyl ethers, and alkylene oxide adducts such as ethylene oxide and propylene oxide; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate and other alkyl (meth)acrylates, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate and other alkyl (meth)acrylates; aromatic vinyl monomers such as styrene; olefin monomers such as ethylene, propylene, and alkyl group-substituted 1-ene monomers; alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; cyclic vinyl monomers such as N-vinylpyrrolidone, acrylonitrile; vinyl formamide, vinyl acetamide, and the like.Among the monomers that form the structural unit (c), esters of unsaturated alcohols having 3 to 8 carbon atoms and carboxylic acids having 2 to 8 carbon atoms; esters of unsaturated carboxylic acids and alkoxypolyalkylene glycols; alkyl(meth)acrylates; aromatic vinyl monomers, olefin monomers, etc. are hydrophobic monomers, and are preferably used in the above-mentioned ratios.

[0035] The form of the vinyl alcohol-based polymer is not particularly limited, and may be dissolved in the composition or may form a membrane such as a microcapsule, but is preferably dissolved. In one aspect, it is preferred that the liquid laundry detergent composition of the present invention does not include a form in which the vinyl alcohol-based polymer is in the form of a microcapsule.

[0036] [Method for producing vinyl alcohol polymer] The method for producing the vinyl alcohol polymer is not particularly limited, but when the vinyl alcohol polymer is a polymer consisting of only the structural unit (a) or the structural units (a) and (b), it is preferably produced by polymerizing vinyl acetate followed by hydrolysis. When the vinyl alcohol polymer has the structural unit (c), it is preferably produced by copolymerizing vinyl acetate with a monomer that forms the structural unit (c), followed by hydrolysis.

[0037] The polymerization temperature of the monomer components in the production of the vinyl alcohol polymer is preferably 0 to 70°C, more preferably 10 to 70°C, even more preferably 20 to 70°C, and particularly preferably 30 to 70°C.

[0038] In the polymerization reaction, it is preferable to use a polymerization initiator. As the polymerization initiator, low-temperature decomposition type radical generators such as diisopropyl peroxydicarbonate, isobutyryl peroxide, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), bis(4-t-butylcyclohexol)peroxydicarbonate, dimyristyl peroxydicarbonate, acetylcyclohexylsulfonyl peroxide, n-propyl peroxydicarbonate, α-cumyl peroxyneodecanoate, and 2,4,4-triethylpentyl peroxyphenoxyacetate can be effectively used, but the initiator is not limited to these. Furthermore, it is also possible to use an initiator such as 2,2'-azobisisobutyronitrile in combination during ultraviolet irradiation. Also effective is a so-called redox initiator system, which is a combination of a peroxide radical initiator with a reducing agent such as dimethylaniline or Q-ascorbic acid and an oxidizing agent such as an iron salt. Radical polymerization can also be initiated effectively by electron beams or radiation.

[0039] A chain transfer agent may be used in the polymerization reaction. Examples of the chain transfer agent include mercaptans such as mercaptoethanol, thioglycerol, thioglycolic acid, 3-mercaptopropionic acid, thiomalic acid, and 2-mercaptoethanesulfonic acid. The method for adding the mercaptans is not particularly limited, but a predetermined amount may be added to the polymerization system before the start of polymerization, and once the polymerization has substantially started, the mercaptan may be continuously supplied to the polymerization system at a constant rate.

[0040] For the vinyl alcohol polymer, the initiation of saponification of polyvinyl acetate ester is preferably carried out in an alcohol containing an alkali catalyst at a predetermined concentration or more, and when the alcohol is methanol, it is desirable that the initiation of the saponification reaction of at least polyvinyl acetate ester be carried out in methanol containing 0.18 mol / L or more of the alkali catalyst.

[0041] The alkali catalyst used in the saponification reaction is not particularly limited, but is preferably an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, or lithium hydroxide, more preferably sodium hydroxide.

[0042] <Surfactant> The surfactant contained in the liquid laundry detergent composition of the present invention is not particularly limited as long as it has a surface-active effect, and examples thereof include anionic surfactants, nonionic surfactants, cationic surfactants, etc. Among these, anionic surfactants and nonionic surfactants are preferred. A preferred embodiment of the present invention is one in which the liquid laundry detergent composition of the present invention contains an anionic surfactant and a nonionic surfactant. In this case, the liquid laundry detergent composition of the present invention can exhibit better cleaning performance.

[0043] (Anionic Surfactant) The anionic surfactant is not particularly limited as long as it is a surfactant having a hydrophobic group and a hydrophilic group that dissociates into anions. For example, the anionic surfactant may be a surfactant represented by the following formula (3): １ -(O) ｍ - (A １ O) ｎ１ -W (in the formula, R １ are the same or different and represent a hydrocarbon group having 6 to 24 carbon atoms. １ O may be the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. １ represents the average number of moles of oxyalkylene groups added, represented by O, and is an integer of 0 to 50. m is 0 or 1. W represents a hydrophilic group that dissociates into anions.

[0044] Above A １Each O is the same or different and is an oxyalkylene group having 2 to 18 carbon atoms, preferably 2 to 8, more preferably 2 to 4 carbon atoms. These oxyalkylene groups are alkylene oxide adducts, and specific examples of alkylene oxides are as described above. Preferably, they are ethylene oxide, propylene oxide, or butylene oxide, more preferably ethylene oxide or propylene oxide. Furthermore, when the oxyalkylene group is an adduct of any two or more alkylene oxides selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc., it may be in any form such as random addition, block addition, or alternating addition. In order to ensure a balance between hydrophilicity and hydrophobicity, it is preferable that the oxyalkylene groups in the polyalkylene glycol contain oxyethylene groups as an essential component, more preferably 50 mol % or more of oxyethylene groups, even more preferably 80 mol % or more of oxyethylene groups, and particularly preferably 90 mol % or more of oxyethylene groups.

[0045] The above n1 may be any value from 0 to 50, preferably from 0 to 40, and more preferably from 0 to 30.

[0046] R １ The hydrocarbon group in is not particularly limited, and examples thereof include an alkyl group, an alkenyl group, an aryl group, an aralkyl group, etc. The alkyl group and the alkenyl group may be linear or branched.

[0047] Examples of the alkyl group include an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, a neohexyl group, a 2-ethylhexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, a neoheptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, a neooctyl group, an n-nonyl group, an isononyl group, a sec-nonyl group, a tert-nonyl group, and a tert-nonyl group. nonyl group, neononyl group, n-decyl group, isodecyl group, sec-decyl group, tert-decyl group, neodecyl group, n-undecyl group, isoundecyl group, sec-undecyl group, tert-undecyl group, neoundecyl group, n-dodecyl group, isododecyl group, sec-dodecyl group, tert-dodecyl group, neododecyl group, n-tridecyl group, isotridecyl group, sec-tridecyl group, tert-tridecyl group, neotridecyl group, Decyl group, n-tetradecyl group, isotetradecyl group, sec-tetradecyl group, tert-tetradecyl group, neotetradecyl group, n-pentadecyl group, isopentadecyl group, sec-pentadecyl group, tert-pentadecyl group, neopentadecyl group, n-hexadecyl group, isohexadecyl group, sec-hexadecyl group, tert-hexadecyl group, neohexadecyl group, n-heptadecyl group, isoheptadecyl group, s Examples thereof include an ec-heptadecyl group, a tert-heptadecyl group, a neoheptadecyl group, an n-octadecyl group, an isooctadecyl group, a sec-octadecyl group, a tert-octadecyl group, a neooctadecyl group, an n-nonadecyl group, an isononadecyl group, a sec-nonadecyl group, a tert-nonadecyl group, a neononadecyl group, an n-icosyl group, an isoicosyl group, a sec-icosyl group, a tert-icosyl group, and a neoicosyl group.

[0048] Examples of the alkenyl group include a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a dodecenyl group, an octadecenyl group, and an icosenyl group.

[0049] Examples of the aryl group include a phenyl group, a methylphenyl group, a 1-methoxy-4-methylphenyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a butylmethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a dibutylphenyl group, a biphenyl group, a naphthyl group, etc. Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a benzhydryl group, a biphenylmethyl group, a biphenylethyl group, a naphthylmethyl group, a naphthylethyl group, etc.

[0050] R １ The hydrocarbon group has 6 to 24 carbon atoms, preferably 6 to 22 carbon atoms, more preferably 8 to 20 carbon atoms, and even more preferably 8 to 18 carbon atoms.

[0051] The hydrophilic group in W that dissociates into an anion is not particularly limited, and examples thereof include a sulfate (salt) group, a sulfonic acid (salt) group, a carboxylic acid (salt) group, and a phosphate (salt) group. Preferred are sulfate groups, sulfonate groups, and carboxylate groups.

[0052] Examples of anionic surfactants include alkyl or alkenyl sulfate ester salts; polyoxyalkylene alkyl or alkenyl ether sulfate ester salts having an oxyalkylene group; anionic surfactants having a sulfonate group; fatty acids or salts thereof; and the like.

[0053] More specific examples of the alkyl or alkenyl sulfate ester salts include alkyl sulfate ester salts in which the alkyl group has 10 to 18 carbon atoms, and alkenyl sulfate ester salts in which the alkenyl group has 10 to 18 carbon atoms.

[0054] More specific examples of the polyoxyalkylene alkyl or alkenyl ether sulfate salts having an oxyalkylene group include polyoxyalkylene alkyl ether sulfate salts having an alkyl group with 10 to 18 carbon atoms and an average number of added moles of alkylene oxide of 1 to 5; and polyoxyalkylene alkenyl ether sulfate salts having an alkenyl group with 10 to 18 carbon atoms and an average number of added moles of alkylene oxide of 1 to 5. Among these, polyoxyethylene alkyl ether sulfate salts having an average number of added moles of ethylene oxide of 1 to 3 are preferred, and polyoxyethylene alkyl ether sulfate salts having an alkyl group with 12 to 14 carbon atoms and an average number of added moles of ethylene oxide of 1 to 3 are more preferred, and sodium salts thereof are even more preferred.

[0055] More specific examples of the anionic surfactant having a sulfonate group include one or more anionic surfactants selected from alkylbenzenesulfonates having an alkyl group containing 10 to 18 carbon atoms, alkenylbenzenesulfonates having an alkenyl group containing 10 to 18 carbon atoms, alkanesulfonates having an alkyl group containing 10 to 18 carbon atoms, α-olefinsulfonates having an α-olefin moiety containing 10 to 18 carbon atoms, α-sulfofatty acid salts having a fatty acid moiety containing 10 to 18 carbon atoms, α-sulfofatty acid lower alkyl ester salts having a fatty acid moiety containing 10 to 18 carbon atoms and an ester moiety containing 1 to 5 carbon atoms, and internal olefinsulfonates having 12 to 16 carbon atoms. Among these, alkylbenzenesulfonates having an alkyl group containing 11 to 16 carbon atoms are preferred, and sodium alkylbenzenesulfonate having an alkyl group containing 11 to 16 carbon atoms is more preferred.

