Liquid fabric softener composition

Abstract

To provide a liquid fabric softener composition with excellent antibacterial properties. [Solution] A liquid fabric softener composition comprising: (A) component: at least one compound selected from the group consisting of amine compounds having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms separated by ester groups and / or amide groups, salts thereof, and quaternary compounds thereof; (B) component: a nonionic surfactant; and (C) component: a quaternary ammonium salt compound represented by the following formula (C). 1 R is an alkyl or alkenyl group having 12 to 18 carbon atoms. 2 , R 3 and R 4 Each of these is an alkyl group having 1 to 3 carbon atoms, and X - This is an alkyl sulfate ion having an alkyl group with 1 to 3 carbon atoms. [Formula 1] JPEG2026091084000010.jpg24123

Description

[Technical Field]

[0001] This invention relates to a liquid fabric softener composition. [Background technology]

[0002] When wet textile products are dried in damp environments such as indoors, they are prone to developing a musty odor. To suppress the growth of microorganisms that cause this musty odor and thus prevent its occurrence, textile products are sometimes treated with a liquid fabric softener composition that has antibacterial properties.

[0003] Amine compounds having 1 to 3 long-chain hydrocarbon groups separated by ester or amide groups, their salts, and their quaternary derivatives function as softening base materials in liquid fabric softener compositions and also exhibit antibacterial properties. Furthermore, quaternary ammonium salts may be included in liquid fabric softener compositions as antibacterial agents (Patent Documents 1-2). However, while these ingredients exhibit some antibacterial effects, they do not completely eliminate consumers' concerns about odors in their clothing, and further improvements in performance are desired. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2003-105668 [Patent Document 2] Japanese Patent Publication No. 2023-167990 [Overview of the project] [Problems that the invention aims to solve]

[0005] This invention has been made in view of the above problems, and provides a liquid fabric softener composition with excellent antibacterial effect. [Means for solving the problem]

[0006] The present invention has the following aspects. <1> A liquid fabric softener composition, (A) Components: At least one compound selected from the group consisting of amine compounds having 1 to 3 hydrocarbon groups with 10 to 26 carbon atoms separated by an ester group (-COO-) and / or an amide group (-NHCO-), salts thereof, and quaternary compounds thereof, (B) Ingredients: Nonionic surfactant, (C) Component: See formula (C) below [ka] (In the formula, R 1 R is an alkyl or alkenyl group having 12 to 18 carbon atoms. 2 , R 3 and R 4 Each of these is an alkyl group having 1 to 3 carbon atoms, and X - (This is an alkyl sulfate ion having an alkyl group with 1 to 3 carbon atoms.) A quaternary ammonium salt compound represented by, A liquid fabric softener composition containing the following: <2> The content of component (C) is 0.1% by mass or more and less than 1% by mass relative to the total mass of the liquid softener composition. <1> The liquid fabric softener composition described above. <3> The content of component (A) is 5% by mass or more and less than 15% by mass relative to the total mass of the liquid softener composition. <1> or <2> The liquid fabric softener composition described above. <4> The content of component (B) is 1% by mass or more and less than 3% by mass relative to the total mass of the liquid softener composition. <1> ~ <3> A liquid fabric softener composition as described in any of the following. <5> It is an opaque type. <1> ~ <4> A liquid fabric softener composition as described in any of the following. <6> The pH is between 2 and 4. <1> ~ <5> A liquid fabric softener composition as described in any of the following. [Effects of the Invention]

[0007] According to the present invention, a liquid fabric softener composition with excellent antibacterial properties can be provided. [Brief explanation of the drawing]

[0008] [Figure 1] This graph shows the results of Test Example 1. [Modes for carrying out the invention]

[0009] [Liquid fabric softener composition] A liquid softener composition according to one embodiment of the present invention comprises component (A), component (B), and component (C).

[0010] <(A) component> Component (A) is at least one compound selected from the group consisting of amine compounds having 1 to 3 hydrocarbon groups with 10 to 26 carbon atoms separated by an ester group (-COO-) and / or an amide group (-NHCO-), salts thereof, and quaternary compounds thereof. (A) Component is a softening base material and is added to the liquid softener composition to impart the effect of giving softness (texture) to textile products.

[0011] The number of carbon atoms in a hydrocarbon group having 10 to 26 carbon atoms (hereinafter also referred to as a "long-chain hydrocarbon group") is preferably 14 to 22, and more preferably 16 to 20. When the number of carbon atoms is 10 or more, the flexibility-imparting effect is good, and when it is 26 or less, the handling properties of the liquid softener composition are good. The long-chain hydrocarbon group may be saturated or unsaturated. If the long-chain hydrocarbon group is unsaturated, the position of the double bond may be anywhere, but if there is only one double bond, it is preferable that the double bond be located in the center or around the center of the long-chain hydrocarbon group. The long-chain hydrocarbon group may be a linear hydrocarbon group or a hydrocarbon group containing a ring in its structure, and is preferably a linear hydrocarbon group. The linear hydrocarbon group may be linear or branched. The linear hydrocarbon group is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group. The long-chain hydrocarbon group is segmented by a segmentation group. The segmentation may be at one location or at two or more locations. Preferably, it is at one location. The segmentation group is an ester group (-COO-) or an amide group (-NHCO-). When the long-chain hydrocarbon group has two or more segmentation groups, each segmentation group may be the same or different. Note that the carbon atoms contained in the segmentation group are to be counted as part of the carbon number of the long-chain hydrocarbon group. The long-chain hydrocarbon group is usually introduced by using industrially used tallow-derived unhydrogenated fatty acids, fatty acids obtained by hydrogenating or partially hydrogenating the unsaturated part, unhydrogenated fatty acids or fatty acid esters derived from plants such as palm coconut and oil coconut, or fatty acids or fatty acid esters obtained by hydrogenating or partially hydrogenating the unsaturated part, etc.

