JP6961378B2 - Liquid fabric softener composition - Google Patents

Description

The present invention relates to a liquid softener composition. More specifically, the present invention relates to a liquid softener composition capable of sustainably exhibiting a scent intended at the time of design while suppressing the generation of offensive odors.

In recent years, various functions have been required for liquid softeners, and various measures have been taken to meet such demands.
For example, a fragrance component having a mercapto group (-SH group) has a low scent threshold, and is therefore used to impart a characteristic scent in a small amount.
Further, an amino acid having a mercapto group (for example, cysteine) is used as a formaldehyde reducing agent (formaldehyde scavenger) having an adverse effect on the human body.
Further, isothiazolin-based compounds are used as preservatives and antibacterial agents (Patent Documents 1 to 3).
In addition, liquid softeners that suppress unpleasant odors and prevent static electricity when the room is dried have also been developed (Patent Documents 4 to 5).

Japanese Unexamined Patent Publication No. 2001-192966 Japanese Unexamined Patent Publication No. 2007-51380 Japanese Unexamined Patent Publication No. 11-181681 Japanese Unexamined Patent Publication No. 2004-21215 Japanese Unexamined Patent Publication No. 2003-105669

However, when a compound having a mercapto group is blended into a liquid softener composition, a sulfur-like offensive odor may be generated from the liquid softener composition, and the pleasant scent intended at the time of design may not be realized. The inventor found it.

As a result of diligent studies on the above problems, the present inventor obtained a liquid softener obtained by adding an isothiazoline-based compound having a specific cyclic structure to a liquid softener composition containing a compound having a mercapto group. It has been found that the composition suppresses the generation of offensive odors after storage and can sustainably exhibit the scent (good scent) intended at the time of design. The present invention has been made based on this finding.

（式中、
Ｒ¹は、炭素数２〜８のアルキレン基、又は、炭素数２〜８のアルケニレン基を示し、
Ｒ²は、水素、炭素数１〜１８の置換又は非置換のアルキル基、炭素数２〜８の置換又は非置換のアルケニル基、又は、炭素数２〜８の置換又は非置換のアルキニル基を示し、
Ｘ¹は水素原子、ハロゲン原子、炭素数１〜４のアルキル基、又は、炭素数１〜４のヒドロキシアルキル基を示し、
ａは０〜６の整数を示す。）
を含有し、
（Ｃ）成分の（Ｂ）成分に対する質量比（（Ｃ）／（Ｂ））が０．１〜５００である、液体柔軟剤組成物。

〔２〕（Ａ）成分が、一般式（Ａ１−１）〜（Ａ１−８）で表される化合物、それらの塩及びそれらの４級化物からなる群から選ばれる少なくとも１種の化合物である、前記〔１〕に記載の液体柔軟剤組成物。

〔（Ａ１−１）式中、Ｒ⁷及びＲ⁸はそれぞれ独立に、炭素数１０〜２６の炭化水素基であり、
（Ａ１−２）〜（Ａ１−８）の各式中、Ｒ⁹及びＲ¹⁰はそれぞれ独立に、炭素数７〜２１の炭化水素基である。〕

〔３〕（Ｂ）成分が、香料及び／又はホルムアルデヒドスカベンジャーである、前記〔１〕又は〔２〕に記載の液体柔軟剤組成物。

〔４〕（Ｂ）成分が、８−メルカプトメントン、チオゲラニオール、２−フランメンテンチオール、１−ドデカンチオール、４−メトキシ−２−メチル−２−ブタンチオール及びリモネンチオールからなる群より選ばれる香料の１種以上である、前記〔１〕〜〔３〕のいずれか１項に記載の液体柔軟剤組成物。

〔５〕（Ｂ）成分が、システイン、システアミン及びグルタチオンからなる群より選ばれるホルムアルデヒドスカベンジャーの１種以上である、前記〔１〕〜〔３〕のいずれか１項に記載の液体柔軟剤組成物。

〔６〕（Ｃ）成分が、１，２−ベンズイソチアゾリン−３−オン（ＢＩＴ）、２−メチル−４，５−トリメチレン−４−イソチアゾリン−３−オン（ＭＴＩ）、Ｎ−メチル−１，２−ベンズイソチアゾリン−３−オン、及び、Ｎ−(ｎ−ブチル)−１，２−ベンズイソチアゾリン−３−オンからなる群より選ばれる１種以上である、前記〔１〕〜〔５〕のいずれか１項に記載の液体柔軟剤組成物。

〔７〕（Ｃ）／（Ｂ）が１〜１００である、前記〔１〕〜〔６〕のいずれか１項に記載の液体柔軟剤組成物。 That is, the present invention relates to the following [1] to [7].
[1] A liquid softener composition.
The following components (A) to (C):
(A) An amine compound having 1 to 3 hydrocarbon groups having 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 salts and quaternized products thereof,
(B) A compound having one or more mercapto groups (-SH) in the molecule, and (C) a compound represented by the following formula (C-1).

