TW201710490A - Liquid softener composition - Google Patents

Abstract

The present invention provides a liquid softener composition that can sustain exhibition of a scent intended at design, while suppressing occurrence of offensive smells. Specifically, provided is a liquid softener composition obtained by blending the following ingredients (A)-(C): (A) at least one compound selected from the group consisting of an amine-based compound having 1-3 hydrocarbon groups that are each optionally interrupted by an ester group (-COO-) and/or an amide group (-NHCO-) and that each have within a molecule thereof 10-26 carbon atoms, and salts and quaternary substances of the compound; (B) a sulfur-containing fragrance precursor; and (C) an antioxidant and/or a silicone compound.

Description

Liquid softener composition

This invention relates to a liquid softener composition. More specifically, the present invention relates to a liquid softener composition capable of suppressing the generation of an offensive odor and continuously exhibiting the desired aroma at the time of design.

In recent years, as a function of a softener, a consumer who requires the sustainability of a fragrance has been increasing, and various methods have been adopted. As one of the methods for achieving the persistence of flavor, a technique of using a fragrance precursor which chemically bonds a fragrance to a non-volatile matrix has been widely known in the fields of softeners, bleaches, and detergents (Patent Documents 1 to 4) ). The fragrance precursor is cleaved by the triggering of light or heat, water, etc., thereby continuously emitting a fragrance. In particular, it is known that the sulphur-containing flavor precursor of the thiol-bonded sulphur-containing sulphur-containing scent is excellent in persistence (Patent Document 1). [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-511710 (Patent Document 2) Japanese Patent Publication No. 2014-511414 (Patent Document 3) Japanese Patent Laid-Open Publication No. 2012-530812 [Patent Document 4] International Publication No. 2014 /176392

[Problems to be Solved by the Invention] However, the present inventors have found that when a sulfur-containing fragrance precursor is formulated into a liquid softener composition, a sulfur-like odor is generated from the liquid softener composition, and the design is not intended. A refreshing scent achieved. [Means for solving the problem]

The present inventors have made an effort to study the above-mentioned problems, and as a result, it has been found that when an antioxidant and/or an oxime compound is added to a liquid softener composition having a sulfur-containing flavor precursor, the generation of the odor can be suppressed and the design can be continued. The desired aroma (excellent fragrance). The present invention is based on the insights.

That is, the present invention relates to the following. A liquid softener composition comprising the following components (A) to (C): (A) at least one compound selected from the group consisting of an amine compound, a salt thereof and a quaternary compound thereof, The amine compound has one to three hydrocarbon groups having 10 to 26 carbon atoms which can be cleaved by an ester group (-COO-) and/or a mercaptoamine group (-NHCO-) in the molecule, and (B) a sulfur-containing spice precursor. And (C) an antioxidant and/or an anthrone compound. 2. The liquid softener composition according to 1, wherein the mass ratio of the component (B) to the component (C) ((B)/(C)) is 0.001 to 10. 3. The liquid softener composition according to the above 1 or 2, wherein the component (A) is a compound selected from the group consisting of the formula (A1-1) to the formula (A1-8), the salts thereof, and At least one compound of the group consisting of the quaternary compounds, [Chemical 1] In the formula (A1-1), R ⁷ and R ⁸ are each independently a hydrocarbon group having 10 to 26 carbon atoms, and in each of the formulae (A1-2) to (A1-8), R ⁹ and R ¹⁰ are each independently It is a hydrocarbon group having 7 to 21 carbon atoms]. 4. The liquid softener composition according to any one of 1 to 3, wherein the component (B) is at least one compound represented by the formula (B-1), YSGQ (B-1) Y represents a group selected from the group consisting of formula (Y-1) to formula (Y-7) or an isomer thereof, In each of the formulae (Y-1) to (Y-7), the wavy line indicates the position of the YS bond, the broken line indicates the position of the single bond or the double bond, S represents a sulfur atom, and G represents two. a divalent or trivalent group derived from a linear or branched alkyl or alkenyl group of 15 carbon atoms (the divalent or trivalent group may be selected from -OR ¹¹ group, -NR, as the case may be) ¹¹ ₂ , -COOR ¹¹ group and R ¹¹ group (in each group, R ¹¹ represents a hydrogen atom or a C1 to C6 alkyl group or an alkenyl group) is substituted by one or more groups, and Q represents hydrogen An atom, a -SY group or a -NR ¹² -Y group (in each group, Y is as defined above, and R ¹² is a hydrogen atom or a methyl group)]. 5. The liquid softener composition according to item 4, wherein the compound represented by the formula (B-1) is selected from the group consisting of 3-(dodecylthio)-1-(2,6,6-tri Methylcyclohex-3-ene-1-butanone (3-(dodecylthio)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone) and 4-(dodecylthio)-4-(2,6,6-trimethylcyclohex-2-en-1-yl)-2-butanone (4-(dodecylthio)-4-(2) , 6,6-trimethyl-2-cyclohexen-1-yl) -2-butanone) group. The liquid softener composition according to any one of 1 to 5, wherein the component (C) is selected from the group consisting of butylated hydroxytoluene (BHT) and butylated hydroxyanisole (butylated hydroxyanisole). At least one antioxidant in the group consisting of BHA), p-methoxyphenol, and uric acid. 7. The liquid softener composition according to any one of 1 to 6, wherein the component (C) is selected from the group consisting of dimethyl fluorenone, polyether modified fluorenone and amino modified fluorenone. At least one anthrone compound in the group. The liquid softener composition according to any one of the above 1 to 7, which comprises an antioxidant and an anthrone compound as the component (C). [Effects of the Invention]

As shown in the examples to be described later, the liquid softener composition of the present invention can suppress the generation of an offensive odor and continuously exhibit the desired flavor (excellent fragrance) at the time of design. Accordingly, the present invention is useful as a liquid softener composition having added value not found in previous liquid softener compositions.

The liquid softener composition of the present invention contains the following components (A) to (C): (A) at least one compound selected from the group consisting of an amine compound, a salt thereof and a quaternary compound thereof, The amine compound has one to three hydrocarbon groups having 10 to 26 carbon atoms which may be cleaved by an ester group (-COO-) and/or a mercapto group (-NHCO-), and (B) a sulfur-containing fragrance precursor. And (C) an antioxidant and/or an anthrone compound.

[Component (A)] The component (A) is [at least one compound selected from the group consisting of an amine compound, a salt thereof, and a quaternary compound thereof, and the amine compound has one to three molecules in the molecule. The ester group (-COO-) and/or the mercapto group (-NHCO-) is a hydrocarbon group having 10 to 26 carbon atoms cut off, and is a cationic surfactant. The component (A) is formulated to impart a softness (soft touch) to the fiber product (that is, the original function of the softener) to the liquid softener composition. The hydrocarbon group having 10 to 26 carbon atoms (hereinafter referred to as "long-chain hydrocarbon group" in the present specification) has a carbon number of 10 to 26, preferably 17 to 26, more preferably 19 to 24. When the carbon number is 10 or more, the flexibility imparting effect is good, and when it is 26 or less, the workability of the liquid softener composition is good. The long chain hydrocarbyl group may be saturated or unsaturated. In the case where the long-chain hydrocarbon group is unsaturated, the position of the double bond may be at any position. In the case where the double bond is one, the position of the double bond is preferably the center of the long-chain hydrocarbon group, or the central value is distributed. center. The long-chain hydrocarbon group may be a chain hydrocarbon group or a hydrocarbon group containing a ring in the structure, preferably a chain hydrocarbon group. The chain hydrocarbon group may be either a linear chain or a branched chain. The chain hydrocarbon group is preferably an alkyl group or an alkenyl group, more preferably an alkyl group.