[0012] In an amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms segmented by an ester group (-COO-) or an amide group (-NHCO-) in the molecule (hereinafter, sometimes simply referred to as "amine compound" in this specification), the number of long-chain hydrocarbon groups is 1 to 3. Preferably, it is 2 (secondary amine compound) or 3 (tertiary amine compound), and more preferably 3. Examples of the amine compound include a compound represented by the following formula (A1). [Chemical formula] (In the formula, R 5 ~R 7 are each independently, -CH2CH(Y 1 )OCOR 10 (Y 1 is a hydrogen atom or CH3, and R 10 is a hydrocarbon group having 7 to 21 carbon atoms), -(CH2) n1 NHCOR 11 (n1 is 2 or 3, and R 11 is a hydrocarbon group having 7 to 21 carbon atoms), a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, -CH2CH(Y 2 )OH(Y 2(is a hydrogen atom or CH3), or -(CH2) n2 NH2 (where n2 is 2 or 3), R 5 ~R 7 At least one of them is -CH2CH(Y 1 )OCOR 10 or -(CH2) n1 NHCOR 11 (That is the case.)

[0013] The group "-CH2CH(Y)" in equation (A1) 1 )OCOR 10 "In the middle, Y 1 A hydrogen atom is preferred as the atom. R 10 As such, a hydrocarbon group having 15 to 19 carbon atoms is preferred. The compound represented by formula (A1) contains R 10 When there are multiple R 10 They may be identical to each other, or they may be different to each other. R 10 The hydrocarbon group is a fatty acid (R) with 8 to 22 carbon atoms. 10 It is a residue (fatty acid residue) obtained by removing the carboxyl group from COOH, R 10 The fatty acids that form the basis of (R 10 COOH) may be a saturated or unsaturated fatty acid, and may be a straight-chain or branched fatty acid. Among these, saturated or unsaturated straight-chain fatty acids are preferred. In order to impart good water absorption to softened clothing, R 10 The saturated / unsaturated ratio (mass ratio) of the fatty acids that form the basis is preferably 90 / 10 to 0 / 100, more preferably 90 / 10 to 40 / 60, and particularly preferably 90 / 10 to 70 / 30. R 10 When is an unsaturated fatty acid residue, both cis and trans isomers may exist, but the mass ratio of the cis / trans isomer is preferably 40 / 60 to 100 / 0, and particularly preferably 70 / 30 to 90 / 10. R 10Specifically, examples of fatty acids that can be used as the basis for this include stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, elaidic acid, linoleic acid, partially hydrogenated palm oil fatty acid (iodine value 10-60), and partially hydrogenated beef tallow fatty acid (iodine value 10-60). In particular, it is preferable to use a fatty acid composition prepared by combining two or more types selected from stearic acid, palmitic acid, myristic acid, oleic acid, elaidic acid, and linoleic acid in predetermined amounts, so as to satisfy the following conditions (a) to (c). (a) The ratio (mass ratio) of saturated fatty acids to unsaturated fatty acids is 90 / 10 to 0 / 100, more preferably 90 / 10 to 40 / 60, and particularly preferably 90 / 10 to 70 / 30. (b) The ratio (mass ratio) of the cis / trans isomer is 40 / 60 to 100 / 0, more preferably 70 / 30 to 90 / 10. (c) Fatty acids with 18 carbon atoms make up 60% by mass or more, preferably 80% by mass or more, fatty acids with 20 carbon atoms make up less than 2% by mass, and fatty acids with 21 to 22 carbon atoms make up less than 1% by mass.

[0014] In formula (A1), the base "-(CH2) n1 NHCOR 11 In this context, 3 is preferred for n1. R 11 As such, a hydrocarbon group having 15 to 19 carbon atoms is preferred. The compound represented by formula (A1) contains R 11 When there are multiple R 11 They may be identical to each other, or they may be different to each other. R 11 For example, R 10 Similar examples can be specifically cited.

[0015] In equation (A1), R 5 ~R 7 At least one of them is -CH2CH(Y 1 )OCOR 10 or -(CH2) n1 NHCOR 11 That is. R 5 ~R 7 Two of them are -CH2CH(Y1 )OCOR 10 or -(CH2) n1 NHCOR 11 It is preferable that this be the case. R 5 ~R 7 One or two of them are -CH2CH(Y 1 )OCOR 10 or -(CH2) n1 NHCOR 11 If so, the remaining two or one is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, -CH2CH(Y 2 )OH, or -(CH2) n2 NH2 is an alkyl group with 1 to 4 carbon atoms, -CH2CH(Y 2 )OH, or -(CH2) n2 It is preferable that it be NH2. Here, the alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group, and a methyl group is particularly preferred. -CH2CH(Y 2 )Y in OH 2 is -CH2CH(Y 1 )OCOR 10 Y inside 1 It is similar to -(CH2). n2 In NH2, n2 is -(CH2) n1 NHCOR 11 It is the same as n1 inside.

[0016] Preferred examples of compounds represented by formula (A1) include tertiary amine compounds represented by the following formulas (A1-1) to (A1-7). [ka] In each of the formulas ((A1-1) to (A1-7), R 8 Each of these is independently a hydrocarbon group having 7 to 21 carbon atoms, and in formulas (A1-6) to (A1-7), R 9 Each of these is independently a hydrocarbon group having 7 to 21 carbon atoms.

[0017] R 8 and R 9As for the hydrocarbon group having 7 to 21 carbon atoms in the above formula (A1), R 10 Examples include hydrocarbon groups having 7 to 21 carbon atoms, and preferably alkyl and alkenyl groups having 15 to 17 carbon atoms. Note that R is included in the formula. 8 When there are multiple R 8 They may be identical to each other, or they may be different to each other.

[0018] Salts of amine compounds are obtained by neutralizing the amine compound with an acid. The acid used for neutralization can be either an organic or inorganic acid, such as hydrochloric acid, sulfuric acid, or methyl sulfuric acid. Neutralization of amine compounds can be carried out by known methods. Quaternary compounds of amine compounds are obtained by reacting the amine compound with a quaternizing agent. Examples of quaternizing agents include alkyl halides such as methyl chloride and dialkyl sulfates such as dimethyl sulfate. When these quaternizing agents are reacted with an amine compound, the alkyl group of the quaternizing agent is introduced to the nitrogen atom of the amine compound, and a salt of a quaternary ammonium ion and a halogen ion or monoalkyl sulfate ion is formed. The alkyl group introduced by the quaternizing agent is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. Quaternary amine compounds can be carried out by known methods.

