JP2021107591A - Liquid softener composition - Google Patents

Abstract

To provide a liquid softener having a superior deodorant effect, and superior in usability and freeze recoverability.SOLUTION: The present invention provides a liquid softener composition characterized by comprising the following compositions (A) to (D): (A) a compound selected from the group consisting of an amine compound that has one to three C10-26 hydrocarbon group(s) in a molecule thereof, and may be interrupted by an ester group and/or an amide group, a salt thereof, and a quaternary compound thereof; (B) a water soluble salt of a divalent metal; (C) a compound selected from the group consisting of an amino carboxylic acid compound of a specific structure, ricinoleic acid, and a salt thereof; and (D) a nonionic surfactant, the ratio of the total mass of the component (B) and the component (C) to the mass of the component (A): [B+C]/A being 0.01-0.5, the ratio of the total mass of the component (B) and the component (C) to the mass of the component (D): [B+C]/D being 0.1-4.SELECTED DRAWING: None

Description

The present invention relates to a liquid softener composition.

In recent years, the market size of fabric softeners in Japan has been expanding, and the share of fabric softeners having a deodorant function is increasing year by year. On the other hand, most of the current deodorant technologies rely on masking by scent, and there are concerns about problems such as smearing.
Therefore, there is a demand for deodorizing technology that does not rely on scents. As a specific example thereof, a technique of blending a water-soluble inorganic zinc compound (zinc chloride or the like) and a water-soluble zinc hydroxycarboxylate (zinc citrate or the like) into a liquid softener is known (Patent Document 1).
Further, although it is not a softener, a deodorant in which a water-soluble salt of a divalent metal (zinc sulfate or the like) and a chelating agent (methylglycin diacetic acid or the like) are used in combination is known (Patent Document 2).
In addition, a technique for blending methylglycine diacetic acid in order to improve the hue stability of the softener is known (Patent Document 3).

International Publication No. 2009/075284 International Publication No. 2012/090989 Japanese Unexamined Patent Publication No. 2015-200049

However, when the present inventor examined the techniques of Patent Documents 1 and 2, he found a problem. Regarding the technique of Patent Document 1, there is a problem that a sufficient deodorizing effect cannot be obtained only by blending a zinc compound, and depending on the type of the zinc compound, the viscosity of the softener is significantly lowered or increased, and the usability is lowered. A challenge was found. Regarding the technique of Patent Document 2, it has been found that when a water-soluble salt of a divalent metal or a chelating agent is blended with a softener, the usability is lowered.

As a result of diligent studies on the above problems, the present inventor has found that (A) a specific type of cationic surfactant, (B) a water-soluble salt of a divalent metal, and (C) a specific type of aminocarboxylic acid compound or ricinoleic acid. , (D) It was found that a liquid softener having excellent deodorizing effect (particularly, deodorizing effect on room drying odor), usability and freeze-restoring property can be obtained by blending with a nonionic surfactant in a specific ratio. .. The present invention has been made based on this finding.

（式中、
Ａ^Iは、炭素数８〜２２の直鎖又は分岐アルキル基、スルホ基、アミノ基、水酸基、水素原子又はＣＯＯＭ^Iであり、
Ｍ^Iは、互いに同一でも異なっていてもよく、水素原子、アルカリ金属、アルカリ土類金属、カチオン性アンモニウム基、及びアルカノールアミンからなる群より選ばれ、
ｍ^I及びｎ^Iは、それぞれ０〜２の整数である。）

（式中、
Ｘ^II-1〜Ｘ^II-4は、同一でも異なっていてもよく、水素原子、アルカリ金属、アルカリ土類金属、カチオン性アンモニウム基、及びアルカノールアミンからなる群より選ばれ、
Ｑ^IIは、水素原子、又は炭素数８〜２２の直鎖又は分岐アルキル基であり、
Ｒ^IIは、水素原子又は水酸基であり、
ｎ^IIは、０又は１である。）

（式中、
Ｒ^IIIは、炭素数８〜２２の直鎖又は分岐のアルキル又はアルケニル基であり、
Ａ^IIIは、Ｈ、メチル基又は（ＣＨ₂）ｍ^III−ＣＯＯＸ^IIIであり、
ｍ^IIIは、１〜３であり、
Ｘ^IIIは、Ｈ、アルカリ金属、アルカリ土類金属、アルカノールアミン又はＮＨ₄であり、
ｎ^IIIは、１〜３である。）

（式中、
Ｘ^IVは、水素原子、アルカリ金属又はアルカリ土類金属であり、
ｎ^IVは１又は２である。）、並びに
（Ｄ）ノニオン界面活性剤
を含み、
（Ｂ）成分と（Ｃ）成分の合計の（Ａ）成分に対する質量比（〔Ｂ＋Ｃ〕／Ａ）が０．０１〜０．５であり、かつ
（Ｂ）成分と（Ｃ）成分の合計の（Ｄ）成分に対する質量比（〔Ｂ＋Ｃ〕／Ｄ）が０．１〜４であることを特徴とする、液体柔軟剤組成物。
〔２〕（Ｂ）成分が、水溶性亜鉛塩又は水溶性銅塩である、前記〔１〕に記載の液体柔軟剤組成物。
〔３〕（Ｃ）成分が、式（Ｉ）で表される化合物又はその塩、又は、リシノール酸又はその塩である、前記〔１〕又は〔２〕に記載の液体柔軟剤組成物。
〔４〕（Ｂ）成分と（Ｃ）成分の合計の（Ａ）成分に対する質量比（〔Ｂ＋Ｃ〕／Ａ）が０．２５〜０．４５である、前記〔１〕〜〔３〕のいずれか１項に記載の液体柔軟剤組成物。
〔５〕（Ｂ）成分と（Ｃ）成分の合計の（Ｄ）成分に対する質量比（〔Ｂ＋Ｃ〕／Ｄ）が１〜２である、前記〔１〕〜〔４〕のいずれか１項に記載の液体柔軟剤組成物。
〔６〕（Ｄ）成分が、炭素数１０〜１８のアルキル基を有し、エチレンオキシドの平均付加モル数が２０〜８０モルのポリオキシエチレンアルキルエーテルである、前記〔１〕〜〔５〕のいずれか１項に記載の液体柔軟剤組成物。 That is, the present invention relates to the following [1] to [6].
[1] A liquid softener composition, wherein the following components (A) to (D):
(A) From the group consisting of an amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms in the molecule, a salt thereof, and a quaternary compound thereof, which may be separated by an ester group and / or an amide group. Compound of choice,
(B) Water-soluble salt of divalent metal,
Compounds selected from the group consisting of aminocarboxylic acid compounds represented by formulas (I) to (IV), ricinoleic acid and salts thereof, (C).