The long-chain hydrocarbon group may be cleaved by an ester group (-COO-) and/or a guanamine group (-NHCO-). That is, the long-chain hydrocarbon group may be one in which at least one of the cleavage groups selected from the group consisting of an ester group and a guanamine group is contained in the carbon chain, and the carbon chain is cleaved by the cleavage group. When the cutting base is provided, it is preferable in terms of improving biodegradability and the like. In the case of having the above-mentioned cut group, the number of the cut groups of one long-chain hydrocarbon group may be one or two or more. That is, the long-chain hydrocarbon group may be cut by one of the cut bases, or may be cut by the cut base at two or more places. In the case of having two or more cutting groups, the respective cutting groups may be the same or different. Further, in the case where the long-chain hydrocarbon group has a cleavage group in the carbon chain, the carbon atom of the cleavage group is calculated as the carbon number of the long-chain hydrocarbon group. A long-chain hydrocarbon group is a fatty acid obtained by hydrogenating or partially hydrogenating an unsaturated portion by using an unhydrogenated fatty acid derived from industrially used tallow, and an unhydrogenated fatty acid or fatty acid derived from a plant such as palm tree or oil coconut. The ester or a fatty acid or a fatty acid ester obtained by hydrogenating or partially hydrogenating an unsaturated portion is introduced. As the amine compound, a secondary amine compound (two in a long-chain hydrocarbon group) or a tertiary amine compound (three in a long-chain hydrocarbon group) is preferable, and a tertiary amine compound is more preferable.

The amine compound is a compound represented by the following formula (A1). [Chemical 2] In the formula, R ¹ to R ³ are each independently a hydrocarbon group having 10 to 26 carbon atoms, and -CH ₂ CH(Y)OCOR ⁴ (Y is a hydrogen atom or CH ₃ , and R ⁴ is a hydrocarbon group having 7 to 21 carbon atoms) , -(CH ₂ ) _n NHCOR ⁵ (n is 2 or 3, R ⁵ is a hydrocarbon group having 7 to 21 carbon atoms), a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and -CH ₂ CH(Y)OH (Y) Is a hydrogen atom or CH ₃ ), or -(CH ₂ ) _n NH ₂ (n is 2 or 3), at least one of R ¹ to R ³ is a hydrocarbon group having 10 to 26 carbon atoms, -CH ₂ CH(Y) OCOR ⁴ or -(CH ₂ ) _n NHCOR ⁵ ].

In the general formula (A1), the hydrocarbon group having 10 to 26 carbon atoms in R ¹ to R ³ preferably has 17 to 26 carbon atoms, more preferably 19 to 24 carbon atoms. The hydrocarbon group may be saturated or unsaturated. As the hydrocarbon group, an alkyl group or an alkenyl group is preferred. In -CH ₂ CH(Y)OCOR ⁴ , Y is a hydrogen atom or CH ₃ , and particularly preferably a hydrogen atom. R ⁴ is a hydrocarbon group having 7 to 21 carbon atoms, preferably a hydrocarbon group having 15 to 19 carbon atoms. When a plurality of R ⁴ are present in the compound represented by the formula (A1), the plurality of R ^{4 's} may be the same or different.

R ⁴ is a hydrocarbon group obtained by removing the carboxyl residues (fatty acid residue) from a fatty acid having 8 to 22 (of COOH R ⁴⁾ carbon atoms in a source of the fatty acid R ⁴ (R ⁴ of COOH) can also be a saturated fatty acid It may be an unsaturated fatty acid, and may be a linear fatty acid or a branched fatty acid. Among them, a saturated or unsaturated linear fatty acid is preferred. In order to impart good water absorbability to the softened garment, the saturated/unsaturated ratio (mass ratio) of the fatty acid which is the source of R ⁴ is preferably from 90/10 to 0/100, more preferably from 80/20 to 0. /100. In the case where R ⁴ is an unsaturated fatty acid residue, a cis form and a trans form are present, and the mass ratio of the cis form to the trans form is preferably 40/60 to 100/0. Good for 70/30~90/10.

Specific examples of the fatty acid which is the source of R ⁴ include stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, elaidic acid, linoleic acid, and partially hydrogenated palm oil fatty acid (iodine price 10). ～60), or partially hydrogenated tallow fatty acid (iodine price 10 to 60). In particular, it is preferred to use two or more selected from the group consisting of stearic acid, palmitic acid, myristic acid, oleic acid, oleic acid, and linoleic acid in a predetermined amount to satisfy the following conditions (a). - Condition (c) to adjust the fatty acid composition. (a) The ratio (mass ratio) of the saturated fatty acid/unsaturated fatty acid is 90/10 to 0/100, more preferably 80/20 to 0/100. (b) The ratio (mass ratio) of the cis isomer/trans isomer is 40/60 to 100/0, more preferably 70/30 to 90/10. (c) The fatty acid having a carbon number of 18 is 60% by mass or more, preferably 80% by mass or more, the fatty acid having 20 carbon atoms is less than 2% by mass, and the fatty acid having 21 to 22 carbon atoms is less than 1% by mass.

In the group "-(CH ₂ ) _n NHCOR ⁵ " in the formula (A1), n is 2 or 3, and particularly preferably 3. R ⁵ is a hydrocarbon group having 7 to 21 carbon atoms, preferably a hydrocarbon group having 15 to 19 carbon atoms. When a plurality of R ⁵ are present in the compound represented by the formula (A1), the plurality of R ^{5 's} may be the same or different from each other. Specific examples of R ⁵ include the same as those of R ⁴ .

In the formula (A1), at least one of R ¹ to R ³ is a long-chain hydrocarbon group (hydrocarbon group having 10 to 26 carbon atoms), -CH ₂ CH(Y)OCOR ⁴ or -(CH ₂ ) _n NHCOR ⁵ ), Preferably, two are long chain hydrocarbon groups. In the case where one or both of R ¹ to R ³ is a long-chain hydrocarbon group, the remaining two or one are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, -CH ₂ CH(Y)OH or -(CH) ₂ ) _n NH ₂ , preferably an alkyl group having 1 to 4 carbon atoms, -CH ₂ CH(Y)OH or -(CH ₂ ) _n NH ₂ . Here, the alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group, and particularly preferably a methyl group. Y in -CH ₂ CH(Y)OH is the same as Y in -CH ₂ CH(Y)OCOR ⁴ . _{n in} -(CH ₂ ) _n NH ₂ is the same as n in -(CH ₂ ) _n NHCOR ⁵ .

Preferable examples of the compound represented by the formula (A1) include compounds represented by the following formula (A1-1) to formula (A1-8). [Chemical 3] In the formula ((A1-1), R ⁷ and R ⁸ each independently represent a hydrocarbon group having 10 to 26 carbon atoms. In each of the formulae (A1-2) to (A1-8), R ⁹ and R ¹⁰ are each independently a hydrocarbon group having 7 to 21 carbon atoms.

The hydrocarbon group in R ⁷ and R ⁸ is the same as the hydrocarbon group having 10 to 26 carbon atoms in R ¹ to R ³ in the above formula (A1). The hydrocarbon group having 7 to 21 carbon atoms in R ⁹ and R ¹⁰ is the same as the hydrocarbon group having 7 to 21 carbon atoms in R ^{4 of the} above formula (A1). Furthermore, when a plurality of R ⁹ are present in the formula, the plurality of R ⁹ may be identical to each other or different from each other.