[0019] Component (A) is preferably at least one selected from the group consisting of compounds represented by formula (A1), salts thereof, and quaternary compounds thereof, more preferably at least one selected from the group consisting of compounds represented by formulas (A1-1) to (A1-7), salts thereof, and quaternary compounds thereof, and even more preferably at least one selected from the group consisting of compounds represented by formulas (A1-3) to (A1-5), salts thereof, and quaternary compounds thereof.

[0020] (A) Component is a known substance, and may be a commercially available product or one manufactured by a known method. For example, compounds represented by formulas (A1-1) to (A1-7) can be synthesized by the method described in Japanese Patent Publication No. 2023-167990. (A) Component may be a single type or a combination of multiple types (for example, a mixture of compounds represented by general formulas (A1-3) to (A1-5)).

[0021] The content of component (A) is preferably 5% by mass or more, more preferably 7% by mass or more, and preferably less than 15% by mass, and more preferably 12% by mass or less, based on the total mass of the liquid fabric softener composition. The above lower limit and upper limit can be combined as appropriate. When the content of component (A) is 5% by mass or more, the softening effect is better. When the content of component (A) is less than 15% by mass, the viscosity stability of the liquid fabric softener composition during long-term storage is better.

[0022] <(B) component> Component (B) is a nonionic surfactant. Component (B) is added to stabilize component (A) in the liquid fabric softener composition.

[0023] (B) As component (B), any component known in the field of liquid softener compositions can be used without particular limitation. Examples include alkylene oxide adducts of alcohols, amines, or fatty acids.

[0024] Each carbon chain portion of the alcohol, amine, and fatty acid may be branched or linear, and may be unsaturated. Furthermore, the carbon chain may have a distribution. The number of carbon atoms in the carbon chain is preferably 6 to 20, more preferably 8 to 18. If the carbon chain is linear, the number of carbon atoms is preferably 6 to 14, more preferably 8 to 12, and most preferably 8 to 10. If the carbon chain is branched, the number of carbon atoms is preferably 6 to 18, more preferably 9 to 18, and most preferably 13. (B) As raw materials for component (B), Exxon Chemical's Exal, BASF's LUTENSOL series, Kyowa Hakko Kogyo's Oxocol, Hoechst AG's GENAPOL series, Shell's DOBANOL series, etc., can be used. If component (B) is an alkylene oxide adduct of an alcohol, either a primary alcohol or a secondary alcohol can be used. A C13 alcohol can be produced using dodecene as a raw material, for example, but the starting material can be either butylene or propylene. If the carbon chain contains an unsaturated group, it is particularly preferable that the number of carbon atoms is 18. The stereoisomer structure of the unsaturated group may be the cis isomer, the trans isomer, or a mixture of both, but it is particularly preferable that the ratio of the cis / trans isomer is 25 / 75 to 100 / 0 (by mass).

[0025] As the alkylene oxide, ethylene oxide (EO) is preferred, but EO may also be added along with propylene oxide (PO) or butylene oxide (BO). The average number of moles of EO added is preferably 10 to 100 moles, more preferably 20 to 80 moles, and particularly preferably 40 to 70 moles. The average number of moles of PO or BO added along with EO is preferably 1 to 5, and more preferably 1 to 3 moles. In this case, EO may be added first, then PO or BO, or PO or BO may be added first, then EO.

[0026] (B) Specific examples of component include the average EO9PO1 adduct of nonyl alcohol, the average EO40 molar adduct of primary isononyl alcohol, the average EO20 molar adduct of primary isodecyl alcohol, the average EO20 molar adduct of lauryl alcohol, the average EO60 molar adduct of primary isohexadecyl alcohol, the average EO60 molar adduct of primary isotridecyl alcohol, the average EO50 molar adduct of tridecyl alcohol, the average EO60 adduct of beef tallow alkylamine, the average EO60 adduct of beef tallow alkylamine, the average EO50 adduct of oleylamine, and the average EO20 molar adduct of lauric acid. Commercially available products include the Emarex series from Nippon Emulsion, the Emarumin series from Sanyo Chemical Industries, the Leocol TDA series and Esomin series from Lion Specialty Chemicals, the Softanol series from Nippon Shokubai, and the LUTESOL series from BASF. (B) Component may be a single type or multiple types may be used in combination.

[0027] The content of component (B) is preferably 1% by mass or more, more preferably 1.2% by mass or more, less than 3% by mass, and more preferably 2.5% by mass or less, relative to the total mass of the liquid fabric softener composition. The above lower and upper limits can be combined as appropriate. When the content of component (B) is 1% by mass or more, the stabilizing effect of component (A) is better. When the content of component (B) is less than 3% by mass, the viscosity stability of the liquid fabric softener composition during long-term storage is better.

[0028] <(C) component> Component (C) is a quaternary ammonium salt compound represented by the following formula (C). (C) Component is added to the liquid fabric softener composition to impart antibacterial properties to the treated object and to suppress the generation of musty odors.

[0029] [ka] (In the formula, R 1 R is an alkyl or alkenyl group having 12 to 18 carbon atoms.2 , R 3 and R 4 Each of these is an alkyl group having 1 to 3 carbon atoms, and X - (This is an alkyl sulfate ion having an alkyl group with 1 to 3 carbon atoms.)

[0030] R 1 The alkyl or alkenyl group has 12 to 18 carbon atoms, with 16 being preferred. A carbon number of 14 to 18 atoms provides superior antibacterial effects. The alkyl or alkenyl group may be linear or branched, but linear is preferred. R 3 and R 4 Examples of alkyl groups include methyl, ethyl, and propyl groups, with methyl being preferred. X - Examples include methyl sulfate ions and ethyl sulfate ions, with methyl sulfate ions being preferred.

[0031] (C) Specific examples of components include, but are not limited to, hexadecyltrimethylammonium methosulfate (product name "Lipocard 16-50MSE", manufactured by Lion Specialty Chemicals Co., Ltd.). (C) Component may be a single type or multiple types may be used in combination.