(During the ceremony,
A ^I is a linear or branched alkyl group having 8 to 22 carbon atoms, a sulfo group, an amino group, a hydroxyl group, a hydrogen atom or a COOM ^I,
M ^I may be the same or different from each other, a hydrogen atom, an alkali metal, alkaline earth metal, a cationic ammonium group, and selected from the group consisting of alkanolamine,
m ^I and n ^I are integers of 0 to 2, respectively. )

(During the ceremony,
X ^{II-1 to} X ^II-4 may be the same or different and are selected from the group consisting of hydrogen atoms, alkali metals, alkaline earth metals, cationic ammonium groups, and alkanolamines.
Q ^II is a hydrogen atom or a linear or branched alkyl group having 8 to 22 carbon atoms.
R ^II is a hydrogen atom or a hydroxyl group,
n ^II is 0 or 1. )

(During the ceremony,
R ^III is a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms.
A ^III is an H, methyl group or (CH ₂ ) m ^III- COOX ^III .
m ^III is 1-3
X ^III is H, alkali metal, alkaline earth metal, alkanolamine or NH ₄ .
n ^III is 1-3. )

(During the ceremony,
X ^IV is a hydrogen atom, alkali metal or alkaline earth metal,
n ^IV is 1 or 2. ), And (D) nonionic surfactant,
The mass ratio ([B + C] / A) of the total of the components (B) and (C) to the component (A) is 0.01 to 0.5, and the total of the components (B) and (C) (D) A liquid softener composition, wherein the mass ratio ([B + C] / D) to the component is 0.1 to 4.
[2] The liquid softener composition according to the above [1], wherein the component (B) is a water-soluble zinc salt or a water-soluble copper salt.
[3] The liquid softener composition according to the above [1] or [2], wherein the component (C) is a compound represented by the formula (I) or a salt thereof, or ricinoleic acid or a salt thereof.
[4] Any of the above [1] to [3], wherein the mass ratio ([B + C] / A) of the total of the components (B) and (C) to the component (A) is 0.25 to 0.45. The liquid softener composition according to item 1.
[5] In any one of the above [1] to [4], the mass ratio ([B + C] / D) of the total of the components (B) and (C) to the component (D) is 1 to 2. The liquid softener composition according to the above.
[6] The above-mentioned [1] to [5], wherein the component (D) is a polyoxyethylene alkyl ether having an alkyl group having 10 to 18 carbon atoms and having an average addition mole number of ethylene oxide of 20 to 80 moles. The liquid softener composition according to any one of the following items.

As shown in Examples described later, the liquid softener composition of the present invention is excellent in deodorant effect, usability and freeze-restorability. Therefore, the present invention is useful as a softener having added value not found in conventional products.

[Component (A): Cationic surfactant]
The component (A) is "from 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 and / or an amide group, a salt thereof, and a quaternized product thereof. It is a cationic surfactant which is a "compound selected from the group".
The component (A) is blended to impart a softening effect to the liquid softener composition.

The hydrocarbon group having 10 to 26 carbon atoms (hereinafter, may be referred to as “long chain hydrocarbon group” in the present specification) has 10 to 26 carbon atoms, preferably 17 to 26, more preferably 19 to 24. preferable. When the number of carbon atoms is 10 or more, the flexibility is good, and when the number of carbon atoms is 26 or less, the handleability is good. The long-chain hydrocarbon group may be saturated or unsaturated. When the long-chain hydrocarbon group is unsaturated, the position of the double bond may be anywhere, but when there is one double bond, the position of the double bond is long-chain hydrocarbon. It is preferably located in the center of or around the center of the hydrogen group.
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 and the like.
When having the dividing group, the number of dividing groups contained in one long-chain hydrocarbon group may be one or two or more. That is, the long-chain hydrocarbon group may be divided at one place by the dividing group or at two or more places. When having two or more dividing groups, each dividing group may be the same or different.
When a dividing group is contained in the carbon chain, the carbon atom contained in the dividing group shall be counted as the number of carbon atoms of the long-chain hydrocarbon group.
Long-chain hydrocarbon groups are usually industrially used unhydrogenated beef fat-derived fatty acids, fatty acids obtained by hydrogenating or partially hydrogenating unsaturated portions, and plant-derived unhydrogenated fatty acids such as palm palms and oil palms. It is introduced by using a hydrogenated fatty acid or fatty acid ester, or a fatty acid or fatty acid ester obtained by hydrogenating or partially hydrogenating an unsaturated portion.
As the amine compound as the component (A), a secondary amine compound or a tertiary amine compound 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。）若しくは−（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、又は−（ＣＨ₂）_nＮＨ₂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。〕 More specifically, the amine compound as the component (A) includes a compound 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) or − (CH ₂ ) _n NHCOR ⁵ (n is 2 or 3 and R ⁵ is a hydrocarbon group with 7-21 carbon atoms), hydrogen atom, carbon number Alkyl groups 1 to 4, -CH ₂ CH (Y) OH, or-(CH ₂ ) _n NH ₂ , and ^{at least one of R 1 to} R ³ is a hydrocarbon group having 10 to 26 carbon atoms. , -CH ₂ CH (Y) OCOR ⁴ or-(CH ₂ ) _n NHCOR ⁵ . ]

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

Hydrocarbon group R ⁴ is a residue obtained by removing a carboxy group from a fatty acid having 8 to 22 carbon atoms (R ⁴ COOH) (fatty acid residues), R ⁴ Nomoto become fatty (R ⁴ COOH) is , Saturated fatty acid or unsaturated fatty acid, and may be linear fatty acid or branched fatty acid. Of these, saturated or unsaturated linear fatty acids are preferable. The saturation / unsaturated ratio (mass ratio) of the fatty acid ^{that is the source of R 4} is preferably 90/10 to 0/100, and 80/20 to 0, in order to impart good water absorption to the softened clothing. / 100 is more preferable.
When R ⁴ is an unsaturated fatty acid residue, cis and trans isomers are present, but the mass ratio of cis isomer / trans isomer is preferably 40/60 to 100/0, preferably 70/30 to 90/10. Especially preferable.