The component (A) may be a salt of an amine compound. A salt of an amine compound can be obtained by neutralizing the amine compound with an acid. The acid used for the neutralization of the amine compound may be an organic acid or a mineral acid, and examples thereof include hydrochloric acid, sulfuric acid, and methyl sulfuric acid. Neutralization of the amine compound can be carried out by a known method.

The component (A) may also be a quaternary compound of an amine compound. The quaternary compound of the amine compound is obtained by reacting a quaternizing agent with the amine compound. Examples of the quaternizing agent used for the quaternization of the amine compound include a halogenated alkyl group such as a chloromethyl group or a dialkyl sulfuric acid such as dimethyl sulfate. When an amine compound is reacted with the quaternizing agent, an alkyl group of a quaternizing agent is introduced into a nitrogen atom of the amine compound to form a salt of a quaternary ammonium ion and a halide ion or a monoalkyl sulfate ion. 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. The quaternization of the amine compound can be carried out by a known method.

The component (A) is preferably at least one selected from the group consisting of a compound represented by the formula (A1), a salt thereof and a quaternary compound thereof, and more preferably selected from the formula (A1-1). At least one selected from the group consisting of a compound represented by the formula (A1-8), a salt thereof, and a quaternary compound thereof is particularly preferably selected from the group consisting of the formula (A1-4) to the formula (A1-6). At least one of the group consisting of a compound, a salt thereof, and a quaternary compound thereof. Particularly preferred is a quaternary compound of the compound represented by the formula (A1-4), a quaternary compound of the compound represented by the formula (A1-5), and a compound of the compound represented by the formula (A1-6). The grades are used in combination.

The compound represented by the formula (A1) and the formula (A1-1) to the formula (A1-8), the salt thereof and the quaternary compound thereof can be used commercially or by a known method. .

For example, a compound represented by the formula (A1-2) (hereinafter referred to as "compound (A1-2)") and a compound represented by the formula (A1-3) (hereinafter referred to as "compound (A1-3)" are included. The composition of the fatty acid methyl ester composition obtained by substituting the fatty acid composition described in the column of R ^{4 of the} general formula (A1) or the fatty acid in the fatty acid composition with the methyl ester of the fatty acid And synthesized by condensation reaction with methyldiethanolamine. In this case, it is preferable that the ratio of the ratio represented by the compound (A1-2)/compound (A1-3) is 99/1 to 50/50 in terms of the mass ratio. synthesis. Further, in the case of using the quaternary compound, it is more preferred to use dimethyl sulfate as the quaternizing agent. In this case, from the viewpoint of imparting flexibility, it is preferable that the ratio of the presence of the quaternary compound of the compound (A1-2) or the quaternary compound of the compound (A1-3) is 99/by mass ratio. 1 to 50/50 synthesis.

The compound represented by the formula (A1-4) (hereinafter referred to as "compound (A1-4)") and the compound represented by the formula (A1-5) (hereinafter referred to as "compound (A1-5)") The composition of the compound represented by the formula (A1-6) (hereinafter referred to as "compound (A1-6)") can be represented by the fatty acid composition or fatty acid described in the column of R ^{4 of the} formula (A1). The methyl ester composition is synthesized by a condensation reaction with triethanolamine. In this case, the content ratio of each component to the total mass of the compound (A1-4), the compound (A1-5), and the compound (A1-6) is preferably a compound (A1-4). ) is 1% by mass to 60% by mass, the compound (A1-5) is 5% by mass to 98% by mass, the compound (A1-6) is 0.1% by mass to 40% by mass, and more preferably the compound (A1-4) is 30% by mass to 60% by mass, the compound (A1-5) is 10% by mass to 55% by mass, and the compound (A1-6) is 5% by mass to 35% by mass. Further, in the case of using the quaternary compound, it is more preferable to use dimethyl sulfate as the quaternizing agent in terms of sufficiently performing the quaternization reaction. From the viewpoint of imparting flexibility, the ratio of the presence of each of the quaternary compounds of the compound (A1-4), the compound (A1-5), and the compound (A1-6) is preferably a mass ratio of the compound (A1-4). The quaternary compound is from 1% by mass to 60% by mass, the quaternary compound of the compound (A1-5) is from 5% by mass to 98% by mass, and the quaternary compound of the compound (A1-6) is from 0.1% by mass to 40% by mass. More preferably, the quaternary compound of the compound (A1-4) is 30% by mass to 60% by mass, and the quaternary compound of the compound (A1-5) is 10% by mass to 55% by mass, and the compound (A1-6) The quaternary compound is 5% by mass to 35% by mass. Further, when the compound (A1-4), the compound (A1-5), and the compound (A1-6) are subjected to quaternization, an esteramine which is not subjected to quaternization is usually left after the quaternization reaction. In this case, the ratio of the "quaternary compound/esterified amine ester" is preferably in the range of 70/30 to 99/1 by mass.

The compound represented by the formula (A1-7) (hereinafter referred to as "compound (A1-7)") and the compound represented by the formula (A1-8) (hereinafter referred to as "compound (A1-8)") may be used. It is synthesized by a condensation reaction of a fatty acid composition described in the column of R ^{4 of the} general formula (A1) with N-(2-hydroxyethyl)-N-methyl-1,3-propanediamine. The N-(2-hydroxyethyl)-N-methyl-1,3-propanediamine is described by J. Org. Chem., 26, 3409 (1960). A well-known method is synthesized from an adduct of N-methylethanolamine and acrylonitrile. In this case, it is preferred that the ratio of the compound represented by the compound (A1-7)/compound (A1-8) is 99/1 to 50/50 by mass ratio. Further, in the case of using the quaternary compound, it is preferred to use a chloromethyl group as the quaternization agent, and it is preferably a "quaternary compound of the compound (A1-7)/quaternary compound of the compound (A1-8)" The ratio of existence indicated is synthesized in such a manner that the mass ratio is from 99/1 to 50/50.

The component (A) may be an amine compound, a salt thereof or a quaternary compound thereof, or a mixture of two or more kinds thereof, for example, a compound represented by the formula (A1-4) to the formula (A1-6). Use as a mixture.

The amount of the component (A) is not particularly limited as long as it can achieve the purpose of blending, and is preferably 5% by mass to 50% by mass, and more preferably 8% by mass based on the total mass of the liquid softener composition. ～30% by mass, and more preferably 10% by mass to 20% by mass.

[(B) component] The component (B) is a sulfur-containing spice precursor. The "sulfur-containing fragrance precursor" refers to a compound obtained by chemically bonding a fragrance to a non-volatile substrate containing sulfur. The fragrance precursor itself does not emit a fragrance, and if the bond between the fragrance and the substrate is cut by heat or light, water, or the like, the fragrance is released, thereby giving off the fragrance. Therefore, it has been found that when the clothes are treated with the fragrance precursor, the effect as a fragrance is exhibited even in the latter half of the time after the clothes are worn or after storage. The component (B) is formulated to impart a fragrance to the fiber product treated with the liquid softener composition.