(During the ceremony,
R ¹ represents an alkylene group having 2 to 8 carbon atoms or an alkaneylene group having 2 to 8 carbon atoms.
R ² contains hydrogen, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms, or a substituted or unsubstituted alkynyl group having 2 to 8 carbon atoms. Show,
X ¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms.
a represents an integer from 0 to 6. )
Contains,
A liquid softener composition having a mass ratio ((C) / (B)) of the component (C) to the component (B) of 0.1 to 500.

[2] 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 products thereof. , The liquid softener composition according to the above [1].

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

[3] The liquid softener composition according to the above [1] or [2], wherein the component (B) is a fragrance and / or formaldehyde scavenger.

[4] A fragrance selected from the group in which the component (B) consists of 8-mercaptomentone, thiogeraniol, 2-franmentenethiol, 1-dodecanethiol, 4-methoxy-2-methyl-2-butanethiol and limonenethiol. The liquid softener composition according to any one of the above [1] to [3], which is one or more of the above.

[5] The liquid softener composition according to any one of [1] to [3] above, wherein the component (B) is one or more of formaldehyde scavengers selected from the group consisting of cysteine, cysteamine and glutathione. ..

[6] The component (C) is 1,2-benzisothiazolin-3-one (BIT), 2-methyl-4,5-trimethylen-4-isothiazolin-3-one (MTI), N-methyl-1, 2. Of the above [1] to [5], which is one or more selected from the group consisting of 2-benzisothiazolin-3-one and N- (n-butyl) -1,2-benzisothiazolin-3-one. The liquid softener composition according to any one of the following items.

[7] The liquid softener composition according to any one of [1] to [6] above, wherein (C) / (B) is 1 to 100.

As shown in Examples described later, the liquid softener composition of the present invention continuously exerts the scent intended at the time of design while suppressing the generation of offensive odors even when a compound having a mercapto group is blended. be able to.
Therefore, the present invention is useful as a liquid softener composition having added value not found in conventional liquid softener compositions.

[(A) component]
The component (A) has 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms in the molecule, which may be separated by an ester group (-COO-) and / or an amide group (-NHCO-). It is a cationic surfactant which is "at least one compound selected from the group consisting of an amine compound, a salt thereof and a quaternary compound thereof".
The component (A) is blended to impart the effect of imparting flexibility (texture) to the textile product (that is, the original function of the softener) to the liquid softener composition.
The hydrocarbon group having 10 to 26 carbon atoms (hereinafter, may be referred to as “long-chain hydrocarbon group” in the present specification) has 10 to 26 carbon atoms, preferably 17 to 26, and more preferably 19 to 24. .. When the number of carbon atoms is 10 or more, the effect of imparting flexibility is good, and when the number of carbon atoms is 26 or less, the handleability 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 long-chain hydrocarbon. It is preferably distributed at the center of the hydrogen group or around the median value.
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 either 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 dividing group selected from the group consisting of an ester group and an amide group in the carbon chain, and the carbon chain is divided by the dividing group. You may. Having the dividing group is preferable from the viewpoint of improving biodegradability and the like.
When having the dividing group, the number of dividing groups contained in one long-chain hydrocarbon group may be one or two or more. That is, the long-chain hydrocarbon group may be divided at one place by the dividing group or at two or more places. When having two or more dividing groups, each dividing group may be the same or different.
When a long-chain hydrocarbon group has a dividing group in its carbon chain, the carbon atom of the dividing group shall be counted in the number of carbon atoms of the long-chain hydrocarbon group.
Long-chain hydrocarbon groups are usually industrially used unhydrogenated beef fat-derived fatty acids, fatty acids obtained by hydrogenating or partially hydrogenating unsaturated portions, and plant-derived unhydrogenated fatty acids such as palm palms and oil palms. It is introduced by using a hydrogenated fatty acid or fatty acid ester, or a fatty acid or fatty acid ester obtained by hydrogenating or partially hydrogenating 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.

