JP7051499B2 - Liquid composition - Google Patents

Description

The present invention relates to liquid compositions. In particular, the present invention relates to a liquid composition that can sustainably exert a scent intended at the time of design while suppressing the generation of offensive odors, and can be used as a liquid detergent or a liquid softener.

In recent years, various functions have been required for liquid detergents and 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.
In addition, amino acids having a mercapto group (for example, cysteine) are used as a formaldehyde reducing agent (formaldehyde scavenger) that adversely affects the human body.
Isothiazolin-based compounds are used as preservatives and antibacterial agents (Patent Documents 1 to 3).
A technique for improving the detergency of an enzyme-containing detergent using a lower alkyl sulfate is known (Patent Document 4).

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. 10-17993

However, when a compound having a mercapto group, alkyl sulfuric acid or a salt thereof is blended into a liquid composition, a sulfur-like offensive odor may be generated from the liquid composition, and the pleasant scent intended at the time of design may not be realized. , The present inventor has found.

As a result of diligent studies on the above-mentioned problems, the present inventor obtained a liquid obtained by adding an isothiazolin-based compound having a specific cyclic structure to a liquid composition containing a compound having a mercapto group and alkyl sulfuric acid or a salt thereof. It has been found that the composition is capable of suppressing the generation of offensive odors after storage and sustainably exhibiting 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。）、及び
（Ｄ）炭素数１～５のアルキル硫酸又はその塩
を含有する、液体組成物。
〔２〕（Ｃ）成分の（Ｂ）成分に対する質量比（（Ｃ）／（Ｂ））が０．１～５００である、前記〔１〕に記載の液体組成物。
〔３〕（Ｃ）成分の（Ｄ）成分に対する質量比（（Ｃ）／（Ｄ））が０．００２～５である、前記〔１〕又は〔２〕に記載の液体組成物。
〔４〕液体洗浄剤である、前記〔１〕～〔３〕のいずれか１項に記載の液体組成物。
〔５〕液体柔軟剤である、前記〔１〕～〔３〕のいずれか１項に記載の液体組成物。
〔６〕（Ａ）成分が陽イオン界面活性剤である、前記〔１〕～〔５〕のいずれか１項に記載の液体組成物。
〔７〕陽イオン界面活性剤が、エステル基（－ＣＯＯ－）及び／又はアミド基（－ＮＨＣＯ－）で分断されていてもよい、炭素数１０～２６の炭化水素基を分子内に１～３個有するアミン化合物、その塩及びその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、陽イオン界面活性剤である、前記〔６〕に記載の液体組成物。
〔８〕（Ａ）成分が非イオン界面活性剤である、前記〔１〕～〔５〕のいずれか１項に記載の液体組成物。
〔９〕非イオン界面活性剤が、一般式（Ａ２）で表される化合物である、前記〔８〕に記載の液体組成物。
Ｒ₁₁－ＣＯ－（ＯＲ₁₂）m―ＯＲ₁₃ （Ａ２）
（式中、
Ｒ₁₁は炭素数９～１３の炭化水素基であり、
Ｒ₁₂は炭素数２～４のアルキレン基であり、
Ｒ₁₃は炭素数１～４のアルキル基であり、
ｍはＯＲ₁₂の平均繰返し数を示し、５～２５の数である。）
〔１０〕非イオン界面活性剤が、炭素数６～２２の脂肪族アルコールに炭素数２～４のアルキレンオキシドを平均３～３０モル付加したポリオキシアルキレンアルキル（又はアルケニル）エーテルである、前記〔８〕に記載の液体組成物。
〔１１〕非イオン界面活性剤が、炭素数１０～２２のアルキル基又はアルケニル基を有し、エチレンオキシドの平均付加モル数が１０～１００モルであるポリオキシエチレンアルキルエーテルである、前記〔８〕に記載の液体組成物。
〔１２〕（Ａ）成分が陰イオン界面活性剤である、前記〔１〕～〔５〕のいずれか１項に記載の液体組成物。
〔１３〕陰イオン界面活性剤が、下記一般式（Ａ３）又は（Ａ４）で表されるポリオキシアルキレンアルキルエーテル硫酸エステル塩である、である、前記〔１２〕に記載の液体組成物。
Ｒ₁₄Ｏ―（ＥＯ）_p－（ＰＯ）_q ―ＳＯ₃Ｍ （Ａ３）
Ｒ₁₄Ｏ―（ＰＯ）_r－（ＥＯ）_s ―ＳＯ₃Ｍ （Ａ４）
（各式中、
Ｒ₁₄は、炭素数１０～２０のアルキルであり、
ＥＯはエチレンオキシ基を表し、
ＰＯはプロピレンオキシ基を表し、
ｐ及びｑはｐ＋ｑ＝０～５を満たす数であり、
ｒ及びｓはｒ＋ｓ＝０～５を満たす数であり、
Ｍはアルカリ金属である。）
〔１４〕陰イオン界面活性剤が、α－スルホ脂肪酸エステル塩である、前記〔１２〕に記載の液体組成物。
〔１５〕陰イオン界面活性剤が、直鎖アルキルベンゼンスルホン酸である、前記〔１２〕に記載の液体組成物。
〔１６〕（Ｂ）成分が、香料成分である、前記〔１〕～〔１５〕のいずれか１項に記載の液体組成物。
〔１７〕（Ｂ）成分が、ホルムアルデヒドスカベンジャーである、前記〔１〕～〔１５〕のいずれか１項に記載の液体組成物。
〔１８〕（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、前記〔１〕～〔１７〕のいずれか１項に記載の液体組成物。
〔１９〕（Ｄ）成分が、メチル硫酸ナトリウム、エチル硫酸ナトリウム及びメチル硫酸カリウムからなる群より選ばれる、前記〔１〕～〔１８〕のいずれか１項に記載の液体組成物。 That is, the present invention relates to the following [1] to [19].
[1] The following components (A) to (D):
(A) Surfactant (excluding alkyl sulfuric acid having 1 to 5 carbon atoms or a salt thereof),
(B) A compound having one or more mercapto groups (-SH) in the molecule,
(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 alkenylene 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 indicates an integer from 0 to 6. ), And (D) a liquid composition containing alkyl sulfuric acid having 1 to 5 carbon atoms or a salt thereof.
[2] The liquid composition according to the above [1], wherein the mass ratio ((C) / (B)) of the component (C) to the component (B) is 0.1 to 500.
[3] The liquid composition according to the above [1] or [2], wherein the mass ratio ((C) / (D)) of the component (C) to the component (D) is 0.002 to 5.
[4] The liquid composition according to any one of [1] to [3] above, which is a liquid detergent.
[5] The liquid composition according to any one of [1] to [3] above, which is a liquid softener.
[6] The liquid composition according to any one of [1] to [5] above, wherein the component (A) is a cationic surfactant.
[7] The cationic surfactant may have 1 to 26 hydrocarbon groups having 10 to 26 carbon atoms, which may be separated by an ester group (-COO-) and / or an amide group (-NHCO-). The liquid composition according to the above [6], which is a cationic surfactant which is at least one compound selected from the group consisting of an amine compound having three elements, a salt thereof and a quaternary compound thereof.
[8] The liquid composition according to any one of [1] to [5] above, wherein the component (A) is a nonionic surfactant.
[9] The liquid composition according to the above [8], wherein the nonionic surfactant is a compound represented by the general formula (A2).
R ₁₁ -CO- (OR ₁₂ ) m-OR ₁₃ (A2)
(During the ceremony,
R ₁₁ is a hydrocarbon group having 9 to 13 carbon atoms.
R ₁₂ is an alkylene group having 2 to 4 carbon atoms.
R ₁₃ is an alkyl group having 1 to 4 carbon atoms.
m indicates the average number of repetitions of OR ₁₂ , which is a number of 5 to 25. )
[10] The nonionic surfactant is a polyoxyalkylene alkyl (or alkenyl) ether obtained by adding an average of 3 to 30 mol of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms. 8] The liquid composition according to.
[11] The nonionic surfactant is a polyoxyethylene alkyl ether having an alkyl group or an alkenyl group having 10 to 22 carbon atoms and having an average addition molar number of ethylene oxide of 10 to 100 mol. The liquid composition according to.
[12] The liquid composition according to any one of [1] to [5] above, wherein the component (A) is an anionic surfactant.
[13] The liquid composition according to the above [12], wherein the anionic surfactant is a polyoxyalkylene alkyl ether sulfate ester salt represented by the following general formula (A3) or (A4).
R ₁₄ O- (EO) _p- (PO) _q -SO ₃ M (A3)
R ₁₄ O- (PO) _r- (EO) _s -SO ₃ M (A4)
(In each formula,
R ₁₄ is an alkyl having 10 to 20 carbon atoms and has 10 to 20 carbon atoms.
EO stands for ethyleneoxy group
PO stands for propyleneoxy group
p and q are numbers that satisfy p + q = 0 to 5, and are numbers.
r and s are numbers satisfying r + s = 0 to 5, and are numbers.
M is an alkali metal. )
[14] The liquid composition according to the above [12], wherein the anionic surfactant is an α-sulfofatty acid ester salt.
[15] The liquid composition according to the above [12], wherein the anionic surfactant is a linear alkylbenzene sulfonic acid.
[16] The liquid composition according to any one of [1] to [15] above, wherein the component (B) is a fragrance component.
[17] The liquid composition according to any one of [1] to [15] above, wherein the component (B) is a formaldehyde scavenger.
[18] The component (C) is 1,2-benzisothiazolin-3-one (BIT), 2-methyl-4,5-trimethylen-4-isothiazolin-3-one (MTI), N-methyl-1, The item according to any one of [1] to [17] above, which is selected from the group consisting of 2-benzisothiazolin-3-one and N- (n-butyl) -1,2-benzisothiazolin-3-one. Liquid composition.
[19] The liquid composition according to any one of [1] to [18] above, wherein the component (D) is selected from the group consisting of sodium methyl sulfate, sodium ethyl sulfate and potassium methyl sulfate.