As the sulfur-containing flavor precursor, it can be used in a liquid softener composition without any particular limitation. It is preferred to use a compound represented by the following formula (B-1) as the component (B), that is, a sulfur-containing flavor precursor. Y-S-G-Q (B-1)

In the formula (B-1), Y represents a group selected from the group consisting of the group (Y-1) to the group (Y-7) shown below or an isomer thereof, In each of the formulae (Y-1) to (Y-7), the wavy line indicates the position of the YS bond, the broken line indicates the position of the single bond or the double bond, S represents a sulfur atom, and G represents two. a divalent or trivalent group derived from a linear or branched alkyl or alkenyl group of 15, preferably 10 to 14 carbon atoms (the divalent or trivalent group may be optionally One or more selected from the group consisting of -OR ¹¹ group, -NR ¹¹ ₂ group, -COOR ¹¹ group and R ¹¹ group (wherein R ¹¹ represents a hydrogen atom or a C1 to C6 alkyl group or an alkenyl group) Substituting for a group), Q represents a hydrogen atom, a -SY group or a -NR ¹² -Y group (in each group, Y is as defined above, and R ¹² is a hydrogen atom or a methyl group). Here, the "isomer" of the group represented by each of the formulae (Y-1) to (Y-7) in the general formula (B-1) means that the hetero group of each group can be chemically employed. A body, such as a stereoisomer.

The compound represented by the formula (B-1) may be used alone or in combination of two or more.

Preferred examples of the compound represented by the formula (B-1) include a group selected from methyl 2-(4-oxo-4-(2,6,6-trimethylcyclohex-3-ene)- 1-yl)butan-2-ylamino)-3-(4-oxo-4-(2,6,6-trimethylcyclohex-3-en-1-yl)butan-2- Propionate or ethyl 2-(4-oxo-4-(2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-ylamino)- 3-(4-oxo-4-(2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-ylthio)propionate, methyl 2-(4- Oxo-4-(2,6,6-trimethylcyclohex-2-en-1-yl)butan-2-ylamino)-3-(4-oxo-4-(2,6) ,6-trimethylcyclohex-2-en-1-yl)butan-2-ylthio)propionate or ethyl 2-(4-oxo-4-(2,6,6-trimethyl) Cyclohexyl-2-en-1-yl)butan-2-ylamino)-3-(4-oxo-4-(2,6,6-trimethylcyclohex-2-ene-1 -yl)butan-2-ylthio)propionate, methyl 2-(2-oxo-4-(2,6,6-trimethylcyclohex-1-en-1-yl)butane 4-ylamino)-3-(2-oxo-4-(2,6,6-trimethylcyclohex-1-en-1-yl)butan-4-ylthio)propionate Or ethyl 2-(2-oxo-4-(2,6,6-trimethylcyclohex-1-en-1-yl)butan-4-ylamino)-3-(2-oxo Derivative 4-(2,6,6-trimethylcyclohex-1-en-1-yl)butan-4-ylthio)propionate, methyl 2-(2- -4--4-(2,6,6-trimethylcyclohex-2-en-1-yl)butan-4-ylamino)-3-(2-oxo-4-(2,6, 6-Trimethylcyclohex-2-en-1-yl)butan-4-ylthio)propionate or ethyl 2-(2-oxo-4-(2,6,6-trimethyl) Cyclohex-2-en-1-yl-butan-4-ylamino)-3-(2-oxo-4-(2,6,6-trimethylcyclohex-2-ene-1- Butyl-4-ylthio)propionate, 3-(dodecylthio)-1-(2,6,6-trimethylcyclohex-3-en-1-yl)-1 -butanone, 3-(dodecylthio)-1-(2,6,6-trimethylcyclohex-2-en-1-yl)-1-butanone, 4-(dodecane Thio)-4-(2,6,6-trimethylcyclohex-2-en-1-yl)-2-butanone, 4-(dodecylthio)-4-(2, 6,6-trimethylcyclohex-1-en-1-yl)-2-butanone, 2-dodecylmercapto-5-methyl-heptan-4-one, 2-cyclohexyl-1 a compound of the group consisting of dodecyldecyl-hept-6-en-3-one and 3-(dodecylthio)-5-isopropenyl-2-methylcyclohexanone. From the viewpoint of enhancing the sustainability of the flavor, it is further preferred to be selected from 3-(dodecylthio)-1-(2,6,6-trimethylcyclohex-3-en-1- 1-butanone, 4-(dodecylthio)-4-(2,6,6-trimethylcyclohex-2-en-1-yl)-2-butanone, 4- (dodecylthio)-4-(2,6,6-trimethylcyclohex-1-en-1-yl)-2-butanone and 3-(dodecylthio)-5 a compound of the group consisting of -isopropenyl-2-methylcyclohexanone, preferably selected from the group consisting of 3-(dodecylthio)-1-(2,6,6-trimethyl) Cyclohex-3-en-1-yl)-1-butanone and 4-(dodecylthio)-4-(2,6,6-trimethylcyclohex-2-en-1- a compound in the group consisting of -2-butanone.

Sulfur-containing flavor precursors are readily available in the market or can be synthesized by well-known methods.

As the component (B), a sulfur-containing flavor precursor may be used alone, or a mixture of two or more kinds may be used.

The amount of the component (B) is not particularly limited as long as it can achieve the purpose of blending, and is preferably 0.0001% by mass to 1% by mass, and more preferably 0.005% by mass based on the total mass of the liquid softener composition. It is preferably 0.5% by mass, and more preferably 0.01% by mass to 0.2% by mass.

[Component (C)] The component (C) is an antioxidant (hereinafter also referred to as "(C1) component") and/or an anthrone compound (hereinafter also referred to as "(C2) component").

[Component (C1): Antioxidant] The antioxidant as the component (C1) is used for the purpose of suppressing generation of sulfur-like odor derived from the component (B) (sulfur-containing flavor precursor). As the antioxidant, a compound known to have an antioxidant effect can be usually used without particular limitation. Therefore, any of a water-soluble antioxidant and an oil-soluble antioxidant can be used, and an oil-soluble antioxidant is preferred. Specific examples of the component (C1) include dibutylhydroxytoluene (BHT), butylhydroxymethoxybenzene (BHA), p-methoxyphenol, β-naphthol, and phenyl-α-naphthylamine. , tetramethyldiaminodiphenylmethane, γ-sterzanol, vitamin E (α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol), uric acid, vitamin C (L-ascorbic acid), trehalose, 2,2'-ethylenebis(4,6-di-t-butylphenol), tris(tetramethylhydroxypiperidinol)·1/3 citrate, Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, quercetin and 4,4'-bis(α,α-dimethylbenzyl)diphenyl Alkylamine and the like. Among these, at least one selected from the group consisting of phenolic antioxidants as oil-soluble antioxidants is preferred, and is preferably selected from the group consisting of dibutylhydroxytoluene (BHT), butylhydroxymethoxybenzene (BHA), and 2,2. At least one of '-ethylene bis(4,6-di-tert-butylphenol), p-methoxyphenol, and γ-net alcohol. More preferably selected from the group consisting of dibutylhydroxytoluene (BHT), butylhydroxymethoxybenzene (BHA), p-methoxyphenol and 2,2'-ethylene bis(4,6-di-t-butyl) The compound in the group consisting of phenol) is further preferably dibutylhydroxytoluene (BHT).

The component (C1) can be easily obtained in the market or can be synthesized by a known method.

The component (C1) may be used alone or in combination of two or more.

The amount of the component (C1) is not particularly limited as long as it can achieve the purpose of blending, and is preferably 0.001% by mass to 5% by mass, and more preferably 0.005% by mass based on the total mass of the liquid softener composition. ～2质量%, more preferably 0.01% by mass to 1% by mass, particularly preferably 0.01% by mass to 0.1% by mass. When the blending amount is from 0.001% by mass to 5% by mass, an excellent blending effect can be obtained.