［式中、Ｒ¹〜Ｒ³はそれぞれ独立に、炭素数１０〜２６の炭化水素基、−ＣＨ₂ＣＨ（Ｙ）ＯＣＯＲ⁴（Ｙは水素原子又はＣＨ₃であり、Ｒ⁴は炭素数７〜２１の炭化水素基である。）、−（ＣＨ₂）_nＮＨＣＯＲ⁵（ｎは２又は３であり、Ｒ⁵は炭素数７〜２１の炭化水素基である。）、水素原子、炭素数１〜４のアルキル基、−ＣＨ₂ＣＨ（Ｙ）ＯＨ（Ｙは水素原子又はＣＨ₃である）、又は、−（ＣＨ₂）_nＮＨ₂（ｎは２又は３である）であり、
Ｒ¹〜Ｒ³のうちの少なくとも１つは、炭素数１０〜２６の炭化水素基、−ＣＨ₂ＣＨ（Ｙ）ＯＣＯＲ⁴、又は−（ＣＨ₂）_nＮＨＣＯＲ⁵である。］ Examples of the amine compound include compounds represented by the following general formula (A1).

[In the formula, 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 has 7 carbon atoms. ~ 21 hydrocarbon groups.),-(CH ₂ ) _n NHCOR ⁵ (n is 2 or 3, R ⁵ is a hydrocarbon group with 7-21 carbon atoms), hydrogen atom, carbon number. Alkyl groups 1-4, −CH ₂ CH (Y) OH (Y is a hydrogen atom or CH ₃ ), or − (CH ₂ ) _n NH ₂ (n is 2 or 3).
At ^{least one of R 1 to} R ³ is a hydrocarbon group having 10 to 26 carbon atoms, −CH ₂ CH (Y) OCOR ⁴ , or − (CH ₂ ) _n NHCOR ⁵ . ]

In the general formula (A1), the number of carbon atoms of the hydrocarbon group having 10 to 26 carbon atoms in ^{R 1 to} R ^{3 is preferably 17 to 26, more preferably 19 to 24.} The hydrocarbon group may be saturated or unsaturated. As the hydrocarbon group, an alkyl group or an alkenyl group is preferable.
-CH _{2 In} 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 acid or unsaturated fatty acid, and may be linear fatty acid or branched fatty acid. Of these, saturated or unsaturated linear fatty acids are preferable. The saturation / unsaturated ratio (mass ratio) of the fatty acid ^{that is the source of R 4} is preferably 90/10 to 0/100, and 80/20 to 0, in order to impart good water absorption to the soft-treated clothing. More preferred than / 100.
When R ⁴ is an unsaturated fatty acid residue, cis and trans isomers are present, but the mass ratio of cis isomer / trans isomer is preferably 40/60 to 100/0, preferably 70/30 to 90/10. Especially preferable.

Specific examples of fatty acids that form the basis 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 Examples thereof include partially hydrogenated beef fatty acid (iodine value 10 to 60). Among them, fatty acids prepared by combining two or more kinds 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 the 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 form 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 are the same as those of ^{R 4.}

In the 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 long-chain hydrocarbon groups.
When ^{one or two of R 1 to} R ³ are long-chain hydrocarbon groups, the remaining two or one are hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, -CH ₂ CH (Y). It is preferably OH or − (CH ₂ ) _n NH ₂ , 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 . − (CH ₂ ) _{n n in} NH ₂ is similar to _{n in} − (CH ₂ ) n NHCOR ^5.

〔（Ａ１−１）式中、Ｒ⁷及びＲ⁸はそれぞれ独立に、炭素数１０〜２６の炭化水素基である。（Ａ１−２）〜（Ａ１−８）の各式中、Ｒ⁹及びＲ¹⁰はそれぞれ独立に、炭素数７〜２１の炭化水素基である。〕 Preferred 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 each of the formulas (A1-2) to (A1-8), R ⁹ and R ¹⁰ are independently hydrocarbon groups having 7 to 21 carbon atoms. ]

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

The component (A) 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 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 carried out by a known method.

The component (A) may be a quaternized product of an 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 quaternization of the amine compound include alkyl halides such as methyl chloride and dialkyl sulfuric acid such as dimethyl sulfate. When these quaternary agents are reacted with an amine compound, an alkyl group of the quaternary agent is introduced into the nitrogen atom of the amine compound, and a salt of the 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 carried out by a known method.

From the viewpoint of further suppressing the generation of offensive odor from the liquid softener composition, the amount of the quaternizing agent (particularly dimethyl sulfate) used when quaternizing the amine compound is based on 1 equivalent of the amino group of the amine compound. It is preferably 1.0 equivalent or less, more preferably 0.99 equivalent or less, still more preferably 0.98 equivalent or less, and most preferably 0.97 equivalent or less.

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

As the compounds represented by the general formulas (A1) and (A1-1) to (A1-8), salts thereof and quaternized products thereof, commercially available ones may be used, and those produced by a known method are used. You may.