[0032] The content of component (C) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, less than 1% by mass, and more preferably 0.5% by mass or less, relative to the total mass of the liquid fabric softener composition. The above lower and upper limits can be combined as appropriate. When the content of component (C) is 0.1% by mass or more, the antibacterial effect is better. When the content of component (C) is less than 1% by mass, the storage stability of the liquid fabric softener composition is good.

[0033] <Other ingredients> The liquid fabric softener composition may further contain other components besides the above-mentioned components (A) to (C), as necessary, to the extent that it does not impair the effects of the invention. Examples of other components include water, water-soluble solvents, viscosity modifiers, pH adjusters, silicones, preservatives, antibacterial agents (excluding components (A) and (C)), microcapsules, fragrances not encapsulated in capsules, dextrins, and the like.

[0034] [Water] The liquid softener composition of this embodiment is preferably an aqueous composition containing water. As the water, tap water, ion-exchanged water, pure water, distilled water, etc. can all be used. Among them, ion-exchanged water is preferable.

[0035] The content of water is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, based on the total mass of the liquid softener composition. When the content of water is 50% by mass or more, the handling property becomes better.

[0036] [Water-soluble solvent] The water-soluble solvent can be blended to improve the stability of the liquid softener composition, particularly the freeze-thaw stability. As the water-soluble solvent, one or more selected from the group consisting of alcohols having 1 to 4 carbon atoms, glycol ether solvents, and polyhydric alcohols are preferable. Specifically, at least one selected from the group consisting of ethanol, isopropanol, glycerin, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, hexylene glycol, polyoxyethylene phenyl ether, and the solvent represented by the following formula (X) is preferable. R 15 -O-(C2H4O) y -(C3H6O) z -H ···(X) (In the formula, R 15 is an alkyl group or alkenyl group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and y and z are the average number of added moles, respectively. y is 1 to 10, preferably 2 to 5, and z is 0 to 5, preferably 0 to 2.) Among those listed above, ethanol, ethylene glycol, butyl carbitol, propylene glycol, dipropylene glycol monomethyl ether, and diethylene glycol monobutyl ether are preferred.

[0037] When the liquid fabric softener composition contains a water-soluble solvent, the content of the water-soluble solvent is not particularly limited, but is preferably 0 to 30% by mass, more preferably 0.01 to 25% by mass, and even more preferably 0.1 to 20% by mass, relative to the total mass of the liquid fabric softener composition.

[0038] [Viscosity modifier] Viscosity modifiers can be added to improve the usability of the liquid softener composition. Specific examples of viscosity modifiers include calcium chloride, magnesium chloride, sodium chloride, sodium p-toluenesulfonate, and sodium citrate. Among these, calcium chloride, magnesium chloride, and sodium citrate are preferred. Viscosity modifiers may be used individually or in combination of multiple types. If the liquid fabric softener composition contains a viscosity modifier, the viscosity modifier content is preferably 0.001 to 0.5% by mass, more preferably 0.003 to 0.2% by mass, and even more preferably 0.005 to 0.1% by mass, relative to the total mass of the liquid fabric softener composition.

[0039] [pH adjuster] pH adjusters can be added to liquid fabric softener compositions to adjust their pH. Specific examples of pH adjusters include hydrochloric acid, sulfuric acid, phosphoric acid, alkyl sulfuric acid, benzoic acid, p-toluenesulfonic acid, citric acid, malic acid, succinic acid, lactic acid, glycolic acid, hydroxyethanediphosphonic acid, phytic acid, ethylenediaminetetraacetic acid, short-chain amine compounds such as dimethylamine, alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates, alkali metal silicates, and the like.

[0040] [silicone] Silicone can be incorporated primarily to further improve fragrance longevity. Silicone can be used without particular limitation any components known in the field of liquid softener compositions. The molecular structure of silicone may be linear, branched, or crosslinked. Furthermore, the silicone may be a modified silicone. The modified silicone may be modified with one or more organic functional groups. Silicone can be used in oil form, or in emulsion form dispersed with any emulsifier. Specific examples of silicones include dimethyl silicone, polyether-modified silicone, methylphenyl silicone, alkyl-modified silicone, higher fatty acid-modified silicone, methyl hydrogen silicone, fluorine-modified silicone, epoxy-modified silicone, carboxy-modified silicone, carbinol-modified silicone, and amino-modified silicone. Among these, dimethyl silicone, polyether-modified silicone, and amino-modified silicone are preferred from the viewpoint of versatility and improved fragrance persistence. From the viewpoint of further improving fragrance persistence and handling during manufacturing, polyether-modified silicone and amino-modified silicone are preferred.

[0041] There are no particular restrictions on the kinematic viscosity of dimethyl silicone, but it is generally between 1 and 100,000,000 mm². 2 / s is preferred, and 10 to 10,000,000 mm 2 / s is more preferable, 100~1,000,000mm 2 / s is even more preferable. Dimethyl silicone may be in the form of an oil or an emulsion.

[0042] Specific examples of polyether-modified silicones include copolymers of alkylsiloxanes and polyoxyalkylenes. The alkyl group of the alkylsiloxane preferably has 1 to 3 carbon atoms. The alkylene group of the polyoxyalkylene preferably has 2 to 5 carbon atoms. Preferred polyether-modified silicones include copolymers of dimethylsiloxane and polyoxyalkylene (such as polyoxyethylene, polyoxypropylene, and random or block copolymers of ethylene oxide and propylene oxide). Specific examples include, for example, the compounds represented by the following formula (I).

[0043] [Chemical Formula] (In the formula, M, N, a, and b are each independently the average degree of polymerization, and R 21 is a hydrogen atom or an alkyl group.)