As shown in Examples described later, the liquid composition of the present invention maintains the scent intended at the time of design while suppressing the generation of offensive odors even when a compound having a mercapto group, alkyl sulfuric acid or a salt thereof is blended. Can be demonstrated effectively.
Therefore, the present invention is useful as a product having added value not found in conventional liquid detergents and liquid softeners.

[(A) component]
The component (A) is a surfactant. The component (A) is blended for the purpose of cleaning textile products, imparting flexibility (texture) to textile products, and the like.
Specific examples of the surfactant include a cationic surfactant, an amphoteric ionic surfactant, a nonionic surfactant and an anionic surfactant.
However, even if it is a surfactant, the compound which is "alkylsulfuric acid having 1 to 5 carbon atoms or a salt thereof" is not included in the component (A). "Alkyl sulfuric acid having 1 to 5 carbon atoms or a salt thereof" can be used as the component (D).

[Cationic surfactant]
As the cationic surfactant, those that can be used as a liquid detergent or a liquid softener can be used without particular limitation, and the following are preferable.

(1) 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 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 carbon atoms. It is about 26, 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 composition is good.
The long-chain hydrocarbon group may be saturated or unsaturated. If the long-chain hydrocarbon group is unsaturated, the position of the double bond may be anywhere, but if there is one double bond, the position of the double bond is long-chain hydrocarbon. It is preferably distributed in the center of the hydrogen group or centered on the median value.
The long-chain hydrocarbon group may be a chain hydrocarbon group or a hydrocarbon group having 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.
When having the dividing group, the number of dividing groups 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 the long-chain hydrocarbon group has a dividing group in its carbon chain, the carbon atom of the dividing group shall be counted as the number of carbon atoms of the long-chain hydrocarbon group.
The long-chain hydrocarbon group is usually an unhydrogenated fatty acid derived from beef fat, which is industrially used, a fatty acid obtained by hydrogenating or partially hydrogenating an unsaturated portion, and an unhydrogenated fatty acid derived from plants such as palm palm and oil palm. 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. An alkyl group of 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 a plurality of R ^4s are present in the compound represented by the general formula (A1), the plurality of R ^4s may be the same as each other or may be different from each other.

The hydrocarbon group of R ⁴ is a residue (fatty acid residue) obtained by removing a carboxy group from a fatty acid (R ⁴ COOH) having 8 to 22 carbon atoms, and the fatty acid (R ⁴ COOH) that is the source of R ⁴ 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. In order to impart good water absorption to the soft-treated garment, 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. More preferred than / 100.
When R ⁴ is an unsaturated fatty acid residue, cis-form and trans-form are present, but the mass ratio of cis-form / trans-form is preferably 40/60 to 100/0, preferably 70/30 to 90/10. Especially preferable.

Specific examples of the 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 acid (iodine value 10-60), and Partially hydrogenated beef fatty acid (iodine value 10 to 60) and the like can be mentioned. 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 ratio (mass ratio) of the cis-form / trans-form 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 a plurality of R ^5s are present in the compound represented by the general formula (A1), the plurality of R ^5s may be the same as each other or may be different from each other.
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 a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and -CH ₂ CH (Y). It is preferably OH or − (CH ₂ ) _n NH ₂ , preferably an alkyl group having 1 to 4 carbon atoms, −CH ₂ CH (Y) OH, or − (CH ₂ ) _n NH ₂ . Here, as the alkyl group having 1 to 4 carbon atoms, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable. Y in -CH ₂ CH (Y) OH is the same as Y in -CH ₂ CH (Y) OCOR ⁴ . -(CH ₂ ) _{n n} in NH ₂ is the same as 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). When a plurality of R ^9s are present in the equation, the plurality of R ^9s may be the same as each other or may be different from each other.

The cationic surfactant may be a salt of an amine compound.
The salt of the 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, dimethyl sulfate, and methyl sulfuric acid. Neutralization of the amine compound can be carried out by a known method.

The cationic surfactant may be a quaternized product of an amine compound.
The quaternized product of the 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 dialkylsulfuric acid such as dimethyl sulfate. When these quaternary agents are reacted with the amine compound, the 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 the halogen ion or the 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.
When the compound represented by the general formula (A1) is prepared as a composition, "alkyl sulfate ions having 1 to 5 carbon atoms" are used as counterions of the compound represented by the general formula (A1) in the composition. However, this counterion does not correspond to the component (D) described later.

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 the amount of one amino group equivalent 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.

As a cationic surfactant,
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 compounds 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 compounds 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. May be.

For example, a compound represented by the general formula (A1-2) (hereinafter referred to as “compound (A1-2)”) and a compound represented by the general formula (A1-3) (hereinafter referred to as “compound (A1-3)”). The 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 the 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 it.
Further, when the quaternary 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 "quaternary compound (A1-2) / quaternizing 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 described in the column of R ⁴ of the general formula (A1) or the fatty acid composition. It can be synthesized by a condensation reaction between a fatty acid methyl ester composition and triethanolamine. At that time, the content ratio of each component to the total mass of the compounds (A1-4), (A1-5) and (A1-6) is 1 to 60 for the compound (A1-4) from the viewpoint of imparting flexibility. It is preferable that the content is% by mass, 5 to 98% by mass of the compound (A1-5), 0.1 to 40% by mass of the compound (A1-6), and 30 to 60% by mass of the compound (A1-4). It is more preferable that (A1-5) is 10 to 55% by mass and the compound (A1-6) is 5 to 35% by mass.
Further, when the quaternizing product is used, it is more preferable to use dimethyl sulfate as the quaternizing agent in terms of sufficiently advancing the quaternization reaction. The abundance ratio of each of the quaternized compounds of the compounds (A1-4), (A1-5) and (A1-6) is a mass ratio from the viewpoint of imparting flexibility, and the quaternized compound of the compound (A1-4) is 1. It is preferable that the content is -60% by mass, the quaternizing compound (A1-5) is 5 to 98% by mass, and the quaternizing compound (A1-6) is 0.1 to 40% by mass, preferably the compound (A1-6). The quaternary product of 4) is 30 to 60% by mass, the quaternary product of compound (A1-5) is 10 to 55% by mass, and the quaternary 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, an ester amine 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 ^R4 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 compound 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.

（式中、
Ｒ₉は、炭素数８～２０のアルキル基、炭素数８～２０のアルケニル基又は炭素数８～２０のアルカノイル基を表し；
Ａ¹Ｏ及びＡ²Ｏは、それぞれ独立に、炭素数２～４のオキシアルキレン基を表し；
ａ及びｂは、ａ＋ｂ＝１～１００を満たす整数である。） (2) Polyoxyalkylene amine, a salt thereof or a quaternary product thereof Examples of the polyoxyalkylene amine include compounds represented by the following general formulas (C4-i) or (C4-ii).

