KR102573429B1 - liquid softener composition - Google Patents

Abstract

The present invention provides a liquid softener composition capable of continuously exhibiting a fragrance intended at the time of design while suppressing the occurrence of off-flavor. Specifically, a liquid softening agent composition obtained by blending the following components (A) to (C) is provided. (A) An amine compound having 1 to 3 hydrocarbon groups of 10 to 26 carbon atoms in a molecule, which may be branched by an ester group (-COO-) and/or an amide group (-NHCO-), a salt thereof, and a quaternary product thereof At least one compound selected from the group consisting of (B) a sulfur-containing perfume 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, the present invention relates to a liquid softener composition capable of continuously exhibiting a fragrance intended at the time of design while suppressing the occurrence of off-flavor.

In recent years, an increasing number of consumers require the persistence of fragrance as a function of a softener, and various measures are being taken for this.

As one of the means for achieving the persistence of fragrance, a technology using a fragrance precursor chemically bonded to a fragrance and a non-volatile substrate is known in the fields of softening agents, bleaching agents, and detergents (Patent Document 1). ~4). Perfume precursors continuously emit fragrance as bonds are cleaved by a trigger such as light, heat, or water. In particular, it is known that a sulfur-containing perfume precursor formed by combining a thiol with an α,β-unsaturated ketone type perfume has excellent fragrance persistence (Patent Document 1).

Patent Document 1: Japanese Patent Publication No. 2005-511710 Patent Document 2: Japanese Patent Publication No. 2014-511414 Patent Document 3: Japanese Patent Publication No. 2012-530812 Patent Document 4: International Publication No. 2014/176392

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

As a result of intensive studies regarding the above problems, the inventors of the present invention have found that when an antioxidant and/or a silicone compound is added to a liquid softener composition containing a sulfur-containing perfume precursor, the occurrence of off-odor is suppressed, and the fragrance intended at the time of design is continuously maintained. I found something that can be exerted (excellent in reverberation). The present invention has been made based on this knowledge.

That is, the present invention relates to the following.

1. As a liquid softener composition,

The following components (A) to (C):

(A) An amine compound having 1 to 3 hydrocarbon groups of 10 to 26 carbon atoms in a molecule, which may be branched by an ester group (-COO-) and/or an amide group (-NHCO-), a salt thereof, and At least one compound selected from the group consisting of the quaternary compounds;

(B) a sulfur-containing flavor precursor; and

(C) A liquid softener composition containing an antioxidant and/or a silicone compound.

2. The liquid softening agent composition according to 1 above, wherein the mass ratio ((B)/(C)) of component (B) to component (C) is 0.001 to 10.

3. The above 1 or 2, in which 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 quaternary compounds thereof The liquid softener composition described in.

[Formula 1]

[In Formula (A1-1), R ⁷ and R ⁸ are each independently a hydrocarbon group having 10 to 26 carbon atoms,

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

4. (B) The liquid softening agent composition in any one of said 1-3 which is at least 1 sort(s) of compound represented by general formula (B-1) as a component.

Y-S-G-Q (B-1)

[during expression,

Y represents a group selected from the group consisting of formulas (Y-1) to (Y-7) or an isomer thereof;

(In each formula of (Y-1) to (Y-7), the broken line represents the position of the Y-S bond, and the dotted line represents the position of a single bond or double bond),

S represents a sulfur atom,

G represents a divalent or trivalent group derived from a linear or branched chain alkyl or alkenyl group having 2 to 15 carbon atoms (the divalent or trivalent group is optionally -OR ¹¹ , -NR ¹¹ ₂ , -COOR ¹¹ and R ¹¹ groups (in each group, R ¹¹ represents a hydrogen atom or a C1-C6 alkyl group or an alkenyl group), which may be substituted with one or more groups selected from the group consisting of;

Q represents a hydrogen atom, a -SY 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 formula (B-1) is 3-(dodecylthio)-1-(2,6,6-trimethylcyclohexa-3-en-1-yl)-1-butanone and The liquid softener composition according to 4 above, selected from the group consisting of 4-(dodecylthio)-4-(2,6,6-trimethylcyclohexa-2-en-1-yl)-2-butanone.

6. (C) component, dibutylhydroxytoluene (BHT), butylhydroxyanisole (BHA),

The liquid softener composition according to any one of 1 to 5 above, which is at least one antioxidant selected from the group consisting of p-methoxyphenol and uric acid.

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

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

As will be shown in the examples described later, the liquid softener composition of the present invention can continuously exhibit the fragrance intended at the time of design (excellent in fragrance) while suppressing the generation of off-flavor.

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 contains the following components (A) to (C):

(A) An amine compound having 1 to 3 hydrocarbon groups of 10 to 26 carbon atoms in a molecule, which may be branched by an ester group (-COO-) and/or an amide group (-NHCO-), a salt thereof, and a quaternary product thereof At least one compound selected from the group consisting of

(B) a sulfur-containing flavor precursor; and

(C) Contains an antioxidant and/or a silicone compound.

[Component (A)]

Component (A) is "an amine compound having 1 to 3 hydrocarbon groups of 10 to 26 carbon atoms in a molecule, which may be branched by an ester group (-COO-) and/or an amide group (-NHCO-), a salt thereof, and It is a cationic surfactant which is "at least 1 sort(s) of compound selected from the group which consists of the quaternary material."

Component (A) is blended in order to impart to the liquid softener composition the effect of imparting flexibility (tactile feel) to textiles (ie, the original function of the softener).

The number of carbon atoms of the hydrocarbon group having 10 to 26 carbon atoms (hereinafter sometimes referred to as "long-chain hydrocarbon group" in this specification) is 10 to 26, preferably 17 to 26, and more preferably 19 to 24. When the carbon number is 10 or more, the effect of imparting flexibility is good, and when the carbon number 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 any position, but when there is only one double bond, the position of the double bond is the center of the long-chain hydrocarbon group or distributed around the central value. desirable.

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 linear or branched. As a 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 segmented into an ester group (-COO-) and/or an amide group (-NHCO-). That is, the long-chain hydrocarbon group may have at least one branching group selected from the group consisting of an ester group and an amide group in its carbon chain, and the carbon chain may be branched by the branching group. Having the branching group is preferable from the point of improving biodegradability and the like.