[0044] In formula (I), M is preferably from 10 to 10,000, more preferably from 100 to 300. N is preferably from 1 to 1,000, more preferably from 1 to 100. Further, it is preferable that M > N. a is preferably from 2 to 100, more preferably from 2 to 50. b is preferably from 0 to 50, more preferably from 0 to 10. R 21 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0045] The polyether-modified silicone represented by formula (I) can generally be produced by subjecting an organohydropolysiloxane having a Si-H group and a polyoxyalkylene alkyl ether having a carbon-carbon double bond at the terminal, such as polyoxyalkylene allyl ether, to an addition reaction under a platinum catalyst. In this case, there may be slightly contained unreacted polyoxyalkylene alkyl ether or organohydropolysiloxane having a Si-H group in the product. Since the organohydropolysiloxane having a Si-H group has high reactivity, its abundance in the polyether-modified silicone is preferably 30 ppm or less (as the amount of Si-H).

[0046] A preferred polyether-modified silicone is a linear polysiloxane-polyoxyalkylene block copolymer represented by the following formula (II).

[0047] [ka] (In the formula, A, B, h, and i are the average degrees of polymerization, and R 22 R is a hydrogen atom or an alkyl group, 23 (This is an alkylene group.)

[0048] In formula (II), A is preferably between 5 and 10,000. B is preferably between 2 and 10,000. h is preferably between 2 and 100. i is preferably between 0 and 50. R 22 The hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred. R 23 A C1-C5 allele group is preferred.

[0049] A linear polysiloxane-polyoxyalkylene block copolymer represented by formula (II) can be produced by reacting a polyoxyalkylene compound having a reactive end group with a dihydrocarbylsiloxane having an end group that reacts with the reactive end group of the compound. The viscosity of such polyether-modified silicones increases as the polyoxyalkylene chains of the side chains become longer and the degree of polymerization of the polysiloxane chains increases. Therefore, in order to improve workability during production and facilitate blending into aqueous compositions, it is preferable to blend them in the form of a premix with a water-soluble organic solvent. Examples of water-soluble organic solvents include ethanol, dipropylene glycol, and butyl carbitol.

[0050] More specifically, examples of polyether-modified silicones include SH3772M, SH3775M, FZ-2166, FZ-2120, L-720, SH8700, L-7002, L-7001, SF8410, FZ-2164, FZ-2203, and FZ-2208 from Toray Dow Corning Co., Ltd.; KF352A, KF615A, X-22-6191, X-22-4515, KF-6012, and KF-6004 from Shin-Etsu Chemical Co., Ltd.; and TSF4440, TSF4441, TSF4445, TSF4450, TSF4446, TSF4452, and TSF4460 from Momentive Performance Materials Japan LLC.

[0051] Amino-modified silicones are formed by introducing amino groups to the terminal or side chains of a dimethyl silicone skeleton. Other substituents such as hydroxyl groups, alkyl groups, or phenyl groups may also be introduced. The amino-modified silicone may be in the form of an oil, or it may be in the form of an amino-modified silicone emulsion emulsified using a nonionic surfactant or a cationic surfactant as an emulsifier. A preferred base oil in an amino-modified silicone oil or emulsion is a compound represented by the following formula (III).

[0052] [ka] (In the formula, R 24 and R 26 These are a methyl group, a hydroxyl group, or a hydrogen atom, which may be the same or different from each other. R 25 is, -(CH2) n -A 1 , or -(CH2) n -NHCO-(CH2) m -A 1 (In each formula, A 1 is -N(R 27 )(R 28 ), -N + (R 27 )(R 28 )(R29 )·Z - (In each formula, R 27 , R 28 and R 29 These may be the same or different, and may be a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, or -(CH2) n -NH2 (where n is between 0 and 12), Z - (wherein m is a fluoride ion, chloride ion, bromide ion, iodide ion, methyl sulfate ion, or ethyl sulfate ion), and the values ​​of m and n may be the same or different, and are integers from 0 to 12. p and q represent the degree of polymerization of the polysiloxane, and may be the same or different. p is between 0 and 20000, preferably between 10 and 10000, and q is between 1 and 500, preferably between 1 and 100.

[0053] The amino-modified silicone oil has a kinematic viscosity of 50-20000 mmHg at 25°C. 2 It is preferable that it be / s, and 100 to 10000 mm 2 It is more preferable to use / s. Commercially available amino-modified silicones can be used. Examples of amino-modified silicone oils include those sold by Toray Dow Corning Ltd. as SF-8417, BY16-892, and BY16-890, and those sold by Shin-Etsu Chemical Co., Ltd. as KF-864, KF-860, KF-8004, KF-8002, KF-8005, KF-867, KF-861, KF-880, and KF-867S. Examples of amino-modified silicone emulsion types include those sold by Toray Dow Corning Co., Ltd. as SM8904, BY22-079, FZ-4671, and FZ-4672; those sold by Shin-Etsu Chemical Co., Ltd. as part of the Polon series, including PolonMF-14, PolonMF-29, PolonMF-14D, PolonMF-44, PolonMF-14EC, and PolonMF-52; and those sold by Asahi Kasei Wacker Silicone Co., Ltd. as WACKER FC201.

[0054] Silicone may be used individually or as a mixture of two or more types. When a liquid fabric softener composition contains silicone, the amount of silicone is not particularly limited as long as it is sufficient to achieve the intended purpose of the formulation. However, it is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and even more preferably 0.1 to 5% by mass, relative to the total mass of the liquid fabric softener composition.