Specific examples of 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 to 60), and a portion. Examples thereof include hydrogenated beef fatty acid (iodine value 10 to 60). Among them, fatty acids prepared by combining two or more kinds selected from stearic acid, palmitic acid, myristic acid, oleic acid, elaidic acid, and linoleic acid in predetermined amounts to satisfy the following conditions (a) to (c). It is preferable to use the composition.
(A) The ratio (mass ratio) of saturated fatty acid / unsaturated fatty acid is 90/10 to 0/100, more preferably 80/20 to 0/100. (B) The cis / trans form ratio (mass ratio) is 40/60 to 100/0, more preferably 70/30 to 90/10. (C) The fatty acid having 18 carbon atoms is 60% by mass or more, preferably 80% by mass or more, the fatty acid having 20 carbon atoms is less than 2% by mass, and the fatty acid having 21 to 22 carbon atoms is less than 1% by mass. ..

-(CH ₂ ) _{n In} NHCOR ⁵ , n is 2 or 3, and 3 is particularly preferable. R ⁵ is a hydrocarbon group having 7 to 21, preferably 15 to 19 carbon atoms. When the compound represented by the general formula (A1) R ⁵ there are a plurality, may be R ⁵ of said plurality of mutually identical, may be different. Examples of R ⁵ include those similar to ^{R 4.}

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 ). Two are preferably long-chain hydrocarbon groups. When ^{one or two of R 1 to} R ³ are long-chain hydrocarbon groups, the remaining two or one are hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, -CH ₂ CH (Y). It is preferably OH or − (CH ₂ ) _n NH ₂ , an alkyl group having 1 to 4 carbon atoms, −CH ₂ CH (Y) OH, or − (CH ₂ ) _n NH ₂ . Of these, as the alkyl group having 1 to 4 carbon atoms, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable. Y in −CH ₂ CH (Y) OH is the same as Y in −CH ₂ CH (Y) OCOR ⁴ . − (CH ₂ ) _{n n in} NH ₂ is similar to _{n in} − (CH ₂ ) n NHCOR ^5.

〔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。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, R ⁷ and R ⁸ are each independently a hydrocarbon group having 10 to 26 carbon atoms. R ⁹ and R ¹⁰ are each independently a hydrocarbon group 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.
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.} When R ⁹ is more present in the formula, R ⁹ of the plurality of may be the same as each other, may be different.

The component (A) may be a salt of an amine compound or a quaternary product.
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, and methyl sulfuric acid. Neutralization of the amine compound can be carried out by a known method.
A quaternized product of an amine compound is obtained by reacting the amine compound with a quaternizing agent. Examples of the quaternizing agent used for quaternization of the amine compound include alkyl halides such as methyl chloride and dialkyl sulfuric acid such as dimethyl sulfate. When these quaternary agents are reacted with an amine compound, an alkyl group of the quaternary agent is introduced into the nitrogen atom of the amine compound, and a salt of the quaternary ammonium ion and a halogen ion or a monoalkyl sulfate ion is formed. .. The alkyl group introduced by the quaternizing agent is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. The quaternization of the amine compound can be carried out by a known method.

As the component (A), at least one selected from the group consisting of the compound represented by the general formula (A1), a salt thereof and a quaternized product thereof is preferable, and the general formulas (A1-1) to (A1-) are used. 8), at least one selected from the group consisting of the salt thereof and the quaternized compound thereof is more preferable, and (A1-4) to (A1-6) (in each formula, R ⁹ is an alkyl group having 15 to 17 carbon atoms. And an alkenyl group), at least one selected from the group consisting of salts thereof and quaternized compounds thereof is particularly preferred.

As the compound represented by the general formula (A1), a salt thereof and a quaternized product thereof, a commercially available compound may be used, or a compound produced by a known method may be used.
For example, a compound represented by the general formula (A1-2) (hereinafter, “compound (A1-2)”) and a compound represented by the general formula (A1-3) (hereinafter, “compound (A1-3)”) are , The fatty acid composition, or a 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, can be synthesized by a condensation reaction of methyl diethanolamine. At that time, from the viewpoint of improving the flexibility, the compound is synthesized so that the abundance ratio represented by "Compound (A1-2) / Compound (A1-3)" is 99/1 to 50/50 in terms of mass ratio. It is preferable to do so.
Further, when the quaternized product is used, it is more preferable to use dimethyl sulfate as the quaternizing agent. At that time, from the viewpoint of flexibility, the abundance ratio represented by "quaternized compound (A1-2) / quaternized compound (A1-3)" is 99/1 to 50/50 in terms of mass ratio. It is preferable to synthesize so as to become.

Compounds represented by the general formula (A1-4) (hereinafter, "Compound (A1-4)"), compounds represented by the general formula (A1-5) (hereinafter, "Compound (A1-5)"), general formula. The compound represented by (A1-6) (hereinafter, “Compound (A1-6)”) can be synthesized by a condensation reaction of the above fatty acid composition or fatty acid methyl ester composition with 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 masses of the compound (A1-4) from the viewpoint of flexibility. %, Compound (A1-5) is preferably 5 to 98% by mass, compound (A1-6) is preferably 0.1 to 40% by mass, compound (A1-4) is 30 to 60% by mass, and compound (A1-4) is 30 to 60% by mass. 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 quaternized product is used, it is more preferable to use dimethyl sulfate as the quaternizing agent from the viewpoint of sufficiently advancing the quaternization reaction. The abundance ratio of each quaternized compound (A1-4), (A1-5), and (A1-6) is a mass ratio from the viewpoint of flexibility, and the quaternized product of compound (A1-4) is 1 to 1. It is preferable that 60% by mass, the quaternized product of the compound (A1-5) is 5 to 98% by mass, and the quaternized product of the compound (A1-6) is 0.1 to 40% by mass, and the compound (A1-4). ) Is 30 to 60% by mass, the quaternary compound (A1-5) is 10 to 55% by mass, and the quaternized compound (A1-6) is 5 to 35% by mass. preferable. Further, when the compounds (A1-4), (A1-5), and (A1-6) are quaternized, generally, the esteramine that has not been quaternized remains even after the quaternization reaction. At that time, the ratio of "quaternized / non-quaternized esteramine" is preferably in the range of 70/30 to 99/1.

The compound represented by the general formula (A1-7) (hereinafter, “compound (A1-7)”) and the compound represented by the general formula (A1-8) (hereinafter, “compound (A1-8)”) are described above. From the fatty acid composition and the adduct of N-methylethanolamine and acrylonitrile, J. Org. Chem. , 26, 3409 (1960), which 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.

