Liquid cleaning products

Abstract

To provide a liquid detergent article that has excellent detergency but yet suppresses the time-dependent embrittlement of a container made from a water-soluble film, and can maintain an excellent feel and appearance.SOLUTION: The present invention relates to a liquid detergent article in which a liquid detergent composition is enclosed in a container made of a water-soluble film. The liquid detergent composition contains: component (A) of a surfactant; component (B) of carbonate; and component (C), wherein the content of the component (B) is 0.1-5 mass% with respect to the total mass of the liquid detergent composition, and the component (C) is selected from component (C1) of glycerin etc., component (C2) of propylene glycol etc., and component (C3) of sorbitol.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a liquid detergent article in which a liquid detergent composition is sealed in a container made of a water-soluble film. [Background technology]

[0002] Various liquid laundry detergent compositions have been proposed. For example, Patent Document 1 discloses a liquid laundry detergent composition containing an alkali metal carbonate or alkali metal hydrogencarbonate and an inorganic silicon compound in addition to a surfactant. Carbonates such as alkali metal carbonates are known as components that improve detergency.

[0003] On the other hand, a liquid detergent article (so-called liquid tablet detergent) in which a liquid detergent composition is sealed in a container made of a water-soluble film is known (Patent Document 2). Liquid tablet detergents save users the trouble of measuring out the liquid detergent composition and eliminate the risk of spilling the liquid detergent composition during the measuring process, and are therefore attracting attention as liquid detergent products that are highly convenient for cleaning textile products such as clothing. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-169439 [Patent Document 2] Special Publication No. 2008-518861 Summary of the Invention [Problem to be solved by the invention]

[0005] The present inventors investigated the incorporation of carbonate into a liquid detergent composition enclosed in a water-soluble film container in order to enhance the detergency of a convenient liquid tablet detergent. However, when the present inventors formed a liquid detergent composition containing sodium carbonate into tablets and stored them, they found that the water-soluble film became brittle, causing minute cracks on the surface, making the tablets cloudy and rough. Therefore, an object of the present invention is to provide a liquid detergent article that has excellent cleaning power, while suppressing embrittlement of the water-soluble film container over time and maintaining a good feel and appearance. [Means for solving the problem]

[0006] In order to achieve the above object, the present invention employs the following configuration. [1] A liquid detergent article in which a liquid detergent composition is enclosed in a container made of a water-soluble film, The liquid detergent composition contains the following component (A), the following component (B), and component (C) which is one or more selected from the following components (C1), (C2), and (C3): A liquid detergent article, wherein the content of the following component (B) is 0.1 to 5 mass % relative to the total mass of the liquid detergent composition: (A) Component: surfactant. (B) Ingredient: Carbonate. Component (C1): One or more selected from the group consisting of glycerin, (poly)alkylene glycol (mono- or di-)alkyl ethers consisting of a (poly)alkylene glycol unit having 2 to 4 carbon atoms and an alkanol having 1 to 5 carbon atoms, and alkyl glyceryl ethers having an alkyl having 1 to 8 carbon atoms. Component (C2): one or more selected from propylene glycol and 3-methoxy-3-methyl-1-butanol. (C3) Ingredient: Sorbitol. [Effects of the Invention]

[0007] The liquid detergent article of the present invention has excellent detergency, while suppressing embrittlement of the water-soluble film container over time, and can maintain a good feel and appearance. DETAILED DESCRIPTION OF THE INVENTION

[0008] The liquid detergent article of the present invention is a liquid detergent composition enclosed in a container made of a water-soluble film. In this specification and claims, water solubility means that a 30 mm square water-soluble film test piece is placed in 300 mL of water at 25°C and stirred, and completely dissolves within 120 seconds.

[0009] [Water-soluble film] Examples of resins constituting the water-soluble film that constitutes the container include polyvinyl alcohol, polyvinylpyrrolidone, polyalkylene oxide, acrylamide, acrylic acid, cellulose, cellulose ether, cellulose ester, cellulose amide, polyvinyl acetate, polycarboxylic acid or its salt, polyamino acid or peptide, polyamide, polyacrylamide, copolymer of maleic acid and acrylic acid, polysaccharides including starch and gelatin, natural rubbers such as xanthan or carrageenan, etc. Among these materials, polyvinyl alcohol is preferred.

[0010] The water-soluble film contains a plasticizer, which may be one or more of polyhydric alcohols such as glycerin, diglycerin, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, trimethylolpropane, pentaerythritol, or 1,3-butanediol, polyethers such as polyethylene glycol or polypropylene glycol, polyvinylamides such as polyvinylpyrrolidone, phenol derivatives such as bisphenol A or bisphenol S, amide compounds such as N-methylpyrrolidone or dimethylacetamide, compounds in which ethylene oxide is added to polyhydric alcohols such as glycerin, pentaerythritol, or sorbitol, or water.

[0011] For the purpose of improving water solubility, it is preferable to use glycerin, diglycerin, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, trimethylolpropane, polyethylene glycol, or polyvinylpyrrolidone, and in particular, from the viewpoint of the effect of suppressing a decrease in water solubility of the film due to bleed-out of the plasticizer, it is particularly preferable to use glycerin, diglycerin, trimethylolpropane, polyethylene glycol, or polyvinylpyrrolidone.

[0012] The content of the plasticizer contained in the water-soluble film is preferably 1 to 50 mass % relative to the mass of the polyvinyl alcohol, and more preferably 20 to 40 mass %. When the content of the plasticizer contained in the water-soluble film is within the above-mentioned preferred range, the container can be given appropriate flexibility.

[0013] The water-soluble film may contain additives such as inorganic fillers (e.g., silica, heavy, light or surface-treated calcium carbonate, aluminum hydroxide, aluminum oxide, titanium oxide, diatomaceous earth, barium sulfate, calcium sulfate, zeolite, zinc oxide, silicic acid, silicates, mica, magnesium carbonate, kaolin, clays such as halloysite, pyrophyllite and sericite, talc, etc.), colorants, fragrances, extenders, antifoaming agents, release agents, UV absorbers, surfactants, carboxymethylcellulose, polyacrylamide, polyacrylic acid or salts thereof, methylcellulose, hydroxymethylcellulose, and other water-soluble polymers, as needed.

[0014] Examples of commercially available water-soluble films include those sold by Monosol LLC (Merrillville, Indiana, USA) under the trade names Monosol M8310, M8312, M8775, M8630, M7061, and M8900.

[0015] [Liquid detergent composition] The liquid detergent composition contains components (A), (B), and (C). It may also contain enzymes, chelating agents, antibacterial agents, antioxidants, other ingredients, and other solvents as needed. The liquid detergent composition of the present invention preferably contains less water than conventional detergent compositions.

[0016] <Component (A): Surfactant> Examples of the component (A) include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and semi-polar surfactants. As the component (A), one type of surfactant may be used, or two or more types may be used in combination. From the viewpoint of further enhancing detergency, the component (A) preferably contains a nonionic surfactant and an anionic surfactant. In addition to the nonionic surfactant and the anionic surfactant, one or more of a cationic surfactant, an amphoteric surfactant and a semi-polar surfactant may be used in combination.

[0017] <Nonionic surfactants> Examples of nonionic surfactants include polyoxyalkylene-type nonionic surfactants, alkylphenols, alkylene oxide adducts of higher amines, etc., polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamines, fatty acid alkanolamides, polyhydric alcohol fatty acid esters or their alkylene oxide adducts, polyhydric alcohol fatty acid ethers, alkyl (or alkenyl) amine oxides, alkylene oxide adducts of hydrogenated castor oil, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, alkyl glycosides, etc. In this specification, higher amine means an amine having 8 to 22 carbon atoms.

