WO2017018343A1

WO2017018343A1 - Liquid softener composition

Info

Publication number: WO2017018343A1
Application number: PCT/JP2016/071543
Authority: WO
Inventors: 亮橋本; 英史小倉
Original assignee: ライオン株式会社
Priority date: 2015-07-24
Filing date: 2016-07-22
Publication date: 2017-02-02
Also published as: JP2017025448A; MY189506A; KR102573429B1; KR20180028405A; TWI759269B; JP6560558B2; TW201710490A

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

The present invention relates to a liquid softener composition. In detail, this invention relates to the liquid softening agent composition which can exhibit the fragrance intended at the time of design continuously, suppressing generation | occurrence | production of a strange odor.

In recent years, an increasing number of consumers are demanding the sustainability of fragrance as a function of a softening agent, and various measures have been taken against it.
As one of means for achieving fragrance persistence, a technique using a fragrance precursor obtained by chemically combining a fragrance and a non-volatile substrate is known in the fields of softeners, bleaches and detergents ( Patent Documents 1 to 4). The perfume precursor continuously releases a scent by being disconnected by a trigger such as light, heat, water or the like. In particular, it is known that a sulfur-containing fragrance precursor formed by bonding a thiol and an α, β-unsaturated ketone type fragrance is excellent in scent sustainability (Patent Document 1).

JP-T-2005-511710 Special table 2014-511414 gazette Special table 2012-530812 International Publication No. 2014/176392

However, when the sulfur-containing fragrance precursor is blended into the liquid softener composition, the present inventors have found that a sulfur-like odor is generated from the liquid softener composition, and the pleasant fragrance intended at the time of design cannot be realized. I found it.

As a result of intensive studies on the above problems, the present inventor added an antioxidant and / or a silicone compound to the sulfur-containing fragrance precursor-containing liquid softener composition, and the generation of off-flavor was suppressed and was intended at the time of design It was found that the scent can be exerted continuously (excellent fragrance). The present invention has been made based on this finding.

That is, the present invention relates to the following.
1. A liquid softener composition comprising:
The following components (A) to (C):
(A) an amine compound having 1 to 3 hydrocarbon groups of 10 to 26 carbon atoms in the molecule, which may be separated by an ester group (—COO—) and / or an amide group (—NHCO—), At least one compound selected from the group consisting of a salt and a quaternized product thereof,
(B) a sulfur-containing fragrance precursor, and
(C) an antioxidant and / or a silicone compound,
A liquid softener composition comprising:

2. 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 component (A) is at least one compound selected from the group consisting of compounds represented by the general formulas (A1-1) to (A1-8), salts thereof and quaternized compounds thereof. Or the liquid softening agent composition of 2.

[In the formula (A1-1), R ⁷ and R ⁸ are each independently a hydrocarbon group having 10 to 26 carbon atoms,
In the formulas (A1-2) to (A1-8), R ⁹ and R ¹⁰ are each independently a hydrocarbon group having 7 to 21 carbon atoms. ]

4). 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 general formula (B-1).
YSGQ (B-1)
[Where,
Y represents a group selected from the group consisting of formulas (Y-1) to (Y-7) or an isomer thereof,

(In the formulas (Y-1) to (Y-7), the wavy line represents the position of the YS bond, and the dotted line represents the position of the single bond or the double bond).
S represents a sulfur atom,
G represents a divalent or trivalent group derived from a linear or branched alkyl group or alkenyl group having 2 to 15 carbon atoms (the divalent or trivalent group is One optionally selected from the group consisting of —OR ¹¹ , —NR ¹¹ ₂ , —COOR ¹¹ and R ¹¹ groups, wherein R ¹¹ represents a hydrogen atom or a C1-C6 alkyl group or alkenyl group. Optionally substituted with the above groups),
Q represents a hydrogen atom, a —S—Y group or a —NR ¹² —Y group (in each group, Y is defined as described above, and R ¹² is a hydrogen atom or a methyl group). ]

5). The compound represented by the general formula (B-1) is 3- (dodecylthio) -1- (2,6,6-trimethylcyclohex-3-en-1-yl) -1-butanone and 4- (dodecylthio). 5. The liquid softener composition as described in 4 above, which is selected from the group consisting of 4- (2,6,6-trimethylcyclohex-2-en-1-yl) -2-butanone.

6). Any one of 1 to 5 above, wherein the component (C) is at least one antioxidant selected from the group consisting of dibutylhydroxytoluene (BHT), butylhydroxyanisole (BHA), p-methoxyphenol and uric acid. Item 2. A liquid softener composition according to Item.

7). 7. The liquid softener composition according to any one of 1 to 6, wherein the component (C) is at least one silicone compound selected from the group consisting of dimethyl silicone, polyether-modified silicone, and amino-modified silicone.

8). 8. The liquid softener composition as described in any one of 1 to 7 above, which comprises an antioxidant and a silicone compound as component (C).

As shown in the examples described later, the liquid softener composition of the present invention can continuously exhibit the scent intended at the time of design (excellent fragrance property) while suppressing the generation of a strange odor.
Therefore, the present invention is useful as a liquid softener composition having added value not found in conventional liquid softener compositions.

The liquid softener composition of the present invention comprises the following components (A) to (C):
(A) an amine compound having 1 to 3 hydrocarbon groups of 10 to 26 carbon atoms in the molecule, which may be separated by an ester group (—COO—) and / or an amide group (—NHCO—), At least one compound selected from the group consisting of a salt and a quaternized product thereof,
(B) a sulfur-containing fragrance precursor, and
(C) an antioxidant and / or a silicone compound,
Containing.

[(A) component]
The component (A) has “1 to 3 hydrocarbon groups having 10 to 26 carbon atoms, which may be separated by an ester group (—COO—) and / or an amide group (—NHCO—) in the molecule. A cationic surfactant which is “at least one compound selected from the group consisting of an amine compound, a salt thereof and a quaternized product thereof”.
(A) component is mix | blended in order to provide the effect (namely, softener original function) which gives a softness | flexibility (texture) to a textile product to a liquid softener composition.
The hydrocarbon group having 10 to 26 carbon atoms (hereinafter sometimes referred to as “long-chain hydrocarbon group” in the present specification) has 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 handling property of the liquid softener composition is good.
The long chain hydrocarbon group may be saturated or unsaturated. When the long chain hydrocarbon group is unsaturated, the position of the double bond may be anywhere, but when there is one double bond, the position of the double bond is the long chain carbonization. The center of the hydrogen group is preferably distributed around the median.
The long chain hydrocarbon group may be a chain hydrocarbon group or a hydrocarbon group containing a ring in the structure, and is preferably a chain hydrocarbon group. The chain hydrocarbon group may be linear or branched. As the chain hydrocarbon group, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable.