[0055] [Preservatives] Preservatives can be added primarily to enhance the preservative and antibacterial properties of liquid fabric softener compositions and to maintain their preservative effect during long-term storage. As preservatives, any known components in the field of liquid fabric softener compositions can be used without particular limitation. Specific examples include isothiazolone-based organosulfur compounds, benzisothiazolone-based organosulfur compounds, benzoic acids, and 2-bromo-2-nitro-1,3-propanediol. Examples of isothiazolone-type organosulfur compounds include 5-chloro-2-methyl-4-isothiazolin-3-one, 2-n-butyl-3-isothiazolone, 2-benzyl-3-isothiazolone, 2-phenyl-3-isothiazolone, 2-methyl-4,5-dichloroisothiazolone, 5-chloro-2-methyl-3-isothiazolone, 2-methyl-4-isothiazolin-3-one, and mixtures thereof. Among these, 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one are preferred, and a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one is more preferred. A mixture in which the former is about 77% by mass and the latter is about 23% by mass, or a diluted solution thereof (e.g., isothiazolone solution), is particularly preferred. Examples of benzisothiazolon-type organosulfur compounds include 1,2-benzisothiazolin-3-one, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, related compounds such as dithio-2,2-bis(benzmethylamide), and mixtures thereof. Among these, 1,2-benzisothiazolin-3-one is particularly preferred. Examples of benzoic acids include benzoic acid or its salts, p-hydroxybenzoic acid or its salts, methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, propyl p-hydroxybenzoate, butyl p-hydroxybenzoate, and benzyl p-hydroxybenzoate. When a liquid fabric softener composition contains a preservative, the amount of preservative is not particularly limited as long as it is sufficient to achieve the intended purpose of the formulation, but it is preferably 0.0001 to 1% by mass relative to the total mass of the liquid fabric softener composition. If the amount is 0.0001% by mass or more, the preservative effect is sufficiently obtained, and if it is 1% by mass or less, the high storage stability of the liquid fabric softener composition can be sufficiently maintained.

[0056] [Antibacterial agent] Antimicrobial agents can be added to textile products to impart higher antimicrobial properties and to improve the shelf life of liquid fabric softener compositions. As antibacterial agents, any known components in the field of liquid fabric softener compositions can be used without particular limitation. Specific examples include diclosan, triclosan, benzalkonium chloride, bis-(2-pyridylthio-1-oxide)zinc, 8-oxyquinoline, biguanide compounds (e.g., polyhexamethylene biguanide), chlorohexidine hydrochloride, and polylysine. Among these, benzalkonium chloride, biguanide compounds, and chlorohexidine hydrochloride are preferred. When a liquid fabric softener composition contains an antibacterial agent, the amount of the antibacterial agent is not particularly limited as long as it is sufficient to achieve the intended purpose of the formulation, but it is preferably 0.001 to 5% by mass relative to the total mass of the liquid fabric softener composition.

[0057] [Functional Capsules] Functional capsules can be incorporated into liquid fabric softener compositions to impart various functions derived from the core material contained within the capsule. A functional capsule consists of a core material and a wall material that covers the core material.

[0058] As the core material, any material commonly used as a capsule encapsulant in the liquid fabric softener field can be used without particular restrictions. Specific examples include fragrances, essential oils, whitening agents, insect repellents, silicones, waxes, flavorings, vitamins, skincare agents, enzymes, probiotics, dyes, pigments, fragrance precursors, cooling agents, warming agents, attractants such as pheromones, antibacterial agents, bleaching agents, flavorings, sweeteners, waxes, pharmaceuticals, fertilizers, and herbicides. The core material may be of a single type or a combination of multiple types.

[0059] As the wall material, any material commonly used as encapsulation material in the field of liquid softener compositions can be used without particular limitations. Specific examples include natural polymers such as gelatin and agar, oily film-forming substances such as oils and waxes, and synthetic polymers such as polyacrylic acid, polyvinyl, polymethacrylic acid, melamine, and urethane. One of these can be used alone or two or more can be used in appropriate combination.

[0060] Specific examples of encapsulated fragrances with fragrance as the core substance include Firmenich's BLUEFLOWERPOP "FFMHN2814," Givaudan's GREEN BREEZE CAPS, ORCHARD GARDEN CAPS, RAINBOW CAPS, VELVET CAPS, AURORACAPS, and COSMICCAPS, and IFF's UNICAP101 and UNICAP503. Specific examples of cooling capsules that use a cooling agent as the core material include MultiSal SalCool, HydroSal FreshCool, and SalSphere SalCool from SALVONA Technologies, and NeoAge AROMA-C from Nikka Chemical Co., Ltd. Specific examples of heat-sensitive capsules that use a heat-sensitive agent as the core material include Riken Resin RMC-TO manufactured by Miki Riken Co., Ltd., and Hydrosal Heat manufactured by Salvona Technologies. Other specific examples include Riken Resin NFHO-W (antibacterial effect), Riken Resin RMC-HBP (insect repellent effect), and RMC-PT (insect repellent effect) manufactured by Miki Riken Co., Ltd.

[0061] The average particle size of the functional capsules is preferably 10 to 30 μm. Functional capsules having the above particle size exhibit excellent adsorption to textile products and can be stably dispersed in liquid softener compositions.

[0062] Functional capsules may be of a single type or multiple types may be used in combination. When a liquid fabric softener composition contains functional capsules, the amount of functional capsules is not particularly limited as long as the purpose of formulation is achieved, but is preferably 0.0001 to 1% by mass relative to the total mass of the liquid fabric softener composition.

[0063] [Fragrance] Fragrances can be added to liquid fabric softener compositions to add fragrance, or to textile products after treatment with the liquid fabric softener composition. Fragrances may also be added to textile products to provide odor-resistant properties through their masking effect. While there are no particular limitations on the fragrances that can be used in the liquid fabric softener field, lists of usable fragrance raw materials are found in various publications, such as "Perfume and Flavor Chemicals," Vol. I and II, Steffen Arctander, Allured Pub. Co. (1994), "Synthetic Fragrances: Chemistry and Product Knowledge," by Motoichi Indo, Chemical Daily Co. (1996), "Perfume and Flavor Materials of Natural Origin," Steffen Arctander, Allured Pub. Co. (1994), "Encyclopedia of Fragrances," edited by the Japan Fragrance Association, Asakura Shoten (1989), "Perfumery Material Performance V.3.3," Boelens Aroma Chemical Information Service (1996), and "Flower oils and Floral Compounds In Perfumery," Danute Lajaujis Anonis, Allured Pub. Co. (1993). Fragrance may be used as a single type, or multiple types may be used in combination (fragrance composition). The fragrance composition may contain solvents commonly used in liquid fabric softener compositions. Examples of solvents for fragrances include dipropylene glycol (DPG) and isopropyl myristerate (IPM).