[0056] The fatty acid or salt thereof may be a fatty acid or salt thereof having 10 to 20 carbon atoms. The fatty acid or salt thereof preferably has 12 to 18 carbon atoms, and more preferably has 14 to 18 carbon atoms.

[0057] (Nonionic Surfactant) The nonionic surfactant is not particularly limited as long as it has a hydrophobic group and a hydrophilic group that does not dissociate into ions, such as a hydroxy group, an ether group, or an ester group. For example, the nonionic surfactant may be a surfactant represented by the following formula (4-1) and / or (4-2):２ -O-(A ２ O) ｎ２ -H (4-1) R ３ -COO-(A ３ O) ｎ３ -R ４ (4-2) (wherein, R ２ , R ３ are the same or different and represent a hydrocarbon group having 6 to 24 carbon atoms. ４ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ２ O.A. ３ O may be the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. ２ n3 represents the average number of moles of oxyalkylene groups added, and is an integer of 1 to 50. ３ represents the average number of moles of oxyalkylene groups added, represented by O, and is an integer of 5 to 50.

[0058] The above R ２ , R ３ The hydrocarbon group in is not particularly limited, and examples thereof include an alkyl group, an alkenyl group, an aryl group, and an aralkyl group. The alkyl group and the alkenyl group may be linear or branched. Specific examples of the alkyl group, the alkenyl group, the aryl group, and the aralkyl group are as described above.

[0059] The above R ２ , R ３ The hydrocarbon group has 6 to 24 carbon atoms, preferably 6 to 22 carbon atoms, more preferably 8 to 20 carbon atoms, and even more preferably 8 to 18 carbon atoms.

[0060] Above A ２ O.A. ３ Specific examples and preferred forms of O are: A １ Same as O.

[0061] The above n2 and n3 are preferably 1 to 30, more preferably 1 to 22, even more preferably 2 to 18, and particularly preferably 3 to 16.

[0062] -(A ２ O) ｎ２ -ga,-(EO)ｎ２’ - (PO) ｎ２’’ In the above formula, n2' is the average number of moles of EO added and is a number from 1 to 20, preferably from 2 to 10. n2'' is the average number of moles of PO added and is a number from 1 to 20, preferably from 2 to 10.

[0063] Specific examples of the nonionic surfactant include compounds in which 1 to 50 moles of ethylene oxide (EO) and / or propylene oxide (PO) are added to an alkyl alcohol having 6 to 24 carbon atoms. The total number of moles of EO and PO added is more preferably 2 to 30, even more preferably 2 to 25, and particularly preferably 3 to 20. The alkyl alcohol may be linear or branched, and an embodiment in which the alkyl alcohol is a primary or secondary alcohol is one of the preferred embodiments of the present invention. Furthermore, an embodiment in which only ethylene oxide is added to the alkyl alcohol, and an embodiment in which propylene oxide and ethylene oxide are block-added to the alkyl alcohol in this order are also preferred embodiments of the present invention.

[0064] (Cationic surfactant) The cationic surfactant is not particularly limited as long as it is a surfactant having a hydrophobic group and a hydrophilic group that dissociates into a cation, and examples thereof include quaternary ammonium salt type cationic surfactants. Examples of quaternary ammonium salt type cationic surfactants include quaternary ammonium salts in which, of the four groups bonded to a nitrogen atom, one or two are hydrocarbon groups having 6 to 24 carbon atoms, and the remaining are hydrocarbon groups having 1 to 3 carbon atoms. Examples of cationic surfactants include those represented by the following formula (5);

[0065]

[0066] (In the formula, R ５ is a chain hydrocarbon group having 8 to 24 carbon atoms, and R ６ is a chain hydrocarbon group having 8 to 24 carbon atoms, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, and R ７ and R ８are the same or different and are alkyl groups having 1 to 3 carbon atoms or hydroxyalkyl groups having 1 to 3 carbon atoms, and X － is an alkyl sulfate ion having 1 to 3 carbon atoms, or a halide ion.

[0067] In the above formula (5), R ５ The number of carbon atoms in the chain hydrocarbon group is preferably 9 to 18, more preferably 10 to 14, and even more preferably 10 to 12. ６ is a chain hydrocarbon group having 8 to 24 carbon atoms, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and R ６ The number of carbon atoms in the chain hydrocarbon group is preferably 9 to 18, more preferably 10 to 14, and even more preferably 10 to 12. ６ The chain hydrocarbon group of R is preferably an alkyl group or an alkenyl group, more preferably an alkyl group. ７ , R ８ are the same or different and are a methyl group, an ethyl group, or a hydroxyalkyl group having 1 to 3 carbon atoms. ５ , R ６ Specific examples of the chain hydrocarbon group of X include an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, and a hexadecyl group, with a nonyl group and a decyl group being preferred, and a decyl group being more preferred.Specific examples of the hydroxyalkyl group having 1 to 3 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group. － is CH ３ SO ４ － , C.H. ３ CH ２ SO ４ － , or a halide ion.

[0068] More specific examples of the compound represented by formula (5) include one or more compounds selected from N-ethyl-N,N-dimethyltetradecylammonium salt, trimethylhexadecyl salt, N,N-dioctyl-N,N-dimethylammonium salt, N,N-dinonyl-N,N-dimethylammonium salt, N,N-didecyl-N,N-dimethylammonium salt, N,N-dioctyl-N-ethyl-N-methylammonium salt, N,N-dinonyl-N-ethyl-N-methylammonium salt, and N,N-didecyl-N-ethyl-N-methylammonium salt. Mono-long chain ammonium salts and di-long chain ammonium salts can also be used in combination. Of these, N,N-didecyl-N-ethyl-N-methylammonium salt is preferred. The counter ion for these salts is CH ３ SO ４ － , C.H. ３ CH ２ SO ４ － , or a halide ion such as chloride ion.

[0069] The content of the cationic surfactant is not particularly limited, but is preferably 0 to 50% by mass, more preferably 0 to 40% by mass, and even more preferably 0 to 30% by mass, relative to 100% by mass of the composition.

[0070] <Polyalkylene glycol compound> The liquid laundry detergent composition preferably contains a polyalkylene glycol compound, which provides the composition with better compatibility with surfactants. The polyalkylene glycol compound is not particularly limited as long as it is a compound having a polyoxyalkylene group, and examples thereof include polyalkylene glycols containing alkylene glycol units having from 2 to 4 carbon atoms, such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol; monoalkyl ethers of polyalkylene glycols having alkylene glycol units having from 2 to 4 carbon atoms and an alkyl group having from 1 to 4 carbon atoms, such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, and diethylene glycol monobutyl ether; aromatic alkyl ethers of polyalkylene glycols having alkylene glycol units having from 2 to 3 carbon atoms, such as diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, polyethylene glycol monophenyl ether having an average molecular weight of about 480, and diethylene glycol monobenzyl ether; and alkylene oxide adducts of polyalkyleneimines, such as polyethyleneimine.

[0071] The average number of moles of oxyalkylene groups added in the polyalkylene glycol compound is not particularly limited, but is preferably 2 to 500. It is more preferably 10 to 400, even more preferably 20 to 300, still more preferably 30 to 250, still more preferably 40 to 200, and particularly preferably 50 to 150.

[0072] When the polyalkylene glycol compound is an alkylene oxide adduct of a polyalkyleneimine, the ratio of oxyalkylene groups to 1 mole of nitrogen atoms is preferably 1 to 100 moles, more preferably 5 to 50 moles, and even more preferably 10 to 30 moles.

[0073] When the polyalkylene glycol compound is an alkylene oxide adduct of a polyalkyleneimine, the number average molecular weight of the polyalkyleneimine is not particularly limited, but is preferably 100 to 100,000, more preferably 200 to 50,000, even more preferably 300 to 10,000, still more preferably 400 to 5,000, and even more preferably 500 to 3,000.

[0074] <Other Components> The liquid laundry detergent composition may contain other components in addition to the vinyl alcohol polymer and the surfactant. The other components are not particularly limited, but examples thereof include the following components (1) to (11).

[0075] (1) Enzyme The liquid laundry detergent composition of the present invention preferably contains an enzyme from the viewpoint of its detergency against various stains adhering to clothing. The enzyme is not particularly limited as long as it decomposes stain components, and examples thereof include carbohydrate-degrading enzymes, protease, lipase, oxidoreductase, and other decomposing enzymes, which may be used alone or in combination of two or more thereof.

[0076] Examples of the carbohydrate-degrading enzyme include amylase, sucrase, maltase, lactase, pullulanase, fructofuranosidase, cellulase, hemicellulase, xylanase, pectinase, pentosanase, malanase, β-glucanase, and arabinosidase. From the viewpoint of improving cleaning performance and maintaining cleaning performance after storage, the carbohydrate-degrading enzyme is preferably amylase, and more preferably α-amylase. Specific examples of commercially available enzymes that can be used include Rapidase (trade name, manufactured by Gist Brokers), Termamyl, Duramyl, Stainzyme, and Amplify Prime 100L (trade names, manufactured by Novozym Japan Co., Ltd.), Plaster ST and Plaster OxAm (trade names, manufactured by Genencor International), and Preferenz S210 (trade name, manufactured by DuPont Co., Ltd.).

[0077] The proteolytic enzymes are not particularly limited, but include proteases such as pepsin, trypsin, peptidase, etc. The lipolytic enzymes include lipase, phospholipase, lipoxygenase, etc.

[0078] The oxidoreductase is not particularly limited, but examples thereof include peroxidase, reductase, oxidase, phenol oxidase, and laccase.

[0079] The other decomposing enzymes include, but are not limited to, esterase, cutinase, keratanase, ligninase, tannase, hyaluronidase, chondroitinase, and the like.

[0080] The enzyme is preferably an enzyme containing protease, since this provides better cleaning performance for stains caused by spilled food such as meat sauce adhering to clothing stained with sebum.

[0081] The content of the enzyme is not particularly limited, but is preferably 0.01 to 3% by mass, more preferably 0.05 to 2% by mass, and even more preferably 0.1 to 1% by mass, relative to 100% by mass of the liquid laundry detergent composition.

[0082] (2) Alkaline Agent: The liquid laundry detergent composition of the present invention preferably contains an alkaline agent to improve detergency. Examples of alkaline agents include inorganic alkaline agents such as alkali metal hydroxides and alkali metal carbonates, and alkanolamines in which at least one but not more than three of the groups bonded to the nitrogen atom are alkanol groups having from 2 to 4 carbon atoms, and the remaining groups are alkyl groups or hydrogen atoms having from 1 to 4 carbon atoms. Among these, the alkanol group is preferably a hydroxyalkyl group, and more preferably a hydroxyethyl group. A hydrogen atom or a methyl group is preferred, with a hydrogen atom being particularly preferred, other than the alkanol group. Examples of alkanolamines include alkanolamines such as 2-aminoethanol, N-methylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, diethanolamine, N-methyldiethanolamine, and triethanolamine. In the present invention, component (2) is preferably an alkanolamine selected from monoethanolamine and triethanolamine, with monoethanolamine being more preferred. The alkaline agent, component (2), can also be used to adjust the pH of the liquid laundry detergent composition of the present invention to a predetermined value. In the liquid laundry detergent composition of the present invention, component (2) may be blended in an amount sufficient to achieve the above-mentioned pH. The blending amount of component (2) is preferably 0.01 to 10% by mass, more preferably 0.5 to 8% by mass, based on 100% by mass of the composition. In the present invention, the blending amount of the alkaline agent of component (2), particularly the alkanolamine, includes the amount derived from other components, such as counterions of anionic surfactants, blended in the composition.