The long chain hydrocarbon group may be separated by an ester group (—COO—) and / or an amide group (—NHCO—). That is, the long-chain hydrocarbon group has at least one kind of splitting group selected from the group consisting of an ester group and an amide group in the carbon chain, and the carbon chain is split by the splitting group. May be. Having the splitting group is preferable from the viewpoint of improving biodegradability.
When it has this dividing group, the number of the dividing groups which one long-chain hydrocarbon group has may be one, or may be two or more. That is, the long chain hydrocarbon group may be divided at one place by a dividing group, or may be divided at two or more places. When having two or more splitting groups, each splitting group may be the same or different.
In addition, when a long chain hydrocarbon group has a splitting group in the carbon chain, the carbon atom which a splitting group shall count to the carbon number of a long chain hydrocarbon group.
The long-chain hydrocarbon group is usually an unhydrogenated fatty acid derived from beef tallow, which is used industrially, a fatty acid obtained by hydrogenation or partial hydrogenation of an unsaturated part, palm-derived palm oil, oil palm-derived It is introduced by using a hydrogenated fatty acid or fatty acid ester, or a fatty acid or fatty acid ester obtained by hydrogenation or partial hydrogenation of an unsaturated portion.
As the amine compound, a secondary amine compound (the number of long-chain hydrocarbon groups is 2) or a tertiary amine compound (the number of long-chain hydrocarbon groups is 3) is preferable, and a tertiary amine compound is more preferable.

As an amine compound, the compound represented by the following general formula (A1) is mentioned.

[Wherein R ¹ to R ³ are each independently a hydrocarbon group having 10 to 26 carbon atoms, —CH ₂ CH (Y) OCOR ⁴ (Y is a hydrogen atom or CH ₃ , and R ⁴ is 7 carbon atoms) -(CH ₂ ) _n NHCOR ⁵ (n is 2 or 3, R ⁵ is a hydrocarbon group having 7 to 21 carbon atoms), hydrogen atom, carbon number 1 to 4 alkyl groups, —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 general formula (A1), the carbon number of the hydrocarbon group having 10 to 26 carbon atoms in R ¹ to R ³ is preferably 17 to 26, and more preferably 19 to 24. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group is preferably an alkyl group or an alkenyl group.
In —CH ₂ CH (Y) OCOR ⁴ , Y is a hydrogen atom or CH ₃ , and a hydrogen atom is particularly preferable. R ⁴ is a hydrocarbon group having 7 to 21 carbon atoms, preferably a hydrocarbon group having 15 to 19 carbon atoms. When the compound represented by the general formula (A1) R ⁴ there are a plurality, may be R ⁴ of said plurality of mutually identical, may be different.

Hydrocarbon group R ⁴ is a residue obtained by removing a carboxy group from a fatty acid having 8 to 22 carbon atoms (R ⁴ COOH) (fatty acid residues), R ⁴ Nomoto become fatty (R ⁴ COOH) is Saturated fatty acids or unsaturated fatty acids may be used, and straight-chain fatty acids or branched fatty acids may be used. Of these, saturated or unsaturated linear fatty acids are preferred. In order to impart good water absorption to the soft-treated garment, the saturated / unsaturated ratio (mass ratio) of the fatty acid serving as the R ⁴ is preferably 90/10 to 0/100, more preferably 80/20 to 0 / 100 is more preferable.
When R ⁴ is an unsaturated fatty acid residue, a cis isomer and a trans isomer exist, and the mass ratio of cis isomer / trans isomer is preferably 40/60 to 100/0, and 70/30 to 90/10. Particularly preferred.

Specific examples of fatty acids based on R ⁴ include stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, elaidic acid, linoleic acid, partially hydrogenated palm oil fatty acid (iodine value 10 to 60), Examples include partially hydrogenated beef tallow fatty acid (iodine value 10 to 60). Among them, fatty acids prepared by combining two or more selected from stearic acid, palmitic acid, myristic acid, oleic acid, elaidic acid, and linoleic acid in predetermined amounts to satisfy the following conditions (a) to (c): It is preferable to use a composition.
(A) The ratio (mass ratio) of saturated fatty acid / unsaturated fatty acid is 90/10 to 0/100, more preferably 80/20 to 0/100.
(B) The cis / trans ratio (mass ratio) is 40/60 to 100/0, more preferably 70/30 to 90/10.
(C) The fatty acid having 18 carbon atoms 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 general formula (A1), n is 2 or 3, and 3 is particularly preferable.
R ⁵ is a hydrocarbon group having 7 to 21 carbon atoms, preferably a hydrocarbon group having 15 to 19 carbon atoms. When the compound represented by the general formula (A1) R ⁵ there are a plurality, may be R ⁵ of said plurality of mutually identical, may be different.
Specific examples of R ⁵ include the same as R ⁴ .

In General 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.
When one or two of R ¹ to R ³ are long-chain hydrocarbon groups, the remaining two or one is 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, as the alkyl group having 1 to 4 carbon atoms, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable. 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 general formula (A1) include compounds represented by the following general formulas (A1-1) to (A1-8).

[In the formula (A1-1), R ⁷ and R ⁸ are each independently a hydrocarbon group having 10 to 26 carbon atoms. In the formulas (A1-2) to (A1-8), R ⁹ and R ¹⁰ are each independently a hydrocarbon group having 7 to 21 carbon atoms. ]

Examples of the hydrocarbon group for R ⁷ and R ⁸ include the same hydrocarbon groups as those having 10 to 26 carbon atoms for R ¹ to R ³ in the general formula (A1).
Examples of the hydrocarbon group having 7 to 21 carbon atoms in R ⁹ and R ¹⁰ include those similar to the hydrocarbon group having 7 to 21 carbon atoms in R ⁴ of the general formula (A1). Incidentally, when the R ⁹ there are a plurality in the formula, R ⁹ of the plurality of it may be the same as each other, may be different.