[0064] [Dextrins] Examples of dextrins include cyclodextrins and highly branched cyclic dextrins. Highly branched cyclic dextrins are glucans with a degree of polymerization ranging from 50 to 10000, having an internally branched cyclic structure and an externally branched structure, where the internally branched cyclic structure is a cyclic glucan chain formed by α-1,4-glucosidic bonds and α-1,6-glucosidic bonds, and the externally branched structure is an acyclic glucan chain bonded to the internally branched cyclic structure. Examples of highly branched cyclic dextrins include cluster dextrin (manufactured by Glico Nutrition Foods Co., Ltd.). Dextrins may be used individually or in combination of two or more as appropriate.

[0065] <Liquid properties of liquid fabric softener compositions> From the viewpoint of the storage stability of the liquid fabric softener composition, the pH of the liquid fabric softener composition is preferably 2 to 4, and more preferably 2 to 3. pH is the value at 25°C. The pH adjusting agent described above can be used to adjust the pH.

[0066] The thixotropy index (TI) value of the liquid fabric softener composition at 25°C is preferably 2.0 or higher, more preferably 2.0 to 5.0, and even more preferably 2.5 to 4.0. A TI value of 2.0 or higher provides excellent thixotropy, further improving the dispersion stability of functional capsules and the like. On the other hand, a TI value of 5.0 or lower can suppress problems such as difficulty in dispensing the liquid fabric softener composition into the cap during metering.

[0067] The TI value was calculated using the following formula based on the viscosity values ​​after 10 rotations at rotation speeds of 6 rpm and 60 rpm for a composition adjusted to 25°C, using a Type B viscometer (TOKIMEC, rotor No. 2). TI value = (6 rpm viscosity value) / (60 rpm viscosity value) This TI value measures the dependence of shear rate (viscometer rotation speed) on viscosity and is used as an indicator of thixotropy. For Newtonian fluids like water, where viscosity does not change with shear rate, the TI value is 1. If the TI value is greater than 1, it indicates that the liquid has higher viscosity at lower shear forces compared to when the shear force is higher, and the liquid exhibits thixotropy.

[0068] The viscosity of the liquid fabric softener composition at 25°C is preferably 1 to 1000 MPa·s. When the viscosity is within this range, usability, separation stability of the fabric softener liquid, and dispersion stability of functional particles are good. The viscosity values ​​mentioned above are measured using a Type B viscometer at a rotational speed of 30 rpm.

[0069] From the viewpoint of visibility, the liquid fabric softener composition is preferably of the emulsion type. "Emulsification" refers to a condition where, using a glass cell with a 10 mm optical path length as the measurement cell and placing deionized water in the control cell, the visible light transmittance (wavelength 660 nm) of the sample is less than 30%.

[0070] <Method for preparing a liquid fabric softener composition> The method for preparing the liquid fabric softener composition is not particularly limited. The liquid fabric softener composition can be produced by known methods, for example, by methods similar to those used for conventional liquid fabric softener compositions using a cationic surfactant as the main component. For example, a liquid softener composition can be produced by mixing components (A), (B), and (C), along with other components as needed, to prepare an oil phase; mixing the resulting oil phase with an aqueous phase containing water under conditions of a temperature above the melting point of component (A) to prepare an emulsion; and adding and mixing other components to the resulting emulsion as needed.

[0071] <How to use liquid fabric softener composition> There are no particular restrictions on the method of using the liquid fabric softener composition, and it can be used in the same way as general fabric softener compositions. For example, one method is to dissolve the liquid fabric softener composition in the rinse water during the rinsing stage of washing and treat the garment (textile product), or to dissolve the liquid fabric softener composition in water in a container such as a basin, and then immerse the textile product in it for treatment. In either case, the liquid fabric softener composition is used after being diluted to an appropriate concentration, but the bath ratio (mass ratio of the treatment solution to the textile product) is preferably 3 to 100 times, and particularly preferably 5 to 50 times. Specifically, it is used in an amount such that the concentration of component (A) is preferably 0.01 ppm to 1000 ppm, and more preferably 0.1 ppm to 300 ppm, relative to the total amount of water used. The amount of liquid fabric softener composition used on the item to be washed (textile product) is preferably 0.3 to 2.0% owf (on the weight of fabric), more preferably 0.5 to 1.5% owf. Within this range, sufficient softening and antibacterial effects are easily obtained. The types of textile products treated with the liquid fabric softener composition are not particularly limited and include, for example, clothing, curtains, sofas, carpets, towels, handkerchiefs, sheets, and pillowcases. The materials are also not particularly limited and may be natural fibers such as cotton, silk, or wool, or synthetic fibers such as polyester.

[0072] <Features of this liquid fabric softener composition> This fabric softener is preferable to fabric softeners that use antibacterial agents containing chloride ions as counterions, because it reduces corrosion of stainless steel kettles during manufacturing. [Examples]

[0073] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description. In the examples, the amount of each component is shown in mass % (on a pure content basis unless otherwise specified).

[0074] (Raw materials used) [(A) component] The following A-1 was used. A-1: Cationic surfactant as described in Example 4 of Japanese Patent Publication No. 2003-12471 (85% purity, melting point 37°C). A-1 is a compound represented by the above formulas (A1-3), (A1-4), and (A1-5) (wherein R is the first character of each formula). 8 The composition contains a quaternary nucleotide (which is an alkyl group and alkenyl group having 15 to 17 carbon atoms) that has been quaternized with dimethyl sulfate.

[0075] [(B) Component] The following B-1 was used. B-1: Ethylene oxide adduct of primary isotridecyl alcohol (product name "Leocol TDA-400-75", manufactured by Lion Specialty Chemicals Co., Ltd., average number of moles of ethylene oxide added: 40, purity: 75%).

[0076] [Quaternary ammonium salt compounds (component (C) and its comparative products)] The following C-1 to C-5 were used. C-1: Tetradecyltrimethylammonium methosulfate. C-2: Hexadecyltrimethylammonium methosulfate (product name "Lipocard 16-50MSE", manufactured by Lion Specialty Chemicals Co., Ltd.). C-3: Benzalkonium chloride (product name "Lipocard CB-50", manufactured by Lion Specialty Chemicals Co., Ltd.). C-4: Dodecyltrimethylammonium chloride (product name "Lipocard 12-37w", manufactured by Lion Specialty Chemicals Co., Ltd.). C-5: Cetyltrimethylammonium chloride (product name "Lipocard 16-29", manufactured by Lion Specialty Chemicals Co., Ltd.).