In the case of having the branching group, the number of branching groups that one long-chain hydrocarbon group has may be one or two or more. That is, the long-chain hydrocarbon group may be parted at one place or at least two places by the branching machine. In the case of having two or more branching groups, each branching group may be the same or different.

In addition, when a long-chain hydrocarbon group has a branching group in its carbon chain, the carbon atom which a branching group has is counted as carbon number of a long-chain hydrocarbon group.

The long-chain hydrocarbon group is an unhydrogenated fatty acid derived from beef tallow, which is usually used industrially, a fatty acid obtained by hydrogenating or partially hydrogenating an unsaturated part, and an unhydrogenated fatty acid derived from plants such as palm and oil palm. Alternatively, it is introduced by using a fatty acid ester or a fatty acid or fatty acid ester obtained by hydrogenating or partially hydrogenating an unsaturated part.

As an amine compound, a secondary amine compound (the number of long-chain hydrocarbon groups is two) or a tertiary amine compound (the number of long-chain hydrocarbon groups is three) 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.

[Formula 2]

[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 a hydrocarbon group having 7 to 21 carbon atoms group.), -(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, -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), as for carbon number of the hydrocarbon group of 10-26 carbon atoms in ^R1 - ^R3 , 17-26 are preferable and 19-24 are more preferable. The hydrocarbon group may be saturated or unsaturated. As the hydrocarbon group, an alkyl group or an alkenyl group is preferable.

Among -CH ₂ CH(Y)OCOR ⁴ , Y is a hydrogen atom or CH ₃ , and a hydrogen atom is particularly preferred. R ⁴ is a hydrocarbon group of 7 to 21 carbon atoms, preferably a hydrocarbon group of 15 to 19 carbon atoms. When there are a plurality of R ⁴ in the compound represented by the general formula (A1), the plurality of R ⁴ may be the same or different.

The hydrocarbon group of R ⁴ is a residue (fatty acid residue) obtained by removing a carboxy group from a fatty acid having 8 to 22 carbon atoms (R ⁴ COOH), and the fatty acid (R ⁴ COOH) that is the basis of R ⁴ may be a saturated fatty acid or an unsaturated fatty acid; Further, a straight-chain fatty acid or a branched fatty acid may be used. Among them, saturated or unsaturated straight-chain fatty acids are preferred. In order to impart good absorbency to the softened clothing, the saturated/unsaturated ratio (mass ratio) of the fatty acids that are the basis of R ⁴ is preferably 90/10 to 0/100, more preferably 80/20 to 0/100. do.

When R ⁴ is an unsaturated fatty acid residue, cis-isomers and trans-isomers exist, but the mass ratio of cis-isomers to trans-isomers is preferably 40/60 to 100/0, particularly preferably 70/30 to 90/10.

Specific examples of fatty acids as a base of R ⁴ include stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, elaidic acid, linoleic acid, partially hydrogenated palm oil fatty acids (iodine value 10 to 60), and partially hydrogenated fatty acids. tallow fatty acid (iodine value of 10 to 60); and the like. Among them, a fatty acid composition prepared by combining predetermined amounts of at least two selected from stearic acid, palmitic acid, myristic acid, oleic acid, elaidic acid and linoleic acid, and adjusting the following conditions (a) to (c). It is preferable to use

(a) The ratio (mass ratio) of saturated fatty acids to unsaturated fatty acids is 90/10 to 0/100, more preferably 80/20 to 0/100.

(b) The cis-isomer/trans-isomer ratio (mass ratio) is 40/60 to 100/0, more preferably 70/30 to 90/10.

(c) 60 mass% or more of C18 fatty acids, preferably 80 mass% or more, less than 2 mass% of C20 fatty acids, and less than 1 mass% of C21 to C22 fatty acids.

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 of 7 to 21 carbon atoms, preferably a hydrocarbon group of 15 to 19 carbon atoms. When a plurality of R ⁵ groups are present in the compound represented by the general formula (A1), the plurality of R ⁵ groups may be the same or different.

As R ⁵ , those similar to those of R ⁴ can be specifically mentioned.

In Formula (A1), at least one of R ¹ to R ³ is a long-chain hydrocarbon group (a hydrocarbon group having 10 to 26 carbon atoms), -CH ₂ CH(Y)OCOR ⁴ , or -(CH ₂ ) _n NHCOR ⁵ ) And, it is preferable that two are long-chain hydrocarbon groups.

When one or two of R ¹ to ^{R 3} are long-chain hydrocarbon groups, the other 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, as a C1-C4 alkyl group, a methyl group or an ethyl group is preferable, and a methyl group is especially 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).

[Formula 3]

[In Formula (A1-1), R ⁷ and R ⁸ are each independently a hydrocarbon group having 10 to 26 carbon atoms. In each formula of (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 hydrocarbon groups having 10 to 26 carbon atoms in 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 the same hydrocarbon group having 7 to 21 carbon atoms in R ⁴ in the general formula (A1). In addition, when a plurality of R ⁹ are present in the formula, the plurality of R ⁹ may be the same or different.

(A) Component may be a salt of an amine compound.

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

(A) Component may be a quaternized substance of an amine compound.

The quaternized substance of an amine compound is obtained by making the amine compound react with a quaternizing agent. As a quaternization agent used for quaternization of an amine compound, alkyl halides, such as methyl chloride, and dialkyl sulfuric acid, such as dimethyl sulfuric acid, etc. are mentioned, for example. When these quaternizing agents are reacted with an amine compound, an alkyl group of the quaternizing agent is introduced into a nitrogen atom of the amine compound, and a salt of quaternary ammonium ion and halogen ion or monoalkyl sulfate ion is formed. The alkyl group introduced by the quaternizing agent is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. Quaternization of an amine compound can be performed by a well-known method.

(A) As a component,

At least one selected from the group consisting of compounds represented by the general formula (A1), salts thereof and quaternary compounds thereof is preferred,

At least one selected from the group consisting of compounds represented by general formulas (A1-1) to (A1-8), salts thereof and quaternary compounds thereof is more preferable,

At least one selected from the group consisting of compounds represented by general formulas (A1-4) to (A1-6), salts thereof, and quaternary compounds thereof is particularly preferred.