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

The component (A) may be a quaternized amine compound.
A quaternized product of an amine compound is obtained by reacting the amine compound with a quaternizing agent. Examples of the quaternizing agent used for quaternizing the amine compound include alkyl halides such as methyl chloride and dialkyl sulfuric acids such as dimethyl sulfate. When these quaternizing agents are reacted with an amine compound, the alkyl group of the quaternizing agent is introduced into the nitrogen atom of the amine compound, and a salt of a quaternary ammonium ion and a halogen ion or a 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. The quaternization of the amine compound can be performed by a known method.

As the component (A),
At least one selected from the group consisting of the compound represented by the general formula (A1), a salt thereof, and a quaternized product thereof is preferable.
More preferred is at least one selected from the group consisting of compounds represented by the general formulas (A1-1) to (A1-8), salts thereof and quaternized products thereof,
Particularly preferred is at least one selected from the group consisting of compounds represented by general formulas (A1-4) to (A1-6), salts thereof and quaternized products thereof.
In particular, a quaternized product of the compound represented by the general formula (A1-4), a quaternized product of the compound represented by (A1-5), and a quaternized product of the compound represented by (A1-6). It is preferable to use together.

As the compounds represented by the general formulas (A1) and (A1-1) to (A1-8), salts thereof and quaternized products thereof, commercially available products may be used, or those prepared by known methods may be used. May be.

For example, a compound represented by the general formula (A1-2) (hereinafter referred to as “compound (A1-2)”) and a compound represented by the general formula (A1-3) (hereinafter referred to as “compound (A1-3)”). The fatty acid composition described in the R ⁴ column of the general formula (A1), or a fatty acid methyl ester composition obtained by replacing the fatty acid in the fatty acid composition with a methyl ester of the fatty acid, and methyl It can be synthesized by a condensation reaction with diethanolamine. At this time, from the viewpoint of improving flexibility, the abundance ratio represented by “compound (A1-2) / compound (A1-3)” is 99/1 to 50/50 in mass ratio. It is preferable to synthesize.
Furthermore, when the quaternized product is used, it is more preferable to use dimethyl sulfate as a quaternizing agent. At that time, from the viewpoint of imparting flexibility, the abundance ratio represented by “a quaternized compound (A1-2) / a quaternized compound (A1-3)” is 99/1 to 50/50 in mass ratio. It is preferable to synthesize so that

A compound represented by the general formula (A1-4) (hereinafter referred to as “compound (A1-4)”) and a compound represented by the general formula (A1-5) (hereinafter referred to as “compound (A1-5)”) And a compound represented by the general formula (A1-6) (hereinafter referred to as “compound (A1-6)”) is a fatty acid composition described in the R ⁴ column of the general formula (A1) or It can be synthesized by a condensation reaction between a fatty acid methyl ester composition and triethanolamine. At that time, the content ratio of each component to the total mass of the compounds (A1-4), (A1-5) and (A1-6) is 1 to 60 for the compound (A1-4) from the viewpoint of imparting flexibility. The compound (A1-5) is preferably 5 to 98% by mass, the compound (A1-6) is preferably 0.1 to 40% by mass, the compound (A1-4) is 30 to 60% by mass, the compound More preferably, (A1-5) is 10 to 55% by mass, and compound (A1-6) is 5 to 35% by mass.
In addition, when using the quaternized product, it is more preferable to use dimethyl sulfate as a quaternizing agent in that the quaternization reaction proceeds sufficiently. The abundance ratio of each of the quaternized compounds (A1-4), (A1-5) and (A1-6) is a mass ratio from the viewpoint of imparting flexibility, and the quaternized compound (A1-4) is 1 The quaternized product of the compound (A1-5) is preferably 5 to 98% by mass, and the quaternized product of the compound (A1-6) is preferably 0.1 to 40% by mass. The quaternized product of 4) is 30 to 60% by mass, the quaternized product of compound (A1-5) is 10 to 55% by mass, and the quaternized product of compound (A1-6) is 5 to 35% by mass. More preferred.
In addition, when the compounds (A1-4), (A1-5) and (A1-6) are quaternized, esteramine which is not quaternized generally remains after the quaternization reaction. In this case, the ratio of “quaternized product / non-quaternized ester amine” is preferably in the range of a mass ratio of 70/30 to 99/1.

A compound represented by the general formula (A1-7) (hereinafter referred to as “compound (A1-7)”) and a compound represented by the general formula (A1-8) (hereinafter referred to as “compound (A1-8)”) From the fatty acid composition described in the R ⁴ column of the general formula (A1) and the adduct of N-methylethanolamine and acrylonitrile, J. Org. Org. Chem. , 26, 3409 (1960), by a condensation reaction with N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine synthesized by a known method. In that case, it is preferable to synthesize so that the abundance ratio represented by “compound (A1-7) / compound (A1-8)” is 99/1 to 50/50 by mass ratio.
When the quaternized product is used, methyl chloride is preferably used as the quaternizing agent, which is expressed by “a quaternized compound (A1-7) / a quaternized compound (A1-8)”. The abundance ratio is preferably 99/1 to 50/50 by mass ratio.

As the component (A), one type of amine compound, a salt thereof or a quaternized product thereof may be used alone, or a mixture of two or more types, for example, in the general formulas (A1-4) to (A1-6) You may use as a mixture of the compound represented.

The blending amount of the component (A) is not particularly limited as long as it can achieve the blending purpose, but is preferably 5 to 50% by mass, more preferably 8 to 30% by mass with respect to the total mass of the liquid softening agent composition. More preferably, it is 10 to 20% by mass.

[Component (B)]
(B) A component is a sulfur containing fragrance | flavor precursor. The “sulfur-containing fragrance precursor” refers to a compound obtained by chemically combining a fragrance and a non-volatile substrate containing sulfur. Although the fragrance precursor itself does not give a fragrance, the fragrance is released when the bond between the fragrance and the substrate is cut by a trigger such as heat, light, water, etc. to give a fragrance. Therefore, it is known that when clothing is treated with a fragrance precursor, the effect as a fragrance is exhibited even in the latter half of the use scene, such as after wearing or storage of the clothing.
(B) A component is mix | blended for the fragrance to the textiles after a process by a liquid softening agent composition.