[0018] Among the above nonionic surfactants, polyoxyalkylene nonionic surfactants are preferred from the viewpoints of excellent sebum cleansing power, appropriate viscosity, and enhanced storage stability. Examples of polyoxyalkylene-type nonionic surfactants include a compound represented by the following general formula (a1) (hereinafter, sometimes referred to as "compound (a1)") and a compound represented by the following general formula (a2) (hereinafter, sometimes referred to as "compound (a2)"). The compound (a1) is a fatty acid alkenyl ester. The compound (a2) is an alcohol-type nonionic surfactant. R 11 -C(=O)O-[(EO) s / (PO) t ]-(EO) u -R 12 (a1) R 13 -O-[(EO) v / (PO) w ]-(EO) x -H···(a2)

[0019] In general formula (a1), R 11 is a hydrocarbon group having 7 to 22 carbon atoms, and R 12 represents an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, EO represents an oxyethylene group, PO represents an oxypropylene group, s represents the average number of repeats of EO and is a number from 3 to 20, t represents the average number of repeats of PO and is a number from 0 to 6, and u represents the average number of repeats of EO and is a number from 0 to 20. When t is 1 or more, [(EO) s / (PO) t In the above formula, the oxyethylene group and the oxypropylene group may be randomly polymerized or block polymerized. The average number of repetitions can be measured by gas chromatography or the like.

[0020] In general formula (a2), R 13 is a hydrocarbon group having 7 to 22 carbon atoms, EO represents an oxyethylene group, PO represents an oxypropylene group, v represents the average number of repeats of EO and is a number from 3 to 20, w represents the average number of repeats of PO and is a number from 0 to 6, and x represents the average number of repeats of EO and is a number from 0 to 20. When w is 1 or more, [(EO)v / (PO) w In the above formula, the oxyethylene group and the oxypropylene group may be randomly polymerized or block polymerized. The average number of repetitions can be measured by gas chromatography or the like.

[0021] In general formula (a1), R 11 The hydrocarbon group preferably has 8 to 22 carbon atoms, more preferably 9 to 21 carbon atoms, more preferably 10 to 21 carbon atoms, and even more preferably 11 to 18 carbon atoms. 11 The hydrocarbon group may be a straight chain or a branched chain, and may or may not have an unsaturated bond. R 12 The alkyl group has 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. R 12 The alkenyl group in has 2 to 6 carbon atoms, preferably 2 to 3 carbon atoms. s+u is preferably 3 to 20, more preferably 5 to 18. When s+u is equal to or greater than the lower limit, deterioration of the raw material odor is easily suppressed. When s+u is equal to or less than the upper limit, the HLB value can be suppressed, and the cleansing ability against sebum stains is easily improved. The HLB value indicates the degree of affinity of a surfactant for water and oil. The HLB value ranges from 0 to 20, with the closer to 0 the higher the lipophilicity and the closer to 20 the higher the hydrophilicity. t is a number of 0 to 6, and preferably 0 to 3. If t exceeds the upper limit, the storage stability of the liquid detergent at high temperatures tends to decrease.

[0022] In general formula (a2), R 13 The number of carbon atoms is preferably 10 to 22, more preferably 10 to 20, and even more preferably 10 to 18. R 13 may be a straight-chain hydrocarbon group, or may be a group selected from a branched-chain primary hydrocarbon group and a straight-chain secondary hydrocarbon group. R 13When is a linear hydrocarbon group, v+x is preferably 3 to 20, more preferably 5 to 18, further preferably 6 to 18, and particularly preferably 7 to 15. w is a number of 0 to 6, and preferably 0 to 3. R 13 When is a group selected from branched chain primary hydrocarbon groups and straight chain secondary hydrocarbon groups, v+x is preferably 3 to 18, particularly preferably 3 to 8, and w is preferably 0.

[0023] The mole number distribution of ethylene oxide or propylene oxide added is not particularly limited. The distribution of the number of moles of ethylene oxide or propylene oxide added tends to vary depending on the reaction method used to produce the nonionic surfactant. For example, when ethylene oxide or propylene oxide is added to a hydrophobic raw material using a common alkali catalyst such as sodium hydroxide or potassium hydroxide, the distribution of the number of moles of ethylene oxide or propylene oxide added tends to be relatively wide. 3+ , Ga 3+ , In 3+ , Tl 3+ , Co 3+ ,Sc. 3+ , La 3+ , Mn 2+ When ethylene oxide or propylene oxide is added to a hydrophobic raw material using a specific alkoxylation catalyst such as magnesium oxide to which a metal ion such as ethylene oxide or propylene oxide has been added, the mole number distribution of the ethylene oxide or propylene oxide added tends to be a relatively narrow distribution.

[0024] <Anionic surfactants> Examples of anionic surfactants include carboxylic acid-type anionic surfactants such as linear alkylbenzenesulfonic acid or its salt (LAS), α-olefinsulfonic acid or its salt (AOS), linear or branched alkyl sulfate ester or its salt (AS), polyoxyalkylene alkyl(alkenyl) ether sulfate ester or its salt (AES), alkyl group-containing alkanesulfonic acid or its salt, α-sulfofatty acid ester or its salt, internal olefinsulfonic acid or its salt (IOS), hydroxyalkanesulfonic acid or its salt (HAS), alkyl ether carboxylic acid or its salt, polyoxyalkylene ether carboxylic acid or its salt, alkylamide ether carboxylic acid or its salt, alkenylamide ether carboxylic acid or its salt, and acylaminocarboxylic acid or its salt; and phosphate ester-type anionic surfactants such as alkyl phosphate ester or its salt, polyoxyalkylene alkyl phosphate ester or its salt, polyoxyalkylene alkylphenyl phosphate ester or its salt, and glycerin fatty acid ester monophosphate ester or its salt. Examples of salt forms of anionic surfactants include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, etc.), and alkanolamine salts (monoethanolamine salts, diethanolamine salts, etc.). These anionic surfactants may be used alone or in combination of two or more. The anionic surfactants are preferably LAS, AOS, AS, and AES, and among them, LAS and AES are more preferred from the viewpoint of enhancing detergency. The liquid detergent preferably contains at least AES, and more preferably contains both LAS and AES.

[0025] The polyoxyalkylene alkyl(alkenyl) ether sulfate or its salt (AES) is represented by the following general formula (A4). R 17 -O-[(EO) m / (PO) n ]-SO3 - M + ···(A4) (In general formula (A4), R 17 is a linear or branched alkyl group having 8 to 20 carbon atoms or a linear or branched alkenyl group having 8 to 20 carbon atoms. EO is an oxyethylene group. PO is an oxypropylene group. m is a number of 0.1 or more representing the average number of repetitions of EO. n is a number of 0 to 6 representing the average number of repetitions of PO. [(EO) m / (PO) n ] indicates that there is no restriction on the order of EO and PO, and M + is the countercation.)

[0026] The AES preferably has a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms, to which an average of 1 to 5 moles of alkylene oxide is added. The number of carbon atoms in the alkyl or alkenyl group is preferably 10 to 20, more preferably 12 to 14. In particular, a linear alkyl group having 10 to 20 carbon atoms is preferred, and a linear alkyl group having 12 to 14 carbon atoms is more preferred. Specific examples include a dodecyl group, a tridecyl group, and a tetradecyl group.

[0027] m is preferably from 0.1 to 5, more preferably from 0.1 to 3, further preferably from 0.5 to 2, and particularly preferably from 0.5 to 1.5. n is 0 to 6, preferably 0 to 3, and more preferably 0. m+n is preferably greater than 0, and more preferably 1 to 5.

[0028] If n is not 0, that is, if AES has EO and PO, then [(EO) m / (PO) n In the above, there is no particular limitation on the distribution (arrangement order) of EO and PO, and they may be arranged in a block form or randomly. 17 -O-" or PO may be bonded to "R 17 It may be bonded to "-O-". Examples of methods for arranging EO and PO in a block form include a method of introducing ethylene oxide and then propylene oxide, a method of introducing propylene oxide and then ethylene oxide, and a method of introducing ethylene oxide, then propylene oxide, and then ethylene oxide.