[(C2) component: anthrone compound] The component (C2) is an anthrone compound, but the type thereof is not particularly limited and can be appropriately selected. The component (C2) is used for the purpose of suppressing the generation of sulfur-like odor derived from the component (B) (sulfur-containing flavor precursor). Further, the present invention is not limited by a specific theory, and an anthrone compound having a property of excellent gas absorbability (solubility) captures a malodorous substance (gas) generated by decomposition of a sulfur-containing fragrance precursor, and therefore it is considered that such as suppression can be suppressed. The production of sulfur-like odor. The molecular structure of the anthrone compound may be linear or branched, and may also be crosslinked. Further, the anthrone compound may be a modified indolinone compound which may be modified by one organic functional group or may be modified by two or more organic functional groups. The anthrone compound can be used in the form of an oil, or can be used in the state of being dispersed by an emulsifier. Specific examples of the anthrone compound include dimethyl fluorenone, polyether modified fluorenone, methyl phenyl fluorenone, alkyl modified fluorenone, higher fatty acid modified fluorenone, and methylhydroquinone. A ketone, a fluorine-modified fluorenone, an epoxy-modified fluorenone, a carboxy-modified fluorenone, a methanol-based modified fluorenone or an amine-based fluorenone. Among these, from the viewpoint of improving the compounding effect, polyether modified fluorenone, amino modified fluorenone and dimethyl fluorenone are preferred, and polyether modified fluorenone and amine modified are preferred. Anthrone.

Specific examples of the polyether modified fluorenone include a copolymer of an alkyl siloxane and a polyoxyalkylene group. Further, the alkyl group of the alkyl siloxane has a carbon number of preferably 1 to 3, and the alkylene group of the polyoxyalkylene group preferably has 2 to 5 carbon atoms. Among these, as the polyether modified fluorenone, dimethyl methoxy oxane and polyoxyalkylene group (polyoxyalkylene, polyoxypropylidene, ethylene oxide and propylene oxide) are preferred. Copolymers of random or block copolymers, etc.). Specific examples of such a polyether-modified fluorenone include a compound represented by the following formula (I), a compound represented by the following formula (II), and the like.

General formula (I): [Chemical 4]

In the above formula (I), M, N, a and b represent the average degree of polymerization, and R represents hydrogen or an alkyl group. Here, M is from 10 to 10,000, more preferably from 100 to 300. N is from 1 to 1,000, more preferably from 1 to 100. Further, M>N. a is 2 to 100, more preferably 2 to 50. b is 0 to 50, more preferably 0 to 10. R is hydrogen or an alkyl group having 1 to 4 carbon atoms.

The polyether modified fluorenone represented by the above formula (I) can be usually obtained by a platinum catalyst such as polyoxyalkylene alkyl allylate having a polyoxyalkylene group having a carbon-carbon double bond at the end. The ether is produced by an addition reaction with an organic hydrogen polyoxyalkylene having a Si-H group. Therefore, there are sometimes some unreacted polyoxyalkylene alkyl ethers or organic hydrogen polyoxyalkylenes having a Si-H group in the polyether modified fluorenone. The organic hydrogen polyoxyalkylene having a Si-H group has high reactivity, and therefore the amount of the polyether modified anthrone is preferably 30 ppm or less (the amount of Si-H).

General formula (II):

In the formula (II), A, B, h and i represent the average degree of polymerization, R represents an alkyl group, and R' represents hydrogen or an alkyl group. Here, A is 5 to 10,000, and B is 2 to 10,000. h is 2 to 100, and i is 0 to 50. R is preferably an alkyl group having 1 to 5 carbon atoms. R' is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms.

The linear polyoxyalkylene-polyoxyalkylene alkyl block copolymer represented by the formula (II) can be obtained by reacting a polyoxyalkylene group compound having a reactive terminal group with the compound It is produced by reacting a hydrocarbyl oxirane of a terminal group of a reactive terminal group reaction. Since the polyether-modified anthrone has a long polyalkylene chain length of a side chain, the polymerization degree of the polyoxyalkylene chain is higher, and the viscosity is higher, so that workability at the time of production and preparation into an aqueous composition are easily improved. Therefore, it is preferably supplied in a form mixed with a water-soluble organic solvent in advance. Examples of the water-soluble organic solvent include ethanol, dipropylene glycol, and butyl carbitol.

As the polyether modified fluorenone, more specifically, for example, SH3772M, SH3775M, FZ-2166, FZ-2120, L-720, and SH8700 manufactured by Toray Dow Corning Co., Ltd. , L-7002, L-7001, SF8410, FZ-2164, FZ-2203, FZ-2208, KF352A, KF615A, X-22-6191, X-22-4515, KF-6012 manufactured by Shin-Etsu Chemical Co., Ltd. , KF-6004, etc., TSF4440, TSF4441, TSF4445, TSF4450, TSF4446, TSF4452, TSF4460, etc. manufactured by Momentive Performance Materials Japan Co., Ltd.

The amine-based fluorenone is an fluorenone oil which introduces an amine group at the terminal or side chain of the dimethyl fluorenone skeleton, and may be substituted with a substituent such as a hydroxyl group, an alkyl group or a phenyl group in addition to the amine group. In addition, the amino-based modified fluorenone may be in the form of an oil, or may be an amine-based modified emulsifier which emulsifies a nonionic surfactant or a cationic surfactant (which may also be the component (A)) as an emulsifier. The state of the ketone emulsion. The base oil in the case of an oil or emulsion of a preferred amine-based fluorenone is represented by the following formula (III). [Chemical 5]

In the formula (III), R ₁ and R ₆ may be the same or different from each other, and represent any of a methyl group, a hydroxyl group and hydrogen. R ₂ represents any of -(CH ₂ ) _n -A ₁ and -(CH ₂ ) _n -NHCO-(CH ₂ ) _m -A ₁ . A ₁ represents any of -N(R ₃ )(R ₄ ) and -N ⁺ (R ₃ )(R ₄ )(R ₅ )·X ^- . R ₃ to R ₅ may be the same or different from each other, and may represent any of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, and -(CH ₂ ) _n -NH ₂ . X ^- represents any one of a fluoride ion, a chloride ion, a bromide ion, an iodide ion, a sulfate methyl ion, and an ethyl sulfate ion. The values of m and n may be the same as each other or different, and represent an integer of 0 to 12. The values of p and q indicate the degree of polymerization of polyoxyalkylene, and may be the same or different, p represents 0 to 20,000, preferably 10 to 10,000, and q represents 1 to 500, preferably 1 to 100.

When the oil using the amine-modified fluorenone is used as the component (C2), the dynamic viscosity at 25 ° C is preferably from 50 mm ² /s to 20000 mm ² /s, more preferably from 100 mm ² /s to 10000 mm ² /s. When the dynamic viscosity is in the above range, a high blending effect is exhibited, and the manufacturability is good, and the workability of the composition is also easy, which is preferable. As the amino-based fluorenone, a commercially available one can be used, for example, as an amine-based fluorenone oil, and SF-8417, BY16-892, and Toray Dow Corning Co., Ltd. can be cited. BY16-890 is sold by KF-864, KF-860, KF-8004, KF-8002, KF-8005, KF-867, KF-861, KF-880, KF-867S, etc. . As the amine-based modified fluorenone emulsion type, Toray Dow Corning Co., Ltd., sold by SM8904, BY22-079, FZ-4671, FZ-4672, Shin-Etsu Chemical Co., Ltd. Polon MF-14, Polon MF-29, Polon MF-14D, Polon MF-44, Polon sold in the Polon series ) MF-14EC, Polon MF-52.