[0077] [Other ingredients] The following ingredients were used in common. Water: Deionized water. Water-soluble solvent: Ethanol (100% pure). Viscosity modifier: Calcium chloride dihydrate (100% pure). pH adjuster: Hydrochloric acid (1 mol / L reagent, manufactured by Kanto Chemical Co., Ltd.).

[0078] (Test Example 1) <Preparation of liquid fabric softener composition> A liquid fabric softener composition was prepared using a stainless steel container (100 mm inner diameter, 150 mm height) and a stirrer (homomicker, manufactured by Primix) according to the following procedure. First, component (A), component (B), quaternary ammonium salt compound, and water-soluble solvent were mixed and stirred to obtain the oil phase. On the other hand, deionized water was used as the aqueous phase for balancing. The mass of the deionized water for balancing was equivalent to the remainder after subtracting the amount of the oil phase from 480g. Next, the aqueous phase, heated to above the melting point of component (A), was placed in a stainless steel container and stirred. The oil phase, also heated to above the melting point of component (A), was then added and stirred. Stirring was performed at a rotation speed of 5,000 rpm for 3 minutes after the addition of the oil phase. Subsequently, a viscosity modifier was added, and if necessary, an appropriate amount of pH adjuster was added to adjust the pH to 2.5 (at 25°C). Furthermore, deionized water was added to bring the total mass to 500g to obtain the desired liquid softener composition. Upon visual inspection of their appearance, each liquid softener composition in the examples and comparative examples was found to be opaque, as it was not transparent but rather cloudy to the extent that it could be immediately determined that its visible light transmittance under the aforementioned conditions was less than 30%. In Table 1, the "appropriate amount" of pH adjuster is the amount that brings the pH of the liquid fabric softener composition to 2.5. The "balance" of water is the amount that brings the total mass of the liquid fabric softener composition to 100%. The amounts of other ingredients are expressed as a percentage (%) of the total mass of the liquid fabric softener composition. The obtained liquid fabric softener compositions were evaluated as follows.

[0079] [Table 1]

[0080] <Evaluation of antibacterial activity against Staphylococcus aureus> [Treatment of test cloth] A test cloth was treated once using a simple beaker method with a liquid fabric softener composition. Specifically, water was placed in a beaker, the liquid fabric softener was dissolved in it, and then a test cloth in an amount that resulted in a bath ratio of 20 was added. After stirring for 3 minutes, the test cloth was removed and air-dried. Cotton Kanakine was used as the test cloth. The amount of liquid fabric softener composition used was 0.78% owf (on the weight of fabric).

[0081] [Antibacterial test] The treated test cloth was subjected to an antibacterial activity test against Staphylococcus aureus in accordance with the bacterial solution absorption method specified in JIS L 1902, following the procedure below, and the antibacterial activity value (Δlog) was determined. 10 The number of viable bacteria was calculated. If the antibacterial activity value is 2.2 or higher, it can be judged that there is an antibacterial effect. The 0.4g of the aforementioned test cloth was placed in a vial, and a bacterial suspension of Staphylococcus aureus (1 × 10) was prepared using a 20-fold diluted nutrient medium. 5 ~3×10 5 0.2 mL of CFU / mL was inoculated and allowed to stand at 37°C for 18 hours. Then, 20 mL of the extract (SCDLP medium) was added to a vial and stirred to extract bacteria from the test cloth. Tenfold serial dilutions were performed using SCDLP medium, and 1 mL of the resulting dilution was taken and mixed onto 15 mL of SCDLP agar medium that had been sterilized by autoclaving and kept warm at 50°C. The mixture was then incubated in a 37°C incubator for 1-2 days. After incubation, the number of colonies was counted to determine the number of viable bacteria. The same procedure was performed on untreated cloth to measure the number of viable bacteria, and the antibacterial activity value was calculated using these measurements.

[0082] [result] The results of the antibacterial test are shown in Figure 1. Test cloths treated with the liquid fabric softener composition of Comparative Example 1, which does not contain quaternary ammonium salt compounds, showed no antibacterial effect against Staphylococcus aureus. Test fabrics treated with the liquid fabric softener compositions of Examples 1-2 and Comparative Examples 2-4, which contain quaternary ammonium salt compounds, showed antibacterial effects against Staphylococcus aureus. In particular, the test fabrics treated with the liquid fabric softener compositions of Examples 1-2 showed superior antibacterial effects.

Claims

1. A liquid fabric softener composition, (A) Components: At least one compound selected from the group consisting of amine compounds having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms separated by an ester group (-COO-) and / or an amide group (-NHCO-), salts thereof, and quaternary compounds thereof, (B) Ingredients: Nonionic surfactant, (C) Component: Formula (C) below 【Chemistry 1】 (In the formula, R １ R is an alkyl or alkenyl group having 12 to 18 carbon atoms. ２ , R ３ and R ４ Each of these is an alkyl group having 1 to 3 carbon atoms, and X － (This refers to an alkyl sulfate ion having an alkyl group with 1 to 3 carbon atoms.) A quaternary ammonium salt compound represented by, A liquid fabric softener composition containing the following:

2. The liquid fabric softener composition according to claim 1, wherein the content of component (C) is 0.1% by mass or more and less than 1% by mass with respect to the total mass of the liquid fabric softener composition.

3. The liquid fabric softener composition according to claim 1 or 2, wherein the content of component (A) is 5% by mass or more and less than 15% by mass with respect to the total mass of the liquid fabric softener composition.

4. The liquid fabric softener composition according to claim 1 or 2, wherein the content of component (B) is 1% by mass or more and less than 3% by mass relative to the total mass of the liquid fabric softener composition.

5. A liquid softener composition according to claim 1 or 2, which is of the emulsion type.

6. A liquid softener composition according to claim 1 or 2, wherein the pH is 2 to 4.

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