[0083] (3) Chelating Agents Specific examples of the chelating agent include aminopolyacetic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and hydroxyethyliminodiacetic acid, or salts thereof; organic acids such as citric acid, lactic acid, tartaric acid, and malic acid, or salts thereof; 1-hydroxyethylidene-1,1-diphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid), alkali metal or lower amine salts thereof; and nitrotriacetate. The content of the chelating agent (3), considered as an acid form, is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 4% by mass or less, and even more preferably 0.1% by mass or more and 3% by mass or less, based on 100% by mass of the composition. The liquid laundry detergent composition of the present invention may contain nitrotriacetate, but compositions in which the weight ratio of the vinyl alcohol polymer to the nitrotriacetate (vinyl alcohol polymer / nitrotriacetate) is 0.1 to 2 are preferably excluded from the present invention. In the liquid laundry detergent composition, the ratio of nitrotriacetate relative to 100% by mass of the vinyl alcohol-based polymer is preferably 33% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, particularly preferably 10% by mass or less, and most preferably 0% by mass, relative to 100% by mass of the vinyl alcohol-based polymer.

[0084] (4) Anti-redeposition agent and / or polymer dispersant Examples of the anti-redeposition agent and / or polymer dispersant include polyacrylic acid, polymaleic acid, carboxymethyl cellulose, etc. The content of the anti-redeposition agent and / or polymer dispersant is preferably 0.01% by mass or more and 10% by mass or less, relative to 100% by mass of the composition.

[0085] (5) Bleaching Agent Examples of bleaching agents include hydrogen peroxide, sodium percarbonate, sodium perborate, etc. The content of the bleaching agent is preferably 0.01% by mass or more and 10% by mass or less relative to 100% by mass of the composition.

[0086] (6) Bleaching activator Examples of the bleaching activator include tetraacetylethylenediamine and bleaching activators represented by general formulas (I-2) to (I-7) described in JP-A-6-316700. The content of the bleaching activator is preferably 0.01% by mass or more and 10% by mass or less, relative to 100% by mass of the composition.

[0087] (7) Fluorescent Dye Examples of the fluorescent dye include fluorescent dyes commercially available under the trade names of Tinopal CBS (manufactured by Ciba Specialty Chemicals) and Whitex SA (manufactured by Sumitomo Chemical Co., Ltd.) The content of the fluorescent dye is preferably 0.001% by mass or more and 1% by mass or less relative to 100% by mass of the composition.

[0088] (8) Antioxidant Examples of the antioxidant include butylhydroxytoluene, distyrenated cresol, sodium sulfite, sodium hydrogen sulfite, etc. The content of the antioxidant is preferably 0.01% by mass or more and 2% by mass or less, based on 100% by mass of the composition.

[0089] (9) It is preferable to contain appropriate amounts of coloring matter, fragrance, antibacterial preservative, and antifoaming agent such as silicone.

[0090] (10) Organic Solvent Having a Hydroxyl Group As the organic solvent having a hydroxyl group, one or more compounds selected from the following components (10-1) to (10-5) are used: Component (10-1): Monohydric alcohol having an aliphatic hydrocarbon group having from 2 to 6 carbon atoms Examples of the component (10-1) include monohydric alcohols selected from ethanol, 1-propanol, 2-propanol, and 1-butanol.

[0091] Component (10-2): Dihydric to hexahydric alcohol having 2 to 6 carbon atoms Examples of component (10-2) include dihydric or trihydric alcohols selected from ethylene glycol, propylene glycol, butylene glycol, 2-methyl-2,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, and glycerin. 2-Methyl-2,4-pentanediol is also known as hexylene glycol.

[0092] Component (10-3): Monoalkyl ether of monoalkylene glycol having an alkylene glycol unit having from 2 to 4 carbon atoms and an alkyl group having from 1 to 4 carbon atoms. Examples of the component (10-3) include compounds selected from 1-methoxy-2-propanol and 1-ethoxy-2-propanol.

[0093] Component (10-4): Alkyl glyceryl ether having an alkyl having 1 to 8 carbon atoms Examples of the component (10-4) include alkyl glyceryl ethers selected from 1-methyl glyceryl ether, 2-methyl glyceryl ether, 1,3-dimethyl glyceryl ether, 1-ethyl glyceryl ether, 1,3-diethyl glyceryl ether, triethyl glyceryl ether, 1-pentyl glyceryl ether, 2-pentyl glyceryl ether, 1-octyl glyceryl ether, and 2-ethylhexyl glyceryl ether.

[0094] Component (10-5): Aromatic alkyl ether of monoalkylene glycol having an alkylene glycol unit having 2 or 3 carbon atoms. Examples of component (10-5) include 2-phenoxyethanol and 2-benzyloxyethanol.

[0095] From the viewpoint of further improving storage stability at low temperatures, the component (10) is preferably one or more compounds selected from the component (10-1), the component (10-2), the component (10-3), and the component (10-4). More specifically, the liquid laundry detergent composition of the present invention preferably contains ethanol and / or 2-phenoxyethanol. The liquid laundry detergent composition of the present invention preferably contains ethanol and / or 2-phenoxyethanol as the organic solvent having a hydroxyl group. The content of the component (10) is preferably 1 to 40% by mass, more preferably 4 to 20% by mass, and even more preferably 5 to 10% by mass, relative to 100% by mass of the composition.

[0096] (11) Hydrotrope Agent A hydrotrope agent can be added to improve the stability of the liquid laundry detergent composition. The hydrotrope agent of the present invention is an organic compound having an anionic group, and examples thereof include alkylbenzenecarboxylic acids or alkylbenzenesulfonic acids or their salts containing one or two alkyl groups selected from methyl, ethyl, or propyl groups and one sulfonic acid or carboxylic acid group, as well as benzoic acid or its salts. More specifically, examples include paratoluenesulfonic acid, cumenesulfonic acid, metaxylenesulfonic acid, and benzoic acid, and alkali metal salts are preferred. In the present invention, paratoluenesulfonic acid or its alkali metal salts are preferred, and may be added as an acid and neutralized with an alkali agent in the composition. The liquid laundry detergent composition of the present invention may contain a hydrotrope agent in an amount of preferably 0.1 to 5% by mass, more preferably 0.5 to 4% by mass, and even more preferably 1 to 3% by mass, calculated as the acid-type compound.

[0097] The liquid laundry detergent composition of the present invention can exhibit excellent cleaning performance even when the surfactant concentration is high, and therefore can be suitably used as a concentrated liquid laundry detergent, etc. The liquid laundry detergent composition of the present invention may be used as a concentrated liquid laundry detergent in a form enclosed in a detergent packaging film described below. In this case, for example, the liquid laundry detergent composition may contain a film-derived component. The liquid laundry detergent composition of the present invention can exhibit excellent cleaning performance even when it contains a film-derived component. Examples of the film-derived component include the water-soluble polymer described below. The content of the film-derived component in the liquid laundry detergent composition is not particularly limited, but is preferably 0 to 20% by mass relative to 100% by mass of the composition. It is more preferably 0 to 15% by mass, and even more preferably 0 to 10% by mass.

[0098] The content of the film-derived component in the liquid laundry detergent composition is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, even more preferably 2 to 15% by mass, and particularly preferably 3 to 10% by mass, based on 100% by mass of the surfactant.

[0099] [Composite Composition] The present invention also relates to a composite composition in which a liquid laundry detergent composition is encapsulated in a detergent packaging film, the liquid laundry detergent composition comprising a vinyl alcohol-based polymer and a surfactant, the vinyl alcohol-based polymer having a structural unit (a) represented by the above formula (1) and optionally a structural unit (b) represented by the above formula (2) and a structural unit (c) other than the structural units (a) and (b), wherein the content ratio of each structural unit relative to the total amount of all structural units (100 mol %) is structural unit (a) / structural unit (b) / other structural unit (c) = 50-100 / 0-50 / 0-20 mol %, thereby enabling the proportion of cleaning components in the liquid laundry detergent composition to be further increased.

[0100] The preferred form of the liquid laundry detergent composition in the above composite composition is the same as that described above for the liquid laundry detergent composition.

[0101] The film for packaging the detergent in the composite composition is not particularly limited as long as it can encapsulate the liquid laundry detergent composition of the present invention, but is preferably water-soluble. A water-soluble polymer is more preferred. Examples of water-soluble polymers include polyvinyl alcohol, polyalkylene glycol, starch or modified starch, cellulose or modified cellulose, polyacrylate, polymethacrylate, polyacrylamide, and polyvinylpyrrolidone. One or more of these may be used. Among these, polyvinyl alcohol is preferred.

[0102] The average degree of polymerization of the polymer constituting the film is not particularly limited, but is preferably 500 to 10,000, more preferably 1,000 to 8,000, and even more preferably 1,000 to 5,000.

[0103] The thickness of the film is not particularly limited, but is preferably 20 μm to 150 μm, more preferably 35 μm to 125 μm, and even more preferably 50 μm to 100 μm.

[0104] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by weight" and "%" means "% by mass."

[0105] <Measurement of Average Degree of Polymerization> The average degree of polymerization of a polymer can be determined by the method described in JIS K6726. Alternatively, the average degree of polymerization of a polymer can be determined by GPC measurement of the polymer. Apparatus: Alliance HPLC manufactured by Waters Detector: RI Column: Shodex OHpak SB-806M HQ x 3 Temperature: 40°C Flow rate: 1.0 mL / min Calibration curve: PEG standard sample manufactured by GL Sciences, Mw = 194, 410, 615, 1020, 1450, 3860, 8160, 16100, 21160, 49930, 67600, 96100, 205500, 542500, 942000 Eluent: 100 mM aqueous sodium phosphate / acetonitrile = 92 / 8

[0106] <Measurement of Saponification Degree> The saponification degree of a polymer can be determined by the method described in JIS K6726. １ The degree of saponification of the polymers obtained in the following production examples can also be determined by H NMR measurement. １ Calculated from H NMR measurement. Apparatus: Varian VNMRS600 Nuclide: １ H resonance frequency: 600 MHz Signal acquisition time: 3.4 seconds Delay time: 5 seconds Solvent: dimethyl sulfoxide-d6 Number of accumulations: 16 Calculation was performed from the ratio of the peak area from 1.90 to 2.30 ppm (derived from acetate ester in the side chain) to the peak area from 1.20 to 1.90 ppm (derived from methylene protons in the polymer main chain) in the obtained spectrum.