[0029] (higher fatty acids) A "higher fatty acid" is a fatty acid having 8 to 22 carbon atoms. By including a higher fatty acid (salt), the liquid detergent composition can improve its rinsing properties. Improving the rinsing properties allows for a reduction in the number of rinsing steps required after the cleaning step. The incorporation of higher fatty acids (salts) tends to reduce liquid stability. By adjusting the pH of the liquid detergent composition to above 7, liquid stability can be improved. The higher fatty acid is preferably a chain monocarboxylic acid having 8 to 18 carbon atoms.

[0030] The higher fatty acid is represented by the following general formula (A5). R 1 -COOH···(A5) (In formula general (A5), R 1 is an aliphatic hydrocarbon group having 7 to 17 carbon atoms. In general formula (A5), R 1 The aliphatic hydrocarbon group R may be linear or branched. 1 As the alkyl group, a straight or branched chain alkyl group or a straight or branched chain alkenyl group is preferred. R 1 The number of carbon atoms in R is 7 to 17, and preferably 11 to 17. 1 If the number of carbon atoms in R is equal to or greater than the lower limit, the effect of preventing recontamination is enhanced. 1 When the number of carbon atoms is equal to or less than the upper limit, the solubility in water is increased.

[0031] Examples of salt forms of higher fatty acids (salts) include alkali metal salts, alkaline earth metal salts, amine salts, and ammonium salts. Examples of alkali metal salts include sodium salts and potassium salts. Examples of alkaline earth metal salts include calcium salts and magnesium salts. Examples of amine salts include alkanolamine salts (monoethanolamine salts, diethanolamine salts, triethanolamine salts, etc.). These higher fatty acids (salts) may be used alone or in combination of two or more. Furthermore, the higher fatty acids (salts) may be a mixture of fatty acids with a single chain length or a mixture of fatty acids with two or more chain lengths. The higher fatty acid (salt) preferably contains coconut fatty acid or a salt thereof.

[0032] Cationic surfactants Examples of cationic surfactants include long-chain aliphatic amidoalkyl tertiary amines or salts thereof, such as caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, behenic acid dimethylaminopropylamide, and oleic acid dimethylaminopropylamide; aliphatic ester alkyl tertiary amines or salts thereof, such as palmitate ester propyldimethylamine and stearate ester propyldimethylamine; palmitic acid diethanolaminopropylamide; and quaternized compounds such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, and alkylpyridinium salts. Examples of salt forms of cationic surfactants include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, etc.), and alkanolamine salts (monoethanolamine salts, diethanolamine salts, etc.). These cationic surfactants may be used alone or in combination of two or more.

[0033] <Amphoteric surfactant> Examples of amphoteric surfactants include alkylbetaine type, alkylamidebetaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamidecarboxylic acid type, amide amino acid type, and phosphoric acid type amphoteric surfactants. These amphoteric surfactants may be used alone or in combination of two or more.

[0034] Semi-polar surfactants Examples of the semi-polar surfactant include alkylamine oxide and alkylamidopropyldimethylamine oxide. These semi-polar surfactants may be used alone or in combination of two or more.

[0035] The total content of component (A) is 40% by mass or more, preferably 45% by mass or more, based on the total mass of the liquid detergent composition. The total content of component (A) is preferably 75% by mass or less, more preferably 70% by mass or less, based on the total mass of the liquid detergent composition. That is, the total content of component (A) is preferably 40 to 75% by mass, more preferably 45 to 70% by mass, based on the total mass of the liquid detergent composition. If the total content of component (A) is equal to or greater than the above lower limit, sufficient detergency can be obtained.

[0036] When component (A) contains a nonionic surfactant, the content of the nonionic surfactant is preferably 20 to 60 mass %, more preferably 25 to 40 mass %, and particularly preferably 25 to 35 mass %, based on the total mass of the liquid detergent composition. When the content of the nonionic surfactant is equal to or greater than the above-mentioned lower limit, the liquid detergent composition can be imparted with high cleaning performance. On the other hand, when the content of the nonionic surfactant is equal to or less than the above-mentioned upper limit, the stability of the liquid detergent composition can be ensured.

[0037] When component (A) contains an anionic surfactant, the content of the anionic surfactant is preferably 1 to 40 mass% relative to the total mass of the liquid detergent composition, more preferably 10 to 35 mass%, and even more preferably 15 to 30 mass%. When the content of the anionic surfactant is equal to or greater than the above-mentioned lower limit, protein detergency can be ensured. When the content of the anionic surfactant is equal to or less than the above-mentioned upper limit, stability of the liquid detergent composition can be ensured.

[0038] When the anionic surfactant contains LAS, the content of LAS is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, and even more preferably 10 to 20% by mass, based on the total mass of the liquid detergent composition. When the content of LAS is equal to or greater than the lower limit, recontamination of clothes is prevented. When the content of LAS is equal to or less than the upper limit, blend stability is ensured. When the anionic surfactant contains AES, the content of AES is preferably 1 to 20 mass%, more preferably 1 to 15 mass%, and even more preferably 1 to 10 mass%, relative to the total mass of the liquid detergent composition. When the content of AES is equal to or greater than the above-mentioned lower limit, sebum cleansing power can be ensured. When the content of AES is equal to or less than the above-mentioned upper limit, appearance stability can be ensured.

[0039] When component (A) contains a higher fatty acid (salt), the content of the higher fatty acid (salt) is preferably 1 to 10 mass %, more preferably 1 to 8 mass %, and even more preferably 2 to 5 mass %, relative to the total mass of the liquid detergent composition. When the content of the higher fatty acid (salt) is equal to or greater than the above lower limit, rinsing performance can be further improved. When the content of the higher fatty acid (salt) is equal to or less than the above upper limit, liquid stability can be further improved.

[0040] It is preferable to use a nonionic surfactant and an anionic surfactant in combination as component (A). The total content of the nonionic surfactant and the anionic surfactant is preferably from 35 to 70 mass %, more preferably from 40 to 60 mass %, based on the total mass of the liquid detergent composition. The mass ratio of nonionic surfactant to anionic surfactant (hereinafter also referred to as "nonionic / anionic ratio") is preferably 0.7 or more, more preferably 1 or more, and even more preferably 1.2 or more. The nonionic / anionic ratio is preferably 10 or less, more preferably 5 or less, and particularly preferably 2 or less. That is, the nonionic / anionic ratio is preferably 0.7 or more, preferably 1 to 10, more preferably 1.2 to 5, and even more preferably 1.2 to 2. When the nonionic / anionic ratio is above the lower limit, sebum cleansing power can be ensured.

[0041] When component (A) contains a cationic surfactant, the content of the cationic surfactant is preferably 0.1 to 10 mass %, more preferably 1 to 5 mass %, relative to the total mass of the liquid detergent composition. When component (A) contains an amphoteric surfactant, the content of the amphoteric surfactant is preferably 0.1 to 10 mass %, more preferably 1 to 5 mass %, relative to the total mass of the liquid detergent composition. When component (A) contains a semi-polar surfactant, the content of the semi-polar surfactant is preferably 0.1 to 10 mass %, more preferably 1 to 5 mass %, based on the total mass of the liquid detergent composition.

[0042] <Component (B): Carbonate> Examples of carbonates include sodium carbonate, sodium bicarbonate, a double salt of sodium carbonate and sodium bicarbonate (sodium sesquicarbonate), potassium carbonate, and potassium bicarbonate. As the carbonate, sodium carbonate and potassium carbonate are preferred, and sodium carbonate is more preferred, since they can further enhance the detergency of the liquid detergent. One type of carbonate may be used alone, or two or more types may be used in combination.

[0043] The carbonate content is 0.1 to 5 mass%, preferably 0.5 to 2.5 mass%, more preferably 0.8 to 2.0 mass%, and even more preferably 1.0 to 1.5 mass%, relative to the total mass of the liquid detergent composition. When the carbonate content is equal to or greater than the above lower limit, the detergency of the liquid detergent can be further improved, while when the carbonate content is equal to or less than the above upper limit, the liquid detergent stability is good and embrittlement and whitening of the water-soluble film are less likely to occur.