When dimethyl fluorenone is used as the component (C2), the dynamic viscosity (25 ° C) is not particularly limited, and is preferably 1 mm ² /s to 100,000,000 mm ² /s, more preferably 10 mm ² /s ～ 10,000,000 mm ² /s, and preferably 100 mm ² /s to 1,000,000 mm ² /s. Further, the methyl ketone may be an oil or an emulsion. As dimethyl fluorenone, a commercially available one can be used. As dimethyl fluorenone, for example, Toray Dow Corning Co., Ltd. is commercially available as BY 22-050A.

The component (C2) may be used alone or in combination of two or more.

The amount of the component (C2) is not particularly limited as long as it can achieve the purpose of blending, and is preferably 0.001% by mass to 10% by mass, and more preferably 0.005% by mass based on the total mass of the liquid softener composition. ～5% by mass, more preferably 0.01% by mass to 5% by mass, particularly preferably 0.1% by mass to 5% by mass.

As the component (C), either the (C1) component or the (C2) component may be used alone, or the (C1) component and the (C2) component may be used in combination. When the component (C1) and the component (C2) are used in combination, a higher blending effect can be exhibited, which is preferable. When the (C1) component and the (C2) component are used in combination, the mass ratio of the (C1) component to the (C2) component ((C1)/(C2)) can be obtained in terms of achieving a higher compounding effect. It is preferably 0.0001 to 5, more preferably 0.001 to 1, and still more preferably 0.002 to 0.1. In addition, when the component (C1) and the component (C2) are used in combination, the total amount of the component (C1) and the component (C2) is not particularly limited as long as it can be used for the purpose of blending, and is soft with respect to the liquid. The total mass of the agent composition is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 5% by mass, even more preferably 0.05% by mass to 5% by mass.

In the present invention, the mass ratio of the component (B) to the component (C) ((B)/(C)) is preferably 0.001 to 10, more preferably 0.005 to 10, still more preferably 0.01 to 5. When (B)/(C) is set to 0.001 to 10, a higher (C) component can be obtained (the effect of suppressing the generation of odor such as sulfur), and the liquid softener composition can be suppressed. The viscosity is increased to maintain the usability more satisfactorily. Further, when the component (C1) is used alone as the component (C), the mass ratio of the component (B) to the component (C) ((B)/(C1)) is preferably 0.01 to 10, more preferably 0.1 to 10, and more preferably 0.5 to 5. Further, when the component (C2) is used alone as the component (C), the mass ratio of the component (B) to the component (C) ((B)/(C2)) is preferably 0.001 to 1, more preferably 0.005 to 0.5, and more preferably 0.01 to 0.1.

Arbitrary component Any component other than the essential components (A) to (C) may be blended into the liquid softener composition of the present invention as needed within the range which does not impair the effects of the present invention. As an arbitrary component, the component normally mix|blended with the liquid softener composition is mentioned. Specific examples include water, nonionic surfactants, perfumes, water-soluble salts, dyes, water-soluble solvents, preservatives, ultraviolet absorbers, antibacterial agents, deodorants, skin care ingredients, and the like. . Hereinafter, a number of arbitrary components will be described in detail.

Water The liquid softener composition of the present invention is preferably an aqueous composition containing water. As the water, any of tap water, purified water, pure water, distilled water, ion-exchanged water, or the like can be used. Among them, ion-exchanged water is preferred. The amount of water to be formulated is not particularly limited, and may be appropriately formulated in order to achieve a desired composition.

Nonionic surfactant (hereinafter also referred to as "(D) component") The nonionic surfactant can be used to emulsify the oil-soluble component in the emulsion mainly in the case where the liquid softener composition of the present invention is an emulsion. The dispersion stability is formulated for the purpose. When a nonionic surfactant is formulated, it is easy to ensure a sufficient level of freeze recovery stability in terms of commercial value. As the nonionic surfactant, for example, a polyol, a higher alcohol, a higher amine or a higher fatty acid can be used. More specifically, a fatty acid ester or pentaerythritol in which an aliphatic group having 10 to 22 carbon atoms is ester-bonded on glycerin or pentaerythritol; an alkyl group or an alkenyl group having 10 to 22 carbon atoms, and ethylene oxide; The average addition molar number is from 10 moles to 100 moles of polyoxyethylidene ether; polyoxyalkylene fatty acid alkyl (the alkyl group has 1 to 3 carbon atoms) ester; a polyoxyalkyleneamine having an average addition molar number of from 10 moles to 100 moles; an alkyl polyglucoside having an alkyl or alkenyl group having from 8 to 18 carbon atoms; The average addition molar amount is from 10 moles to 100 moles of hardened castor oil. Among them, a polyoxyalkylene ether having an alkyl group having 10 to 18 carbon atoms and an average addition mole number of ethylene oxide of 20 to 80 moles is preferred. The nonionic surfactant may be used singly or as a mixture of two or more. The amount of the nonionic surfactant to be added is not particularly limited as long as it can achieve the purpose of blending, and is preferably 0.01% by mass to 10% by mass, and more preferably 0.1% by mass based on the total mass of the liquid softener composition. From 8% by mass to 8% by mass, more preferably from 0.5% by mass to 5% by mass.

Perfume (hereinafter also referred to as "(E) component)) A fragrance other than the component (B) (sulfur-containing flavor precursor) may be blended as an optional component in the liquid softener composition. As the perfume, a perfume which is generally used in the technical field can be used, and it is not particularly limited, and a list of usable perfume raw materials can be used in various documents such as "Perfume and Flavor Chemicals", Vol. I and II, Steffen Arctander, Allured Pub. Co. (1994) and "Synthetic Fragrance Chemistry and Commodity Knowledge", Shinto Yuichi, Chemical Industry Daily (1996) and "Flavours and Flavors" Perfume and Flavor Materials of Natural Origin, Steffen Arctander, Allured Pub. Co. (1994) and Fragrance Encyclopedia, Japanese Spice Association, Asakura Bookstore (1989) and "Perfumery Material Performance V.3.3", Boelens Aroma Chemical Information Service (1996) and "Flower oils and Floral Compounds" In Perfumery)", Danute Lajaujis Anonis, Glamour Publishing Company (Allur Ed Pub. Co.) (1993) and others are described. The fragrance may be used alone or in combination of two or more. The amount of the fragrance is not particularly limited as long as it is a target for the purpose of blending, and is preferably 0.1% by mass to 3% by mass, and more preferably 0.5% by mass to 2% by mass based on the total mass of the liquid softener composition. % is further preferably 0.5% by mass to 1.5% by mass.

Water-soluble salts (hereinafter also referred to as "(F) components") Water-soluble salts can be formulated for the purpose of controlling the viscosity of the liquid softener composition. As the water-soluble salt, any of an inorganic salt and an organic salt can be used. Specifically, calcium chloride, magnesium chloride, sodium chloride, sodium p-toluenesulfonate or the like can be used, and among them, calcium chloride or magnesium chloride is preferred. The water-soluble salts may be used singly or as a mixture of two or more kinds. The amount of the water-soluble salt is not particularly limited as long as it can achieve the purpose of blending, and is 0% by mass to 1% by mass based on the total mass of the liquid softener composition. Further, the water-soluble salts can also be formulated in any step of the manufacture of the liquid softener composition.

pH of the liquid softener composition The pH of the liquid softener composition is not particularly limited, and it is preferably from the viewpoint of suppressing hydrolysis of the ester group contained in the molecule of the component (A) accompanying the storage elapsed time. The pH at 25 ° C is adjusted to a range of 1 to 6, more preferably to a range of 2 to 4. In addition, in order to further suppress decomposition of the sulfur-containing flavor precursor as the component (B), it is preferred to set the pH of the liquid softener composition at 25 ° C to 8 or less, more preferably 6 or less. For pH adjustment, hydrochloric acid, sulfuric acid, phosphoric acid, alkyl sulfuric acid, benzoic acid, p-toluenesulfonic acid, citric acid, malic acid, succinic acid, lactic acid, glycolic acid, hydroxyethane diphosphonic acid, phytic acid can be used. (phytic acid), short-chain amine compounds such as ethylenediaminetetraacetic acid, triethanolamine, diethanolamine, dimethylamine, N-methylethanolamine, N-methyldiethanolamine, alkali metal hydroxides such as sodium hydroxide, A pH adjuster such as an alkali metal carbonate or an alkali metal ruthenate.