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 composition containing ()) is ^{the fatty acid composition described in the column of R 4} of the general formula (A1), or the fatty acid methyl ester composition in which the fatty acid in the fatty acid composition is replaced with the methyl ester of the fatty acid, and methyl. It can be synthesized by a condensation reaction with diethanolamine. At that time, from the viewpoint of improving the flexibility imparting, the abundance ratio represented by "Compound (A1-2) / Compound (A1-3)" is set to 99/1 to 50/50 in terms of mass ratio. It is preferable to synthesize.
Further, when the quaternized product is used, it is more preferable to use dimethyl sulfate as the quaternizing agent. At that time, from the viewpoint of imparting flexibility, the abundance ratio represented by "quaternized compound (A1-2) / quaternized compound (A1-3)" is 99/1 to 50/50 in terms of mass ratio. It is preferable to synthesize so as to be.

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)"). The composition containing the compound represented by the general formula (A1-6) (hereinafter referred to as “compound (A1-6)”) is the fatty acid composition or the fatty acid composition described in the column ^{of R 4 of the general formula (A1).} It can be synthesized by a condensation reaction of 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) was 1 to 60 for the compound (A1-4) from the viewpoint of imparting flexibility. It is preferably 5 to 98% by mass of the compound (A1-5) and 0.1 to 40% by mass of the compound (A1-6), and 30 to 60% by mass of the compound (A1-4) and the compound. It is more preferable that (A1-5) is 10 to 55% by mass and compound (A1-6) is 5 to 35% by mass.
Further, when the quaternized product is used, it is more preferable to use dimethyl sulfate as the quaternizing agent from the viewpoint of sufficiently advancing the quaternization reaction. The abundance ratio of each quaternized compound (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 It is preferably ~ 60% by mass, the quaternized compound (A1-5) is 5 to 98% by mass, and the quaternized compound (A1-6) is 0.1 to 40% by mass, preferably the compound (A1-). 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.
When the compounds (A1-4), (A1-5) and (A1-6) are quaternized, generally, the esteramine that has not been quaternized remains even after the quaternization reaction. At that time, the ratio of "quaternized / non-quaternized esteramine" is preferably in the 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)") are ^{From the fatty acid composition described in the column of R 4} of the general formula (A1) and the adduct of N-methylethanolamine and acrylonitrile, J. Org. Chem. , 26, 3409 (1960), can be synthesized by a condensation reaction with N- (2-hydroxyethyl) -N-methyl-1,3-propylene diamine synthesized by a known method. At that time, it is preferable to synthesize the compound so that the abundance ratio represented by "Compound (A1-7) / Compound (A1-8)" is 99/1 to 50/50 in terms of mass ratio.
When the quaternized product is used, it is preferable to use methyl chloride as the quaternizing agent, which is represented by "quaternized product of compound (A1-7) / quaternized product of compound (A1-8)". It is preferable to synthesize the compounds so that the abundance ratio is 99/1 to 50/50 in terms of mass ratio.

As the component (A), one kind of amine compound, a salt thereof or a quaternary compound thereof may be used alone, or a mixture consisting of two or more kinds, for example, in the general formulas (A1-4) to (A1-6). It may be used as a mixture of the represented compounds.

The blending amount of the 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 10 to 20% by mass.

[(B) component]
The component (B) is a compound having one or more mercapto groups (-SH) in the molecule.
The component (B) is blended in order to achieve a blending purpose set according to the type (for example, fragrance (fragrance), reduction of formaldehyde (formaldehyde scavenger), etc.).
Further, the component (B) is not particularly limited as long as it can be blended into the liquid softener composition to achieve the above-mentioned blending purpose.

When the component (B) is a fragrance, the type of fragrance / flavor is not particularly limited, and examples thereof include grapefruit-like, spice-like, and lavender-like fragrances / flavors.
Specific examples of the component (B) used as a fragrance component include propyl mercaptan, isopropyl mercaptan, 2-methyl-3-butane thiol, isoamyl mercaptan, thiogeraniol, thionerol, limonene thiol, 8-mercaptomentone, phenyl mercaptan, o. -Thiocresol, 2-ethylthiophenol, 1-dodecanethiol, 2-naphthyl mercaptan, furfuryl mercaptan, 2-methyl-3-franthiol, 3-mercaptohexyl hexanoate, 4-methoxy-2-methyl-2 -Butan thiol, 2- (4-methyl-1-cyclohexa-3-enyl) propan-2-thiol, 3-mercaptoisobutyric acid, 4-methyl-4-mercapto-2-pentanone, 3-mercaptohexanol, 3- Examples thereof include mercaptohexyl acetate and 2-furmententhiol. Among these, 8-mercaptomentone, thiogeraniol, 2-franmentenethiol, 1-dodecanethiol, 4-methoxy-2-methyl-2-butanethiol and limonenethiol are preferable, and 8-mercaptomentone and thiogeraniol are preferable. More preferred.