As a sulfur containing fragrance | flavor precursor, what is generally used for the liquid softening agent composition can be especially used without a restriction | limiting. Preferably, a compound represented by the following general formula (B-1) can be used as the sulfur-containing fragrance precursor of the component (B).
YSGQ (B-1)

In general formula (B-1),
Y represents a group selected from the group consisting of the following groups (Y-1) to (Y-7) or an isomer thereof,

(In the formulas (Y-1) to (Y-7), the wavy line represents the position of the YS bond, and the dotted line represents the position of the single bond or the double bond).
S represents a sulfur atom,
G represents a divalent or trivalent group derived from a linear or branched alkyl group or alkenyl group having 2 to 15, preferably 10 to 14 carbon atoms (the divalent or trivalent group). The trivalent group is optionally a group consisting of —OR ¹¹ , —NR ¹¹ ₂ , —COOR ¹¹ and R ¹¹ groups (wherein R ¹¹ represents a hydrogen atom, a C1-C6 alkyl group or an alkenyl group). Optionally substituted with one or more groups selected from
Q represents a hydrogen atom, a —S—Y group or a —NR ¹² —Y group (in each group, Y is defined as described above, and R ¹² is a hydrogen atom or a methyl group).
Here, “isomers” of the groups represented by the formulas (Y-1) to (Y-7) in the general formula (B-1) are isomers that each group can adopt on the chemical structure. For example, stereoisomers.

As the compound represented by the general formula (B-1), one type may be used alone, or two or more types may be appropriately combined.

Preferred examples of the compound represented by the general formula (B-1) include methyl or ethyl 2- (4-oxo-4- (2,6,6-trimethylcyclohex-3-en-1-yl) butane. -2-ylamino) -3- (4-oxo-4- (2,6,6-trimethylcyclohex-3-en-1-yl) butan-2-ylthio) propanate, methyl or ethyl 2- (4- Oxo-4- (2,6,6-trimethylcyclohex-2-en-1-yl) butan-2-ylamino) -3- (4-oxo-4- (2,6,6-trimethylcyclohexa-) 2-En-1-yl) butan-2-ylthio) propanate, methyl or ethyl 2- (2-oxo-4- (2,6,6-trimethylcyclohex-1-en-1-yl) butane-4 -Ilamino) -3- (2-Oki -4- (2,6,6-trimethylcyclohex-1-en-1-yl) butan-4-ylthio) propanate, methyl 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-en-1-yl) butane-4- Ylthio) propanate, 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- (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, 2-dodecylsulfanyl-5-methyl-heptan-4-one, 2-cyclohexyl-1-dodecylsulfanyl-hept-6 And a compound selected from the group consisting of -en-3-one and 3- (dodecylthio) -5-isopropenyl-2-methylcyclohexanone.
From the viewpoint of increasing the scent durability, 3- (dodecylthio) -1- (2,6,6-trimethylcyclohex-3-en-1-yl) -1-butanone, 4- (dodecylthio) is more preferable. -4- (2,6,6-trimethylcyclohex-2-en-1-yl) -2-butanone, 4- (dodecylthio) -4- (2,6,6-trimethylcyclohex-1-ene- And a compound selected from the group consisting of 1-yl) -2-butanone and 3- (dodecylthio) -5-isopropenyl-2-methylcyclohexanone,
Most preferably, 3- (dodecylthio) -1- (2,6,6-trimethylcyclohex-3-en-1-yl) -1-butanone and 4- (dodecylthio) -4- (2,6,6 And a compound selected from the group consisting of -trimethylcyclohex-2-en-1-yl) -2-butanone.

The sulfur-containing fragrance precursor can be easily obtained on the market or can be synthesized by a known method.

As the component (B), one type of sulfur-containing fragrance precursor may be used alone, or a mixture of two or more types may be used.

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

[Component (C)]
Component (C) is an antioxidant (hereinafter also referred to as “(C1) component”) and / or a silicone compound (hereinafter also referred to as “(C2) component”).

[(C1) component: antioxidant]
The antioxidant which is (C1) component is used in order to suppress generation | occurrence | production of the sulfur-like off-flavor derived from (B) component (sulfur containing fragrance | flavor precursor).
As the antioxidant, a compound generally known to have an antioxidant effect can be used without particular limitation. Therefore, both water-soluble antioxidants and oil-soluble antioxidants can be used, but oil-soluble antioxidants are preferred.
Specific examples of the component (C1) include dibutylhydroxytoluene (BHT), butylhydroxyanisole (BHA), p-methoxyphenol, β-naphthol, phenyl-α-naphthylamine, tetramethyldiaminodiphenylmethane, γ-oryzanol, Vitamin E (α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol), uric acid, vitamin C (L-ascorbic acid), trehalose, 2,2'-ethylidenebis (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) diphenylamine and the like.
In these, at least 1 sort (s) chosen from the phenolic antioxidant which is an oil-soluble antioxidant is preferable, Dibutylhydroxytoluene (BHT), butylhydroxyanisole (BHA), 2,2'- ethylidenebis (4,4) 6-di-t-butylphenol), p-methoxyphenol and γ-oryzanol are preferred.
More preferably, it is a compound selected from the group consisting of dibutylhydroxytoluene (BHT), butylhydroxyanisole (BHA), p-methoxyphenol and 2,2′-ethylidenebis (4,6-di-t-butylphenol). More preferred is dibutylhydroxytoluene (BHT).

The component (C1) is easily available on the market or can be synthesized by a known method.

(C1) A component may be used individually by 1 type and may combine 2 or more types suitably.

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

[(C2) component: silicone compound]
The component (C2) is a silicone compound, and 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 a sulfur-like odor originating from the component (B) (sulfur-containing fragrance precursor).
In addition, although this invention is not limited by a specific theory, the bad smell substance (gas) which the silicone compound which has the property of being excellent in gas absorptivity (solubility) decomposes | disassembles a sulfur containing fragrance | flavor precursor. ) Is considered to suppress sulfur-like off-flavors.
The molecular structure of the silicone compound may be linear, branched, or cross-linked. The silicone compound may be a modified silicone compound, and the modified silicone compound may be modified with one organic functional group or modified with two or more organic functional groups. It may be.
The silicone compound can be used in the state of oil, and can also be used in the state of an emulsion dispersed by any emulsifier.
Specific examples of the silicone compound include, for example, 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. Examples include modified silicone and amino-modified silicone.
Among these, from the viewpoint of improving the blending effect, polyether-modified silicone, amino-modified silicone and dimethylsilicone are preferable, and polyether-modified silicone and amino-modified silicone are more preferable.