The component (A) is a known substance and is easily available on the market or can be prepared.

As the component (A), a single type may be used, or a plurality of types may be used in combination.

The content of the component (A) is not particularly limited as long as it achieves the purpose of compounding and satisfies the compounding ratio with other components described later, but is, for example, 4 to 16% by mass with respect to the total mass of the liquid softener composition. It is preferably 6 to 14% by mass, more preferably 8 to 12% by mass. When the content of the component (A) is 4% by mass or more, a more improved flexibility-imparting effect can be obtained, and when it is 16% by mass or less, a softener viscosity that enables better usability can be obtained.

[Component (B): water-soluble salt of divalent metal]
The component (B) is blended to impart a deodorizing effect to the liquid softener composition.
"Water-soluble" means dissolving 10 g or more in 1 liter of water at 25 ° C.
Specific examples of the component (B) include water-soluble zinc salts (zinc sulfate, zinc chloride, etc.), water-soluble copper salts (copper sulfate, copper chloride, etc.), water-soluble iron salts (iron sulfate, etc.), and water-soluble manganese. Examples include salts (manganese chloride, etc.). The component (B) also includes these hydrates.
As the component (B), a water-soluble zinc salt and a water-soluble copper salt are preferable from the viewpoint of deodorizing performance.
As the water-soluble zinc salt, zinc sulfate and zinc chloride are preferable.
As the water-soluble copper salt, copper sulfate and its hydrate are preferable, copper sulfate hydrate is more preferable, and copper sulfate pentahydrate is further preferable.

The component (B) is a known substance and is easily available on the market or can be prepared.

A single type of the component (B) may be used, or a plurality of types may be used in combination. When two or more types are used in combination, it is preferable to contain a zinc salt.

The content of the component (B) is not particularly limited as long as it achieves the purpose of blending and satisfies the blending ratio with other components described later, but is, for example, 0.05 to 3 mass with respect to the total mass of the liquid softener composition. %, preferably 0.1 to 3% by mass, more preferably 0.5 to 2.5% by mass, still more preferably 1.5 to 2.5% by mass. When the component (B) is a hydrate, it means the content as an anhydride. When the content of the component (B) is 0.05% by mass or more, a further improved deodorizing effect can be obtained, and when it is 3% by mass or less, a softener viscosity that enables better usability can be obtained. ..

[Component (C): aminocarboxylic acid compound, ricinoleic acid and salts thereof]
The component (C) is blended to impart a deodorizing effect to the liquid softener composition.
The component (C) is a compound represented by the following formulas (I) to (IV), ricinoleic acid and a salt thereof.

In formula (I), A ^I represents a linear or branched alkyl group having 8 to 22 carbon atoms, a sulfo group, an amino group, a hydroxyl group, a hydrogen atom or COM ^I. The _{^{A I, CH 3, OH,}} H, COOM I are preferred, CH _3, H, more preferably, CH ₃ are particularly preferred.
M ^I may be the same or different from each other, respectively a hydrogen atom, an alkali metal, alkaline earth metal, a cationic ammonium group, the one selected from the group consisting of alkanolamines. As the alkali metal, sodium and potassium are preferable. As the alkanolamine, monoethanolamine, diethanolamine, and triethanolamine are preferable. The M ^I, the alkali metals are preferred, sodium being particularly preferred.
m ^I and n ^I are integers of 0 to 2, respectively. m ^I is preferably 0 or 1. n ^I is preferably 0 or 1. If both m ^I and n ^I are 0, then A ^I is CH ₃ .

Among the compounds represented by the formula (I), methylglycin diacetic acid (MGDA), aspartic acid diacetic acid (ASDA), isoselin diacetic acid (ISDA), β-alanine diacetic acid (ADAA), and serine diacetic acid are suitable. (SDA), diacetic acid glutamate (GLDA), or salts thereof. Of these, MGDA or a salt thereof is preferable.

In formula (II), X ^{II-1 to} X ^II-4 may be the same or different, and are selected from the group consisting of hydrogen atom, alkali metal, alkaline earth metal, cationic ammonium group, and alkanolamine, respectively. Represents a species. As the alkali metal, sodium and potassium are preferable. As the alkanolamine, monoethanolamine, diethanolamine, and triethanolamine are preferable. As X ^{II-1 to} X ^II-4 , alkali metals are preferable, and sodium is particularly preferable.
Q ^II represents a hydrogen atom or a linear or branched alkyl group having 8 to 22 carbon atoms.
R ^II represents a hydrogen atom or a hydroxyl group.
n ^II represents 0 or 1.

Among the compounds represented by the formula (II), suitable ones include iminosuccinic acid (IDS), hydroxyiminosuccinic acid (HIDS), or salts thereof, and IDS or a salt thereof is more preferable. ..

In formula (III), R ^III represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms.
A ^III represents H, a methyl group or (CH ₂ ) m ^III- COOX ^III . As A ^III , (CH ₂ ) m ^III- COOX ^III is preferable. m ^III represents any number from 1 to 3.
X ^III represents H, alkali metal, alkaline earth metal, alkanolamine or NH ₄ . As the alkali metal, sodium and potassium are preferable. As the alkanolamine, monoethanolamine, diethanolamine, and triethanolamine are preferable.
n ^III represents any of 1-3.

Specific examples of the compound represented by the formula (III) include
Alkyl and alkenylaminoacetates such as sodium octylaminoacetate, sodium laurylaminoacetate, sodium myristylaminoacetate, sodium palmitylaminoacetate, sodium oleylaminoacetate;
Alkyl and alkenylaminopropionates such as sodium octylaminopropionate, sodium decylaminopropionate, sodium laurylaminopropionate, sodium myristylaminopropionate, sodium palmitylaminopropionate, sodium oleylaminopropionate;
N-alkyl and alkenylglycine salts such as N-octylglycine sodium, N-decylglycine sodium, N-laurylglycine sodium, N-myristylglycine sodium, N-palmitylglycine sodium, N-oleylglycine sodium;
N-octyl-N-methyl-β-alanine sodium, N-decyl-N-methyl-β-alanine sodium, N-dodecyl-N-methyl-β-alanine sodium, N-myristyl-N-methyl-β-alanine N-alkyl and alkenyl-N-methyl-β-alanine salts such as sodium, N-palmityl-N-methyl-β-alanine sodium, N-oleyl-N-methyl-β-alanine sodium;
Alkyl and alkenylaminodiacetate such as sodium octylaminodiacetate, sodium decylaminodiacetate, sodium laurylaminodiacetate, sodium myristylaminodiacetate, sodium palmitylaminodiacetate, sodium oleylaminodiacetate; and octylaminodipropionate. Alkyl and alkenylaminodipropionates such as sodium, sodium decylaminodipropionate, sodium laurylaminodipropionate, sodium myristylaminodipropionate, sodium palmitylaminodipropionate, sodium oleylaminodipropionate, etc. Be done.
Among these, alkyl and alkenylaminodiacetic acid salts are preferable from the viewpoint of storage stability, and among them, decylaminodiacetic acid, laurylaminodiacetic acid, myristylaminodiacetic acid, palmitylaminodiacetic acid or salts thereof are preferable, and lauryl is particularly preferable. Aminodiacetic acid, myristylaminodiacetic acid, palmitylaminodiacetic acid or salts thereof are more preferable.