(During the ceremony,
R ₉ represents an alkyl group having 8 to 20 carbon atoms, an alkenyl group having 8 to 20 carbon atoms or an alkanoyl group having 8 to 20 carbon atoms;
A ¹ O and A ² O each independently represent an oxyalkylene group having 2 to 4 carbon atoms;
a and b are integers satisfying a + b = 1 to 100. )

（式中、
Ｒ₁₀は、エステル基またはアミド基で分断されていない炭素数８～２０のアルキル基、炭素数８～２０のアルケニル基又は炭素数８～２０のアルカノイル基を表し；
Ｒ₁₁は、水素原子、メチル基、エチル基、ベンジル基又はヒドロキシエチル基を表し；
ｍは１～４の整数であり；
Ｘ^m-はｍ価の無機酸又は有機酸のアニオンを表し；
Ａ³Ｏ及びＡ⁴Ｏは、それぞれ独立に、炭素数２～４のオキシアルキレン基を表し；
ｃ及びｄは、ｃ＋ｄ＝１～１００を満たす数である。） The hydrocarbon group of R ₉ in the general formula (C4-i) preferably has 8 to 18, more preferably 10 to 18, still more preferably 10 to 14, and particularly preferably 12. When the hydrocarbon group of R ₉ has 8 to 18 carbon atoms, the freeze-restorability of the liquid composition can be further enhanced, and the dispersibility of the capsule particles when the capsule particles are blended can be further enhanced. can.
A ¹ O and A ² O in the general formula (C4-i) are oxyalkylene groups having 2 to 4 carbon atoms independently, and may contain two or more kinds of groups, and include two or more kinds. In that case, it may be added in a block shape or in a random shape.

(During the ceremony,
R ₁₀ represents an alkyl group having 8 to 20 carbon atoms, an alkenyl group having 8 to 20 carbon atoms or an alkanoyl group having 8 to 20 carbon atoms, which is not divided by an ester group or an amide group;
R ₁₁ represents a hydrogen atom, a methyl group, an ethyl group, a benzyl group or a hydroxyethyl group;
m is an integer from 1 to 4;
X ^m- represents an anion of m-valent inorganic or organic acid;
A ³ O and A ⁴ O each independently represent an oxyalkylene group having 2 to 4 carbon atoms;
c and d are numbers satisfying c + d = 1 to 100. )

The hydrocarbon group of R ₁₀ in the general formula (C4-ii) preferably has 8 to 18, more preferably 10 to 18, still more preferably 10 to 14, and particularly preferably 12. When the hydrocarbon group of R ₁₀ has 8 to 18 carbon atoms, the dispersibility of the capsule particles can be further enhanced, and the freeze-restorability of the liquid composition can be further enhanced.
R ₁₁ in the general formula (C4-ii) is preferably a methyl group.
Examples of X ^m- in the general formula (C4-ii) include anion of methyl sulfuric acid, bromine, chlorine and the like, and chlorine is preferable.
A ³ O and A ⁴ O are each independently an oxyalkylene group having 2 to 4 carbon atoms, and may contain two or more kinds of groups. If two or more kinds are contained, they are added in a block shape. It may be added randomly.
As the polyoxyalkylene amine, a compound represented by the general formula (C4-ii) is preferable.

Examples of the compound represented by the general formula (C4-i) include dodecylamine ethylene oxide 2 mol adduct, dodecylamine ethylene oxide 5 mol adduct, dodecylamine ethylene oxide 15 mol adduct, and dodecylamine ethylene oxide 20 mol adduct. Adduct, coconut alkyl (alkenyl) amine ethylene oxide 2 mol adduct, coconut alkyl (alkenyl) amine ethylene oxide 5 mol adduct, coconut alkyl (alkenyl) amine ethylene oxide 15 mol adduct, coconut alkyl (alkenyl) amine ethylene oxide 20 mol adduct , Tetradecylamine ethylene oxide 30 mol adduct, hexadecylamine ethylene oxide 40 mol adduct, tallowalkylamine ethylene oxide 2 mol adduct, tallowalkylamine ethylene oxide 5 mol adduct, tallowalkyl (alkenyl) amine ethylene oxide 10 adduct Molar adduct, cured tallowalkylamine ethylene oxide 2 mol adduct, oleylamine ethylene oxide 2 mol adduct, oleylamine ethylene oxide 7 mol adduct, oleylamine ethylene oxide 10 mol adduct, hexadecylamine ethylene oxide 30 mol / propylene oxide 5 Morrandom adduct, 25 mol decylamine ethylene oxide / 5 mol propylene oxide block adduct, 22 mol hexadecylamine ethylene oxide / 3 mol propylene oxide 3 random adduct, 27 mol hexadecylamine ethylene oxide / 5 mol propylene oxide random adduct Examples thereof include hexadecylamine ethylene oxide 40 / propylene oxide 10 mol random adduct, decylamine ethylene oxide 24 mol / propylene oxide 3 mol block adduct and the like.

Examples of the compound represented by the general formula (C4-ii) include dodecylmethylammonium ethyleneoxide 15 mol additive hydrochloride, dodecylmethylammonium ethyleneoxide 20 mol additive hydrochloride, and coconut alkyl (alkenyl) methylammonium ethylene oxide 15. Mole adduct hydrochloride, coconut alkyl (alkenyl) methylammonium ethylene oxide 20 mol adduct hydrochloride, tetradecylmethylammonium ethylene oxide 30 mol adduct methyl sulfate, tetradecylammonium ethylene oxide 30 mol adduct citrate, hexadecyl Ethylammonium ethylene oxide 40 mol adduct Ethyl sulfate, octadecylmethylammonium ethyleneoxide 25 mol adduct hydrochloride, oleylmethylammonium ethyleneoxide 2 mol adduct hydrochloride and hexadecylethylammonium ethylene oxide 30 mol / propylene oxide 5 mol random Additives such as methyl sulfate and the like can be mentioned.
When the compound represented by the general formula (C4-ii) is prepared as a composition, the compound represented by the general formula (C4-ii) contains "1 to 5 carbon atoms" as a counter ion. Alkyl sulfate ion ", but this counterion does not correspond to the component (D) described later.

[By-product of cationic surfactant]
When a salt obtained by neutralizing an amine compound with dialkylsulfuric acid (for example, dimethylsulfate) as an acid is used as a cationic surfactant (component (A)), alkylsulfuric acid (for example, a by-product of the salt) is used. , Methylsulfate) may be included in the liquid composition. When this alkyl sulfuric acid corresponds to "alkyl sulfuric acid having 1 to 5 carbon atoms or a salt thereof", it may be used as the component (D). However, the "alkyl sulfate ion having 1 to 5 carbon atoms" existing as the counterion of the cationic surfactant does not correspond to the component (D).
When a quaternary product obtained by reacting dialkylsulfuric acid (for example, dimethyl sulfate) as a quaternizing agent with an amine compound is used as a cationic surfactant (component (A)), the quaternizing product is used. Alkyl sulfuric acid (eg, methyl sulfuric acid), which is a by-product, may be included in the liquid composition. When this alkyl sulfuric acid corresponds to "alkyl sulfuric acid having 1 to 5 carbon atoms or a salt thereof", it may be used as the component (D). However, the "alkyl sulfate ion having 1 to 5 carbon atoms" existing as the counterion of the cationic surfactant does not correspond to the component (D).
The amount of component (D) present as a by-product can be measured, for example, by high performance liquid chromatography (HPLC) method.

Cationic surfactants are readily available on the market or are available for synthesis.
One type of cationic surfactant may be used alone, or two or more types may be used in combination as appropriate.

The content of the cationic surfactant is not particularly limited as long as it can achieve the compounding purpose, but is preferably 5 to 50% by mass, more preferably 8 to 30% by mass, and further, with respect to the total mass of the liquid composition. It is preferably 10 to 20% by mass.

[Amphoteric ion surfactant]
As the amphoteric ion surfactant, those that can be used for liquid detergents and liquid softeners can be used without particular limitation, and examples thereof include betaine, N-alkyl amino acids, N-alkenyl amino acids, and salts thereof. ..
Examples of betaine include alkyl betaine, amide betaine, amide propyl betaine, carbobetaine, sulfobetaine, amide sulfobetaine, imidazolinium betaine, phosphobetaine, and aminopropionate.
An N-alkyl amino acid or N-alkenyl amino acid has an alkyl group or an alkenyl group bonded to a nitrogen atom, and one or two "-R-COOH" (in the formula, R indicates a divalent hydrocarbon group. It is preferably an alkylene group, and particularly preferably has a structure in which a group represented by 1 to 2 carbon atoms is bonded. In the compound to which one "-R-COOH" is bonded, a hydrogen atom is further bonded to the nitrogen atom. One "-R-COOH" is called a mono body, and two things are called a di body. As the amphoteric ion surfactant, either mono-form or di-form can be used. In each of the N-alkyl amino acid and the N-alkenyl amino acid, the alkyl group and the alkenyl group may be linear or branched chain.