Specific examples of the polyether-modified silicone include, for example, a copolymer of alkylsiloxane and polyoxyalkylene. The carbon number of the alkyl group of the alkylsiloxane is preferably 1 to 3, and the carbon number of the alkylene group of the polyoxyalkylene is preferably 2 to 5. Among these, the polyether-modified silicone is preferably a copolymer of dimethylsiloxane and polyoxyalkylene (polyoxyethylene, polyoxypropylene, a random or block copolymer of ethylene oxide and propylene oxide, etc.). Specific examples of such a polyether-modified silicone include, for example, a compound represented by the following general formula (I), a compound represented by the following general formula (II), and the like.

Formula (I):

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

The polyether-modified silicone represented by the general formula (I) generally has an organohydrogenpolysiloxane having a Si—H group and a carbon-carbon double bond such as polyoxyalkylene allyl ether at the terminal. It can be produced by addition reaction of polyoxyalkylene alkyl ether with a platinum catalyst. Therefore, the polyether-modified silicone may contain a slight amount of unreacted polyoxyalkylene alkyl ether or organohydrogenpolysiloxane having a Si—H group. Since the organohydrogenpolysiloxane having a Si—H group has high reactivity, the abundance in the polyether-modified silicone is preferably 30 ppm or less (as the amount of Si—H).

General formula (II):

In the general formula (II),
A, B, h, and i are average degrees of polymerization,
R represents an alkyl group;
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 polysiloxane-polyoxyalkylene block copolymer represented by the general formula (II) has a polyoxyalkylene compound having a reactive terminal group and a terminal group that reacts with the reactive terminal group of the compound. It can be produced by reacting with dihydrocarbylsiloxane. Such polyether-modified silicone has a longer side chain polyoxyalkylene chain, and the higher the degree of polymerization of the polysiloxane chain, the higher the viscosity. Therefore, it is easy to improve workability during production and blend into aqueous compositions. Therefore, it is preferable to use it in the form of a premix with a water-soluble organic solvent. Examples of the water-soluble organic solvent include ethanol, dipropylene glycol, butyl carbitol and the like.

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

The amino-modified silicone is a silicone oil in which an amino group is introduced into the terminal or side chain of the dimethyl silicone skeleton, and a substituent such as a hydroxyl group, an alkyl group, or a phenyl group may be introduced in addition to the amino group. The amino-modified silicone may be in the form of an oil, or may be in the form of an amino-modified silicone emulsion emulsified with a nonionic surfactant or a cationic surfactant (may be the component (A) described above) as an emulsifier.
A preferred amino-modified silicone oil or base oil in the case of an emulsion is represented by the following general formula (III).

In formula (III), R ₁ and R ₆ may be the same as or different from each other and each represents a methyl group, a hydroxyl group, or hydrogen. R ₂ represents any _one of — (CH ₂ ) _n —A ₁ and — (CH ₂ ) _n —NHCO— (CH ₂ ) _m —A ₁ . A ₁ represents any _one of —N (R ₃ ) (R ₄ ) and —N ⁺ (R ₃ ) (R ₄ ) (R ₅ ) · X ⁻ . R ₃ to R ₅ may be the same as or different from each other, and are any of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, and — (CH ₂ ) _n —NH ₂ . Represents. X ⁻ represents any one of fluorine ion, chlorine ion, bromine ion, iodine ion, methyl sulfate ion, and ethyl sulfate ion. The values of m and n may be the same as or different from each other, and represent an integer of 0 to 12. The values of p and q represent the degree of polymerization of the polysiloxane, and may be the same or different from each other. p is 0 to 20000, preferably 10 to 10,000, q is 1 to 500, preferably 1 to 100 are represented.

When an amino-modified silicone oil is used as the component (C2), the kinematic viscosity at 25 ° C. is preferably 50 to 20000 mm ² / s, and more preferably 100 to 10,000 mm ² / s. A kinematic viscosity in this range is preferable because a high blending effect is exhibited, manufacturability is good, and the composition is easy to handle.
Commercially available amino-modified silicones can be used. For example, amino-modified silicone oils sold by Toray Dow Corning Co., Ltd. as SF-8417, BY16-892, BY16-890. From Shin-Etsu Chemical Co., Ltd., KF-864, KF-860, KF-8004, KF-8002, KF-8005, KF-867, KF-861, KF-880, KF-867S and the like can be mentioned.
The amino-modified silicone emulsion type is sold by Toray Dow Corning Co., Ltd. as SM8904, BY22-079, FZ-4671, FZ-4672, and sold by the Shin-Etsu Chemical Co., Ltd. in the Polon series. Polon MF-14, Polon MF-29, Polon MF-14D, Polon MF-44, Polon MF-14EC, Polon MF-52.

(C2) the case of using dimethyl silicone as the ingredient, its kinematic viscosity (25 ° C.) is not particularly limited to, preferably 1 ~ 100,000,000mm ² / s, more preferably 10 ~ 10,000,000mm ² / s 100 to 1,000,000 mm ² / s is more preferable. The methyl silicone may be an oil or an emulsion.
A commercially available dimethyl silicone can be used. Examples of dimethyl silicone include those sold by Toray Dow Corning Co., Ltd. as BY 22-050 A.

(C2) A component may be used individually by 1 type, and may combine 2 or more types suitably.

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

As the component (C), either the component (C1) or the component (C2) may be used alone, or the component (C1) and the component (C2) may be used in combination. It is preferable to use the component (C1) and the component (C2) in combination because a higher blending effect can be exhibited. When the component (C1) and the component (C2) are used in combination, the mass ratio ((C1) / (C2)) between the component (C1) and the component (C2) can obtain a higher blending effect. , 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 blending amount of the component (C1) and the component (C2) is not particularly limited as long as the blending purpose can be achieved. The amount is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, and still more preferably 0.05 to 5% by mass with respect to the total mass of the agent composition.

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, and still more preferably 0. .01-5. When (B) / (C) is set to 0.001 to 10, a higher blending effect of component (C) (sulfur-like off-flavor generation suppression effect) can be obtained, and the liquid softener composition has a significant viscosity. An increase can be suppressed and usability can be kept better.
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, it is 0.1 to 10, more preferably 0.5 to 5.
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, it is 0.005 to 0.5, and still more preferably 0.01 to 0.1.