[0107] <Evaluation 1 of Muddy Stain Detergency> [Cleaning Process] (1) A muddy soiled cloth KC-140 (manufactured by Warwick Equest) and a standard white cloth were subjected to L ＊ , a ＊ , b ＊The value of was measured. (2) 956.3 g of ion-exchanged water was added to 59.0 g of calcium chloride dihydrate and 27.2 g of magnesium chloride hexahydrate to prepare hard water mother liquor (i). (3) 15.5 g of sodium bicarbonate, 884.5 g of pure water, and 100 g of 0.1 M HCl aqueous solution were mixed to prepare 1,000 g of base solution (ii). (4) A 1% polymer aqueous solution was prepared with ion-exchanged water so that the polymer solids content was 1%. (5) 197.03 g of ion-exchanged water was added to 47.37 g of sodium alkylbenzene sulfonate (hereinafter referred to as LAS) aqueous solution (Neopelex G25, manufactured by Kao Corporation) and stirred to prepare a 5% LAS aqueous solution (iii). (6) 4090.4 g of ion-exchanged water was added to 21.0 g of hard water mother liquor (i) and stirred, and then 0.2 g of detergent packaging film from a commercially available detergent, 84.0 g of a 5% LAS aqueous solution (iii), and 4.4 g of the base solution (ii) were added and stirred to prepare detergent solution (iv). (7) Using a Tergot-o-meter (manufactured by Daiei Scientific Co., Ltd., product name: TM-4), 995.0 g of detergent solution (iv) was added to each of four pots and the temperature was adjusted to 35°C. (8) 5.0 g of ion-exchanged water or a 1% polymer aqueous solution was added to the pot and stirred for 1 minute. (9) Three mud-stained cloths and a liquor ratio adjustment cloth (enough to make the total weight of the cloths 50 g) were added to each pot, and a washing step was carried out at 120 rpm for 20 minutes. (10) The soiled cloth and the liquor ratio adjusted cloth were removed from each pot, the water was drained by hand, and then dewatered for 1 minute in a dehydrator. [Rinsing process] (1) 4179.0 g of ion-exchanged water was added to 21.0 g of hard water mother liquor (i) and stirred to prepare a rinse solution. (2) 1000 g of rinse solution was placed in a pot and adjusted to 35°C, after which the washed soiled cloth and the liquor ratio adjusted cloth were added and stirred at 120 rpm for 3 minutes to rinse. (3) The soiled cloth and the liquor ratio adjusted cloth were removed from each pot, the water was drained by hand, and then dewatered for 1 minute in a dehydrator. (4) Steps (1) to (3) were repeated again. [Drying process] The soiled cloths that had been subjected to the washing and rinsing processes were air-dried overnight. [Calculation of cleaning rate] The mud-stained cloths and the standard white cloth after washing were measured using the DigiEye System. ＊ , a ＊ , b ＊The value of SRI (Stain Removal Index) was calculated from the following formula (II).

[0108] <Evaluation 2 of Detergency for Muddy Stain> The cleaning ratio (SRI) was calculated in the same manner as in the above <Evaluation 1 of Detergency for Muddy Stain>, except that step (5) in the [Cleaning Step] was changed to the following step (5'): (5') 168.43 g of ion-exchanged water was added to 29.07 g of an aqueous solution of sodium alkylbenzene sulfonate (hereinafter referred to as LAS) (Neopelex G25, manufactured by Kao Corporation) and stirred, and then 2.50 g of polyoxyethylene lauryl ether (hereinafter referred to as PAE) (Emulgen 108, manufactured by Kao Corporation) was added and stirred to prepare a 5% LAS / PAE aqueous solution (iii').

[0109] <Biodegradability test> The biodegradability test of the obtained vinyl alcohol polymer was carried out in accordance with OECD 301F. Preparation of culture medium: Stock culture medium solutions A to D were prepared by the following method. Solution A: Potassium dihydrogen phosphate (KH ２ P.O. ４ ) 0.850 g, dipotassium hydrogen phosphate (K ２ HPO ４ ) 2.175 g, disodium hydrogen phosphate dodecahydrate (Na ２ HPO ４ ・12H ２ 6.7217 g of ammonium chloride (NH ４ Solution B: 0.050 g of calcium chloride dihydrate (CaCl) was weighed into a 50 ml sample bottle, dissolved in an appropriate amount of water, and transferred to a 100 ml measuring flask, and then water was added up to the marked line. ２ ・2H ２ Solution C: Magnesium sulfate heptahydrate (MgSO ) 3.640 g was dissolved in an appropriate amount of water and transferred to a 100 ml measuring flask, and water was added up to the marked line. ４ ・7H ２ Solution D: Iron (III) chloride hexahydrate (FeCl ３ ・6H ２O) 0.025 g was dissolved in an appropriate amount of water and transferred to a 100 ml volumetric flask, and water was added up to the mark. The above stock medium solutions A to D were adjusted to 25°C. 10 ml of A was added to a 1 L volumetric flask using a whole pipette and diluted with approximately 800 ml of water. Then, 1 ml each of B, C, and D was added using a whole pipette and diluted up to the mark with water adjusted to 25°C. Multiple batches of the above medium were prepared according to the amount required for the test. The prepared medium was transferred to a 5 L beaker, mixed, and bubbled for at least 1 hour while stirring. Sludge Solution Preparation: The sludge used for the biodegradability test was obtained from the Minami Suita Sewage Treatment Plant. First, the concentration of the obtained sludge was measured using the following method. The obtained sludge was bubbled while stirring, and 5 ml was taken using a whole pipette and suction filtered using filter paper. Five sheets of filter paper containing sludge were prepared in this manner and dried in a dryer at 105°C for 1 hour. The sludge concentration was calculated from the average weight loss of the five sheets. This sludge was diluted with the culture medium prepared above to prepare a 1000 ppm sludge solution. Preparation of polymer aqueous solution: The obtained polymer was diluted with pure water to obtain a 2% polymer aqueous solution. Furthermore, as a standard substance, sodium benzoate was diluted with pure water to obtain a 2% sodium benzoate aqueous solution. BOD test: A pressure sensor-type BOD meter was used to measure the BOD. 144.75 g of the culture medium prepared above was weighed into a flask, and 0.75 g of a 2% polymer aqueous solution was added. Note that 0.75 g of pure water was added for the blank measurement, and 0.75 g of a 2% sodium benzoate aqueous solution was added for the standard substance measurement. The pH of the solution was then measured, and the pH was adjusted with 0.1 M hydrochloric acid aqueous solution to a pH of 7.4 ± 0.2. Then, 4.5 ml of 1000 ppm sludge solution was added to prepare the test solution. ２ CO in the absorbent holder ２1.8 g of absorbent (Yabashiri lime) was placed in the flask and set, and a BOD sensor was attached. The flask with the BOD sensor attached was stirred in a thermostatic bath at 24°C, and the BOD value was calculated from the pressure sensor. Calculation of decomposition rate: The theoretical oxygen demand (ppm) of the polymer was calculated, and the decomposition rate was calculated from the difference between the BOD value of the blank measurement and the BOD value measured using a polyalkylene oxide-containing compound. The decomposition rate 28 days after the start of the test was taken as the biodegradation rate. [Formula] Decomposition rate (%) = (biochemical oxygen consumption derived from the polymer) / (theoretical oxygen demand of the polymer) x 100

[0110] <Production Example 1> A glass reaction vessel equipped with a thermometer, a nitrogen inlet tube, a reflux condenser, and a stirrer was charged with 53.36 g of ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and the atmosphere inside the reaction vessel was replaced with nitrogen and then heated to 60°C with stirring. With stirring, a total of two types of solution were added dropwise into the reaction vessel at 60°C using separate dropping nozzles: 75.00 g of vinyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and an initiator solution (a mixed solution of 2.16 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., V-65) and 19.47 g of ethanol). The addition of the vinyl acetate and initiator solution began simultaneously, with the vinyl acetate being added over 180 minutes and the initiator solution being added over 240 minutes. After completion of all additions, the reaction solution was further heated and aged at 60°C for 8 hours to obtain a polyvinyl acetate solution. Next, 120.00 g of the obtained polyvinyl acetate solution was charged into a glass reaction vessel equipped with a thermometer and a stirrer, and 180 g of methanol was added and heated to 50°C while stirring to obtain a homogeneous solution. Subsequently, 13.94 g of a 4% sodium hydroxide-methanol suspension was added, and the mixture was stirred while maintaining the temperature at 50°C. After 120 minutes, precipitation of a polymer was confirmed, and the reaction mixture was filtered using a Kiriyama funnel to recover the precipitate. Subsequently, the precipitate was dried under reduced pressure at 60°C for 3 hours to obtain Polymer 1. The degree of polymerization was 192, and the degree of saponification was 97%.

[0111] <Production Example 2> 17.30 g of ethanol was charged into a glass reaction vessel equipped with a thermometer, a nitrogen inlet tube, a reflux condenser, and a stirrer. The atmosphere inside the reaction vessel was replaced with nitrogen, and the temperature was raised to 60 ° C. while stirring. With stirring, a total of two types of solution, 75.00 g of vinyl acetate and an initiator solution (a mixed solution of 8.66 g of V-65 and 49.05 g of ethanol), were added dropwise from separate dropping nozzles into the reaction vessel at 60 ° C. With regard to the start time of the dropwise addition, the vinyl acetate and initiator solution were added dropwise simultaneously, with the vinyl acetate being added over 180 minutes and the initiator solution being added over 240 minutes. After the completion of all the dropwise additions, the reaction solution was heated and aged at 60 ° C. for an additional 8 hours to obtain a polyvinyl acetate solution. Next, 12.47 g of the obtained polyvinyl acetate solution was charged into a glass reaction vessel equipped with a thermometer and a stirrer chip for stirring, and 17.53 g of methanol was added and the mixture was heated to 40 ° C. while stirring to obtain a homogeneous solution. Subsequently, 1.39 g of a 2% sodium hydroxide-methanol solution was added, and the mixture was stirred while maintaining the temperature at 40°C. After 17 minutes, precipitation of a polymer was confirmed, and 0.69 g of 1 M hydrochloric acid was added and the mixture was thoroughly stirred to terminate the reaction. The reaction product was collected in an eggplant-shaped flask, and the solvent was removed using an evaporator. After that, the reaction product was dried under reduced pressure at 60°C for 3 hours, yielding Polymer 2. The degree of polymerization was 157, and the degree of saponification was 88%.