Amphoteric ion surfactants are readily available on the market or are available for synthesis.
One type of amphoteric ion surfactant may be used alone, or two or more types may be used in combination as appropriate.

The content of the amphoteric ion surfactant is not particularly limited as long as the compounding purpose can be achieved, but is preferably 0.01 to 30% by mass, more preferably 0.1 to 5% by mass, based on the total mass of the liquid composition. It is by mass, more preferably 0.5 to 5% by mass.

[Nonionic surfactant]
As the nonionic surfactant, those that can be used as a liquid detergent and a liquid softener can be used without particular limitation.
When the liquid composition of the present invention is applied as a liquid detergent, the nonionic surfactant is, for example, a compound represented by the following general formula (A2).

R ₁₁ -CO- (OR ₁₂ ) m-OR ₁₃ (A2)

(During the ceremony,
R ₁₁ is a hydrocarbon group having 9 to 13 carbon atoms.
R ₁₂ is an alkylene group having 2 to 4 carbon atoms.
R ₁₃ is an alkyl group having 1 to 4 carbon atoms.
m indicates the average number of repetitions of OR ₁₂ , which is a number of 5 to 25. )

In the general formula (A2), the hydrocarbon group of R ₁₁ may be linear, branched or chain-like, or may contain a cyclic structure. The hydrocarbon group of R ₁₁ is preferably an aliphatic hydrocarbon group, and a linear or branched alkyl group or a linear or branched alkenyl group is more preferable.
The carbon number of R ₁₁ is 9 to 13, preferably 10 to 13, and more preferably 11 to 13. When the carbon number of R ₁₁ is 9 or more, the detergency is enhanced. On the other hand, when the carbon number of R ₁₁ is 13 or less, the liquid stability is improved, and gelation is particularly suppressed.
In the general formula (A2), R ₁₂ is an alkylene group having 2 to 4 carbon atoms, and an ethylene group or a propylene group is preferable.
A plurality of R _12s may be the same or different from each other. That is, the alkylene group of R ₁₂ may be used alone or in combination of two or more. Among them, the m OR _12s in the formula are all oxyethylene groups or a mixture of oxyethylene groups and oxypropylene groups because the foaming at the time of washing is good and the cost is low. preferable.
When two or more kinds of alkylene groups of R ₁₂ are combined, the addition method of OR ₁₂ is not particularly limited. For example, when an oxyethylene group and an oxypropylene group are mixed, the addition method is random addition. It may be present, or it may be a block addition. Examples of the block addition method include a method of adding propylene oxide after adding ethylene oxide, a method of adding ethylene oxide after adding propylene oxide, and a method of adding propylene oxide after adding ethylene oxide and further adding ethylene oxide. Can be mentioned.
In the general formula (A2), R ₁₃ is an alkyl group having 1 to 4 carbon atoms, and an alkyl group having 1 to 3 carbon atoms is preferable. Specific examples of R ₁₃ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group, with a methyl group and an ethyl group being preferred, and a methyl group being more preferred. When the carbon number of R ₁₃ is 1 or more, precipitation during low temperature storage is likely to be suppressed. On the other hand, when the carbon number of R ₁₃ is 4 or less, the solubility of the liquid detergent in water under low temperature conditions is enhanced.
In the general formula (A2), m indicates the average number of repetitions of OR ₁₂ , and is a number of 5 to 25. When m is at least the lower limit value, the detergency, particularly the detergency against sebum stains, is improved. On the other hand, when m is not more than the upper limit value, the solubility of the liquid detergent in water is improved.
When OR ₁₂ is all oxyethylene groups, m is preferably 5 to 20, more preferably 12 to 18.
When OR ₁₂ is a mixture of an oxyethylene group and an oxypropylene group, m is particularly preferably 12 to 21. At this time, the average number of repetitions of the oxypropylene group is preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less. When the average number of repetitions of the oxypropylene group is 5 or less, the detergency and the liquid stability as a liquid detergent (transparency uniformity, stability over time, etc.) can be well maintained.

In the nonionic surfactant represented by the general formula (A2), the narrow ratio indicating the ratio of the distribution of the compounds having different numbers of repetitions of OR ₁₂ is preferably 20% by mass or more. The upper limit of the narrow ratio is preferably 80% by mass or less. The narrow ratio is more preferably 20 to 50% by mass, and further preferably 30 to 45% by mass because the liquid stability and the solubility in water are further improved. The higher the narrow ratio, the easier it is to obtain good detergency.

数式（Ｓ）において、ｍ_maxは、一般式（Ａ２）で表される成分全体の中に最も多く存在するアルキレンオキシド付加体のアルキレンオキシドの付加モル数を示す。
数式（Ｓ）中、ｉはアルキレンオキシドの付加モル数を示す。
数式（Ｓ）中、Ｙｉは、一般式（Ａ２）で表される成分全体の中に存在するアルキレンオキシドの付加モル数がｉであるアルキレンオキシド付加体の割合（質量％）を示す。
ナロー率は、たとえば非イオン界面活性剤の製造方法等によって制御することができる。 As used herein, the term "narrow ratio" refers to a value represented by the following mathematical formula (S), which indicates the ratio of distribution of alkylene oxide adducts having different numbers of moles of alkylene oxide added.

In the formula (S), m _max indicates the number of moles of alkylene oxide added, which is the most abundant alkylene oxide adduct in the whole component represented by the general formula (A2).
In formula (S), i indicates the number of moles of alkylene oxide added.
In the formula (S), Yi indicates the ratio (mass%) of the alkylene oxide adduct in which the number of moles of the alkylene oxide added in the whole component represented by the general formula (A2) is i.
The narrow ratio can be controlled by, for example, a method for producing a nonionic surfactant.

The method for producing the nonionic surfactant represented by the general formula (A2) is not particularly limited, but for example, a surface-modified composite metal oxide catalyst is used to add an alkylene oxide to the fatty acid alkyl ester. It can be easily produced by a method of addition polymerization (see JP-A-2000-144179).
Specific examples of such a surface-modified composite metal oxide catalyst include metal ions (Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl) surface-modified with a metal hydroxide or the like. The surface was modified with a composite metal oxide catalyst such as magnesium oxide to which ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ²⁺ , etc. were added, a metal hydroxide and / or a metal alkoxide, etc. It is a fired product catalyst for hydrotalcite.
Further, in the surface modification of the composite metal oxide catalyst, the mixing ratio of the composite metal oxide with the metal hydroxide and / or the metal alkoxide is adjusted with respect to 100 parts by mass of the composite metal oxide. The ratio of the substance and / or the metal alkoxide is preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass.
As the nonionic surfactant represented by the general formula (A2), one type may be used alone, or two or more types may be used in combination as appropriate.

Examples of the nonionic surfactant other than the compound represented by the general formula (A2) include the following (1) to (7).

(1) An average of 3 to 30 mol, preferably 3 to 20 mol, more preferably 5 to 20 mol of an alkylene oxide having 2 to 4 carbon atoms was added to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. Polyoxyalkylene alkyl (or alkenyl) ether.
Among (1), polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are suitable. Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols. Further, the alkyl group may be a branched chain. As the aliphatic alcohol, primary alcohol is preferable.

(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(3) Polyoxyethylene sorbitan fatty acid ester.
(4) Polyoxyethylene sorbitol fatty acid ester.
(5) Polyoxyethylene fatty acid ester.
(6) Polyoxyethylene hydrogenated castor oil.
(7) Glycerin fatty acid ester.

As the nonionic surfactant, the one of the above (1) is preferable. In (1), the distribution of the number of added moles of EO or PO is not particularly limited, and is likely to fluctuate depending on the reaction method at the time of producing (1). For example, in the distribution of the number of added moles of EO or PO, ethylene oxide or propylene oxide is added to a hydrophobic group raw material (primary or secondary higher alcohol) using a general alkaline catalyst such as sodium hydroxide or potassium hydroxide. When they are used, they tend to have a relatively wide distribution. Further, metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ and Mn ²⁺ described in JP-A-6-15038 were added. When ethylene oxide or propylene oxide is added to the hydrophobic group raw material using a specific alkoxylation catalyst such as magnesium oxide, the distribution tends to be relatively narrow.