Optional Components In the liquid softener composition of the present invention, optional components other than the essential components (A) to (C) described above may be blended as necessary within the range not impairing the effects of the present invention.
As an optional component, the component generally mix | blended with a liquid softening agent composition can be mention | raise | lifted. Specific examples include water, nonionic surfactants, fragrances, water-soluble salts, dyes, water-soluble solvents, preservatives, ultraviolet absorbers, antibacterial agents, deodorants, and skin care ingredients.
Hereinafter, some optional components will be described in detail.

Liquid softener composition of the water present invention is preferably an aqueous composition comprising water.
As the water, any of tap water, purified water, pure water, distilled water, ion exchange water and the like can be used. Of these, ion-exchanged water is preferred.
The blending amount of water is not particularly limited, and can be appropriately blended in order to achieve a desired component composition.

Nonionic surfactant (hereinafter also referred to as “component (D)”)
When the liquid softening agent composition of this invention is an emulsion, a nonionic surfactant can be mix | blended mainly in order to improve the emulsion dispersion stability of the oil-soluble component in an emulsion. When a nonionic surfactant is blended, freeze recovery stability at a level sufficient for commercial value can be easily secured.
As the nonionic surfactant, for example, those derived from polyhydric alcohols, higher alcohols, higher amines or higher fatty acids can be used. More specifically, a glycerin fatty acid ester or pentaerythritol in which a glycerin or pentaerythritol is ester-bonded with a fatty acid having 10 to 22 carbon atoms; an alkyl group or an alkenyl group having 10 to 22 carbon atoms; Polyoxyethylene alkyl ether having 10 to 100 moles; polyoxyethylene fatty acid alkyl (1 to 3 carbon atoms of the alkyl) ester; polyoxyethylene alkylamine having an average addition mole number of ethylene oxide of 10 to 100 moles; Examples thereof include alkyl polyglucosides having 8 to 18 alkyl groups or alkenyl groups; hydrogenated castor oil having an average addition mole number of ethylene oxide of 10 to 100 moles. Of these, polyoxyethylene alkyl ethers having an alkyl group having 10 to 18 carbon atoms and an average addition mole number of ethylene oxide of 20 to 80 moles are preferred.
A nonionic surfactant may be used individually by 1 type, and may be used as a mixture which consists of 2 or more types.
The blending amount of the nonionic surfactant is not particularly limited as long as it can achieve the blending purpose, but is preferably 0.01 to 10% by mass, more preferably 0.1%, based on the total mass of the liquid softening agent composition. It is ˜8% by mass, more preferably 0.5 to 5% by mass.

Fragrance (hereinafter also referred to as “(E) component”)
In the liquid softening agent composition, a fragrance other than the component (B) (sulfur-containing fragrance precursor) can be blended as an optional component.
As the fragrance, a general-purpose fragrance can be used in the technical field and is not particularly limited. However, a list of fragrance raw materials that can be used is various documents such as “Perfume and Flavor Chemicals”, Vol. I and II, Steffen Arctander, Allured Pub. Co. (1994) and "Synthetic fragrance chemistry and commercial knowledge", Motoichi Into, Kagaku Kogyo Nipposha (1996) and "Perfume and Flavor Materials of Natural Origin", Stephen Arctander, Allred Pub. Co. (1994) and "Encyclopedia of Scents", edited by Japan Fragrance Association, Asakura Shoten (1989) and "Performer Material Performance V.3.3", Boelens Aroma Chemical Information Service (1996) and "Flower oil". , Danute Lajaujis Anonis, Allured Pub. Co. (1993).
As the fragrance, one type of fragrance may be used alone, or a mixture of two or more types may be used.
The blending amount of the fragrance is not particularly limited as long as it is an amount that can achieve the blending purpose, but is preferably 0.1 to 3% by mass with respect to the total mass of the liquid softening agent composition, and more preferably 0.8%. It is 5 to 2% by mass, more preferably 0.5 to 1.5% by mass.

Water-soluble salts (hereinafter also referred to as “component (F)”)
Water-soluble salts can be blended for the purpose of controlling the viscosity of the liquid softener composition. As the water-soluble salts, both inorganic salts and organic salts can be used. Specifically, calcium chloride, magnesium chloride, sodium chloride, sodium p-toluenesulfonate, and the like can be used, among which calcium chloride and magnesium chloride are preferable.
One type of water-soluble salt may be used alone, or a mixture of two or more types may be used.
The blending amount of the water-soluble salt is not particularly limited as long as it can achieve the blending purpose, but is 0 to 1% by mass with respect to the total mass of the liquid softening agent composition. In addition, you may mix | blend water-soluble salt in any process of liquid softening agent composition manufacture.

PH of liquid softener composition
The pH of the liquid softener composition is not particularly limited, but the pH at 25 ° C. is in the range of 1 to 6 from the viewpoint of suppressing hydrolysis of the ester group contained in the molecule of the component (A) that accompanies storage days. It is preferable to adjust, and it is more preferable to adjust to the range of 2-4.
In order to further suppress the decomposition of the sulfur-containing fragrance precursor of component (B), the pH of the liquid softening agent composition is preferably 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, hydroxyethanediphosphonic acid, phytic acid, ethylenediaminetetraacetic acid, PH of short chain amine compounds such as triethanolamine, diethanolamine, dimethylamine, N-methylethanolamine, N-methyldiethanolamine, alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates, alkali metal silicates, etc. A regulator can be used.

Viscosity of liquid softening agent composition The viscosity of the liquid softening agent composition is not particularly limited as long as its usability is not impaired, but the viscosity at 25 ° C is preferably less than 1000 mPa · s. In view of the increase in viscosity due to storage aging, the viscosity of the liquid softener composition immediately after production at 25 ° C. is more preferably less than 800 mPa · s, and even more preferably less than 500 mPa · s. When it is in such a range, the usability such as handling property at the time of loading into the washing machine is good.
The viscosity of the liquid softening agent composition can be measured using a B-type viscometer (manufactured by TOKIMEC).