In particular, a combination of a quaternary compound of a compound represented by general formula (A1-4), a quaternary compound of a compound represented by (A1-5), and a quaternary compound of a compound represented by (A1-6) it is desirable

As the compounds represented by the general formulas (A1) and (A1-1) to (A1-8), salts thereof and quaternary compounds thereof, commercially available products or products produced by known methods may be used. good night.

For example, a compound represented by general formula (A1-2) (hereinafter referred to as "compound (A1-2)") and a compound represented by general formula (A1-3) (hereinafter referred to as "compound (A1-3)" The composition containing ") is the fatty acid composition described in the R ⁴ column of the general formula (A1), or a fatty acid methyl ester composition in which the fatty acid in the fatty acid composition is substituted with the methyl ester of the fatty acid, and methyldiethane It can be synthesized by condensation reaction with amines. At that time, from the viewpoint of improving flexibility, it is preferable to synthesize the compound so that the abundance ratio expressed as "compound (A1-2)/compound (A1-3)" is 99/1 to 50/50 in terms of mass ratio.

Moreover, when using the quaternized substance, it is more preferable to use dimethylsulfuric acid as a quaternizing agent. At that time, from the viewpoint of imparting flexibility, synthesizing such that the abundance ratio expressed as "quaternary compound of compound (A1-2)/quaternary compound of compound (A1-3)" is 99/1 to 50/50 in terms of mass ratio. it is desirable

A compound represented by general formula (A1-4) (hereinafter referred to as “compound (A1-4)”) and a compound represented by general formula (A1-5) (hereinafter referred to as “compound (A1-5)”) And, a composition containing a compound represented by formula (A1-6) (hereinafter referred to as "compound (A1-6)") is the fatty acid composition or fatty acid methyl ester described in the R ⁴ column of formula (A1). It can be synthesized by a condensation reaction between the composition and triethanolamine. In that case, the content ratio of the individual components to the total mass of the compounds (A1-4), (A1-5) and (A1-6) is 1 to 60 masses of the compound (A1-4) from the viewpoint of imparting flexibility. %, compound (A1-5) is 5 to 98% by mass, compound (A1-6) is preferably 0.1 to 40% by mass, compound (A1-4) is 30 to 60% by mass, compound (A1-5 ) is more preferably 10 to 55% by mass, and 5 to 35% by mass of the compound (A1-6).

Moreover, when using this quaternized substance, it is more preferable to use dimethylsulfuric acid as a quaternization agent from the point of fully advancing a quaternization reaction. The ratio of the quaternary compounds of compounds (A1-4), (A1-5) and (A1-6) is 1 to 60 in terms of mass ratio from the viewpoint of imparting flexibility. It is preferable that the mass %, the quaternary compound of compound (A1-5) is 5-98 mass %, and the quaternary compound of compound (A1-6) is 0.1-40 mass %, and the quaternary compound of compound (A1-4) is 0.1-40 mass % It is more preferable that the cargo is 30 to 60 mass%, the quaternary cargo of compound (A1-5) is 10 to 55 mass%, and the quaternary cargo of compound (A1-6) is 5 to 35 mass%.

In addition, when quaternizing compounds (A1-4), (A1-5) and (A1-6), generally

Unquaternized esteramine remains after the quaternization reaction. In that case, it is preferable that the ratio of the "quaternary material/non-quaternized ester amine" is within the mass ratio range of 70/30 to 99/1.

The compound represented by the general formula (A1-7) (hereinafter referred to as “compound (A1-7)”) and the compound represented by the general formula (A1-8) (hereinafter referred to as “compound (A1-8)”) , in the fatty acid composition described in the column of R ⁴ of general formula (A1), and an adduct of N-methylethanolamine and acrylonitrile, J. Org. It can be synthesized by condensation reaction with N-(2-hydroxyethyl)-N-methyl-1,3-propylenediamine synthesized by a known method described in Chem., 26, 3409 (1960). 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 in terms of mass ratio.

In addition, when using the quaternary material, it is preferable to use methyl chloride as the quaternization agent, and it is represented by "quaternary material of compound (A1-7)/quaternary material of compound (A1-8)" It is preferable to synthesize so that the abundance ratio is 99/1 to 50/50 in terms of mass ratio.

(A) component may be used independently of one type of amine compound, its salt or its quaternary compound, or a mixture consisting of two or more types, for example, general formulas (A1-4) to (A1-6) ) may be used as a mixture of the compounds represented by

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

[(B) component]

(B) component is a sulfur-containing fragrance precursor. A "sulfur-containing perfume precursor" refers to a compound in which a perfume and a non-volatile substrate containing sulfur are chemically bonded. The spice precursor itself does not emit fragrance, but when the bond between the spice and the substrate is cleaved by a trigger such as heat, light, or water, the spice is released and emits a fragrance. Therefore, it is known that when clothing is treated with a fragrance precursor, the effect as a fragrance is exerted even in the latter half of the use scene, such as after the clothing is worn or stored.

Component (B) is blended for adding fragrance to textiles after treatment with the liquid softening agent composition.

As the sulfur-containing perfume precursor, those generally used in liquid softener compositions can be used without particular limitation. Preferably, a compound represented by the following general formula (B-1) can be used as the sulfur-containing spice precursor of component (B).

Y-S-G-Q (B-1)

In the general formula (B-1),

Y represents a group selected from the group consisting of groups (Y-1) to (Y-7) shown below or an isomer thereof;

(In each formula of (Y-1) to (Y-7), the broken line represents the position of the Y-S bond, and the dotted line represents the position of a single bond or 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, in the case of Substituted with one or more groups selected from the group consisting of -OR ¹¹ , -NR ¹¹ ₂ , -COOR ¹¹ and R ¹¹ groups (in each group, R ¹¹ represents a hydrogen atom or a C1-C6 alkyl group or an alkenyl group) may be),

Q represents a hydrogen atom, -SY group, or -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, the "isomer" of the group represented by each formula of (Y-1) to (Y-7) in the general formula (B-1) refers to isomers that each group can take in terms of chemical structure, for example, stereoisomers. say

The compound represented by general formula (B-1) may be used individually by 1 type, and may suitably combine 2 or more types.