[0044] <(C) component> In the liquid detergent article of the present invention, the liquid detergent composition contains component (C), which prevents the water-soluble film container from becoming brittle over time and allows the container to maintain a good feel and appearance.

[0045] The component (C) is at least one selected from the following components (C1), (C2), and (C3). Component (C1): One or more selected from the group consisting of glycerin, (poly)alkylene glycol (mono- or di-)alkyl ethers consisting of a (poly)alkylene glycol unit having 2 to 4 carbon atoms and an alkanol having 1 to 5 carbon atoms, and alkyl glyceryl ethers having an alkyl having 1 to 8 carbon atoms. Component (C2): one or more selected from propylene glycol and 3-methoxy-3-methyl-1-butanol. (C3) Ingredient: Sorbitol.

[0046] Examples of the (poly)alkylene glycol (mono- or di-)alkyl ether (C1) component, which is composed of a (poly)alkylene glycol having an alkylene glycol unit having 2 to 4 carbon atoms and an alkanol having 1 to 5 carbon atoms, include diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol.

[0047] Examples of alkyl glyceryl ethers having an alkyl group having 1 to 8 carbon atoms, which are the component (C1), include 1,3-dimethyl glyceryl ether, ethyl glyceryl ether, 1,3-diethyl glyceryl ether, triethyl glyceryl ether, pentyl glyceryl ether, octyl glyceryl ether, 2-ethylhexyl glyceryl ether, and diethylene glycol monobutyl ether.

[0048] The total content of component (C) is preferably 25 to 45 mass %, more preferably 30 to 42 mass %, and even more preferably 35 to 40 mass %, based on the total mass of the liquid detergent composition. When the total content of component (C) is equal to or greater than the above-mentioned preferable lower limit, embrittlement of the water-soluble film is suppressed, so that the liquid detergent package is less likely to break, and the solubility of the water-soluble film is also improved. On the other hand, if the water content exceeds the above-mentioned preferable upper limit, no corresponding effect of improving embrittlement is observed, which is economically disadvantageous. On the other hand, if the water content is equal to or less than the above-mentioned preferable upper limit, the softening of the water-soluble film container does not proceed too much, and the appearance and feel of the container are easily maintained.

[0049] The content of the component (C1) is preferably from 1 to 15 mass %, more preferably from 3 to 10 mass %, and even more preferably from 5 to 8 mass %, relative to the total mass of the liquid detergent composition. The ratio of the content of the component (C1) to the total content of the component (C) [(C1) / (C)] is preferably from 0.02 to 0.6, more preferably from 0.07 to 0.3, and even more preferably from 0.12 to 0.23. When the content of the component (C1) or the ratio of the component (C) to the total content of the component (C) is at least the above-mentioned preferable lower limit, embrittlement of the water-soluble film is suppressed. When the content of the component (C1) or the ratio of the component (C) to the total content is equal to or less than the above-mentioned preferable upper limit, the softening of the water-soluble film container does not proceed too much, and the appearance and feel are easily maintained.

[0050] The content of the component (C2) is preferably from 5 to 30 mass %, more preferably from 10 to 28 mass %, and even more preferably from 15 to 25 mass %, based on the total mass of the liquid detergent composition. The ratio of the content of the component (C2) to the total content of the component (C) [(C2) / (C)] is preferably from 0.3 to 0.7, more preferably from 0.4 to 0.7, and even more preferably from 0.4 to 0.6. When the content of the component (C2) or the ratio of the component (C) to the total content of the component (C) is at least the above-mentioned preferable lower limit, the appearance stability and good flowability can be ensured, and embrittlement of the water-soluble film can be suppressed. When the content of the component (C2) or the ratio of the component (C) to the total content is equal to or less than the above-mentioned preferable upper limit, the softening of the water-soluble film container does not proceed too much, and the appearance and feel are easily maintained.

[0051] The content of the component (C3) is preferably from 1 to 15 mass %, more preferably from 3 to 12 mass %, and even more preferably from 5 to 10 mass %, based on the total mass of the liquid detergent composition. The ratio of the content of the component (C3) to the total content of the component (C) [(C3) / (C)] is preferably from 0.02 to 0.6, more preferably from 0.07 to 0.4, and even more preferably from 0.12 to 0.29. When the content of the component (C3) or the ratio of the component (C) to the total content of the component (C) is at least the above-mentioned preferable lower limit, embrittlement of the water-soluble film is suppressed. When the content of component (C3) or the ratio of component (C) to the total content is equal to or less than the above-mentioned preferable upper limit, the softening of the water-soluble film container does not proceed too much, and the appearance and feel are easily maintained, and the low-temperature stability is also good.

[0052] The ratio of the content of component (C1) to the total content of components (C2) and (C3), [(C1) / ((C2)+(C3))], is preferably 0.05 to 1, more preferably 0.1 to 0.5, and particularly preferably 0.1 to 0.3. When [(C1) / ((C2)+(C3))] is in this range, embrittlement of the water-soluble film is suppressed, and containers made of the water-soluble film do not soften too much, making it easier to maintain their appearance and feel.

[0053] The composition may contain other components that function as plasticizers other than the component (C) as long as the effects of the present invention are not impaired. Other ingredients that function as plasticizers include 2-methyl-1,3-propanediol, methanol, diglycerol, 1,4-butanediol, and urea.

[0054] <Mixing ratio> The ratio of the mass of the component (B) to the mass of the component (A) [(B) / (A)] is preferably 0.01 to 0.1, more preferably 0.02 to 0.06. By keeping it within the above range, the stability of the liquid preparation is excellent. The ratio of the mass of component (C) to the mass of component (A) [(C) / (A)] is preferably 0.2 to 0.8, more preferably 0.3 to 0.7. By keeping it within the above range, the stability and flowability of the liquid preparation will be excellent. The ratio of the mass of the component (B) to the mass of the component (C) [(B) / (C)] is preferably 0.01 to 0.15, more preferably 0.03 to 0.1. By keeping it within the above range, the water-soluble film container has an excellent feel to the touch. The ratio of the mass of component (A) to the mass of component (C) [(A) / (C)] is preferably 1.0 to 5.0, more preferably 1.5 to 3.0. By keeping it within the above range, the stability of the liquid preparation and the tactile feel of the water-soluble film container are excellent. The ratio of the mass of the component (C) to the mass of the component (B) [(C) / (B)] is preferably 8.0 to 40.0, more preferably 10.0 to 35.0. By keeping it within the above range, embrittlement of the water-soluble film container over time is suppressed, and a good feel and appearance can be obtained.

[0055] <Enzyme> The liquid detergent composition of the present invention may contain an enzyme. Examples of enzymes include proteases, amylases, lipases, cellulases, and mannanases. Enzymes are generally commercially available as enzyme-containing preparations (enzyme preparations). When preparing liquid detergents, enzymes are usually blended in the form of enzyme preparations.

[0056] Protease The protease is preferably a protease having serine, histidine, and aspartic acid in the molecule, such as a serine protease. Enzyme preparations containing proteases (protease preparations) are commercially available, and when preparing liquid detergents, proteases are usually incorporated using these protease preparations. Examples of protease preparations include those available from Novozymes under the trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everlase 16L, Everlase 16L TypeEX, Everlase Ultra 16L, Esperase 8L, Alcalase 2.5L, Alcalase Ultra 2.5L, Liquanase 2.5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, and Coronase 48L Progress Uno 100L; and those available from Genencor under the trade names Purafect L, Purafect OX, and Properase L. Of these, Everlase 16L, Alcalase 2.5L, Coronase 48L, and Progress Uno 100L are preferred, with Progress Uno 100L being more preferred. The content of the protease as an enzyme preparation is preferably 0.1 to 5.0% by mass, more preferably 1.0 to 3.0% by mass, relative to the total mass of the liquid detergent composition.