Method for Producing Liquid Softener Composition The liquid softener composition of the present invention can be produced by a known method, for example, a method similar to a conventional method for producing a liquid softener composition using a cationic surfactant as a main agent.
For example, the oil phase containing the component (A), the component (B), the component (C), the component (D) and the component (E) and the aqueous phase are mixed under a temperature condition equal to or higher than the melting point of the component (A). Thus, an emulsion can be prepared, and thereafter, other components can be added and mixed as necessary to the obtained emulsion.
In the oil phase, the component (A), the component (B), the component (C), the component (D), and the component (E) are mixed with the optional component as necessary at a temperature equal to or higher than the melting point of the component (A). Can be prepared.
The aqueous phase can be prepared by mixing water and optional components as necessary.
In addition, the addition method of (B) component, (C) component, (D) component, and (E) component is not limited to the addition method of the said description. That is, the component (B), the component (C), the component (D), and the component (E) may be added and mixed after the emulsion is obtained to produce a liquid softener composition. Well, for example, each component may be added alone, or (B) component, (C) component, (D) component and (E) component are premixed and then added to the oil phase or emulsion May be. The component (D) can also be added after the aqueous phase or emulsion is obtained, or can be added separately in an oil phase and an aqueous phase.

Method of Using Liquid Softener Composition There is no particular limitation on the method of using the liquid softener composition of the present invention, and the liquid softener composition can be used in the same manner as a general liquid softener composition. For example, a method of softening a washing object by dissolving the liquid softener composition of the present invention in rinse water at the stage of rinsing or water in a container such as a tub with the liquid softener composition of the present invention. There is a method in which the product is dissolved, and further, an article to be cleaned is put in and immersed.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this.
In the examples and comparative examples, the blending amounts of the components are all expressed in mass% (in terms of pure content, unless otherwise specified).

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

[(A) component]
The following A-1 to A-3 were used.

A-1: a cationic surfactant (the compound described in Example 4 of JP-A-2003-12471).
A-1 is a compound represented by the general formulas (A1-4), (A1-5) and (A1-6) (in each formula, R ⁹ is an alkyl or alkenyl group having 15 to 17 carbon atoms) ) Is quaternized with dimethyl sulfate.

A-2: Cationic surfactant (manufactured by Stepan, trade name: Stepantex SE-88). A-2 is a compound represented by the general formulas (A1-4), (A1-5) and (A1-6) (in each formula, R ⁹ is an alkyl or alkenyl group having 15 to 17 carbon atoms) ) Is quaternized with dimethyl sulfate.

A-3: Cationic surfactant (made by Tonan Gosei Co., Ltd., trade name: HITEX RO16E). A-3 is a compound represented by the general formulas (A1-4), (A1-5) and (A1-6) (in each formula, R ⁹ is an alkyl or alkenyl group having 15 to 17 carbon atoms) ) Is quaternized with dimethyl sulfate.

[Component (B)]
The following B-1 and 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-T-2005-511710. B-1 is a group represented by the general formula (B-1): YSGGQ, wherein Y is Y-1 (having a double bond at positions 3 and 4), and G is carbon. A dodecyl group consisting of 12 atoms, a compound in which Q is a hydrogen atom.

B-2: 4- (dodecylthio) -4- (2,6,6-trimethylcyclohex-2-en-1-yl) -2-butanone. B-2 was synthesized by the same method as described in Example 4 of JP-T-2005-511710 using dodecanethiol (manufactured by Tokyo Chemical Industry Co., Ltd.) and β-nonone (manufactured by Ve Manfis Fragrance Co., Ltd.) as raw materials. did. In addition, B-2 is a group represented by the general formula (B-1): YSGGQ, wherein Y is Y-2 (having a double bond at positions 1 and 2), and G is carbon. A dodecyl group consisting of 12 atoms, a compound in which Q is a hydrogen atom.

[Component (C)]
The following C1-1 to C1-4 were used as the component (C1).

C1-1: BHT (dibutylhydroxytoluene) Tokyo Chemical Industry Co., Ltd. C1-2: BHA (butylhydroxyanisole) Tokyo Chemical Industry Co., Ltd. C1-3: p-methoxyphenol (Tokyo Chemical Industry Co., Ltd.)
C1-4: Uric acid (Wako Pure Chemical Industries, Ltd.)

The following C2-1 to C2-4 were used as the component (C2).

C2-1: Amino-modified silicone (KF-864) (manufactured by Shin-Etsu Chemical Co., Ltd.)
C2-2: Amino-modified silicone (SM8904) (manufactured by Dow Corning Toray)
C2-3: polyether-modified silicone (Compound B-1 described in Examples of JP 2010-255170 A)
C2-4: Dimethyl silicone (BY 22-050 A) (manufactured by Dow Corning Toray)

[(D) component]
The following D-1 was used as the component (D).

D-1: Nonionic surfactant (primary isotridecyl alcohol ethylene oxide 60 mol adduct. Ethylene oxide added to BASF's Rutensol TO3)

[(E) component]
(E) The fragrance | flavor composition of Table 1 was used as a component.

[(F) component]
As the component (F), calcium chloride (Wako Pure Chemical Industries, Ltd.) was used. The compounding quantity of (F) component in each liquid softening agent composition was 0.6 mass% with respect to the total mass of a liquid softening agent composition.

Furthermore, common component 1 shown in Table 2 was used as an optional component.

Preparation method of liquid softener composition Using a glass container having an inner diameter of 100 mm and a height of 150 mm and a stirrer (Agitator SJ type, manufactured by Shimadzu Corporation), the blending amounts of the respective components are adjusted as shown in Table 3 below. A liquid softener composition was prepared by the following procedure.
First, (A) component, (B) component, (C) component, (D) component, and (E) component were mixed and stirred, and the oil phase mixture was obtained. On the other hand, common component 1 was dissolved in ion-exchange water for balance to obtain an aqueous phase mixture. Here, the mass of ion-exchanged water for balance corresponds to the balance obtained by subtracting the total amount of the oil phase mixture and the component (F) from 980 g.
Next, the oil phase mixture heated above the melting point of component (A) is placed in a glass container and stirred, and the aqueous phase mixture heated above the melting point of component (A) is added in two portions. And stirred. Here, the split ratio of the aqueous phase mixture was 30:70 (mass ratio), and the stirring was performed at a rotational speed of 1,500 rpm for 3 minutes after the first aqueous phase mixture addition and for 2 minutes after the second aqueous phase mixture addition. It was. Thereafter, the component (F) was added. The component (F) was dissolved in ion-exchanged water before addition and used as a 30% wt aqueous solution. If necessary, add a suitable amount of hydrochloric acid (reagent 1 mol / L, Kanto Chemical) or sodium hydroxide (reagent 1 mol / L, Kanto Chemical) to adjust the pH to 2.5, and further adjust the total mass to 1,000 g. Ion exchange water was added so that the desired softener compositions (Examples 1 to 20 and Comparative Examples 1 to 5) were obtained.
In Table 3, the numerical values of the components (A), (B), (C), (D), and (E) are blending amounts (% by mass) with respect to the total mass of the liquid softening agent composition.
In Table 3, “(B) / (C)” indicates the mass ratio of the component (B) to the component (C).