Examples of the non-ionic surfactant of (1) include ethylene (trade name, C13) manufactured by Mitsubishi Chemical Corporation, Neodol (trade name, a mixture of C12 and C13) manufactured by Shell, and Safol 23 manufactured by Sasol. (Trade name, mixture of C12 and C13) and other alcohols to which ethylene oxide equivalent to 12 mol or 15 mol is added; CO-1214 (trade name) or CO- manufactured by Proctor & Gamble. A natural alcohol such as 1270 (trade name) to which ethylene oxide equivalent to 12 mol or 15 mol is added; to a C13 alcohol obtained by subjecting C12 alken obtained by quantifying butene to a oxo method. , 7 mol-equivalent ethylene oxide added (trade name: Lutensol TO7, manufactured by BASF); 9 mol-equivalent ethylene oxide added to C10 alcohol obtained by subjecting pentanol to a garbet reaction (trade name). : Lutensol XP90, manufactured by BASF); C10 alcohol obtained by subjecting pentanol to a garbet reaction to which ethylene oxide equivalent to 7 mol is added (trade name: Lutensol XL70, manufactured by BASF); pentanol is garbed. 6 mol of ethylene oxide added to the C10 alcohol obtained by the reaction (trade name: Lutensol XA60, manufactured by BASF); 9 mol equivalent to the secondary alcohol having 12 to 14 carbon atoms. Alternatively, alcohol is added to ethylene oxide equivalent to 15 mol (trade names: sophthalol 90, sophthalol 150, manufactured by Nippon Catalyst Co., Ltd.), coconut fatty acid methyl (lauric acid / myristic acid (mass ratio) = 8/2). Examples thereof include those to which ethylene oxide equivalent to 15 mol is added using a chemical catalyst (polyoxyethylene coconut fatty acid methyl ester (EO 15 mol)).

The nonionic surfactants described above are readily available on the market or are available for synthesis.
In addition, one type of the nonionic surfactant may be used alone, or two or more types may be used in combination as appropriate.

When the liquid composition of the present invention is applied as a liquid detergent, the content of the nonionic surfactant is not particularly limited as long as it can achieve the compounding purpose, but is preferable with respect to the total mass of the liquid composition, for example. Is 1 to 60% by mass, more preferably 5 to 55% by mass, still more preferably 5 to 50% by mass.

When the liquid composition of the present invention is applied as a liquid softener, the nonionic surfactant is preferably used mainly for the purpose of improving the emulsion dispersion stability of the oil-soluble component in the liquid softener (emulsion). Can be. In particular, 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 that can be blended in the liquid softener, for example, those derived from higher alcohols, higher amines or higher fatty acids can be used. specifically,
A polyoxyethylene alkyl ether having an alkyl group or an alkenyl group having 10 to 22 carbon atoms and having an average number of moles of ethylene oxide added of 10 to 100 mol;
Polyoxyethylene fatty acid alkyl (1 to 3 carbon atoms of the alkyl) ester;
Polyoxyethylene alkylamines with an average added mole number of ethylene oxide of 10-100 mol;
Alkyl polyglucoside having an alkyl group or alkenyl group having 8 to 18 carbon atoms;
Examples thereof include hardened castor oil having an average number of moles of ethylene oxide added of 10 to 100 mol. 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 mol is preferable.

The nonionic surfactants described above are readily available on the market or are available for synthesis.
In addition, one type of the nonionic surfactant may be used alone, or two or more types may be used in combination as appropriate.

When the liquid composition of the present invention is applied as a liquid softener, the content of the nonionic surfactant is not particularly limited as long as it can achieve the compounding purpose, but is preferable with respect to the total mass of the liquid composition, for example. Is 0.01 to 10% by mass, more preferably 0.1 to 8% by mass, still more preferably 0.5 to 5% by mass.
When the content of the nonionic surfactant is at least the above lower limit value, the emulsion dispersion stability of the oil-soluble component in the emulsion and the freeze-restoration stability of the emulsion are further improved. When the content of the nonionic surfactant is not more than the above upper limit value, the increase in the viscosity of the liquid composition can be suppressed and the usability can be improved.

[Anionic surfactant]
As the anionic surfactant, those that can be used as a liquid detergent and a liquid softener can be used without particular limitation.

When the liquid composition of the present invention is applied as a liquid detergent, examples of the anionic surfactant include a polyoxyalkylene alkyl ether sulfate ester salt represented by the following general formula (A3) or (A4). ..

R ₁₄ O- (EO) _p- (PO) _q -SO ₃ M (A3)
R ₁₄ O- (PO) _r- (EO) _s -SO ₃ M (A4)

(In each formula,
R ₁₄ is an alkyl having 10 to 20 carbon atoms and has 10 to 20 carbon atoms.
EO stands for ethyleneoxy group
PO stands for propyleneoxy group
p and q are numbers that satisfy p + q = 0 to 5, and are numbers.
r and s are numbers satisfying r + s = 0 to 5, and are numbers.
M is an alkali metal. )

In the general formulas (A3) and (A4), the alkyl group of R ₁₄ has 10 to 20 carbon atoms, preferably 12 to 14 carbon atoms. The alkyl group of R ₁₄ is preferably derived from a linear primary alcohol, a linear secondary alcohol or a branched alcohol.
In the general formula (A3), p + q is 0 to 5, preferably 0.5 to 4, and more preferably 1 to 3.
In the general formula (A4), r + s is 0 to 5, preferably 0.5 to 4, and more preferably 1 to 3.
The compounds represented by the general formulas (A3) and (A4) preferably contain an ethyleneoxy group, and more preferably contain a propyleneoxy group in the range of 0.2 to 2 moles in terms of the average number of moles added.
In the general formulas (A3) and (A4), M is an alkali metal, preferably sodium and potassium, and more preferably sodium.

Examples of anionic surfactants other than the compounds represented by the general formulas (A3) and (A4) include linear alkylbenzene sulfonic acid or a salt thereof; α-olefin sulfonic acid salt; linear or branched alkyl sulfate ester. Salts; alkane sulfonates having an alkyl group; α-sulfo fatty acid ester salts and the like can be mentioned. Examples of the salt in these anionic surfactants include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.
As the linear alkylbenzene sulfonic acid or a salt thereof, those having 8 to 16 carbon atoms of the linear alkyl group are preferable, and those having 10 to 14 carbon atoms of the linear alkyl group are more preferable.
The α-olefin sulfonate is preferably one having 10 to 20 carbon atoms.
The alkyl sulfate ester salt preferably has an alkyl group having 10 to 20 carbon atoms.
As the alkane sulfonate, those having an alkyl group having 10 to 20 carbon atoms are preferable, those having 14 to 17 carbon atoms are more preferable, and those in which the alkyl group is a secondary alkyl group (that is, a secondary alkane sulfonate) are preferable. The acid salt) is more preferable.
The α-sulfofatty acid ester salt preferably has a fatty acid residue having 10 to 20 carbon atoms.
When the α-sulfo fatty acid ester salt is used as an anionic surfactant (component (A)), sodium methyl sulfate, which is a by-product of the α-sulfo fatty acid ester salt, may be contained in the liquid composition. In this case, the by-product sodium methyl sulfate may be used as the component (D).
The amount of component (D) present as a by-product can be measured, for example, by high performance liquid chromatography (HPLC) method.

Examples of other anionic surfactants include carboxylic acid type nonionic surfactants (higher fatty acid salts having 10 to 20 carbon atoms, alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl (or alkenyl)). Amid ether carboxylate, acylaminocarboxylate, etc.) and; Phosphate ester type nonionic surfactant (alkyl phosphate ester salt, polyoxyalkylene alkyl phosphate ester salt, polyoxyalkylene alkylphenyl phosphate ester salt, etc. Glycerin fatty acid ester monophosphate ester salt, etc.).

Anionic surfactants are readily available on the market or are available for synthesis.
The anionic surfactant may be used alone or in combination of two or more.

When the liquid composition of the present invention is applied as a liquid detergent, the content of the anionic surfactant is not particularly limited as long as it can achieve the compounding purpose, but is preferable with respect to the total mass of the liquid composition, for example. Is 1 to 30% by mass, more preferably 5 to 30% by mass, still more preferably 8 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.).
The component (B) is not particularly limited as long as it can be blended into a liquid 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 -Butanthiol, 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-franmententhiol. 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 content 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 to 0.% With respect to the total mass of the liquid composition. It is 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 alkenylene group having 2 to 8 carbon atoms.
R ² is a 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). 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 an antibacterial agent.