[0112] <Production Example 3> 53.78 g of ethanol was charged into a glass reaction vessel equipped with a thermometer, a nitrogen inlet tube, a reflux condenser, and a stirrer. The atmosphere inside the reaction vessel was replaced with nitrogen and then heated to 60°C while stirring. With stirring, a total of two solutions, a monomer solution (a mixed solution of 150.00 g of vinyl acetate, 3.70 g of 3-mercaptopropionic acid, and 38.43 g of ethanol) and an initiator solution (a mixed solution of 4.33 g of V-65 and 49.77 g of ethanol), were each added dropwise from separate dropping nozzles into the reaction vessel at 60°C. With regard to the start time of the dropwise addition, the monomer solution and the initiator solution were added dropwise simultaneously, with the monomer solution being added dropwise over 180 minutes and the initiator solution being added dropwise over 240 minutes. After completion of all dropwise addition, the reaction solution was heated and aged at 60°C for an additional 8 hours to obtain a polyvinyl acetate solution. Next, 12.47 g of the obtained polyvinyl acetate solution was charged into a glass reaction vessel equipped with a thermometer and a stirring stirrer tip, and 17.72 g of methanol was added and heated to 40°C while stirring to obtain a homogeneous solution. Subsequently, 4.18 g of a 2% sodium hydroxide-methanol solution was added and stirred while maintaining the temperature at 40°C. After 120 minutes, precipitation of the polymer was confirmed, and 2.09 g of 1 M hydrochloric acid was added and stirred thoroughly to terminate the reaction. The reaction product was collected in an eggplant-shaped flask, and the solvent was distilled off using an evaporator. After that, the mixture was dried under reduced pressure at 60°C for 3 hours to obtain Polymer 3. The degree of polymerization was 110, and the degree of saponification was 72%.

[0113] <Production Example 4> A glass reaction vessel equipped with a thermometer and a stirrer was charged with 153.41 g of the polyvinyl acetate solution from Production Example 3, and 221.59 g of methanol was added. The mixture was heated to 40°C with stirring to obtain a homogeneous solution. Subsequently, 34.85 g of a 2% sodium hydroxide-methanol solution was added, and the mixture was stirred while maintaining the temperature at 40°C. After 120 minutes, precipitation of a polymer was confirmed, and the reaction mixture was filtered using a Kiriyama funnel to recover the precipitate. Subsequently, the precipitate was dried under reduced pressure at 60°C for 3 hours to obtain Polymer 4. The degree of polymerization was 110, and the degree of saponification was 93%.

[0114] <Production Example 5> A glass reaction vessel equipped with a thermometer and a stirrer tip was charged with 12.30 g of the polyvinyl acetate solution from Production Example 3, and 17.74 g of methanol was added. The mixture was heated to 40°C with stirring to obtain a homogeneous solution. Subsequently, 4.19 g of a 2% sodium hydroxide-methanol solution was added, and the mixture was stirred while maintaining the temperature at 40°C. After 70 minutes, 2.09 g of 1 M hydrochloric acid was added and the mixture was thoroughly stirred to terminate the reaction. The reaction product was collected in an eggplant-shaped flask, and the solvent was distilled off using an evaporator. The mixture was then dried under reduced pressure at 60°C for 3 hours to obtain Polymer 5. The degree of polymerization was 110, and the degree of saponification was 57%.

[0115] <Production Example 6> 58.41 g of ethanol was charged into a glass reaction vessel equipped with a thermometer, a nitrogen inlet tube, a reflux condenser, and a stirrer. The atmosphere inside the reaction vessel was replaced with nitrogen and then heated to 60 ° C. with stirring. With stirring, a total of two solutions, a monomer solution (a mixed solution of 150.00 g of vinyl acetate and 37.50 g of ethanol) and an initiator solution (a mixed solution of 4.33 g of V-65 and 49.77 g of ethanol), were each added dropwise from separate dropping nozzles into the reaction vessel at 60 ° C. With regard to the start time of dropping, the monomer solution and the initiator solution were started dropwise at the same time, and the monomer solution was added dropwise over 180 minutes and the initiator solution over 240 minutes. After completion of all dropping, the reaction solution was heated and aged at 60 ° C. for an additional 11 hours to obtain a polyvinyl acetate solution. Next, 12.12 g of the obtained polyvinyl acetate solution was charged into a glass reaction vessel equipped with a thermometer and a stirring stirrer tip, and 17.72 g of methanol was added and heated to 40°C while stirring to obtain a homogeneous solution. Subsequently, 1.41 g of a 2% sodium hydroxide-methanol solution was added and stirred while maintaining the temperature at 40°C. After 40 minutes, precipitation of the polymer was confirmed, and 0.70 g of 1 M hydrochloric acid was added and stirred thoroughly to terminate the reaction. The reaction product was collected in an eggplant-shaped flask, and the solvent was distilled off using an evaporator. After that, the mixture was dried under reduced pressure at 60°C for 3 hours to obtain Polymer 6. The degree of polymerization was 185 and the degree of saponification was 77%.

[0116] <Production Example 7> A glass reaction vessel equipped with a thermometer and a stirrer tip was charged with 12.20 g of the polyvinyl acetate solution from Production Example 6, and 17.70 g of methanol was added. The mixture was heated to 40°C with stirring to obtain a homogeneous solution. Subsequently, 1.41 g of a 2% sodium hydroxide-methanol solution was added, and the mixture was stirred while maintaining the temperature at 40°C. After 28 minutes, 0.70 g of 1 M hydrochloric acid was added and the mixture was thoroughly stirred to terminate the reaction. The reaction product was collected in an eggplant-shaped flask, and the solvent was distilled off using an evaporator. The mixture was then dried under reduced pressure at 60°C for 3 hours to obtain Polymer 7. The degree of polymerization was 185, and the degree of saponification was 59%.

[0117] <Production Example 8> 56.10 g of ethanol was charged into a glass reaction vessel equipped with a thermometer, a nitrogen inlet tube, a reflux condenser, and a stirrer. The atmosphere inside the reaction vessel was replaced with nitrogen and then heated to 60°C while stirring. With stirring, a total of two solutions, a monomer solution (a mixed solution of 150.00 g of vinyl acetate, 1.85 g of 3-mercaptopropionic acid, and 37.96 g of ethanol) and an initiator solution (a mixed solution of 4.33 g of V-65 and 49.77 g of ethanol), were each added dropwise from separate dropping nozzles into the reaction vessel at 60°C. With regard to the start time of the dropwise addition, the monomer solution and the initiator solution were added dropwise simultaneously, with the monomer solution being added dropwise over 180 minutes and the initiator solution being added dropwise over 240 minutes. After completion of all the dropwise additions, the reaction solution was further heated and aged at 60°C for 11 hours to obtain a polyvinyl acetate solution. Next, 153.27 g of the obtained polyvinyl acetate solution was charged into a glass reaction vessel equipped with a thermometer and a stirrer, and 221.73 g of methanol was added and heated to 40°C while stirring to obtain a homogeneous solution. Subsequently, 34.80 g of a 2% sodium hydroxide-methanol solution was added and stirred while maintaining the temperature at 40°C. After 450 minutes, precipitation of the polymer was confirmed, and the reaction mixture was filtered using a Kiriyama funnel to recover the precipitate. Subsequently, the precipitate was dried under reduced pressure at 60°C for 3 hours to obtain Polymer 8. The degree of polymerization was 122 and the degree of saponification was 92%.

[0118] <Production Example 9> 3.00 g of polyvinyl alcohol (Fujifilm Wako Pure Chemical Industries, Ltd., Polyvinyl Alcohol 500, fully saponified type) with an average degree of polymerization of 500 and a degree of saponification of approximately 98% was charged into a glass reaction vessel equipped with a thermometer and a stirring stirrer tip, and 40.00 g of pure water was added. The mixture was heated to 90°C with stirring to obtain a homogeneous solution. After the solution was cooled to 50°C, 4.99 g of a 1% aqueous solution of sodium periodate was added and the mixture was stirred while maintaining the temperature at 50°C. After 240 minutes, the reaction product was recovered to obtain Polymer 9. The degree of polymerization was 365 and the degree of saponification was 98%.

[0119] <Production Example 10> A glass reaction vessel equipped with a thermometer and a stirrer was charged with 105.04 g of polyvinyl alcohol (Fujifilm Wako Pure Chemical Industries, Ltd., Polyvinyl Alcohol 1000, partially saponified type) having an average degree of polymerization of 1000 and a degree of saponification of approximately 87%, and 586.60 g of pure water was added and heated to 90°C with stirring to obtain a homogeneous solution. After the solution was cooled to 50°C, 8.40 g of a 10% aqueous solution of sodium periodate was added and stirred while maintaining the temperature at 50°C. After 240 minutes, the reaction product was recovered to obtain Polymer 10. The degree of polymerization was 458 and the degree of saponification was 87%.

[0120] <Polymer 11> Polyvinyl alcohol having an average degree of polymerization of 262 and a degree of saponification of 80% (manufactured by SIGMA-ALDRICH Co., Ltd., polyvinyl alcohol Mw 9000-10000, 80% hydrolyzed) was used.

[0121] <Polymer 12> Polyvinyl alcohol having an average degree of polymerization of 500 and a degree of saponification of about 98% (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., polyvinyl alcohol 1000, fully saponified type) was used.

[0122] <Polymer 13> Polyvinyl alcohol having an average degree of polymerization of 500 and a degree of saponification of about 87% (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., polyvinyl alcohol 500, partially saponified type) was used.

[0123] <Production Example 14> 5.01 g of polyvinyl alcohol (Fujifilm Wako Pure Chemical Industries, Ltd., Polyvinyl Alcohol 500, fully saponified type) with an average degree of polymerization of 500 and a degree of saponification of approximately 98% was placed in a glass reaction vessel equipped with a thermometer and a stirring stirrer tip, and 40.00 g of pure water was added. The mixture was heated to 90°C with stirring to obtain a homogeneous solution. After the solution was cooled to 50°C, 5.00 g of a 2% aqueous solution of sodium periodate was added and the mixture was stirred while maintaining the temperature at 50°C. After 240 minutes, the reaction product was recovered to obtain Polymer 14. The degree of polymerization was 262 and the degree of saponification was 98%.

[0124] <Production Example 15> 6.01 g of polyvinyl alcohol (Fujifilm Wako Pure Chemical Industries, Ltd., Polyvinyl Alcohol 500, partially saponified type) with an average degree of polymerization of 500 and a degree of saponification of approximately 87% was charged into a glass reaction vessel equipped with a thermometer and a stirring stirrer tip, and 32.79 g of pure water was added. The mixture was heated to 90°C with stirring to obtain a homogeneous solution. After the solution was cooled to 50°C, 1.20 g of a 10% aqueous solution of sodium periodate was added and stirred while maintaining the temperature at 50°C. After 240 minutes, the reaction product was recovered to obtain Polymer 15. The degree of polymerization was 279 and the degree of saponification was 87%.

[0125] <Production Example 16> A glass reaction vessel equipped with a thermometer and a stirrer was charged with 105.00 g of polyvinyl alcohol (Fujifilm Wako Pure Chemical Industries, Ltd., polyvinyl alcohol 500, partially saponified) having an average degree of polymerization of 500 and a degree of saponification of approximately 87%, and 573.98 g of purified water was added. The mixture was heated to 90°C with stirring to obtain a homogeneous solution. After the solution was cooled to 50°C, 21.05 g of a 10% aqueous solution of sodium periodate was added dropwise using a dropping funnel over 20 minutes, and the mixture was stirred while maintaining the temperature at 50°C. After 240 minutes, the reaction mixture was recovered to obtain Polymer 16. The degree of polymerization was 266, and the degree of saponification was 87%.