Viscosity of the liquid softener composition The viscosity of the liquid softener composition is not particularly limited as long as it does not impair the usability, and it is preferred that the viscosity at 25 ° C is less than 1000 mPa·s. When the viscosity increase at the time of storage is considered, it is more preferable that the viscosity of the liquid softener composition which has just been manufactured is less than 800 mPa·s at 25 ° C, and preferably less than 500 mPa·s. When it is in such a range, workability and the like at the time of putting in the washing machine are good. Further, the viscosity of the liquid softener composition can be measured using a B-type viscometer (manufactured by TOKIMEC Co., Ltd.).

Method for Producing Liquid Softener Composition The liquid softener composition of the present invention can be produced by a known method, for example, in the same manner as the method for producing a prior liquid softener composition using a cationic surfactant as a main component. For example, the oil phase containing the component (A), the component (B), the component (C), the component (D), and the component (E) can be added to the water phase at a temperature equal to or higher than the melting point of the component (A). The emulsion is prepared by mixing, and then the other components are added to the obtained emulsion as needed, and mixed and produced. The oil phase may be composed of (A) component, (B) component, (C) component, (D) component, (E) component, and optionally any component, at a temperature equal to or higher than the melting point of the component (A). preparation. The aqueous phase can be prepared by mixing water and optionally any of the ingredients. Further, the method of adding the component (B), the component (C), the component (D), and the component (E) is not limited to the above-described addition method. In other words, each component of the component (B), the component (C), the component (D), and the component (E) can be added and mixed to obtain a liquid softener composition, for example, each of which can be separately added. The component (B), the component (C), the component (D), and the component (E) may be previously mixed and added to the oil phase or the emulsion. Further, the component (D) may be added after obtaining an aqueous phase or an emulsion, or may be added to the oil phase or the aqueous phase, respectively.

Method of Using Liquid Softener Composition The method of using the liquid softener composition of the present invention is not particularly limited, and the same method as the general liquid softener composition can be used. For example, there is a method of dissolving the liquid softener composition of the present invention in rinse water in a washing step of washing, softening the object to be washed, or dissolving the liquid softener composition of the present invention in a potting state. The water in the container is further placed in a method of immersing the object to be washed. [Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. In addition, in the examples and the comparative examples, the blending amount of each component indicates the mass % (in terms of purity except for the case where it is specified).

The components and production methods used in the production of the liquid softener compositions of the examples and comparative examples are shown below.

[Component (A)] The following A-1 to A-3 were used. A-1: a cationic surfactant (a compound described in Example 4 of JP-A-2003-12471). A-1 is a composition comprising a compound represented by the general formula (A1-4), the general formula (A1-5), and the general formula (A1-6) (in each formula, R ⁹ is carbon The alkyl group or alkenyl group of 15 to 17 is obtained by quaternization of dimethyl sulfate. A-2: a cationic surfactant (manufactured by Stepan, trade name: Stepantex SE-88). A-2 is a composition containing a compound represented by the general formula (A1-4), the general formula (A1-5), and the general formula (A1-6) (in each formula, R ⁹ is carbon The alkyl group or alkenyl group of 15 to 17 is obtained by quaternization of dimethyl sulfate. A-3: Cationic surfactant (Manufactured by Southeast Synthetic Co., Ltd., trade name: HITEX RO16E). A-3 is a composition comprising a compound represented by the general formula (A1-4), the general formula (A1-5), and the general formula (A1-6) (in each formula, R ⁹ is carbon The alkyl group or alkenyl group of 15 to 17 is obtained by quaternization of dimethyl sulfate.

[Component (B)] The following B-1 to B-2 were used. B-1: 3-(dodecylthio)-1-(2,6,6-trimethylcyclohex-3-en-1-yl)-1-butanone. B-1 is a compound described in Example 4 of JP-A-2005-511710. Further, B-1 is a compound of the formula: (B-1): YSGQ, Y is a group represented by Y-1 (3 position, 4 position has a double bond), and G is 12 containing 12 carbon atoms. An alkyl group, Q is a hydrogen atom. B-2: 4-(dodecylthio)-4-(2,6,6-trimethylcyclohex-2-en-1-yl)-2-butanone. B-2 uses dodecyl mercaptan (manufactured by Tokyo Chemical Industry Co., Ltd.) and β-ionone (manufactured by V. MANE FILS Co., Ltd.) as a raw material, and utilizes The synthesis was carried out in the same manner as described in Example 4 of JP-A-2005-511710. Further, B-2 is a compound of the formula: (B-1): YSGQ, Y is a group represented by Y-2 (1 position, 2 position has a double bond), and G is 12 containing 12 carbon atoms. An alkyl group, Q is a hydrogen atom.

[Component (C)] The following C1-1 to C1-4 were used as the component (C1). C1-1: Dibutylhydroxytoluene (BHT) manufactured by Tokyo Chemical Industry Co., Ltd. C1-2: Butylated Hydroxymethoxybenzene (BHA) manufactured by Tokyo Chemical Industry Co., Ltd. C1-3: p-Methoxyphenol (Tokyo Chemical Industry Co., Ltd.) C1-4: Uric Acid (Wako Pure Chemical Industries Co., Ltd.)

The following C2-1 to C2-4 were used as the component (C2). C2-1: Amine-based modified fluorenone (KF-864) (manufactured by Shin-Etsu Chemical Co., Ltd.) C2-2: Amine-modified fluorenone (SM8904) (Toray Dow Corning Co., Ltd.) C2-3: Polyether modified fluorenone (Compound B-1 described in the examples of JP-A-2010-255170) C2-4: dimethyl fluorenone (BY 22-050 A) ( Toray Dow Corning Co., Ltd.)

[Component (D)] The following D-1 was used as the component (D). D-1: Nonionic surfactant (ethylene oxide 60 molar addition of primary isotridecyl alcohol. Addition of ethylene oxide to Lutensol TO3 manufactured by BASF Founder)

[Component (E)] The fragrance composition described in Table 1 was used as the component (E). [Table 1] Table 1

[Component (F)] Calcium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the component (F). The compounding amount of the component (F) in each of the liquid softener compositions was 0.6% by mass based on the total mass of the liquid softener composition.