Evaluation Method of Liquid Softener Composition The obtained liquid softener composition was evaluated for “fragrance” and “scent persistence” by the following procedure.

<Aroma evaluation of liquid softener composition>
100 mL of the liquid softening agent composition was put in a lightweight PS glass bottle (PS-No. 11, manufactured by Tanuma Glass Industrial Co., Ltd.) and sealed, and the aroma was evaluated according to the following four-stage evaluation criteria. The result expressed as the average score of five professional panelists is shown in the column of “Aroma evaluation” in Table 3. In terms of product value, an average score of 2.0 or less was accepted.

<Evaluation criteria>
0: There is no off-flavor 1: The off-flavor is finally recognizable 2: The off-flavor feels unpleasant 3: There is a clear off-flavor.

<Scent sustainability evaluation>
(Pretreatment of evaluation cloth)
A commercially available cotton towel (manufactured by Toshin Co., Ltd.) was subjected to the following pretreatment three times using a commercial detergent “Top Platinum Clear” (manufactured by Lion Corporation) using a two-tank washing machine (VH-30S manufactured by Toshiba). .
Pretreatment: Standard detergent usage, 30 times the bath ratio, washing with tap water at 45 ° C. for 10 minutes, followed by two cycles of 10 minutes of water rinsing.

(Treatment with a liquid softener composition in the rinsing process during washing)
1. Wash 1.0 kg of pre-cleaned cotton towel (manufactured by Toshin Co., Ltd.) with a commercial detergent “Top Platinum Clear” (manufactured by Lion) using a two-tank washing machine (Toshiba VH-30S) ( Standard use amount, standard course, bath ratio 30 times, use of tap water at 25 ° C.), followed by dehydration for 1 minute, and then a first rinse for 3 minutes. After the first rinse, dehydration was performed for 1 minute, followed by a second rinse for 3 minutes. At the start of this second rinsing, the liquid softener composition obtained in each of the above examples was added, and a softening treatment for 3 minutes (finishing agent 6.67 mL, bath ratio 20 times, using tap water at 25 ° C.) Went. After the softening treatment, dehydration was performed for 1 minute.
After the treatment, the cotton towel was taken out from the two-tank washing machine, dried for 18 hours under constant temperature and humidity conditions of 20 ° C. and 40% RH, and subjected to the evaluation shown below.

(Evaluation of fragrance persistence after application of softener composition)
After the above treatment, the cotton towel was stored for 7 days under the conditions of 20 ° C. and 40 RH, and then the fragrance intensity was subjected to sensory evaluation according to the following 6-step odor intensity display method. The results expressed as the average score of five professional panelists are shown in the column “Scent persistence” in Table 3. In terms of product value, an average score of 2.5 or more was considered acceptable.

<6-level odor intensity display method>
0: Odorless 1: A scent that can be finally detected 2: A scent that understands what scent 3: A scent that can be easily detected 4: A strong scent 5: A strong scent

The present invention can be used in the field of liquid softening agents.

Claims

A liquid softener composition comprising:
The following components (A) to (C):
(A) an amine compound having 1 to 3 hydrocarbon groups of 10 to 26 carbon atoms in the molecule, which may be separated by an ester group (—COO—) and / or an amide group (—NHCO—), At least one compound selected from the group consisting of a salt and a quaternized product thereof,
(B) a sulfur-containing fragrance precursor, and
(C) an antioxidant and / or a silicone compound,
A liquid softener composition comprising:
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 component (A) is at least one compound selected from the group consisting of compounds represented by general formulas (A1-1) to (A1-8), salts thereof, and quaternized compounds thereof. 3. The liquid softener composition according to 1 or 2.

[In the formula (A1-1), R 7 and R 8 are each independently a hydrocarbon group having 10 to 26 carbon atoms,
In the formulas (A1-2) to (A1-8), R 9 and R 10 are each independently 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 general formula (B-1).
YSGQ (B-1)
[Where,
Y represents a group selected from the group consisting of formulas (Y-1) to (Y-7) or an isomer thereof,

(In the formulas (Y-1) to (Y-7), the wavy line represents the position of the YS bond, and the dotted line represents the position of the single bond or the double bond).
S represents a sulfur atom,
G represents a divalent or trivalent group derived from a linear or branched alkyl group or alkenyl group having 2 to 15 carbon atoms (the divalent or trivalent group is One optionally selected from the group consisting of —OR 11 , —NR 11 2 , —COOR 11 and R 11 groups, wherein R 11 represents a hydrogen atom or a C1-C6 alkyl group or alkenyl group. Optionally substituted with the above groups),
Q represents a hydrogen atom, a —S—Y group or a —NR 12 —Y group (in each group, Y is defined as described above, and R 12 is a hydrogen atom or a methyl group). ]
The compound represented by the general formula (B-1) is 3- (dodecylthio) -1- (2,6,6-trimethylcyclohex-3-en-1-yl) -1-butanone and 4- (dodecylthio). 5. The liquid softener composition according to claim 4, selected from the group consisting of) -4- (2,6,6-trimethylcyclohex-2-en-1-yl) -2-butanone.
The component (C) is at least one antioxidant selected from the group consisting of dibutylhydroxytoluene (BHT), butylhydroxyanisole (BHA), p-methoxyphenol and uric acid. 2. A liquid softener composition according to item 1.
The liquid softener composition according to any one of claims 1 to 6, wherein the component (C) is at least one silicone compound selected from the group consisting of dimethyl silicone, polyether-modified silicone, and amino-modified silicone. .
The liquid softener composition according to any one of claims 1 to 7, comprising an antioxidant and a silicone compound as component (C).