[0057] "amylase" α-Amylase, β-amylase, α-glucosidase, glucoamylase; glucoamylase, pullulanase, isoamylase, amylo-1,6 glucosidase / 4-α glucanotransferase, oligo-1,6-glucosidase, etc., which hydrolyze α-1,6 bonds in starch, glycogen, etc., are preferred. Enzyme preparations containing amylase (amylase preparations) are commercially available, and amylase is typically incorporated into liquid detergents. Examples of amylase preparations include Termamyl Ultra 300L, Duramyl 16L, Stainzyme 12L, Promozyme 200L, Amplify Prime 100L, Medley (registered trademark) Core 210L (a mixed enzyme of protease and amylase, all trade names manufactured by Novozymes); Maxamyl (trade name manufactured by Genencor), Pullulanase Amano (trade name manufactured by Amano Pharmaceuticals), and DB-250 (trade name pullulanase derived from Aerobacter aerogenes ATCC9621, crude or crystallized, manufactured by Seikagaku Corporation). Among these, Duramyl 16L, Steinzyme 12L, Termamyl Ultra 300L, and Amplify Prime 100L (all trade names manufactured by Novozymes) are preferred, with Amplify Prime 100L being more preferred. The content of amylase as an enzyme preparation is preferably 0.05 to 3 mass %, more preferably 0.1 to 1 mass %, relative to the total mass of the liquid detergent composition.

[0058] Lipase, cellulase, mannanase Examples of lipase preparations include those available from Novozymes under the trade names Lipex 100L and Lipolase 100L. Examples of cellulase preparations include Carezyme 4500L (trade name, manufactured by Novozymes), Carezyme Premium 4500L (trade name, manufactured by Novozymes), Endrase 5000L (trade name, manufactured by Novozymes), Cellclean 4500T (trade name, manufactured by Novozymes), and Medley Glow 200L (trade name, manufactured by Novozymes). An example of a mannanase preparation is Mannaway 4L, available from Novozymes. These enzyme preparations may be used alone or in combination of two or more. The total content of enzymes other than protease and amylase as an enzyme preparation is preferably 0.01 to 1.5% by mass, more preferably 0.1 to 1.0% by mass, based on the total mass of the liquid detergent composition.

[0059] <Chelating agents (sequestering agents)> The liquid detergent composition of the present invention may contain a chelating agent capable of chelating metal ions. Examples of the chelating agent include organic chelating agents, and specific examples thereof include organic phosphonic acid derivatives such as citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, gluconic acid, nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycoletherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraaminehexaacetic acid, ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, trisodium methylglycinediacetate, 1-hydroxyethane-1,1-diphosphonic acid, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, aminotrimethylenephosphonic acid, and ethylenediaminetetraxymethylenesulfonic acid, or salts thereof. Among these, citric acid and trisodium methylglycine diacetate are more preferred from the viewpoint of low-temperature stability. The chelating agents may be used alone or in combination of two or more.

[0060] <Antibacterial agent> The liquid detergent composition of the present invention may contain an antibacterial agent. By containing an antibacterial agent, antibacterial properties can be imparted to the liquid detergent composition. Examples of the antibacterial agent include known quaternary ammonium salts, phenol derivatives, and diphenyl compounds. Examples of the antibacterial agent include alkyl (C12-C16) trimethylammonium chloride, 5-chloro-2-(2,4-dichlorophenoxy)phenol (common name: triclosan), and 5-chloro-2-(4-chlorophenoxy)phenol (common name: diclosan). The content of the antibacterial agent is preferably 0.05 to 5.0% by mass relative to the total mass of the liquid detergent composition. The antibacterial agent may be used alone or in combination of two or more.

[0061] <Antioxidants> The liquid detergent composition of the present invention may contain an antioxidant. Examples of antioxidants include dibutylhydroxytoluene (BHT) (manufactured by Sumitomo Chemical Co., Ltd., trade name: SUMILZER BHT-R), sodium sulfite, and sodium ascorbate. These antioxidants may be used alone or in combination of two or more. The content of the antioxidant is preferably 0.01 to 3% by mass relative to the total mass of the liquid detergent composition.

[0062] <Other ingredients> The liquid detergent composition of the present invention may contain, in addition to the above components, components (other components) that are commonly used in liquid detergents, as necessary, as long as the effects of the present invention are not impaired. Examples of other components include enzyme stabilizers, hydrotropes, pH adjusters, bleaching agents, dye transfer inhibitors, fluorescent brighteners, soil release agents, dispersants, antifoaming agents, structural viscosity imparting agents, texture improvers such as silicone, preservatives, fragrances, pearlizing agents, emulsifying agents, and general-purpose dyes or pigments as colorants.

[0063] Examples of enzyme stabilizers include boric acid, borax, formic acid or its salts, benzoic acid, lactic acid or its salts, calcium chloride, calcium sulfate, and other calcium salts. These enzyme stabilizers may be used alone or in combination of two or more. The content of the enzyme stabilizer is preferably from 0.01 to 2 mass %, more preferably from 0.1 to 1.5 mass %, based on the total mass of the liquid detergent composition.

[0064] Examples of hydrotropic agents include paratoluenesulfonic acid or its salts, cumenesulfonic acid or its salts, benzoates, and urea. These hydrotropic agents may be used alone or in combination of two or more. The content of the hydrotrope agent is preferably 0.01 to 15% by mass relative to the total mass of the liquid detergent composition.

[0065] Examples of pH adjusters include inorganic acids (hydrochloric acid, sulfuric acid, phosphoric acid, etc.), sodium hydroxide, potassium hydroxide, alkanolamines (monoethanolamine, diethanolamine, etc.), ammonia, etc. These pH adjusters may be used alone or in combination of two or more.

[0066] Bleaching agents include hydrogen peroxide. The content of the bleaching agent is preferably 0.01 to 10% by mass relative to the total mass of the liquid detergent composition.

[0067] Examples of fluorescent brighteners include biphenyl-type fluorescent brighteners such as 4,4'-bis(2-sulfostyryl)biphenyl disodium salt; and stilbene-type fluorescent brighteners such as 4,4'-bis((4-amino-6-morpholino-1,3,5-triazinyl-2)amino)stilbene-2,2'-disulfonate. These fluorescent brightening agents may be used alone or in combination of two or more. The content of the fluorescent brightening agent is preferably 0.01 to 10% by mass relative to the total mass of the liquid detergent composition.

[0068] Examples of soil release agents (SR agents) include polymers having at least one repeating unit selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units, and oxyalkylene units. Examples of such polymers include those described in International Publication No. 2017 / 142012. Commercially available soil release agents include, for example, Clariant's "TexCare SRN-170" product.

[0069] Further, examples of soil release agents include polymers such as alkylene oxide adducts of polyalkyleneamines. Examples of alkylene oxide adducts of polyalkyleneamines include those described in International Publication No. 2017 / 142012 and JP-A No. 2017-514967. Commercially available products include the product name "Sokalan HP20" manufactured by BASF.

[0070] Further, examples of soil release agents include cationized cellulose described in JP 2019-90057 A. These soil release agents may be used alone or in combination of two or more. The content of the soil release agent is preferably 0.1 to 20% by mass based on the total mass of the liquid detergent composition.

[0071] Examples of dispersants include polyacrylic acid and its salts, polymethacrylic acid and its salts, and polymeric polycarboxylic acids and their salts. These dispersants may be used alone or in combination of two or more. The content of the dispersant is preferably 0.01 to 5% by mass relative to the total mass of the liquid detergent composition.

[0072] Examples of the antifoaming agent include fatty acid esters, etc. Specific examples of fatty acid esters include 2-ethylhexyl 2-ethylhexanoate (also known as 2-ethylhexyl isooctanoate, 2H08). These antifoaming agents may be used alone or in combination of two or more. The content of the antifoaming agent is preferably 0.01 to 5% by mass relative to the total mass of the liquid detergent composition.