The component (C) is blended mainly for the purpose of suppressing the generation of offensive odor from the liquid composition due to the blending of the component (B) and the component (D), but at the same time, the liquid composition has antiseptic and antibacterial properties. 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-trimethylen-4-isothiazolin-3-one (MTI), N-methyl-1,2-benzisothiazolin-3-one and 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 content 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 to 1% by mass, based on the total mass of the liquid composition. %, More preferably 0.01 to 1% by mass.

In the liquid 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 1. It is ~ 100, particularly preferably 1 ~ 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 components to give a sulfur-like offensive odor, and the component (B) has a liquid composition. It is decomposed in the substance, and it is considered that the decomposed substance causes a sulfur-like offensive odor. Therefore, the liquid composition of the present invention may contain a decomposition product of the component (B) as long as the effect of the present invention is not impaired.

[(D) component]
The component (D) is an alkyl sulfuric acid having 1 to 5 carbon atoms or a salt thereof. The component (D) is blended for adjusting the viscosity (reducing viscosity) of the liquid composition and improving the activity of the enzyme (arbitrary component).
The alkylsulfuric acid has 1 to 5 carbon atoms, preferably 1 to 2 carbon atoms.
Examples of the counterion species forming a salt with alkyl sulfate include monovalent cations such as alkali metal (sodium, potassium, lithium) ions and ammonium ions, preferably sodium ion and potassium ion.
Specific examples of the component (D) include sodium methyl sulfate, sodium ethyl sulfate and potassium methyl sulfate, and sodium methyl sulfate and potassium methyl sulfate are preferable.
The component (D) may be present in the liquid composition as a by-product of the component (A) (surfactant) as described above, or may be present in the liquid composition by newly adding the component (D). May be good.

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

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

The content of the component (D) is not particularly limited as long as the blending purpose can be achieved, but is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the liquid composition. %, More preferably 0.1 to 1% by mass.

In the liquid composition of the present invention, the mass ratio ((C) / (D)) of the component (C) to the component (D) is preferably 0.002 to 5, more preferably 0.01 to 5, and further. It is preferably 0.01 to 1, particularly preferably 0.02 to 0.5. When (C) / (D) is 0.002 to 5, a higher compounding effect of the component (C) (effect of suppressing the generation of sulfur-like offensive odor) can be obtained.

[Arbitrary component]
The liquid composition of the present invention may contain any components other than the essential components (A) to (D), if necessary, as long as the effects of the present invention are not impaired.
Examples of the optional component include components generally blended in liquid detergents and liquid softeners. Specific examples include water, fragrances, water-soluble salts, enzymes, stabilizers, silicone compounds, water-soluble solvents, dyes, pigments, ultraviolet absorbers, antibacterial agents other than component (C), deodorants, and skin care components. And so on.
Hereinafter, some optional components will be described in detail.

〔water〕
The liquid 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 and 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.

[Fragrance (hereinafter, also referred to as "(E) component")]
A fragrance other than the component (B) (when it is a fragrance) can be added to the liquid composition 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 Service (1996) and "Flowercorpor". , 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.
Further, the fragrance may be an encapsulated fragrance.
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 amount of the fragrance (E) to be blended 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 composition. It is preferably 0.5 to 2% by mass, 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 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 preferable.
The water-soluble salts may be used alone or as a mixture of two or more.
The blending amount of the water-soluble salt is not particularly limited as long as the blending purpose can be achieved, but is 0.01 to 1% by mass with respect to the total mass of the liquid composition. The water-soluble salts may be blended in any step of manufacturing the liquid composition.

〔enzyme〕
The enzyme can be added for the purpose of improving the cleaning ability of the liquid detergent. As the enzyme, an enzyme that can be used as a liquid detergent can be used without particular limitation, and examples thereof include protease and amylase.
The enzyme may be used alone or as a mixture of two or more.
The blending amount of the enzyme is not particularly limited as long as the blending purpose can be achieved, but is, for example, 0.1 to 1% by mass with respect to the total mass of the liquid composition.

[Stabilizer]
Stabilizers can be added for the purpose of improving the stability of liquid compositions (particularly liquid detergents). As the stabilizer, those that can be used as a liquid detergent or a liquid softener can be used without particular limitation, and examples thereof include sodium benzoate and citric acid.
The stabilizer may be used alone or as a mixture of two or more.
The blending amount of the stabilizer is not particularly limited as long as the blending purpose can be achieved, but is, for example, 0.1 to 2% by mass with respect to the total mass of the liquid composition.

[Silicone compound]
The silicone compound can be blended for the purpose of improving the persistence (scenting property) of the scent. The type of the silicone compound is not particularly limited and can be appropriately selected depending on the intended purpose.
The molecular structure of the silicone compound may be linear, branched, or crosslinked.
The silicone compound may be a modified silicone compound. The modified silicone compound may be modified with one type of organic functional group or may be modified with two or more types of organic functional groups.
The silicone compound can be used in the form of an oil or in the form of an emulsion dispersed by any emulsifier.
Specific examples of the silicone compound include, for example, dimethyl silicone, polyether-modified silicone, methylphenyl silicone, alkyl-modified silicone, higher fatty acid-modified silicone, methylhydrogen silicone, fluorine-modified silicone, epoxy-modified silicone, carboxy-modified silicone, and carbinol. Examples thereof include modified silicone and amino-modified silicone.

[Water-soluble solvent]
Water-soluble solvents can be added to adjust viscosity and improve stability.
As the water-soluble solvent, those generally used for liquid detergents and liquid softeners can be used without particular limitation.
The water-soluble solvent is preferably one or more selected from the group consisting of lower (1 to 4 carbon atoms) alcohols, glycol ether solvents, and polyhydric alcohols. Specifically, ethanol, isopropanol, glycerin, ethylene glycol, butyl carbitol, propylene glycol, diethylene glycol, dipropylene glycol, hexylene glycol, polyoxyethylene phenyl ether, dipropylene glycol monomethyl ether, and the following general formula (X). It is preferable to blend a solvent component selected from the water-soluble solvent represented by.

R ¹¹ -O- (C ₂ H ₄ O) y- (C ₃ H ₆ O) z-H ... (X)

(In the formula, R ¹¹ is an alkyl group or an alkenyl group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms. Y and z are the average number of moles of substance added, and y is 1 to 10, preferably 2 to 5 , Z indicates a number of 0 to 5, preferably 0 to 2.])
Among the above, ethanol, ethylene glycol, butyl carbitol, propylene glycol, diethylene glycol monobutyl ether, and dipropylene glycol monomethyl ether are preferable.
One kind of water-soluble solvent may be used alone, or two or more kinds may be used as a mixture.
The content of the water-soluble solvent is not particularly limited as long as the blending purpose can be achieved, but is preferably 0.001 to 30% by mass, more preferably 0.01 to 25% by mass, based on the total mass of the liquid composition. , More preferably 0.1 to 20% by mass.

[Dyes and / or pigments]
Dyes and / or pigments can be blended for the purpose of improving the appearance of the liquid composition. It is preferably one or more of red, blue, yellow or purple water-soluble dyes selected from acid dyes, direct dyes, basic dyes, reactive dyes and mordant / acid mordant dyes.
Specific examples of dyes that can be added are described in the Dye Handbook (edited by the Society of Synthetic Organic Chemistry, published on July 20, 1970, Maruzen Co., Ltd.).
From the viewpoint of storage stability of the liquid composition and dyeability to fibers, acid dyes and direct dyes having at least one functional group selected from hydroxyl groups, sulfonic acid groups, amino groups and amide groups in the molecule, and A reactive dye is preferable, and the content thereof is preferably 1 to 50 ppm, more preferably 1 to 30 ppm with respect to the entire liquid composition (based on mass).
Examples of the dye used in the liquid composition of the present invention include JP-A-6-123081, JP-A-6-123082, JP-A-7-18573, JP-A-8-27669, and JP-A-9-25805. Dyes described in JP-A No. 10-77576, JP-A-11-43865, JP-A-2001-181972, JP-A-2001-348784, and the like can also be used.