Preferable examples of the compound represented by formula (B-1) include methyl or ethyl 2-(4-oxo-4-(2,6,6-trimethylcyclohexa-3-en-1-yl)butan-2- ylamino)-3-(4-oxo-4-(2,6,6-trimethylcyclohexa-3-en-1-yl)butan-2-ylthio)propanate, methyl or ethyl 2-(4 -Oxo-4-(2,6,6-trimethylcyclohexa-2-en-1-yl)butan-2-ylamino)-3-(4-oxo-4-(2,6,6-trimethylcyclo Hexa-2-en-1-yl)butan-2-ylthio)propanate, methyl or ethyl 2-(2-oxo-4-(2,6,6-trimethylcyclohexa-1-en-1- yl)butan-4-ylamino)-3-(2-oxo-4-(2,6,6-trimethylcyclohexa-1-en-1-yl)butan-4-ylthio)propanate, methyl or ethyl 2-(2-oxo-4-(2,6,6-trimethylcyclohexa-2-en-1-yl)butan-4-ylamino)-3-(2-oxo-4-(2, 6,6-trimethylcyclohexa-2-en-1-yl)butan-4-ylthio)propanate, 3-(dodecylthio)-1-(2,6,6-trimethylcyclohexa-3- En-1-yl)-1-butanone, 3-(dodecylthio)-1-(2,6,6-trimethylcyclohexa-2-en-1-yl)-1-butanone, 4-( Dodecylthio)-4-(2,6,6-trimethylcyclohexa-2-en-1-yl)-2-butanone, 4-(Dodecylthio)-4-(2,6,6-trimethyl Cyclohexa-1-en-1-yl) -2-butanone, 2-dodecylsulfanyl-5-methyl-heptan-4-one, 2-cyclohexyl-1-dodecylsulfanyl-hepto-6-en- and compounds selected from the group consisting of 3-one and 3-(dodecylthio)-5-isopropenyl-2-methylcyclohexanone.

From the viewpoint of enhancing the persistence of fragrance, more preferably 3-(dodecylthio)-1-(2,6,6-trimethylcyclohexa-3-en-1-yl)-1-butanone, 4- (Dodecylthio)-4-(2,6,6-trimethylcyclohexa-2-en-1-yl)-2-butanone, 4-(Dodecylthio)-4-(2,6,6- compounds selected from the group consisting of trimethylcyclohexa-1-en-1-yl)-2-butanone and 3-(dodecylthio)-5-isopropenyl-2-methylcyclohexanone;

Most preferably, 3-(dodecylthio)-1-(2,6,6-trimethylcyclohexa-3-en-1-yl)-1-butanone and 4-(dodecylthio)-4- and compounds selected from the group consisting of (2,6,6-trimethylcyclohexa-2-en-1-yl)-2-butanone.

Sulfur-containing spice precursors are easily available on the market, or can be synthesized by known methods.

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

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

[(C) component]

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

[(C1) component: antioxidant]

The antioxidant as component (C1) is used for the purpose of suppressing the occurrence of off-flavors such as sulfur derived from component (B) (sulfur-containing spice precursor).

As the antioxidant, compounds whose antioxidant effect is generally known can be used without particular limitation. Therefore, although both water-soluble antioxidants and oil-soluble antioxidants can be used, oil-soluble antioxidants are preferred.

(C1) Specific examples of the component include dibutylhydroxytoluene (BHT), butylhydroxyanisole (BHA), p-methoxyphenol, β-naphthol, phenyl-α-naphthylamine, and tetramethyldiaminodiphenyl. Methane, 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.

Among these, at least one selected from phenolic antioxidants which are oil-soluble antioxidants is preferred, and dibutylhydroxytoluene (BHT), butylhydroxyanisole (BHA), 2,2'-ethylidenebis(4, At least one selected from 6-di-t-butylphenol), p-methoxyphenol and γ-oryzanol is preferred.

More preferably, dibutylhydroxytoluene (BHT), butylhydroxyanisole (BHA), p-methoxyphenol and 2,2'-ethylidenebis(4,6-di-t-butylphenol) It is a compound selected from the group consisting of dibutyl hydroxytoluene (BHT).

(C1) Component can be easily obtained 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 component (C1) is not particularly limited as long as the blending purpose can be achieved, but is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, based on the total mass of the liquid softener composition. More preferably, it is 0.01-1 mass %, Especially preferably, it is 0.01-0.1 mass %. When the compounding amount is 0.001 to 5% by mass, an excellent compounding effect can be obtained.

[(C2) component: silicone compound]

Component (C2) is a silicone compound, and there is no particular restriction on its type, and it can be selected appropriately.

Component (C2) is used for the purpose of suppressing generation of sulfur-like off-flavor derived from component (B) (sulfur-containing spice precursor).

In addition, although the present invention is not limited by a specific theory, since the silicon compound having the property of being excellent in gas absorption (solubility) captures odorous substances (gas) generated by the decomposition of sulfur-containing spice precursors, sulfur It is thought that the occurrence of off-flavors such as is suppressed.

The molecular structure of the silicone compound may be linear, branched, or crosslinked. Further, the silicone compound may be a modified silicone compound, and the modified silicone compound may be modified by one type of organic functional group or may be modified by two or more types of organic functional groups.

A silicone compound can be used in the state of oil, and can also be used in the state of an emulsion dispersed by an arbitrary 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, methylhydrogen silicone, fluorine-modified silicone, epoxy-modified silicone, carboxy-modified silicone, and carbinol-modified silicone. Silicone, amino-modified silicone, etc. are mentioned.

Among these, from the viewpoint of improving the blending effect, polyether-modified silicone, amino-modified silicone, and dimethyl silicone are preferable, and polyether-modified silicone and amino-modified silicone are more preferable.

Specific examples of the polyether-modified silicone include copolymers of alkylsiloxane and polyoxyalkylene. Moreover, as carbon number of the alkyl group of the said alkylsiloxane, 1-3 are preferable, and as carbon number of the alkylene group of the said polyoxyalkylene, 2-5 are preferable. Among these, as the polyether-modified silicone, a copolymer of dimethylsiloxane and polyoxyalkylene (polyoxyethylene, polyoxypropylene, random or block copolymer of ethylene oxide and propylene oxide, etc.) is preferable. Specific examples of such polyether-modified silicone include compounds represented by the following general formula (I), compounds represented by the following general formula (II), and the like.