[0073] The structural viscosity imparting agent imparts structural viscosity to the liquid detergent composition. By including the structural viscosity imparting agent, the liquid detergent composition is likely to improve the dispersibility of the functionality imparting particles and further increase the storage stability. Examples of structural viscosity imparting agents include acrylic polymers, compounds having a molecular weight of 100 or more and containing a urea group in the molecule, and triglycerides.

[0074] Specific examples of acrylic polymers include the component (E) described in JP 2017-222789 A. Commercially available crosslinked polymers include "Carbopol Aqua 30," "Carbopol Aqua SF-1," and "Carbopol EZ-4" manufactured by Lubrizol, and "ACUSOL 830" manufactured by DOW. Non-crosslinked polymers include "Novethix HC200" manufactured by Lubrizol. One type of acrylic polymer may be used alone, or two or more types may be used in combination.

[0075] Specific examples of compounds having a molecular weight of 100 or more and containing a urea group in the molecule include the component (B) described in JP 2018-59096 A. Commercially available products include, for example, BYK-410, BYK-411, BYK-420, BYK-425, BYK-428, BYK-7411ES, BYK-7420ET, and BYK-D410 manufactured by BYK-Chemie. Compounds having a molecular weight of 100 or more and containing a urea group in the molecule may be used alone or in combination of two or more.

[0076] Specific examples of triglycerides include the component (B1) described in International Publication No. 2014 / 171476. Commercially available products include "Castarwax A Flakes" (trade name) manufactured by NOF Corporation. One type of triglyceride may be used alone, or two or more types may be used in combination.

[0077] As the structural viscosity imparting agent, acrylic polymers and triglycerides are preferred, and acrylic polymers are more preferred. The content of the structural viscosity imparting agent is preferably 0.1 to 5 mass %, more preferably 0.5 to 2.5 mass %, relative to the total mass of the liquid detergent composition. When the content of the structural viscosity imparting agent is equal to or greater than the above lower limit, the liquid stability of the liquid detergent composition is likely to be improved. When the content of the structural viscosity imparting agent is equal to or less than the above upper limit, thickening is suppressed, and the storage stability of the liquid detergent composition can be better maintained.

[0078] Examples of the texture improver include silicones such as dimethyl silicone, polyether-modified silicone, and amino-modified silicone. These silicones include, for example, oil type, oil compound type, solution type, emulsion type, and self-emulsifying type. These texture improvers may be used alone or in combination of two or more. The content of the texture improver is preferably 0.1 to 20% by mass relative to the total mass of the liquid detergent composition.

[0079] Examples of preservatives include "Caisson CG" (trade name) manufactured by Dow Chemical Company, "Acticide MBS" (trade name) manufactured by Thor Japan Co., Ltd., and "NIPACIDE BIT 20" (trade name) manufactured by Clariant. These preservatives may be used alone or in combination of two or more. The content of the preservative is preferably 0.001 to 1% by mass relative to the total mass of the liquid detergent composition.

[0080] Examples of fragrances include those described in "Synthetic Fragrances: Chemistry and Product Knowledge" by Indo Genichi, published by The Chemical Daily in 1996, and "Perfume and Flavor Chemicals" by Stephen Arctander, published by Montclair, NJ in 1969. More specific examples include synthetic fragrances, natural fragrances derived from animals or plants, blended fragrances containing natural fragrances and / or synthetic fragrances, and fragrance components described in JP-A 2002-146399. The fragrance may be blended as a capsule fragrance encapsulated in a capsule formed of a polymer compound. The fragrance may be used alone or in combination of two or more kinds. The content of the fragrance is preferably 0.01 to 2% by mass relative to the total mass of the liquid detergent composition.

[0081] Examples of the opacifier include polystyrene emulsion and polyvinyl acetate emulsion, and typically, emulsions with a solid content of 30 to 50% by mass are preferably used. A specific example is polystyrene emulsion (manufactured by Saiden Chemical Industry Co., Ltd.: trade name Saivinol RPX-196 PE-3, solid content 40% by mass). The blending amount of the emulsifier, ie, the content of the emulsifier in 100% by mass of the liquid detergent composition, is preferably 0.01 to 0.5% by mass.

[0082] Examples of colorants include quinone dyes, triphenylmethane dyes, xanthene dyes, quinoline dyes, and pyrene dyes. In this specification, the abbreviation "CI" stands for Color Index. The structure of each dye is described in the "Legal Dyes Handbook" (edited by the Japan Cosmetic Industry Council) and the "Dye Handbook" (edited by the Society of Synthetic Organic Chemistry). Examples of quinone dyes include CI Solvent Blue 63 (Blue No. 403), and trade names such as Liquitint Blue HP, Liquitint Blue BL, and Liquitint Blue MC manufactured by Milliken. Examples of triphenylmethane dyes include Green No. 3 (CI42053). Examples of quinoline dyes include Yellow No. 203 (CI Acid Yellow 3) and Liquitint YELLOW SY manufactured by Milliken. The content of the colorant is preferably 0.1 to 100 ppm by mass relative to the total mass of the liquid detergent composition.

[0083] <Solvent> In addition to water and component (C) which function as solvents, the liquid detergent composition of the present invention may also contain an organic solvent other than component (C) as another solvent. The water content is preferably less than 20% by mass, more preferably more than 0% by mass and not more than 10% by mass, even more preferably 1 to 9% by mass, particularly preferably 3 to 9% by mass, and most preferably 5 to 8% by mass, relative to the total mass of the liquid detergent composition.

[0084] By setting the water content at or below the preferable upper limit, it is possible to avoid a situation in which the water-soluble film constituting the container is torn, making filling impossible.By setting the water content at or above the preferable lower limit, it is easy to ensure the fluidity required for filling the container. The liquid detergent composition of the present invention has excellent fluidity because it contains less water than ordinary detergent compositions and uses component (C) as a substitute for water to prevent a significant increase in viscosity (gelation).

[0085] Examples of organic solvents other than component (C) include alkanols such as ethanol, 1-propanol, 2-propanol, 1-butanol, and benzyl alcohol, and aromatic ethers of (poly)alkylene glycols having alkylene glycol units having 2 to 3 carbon atoms, such as ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, polyethylene glycol monophenyl ether having an average molecular weight of about 480, ethylene glycol monobenzyl ether, and diethylene glycol monobenzyl ether.

[0086] When the liquid detergent composition of the present invention contains an organic solvent other than the component (C), the content of the organic solvent other than the component (C) is preferably 0.1 to 10 mass %, more preferably 2 to 5 mass %, based on the total mass of the liquid detergent composition. When the content of the organic solvent other than the component (C) is equal to or greater than the lower limit, the liquid stability can be further improved.

[0087] <Physical properties> pH The liquid detergent composition preferably has a pH of 7.0 to 9.5 at 25°C, more preferably 7.5 to 9.0, and more preferably 8.0 to 8.5. When the pH is at least the lower limit of the above range, good cleaning performance is exhibited. When the pH is at most the upper limit, good texture and appearance are easily maintained. The pH of the liquid detergent composition can be adjusted by adding a pH adjuster as needed. The pH in this specification is a value measured at 25°C using a pH meter (manufactured by DKK-TOA Corporation, product name "HM-30G").

[0088] "viscosity" The viscosity of the liquid detergent composition at 25°C is preferably from 10 to 1000 mPa·s, more preferably from 10 to 500 mPa·s, and even more preferably from 10 to 300 mPa·s. The viscosity of the liquid detergent composition is a value measured using a Brookfield viscometer under the following conditions. (Measurement conditions) Rotor: Rotor No. 2. -Rotation speed: 60 rpm ·Measurement temperature: 25℃. Viscosity reading: 30 seconds after rotor starts rotating.