[UV absorber]
The ultraviolet absorber is a drug having an effect of protecting ultraviolet rays, and is a component that absorbs ultraviolet rays, converts them into infrared rays, visible light, and the like and emits them.
Examples of the ultraviolet absorber include aminobenzoic acid derivatives such as p-aminobenzoic acid, ethyl p-aminobenzoate, glyceryl p-aminobenzoate, and amyl p-dimethylaminobenzoate; ethylene glycol salicylate and dipropylene glycol salicylate. , Salicylic acid derivatives such as octyl salicylate, myristyl salicylate; methyl diisopropylcinnamic acid, ethyl p-methoxycinnamic acid, isopropyl p-methoxycinnamic acid, -2-ethylhexyl p-methoxycinnamic acid, p-methoxycinnamic acid. Cinnamic acid derivatives such as butyl; benzophenone derivatives such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2,2'-dihydroxy-4-methoxybenzophenone; urocanic acid, Azol-based compounds such as ethyl urocanate; 4-t-butyl-4'-methoxybenzoylmethane and the like can be mentioned.

[PH of liquid composition]
The pH of the liquid composition is not particularly limited, but when used as a liquid softener, the pH at 25 ° C. is set from the viewpoint of suppressing the hydrolysis of the ester group contained in the molecule of the component (A) over the storage period. The adjustment is preferably in the range of 1 to 6, and more preferably in the range of 2 to 4.
When used as a liquid detergent, the pH at 25 ° C. is preferably adjusted to the range of 5 to 9, and more preferably adjusted to the range of 6 to 9 from the viewpoint of improving the cleaning rate.
For pH adjustment, hydrochloric acid, sulfuric acid, phosphoric acid, alkyl sulfate, benzoic acid, paratoluenesulfonic acid, citric acid, malic acid, succinic acid, lactic acid, glycolic acid, hydroxyethandiphosphonic acid, phytic acid, ethylenediamine tetraacetic acid, Short chain amine compounds such as monoethanolamine, triethanolamine, diethanolamine, dimethylamine, N-methylethanolamine, N-methyldiethanolamine, alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates and alkali metal silicic acids. A pH adjuster such as a salt can be used.

[Viscosity of liquid softener composition]
The viscosity of the liquid 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 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 composition can be measured using a B-type viscometer (manufactured by TOKIMEC).

[Manufacturing method of liquid composition]
Liquid compositions can be produced according to known methods of liquid detergents and fabric softeners. When the liquid composition is used as a liquid softener, it can be produced, for example, by the same method as the conventional method for producing a liquid softener using a cationic surfactant as a main agent.

[How to use the liquid composition]
The use of the liquid composition is not particularly limited, but it can be applied to a liquid detergent, a liquid softener, a bleaching agent, a spray-type fiber treatment agent, and the like. Above all, it is preferable to apply it as a liquid detergent and a liquid softener.
The method for treating textile products (clothes, etc.) with a liquid composition is not particularly limited, and is the same as conventionally known cleaning agents, finishing agents (softeners, adhesives, etc.), spray-type fiber treatment agents, and the like. Can be processed.
When the liquid composition is a liquid softener, for example, a method of dissolving the liquid softener in rinsing water to soften the textile product at the rinsing stage of washing, or water in a container such as a tub of the liquid softener. There is a method of dissolving it in a cloth and further adding a textile product and dipping it.
The liquid softener can be diluted to an appropriate concentration before use. For example, the bath ratio (weight ratio of the treatment liquid to the textile product) is preferably 3 to 100 times, particularly preferably 5 to 50 times. Specifically, the liquid softener is used in an amount such that the concentration of the component (A) is preferably 0.01 ppm to 1000 ppm, more preferably 0.1 ppm to 300 ppm, based on the total amount of water used.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.
In addition, in an Example and a comparative example, the compounding amount of each component shows the mass% (unless specified, the pure content conversion).

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

[(A) component]
The following A-1 to A-8 were used. All of A-1 to A-8 corresponded to the component (A) of the present invention.

A-1: Cation 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.

A-2: Nonionic surfactant (60 mol of ethylene oxide adduct of primary isotridecyl alcohol (polyoxyethylene alkyl ether having an alkyl group having 13 carbon atoms and having an average adduct of 60 mol of ethylene oxide). ). BASF rutensol TO3 with ethylene oxide added)

A-3: Nonionic surfactant (5 mol adduct of ethylene oxide of alcohol having 12 to 14 carbon atoms) (Polypoly having an alkyl group having 12 to 14 carbon atoms and having an average adduct of 5 mol of ethylene oxide. Oxyethylene alkyl ether). Made by THAI ETHOXYLATE. Product name: DEHYDOL (registered trademark) LS5 TH ")

A-4: Anionic surfactant (sodium salt of α-sulfofatty acid ester (manufactured by Lion Eco Chemicals Sdn. Bhd., Trade name MIZULA® FL-80)). The number of carbon atoms in the fatty acid residue is 16 or 18. The amount of methyl sulfuric acid contained in A-4 was 2.8% by mass (in terms of sodium methylsulfate). The amount of methylsulfuric acid should be measured according to the measurement conditions of the ion chromatograph method described in BUNSEKI KAGAKU, Vol.51, No.3, p.141-146 (2002), page 142, right column, lines 10 to 20. Was measured by the HPLC method.

A-5: Anionic surfactant (ether sulfate having an alkyl group having 12 or 14 carbon atoms to which an average of 2 mol of an alkylene oxide having 2 carbon atoms is added (manufactured by Kao Corporation, trade name: EMAL) Trademark) 270N)
A-5 is represented by the general formula (A3) (in the formula, R ₁₄ is an alkyl group having 12 or 14 carbon atoms, p is 2, q is 0, and M is sodium). It is a compound.

A-6: An alkoxylation catalyst for nonionic surfactant (MEE (polyoxyethylene fatty acid methyl ester), coconut fatty acid methyl (mixture of methyl laurate / methyl myristate = 8/2 by mass ratio)). It is prepared by adding 15 mol of ethylene oxide. The detailed synthesis method will be described later.
A-6 is a general formula (A2) (in the formula, R ₁₁ is an alkyl group having 11 carbon atoms and an alkyl group having 13 carbon atoms, R ₁₂ is an ethylene group, R ₁₃ is a methyl group, and m. Is a compound represented by (15).

A-7: Anionic surfactant (LAS (linear alkylbenzene sulfonic acid), manufactured by Lion Corporation. Trade name: Lipon LH-200). The linear alkyl group has 12 to 14 carbon atoms.

A-8: Nonionic surfactant (LMAO (polyoxyethylene alkyl ether), which is a natural alcohol (primary alcohol) having 12 and 14 carbon atoms to which ethylene oxide equivalent to 15 mol is added.

[A-6 synthesis method]
It was synthesized according to the synthesis method described in JP-A-2000-144179.
Alumina hydroxide / magnesium (Kyoward 300 (trade name), manufactured by Kyowa Chemical Industry Co., Ltd.) having a composition of _2.5 MgO / Al 2O ₃ / wH ₂ O is fired at 600 ° C. for 1 hour in a nitrogen atmosphere. A fired alumina-magnesium hydroxide (unmodified) catalyst was obtained. 2.2 g of calcined alumina-magnesium hydroxide (unmodified) catalyst, 2.9 mL of 0.5N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester, and 70 g of myristic acid methyl ester were charged into a 4 L autoclave. The catalyst was modified in the room. Then, after replacing the inside of the autoclave with nitrogen, 1052 g of ethylene oxide was introduced while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa, and the reaction was carried out with stirring.
The obtained reaction solution was cooled to 80 ° C., 159 g of water and 5 g of each of activated clay and diatomaceous earth as filtration aids were added and mixed, and then the catalyst was filtered off to obtain A-6.
The narrow ratio of A-6 was 30% by mass.

[A-8 synthesis method]
861.2 g of CO-1214 (trade name, natural alcohol having 12 and 14 carbon atoms) manufactured by Procter & Gamble and 2.0 g of a 30 mass% NaOH aqueous solution are charged in a pressure resistant reaction vessel, and the reaction vessel is charged. The inside was replaced with nitrogen. Next, after dehydration at a temperature of 100 ° C. and a pressure of 2.0 kPa or less for 30 minutes, the temperature was raised to 160 ° C. Then, while stirring the reaction solution, 760.6 g of ethylene oxide (gaseous) was gradually added to the reaction solution. At this time, ethylene oxide was added by a blowing tube while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C.
After the addition of ethylene oxide was completed, the mixture was aged at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes.
Next, after cooling the temperature to 100 ° C. or lower, 70% by mass p-toluenesulfonic acid was added and neutralized so that the pH of the 1% by mass aqueous solution of the reaction product became about 7, to obtain LMAO.