In formula (IV), X ^IV represents a hydrogen atom, alkali metal or alkaline earth metal.
n ^IV represents 1 or 2, and when n ^IV is 2, X ^IV may be the same or different. The substitution position of the (COOX ^IV ) n ^IV group is not particularly limited, but the α-position is preferable.

リシノール酸の塩としては、ナトリウム塩、亜鉛塩や銅塩等が挙げられる。 Ricinoleic acid (12-hydroxy-9-cis-octadekenic acid) is a compound having the following structure.

Examples of the ricinoleic acid salt include sodium salt, zinc salt, copper salt and the like.

As the component (C), the compound represented by the formula (I) or (II) and a salt thereof and ricinoleic acid are preferable, and MGDA, IDS and salts thereof and ricinoleic acid are particularly preferable. In terms of deodorant effect, MGDA and its salts and ricinoleic acid are most preferable. MGDA is most preferable in terms of deodorant effect, usability of the liquid softener composition, and freeze-restorability.

The component (C) is a known substance and is easily available on the market or can be prepared.

A single type of the component (C) may be used, or a plurality of types may be used in combination.

The content of the component (C) is not particularly limited as long as it achieves the purpose of blending and satisfies the blending ratio with other components described later, but is, for example, 0.05 to 3 mass with respect to the total mass of the liquid softener composition. %, preferably 0.1 to 3% by mass, more preferably 0.5 to 2.5% by mass, still more preferably 1.5 to 2.5% by mass. When the content of the component (C) is 0.05% by mass or more, a further improved deodorizing effect can be obtained, and when it is 3% by mass or less, a softener viscosity that enables better usability can be obtained. ..
The mass ratio of the component (B) to the component (C) ((B) / (C)) is preferably 0.1 to 10, more preferably 0.2 to 5, and even more preferably 0 in terms of deodorizing effect. .5-2.

[Component (D): Nonionic surfactant]
The component (D) is blended to improve the usability and freeze-restorability of the liquid softener composition.
As the component (D), for example, those derived from polyhydric alcohols, higher alcohols, higher amines or higher fatty acids can be used.
As a specific example of the component (D),
Glycerin fatty acid ester or pentaerythritol in which a fatty acid having 10 to 22 carbon atoms is ester-bonded to glycerin or pentaerythritol;
A polyoxyethylene alkyl ether having an alkyl group or an alkenyl group having 10 to 22 carbon atoms and having an average addition mole number of ethylene oxide (EO) of 10 to 100 moles;
Polyoxyethylene fatty acid alkyl (1 to 3 carbon atoms of the alkyl) ester;
Polyoxyethylene alkylamines with an average addition of 10-100 moles of ethylene oxide;
Examples thereof include alkyl polyglucosides having an alkyl group or an alkenyl group having 8 to 18 carbon atoms; and hardened castor oil having an average addition mole number of ethylene oxide of 10 to 100 moles.
As the component (D), 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 (preferably 30 to 60 mol) is preferable.

The component (D) is a known substance and is easily available on the market or can be prepared.

A single type of the component (D) may be used, or a plurality of types may be used in combination.

The content of the component (D) is not particularly limited as long as it achieves the purpose of blending and satisfies the blending ratio with other components described later, but is, for example, 0.5 to 10 mass with respect to the total mass of the liquid softener composition. %, preferably 1 to 5% by mass, more preferably 1.5 to 4% by mass, and particularly preferably 1.5 to 3% by mass. When the content of the component (D) is 0.5% by mass or more, high temperature stability is obtained in addition to improved usability and freeze-restorability, and when it is 10% by mass or less, better usability is obtained. The possible viscosity and separation stability are obtained.

[Mixing ratio of each component]
In the present invention, the mass ratio ([B + C] / A) of the total of the components (B) and (C) ([B + C]) to the component (A) is 0.01 to 0.5, preferably 0.08 to 0.08. It is 0.45, more preferably 0.25 to 0.45. When blended in this ratio, an excellent deodorant effect can be obtained, the liquid softener composition becomes difficult to separate, and usability is improved. This is because when the vesicle composed of the component (A) is excessively incorporated with a part of the component (B) and the component (C), the vesicle particle size is increased and the liquid softener composition is easily separated. However, it is considered that this is because the excessive increase in the vesicle particle size is suppressed by blending in the above mass ratio. However, the present invention is not limited to the above theory.

In the present invention, the mass ratio ([B + C] / D) of the total of the components (B) and (C) ([B + C]) to the component (D) is 0.1 to 4, preferably 0.4 to 2. 5, more preferably 1-2. When blended in this ratio, an excellent deodorant effect is obtained, and the freeze-restorability and usability of the liquid softener composition are further improved. This is because when a part of the component (B) and the component (C) is taken into the vesicle composed of the component (A), the particle size distribution and the excluded volume of the vesicle change, and the liquid softener composition thickens. However, by blending in the above mass ratio, excessive changes in the particle size distribution and exclusion volume of the vesicle are suppressed, and the freeze-restorability is improved by the component (D). Is considered to be. However, the present invention is not limited to the above theory.

[Arbitrary component]
The following optional components other than the essential components (A) to (D) may be added to the liquid softener composition as long as the effects of the present invention are not impaired.