[0089] [Manufacturing method] The liquid detergent article is manufactured, for example, as follows using a mold having a plurality of recesses each having a rectangular shape in plan view. A water-soluble film is placed so as to cover the opening of the recess. The pressure inside the recess is reduced, and the water-soluble film is drawn into the recess to form a storage section with an open top. The size of one storage section is about 20 to 30 mL. Next, the liquid detergent composition is filled into the storage section. After that, another wetted water-soluble film is placed to close and seal the opening of the storage section. Then, by cutting out the film individually, a liquid detergent package in which the liquid detergent composition is filled in a container made of a water-soluble film can be obtained.

[0090] The liquid detergent composition can be produced according to a conventional method for producing a liquid detergent composition, for example, by adding and mixing each component except for the pH adjuster to a portion of water, adding the pH adjuster as needed to adjust the pH, and then adding the remainder of the water to make the total amount 100% by mass.

[0091] [How to use] When the liquid detergent article of the present invention is used as a laundry detergent, it is not necessary to measure out detergent as in the past, and it is sufficient to simply add one liquid detergent article to the washing machine tub, making it simple and convenient. [Example]

[0092] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description. It should be noted that Examples 13 and 19 are reference examples.

[0093] [Raw materials used] The raw materials used in this example are as follows:

[0094] <Water-soluble film> -Water-soluble polyvinyl alcohol film, product name "M8312", manufactured by Monosol LLC. -Water-soluble polyvinyl alcohol film, product name "M8775", manufactured by Monosol LLC.

[0095] <Component (A): Surfactant> AE(7EO): A compound in which 7 moles of ethylene oxide are added to a natural alcohol. In the general formula (a2), R13 represents an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, v=7, w=0, and x=0. This compound was synthesized by the following synthesis method.

[0096] MEE: fatty acid methyl ester ethoxylate (fatty acid carbon number: 12 to 14, average number of moles of EO added: 15), in the above general formula (a1), R 11 = an alkyl group having 11 carbon atoms and an alkyl group having 13 carbon atoms, R 12 = methyl group, s = 15, t = 0, u = 0. Synthesized by the following synthesis method.

[0097] LMAO: Polyoxyethylene alkyl ether (LMAO) is a compound in which 15 moles of ethylene oxide are added to natural alcohols (primary alcohols) with 12 or 14 carbon atoms. Synthesized using the following synthesis method. SOFTANOL 70: A secondary alcohol having 12 to 14 carbon atoms to which 7 moles of ethylene oxide have been added (manufactured by Nippon Shokubai Co., Ltd., product name "SOFTANOL 70")

[0098] AES (2EO): Polyoxyalkylene alkyl ether sulfate (average number of EO moles added: 2). Product name: ASCO 24-2 / 70, manufactured by AK Chemtech. LAS: Linear alkylbenzene sulfonic acid having an alkyl group with 10 to 14 carbon atoms, manufactured by Lion Specialty Chemicals, trade name "Lipon (registered trademark) LH-200". Palm Fatty Acids: Trade name "Palm Fatty Acids", manufactured by PT Musim Mas.

[0099] <<MEE synthesis method>> The synthesis was carried out in accordance with the synthesis method described in JP-A-2000-144179 as follows. Alumina magnesium hydroxide (Kyowa Chemical Industry Co., Ltd., product name "Kyoward 300") with a composition of 2.5MgO·Al2O3·wH2O was calcined at 600°C for 1 hour under a nitrogen atmosphere to obtain a calcined alumina magnesium hydroxide (unmodified) catalyst. 2.2 g of the calcined alumina magnesium hydroxide (unmodified) catalyst, 2.9 mL of 0.5 N potassium hydroxide ethanol solution, 280 g of methyl laurate, and 70 g of methyl myristate were charged into a 4 L autoclave, and the catalyst was modified in the autoclave. The atmosphere inside the autoclave was then purged with nitrogen, and 1052 g of ethylene oxide was introduced and reacted with stirring while maintaining the temperature at 180°C and the pressure at 0.3 MPa. The resulting reaction liquid was cooled to 80°C, and 159 g of water and 5 g each of activated clay and diatomaceous earth as filter aids were added and mixed, and the catalyst was then filtered off to obtain MEE.

[0100] LMAO: Polyoxyethylene alkyl ether (LMAO) is a compound in which 15 moles of ethylene oxide are added to natural alcohols (primary alcohols) with 12 or 14 carbon atoms. Synthesized using the following synthesis method.

[0101] 《LMAO composition method》 861.2 g of Procter & Gamble CO-1214 (trade name) and 2.0 g of a 30% by weight aqueous solution of NaOH were charged into a pressure-resistant reactor, and the atmosphere inside the reactor was replaced with nitrogen. Next, the reactor was dehydrated for 30 minutes at a temperature of 100°C and a pressure of 2.0 kPa or less, and then the temperature was raised to 160°C. Next, 760.6 g of ethylene oxide (gaseous) was gradually added to the reaction solution while stirring. Ethylene oxide was added through a sparge while adjusting the addition rate so that the reaction temperature did not exceed 180°C. After the addition of ethylene oxide was completed, the mixture was aged for 30 minutes at a temperature of 180°C and a pressure of 0.3 MPa or less, and then unreacted ethylene oxide was distilled off for 10 minutes at a temperature of 180°C and a pressure of 6.0 kPa or less. Next, after cooling to a temperature of 100° C. or less, the reaction product was neutralized by adding 70% by mass of p-toluenesulfonic acid so that the pH of a 1% by mass aqueous solution of the reaction product became about 7, thereby obtaining LMAO.

[0102] 《How to synthesize AE(7EO)》 AE(7EO) was obtained in the same manner as AE(15EO), except that the amount of ethylene oxide (gaseous) used was changed from 760.6 g to 355.0 g.

[0103] <Component (B): Carbonate> Sodium carbonate: Product name "soda ash", manufactured by Sumitomo Shoji Chemical Co., Ltd. Sodium bicarbonate: Trade name "Sodium Bicarbonate", manufactured by OCI.

[0104] <Component (C): Plasticizer> Glycerin: Trade name "Glycerin", LG Houshold & Healthcare. Propylene glycol: Product name "Propylene glycol Industry PG-I", manufactured by SKC. Sorbitol: Trade name "D-Sorbitol", manufactured by PAIK KWANG Industrial Co., Ltd.

[0105] <Enzyme> Enzyme 1: Protease / amylase preparation, trade name "Medley Core 210L" manufactured by Novozymes. Enzyme 2: Cellulase preparation, product name "Medley Glow 200L" manufactured by Novozymes.

[0106] <Chelating agents (sequestering agents)> Citric acid: Trade name "Citric Acid", manufactured by Jthus. <Antioxidants> Sodium sulfite: Trade name "Sodium Sulfite, Anhydrous", manufactured by Poohung Photo Chemical Co., Ltd.

[0107] <Fragrance> Fragrance 1: TEA Tree Floral Fragrance, product name "TEA TREE FLORAL", manufactured by Symrise. ·Fragrance 2: Citronella oil, product name "Citronella java oil", manufactured by ETERIS Enterprise PTE. Fragrance 3: Cinnamic Aldehyde, manufactured by Shanghai Pu-jie Fragrance Co., Ltd. Fragrance 4: Fragrance composition A described in Tables 11 to 18 of JP-A No. 2002-146399.

[0108] <Dye> ·Pigment 1: Yellow dye, product name "LIQUITINT YELLOW SY", manufactured by Milliken. ·Pigment 2: Blue dye, product name "LIQUITINT BLUE HP", manufactured by Milliken. ·Pigment 3: Green dye, mixed pigment of product name "LIQUITINT YELLOW SY" and product name "LIQUITINT GLACIER BLUE MC" (mixing ratio 4:1), manufactured by Milliken.