General formula (I):

[Formula 4]

In the general formula (I), M, N, a and b represent average polymerization degrees, and R represents hydrogen or an alkyl group. Here, M is 10 to 10,000, and 100 to 300 are more preferable. N is 1-1,000, and 1-100 are more preferable. Moreover, it is preferable that M>N. a is 2-100, and 2-50 are more preferable. b is 0-50, and 0-10 are more preferable. 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 manufactured by subjecting the polyoxyalkylene alkyl ether contained in to an addition reaction in the presence of a platinum catalyst. Therefore, some unreacted polyoxyalkylene alkyl ethers and organohydrogen polysiloxanes having a Si-H group may be contained in the polyether-modified silicone. Since organohydrogenpolysiloxane having a Si-H group has high reactivity, the amount present in the polyether-modified silicone is preferably 30 ppm or less (as the amount of Si-H).

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) reacts with a polyoxyalkylene compound having a reactive end group and a reactive end group of the compound. It can be prepared by reacting a dihydrocarbylsiloxane having a terminal group. Such polyether-modified silicone has a longer polyoxyalkylene chain as a side chain and a higher degree of polymerization of the polysiloxane chain, so the viscosity increases. In order to facilitate the formulation of, it is preferable to provide for formulation in the form of a premix with a water-soluble organic solvent. Examples of the water-soluble organic solvent include ethanol, dipropylene glycol, and butyl carbitol.

More specifically, as the polyether-modified silicone, for example, SH3772M, SH3775M, FZ-2166, FZ-2120, L-720, SH8700, L-7002, L-720, SH8700, L-7002, L- 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. , TSF4440, TSF4441, TSF4445, TSF4450, TSF4446, TSF4452, TSF4460, etc. manufactured by Momentive Performance Materials Japan Corporation.

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 cationic surfactant (the above-mentioned component (A) may be used 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).

[Formula 5]

In formula (III), R ₁ and R ₆ may be the same as or different from each other and represent either a methyl group, a hydroxyl group or hydrogen. R ₂ represents either -(CH ₂ ) _n -A1 or -(CH ₂ ) _n -NHCO-(CH ₂ ) _m -A ₁ . A ₁ represents either -N(R ₃ )(R ₄ ) or -N ⁺ (R ₃ )(R ₄ )(R ₅ )·X ^- . R ₃ to _{R 5} may be the same or different and represent either a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, or -(CH ₂ ) _n -NH ₂ . X ^- represents either a fluorine ion, a chlorine ion, a bromine ion, an iodine ion, a methyl sulfate ion, or an ethyl sulfate ion. The values of m and n may be the same or different, and represent an integer of 0 to 12. The values of p and q represent the degree of polymerization of the polysiloxane, may be the same or different, p represents 0 to 20000, preferably 10 to 10000, and q represents 1 to 500, preferably 1 to 100.

When amino-modified silicone oil is used as component (C2), the kinematic viscosity at 25°C is preferably 50 to 20000 mm/s, more preferably 100 to 10000 mm/s. When the kinematic viscosity is within this range, while a high compounding effect is expressed, the productivity is good and handling of the composition becomes easy, so it is preferable.

As the amino-modified silicone, commercially available ones can be used. For example, as the amino-modified silicone oil, those sold as SF-8417, BY16-892, BY16-890 from Dore Dow Corning Co., Ltd., new KF-864, KF-860, KF-8004, KF-8002, KF-8005, KF-867, KF-861, KF-880, KF-867S, etc. from S Chemical Industry Co., Ltd. are mentioned.

As amino-modified silicone emulsion type, those sold as SM8904, BY22-079, FZ-4671, FZ-4672 from Dow Corning Dore, and PolonMF- sold as Polon series from Shin-Etsu Chemical Co., Ltd. 14, PolonMF-29, PolonMF-14D, PolonMF-44, PolonMF-14EC, and PolonMF-52.

When dimethylsilicone is used as component (C2), the kinematic viscosity (25°C) is not particularly limited, preferably 1 to 100,000,000 mm/s, more preferably 10 to 10,000,000 mm/s, and 100 to 1,000,000 mm/s. s is more preferred. In addition, methyl silicone may be an oil or an emulsion.

As dimethyl silicone, commercially available ones can be used. As dimethyl silicone, what is sold as BY 22-050 A from Toray Dow Corning Co., Ltd. is mentioned, for example.

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

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

(C) As component, either (C1) component or (C2) component may be used independently, and (C1) component and (C2) component may be used together. Since a higher compounding effect can be exhibited when a component (C1) and a component (C2) are used together, it is preferable. (C1) In the case of using the component and (C2) component together, the mass ratio ((C1)/(C2)) of the component (C1) and the component (C2) is preferable from the viewpoint that a higher compounding effect can be obtained. is 0.0001 to 5, more preferably 0.001 to 1, still more preferably 0.002 to 0.1.

In addition, when using component (C1) and component (C2) together, the compounding quantity of the total of component (C1) and component (C2) is not particularly limited as long as it is an amount that can achieve the blending purpose, but of the liquid softening agent composition With respect to the total mass, it is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, still more preferably 0.05 to 5% by mass.

In the present invention, the mass ratio ((B)/(C)) of component (B) to component (C) is preferably 0.001 to 10, more preferably 0.005 to 10, still more preferably 0.01 to 5. . (B) When / (C) is set to 0.001 to 10, a higher blending effect of the component (C) (an effect of suppressing the occurrence of off-flavors such as sulfur) can be obtained, and a significant increase in viscosity of the liquid softener composition is suppressed. , usability can be better maintained.

Moreover, when component (C1) is used independently as component (C), it is preferable that the mass ratio ((B)/(C1)) of component (B) to component (C) is 0.01 to 10, more preferably It is preferably 0.1 to 10, more preferably 0.5 to 5.

Moreover, when component (C2) is used independently as component (C), it is preferable that the mass ratio ((B)/(C2)) of component (B) to component (C) is 0.001 to 1, more preferably It is preferably 0.005 to 0.5, more preferably 0.01 to 0.1.

random ingredients

In the liquid softening agent composition of the present invention, optional components other than the essential components of the above (A) to (C) may be blended as necessary within a range not impairing the effects of the present invention.