[Ingredient (E): unencapsulated fragrance composition]
The component (E) is a fragrance composition (free fragrance composition) that is not contained in a capsule, which is different from the fragrance composition contained as a core substance in the capsule fragrance (component (H)) described later.
The component (E) is blended in order to improve the deodorizing effect of the liquid softener composition by the masking effect of the aroma.
The component (E) can be appropriately selected from a fragrance composition containing one or more kinds of fragrance components generally used in the liquid softener composition according to the purpose, but all of the fragrance compositions as the component (E) It is preferable to contain 25% by mass or more of a fragrance component having a ClogP value of 5 or more with respect to the mass.
Specific examples of the fragrance component are not particularly limited and may be appropriately selected depending on the intended purpose. For example, aldehydes, phenols, alcohols, ethers, esters, hydrocarbons, ketones and lactones. , Musks, fragrances having a terpene skeleton, natural fragrances, animal fragrances and the like.

Specific examples of each fragrance are as follows.
The aldehydes are not particularly limited and may be appropriately selected depending on the intended purpose. For example, undecylene aldehyde, lauryl aldehyde, aldehyde C-12MNA, mirac aldehyde, α-amylcinnamic aldehyde, cyclamen aldehyde, citral, etc. Examples thereof include citralal, ethyl vanillin, heliotropin, anisaldehyde, α-hexyl cinnamic aldehyde, octanal, rigstral, lilial, lylar, triplar, vanillin and helional.

The phenols are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include eugenol and isoeugenol.

The alcohols are not particularly limited and may be appropriately selected depending on the intended purpose. For example, citronellol, dihydromilsenol, dihydrolinalool, geraniol, linalool, nerol, sandalol, santa rex, tarpineol, tetra. Examples thereof include hydrolinalool, menthol, borneol, 1-decalal, bacdanol, and phenylethyl alcohol.

The ethers are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include sedrumber, glycalva, methyl eugenol and methyl isoeugenol.

The esters are not particularly limited and may be appropriately selected depending on the intended purpose. For example, cis-3-hexenyl acetate, cis-3-hexenyl propionate, cis-3-hexenyl salicylate, p-cresyl. Acetate, pt-butylcyclohexyl acetate, amyl acetate, methyldihydrojasmonate, amyl salicylate, benzyl salicylate, benzyl benzoate, benzyl acetate, sedrill acetate, citronellyl acetate, decahydro-β-naphthyl acetate, dimethylbenzylcal Vinyl Acetate, Erica Propionate, Ethyl Acetate, Erica Acetate, Geranyl Acetate, Geranyl Formate, Hedion, Linalyl Acetate, β-Phenyl Ethyl Acetate, Hexyl Salicylate, Styralyl Acetate, Tarpinyl Acetate, Vetiberyl Acetate, o Examples thereof include -t-butylcyclohexylacetate, manzanate and allyl heptanoate.

The hydrocarbons are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include limonene (particularly d-limonene), α-pinene, β-pinene, myrcene, camphene, terpinolene and the like. Be done.

The ketones are not particularly limited and may be appropriately selected depending on the intended purpose. For example, α-yonone, β-yonone, methyl-β-naphthyl ketone, α-damascenone, β-damascenone, δ-damascenone, etc. Examples include damascenone, cis-jasmon, methyl ionone, allylyonone, cashmere, dihydrojasmon, isoe super, beltfix, isolone diphoranone, corebon, carboxylic, rosephenone, raspberry ketone, dynascon and maltol.

The lactones are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include γ-decalactone, γ-undecalactone, γ-nonalactone, γ-dodecalactone, coumarin and ambroxane. Be done.

The musks are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include cyclopentadecanolide, ethylene brassylate, galaxolide, muskketone, tonalid, tonalide, and nitromusks.

The fragrance having a terpene skeleton is not particularly limited and may be appropriately selected depending on the intended purpose. For example, geraniol (geraniol), nerol, linalool, citronellal, citronellal, menthol, mint, citronellal, milsen, α-pinene. , Β-Pinene, limonene, terpinelol, carboxylic, yonone (eg β-yonone), camphene, borneol and the like.

The natural fragrance is not particularly limited and may be appropriately selected depending on the purpose. For example, orange oil, lemon oil, lime oil, petitgrain oil, yuzu oil, neroli oil, bergamot oil, lavender oil, lavandine oil, etc. Avies oil, anis oil, bay oil, boad rose oil, ylang ylang oil, citronella oil, geranium oil, peppermint oil, peppermint oil, sparemint oil, eucalyptus oil, lemongrass oil, patchouli oil, jasmine oil, rose oil, cedar oil, Essential oils such as vetiver oil, galvanum oil, oak moss oil, pine oil, citrus oil, ebony oil, sardine oil, terepine oil, clove oil, clove leaf oil, cassia oil, nutmeg oil, cananga oil and thyme oil. ..

The animal fragrance is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include beaver fragrance, sacred cat fragrance, castoreum fragrance, and ambergris fragrance.

The component (E) is 25% by mass or more, preferably 30% by mass or more, and more preferably 35% by mass of the fragrance component having a ClogP value of 5 or more with respect to the total mass of the fragrance composition as the component (E). As mentioned above, it is more preferable to contain 40% by mass or more. When the blending amount of the fragrance component having a ClogP value of 5 or more in the component (E) is 25% by mass or more, better scent persistence can be obtained.
The type of fragrance component having a ClogP value of 5 or more is not particularly limited, but preferred examples are ambroxane (5.3), tonalide (6.3), hexyl salicylate (5.1), and galaxolide (6.1). ), Muscone (6.0), Exartride (6.2), Isoe Super (5.2), Beltfix (Acetyl Cedren) (5.0), Cedrill Methyl Ether (5.1), etc. (The number in parentheses represents the ClogP value). Of these, ambroxane, galaxolide, isoe super, and tonalide are more preferable.
The ClogP value is a value obtained by expressing the 1-octanol / water partition coefficient P representing the ratio of equilibrium concentrations in 1-octanol and water for a chemical substance in the form of a logarithmic logP with respect to the base 10. The ClogP value can be obtained by decomposing the chemical structure of a compound into its constituent elements by the f-number method (hydrophobic fragment constant method) and integrating the hydrophobic fragment constant and f-number of each fragment (for example). See Clog 3 Reference Manual Daylight Software 4.34, Albert Leo, David Weininger, Version 1, March 1994).
In general, the larger the ClogP value, the more hydrophobic the fragrance. Therefore, the fragrance composition containing a large amount of the fragrance component having a small ClogP value is more hydrophilic than the fragrance composition containing a large amount of the fragrance component having a large ClogP value. You can say that.