Examples of the component (B) used as a formaldehyde scavenger include amino acids, peptides and proteins having a mercapto group, derivatives thereof and the like. More specifically, cysteine (particularly L-cysteine), cysteamine, glutathione and the like can be mentioned.
Further, the component (B) may be a peptide or enzyme obtained by condensing the above-mentioned amino acid and its derivative.

The component (B) is readily available on the market or can be synthesized by known methods.

The component (B) may be used alone or as a mixture of two or more.

The blending amount of the 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 0.001 with respect to the total mass of the liquid softener composition. It is ~ 0.5% by mass, more preferably 0.001 to 0.2% by mass, and most preferably 0.001 to 0.05% by mass.

（式中、
Ｒ¹は、炭素数２〜８のアルキレン基、又は、炭素数２〜８のアルケニレン基を示し、
Ｒ²は、水素、炭素数１〜１８（好ましくは炭素数１〜６）の置換又は非置換のアルキル基、炭素数２〜８（好ましくは炭素数２〜６）の置換又は非置換のアルケニル基、又は、炭素数２〜８（好ましくは炭素数２〜６）の置換又は非置換のアルキニル基を示し、
Ｘ¹は水素原子、ハロゲン原子（好ましくは塩素）、炭素数１〜４のアルキル基、又は、炭素数１〜４のヒドロキシアルキル基を示し、
ａは０〜６の整数（好ましくは０〜２の整数）を示す。）
なお、Ｒ²としては、水素又は炭素数１〜６の置換又は非置換のアルキル基が好ましい。 [(C) component]
The component (C) is a compound represented by the following formula (C-1).

(During the ceremony,
R ¹ represents an alkylene group having 2 to 8 carbon atoms or an alkaneylene group having 2 to 8 carbon atoms.
R ² is hydrogen, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), and a substituted or unsubstituted alkenyl having 2 to 8 carbon atoms (preferably 2 to 6 carbon atoms). Indicates a group or a substituted or unsubstituted alkynyl group having 2 to 8 carbon atoms (preferably 2 to 6 carbon atoms).
X ¹ represents a hydrogen atom, a halogen atom (preferably chlorine), an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms.
a represents an integer of 0 to 6 (preferably an integer of 0 to 2). )
As R ² , hydrogen or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms is preferable.

The compound represented by the formula (C-1) is generally used as an isothiazolin-based preservative and antibacterial agent.

The component (C) is blended mainly for the purpose of suppressing the generation of offensive odor from the liquid softener composition due to the blending of the component (B), but at the same time, the liquid softener composition is provided with antiseptic and antibacterial properties. It can also be given.

Specific examples of the compound represented by the formula (C-1) include 1,2-benzisothiazolin-3-one (BIT) and 2-methyl-4,5-trimethylone-4-isothiazolin-3-one (MTI). ), N-Methyl-1,2-benzisothiazolin-3-one, N- (n-butyl) -1,2-benzisothiazolin-3-one, 7-methyl-1,2-benzisothiazolin-3-one , 5-tert-Butyl-1,2-benzisothiazolin-3-one, 6-chloro-1,2-benzisothiazolin-3-one and the like, and 1,2-benzisothiazolin-3-one (BIT). ), 2-Methyl-4,5-Trimethylene-4-isothiazolin-3-one (MTI), N-methyl-1,2-benzisothiazolin-3-one, N- (n-butyl) -1,2 -Benzisothiazolin-3-one is preferable, and 1,2-benzisothiazolin-3-one (BIT) is more preferable.

The component (C) is readily available on the market or can be synthesized by known methods.

As the component (C), one type may be used alone, or two or more types may be used in combination as appropriate.

The blending amount of the component (C) 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, based on the total mass of the liquid softener composition. It is ~ 1% by mass, more preferably 0.01 ~ 1% by mass.

In the liquid softener composition of the present invention, the mass ratio ((C) / (B)) of the component (C) to the component (B) is 0.1 to 500, preferably 0.5 to 500, and more preferably 0.5 to 500. Is 1 to 100, particularly preferably 1 to 50. When (C) / (B) is 0.1 to 500, a higher compounding effect of the component (C) (effect of suppressing the generation of sulfur-like offensive odor) can be obtained.

By the way, although the detailed cause of the generation of sulfur-like offensive odor has not been clarified, the odor of the component (B) itself may be mixed with the odor of other softener components to give a feeling of sulfur-like offensive odor, or the component (B) may be present. It is decomposed in the softener, and it is considered that the decomposed product causes a sulfur-like offensive odor. Therefore, the liquid softener composition of the present invention may contain a decomposition product of the component (B) as long as the effects of the present invention are not impaired.