As the optional component, components generally blended in liquid softener compositions can be mentioned. 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 are explained in detail.

water

The liquid softener composition of the present invention is preferably an aqueous composition containing water.

As water, tap water, purified water, pure water, distilled water, ion-exchanged water, etc. can all be used. Among them, ion-exchanged water is suitable.

The blending amount of water is not particularly limited, and can be blended appropriately to achieve a desired component composition.

Nonionic surfactant (hereinafter also referred to as "component (D)" do )

When the liquid softener composition of the present invention is an emulsion, the nonionic surfactant can be mainly incorporated for the purpose of improving the emulsion dispersion stability of the oil-soluble component in the emulsion. When a nonionic surfactant is blended, it is easy to ensure a sufficient level of freeze recovery stability in terms of commercial value.

As the nonionic surfactant, for example, those derived from polyhydric alcohols, higher alcohols, higher amines, or higher fatty acids can be used. More specifically, glycerin fatty acid esters or pentaerythritol obtained by ester bonding of glycerin or pentaerythritol with a fatty acid having 10 to 22 carbon atoms; polyoxyethylene alkyl ether having an alkyl group or alkenyl group of 10 to 22 carbon atoms and having an average added mole number of ethylene oxide of 10 to 100 moles; Polyoxyethylene fatty acid alkyl (C1-C3 of the alkyl) ester; Polyoxyethylene alkylamine whose average added mole number of ethylene oxide is 10-100 mol; Alkyl polyglucoside having an alkyl group or alkenyl group of 8 to 18 carbon atoms; and hydrogenated castor oil having an average number of added moles of ethylene oxide of 10 to 100 moles. Especially, polyoxyethylene alkyl ether having an alkyl group of 10 to 18 carbon atoms and having an average number of added moles of ethylene oxide of 20 to 80 moles is preferable.

A nonionic surfactant may be used individually by 1 type, and may be used as a mixture consisting of 2 or more types.

The blending amount of the nonionic surfactant is not particularly limited as long as the blending purpose can be achieved, but is preferably 0.01 to 10% by mass, more preferably 0.1 to 8% by mass, based on the total mass of the liquid softener composition. More preferably, it is 0.5-5 mass %.

Fragrance (hereinafter also referred to as "(E) component" do )

In the liquid softening agent composition, fragrances other than component (B) (sulfur-containing fragrance precursor) can be blended as optional components.

As the fragrance, a general-purpose fragrance can be used in the art and is not particularly limited, but a list of usable fragrance raw materials can be found in various literatures, for example, "Perfume and Flavor Chemicals", Vol. I and II, Steffen Arctander, Allured Pub. Co. (1994) and 「Synthetic Fragrance Chemistry and Product Knowledge」, Indoumotoichi, Chemical Industry Daily (1996) and 「Perfume and Flavor Materials of Natural Origin」, Steffen Arctander, Allured Pub. Co. (1994) and 「Encyclopedia of Fragrance」, edited by Japan Fragrance Association, Asakura Book Store (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, Allured Pub. Co. (1993) et al.

As the fragrance, one type of fragrance may be used alone or may be used as a mixture of two or more types.

The blending amount of the fragrance is not particularly limited as long as the blending purpose can be achieved, but is preferably 0.1 to 3% by mass, more preferably 0.5 to 2% by mass, and further preferably 0.5 to 2% by mass relative to the total mass of the liquid softener composition. Preferably 0.5 to 1. It is 5 mass %.

Water-soluble salts (hereinafter also referred to as "(F) component" do )

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, although calcium chloride, magnesium chloride, sodium chloride, sodium p-toluenesulfonate, etc. can be used, among them, calcium chloride and magnesium chloride are preferable.

Water-soluble salts may be used individually by one type, or may be used as a mixture consisting of two or more types.

The blending amount of the water-soluble salt is not particularly limited as long as the blending purpose can be achieved, but is 0 to 1% by mass relative to the total mass of the liquid softener composition. In addition, water-soluble salts may be blended in any step of producing the liquid softener composition.

Liquid softener pH of the composition

The pH of the liquid softening agent composition is not particularly limited, but from the viewpoint of suppressing the hydrolysis of the ester group contained in the molecule of component (A) accompanying the age of storage, the pH at 25°C is 1 to 6. It is preferable to adjust in the range of, and it is more preferable to adjust in the range of 2 to 4.

Further, for the purpose of further suppressing the decomposition of the sulfur-containing perfume precursor as component (B), the pH of the liquid softener composition at 25°C 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, triethanolamine, diethanolamine , short-chain amine compounds such as dimethylamine, N-methylethanolamine, and N-methyldiethanolamine, alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates, and pH adjusters such as alkali metal silicates can be used. .

Liquid softener Viscosity of the composition

The viscosity of the liquid softening agent composition is not particularly limited as long as the usability is not impaired, but it is preferable that the viscosity at 25°C is less than 1000 mPa·s. Considering the increase in viscosity due to the age of storage, the viscosity at 25°C of the liquid softener composition immediately after production is more preferably less than 800 mPa·s, and more preferably less than 500 mPa·s. If it exists in such a range, usability, such as handling property at the time of throwing into a washing machine, is favorable.

In addition, the viscosity of the liquid softener composition can be measured using a B-type viscometer (manufactured by TOKIMEC).

Liquid softener Method for preparing the composition

The liquid softener composition of the present invention can be prepared 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, an oil phase containing (A) component, (B) component, (C) component, (D) component, and (E) component, and an aqueous phase of (A) component It can be produced by preparing an emulsion by mixing under a temperature condition equal to or higher than the melting point, and then adding and mixing other components to the obtained emulsion as necessary.

The oil phase can be prepared by mixing (A) component, (B) component, (C) component, (D) component, (E) component and optional components as needed at a temperature equal to or higher than the melting point of component (A). there is.

An aqueous phase can be prepared by mixing water and arbitrary components as needed.