[0126] <Production Example 17> A glass reaction vessel equipped with a thermometer and a stirrer was charged with 105.01 g of polyvinyl alcohol (Fujifilm Wako Pure Chemical Industries, Ltd., polyvinyl alcohol 500, partially saponified) having an average degree of polymerization of 500 and a degree of saponification of approximately 87%, and 532.01 g of purified water was added. The mixture was heated to 90°C with stirring to obtain a homogeneous solution. After the solution was cooled to 50°C, 63.02 g of a 10% aqueous solution of sodium periodate was added dropwise using a dropping funnel over 20 minutes, and the mixture was stirred while maintaining the temperature at 50°C. After 240 minutes, the reaction mixture was recovered to obtain Polymer 17. The degree of polymerization was 122, and the degree of saponification was 87%.

[0127] <Production Example 18> A glass reaction vessel equipped with a thermometer and a stirrer was charged with 105.01 g of polyvinyl alcohol (Fujifilm Wako Pure Chemical Industries, Ltd., Polyvinyl Alcohol 1000, partially saponified type) having an average degree of polymerization of 1000 and a degree of saponification of approximately 87%, and 586.60 g of pure water was added and heated to 90°C with stirring to obtain a homogeneous solution. After the solution was cooled to 50°C, 8.39 g of a 5% aqueous solution of sodium periodate was added and stirred while maintaining the temperature at 50°C. After 120 minutes, the reaction product was recovered to obtain Polymer 18. The degree of polymerization was 610 and the degree of saponification was 87%.

[0128] <Comparative Polymer 1> Polyvinyl alcohol having an average degree of polymerization of 3500 and a degree of saponification of about 88% (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., polyvinyl alcohol 3500, partially saponified type) was used.

[0129] <Comparative Polymer 2> Polyvinyl alcohol having an average degree of polymerization of 1650 and a degree of saponification of about 80% (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., polyvinyl alcohol, average degree of polymerization 1500 to 1800) was used.

[0130] Comparative Polymer 3 Polyvinyl alcohol having an average degree of polymerization of 1000 and a degree of saponification of about 96% (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., polyvinyl alcohol 1000, fully saponified type) was used.

[0131] <Comparative Polymer 4> Polyvinyl alcohol having an average degree of polymerization of 1500 and a degree of saponification of about 88% (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., polyvinyl alcohol (degree of polymerization: about 1500)) was used.

[0132] The degrees of polymerization and saponification of the above polymers 1 to 18 are shown in Table 1, and the degrees of polymerization and saponification of the comparative polymers 1 to 4 are shown in Table 2.

[0133]

[0134]

[0135] Examples 1 to 3 and Comparative Examples 1 to 3 The above-mentioned detergency evaluation 1 was carried out using polymers 1 to 3 obtained in Production Examples 1 to 3 and comparative polymers 1 to 3 obtained in Comparative Production Examples 1 to 3, and a surfactant. The results are shown in Table 3.

[0136]

[0137] Examples 4 and 5 and Comparative Example 4 The above-mentioned detergency evaluation 2 was carried out using polymers 1 and 4 obtained in Production Examples 1 and 4, comparative polymer 3 obtained in Comparative Production Example 3, and a surfactant. The results are shown in Table 4.

[0138]

[0139] <Compatibility Test in Liquid Laundry Detergent Formulation> [Preparation of Liquid Laundry Detergent Formulation] A liquid laundry detergent formulation was prepared using the following method. 0.50 g of lauric acid was dissolved in 1.00 g of ethanol (99.5%). 29.52 g of ion-exchanged water was added to 9.23 g of an aqueous solution of sodium alkylbenzene sulfonate (hereinafter referred to as LAS) (Neopelex G65, manufactured by Kao Corporation) and stirred thoroughly. 4.00 g of propylene glycol and 4.00 g of polyoxyethylene lauryl ether (hereinafter referred to as PAE) (Emulgen 108, manufactured by Kao Corporation) were then added, followed by 0.75 g of citric acid (anhydrous) and stirring thoroughly. A pre-dissolved mixture of lauric acid and ethanol was then added and stirred. 1.00 g of 2-aminoethanol was then added and stirred thoroughly to prepare a liquid laundry detergent formulation with a surfactant concentration of 20%. 0.50 g of lauric acid was dissolved in 1.00 g of ethanol (99.5%). 36.13 g of ion-exchanged water was added to 4.62 g of sodium alkylbenzene sulfonate (hereinafter referred to as LAS) aqueous solution (Neopelex G65, manufactured by Kao Corporation) and stirred thoroughly. Then, 4.00 g of propylene glycol and 2.00 g of polyoxyethylene lauryl ether (hereinafter referred to as PAE) (Emulgen 108, manufactured by Kao Corporation) were added, followed by 0.75 g of citric acid (anhydrous) and stirring thoroughly. A pre-dissolved lauric acid and ethanol mixture was then added and stirred. Then, 1.00 g of 2-aminoethanol was added and stirred thoroughly to prepare a liquid laundry detergent formulation with a surfactant concentration of 10%. 0.50 g of lauric acid was dissolved in 1.00 g of ethanol (99.5%). 22.90 g of ion-exchanged water was added to 13.85 g of an aqueous solution of sodium alkylbenzene sulfonate (hereinafter referred to as LAS) (Neopelex G65, manufactured by Kao Corporation) and stirred thoroughly. Then, 4.00 g of propylene glycol and 6.00 g of polyoxyethylene lauryl ether (hereinafter referred to as PAE) (Emulgen 108, manufactured by Kao Corporation) were added, followed by 0.75 g of citric acid (anhydrous) and stirring thoroughly. A pre-dissolved mixture of lauric acid and ethanol was added and stirred. Then, 1.00 g of 2-aminoethanol was added and stirred thoroughly to prepare a liquid laundry detergent formulation with a surfactant concentration of 30%.

[0140] [Compatibility Test] Polymer aqueous solutions were prepared for polymers 1, 5, 6, 7, 8, 11, 12, and 13 and comparative polymers 3 and 4 so that the polymer concentration was 20%. Compatibility tests were conducted using these polymer aqueous solutions and polymers 9 and 10. The polymer was added to 2.0 g of the prepared liquid laundry detergent formulation at each surfactant concentration so that the polymer concentration was 1%, and the solution was stirred thoroughly. The stirred solution was placed in a cell with an optical path length of 10 mm, and the transmittance was measured using a UV meter (UV-1800, manufactured by Shimadzu Corporation). A solution with a transmittance of 50% or more at 550 nm was considered to be compatible. The results are shown in Table 5, where compatible solutions were assigned a value of 1 and incompatible solutions were assigned a value of 0.

[0141]

[0142] [Calculation of regression equation showing the range of compatibility] When evaluating compatibility using a liquid laundry detergent formulation (liquid laundry detergent composition), a regression equation was calculated to determine the range of compatibility of the vinyl alcohol polymer in the liquid laundry detergent from the surfactant concentration in the evaluation solution and the average degree of polymerization and degree of saponification of the vinyl alcohol polymer. The results shown in Table 5 were entered into the statistical software JMP (manufactured by SAS). In fitting the model in JMP, the compatibility results were used as a nominal scale and the objective variable, and logistic regression was performed using the "surfactant concentration (%) in the compatibility evaluation solution" and the "average degree of polymerization (DP)" and "degree of saponification (mol%)" of the vinyl alcohol polymer as explanatory variables. A prediction equation for the probability of compatibility was calculated using logistic regression. The equation when the significant digits of the prediction equation are three digits is shown below. When the probability of compatibility is ≧0.5, the vinyl alcohol polymer is well soluble in the liquid laundry detergent formulation.

[0143]

[0144] [Compatibility Test with Addition of PEG Compounds] As PEG compounds, an 80% aqueous solution of polyethyleneimine ethoxylate (PN-100, manufactured by Nippon Shokubai Co., Ltd.) was prepared as PEG compound 1, and an 80% aqueous solution of polyethylene glycol 6000 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was prepared as PEG compound 2. A polymer aqueous solution was prepared for polymer 13 so that the polymer concentration was 20%. A compatibility test was conducted using this polymer aqueous solution and polymers 13 to 15. The polymer was added to 2.0 g of the liquid laundry detergent formulation containing each of the surfactant concentrations described above so that the polymer concentration was 1%, and the solution was thoroughly stirred. The transmittance of the solution after stirring was measured, and the compatibility with the liquid laundry detergent formulation was evaluated in the same manner as described above. The PEG compounds described above were then added to the solutions to the concentrations shown in Table 6, stirred, and the compatibility was evaluated again. The results are shown in Table 6. The addition of the PEG compounds improved the compatibility of vinyl alcohol-based polymers in liquid laundry detergent formulations. Furthermore, when ion-exchanged water in an amount equal to the PEG compound shown in Table 6 was added to a mixture of a liquid laundry detergent formulation and a polymer for which the compatibility rating was 0, no improvement in compatibility was observed.

[0145]

[0146] <Evaluation of Enzyme Activity> The activity of the enzyme (protease) was evaluated using the following method. [Preparation of Casein Solution] 0.65 g of casein (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 37.5 g of 0.1 N sodium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were weighed into a beaker and stirred to dissolve. 0.62 g of sodium dihydrogen phosphate dihydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added, followed by 61.85 g of ion-exchanged water and stirring to prepare a casein solution. [Preparation of Trichloroacetic Acid (TCA) Solution] 7.10 g of trichloroacetic acid (TCA) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 92.9 g of ion-exchanged water were weighed into a plastic bottle to prepare a TCA solution. [Preparation of Sample Solution] 59.0 g of calcium chloride dihydrate, 27.2 g of magnesium chloride hexahydrate, and 956.3 g of ion-exchanged water were added to prepare a hard water mother liquor. 0.5 g of the hardness mother liquor was then diluted 1000 times to prepare 3 dH hardness water. Polymer 1 and Polymer 16 were diluted with 3 dH hardness water to a vinyl alcohol polymer concentration of 1%, and the pH was adjusted to 7.5-8.5 with 0.01 N aqueous sodium hydroxide solution. 0.1 g of protease PU100L (Novozymes) was diluted 100 times to prepare a 1% enzyme aqueous solution. 24.9 g of 3 dH hardness water was added to 0.1 g of the 1% enzyme aqueous solution to prepare a blank sample solution. To 0.1 g of a 1% aqueous enzyme solution, 0.25 g of the aforementioned 1% aqueous polymer solution with adjusted pH was added, and then 24.65 g of 3 dH hardness water was added to prepare a sample solution.