[Arbitrary ingredient]
The liquid softener composition of the present invention may contain any component other than the essential components (A) to (C) above, if necessary, as long as the effects of the present invention are not impaired.
Examples of the optional component include components generally blended in the liquid softener composition. Specific examples include water, nonionic surfactants, fragrances, water-soluble salts, dyes, water-soluble solvents (for example, ethanol), preservatives other than component (C), ultraviolet absorbers, and antibacterial agents other than component (C). , Deodorants, skin care ingredients, etc.
Hereinafter, some optional components will be described in detail.

[water]
The liquid softener composition of the present invention is preferably an aqueous composition containing water.
As the water, tap water, purified water, pure water, distilled water, ion-exchanged water, or the like can be used. Of these, ion-exchanged water is preferable.
The blending amount of water is not particularly limited, and can be appropriately blended in order to achieve a desired component composition.

[Nonion surfactant (hereinafter, also referred to as "(D) component")]
When the liquid softener composition of the present invention is an emulsion, the nonionic surfactant can be blended mainly 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 secure a sufficient level of freeze-restoration 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 ester or pentaerythritol in which a fatty acid having 10 to 22 carbon atoms is ester-bonded to glycerin or pentaerythritol; having an alkyl group or alkenyl group having 10 to 22 carbon atoms and having an average number of moles of ethylene oxide added. Polyoxyethylene alkyl ether having 10 to 100 mol; polyoxyethylene fatty acid alkyl (the alkyl having 1 to 3 carbon atoms) ester; polyoxyethylene alkyl amine having an average addition molar number of ethylene oxide of 10 to 100 mol; carbon number. Alkyl polyglucosides having 8 to 18 alkyl or alkenyl groups; hardened castor oil having an average added molar number of ethylene oxide of 10 to 100 mol can be mentioned. Among them, a polyoxyethylene alkyl ether having an alkyl group having 10 to 18 carbon atoms and having an average addition mole number of ethylene oxide of 20 to 80 moles is preferable.
The nonionic surfactant may be used alone or as a mixture of two or more.
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, based on the total mass of the liquid softener 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 softener composition, a fragrance other than the component (B) (when it is a fragrance) can be blended as an optional component.
As the fragrance, a general-purpose fragrance can be used in the art and is not particularly limited, but a list of fragrance raw materials that can be used is described in various documents such as "Perfume and Flavor Chemicals", Vol. I and II, Stephen Arctander, Allured Pub. Co. (1994) and "Synthetic Fragrance Chemistry and Commercial Knowledge", by Motokazu Indo, The Chemical Daily (1996) and "Perfume and Flavor Materials of Natural Origin", Stephen Arctander, Allured Pub. Co. (1994) and "Encyclopedia of Fragrances", edited by Japan Fragrance Association, Asakura Shoten (1989) and "Perfumery Material Chemistry V.3.3", Boelens Aroma Chemical Information Services (1996) and "Flower Force". , Danute Lajaujis Anonis, Allured Pub. Co. (1993) and the like.
Further, the fragrance may be a fragrance composition containing a fragrance precursor. Examples of the fragrance precursor include those represented by [Chemical formula 2] to [Chemical formula 9] described in Table 4 of Japanese Patent Publication No. 2003-534449.
As the fragrance, one kind of fragrance may be used alone, or may be used as a mixture consisting of two or more kinds.
The blending amount of the fragrance as the component (E) is not particularly limited as long as the blending purpose can be achieved, but is preferably 0.1 to 3% by mass with respect to the total mass of the liquid softener composition. , More preferably 0.5 to 2% by mass, still more preferably 0.5 to 1.5% by mass.

[Water-soluble salts (hereinafter, also referred to as "(F) component")]
The 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, but calcium chloride and magnesium chloride are particularly preferable.
The water-soluble salts may be used alone or as a mixture of two or more.
The blending amount of the water-soluble salts is not particularly limited as long as the blending purpose can be achieved, but is 0 to 1% by mass with respect to the total mass of the liquid softener composition. The water-soluble salts may be blended in any step of manufacturing the liquid softener composition.