In addition, the addition method of (B) component, (C) component, (D) component, and (E) component is not limited to the above-mentioned addition method. That is, each component of (B) component, (C) component, (D) component, and (E) component may prepare a liquid softening agent composition by adding and mixing after an emulsion is obtained, for example, each The components may be added independently, respectively, or after premixing the (B) component, (C) component, (D) component, and (E) component, you may add them to the oil phase or emulsion. In addition, (D)component can also be added after a water phase or emulsion is obtained, and can also be divided and added to an oil phase and a water phase.

Liquid softener How to Use the Composition

There is no particular limitation on the method of using the liquid softener composition of the present invention, and it can be used in the same way as a general liquid softener composition. For example, a method of softening the object to be washed by dissolving the liquid softener composition of the present invention in rinsing water in the rinsing step of laundry, dissolving the liquid softener composition of the present invention in water in a container such as a basin, and further There is a method of immersion treatment by adding washing water.

Example

Hereinafter, the present invention will be described in more detail by examples, but the present invention is not limited thereto.

In the above, Examples and Comparative Examples, the compounding amounts of each component are all expressed in mass% (pure fraction conversion, except for the case where there is designation).

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

[Component (A)]

The following A-1 to A-3 were used.

A-1: Cationic surfactant (compound described in Example 4 of Japanese Patent Application Laid-Open No. 2003-12471).

A-1 is a compound represented by general formulas (A1-4), (A1-5) and (A1-6) (in each formula, R ⁹ is an alkyl group or alkenyl group having 15 to 17 carbon atoms) dimethylsulfuric acid It is a composition containing what was quaternized with.

A-2: Cationic surfactant (product made from Stepan, brand name: Stepantex SE-88). A-2 is a compound represented by general formulas (A1-4), (A1-5) and (A1-6) (in each formula, R ⁹ is an alkyl group or alkenyl group having 15 to 17 carbon atoms) dimethylsulfuric acid It is a composition containing what was quaternized with.

A-3: Cationic surfactant (Dounansei Co., Ltd. product, brand name: HITEX RO16E). A-3 is a compound represented by general formulas (A1-4), (A1-5) and (A1-6) (in each formula, R ⁹ is an alkyl group or alkenyl group having 15 to 17 carbon atoms) dimethylsulfuric acid It is a composition containing what was quaternized with.

[(B) component]

The following B-1 to B-2 were used.

B-1: 3-(dodecylthio)-1-(2,6,6-trimethylcyclohexa-3-en-1-yl)-1-butanone. B-1 is a compound described in Example 4 of Japanese Patent Publication No. 2005-511710. In addition, B-1 is a group represented by Y-1 (having double bonds at positions 3 and 4) in the general formula (B-1): Y-S-G-Q, and G is composed of 12 carbon atoms. It is a compound in which a dodecyl group and Q are hydrogen atoms.

B-2: 4-(dodecylthio)-4-(2,6,6-trimethylcyclohexa-2-en-1-yl)-2-butanone. B-2 was synthesized by the same method as described in Example 4 of Japanese Patent Publication No. 2005-511710, using dodecanethiol (manufactured by Tokyo Chemical Industry Co., Ltd.) and β-yonon (manufactured by Bemanpis Fragrance Co., Ltd.) as raw materials. . In addition, B-2 is a group represented by Y-2 (having a double bond at the 1st and 2nd positions) in the general formula (B-1): Y-S-G-Q, G is a dodecyl group having 12 carbon atoms, and Q is a hydrogen atom compound.

[(C) component]

(C1) As the component, C1-1 to C1-4 described below were used.

C1-1: BHT (dibutylhydroxytoluene) manufactured by Tokyo Chemical Industry Co., Ltd.

C1-2: BHA (butyl hydroxyanisole) manufactured by Tokyo Chemical Industry Co., Ltd.

C1-3: p-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)

C1-4: Uric acid (Wako Pure Chemical Industries, Ltd.)

(C2) As a component, the following C2-1 to C2-4 were used.

C2-1: Amino-modified silicone (KF-864) (manufactured by Shin-Etsu Chemical Industry Co., Ltd.)

C2-2: Amino-modified silicone (SM8904) (manufactured by Tore Dow Corning Co., Ltd.)

C2-3: Polyether-modified silicone (Compound B-1 described in Examples of Japanese Patent Laid-Open No. 2010-255170)

C2-4: Dimethyl silicone (BY 22-050 A) (manufactured by Tore Dow Corning Co., Ltd.)

[(D) component]

(D) As a component, D-1 described below was used.

D-1: Nonionic surfactant (1st grade isotridecyl alcohol ethylene oxide 60 mol adduct. ethyleneolside added to Lutensol TO3 manufactured by BASF)

[(E) component]

(E) As a component, the fragrance composition of Table 1 was used.

[Table 1]

[(F) component]

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

Moreover, as an optional component, the common component 1 of Table 2 was used.

[Table 2]

Liquid softener Method for preparing the composition

Using a glass container with an inner diameter of 100 mm and a height of 150 mm and a stirrer (Ajita SJ type, manufactured by Shimadzu Corporation), the blending amount of each component was adjusted as shown in Table 3 below, and liquid was obtained in the following procedure. A softening agent composition was prepared.

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-exchanged water for balance to obtain an aqueous phase mixture. Here, the mass of the ion-exchanged water for balance corresponds to the remainder obtained by deducting the total amount of the oil phase mixture and component (F) from 980 g.

Next, while storing and stirring the oil phase mixture heated above the melting point of component (A) in a glass container, the water phase mixture heated above the melting point of component (A) was divided into two portions and added and stirred. . Here, the division ratio of the aqueous phase mixture was 30:70 (mass ratio), and stirring was performed at a rotational speed of 1,500 rpm for 3 minutes after the first addition of the aqueous phase mixture and for 2 minutes after the second addition of the aqueous phase mixture. Then, component (F) was added. In addition, component (F) was dissolved in ion-exchanged water before addition and used as a 30% wt aqueous solution. In addition, if necessary, hydrochloric acid (reagent 1 mol/L, Gando Chemical) or sodium hydroxide (reagent 1 mol/L, Gando Chemical) is added in an appropriate amount to adjust the pH to 2.5, and the total mass is 1,000 g. Ion-exchanged water was added to obtain the desired softening agent composition (Examples 1 to 20 and Comparative Examples 1 to 5).

In Table 3, the numerical value of each component of (A), (B), (C), (D) and (E) is the compounding amount (mass %) with respect to the total mass of the liquid softening agent composition.