[0147] [Enzyme Activity Evaluation] 3 mL of casein solution was placed in a screw tube using a micropipette and the temperature was adjusted in a 37°C thermostatic bath. While stirring the casein solution in the 37°C thermostatic bath, 3 mL of sample solution was added using a micropipette and stirred for 10 minutes. After 10 minutes of stirring, 3 mL of TCA solution was added and maintained for 30 minutes to stop the enzyme reaction. The reaction solution was filtered through a 0.45 μm syringe filter, and 3 mL was placed in a UV cell, and the absorbance at 280 nm was measured using a UV meter. The measured absorbance was designated as "absorbance after enzyme reaction." 3 mL of casein solution was placed in a screw tube using a micropipette and the temperature was adjusted in a 37°C thermostatic bath. 3 mL of TCA solution was added and stirred. 3 mL of sample solution was then added. The solution was filtered through a 0.45 μm syringe filter, and 3 mL was placed in a UV cell, and the absorbance at 280 nm was measured using a UV meter. The measured absorbance was defined as "enzyme unreacted absorbance." "Absorbance after enzyme reaction" - "enzyme unreacted absorbance" was defined as Δabsorbance. The results are shown in Table 7. A larger Δabsorbance indicates a larger amount of amino acids present in the filtrate and higher enzyme activity.

[0148]

[0149] <Evaluation of Sebum Detergency> [Cleaning Step] (1) Sebum-stained cloth WFK 20D and standard white cloth were stained with L using DigiEye System (manufactured by VeriVide). ＊ , a ＊ , b ＊The value of was measured. (2) 956.3 g of ion-exchanged water was added to 59.0 g of calcium chloride dihydrate and 27.2 g of magnesium chloride hexahydrate to prepare hard water mother liquor (i). (3) 15.5 g of sodium bicarbonate, 884.5 g of pure water, and 100 g of 0.1 M HCl aqueous solution were mixed to prepare 1,000 g of base solution (ii). (4) A 1% polymer aqueous solution was prepared with ion-exchanged water so that the polymer solids content was 1%. (5) 197.03 g of ion-exchanged water was added to 47.37 g of sodium alkylbenzene sulfonate (hereinafter referred to as LAS) aqueous solution (Neopelex G25, manufactured by Kao Corporation) and stirred to prepare a 5% LAS aqueous solution (iii). (6) 4091.7 g of ion-exchanged water was added to 21.0 g of hard water mother liquor (i) and stirred, followed by the addition of 84.0 g of 5% LAS aqueous solution (iii) and 3.4 g of base solution (ii) and stirring to prepare detergent solution (iv). (7) Using a Tergot-o-meter (manufactured by Daiei Scientific Co., Ltd., product name: TM-4), 995.0 g of detergent solution (iv) was added to each of four pots and the temperature was adjusted to 35°C. (8) 5.0 g of ion-exchanged water or a 1% polymer aqueous solution was added to the pot and stirred for 1 minute. (9) Five sebum-stained cloths and a liquor ratio adjustment cloth (enough to make the total weight of the cloths 50 g) were placed in each pot, and a washing step was carried out for 20 minutes at 120 rpm. (10) The soiled cloths and the liquor ratio adjustment cloth were removed from each pot, the water was drained by hand, and the cloths were then dehydrated for 1 minute in a spin dryer. [Rinsing step] (1) 4179.0 g of ion-exchanged water was added to 21.0 g of hard water mother liquor (i) and stirred to prepare a rinse solution. (2) 1000 g of rinse solution was placed in a pot and adjusted to 35°C, after which the washed soiled cloth and the liquor ratio adjusted cloth were added and stirred at 120 rpm for 3 minutes to rinse. (3) The soiled cloth and the liquor ratio adjusted cloth were removed from each pot, drained by hand, and then dehydrated for 1 minute in a spin dryer. (4) Steps (1) to (3) were repeated again. [Drying step] The soiled cloths that had been subjected to the washing and rinsing steps were air-dried overnight. [Calculation of cleaning rate] The muddy soiled cloths and the standard white cloth after washing were measured using the DigiEye System. ＊ , a ＊ , b ＊ The cleaning ratio SRI was calculated, and the difference from the SRI of the blank was taken as ΔSRI. The results are shown in Table 8.

[0150]

[0151] <Biodegradability Evaluation> The above-mentioned biodegradability test was carried out on the above-mentioned polymers 4, 6, 12, 13, and 16 to 18, and the results are shown in Table 9.

[0152]

[0153] <Evaluation 3 of Muddy Stain Detergency> [Cleaning Step] (1) A muddy stained cloth KC-140 (Warwick Equest) and a standard white cloth were subjected to a DigiEye System (VeriVide) with a D65 light source and a L ＊ , a ＊ , b ＊The value of was measured. (2) 956.3 g of ion-exchanged water was added to 59.0 g of calcium chloride dihydrate and 27.2 g of magnesium chloride hexahydrate to prepare hard water mother liquor (i). (3) 15.5 g of sodium bicarbonate, 884.5 g of pure water, and 100 g of 0.1 M HCl aqueous solution were mixed to prepare 1,000 g of base solution (ii). (4) A 1% polymer aqueous solution was prepared with ion-exchanged water so that the polymer solids content was 1%. (5) 197.03 g of ion-exchanged water was added to 47.37 g of sodium alkylbenzene sulfonate (hereinafter referred to as LAS) aqueous solution (Neopelex G25, manufactured by Kao Corporation) and stirred to prepare a 5% LAS aqueous solution (iii). (6) 4170.8 g of ion-exchanged water was added to 9.8 g of hard water mother liquor (i) and stirred, and then 15.1 g of a 5% LAS aqueous solution (iii) and 4.2 g of a base solution (ii) were added and stirred to prepare a detergent solution (iv) with a pH of 8.5. (7) Using a Tergot-o-meter (manufactured by Daiei Scientific Co., Ltd., product name: TM-4), 996.0 g of detergent solution (iv) was added to each of four pots and the temperature was adjusted to 32°C. (8) 4.0 g of ion-exchanged water or a 1% polymer aqueous solution was added to the pot and stirred for 1 minute. (9) Three mud-stained cloths and a liquor ratio adjustment cloth (in an amount such that the total weight of the cloths was 50 g) were placed in each pot, and a washing step was carried out at 100 rpm for 12 minutes. (10) The soiled cloth and the liquor ratio adjusted cloth were removed from each pot, the water was drained by hand, and then dewatered for 1.5 minutes in a dehydrator. [Rinsing process] (1) 4190.2 g of ion-exchanged water was added to 9.8 g of hard water mother liquor (i) and stirred to prepare a rinse solution. (2) 1000 g of rinse solution was placed in a pot and adjusted to 25°C, after which the washed soiled cloth and the liquor ratio adjusted cloth were added and stirred at 100 rpm for 3 minutes to rinse. (3) The soiled cloth and the liquor ratio adjusted cloth were removed from each pot, the water was drained by hand, and then dewatered for 1.5 minutes in a dehydrator. [Drying process] The soiled cloths that had been subjected to the washing and rinsing processes were air-dried overnight. [Calculation of cleaning rate] The mud-stained cloths and the standard white cloth after washing were measured using the DigiEye System with a D65 light source and L ＊ , a ＊ , b ＊The value of the anti-redeposition ability was measured for the white cloth portion of the mud-stained cloth after washing that was not soiled with mud, and for the standard white cloth, using a spectrophotometer (manufactured by Nippon Denshoku Industries Co., Ltd., product name: SE6000) with a D65 light source, a viewing angle of 2°, and L ＊ , a ＊ , b ＊ After washing, the ΔE value of the white cloth portion of the soiled cloth and the standard white cloth was measured. ＊ was calculated from the above formula (III) to evaluate the re-soiling property on the white cloth. ＊ The smaller the value, the less re-contamination occurs and the higher the re-contamination prevention ability.

[0154] <Evaluation 4 of cleaning power for muddy soil> The cleaning rate SRI and anti-redeposition ability ΔE were measured by changing the step (6) in the [Cleaning step] of the above <Evaluation 3 of cleaning power for muddy soil> to the following step (6'), and the other steps were carried out in the same manner. ＊ (6') 60.0 g of ion-exchanged water was added to 10.0 g of a cationic surfactant aqueous solution of dimethyllaurylamine oxide (Amphitol 20N, manufactured by Kao Corporation) and stirred to obtain a 5% aqueous solution of dimethyllaurylamine oxide. 4,175.1 g of ion-exchanged water was added to 9.8 g of hard water mother liquor (i) and stirred, and 11.3 g of a 5% aqueous solution of LAS (iii) and 3.8 g of a 5% aqueous solution of dimethyllaurylamine oxide were added and stirred to prepare a detergent solution (iv) with a pH of 8.5.

[0155] The cleaning rate SRI and anti-resoiling ability ΔE obtained in <Mud soil cleaning power evaluation 3> and <Mud soil cleaning power evaluation 4> ＊ The results are shown in Table 10. This shows that the lower the proportion of cationic surfactant in the surfactants contained in the detergent formulation, the higher both the muddy soil removal rate and the anti-soiling ability.

[0156]

[0157] <Evaluation 1 of cleaning power for food stains> [Cleaning process] (1) A butter-stained cloth KC-132 (Warwick Equest) and a standard white cloth were subjected to a DigiEye System (VeriVide) with a D65 light source. ＊ , a ＊ , b＊ The value of was measured. (2) 956.3 g of ion-exchanged water was added to 59.0 g of calcium chloride dihydrate and 27.2 g of magnesium chloride hexahydrate to prepare hard water mother liquor (i). (3) 15.5 g of sodium bicarbonate, 884.5 g of pure water, and 100 g of 0.1 M HCl aqueous solution were mixed to prepare 1,000 g of base solution (ii). (4) A 1% polymer aqueous solution was prepared with ion-exchanged water so that the polymer solids content was 1%. (5) 197.03 g of ion-exchanged water was added to 47.37 g of sodium alkylbenzene sulfonate (hereinafter referred to as LAS) aqueous solution (Neopelex G25, manufactured by Kao Corporation) and stirred to prepare a 5% LAS aqueous solution (iii). (6) 4141.7 g of ion-exchanged water was added to 9.8 g of hard water mother liquor (i) and stirred, and 42.0 g of 5% LAS aqueous solution (iii) and 6.4 g of base solution (ii) were added and stirred to prepare a detergent solution (iv) with a pH of 8.5. (7) Using a Tergot-o-meter (manufactured by Daiei Scientific Co., Ltd., product name: TM-4), 996.0 g of detergent solution (iv) was added to each of four pots and the temperature was adjusted to 32°C. (8) 4.0 g of ion-exchanged water or a 1% polymer aqueous solution was added to the pot and stirred for 1 minute. (9) Three butter-stained cloths and a liquor ratio adjustment cloth (in an amount such that the total weight of the cloths was 50 g) were placed in each pot, and a washing step was carried out at 100 rpm for 12 minutes. (10) The soiled cloth and the liquor ratio adjusted cloth were removed from each pot, the water was drained by hand, and then dewatered for 1.5 minutes in a dehydrator. [Rinsing process] (1) 4190.2 g of ion-exchanged water was added to 9.8 g of hard water mother liquor (i) and stirred to prepare a rinse solution. (2) 1000 g of rinse solution was placed in a pot and adjusted to 25°C, after which the washed soiled cloth and the liquor ratio adjusted cloth were added and stirred at 100 rpm for 3 minutes to rinse. (3) The soiled cloth and the liquor ratio adjusted cloth were removed from each pot, the water was drained by hand, and then dewatered for 1.5 minutes in a dehydrator. [Drying process] The soiled cloths that had been subjected to the washing and rinsing processes were air-dried overnight. [Calculation of cleaning rate] The butter-stained cloths and the standard white cloth after washing were analyzed using the DigiEye System with a D65 light source and L ＊ , a ＊ , b ＊ The value of was measured, and the cleaning ratio SRI was calculated from the above formula (II).