Further, the common component 1 described in Table 2 was used as an optional component. [Table 2] Table 2. Common ingredients 1

For the preparation of the liquid softener composition, a glass container having an inner diameter of 100 mm and a height of 150 mm and a stirrer (AJITER-SJ type, manufactured by Shimadzu Corporation) are used, and the components are blended as described in Table 3 below. The amounts were adjusted, and a liquid softener composition was prepared in the following order. First, the component (A), the component (B), the component (C), the component (D), and the component (E) are mixed and stirred to obtain an oil phase mixture. On the other hand, the common component 1 is dissolved in the ion exchange water for equilibration to obtain an aqueous phase mixture. Here, the mass of the ion exchange water for balance corresponds to the remainder obtained by subtracting the total amount of the oil phase mixture and the component (F) from 980 g. Then, while the oil phase mixture heated to the melting point or higher of the component (A) is placed in a glass container and stirred, the aqueous phase mixture heated to the melting point of the component (A) is added in two portions and added. Stir. Here, the distribution ratio of the aqueous phase mixture was set to 30:70 (mass ratio), and the mixture was stirred for 3 minutes at the first rotation of the aqueous phase mixture at 1,500 rpm, and stirred for 2 minutes after the second addition of the aqueous phase mixture. . After that, the component (F) is added. Further, the component (F) was dissolved in ion-exchanged water before the addition, and used as a 30% by weight aqueous solution. In addition, if necessary, add an appropriate amount of hydrochloric acid (reagent 1 mol/L, Kanto Chemical) or sodium hydroxide (reagent 1 mol/L, Kanto Chemical) to adjust to pH 2.5, and then add ion-exchanged water to make the overall mass 1,000. g, a target softener composition (Examples 1 to 20 and Comparative Examples 1 to 5) were obtained. In Table 3, the numerical values of the respective components of (A), (B), (C), (D), and (E) are the blending amounts (% by mass) with respect to the total mass of the liquid softener composition. In Table 3, "(B)/(C)" represents the mass ratio of the component (B) to the component (C).

Evaluation method of liquid softener composition The liquid softener composition obtained was evaluated in the following order in terms of "aroma" and "sustainability of flavor".

<Aroma evaluation of the composition of the liquid softener> 100 mL of the liquid softener composition was added to a light-weight PS glass bottle (PS-No. 11, manufactured by Tanabe Soda Industries) and sealed, and the four-stage evaluation was as follows. The benchmark evaluates its aroma. The results expressed in the form of an average score given by five professionals are shown in the column of "aroma evaluation" in Table 3. In terms of the value of the product, the average score of 2.0 or less is set as the pass. <Evaluation Criteria> 0: No odor is observed 1: The odor can be barely recognized 2: The odor is perceived to be undetectable 3: The odor is clearly smelled.

<Flavour persistence evaluation> (pre-treatment of evaluation cloth) The commercially available detergent "Top Platinum Clear" (manufactured by Lion Corporation) was used, and a two-tank washing machine (manufactured by Toshiba) was used. VH-30S), the commercially available cotton towel (manufactured by Tojin Corporation) was subjected to the following three pretreatments as follows. Pretreatment: The washing of the standard amount of detergent, the bath ratio of 30 times, the tap water of 45 ° C for 10 minutes and the continuous water flushing for 10 minutes were cycled twice.

(Treatment of liquid softener composition in the rinsing step during washing) Using a two-tank washing machine (VH-30S manufactured by Toshiba) and using a commercially available detergent "Super Platinum Washing Powder" (manufactured by Lion Corporation) ), 1.0 kg of pre-treated washed cotton towel (manufactured by Dongjin Co., Ltd.) was washed for 10 minutes (standard usage, standard procedure, bath ratio 30 times, tap water using 25 ° C), followed by dehydration for 1 minute, and then A first drop of rinse was performed for 3 minutes. After the first rinse, dehydration was carried out for 1 minute, followed by a second rinse for 3 minutes. At the start of the second rinsing, the liquid softener composition obtained in each of the above examples was added, and softening treatment was carried out for 3 minutes (6.67 mL of processing reagent, 20 times bath ratio, tap water of 25 ° C) . Dehydration was carried out for 1 minute after soft treatment. After the treatment, the cotton towel was taken out from the two-tank washing machine, and dried under constant temperature and humidity conditions of 20 ° C and 40% RH for 18 hours for evaluation as shown below.

(Evaluation of flavor sustainability after application of the softener composition) After the treatment, the cotton towel was stored under the conditions of 20 ° C and 40% RH for 7 days, and then the aroma was expressed according to the following six-stage odor intensity expression. The intensity was evaluated for the function. The results expressed in the form of average scores given by five professionals are shown in the column "Scent Persistence" in Table 3. In terms of the value of the product, the average score of 2.5 or more is set as the pass. <Six-stage odor intensity expression> 0: No odor 1: Aroma that can be barely detected 2: Aroma that confirms a slight scent 3: A scent that can be easily perceived 4: Obvious scent 5: Intense Fragrance [industrial availability]

The invention is useful in the field of liquid softeners.

[Table 3] Table 3

no

no

no

Claims (8)

A liquid softener composition comprising the following components (A) to (C): (A) at least one compound selected from the group consisting of an amine compound, a salt thereof and a quaternary compound thereof, The amine compound has one to three hydrocarbon groups having 10 to 26 carbon atoms which may be cleaved by an ester group (-COO-) and/or a mercapto group (-NHCO-), and (B) a sulfur-containing fragrance precursor. And (C) an antioxidant and/or an anthrone compound. The liquid softener composition according to claim 1, wherein the mass ratio of the component (B) to the component (C) ((B)/(C)) is 0.001 to 10. The liquid softener composition according to the first or second aspect of the invention, wherein the component (A) is a compound selected from the group consisting of the formula (A1-1) to the formula (A1-8), At least one compound of the group consisting of a salt and the quaternary compound, [Chemical 1] In the formula (A1-1), R ⁷ and R ⁸ are each independently a hydrocarbon group having 10 to 26 carbon atoms, and in each of the formulae (A1-2) to (A1-8), R ⁹ and R ¹⁰ are each independently It is a hydrocarbon group having 7 to 21 carbon atoms]. The liquid softener composition according to any one of claims 1 to 3, wherein the component (B) is at least one compound represented by the formula (B-1), YSGQ (B-1) Wherein Y represents a group selected from the group consisting of formula (Y-1) to formula (Y-7) or an isomer thereof, In each of the formulae (Y-1) to (Y-7), the wavy line indicates the position of the YS bond, the broken line indicates the position of the single bond or the double bond, S represents a sulfur atom, and G represents two. a divalent or trivalent group derived from a linear or branched alkyl or alkenyl group of 15 carbon atoms (the divalent group or the trivalent group may be selected from the group consisting of -OR ¹¹ , -NR ¹¹ ₂ group, -COOR ¹¹ group and R ¹¹ group (in each group, R ¹¹ represents a hydrogen atom or a C1 to C6 alkyl group or an alkenyl group), one or more groups are substituted), Q It represents a hydrogen atom, a -SY group or a -NR ¹² -Y group (in each group, Y is as defined above, and R ¹² is a hydrogen atom or a methyl group)]. The liquid softener composition according to claim 4, wherein the compound represented by the formula (B-1) is selected from the group consisting of 3-(dodecylthio)-1-(2,6,6- Trimethylcyclohex-3-en-1-yl)-1-butanone and 4-(dodecylthio)-4-(2,6,6-trimethylcyclohex-2-ene- A group consisting of 1-yl)-2-butanone. The liquid softener composition according to any one of claims 1 to 5, wherein the component (C) is selected from the group consisting of dibutylhydroxytoluene (BHT) and butylhydroxymethoxybenzene (BHA). At least one antioxidant in the group consisting of p-methoxyphenol and uric acid. The liquid softener composition according to any one of claims 1 to 6, wherein the component (C) is selected from the group consisting of dimethyl fluorenone, polyether modified fluorenone, and amine modified hydrazine. At least one anthrone compound in the group consisting of ketones. The liquid softener composition according to any one of claims 1 to 7, which comprises an antioxidant and an anthrone compound as the component (C).