[PH of liquid softener composition]
The pH of the liquid softener composition is not particularly limited, but the pH at 25 ° C. is set in the range of 1 to 6 from the viewpoint of suppressing the hydrolysis of the ester group contained in the molecule of the component (A) with the aging of storage. It is preferable to adjust it, and it is more preferable to adjust it in the range of 2 to 4.
For pH adjustment, hydrochloric acid, sulfuric acid, phosphoric acid, alkyl sulfuric acid, benzoic acid, paratoluenesulfonic acid, citric acid, malic acid, succinic acid, lactic acid, glycolic acid, hydroxyethanediphosphonic acid, phytic acid, ethylenediamine tetraacetic 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 softener composition]
The viscosity of the liquid softener composition is not particularly limited as long as its usability is not impaired, but the viscosity at 25 ° C. is preferably less than 800 mPa · s. Considering 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 500 mPa · s, and even more preferably less than 300 mPa · s. Within such a range, usability such as handleability at the time of putting into the washing machine is good.
The viscosity of the liquid softener composition can be measured using a B-type viscometer (manufactured by TOKIMEC).

[Manufacturing method of liquid softener composition]
The liquid softener composition of the present invention can be produced by a known method, for example, the same method as the conventional method for producing a liquid softener composition using a cationic surfactant as a main agent.
For example, an oil phase containing a component (A), a component (B), a component (D) and a component (E), and an aqueous phase containing a component (C) are placed under temperature conditions equal to or higher than the melting point of the component (A). It can be produced by mixing to prepare an emulsion, and then adding and mixing the component (F) and, if necessary, other components to the obtained emulsion.
The oil phase can be prepared by mixing the components (A), (B), (D), (E) and, if necessary, any component at a temperature equal to or higher than the melting point of the component (A).
The aqueous phase can be prepared by mixing water with the component (C) and, if necessary, any component.
The method of adding the component (B), the component (C), the component (D) and the component (E) is not limited to the above-mentioned addition method. That is, even if each component (B), (C), (D) and (E) is added and mixed after the emulsion is obtained, a liquid softener composition can be produced. Often, for example, each component may be added individually, or the components (B), (C), (D) and (E) are premixed and then added to the oil phase or emulsion. You may. Further, the component (D) can be added after the aqueous phase or emulsion is obtained, or can be added separately in the oil phase and the aqueous phase.

[How to use liquid softener composition]
The method of using the liquid softener composition of the present invention is not particularly limited, and the liquid softener composition can be used in the same manner as a general liquid softener composition. For example, a method of dissolving the liquid softener composition of the present invention in rinsing water at the rinsing stage of washing to soften the object to be washed, or water in a container such as a tub for the liquid softener composition of the present invention. There is a method of dissolving in water and further adding an object to be washed and dipping it.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
In addition, in Examples and Comparative Examples, the compounding amount of each component shows mass% (unless specified, it is converted into pure content).

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-2 were used.

A-1: Cationic surfactant (compound according to 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 group or an alkenyl group having 15 to 17 carbon atoms. ) Is quaternized with dimethyl sulfate. In the preparation of A-1, the amount of the quaternizing agent (dimethyl sulfate) used when quaternizing the amine compound was 0.97 equivalents with respect to 1 equivalent of the amino group of the amine compound.

A-2: Cationic surfactant (compound according to Example 3 of JP-A-2003-12471). 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 group or an alkenyl group having 15 to 17 carbon atoms. ) Is quaternized with dimethyl sulfate. In the preparation of A-2, the amount of the quaternizing agent (dimethyl sulfate) used when quaternizing the amine compound was 0.98 equivalent to 1 equivalent of the amino group of the amine compound.

Both A-1 and A-2 corresponded to the component (A) of the present invention.

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

B-1: 8-Mercapto Menthone (Tokyo Chemical Industry Co., Ltd.)
B-2: 1-Dodecane Thiol (Tokyo Chemical Industry Co., Ltd.)
B-3: L-Cysteine (Tokyo Chemical Industry Co., Ltd.)

All of B-1, B-2 and B-3 corresponded to the component (B) of the present invention.

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

C-1: 1,2-benzisothiazolin-3-one (Clariant Japan Co., Ltd., trade name: Nipacide BIT 20). C-1 is a compound represented by the general formula (C-1) (in the formula, R ¹ is an alkenylene group having 4 carbon atoms, R ² is hydrogen, and a is 0).

C-2: 2-Methyl-4,5-Trimethylene-4-isothiazolin-3-one (Lonza Japan Co., Ltd.). C-2 is a compound represented by the general formula (C-1) (in the formula, R ¹ is an alkylene group having 3 carbon atoms, R ² is a methyl group, and a is 0).

C-3: Isothiazolone solution (Rohm & Haas, trade name: Caisson CG-ICP). C-3 is a mixture of 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one.
C-1 and C-2 corresponded to the component (C) of the present invention, but C-3 did not correspond to the component (C).

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

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

[(E) component]
The fragrance compositions shown in Table 1 were used.

[(F) component]
Calcium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was used. The blending amount of the component (F) in each liquid softener composition was 0.3% by mass with respect to the total mass of the liquid softener composition.