The fragrance composition may contain a liquid softener composition, for example, a finishing agent composition for textile products or a solvent generally used for a softener composition. As fragrance solvents, acetyline (triacetin), MMB acetate (3-methoxy-3-methylbutyl acetate), sucrose diacetate hexaisobutyrate, ethylene glycol dibutyrate, hexylene glycol, dibutyl sebacate, deltil extra ( Isopropyl millistate), methyl carbitol (diethylene glycol monomethyl ether), carbitol (diethylene glycol monoethyl ether), TEG (triethylene glycol), benzyl benzoate (BB), propylene glycol, diethyl phthalate, tripropylene glycol, aborin ( Dimethylphthalate), deltylprime (isopropylpalmitate), dipropylene glycol (DPG), farnesene, dioctyl adipate, tributyrin (glyceryl tributanoate), hydrolite-5 (1,2-pentanediol), propylene glycol diacetate , Cetyl Acetate (Hexadecyl Acetate), Ethyl Avietate, Avalin (Methyl Avietate), Citroflex A-2 (Acetyl Triethyl Citrate), Citroflex A-4 (Tributyl Acetyl Citrate), Citroflex No. 2 (triethylcitrate), Citroflex No. Examples thereof include 4 (tributyl citrate), durafix (methyl dihydroavietate), MITD (isotridecyl myristate), polylimonene (limonene polymer), and 1,3-butylene glycol.
The blending amount of the solvent is, for example, 0.1 to 30% by mass, preferably 1 to 20% by mass, based on the total mass of the fragrance composition.

The fragrance composition may contain a liquid fabric softener composition, for example, a finishing agent composition for textile products or an antioxidant commonly used in fabric softener compositions. Antioxidants for fragrances include 3,5-di-tert-butyl-4-hydroxytoluene (BHT), t-butyl-p-hydroxyanisole (BHA), p-methoxyphenol, β-naphthol, and phenyl-α. -Naphtylamine, tetramethyldiaminodiphenylmethane, γ-orizanol, vitamin E (α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol), 2,2'-ethylidenebis (4,6-di-t-butylphenol) , Tris (tetramethylhydroxypiperidinol) / 1/3 citrate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, quercetin, and 4,4'-bis (α, α) -Dimethylbenzyl) Diphenylamine and the like can be mentioned. It is preferably 3,5-di-tert-butyl-4-hydroxytoluene (BHT).
The blending amount of the antioxidant is, for example, 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the total mass of the fragrance composition.

The content of the component (E) is not particularly limited as long as it can achieve the purpose of blending, but is 0.1 to 2% by mass, preferably 0.5 to 1.5% by mass, based on the total mass of the liquid softener composition. It is mass%. When the content of the component (E) is 0.1% by mass or more, an excellent masking effect can be obtained. When the content of the component (E) is 2% by mass or less, the separation stability of the liquid softener composition can be better maintained.

[(F) component: highly branched cyclic dextrin]
The component (F) is blended in order to further improve the stability (particularly freeze-restorability) of the liquid softener composition and to impart deodorant property and deodorant property to the textile product.
The highly branched cyclic dextrin of the component (F) refers to a glucan having an inner branched cyclic structure portion and an outer branched structural portion and having a weight average degree of polymerization in the range of 50 to 10,000.
A glucan having an inwardly branched cyclic structure portion and an outerly branched annular structure portion is a substance also called a highly branched cyclic dextrin or a cluster dextrin.
The highly branched cyclic dextrin has a structure in which a plurality of (for example, 100) acyclic glucose chains (outer branched structural portions) are bound to one inner branched cyclic structure portion.
The internally branched cyclic structure portion refers to a cyclic structure portion formed by an α-1,4-glucoside bond and an α-1,6-glucoside bond. The inner branched cyclic structure portion of the highly branched cyclic dextrin is composed of about 10 to 100 glucoses. That is, the degree of polymerization of the internally branched cyclic structure portion is in the range of 10 to 100.
The outer branch structure portion means a non-annular structure portion connected to the inner branch annular structure portion. The average degree of polymerization of the acyclic glucose chain constituting the outer branched structural portion of the highly branched cyclic dextrin is 10 to 20. However, the degree of polymerization in one acyclic glucose chain may be 40 or more.
The weight average degree of polymerization of glucose in highly branched cyclic dextrin is in the range of 50 to 10000, specifically in the range of 50 to 5000, and more specifically to about 2500.
The molecular weight of the highly branched cyclic dextrin in the present invention is in the range of about 30,000 to 1,000,000.

Highly branched cyclic dextrins having such a structure and a degree of polymerization (molecular weight) are α-cyclodextrin (degree of polymerization 6) and β-cyclodextrin (degree of polymerization 7), which are general cyclodextrins having a glucose polymerization degree of 6 to 8. ) And γ-cyclodextrin (degree of polymerization 8).

The highly branched cyclic dextrin can be produced, for example, from starch as a raw material by the action of an enzyme called blanching enzyme.
Starch, which is a raw material, consists of amylose in which glucose is linearly bound by an α-1,4-glucoside bond and amylopectin having a complex branched structure by an α-1,6-glucoside bond. Amylopectin is a macromolecule in which a large number of cluster structures are linked.
The enzyme used, blanching enzyme, is a glucan chain transferase that is widely found in animals, plants and microorganisms. The blanching enzyme acts on the seams of the amylopectin cluster structure and catalyzes the reaction that cyclizes it.

Specific examples of the highly branched cyclic dextrin include glucan having an inner branched cyclic structure portion and an outer branched structural portion and having a degree of polymerization in the range of 50 to 10000, which is described in JP-A-8-134104. In the present invention, the highly branched cyclic dextrin can be understood with reference to the description in JP-A-8-134104.

The component (F) can be produced as described above and is easily available on the market. Examples of commercially available products of highly branched cyclic dextrin include "cluster dextrin" (registered trademark) of Glico Foods Co., Ltd.

A single type of the component (F) may be used, or a plurality of types may be used in combination.

The content of the component (F) is not particularly limited as long as the compounding purpose can be achieved, but is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total mass of the liquid softener composition. , More preferably 0.1 to 2% by mass. When the content is 0.01% by mass or more, the compounding effect (particularly, the effect of imparting deodorant property and deodorant property to the fiber) can be sufficiently exhibited. When the content is 10% by mass or less, it is possible to suppress an increase in the viscosity of the liquid softener composition and maintain good usability such as discharge from the container and ease of putting into the inlet of the washing machine. can.