[0158] <Food Soil Detergency Evaluation 2> The cleaning ratio (SRI) was calculated in the same manner as in the above <Food Soil Detergency Evaluation 1>, except that step (6) in the [Cleaning Step] was changed to the following step (6'). (6') 60.0 g of ion-exchanged water was added to 10.0 g of a cationic surfactant aqueous solution of dimethyllaurylamine oxide (Amphitol 20N, manufactured by Kao Corporation) and stirred to obtain a 5% dimethyllaurylamine oxide aqueous solution. 4148.2 g of ion-exchanged water was added to 9.8 g of hard water mother liquor (i) and stirred, and then 31.5 g of a 5% LAS aqueous solution (iii) and 10.5 g of a 5% dimethyllaurylamine oxide aqueous solution were added and stirred to prepare a detergent solution (iv) with a pH of 8.5.

[0159] The results of the cleaning ratio SRI obtained in the food stain cleaning power evaluation 1 (the proportion of cationic surfactant in the surfactants was 0%) and the food stain cleaning power evaluation 2 (the proportion of cationic surfactant in the surfactants was 25%) are shown in Table 11. This shows that the cleaning ratio of food stains is higher when the proportion of cationic surfactant in the surfactants in the detergent formulation is lower.

[0160]

[0161] <Mud Stain Detergency Evaluation 5> [Preparation of Liquid Detergent Formulation 1 for Evaluation] Liquid detergent formulation 1 for evaluation was prepared by the following method. 55.23 g of ion-exchanged water was added to 44.77 g of an LAS aqueous solution (Neopelex G65, manufactured by Kao Corporation) and stirred thoroughly to obtain a 29% LAS aqueous solution. 1.67 g of lauric acid was dissolved in a mixed solution of 0.84 g of ethanol (99.5%) and 1.67 g of propylene glycol. 0.83 g of 2-aminoethanol, 1.67 g of sodium p-toluenesulfonate, and 4.17 g of ion-exchanged water were added to this solution and stirred thoroughly. 65.22 g of a 23% LAS aqueous solution and 2.50 g of citric acid were added to this solution and stirred, followed by the addition of 2.78 g of a 48% sodium hydroxide aqueous solution. Finally, 18.66 g of ion-exchanged water was added and stirred thoroughly. In this way, liquid detergent formulation 1 for evaluation, in which the only surfactant in the detergent formulation was LAS, was obtained. Preparation of Liquid Detergent Formulation 2 for Evaluation Liquid Detergent Formulation 2 for evaluation was prepared by the following method. 64.62 g of ion-exchanged water was added to 35.38 g of an LAS aqueous solution (Neopelex G65, manufactured by Kao Corporation) and stirred thoroughly to obtain a 23% LAS aqueous solution. 1.67 g of lauric acid was dissolved in a mixed solution of 0.84 g of ethanol (99.5%) and 1.67 g of propylene glycol. 0.83 g of 2-aminoethanol, 1.67 g of sodium p-toluenesulfonate, and 4.17 g of ion-exchanged water were added to this solution, followed by 2.50 g of PAE (Emulgen 108, manufactured by Kao Corporation) and stirring thoroughly. 42.93 g of a 29% LAS aqueous solution and 2.50 g of citric acid were added to this solution and stirred, followed by 2.78 g of a 48% sodium hydroxide aqueous solution. Finally, 38.45 g of ion-exchanged water was added and stirred thoroughly. In this way, evaluation liquid detergent formulation 2 containing LAS and PAE as surfactants was obtained. [Cleaning process] (1) The mud-stained cloth KC-140 (Warwick Equest) and the standard white cloth were subjected to L65 light source and DigiEye System (VeriVide). ＊ , a ＊ , b ＊The value of was measured. (2) 956.3 g of ion-exchanged water was added to 59.0 g of calcium chloride dihydrate and 27.2 g of magnesium chloride hexahydrate to prepare hard water mother liquor (i). (3) A 1% polymer aqueous solution was prepared with ion-exchanged water so that the polymer solids content was 1%. (4) 4174.8 g of ion-exchanged water was added to 21.0 g of hard water mother liquor (i) and stirred, and 5.0 g of evaluation liquid detergent formulation 1 or evaluation liquid detergent formulation 2 was added and stirred to prepare detergent solution (ii). (5) Using a Tergot-o-meter (manufactured by Daiei Scientific Co., Ltd., product name: TM-4), 998.0 g of detergent solution (ii) was added to each of four pots and the temperature was adjusted to 32°C. (6) 2.0 g of ion-exchanged water or 1% polymer aqueous solution was added to the pot and stirred for 1 minute. (7) Three pieces of mud-stained fabric and a bath ratio-adjusted fabric (enough to make the total fabric weight 50 g) were placed in each pot, and a washing process was carried out at 100 rpm for 12 minutes. (8) The soiled fabrics and the bath ratio-adjusted fabric were removed from each pot, the water was drained by hand, and then the fabric was dehydrated for 1.5 minutes in a spin dryer. [Rinsing Process] (1) 4179.0 g of ion-exchanged water was added to 21.0 g of hard water mother liquor (i) and stirred to prepare a rinse solution. (2) 1000 g of rinse solution was placed in a pot and adjusted to 25°C, after which the washed soiled fabrics and the bath ratio-adjusted fabric were placed in the pot and stirred at 100 rpm for 3 minutes to rinse. (3) The soiled fabrics and the bath ratio-adjusted fabric were removed from each pot, the water was drained by hand, and then the fabric was dehydrated for 1.5 minutes in a spin dryer. [Drying Process] The soiled fabrics that had undergone the washing and rinsing processes were air-dried overnight. [Calculation of cleaning rate] After cleaning, the mud-stained cloth and the standard white cloth were measured using the DigiEye System and a D65 light source. ＊ , a ＊ , b ＊ The value of the anti-redeposition ability was measured for the white cloth portion of the mud-stained cloth after washing that was not soiled with mud, and for the standard white cloth, using a spectrophotometer (manufactured by Nippon Denshoku Industries Co., Ltd., product name: SE6000) with a D65 light source, a viewing angle of 2°, and L ＊ , a ＊ , b ＊ After washing, the ΔE value of the white cloth portion of the soiled cloth and the standard white cloth was measured. ＊was calculated from the above formula (III) and the re-soiling property on white cloth was evaluated. Detergency evaluation was carried out for each of evaluation liquid detergent formulation 1 (proportion of nonionic surfactant in the surfactants: 0%) and evaluation liquid detergent formulation 2 (proportion of nonionic surfactant in the surfactants: 17%), and the results of evaluation of cleaning rate and anti-re-soiling ability are shown in Table 12. This shows that the higher the proportion of nonionic surfactant in the surfactants in the detergent formulation, the higher both the cleaning rate of muddy soils and the anti-re-soiling ability.

[0162]

Claims

1. A liquid laundry detergent composition comprising a vinyl alcohol polymer and a surfactant, wherein the vinyl alcohol polymer is represented by the following formula (1): and further having a structural unit (a) represented by the following formula (2): and a structural unit (b) represented by the following formula: and a structural unit (c) other than the structural unit (a) and the structural unit (b), wherein the content ratio of each structural unit relative to 100 mol% of the total amount of all structural units is structural unit (a) / structural unit (b) / other structural unit (c) = 50-100 / 0-50 / 0-20 mol%, and the average degree of polymerization is 50-800, the content ratio of the vinyl alcohol-based polymer is 0.3-10 mass% relative to 100 mass% of the liquid laundry detergent composition, the content ratio of the surfactant is 10-80 mass% relative to 100 mass% of the liquid laundry detergent composition, the content ratio of the cationic surfactant is 20 mass% or less relative to 100 mass% of the surfactant, and the content ratio of the inorganic builder is 50 mass% or less relative to 100 mass% of the liquid laundry detergent composition.

2. The liquid laundry detergent composition according to claim 1, wherein the compatibility probability 1 / (1 + Exp(-y)), expressed using y as defined in the following formula (I), is 0.5 or greater: y = 73.7 - 0.418 x α - 0.725 x β - 0.00332 x γ (I) (wherein α represents the surfactant content (mass%) in the evaluation liquid when evaluating compatibility using the liquid laundry detergent composition, β represents the degree of saponification (mol%) of the vinyl alcohol polymer, and γ represents the average degree of polymerization of the vinyl alcohol polymer.) 3. A liquid laundry detergent composition according to claim 1 or 2, wherein the surfactant comprises an anionic surfactant.

4. A liquid laundry detergent composition according to any one of claims 1 to 3, wherein the surfactant comprises an anionic surfactant and a nonionic surfactant.

5. A liquid laundry detergent composition according to any one of claims 1 to 4, wherein the surfactant comprises an anionic surfactant and a nonionic surfactant, and the proportion of the anionic surfactant relative to the total of the anionic surfactant and the nonionic surfactant (100% by mass) is 30% by mass or more.

6. A liquid laundry detergent composition according to claim 4 or 5, wherein the content of the nonionic surfactant is 5 to 70 mass % relative to 100 mass % of the total surfactant amount.

7. A liquid laundry detergent composition according to any one of claims 1 to 6, comprising a polyalkylene glycol compound.

8. The liquid laundry detergent composition according to claim 7, wherein the content of the polyalkylene glycol compound is 100 to 1000% by mass relative to 100% by mass of the vinyl alcohol polymer.

9. A liquid laundry detergent composition according to any one of claims 1 to 8, comprising an enzyme.

10. A composite composition in which a liquid laundry detergent composition is encapsulated in a detergent packaging film, the liquid laundry detergent composition comprising a vinyl alcohol-based polymer and a surfactant, the vinyl alcohol-based polymer being represented by the following formula (1): and further having a structural unit (a) represented by the following formula (2): and a structural unit (c) other than the structural unit (a) and the structural unit (b), wherein the proportions of the structural units relative to 100 mol % of the total amount of all structural units are structural unit (a) / structural unit (b) / other structural unit (c)=50-100 / 0-50 / 0-20 mol %, and the average degree of polymerization is 50-800.

11. The composite composition according to claim 10, wherein the surfactant content is 50 to 80% by weight, based on 100% by weight of the liquid laundry detergent composition.

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