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

[Method for preparing liquid softener composition]
Using a glass container with an inner diameter of 100 mm and a height of 150 mm and a stirrer (Agitator SJ type, manufactured by Shimadzu Corporation), adjust the blending amount of each component as shown in Table 3 below, and follow the procedure below to compose the liquid softener. The thing was prepared.
First, the component (A), the component (B), the component (D) and the component (E) were mixed and stirred to obtain an oil phase mixture. On the other hand, the common component 1 and the component (C) were 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 balance obtained by subtracting the total amount of the oil phase mixture, the common component 1, the component (C) and the component (F) from 980 g.
Next, while storing the oil phase mixture heated above the melting point of the component (A) in a glass container and stirring, the aqueous phase mixture heated above the melting point of the component (A) is added in two portions. And stirred. Here, the division ratio of the aqueous phase mixture is 30:70 (mass ratio), and the stirring is performed at a rotation speed of 1,500 rpm for 3 minutes after the first addition of the aqueous phase mixture and 2 minutes after the second addition of the aqueous phase mixture. rice field. After that, 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 hydrochloric acid (reagent 1 mol / L, Kanto Chemical Co., Inc.) or sodium hydroxide (reagent 1 mol / L, Kanto Chemical Co., Inc.) in an appropriate amount to adjust the pH to 2.5, and further increase the total mass to 1,000 g. Ion-exchanged water was added so as to obtain liquid softener compositions having the compositions shown in Table 3 (Examples 1 to 12 and Comparative Examples 1 and 2).
In Table 3, the numerical values of each component (A), (B), (C), (D), (E) and (F) are the blending amount (mass%) with respect to the total mass of the liquid softener composition. be.
In Table 3, "(C) / (B)" indicates the mass ratio of the component (C) to the component (B).

[Evaluation method of liquid softener composition]
The "fragrance" of the obtained liquid softener composition was evaluated by the following procedure.

<Aroma evaluation 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.) and sealed, and the aroma was evaluated according to the following four-grade evaluation criteria. The results expressed as the average score of the five specialized panelists are shown in the "Aroma evaluation" column of Table 3. In terms of commercial value, the average score was 2.0 or higher.

<Evaluation criteria>
3: No offensive odor.
2: A slight offensive odor is felt but acceptable.
1: I feel a strange odor.
0: A clear offensive odor is felt.

The present invention is available in the field of liquid softeners.

Claims (7)

A liquid fabric softener composition
The following components (A) to (C):
(A) An amine compound having 1 to 3 hydrocarbon groups having 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 salts and quaternized products thereof,
(B) A compound having one or more mercapto groups (-SH) in the molecule, and (C) a compound represented by the following formula (C-1).

(During the ceremony,
R ¹ represents an alkylene group having 2 to 8 carbon atoms or an alkaneylene group having 2 to 8 carbon atoms.
R ² contains hydrogen, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms, or a substituted or unsubstituted alkynyl group having 2 to 8 carbon atoms. Show,
X ¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms.
a represents an integer from 0 to 6. )
Contains,
A liquid softener composition having a mass ratio ((C) / (B)) of the component (C) to the component (B) of 0.5 to 100. Claim that 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 products thereof. The liquid softener composition according to 1.

[In the formula (A1-1), R ⁷ and R ⁸ are each independently a hydrocarbon group having 10 to 26 carbon atoms.
In each of the formulas (A1-2) to (A1-8), R ⁹ and R ¹⁰ are independently hydrocarbon groups having 7 to 21 carbon atoms. ] The liquid softener composition according to claim 1 or 2, wherein the component (B) is a fragrance and / or formaldehyde scavenger. (B) One of the fragrances selected from the group consisting of 8-mercaptomentone, thiogeraniol, 2-franmentenethiol, 1-dodecanethiol, 4-methoxy-2-methyl-2-butanethiol and limonenethiol. The liquid softener composition according to any one of claims 1 to 3 as described above. The liquid softener composition according to any one of claims 1 to 3, wherein the component (B) is one or more of formaldehyde scavengers selected from the group consisting of cysteine, cysteamine and glutathione. The component (C) is 1,2-benzisothiazolin-3-one (BIT), 2-methyl-4,5-trimethylone-4-isothiazolin-3-one (MTI), N-methyl-1,2-benz. The invention according to any one of claims 1 to 5, which is one or more selected from the group consisting of isothiazolin-3-one and N- (n-butyl) -1,2-benzisothiazolin-3-one. Liquid softener composition. The liquid softener composition according to any one of claims 1 to 6, wherein the blending amount of the component (C) is 0.005 to 1% by mass with respect to the total mass of the liquid softener composition.