In Table 3, "(B)/(C)" shows the mass ratio of (B) component with respect to (C) component.

Liquid softener Methods for Evaluating Compositions

About the obtained liquid softening agent composition, "fragrance" and "permanence of a fragrance" were evaluated by the following procedure.

<Evaluation of fragrance of liquid softener composition>

100 ml of the liquid softener composition was placed in a lightweight PS glass bottle (PS-No. 11, manufactured by Tanuma Glass Industry Co., Ltd.), sealed tightly, and the fragrance was evaluated according to the 4-level evaluation criteria shown below. The result expressed as the average score of 5 professional panelists is shown in the column of "fragrance evaluation" of Table 3. In terms of commercial value, an average score of 2.0 or less was regarded as a pass.

<Evaluation Criteria>

0: No off-flavor

1: Off-flavor barely perceptible

2: I feel a strange smell to the extent that I am not worried.

3: It definitely smells bad.

<Evaluation of Persistence of Fragrance>

(Pretreatment of cloth for evaluation)

A commercially available cotton towel (manufactured by Toshin Co., Ltd.) was used with a commercially available detergent "Top Platina Clear" (manufactured by Lion Co., Ltd.) in a two-tank washing machine (VH-30S manufactured by Toshiba), and the following pretreatment was performed three times.

Pretreatment: 10 minutes of washing with standard amount of detergent, 30 times of bath ratio, and 45 ° C.

(Treatment with liquid softener composition in rinsing process during washing)

1.0 kg of pre-treated washed cotton towels (manufactured by Toshin Co., Ltd.) were washed with a commercially available detergent "Top Platina Clear" (manufactured by Lion Co.) for 10 minutes using a 2-tub type washing machine (VH-30S manufactured by Toshiba) (standard amount, standard course) , 30-fold bath ratio, 25°C tap water was used), then dehydration was performed for 1 minute, followed by a first rinse for 3 minutes. After the first rinse, spin-drying was performed for 1 minute, followed by a second rinse for 3 minutes. At the start of this second rinse, the liquid softener composition obtained in each of the above examples was added, and a softening treatment was performed for 3 minutes (6.67 ml of finishing agent, 20 times the bath ratio, and using tap water at 25 ° C.). After the casting treatment, dehydration was performed for 1 minute.

After the treatment, the cotton towel was taken out of the two-tank type washing machine and dried for 18 hours under constant temperature and humidity conditions at 20°C and 40% RH, and was evaluated below.

(Evaluation of fragrance persistence after application of softener composition)

After the treatment, the cotton towels were stored for 7 days under conditions of 20° C. and 40 RH, and then sensory evaluation was performed based on the six-step odor intensity display method described below. The results expressed as the average score of five professional panelists are shown in the column of "fragrance persistence" in Table 3. On the commercial value, 2.5 or more was set as the average score.

<Sixth level odor intensity display method>

0 : Odorless

1: barely perceptible fragrance

2: Fragrance enough to know what kind of fragrance it is

3: easily detectable scent

4 : strong scent

5 : Intense scent

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

[Table 3]

Claims (8)

As a liquid softener composition,
Components (A) to (C) below:
(A) An amine compound having 1 to 3 hydrocarbon groups of 10 to 26 carbon atoms in a molecule, which may be branched by an ester group (-COO-) and/or an amide group (-NHCO-), a salt thereof, and a quaternary product thereof At least one compound selected from the group consisting of
(B) a sulfur-containing spice precursor that is at least one compound represented by formula (B-1)
YSGQ (B-1)
[In the formula,
Y represents a group selected from the group consisting of formulas (Y-1) to (Y-7) or an isomer thereof;

(In each formula of (Y-1) to (Y-7), the broken line represents the position of the YS bond, and the dotted line represents the position of a single bond or double bond),
S represents a sulfur atom,
G represents a divalent or trivalent group derived from a linear or branched chain alkyl or alkenyl group having 2 to 15 carbon atoms (the divalent or trivalent group is optionally -OR ¹¹ , -NR ¹¹ ₂ , -COOR ¹¹ and R ¹¹ groups (in each group, R ¹¹ represents a hydrogen atom or a C1-C6 alkyl group or an alkenyl group), which may be substituted with one or more groups selected from the group consisting of;
Q represents a hydrogen atom, -SY group, or -NR ¹² -Y group (in each group, Y is defined as above, and R ¹² is a hydrogen atom or a methyl group).],
and,
(C) containing at least one antioxidant selected from the group consisting of dibutylhydroxytoluene (BHT), butylhydroxyanisole (BHA), p-methoxyphenol, and uric acid;
A liquid softening agent composition characterized in that the mass ratio ((B)/(C)) of component (B) to component (C) is 0.4 to 4. According to claim 1,
A liquid softening agent composition characterized in that the mass ratio ((B)/(C)) of component (B) to component (C) is 1 to 4. According to claim 1 or 2,
A liquid softening agent composition characterized in that the content of component (B) is 0.0001 to 0.2% by mass with respect to the total mass of the liquid softening agent composition. According to claim 1 or 2,
(A) A liquid softener composition characterized in that component is at least one compound selected from the group consisting of compounds represented by general formulas (A1-1) to (A1-8), salts thereof, and quaternary compounds thereof. .
[Formula 1]

[In Formula (A1-1), R ⁷ and R ⁸ are each independently a hydrocarbon group having 10 to 26 carbon atoms;
In each formula of (A1-2) to (A1-8), R ⁹ and R ¹⁰ are each independently a hydrocarbon group having 7 to 21 carbon atoms.] According to claim 1 or 2,
The compound represented by formula (B-1) is 3-(dodecylthio)-1-(2,6,6-trimethylcyclohexa-3-en-1-yl)-1-butanone and 4- A liquid softener composition characterized by being selected from the group consisting of (dodecylthio)-4-(2,6,6-trimethylcyclohexa-2-en-1-yl)-2-butanone. According to claim 1 or 2,
A liquid softener composition characterized by further containing a silicone compound. According to claim 6,
A liquid softener composition characterized in that the silicone compound is at least one silicone compound selected from the group consisting of dimethyl silicone, polyether-modified silicone, and amino-modified silicone. delete