[0109] <Other> Paratoluenesulfonic acid: Hydrotrope (manufactured by Kyowa Hakko Kirin Co., Ltd., trade name "PTS acid") Sodium lactate: Enzyme stabilizer (Musashino Chemical Laboratory, product name "Sodium Lactate 60E"). MEA (pH adjuster): Monoethanolamine, manufactured by MIWON Chemical Co., Ltd. Antibacterial agent: 5-chloro-2-(4-chlorophenoxy)phenol (common name: dichrosan) (manufactured by BASF, product name "Tinosan HP100"). SR agent: HP20 (ethylene oxide adduct of polyalkyleneimine (manufactured by BASF Ltd., trade name "HP20")) or SRN-170 (polycondensate of polyethylene glycol and dimethyl terephthalate (manufactured by Clariant Ltd., trade name "TexCare SRN-170C"). Water: Purified water, manufactured by Kanto Chemical Co., Ltd.

[0110] [Examples 1 to 21, Comparative Examples 1 to 3] <Preparation of Cleaning Composition> A portion of the water and all of the other ingredients were added to a 500 mL beaker in accordance with the blending amounts in Tables 1 to 4, and the mixture was thoroughly stirred with a magnetic stirrer (manufactured by MITAMURA KOGYO INC.). Next, an appropriate amount of monoethanolamine was added so that the pH at 25°C was 7.0, followed by the addition of sodium carbonate. Without further pH adjustment, water was added to make the total amount 100% by mass, thereby obtaining a liquid detergent composition.

[0111] <Production of liquid detergent article 1> Two 55 mm x 90 mm pieces of the water-soluble film raw rolls shown in Tables 1 to 4 were prepared, and these were overlapped and heat-sealed on three sides to form a bag-shaped storage section. Next, 30 g of the liquid detergent composition of each example was filled into the storage section from the last unsealed side, and then the last side was sealed to obtain liquid detergent article 1.

[0112] <Production of Liquid Detergent Article 2> The mold used had a plurality of rectangular recesses (45 mm long, 45 mm wide, and 12 mm deep) formed in it when viewed from above. A water-soluble film raw sheet shown in Tables 1 to 4 was placed to cover the opening of the recess in the mold, the pressure inside the recess was reduced, and the water-soluble film was drawn into the recess to form a storage section with an open top. Next, 20 g of each liquid detergent composition was filled into the container, and then another wet water-soluble film was placed to cover and seal the opening of the container. Thereafter, the liquid detergent article 2 of each example, in which the liquid detergent composition was filled in a container made of a water-soluble film, was obtained by cutting it out individually.

[0113] [evaluation] <Cleaning power evaluation> A fully automatic washing machine (manufactured by Toshiba, product name: AW-8V2(W)) was charged with 60 L of tap water at 15°C. Liquid detergent article 2 (20 g) from each example was added, along with six undershirts (manufactured by BVD) each made by sewing five pieces of artificially soiled fabric together, and the undershirts were added so that the bath ratio was 15:1. The undershirts with the soiled fabrics sewn onto them were positioned at the bottom, lower, middle, and upper parts of the washing machine. The items were washed once using the fully automatic washing machine's standard course, which consisted of a 10-minute wash, one rinse, and a 3-minute spin cycle, followed by air drying.

[0114] The artificially soiled cloth was measured before and after cleaning using a color difference meter (product name: SE200 model) manufactured by Nippon Denshoku Co., Ltd., and the cleaning rate (%) was calculated using the following formula. The average of 30 pieces (5 x 6) was taken as the average cleaning rate (%). Cleaning rate (%) = (K / S of dirty cloth - K / S of cleaned cloth) / (K / S of soiled cloth - K / S of unsoiled cloth) x 100

[0115] In the above formula, "soiled cloth" refers to each of the soiled cloths mentioned above before cleaning, "cleaned cloth" refers to the soiled cloth after cleaning, and "unsoiled cloth" refers to the original white cloth (raw cloth) with no soil attached. K represents the absorption coefficient, and S represents the scattering coefficient. The cleaning power for each stain was evaluated based on the average cleaning rate (%) according to the following evaluation criteria, and a rating of ⊚ or ◯ was considered to be acceptable. The evaluation results for each example are shown in Tables 1 to 4.

[0116] Evaluation Criteria ◎: Average cleaning rate of 60% or more. ○: Average cleaning rate is 55% or more but less than 60%. △: Average cleaning rate is 50% or more but less than 55%. ×: Average cleaning rate less than 50%.

[0117] <Evaluation of film texture (embrittlement)> The liquid detergent article 2 of each example was stored for one month under conditions of 40°C and 20% RH, and then its appearance and feel were evaluated by 10 panelists according to the following rating criteria. The feel (embrittlement) was evaluated based on the average score of the 10 panelists according to the following rating criteria, and a score of ○ or △ was considered to be acceptable. The evaluation results for each example are shown in Tables 1 to 4.

[0118] Scoring criteria 1 point: Appears cloudy and feels rough to the touch, or looks thin and feels soft and brittle to the touch. 2 points: There is no cloudiness in appearance, but it feels a little rough when touched. 3 points: It appears cloudy on the outside, but does not feel rough to the touch.

[0119] Evaluation Criteria 〇: The average score is 2.5 points or more. △: The average score is between 2.0 and 2.5 points. ×: The average score is less than 2.0 points.

[0120] <Appearance evaluation of liquid detergent products> Each liquid detergent article 2 was stored at 40°C and 20% RH for one month, after which a panel member evaluated the appearance of the contents of the article according to the following criteria. A score of ○ was considered to be acceptable. The evaluation results for each example are shown in Tables 1 to 4.

[0121] Evaluation Criteria 〇: No cloudiness in appearance. ×: Cloudy appearance is observed.

[0122] [Table 1]

[0123] [Table 2]

[0124] [Table 3]

[0125] [Table 4]

[0126] As shown in Tables 1 to 3, good detergency was obtained in all of Examples 1 to 21. In addition, the appearance and feel after storage were also good. In contrast, Comparative Example 1, which did not contain component (B), had poor cleaning power, as shown in Table 4. Furthermore, Comparative Example 2, which contained an excessive amount of component (B), had poor appearance and feel after storage.

Claims

1. A liquid detergent article in which a liquid detergent composition is sealed in a container made of a water-soluble film, The liquid detergent composition contains the following component (A), the following component (B), and the following component (C3): A liquid detergent article, wherein the content of the following component (B) is 0.1 to 5 mass % relative to the total mass of the liquid detergent composition, and the content of the following component (C3) is 1 to 15 mass % relative to the total mass of the liquid detergent composition. Component (A): surfactant. (B) Component: Carbonate. (C3) Component: sorbitol.

2. Further comprising the following component (C1) and the following component (C2): The liquid detergent article according to claim 1, wherein the content of the component (B) is 0.5 to 2.5 mass% relative to the total mass of the liquid detergent composition, the content of the component (C1) described below is 3 to 10 mass% relative to the total mass of the liquid detergent composition, and the content of the component (C2) described below is 10 to 25 mass% relative to the total mass of the liquid detergent composition. Component (C1): One or more selected from the group consisting of glycerin, (poly)alkylene glycol (mono- or di-)alkyl ethers consisting of a (poly)alkylene glycol unit having 2 to 4 carbon atoms and an alkanol having 1 to 5 carbon atoms, and alkyl glyceryl ethers having an alkyl group having 1 to 8 carbon atoms. Component (C2): one or more selected from propylene glycol and 3-methoxy-3-methyl-1-butanol.

3. A liquid detergent article as described in claim 2, wherein the ratio [(C) / (A)] of the total mass of the (C1), (C2), and (C3) components to the mass of the (A) component is 0.3 to 0.

7.

4. A liquid detergent article as described in claim 2 or 3, wherein the ratio [(C3) / (C)] of the content of the (C3) component to the total content of the (C1) component, the (C2) component, and the (C3) component is 0.02 to 0.

6.

5. A liquid detergent article described in any one of claims 2 to 4, wherein the ratio of the content of the (C1) component to the total amount of the (C2) component and the (C3) component [(C1) / ((C2)+(C3))] is 0.1 to 0.3.

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