[(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 (BIT) (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-trimethylethylene-4-isothiazolin-3-one (MTI) (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 to D-2 were used.

D-1: Sodium Methyl Sulfate (Tokyo Chemical Industry Co., Ltd. Product Name: Sodium Methyl Sulfate)

D-2: Sodium ethyl sulfate (Tokyo Chemical Industry Co., Ltd., trade name: Sodium Ethyl Sulfate)

[(E) component]
The fragrance composition E-1 shown in Table 1 was used.

[(F) component]
The following F-1 was used.
F-1: Calcium chloride (manufactured by Wako Pure Chemical Industries, Ltd.)

〔enzyme〕
The following G-1 was used.
G-1: Protease: (manufactured by Novozymes, trade name: Savenase Evity 16L)

[Stabilizer]
The following H-1 to H-2 were used.

H-1: Sodium benzoate (manufactured by Toagosei Co., Ltd. Product name: Sodium benzoate)
H-2: Citric acid: (manufactured by Kanto Chemical Co., Inc., trade name: citric acid)

[PH regulator]
The following I-1 was used.
I-1: MEA (monoethanolamine (manufactured by Nippon Shokubai Co., Ltd., trade name: monoethanolamine))

[(E) component]
In addition to the above-mentioned fragrance composition E-1, E-2 (manufactured by INTERATIONAL FLAVORS & FRAGRANCES, trade name: Mysterious Fly M2) was used as a capsule fragrance.

[Method for preparing liquid detergent: Examples 1 to 17 and Comparative Examples 21 to 22]
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 2 below, and prepare a liquid detergent by the following procedure. bottom.
The components (A) to (D), any component and ion-exchanged water for balance are all stirred and mixed, and if necessary, the pH is adjusted to 7 with an aqueous NaOH solution or an aqueous HCl solution to obtain a liquid detergent. rice field.

[Preparation method of liquid softener: Examples 18 to 20]
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), the blending amount of each component was adjusted as shown in Table 2, and a liquid softener was prepared by the following procedure. ..
First, the component (A), the component (B) and the component (E) were mixed and stirred to obtain an oil phase mixture. On the other hand, the component (C) 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 balance obtained by subtracting the total amount of the oil phase mixture, the component (C), the component (D), the component (F) and the encapsulated fragrance from 980 g.
Next, while the oil phase mixture heated above the melting point of the component (A) is stored in a glass container and stirred, 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 (D), the component (F) and the encapsulated fragrance were added. The component (D), the component (F) and the encapsulated fragrance were dissolved or dispersed 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) or sodium hydroxide (reagent 1 mol / L, Kanto Chemical) in an appropriate amount to adjust the pH to 3.0, and further increase the total mass to 1,000 g. Ion-exchanged water was added so as to obtain a liquid softener having the composition shown in Table 2.

In Table 2, the numerical value of each component is the blending amount (mass%) with respect to the total mass of the liquid composition. Ingredients whose blending amounts are not listed in Table 2 are not blended.
In view of the fact that sodium methylsulfate, which is D-1, was contained as a by-product in A-4, "Derived from A-4" is shown in the D-1 column of Examples 1 and 3 to 11 and Comparative Examples 21 to 22. The total amount of "sodium methyl sulfate" and "sodium methyl sulfate added as D-1" is shown. For Example 2 in which sodium methyl sulfate as D-1 was not used, the blending amount of "sodium methyl sulfate derived from A-4" is described in column D-1.
In Table 2, "(C) / (B)" indicates the mass ratio of the component (C) to the component (B).
In Table 2, "(C) / (D)" indicates the mass ratio of the component (C) to the component (D).

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

[Aroma evaluation of liquid composition]
100 mL of the liquid 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-step evaluation criteria. The results expressed as the average score of the five specialized panelists are shown in the "Aroma evaluation" column of Table 2. In terms of commercial value, the average score was 2.0 or higher.

<Evaluation criteria>
3: There is 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 fields of liquid detergents and fabric softeners.

Claims (18)

The following components (A) to (D):
(A) Surfactant (excluding alkyl sulfuric acid having 1 to 5 carbon atoms or a salt thereof),
(B) A compound having one or more mercapto groups (-SH) in the molecule,
(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 alkenylene 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 indicates an integer from 0 to 6. ), And (D) containing alkyl sulfuric acid having 1 to 5 carbon atoms or a salt thereof ,
The component (B) is 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-mercaptohexylhexanoate, 4-methoxy-2-methyl-2-butanethiol, 2- (4-) Methyl-1-cyclohexa-3-enyl) Propane-2-thiol, 3-mercaptoisobutyric acid, 4-methyl-4-mercapto-2-pentanone, 3-mercaptohexanol, 3-mercaptohexyl acetate, 2-franmententhiol , Cysteine, cysteamine and glutathione, selected from the group
The content of the component (B) is 0.0001 to 1% by mass with respect to the total mass of the liquid composition.
The component (C) is 1,2-benzisothiazolin-3-one (BIT), 2-methyl-4,5-trimethylen-4-isothiazolin-3-one (MTI), N-methyl-1,2-benz. Selected from the group consisting of isothiazolin-3-one and N- (n-butyl) -1,2-benzisothiazolin-3-one.
A liquid composition in which the liquid composition is a detergent or softener composition for fibers . The liquid composition according to claim 1, wherein the mass ratio ((C) / (B)) of the component (C) to the component (B) is 0.1 to 500. The liquid composition according to claim 1 or 2, wherein the mass ratio ((C) / (D)) of the component (C) to the component (D) is 0.002 to 5. The liquid composition according to any one of claims 1 to 3, which is a liquid detergent. The liquid composition according to any one of claims 1 to 3, which is a liquid softener. The liquid composition according to any one of claims 1 to 5, wherein the component (A) is a cationic surfactant. The cationic surfactant has 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms in the molecule, which may be partitioned by an ester group (-COO-) and / or an amide group (-NHCO-). The liquid composition according to claim 6, which 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 liquid composition according to any one of claims 1 to 5, wherein the component (A) is a nonionic surfactant. The liquid composition according to claim 8, wherein the nonionic surfactant is a compound represented by the general formula (A2).
R ₁₁ -CO- (OR ₁₂ ) m-OR ₁₃ (A2)
(During the ceremony,
R ₁₁ is a hydrocarbon group having 9 to 13 carbon atoms.
R ₁₂ is an alkylene group having 2 to 4 carbon atoms.
R ₁₃ is an alkyl group having 1 to 4 carbon atoms.
m indicates the average number of repetitions of OR ₁₂ , which is a number of 5 to 25. ) The eighth aspect of the present invention, wherein the nonionic surfactant is a polyoxyalkylene alkyl (or alkenyl) ether in which an average of 3 to 30 mol of an alkylene oxide having 2 to 4 carbon atoms is added to an aliphatic alcohol having 6 to 22 carbon atoms. Liquid composition. The liquid according to claim 8, wherein the nonionic surfactant is a polyoxyethylene alkyl ether having an alkyl group or an alkenyl group having 10 to 22 carbon atoms and having an average addition molar number of ethylene oxide of 10 to 100 mol. Composition. The liquid composition according to any one of claims 1 to 5, wherein the component (A) is an anionic surfactant. The liquid composition according to claim 12, wherein the anionic surfactant is a polyoxyalkylene alkyl ether sulfate ester salt represented by the following general formula (A3) or (A4).
R ₁₄ O- (EO) _p- (PO) _q -SO ₃ M (A3)
R ₁₄ O- (PO) _r- (EO) _s -SO ₃ M (A4)
(In each formula,
R ₁₄ is an alkyl having 10 to 20 carbon atoms and has 10 to 20 carbon atoms.
EO stands for ethyleneoxy group
PO stands for propyleneoxy group
p and q are numbers that satisfy p + q = 0 to 5, and are numbers.
r and s are numbers satisfying r + s = 0 to 5, and are numbers.
M is an alkali metal. ) The liquid composition according to claim 12, wherein the anionic surfactant is an α-sulfofatty acid ester salt. The liquid composition according to claim 12, wherein the anionic surfactant is a linear alkylbenzene sulfonic acid. The liquid composition according to any one of claims 1 to 15, wherein the component (B) is a fragrance component. The liquid composition according to any one of claims 1 to 15, wherein the component (B) is a formaldehyde scavenger. The liquid composition according to any one of claims 1 to 17 , wherein the component (D) is selected from the group consisting of sodium methyl sulfate, sodium ethyl sulfate and potassium methyl sulfate.