[(G) component: preservative]
The component (G) is mainly blended to maintain antiseptic properties during long-term storage.
Specific examples of the component (G) include isothiazolone-based organic sulfur compounds, benzisothiazolin-based organic sulfur compounds, benzoic acids, 2-bromo-2-nitropropane-1,3-diol and the like.
Examples of isothiazolin-based organic sulfur compounds include 5-chloro-2-methyl-4-isothiazolin-3-one, 2-n-butyl-3-isothiazolinone, 2-benzyl-3-isothiazolinone, and 2-phenyl-3. Included are -isothiazolinone, 2-methyl-4,5-dichloroisothiazolinone, 5-chloro-2-methyl-3-isothiazolinone, 2-methyl-4-isothiazolin-3-one, and mixtures thereof. Preferably, it is a water-soluble mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, more preferably about 77% 5-chloro-2. A water-soluble mixture of −methyl-4-isothiazolin-3-one and about 23% 2-methyl-4-isothiazolin-3-one (eg, isothiazolinone solution).
Examples of benzisothiazolin-based organic sulfur compounds include 1,2-benzisothiazolin-3-one, 2-methyl-4,5-trimethylen-4-isothiazolin-3-one, and dithio- as related compounds. 2,2-Bis (benzmethylamide) and the like can also be used. These compounds can be used in any mixing ratio. Of these, 1,2-benzisothiazolin-3-one is particularly preferable.
Examples of benzoic acids include benzoic acid or a salt thereof, parahydroxybenzoic acid or a salt thereof, methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, butyl paraoxybenzoate, benzyl paraoxybenzoate and the like. can.

The component (G) is a known substance and is easily available on the market or can be prepared.

A single type of the component (G) may be used, or a plurality of types may be used in combination.

The content of the component (G) is not particularly limited as long as the compounding purpose can be achieved, but is preferably 0.0001 to 1% by mass with respect to the total mass of the liquid softener composition.

[(H) component: functional capsule]
The component (H) is blended to impart various functions due to the core substance encapsulated in the capsule to the liquid softener composition.
The functional capsule is composed of a core substance and a wall substance covering the core substance.

As the core substance, a substance generally used as a capsule encapsulating substance in the field of liquid softener can be used without particular limitation. Specific examples include fragrances, essential oils, bleaches, insect repellents, silicones, waxes, flavors, vitamins, skin care agents, enzymes, probiotics, dyes, pigments, fragrance precursors, cooling agents, warming agents, etc. Examples include attractants such as pheromones, antibacterial agents, bleaches, flavors, sweeteners, waxes, chemicals, fertilizers, herbicides and the like.
As the core substance, one type may be used alone, or two or more types may be appropriately combined.

As the wall material, a material generally used as an encapsulation material in the field of liquid softener composition can be used without particular limitation. Specific examples include natural polymers such as gelatin and agar, oil-based film-forming substances such as oils and waxes, and synthetic polymers such as polyacrylic acid, polyvinyl, polymethacrylic acid, melamine, and urethane. Substances and the like can be mentioned, and one of them can be used alone or two or more of them can be used in combination as appropriate.

Specific examples of encapsulated fragrances containing a fragrance as a core material include BLUEFLOWERPOP "FFMHN2814" manufactured by Firmenich, GREEN BREEZE CAPS, GREENBREEZE DeoB, ORCHARD GARDEN CAPS, RAINBOVECAPS, RAINBOVECAPS, RAINBLOW CAPS, And COSMICCAPS, UNICAP101 and UNICAP503 manufactured by IFF, and the like.
Specific examples of the cooling sensation capsule containing a cooling sensation agent as a core substance include MultiSal SalCol, HydroSal FreshCool, SalShere SalCol manufactured by SALVONA Technologies, and Neoage AROMA-C manufactured by Nicca Chemical Co., Ltd.
Specific examples of the warming capsule containing a warming agent as a core substance include Riken Resin RMC-TO manufactured by Miki Riken Co., Ltd., Hydrosal Heat manufactured by SALVONA Technologies, and the like.
Other specific examples include Riken Resin NFHO-W (antibacterial effect), Riken Resin RMC-HBP (insect repellent effect) and RMC-PT (insect repellent effect) manufactured by Miki Riken Co., Ltd.

The average particle size of the functional capsule is preferably 10 μm to 30 μm. The functional capsule having the particle size has excellent adsorptivity to clothing and can be stably dispersed in the liquid softener composition.

The component (H) is a known substance and is easily available on the market or can be prepared.

A single type of the component (H) may be used, or a plurality of types may be used in combination.

The content of the component (H) is not particularly limited as long as the compounding purpose can be achieved, but is preferably 0.0001 to 1% by mass with respect to the total mass of the liquid softener composition.

〔water〕
The liquid softener composition is preferably an aqueous composition containing water.
As the water, tap water, ion-exchanged water, pure water, distilled water and the like can be used. Of these, ion-exchanged water is preferable.
The content of water is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, based on the total mass of the liquid softener composition. When the content is 50% by mass or more, the handleability becomes better.

[PH of liquid softener composition]
The pH of the liquid softener composition is not particularly limited, but the pH at 25 ° C. is set in the range of 1 to 6 from the viewpoint of suppressing the hydrolysis of the ester group contained in the molecule of the component (A) with the aging of storage. It is preferable to adjust it, and it is more preferable to adjust it in the range of 2 to 4. Any inorganic or organic acid and alkali can be used as the pH regulator.

[Viscosity of liquid softener composition]
The viscosity of the liquid softener composition is not particularly limited as long as its usability is not impaired, but the viscosity at 25 ° C. is preferably less than 800 mPa · s. Considering the increase in viscosity due to storage aging, the viscosity of the liquid softener composition immediately after production at 25 ° C. is more preferably less than 500 mPa · s, and even more preferably less than 300 mPa · s. Within such a range, usability such as handleability at the time of putting into the washing machine is good.
The viscosity of the liquid softener composition can be measured using a B-type viscometer (manufactured by TOKIMEC).

〔Production method〕
The liquid softener composition can be produced by a known method, for example, the same method as the conventional method for producing a liquid softener composition using a cationic surfactant as a main agent.
For example, an oil phase containing a component (A), a component (D), and a component (E) and an aqueous phase containing a component (G) are mixed under a temperature condition equal to or higher than the melting point of the component (A) to form an emulsion. After that, the component (B), the component (C), and other components, if necessary, are added to and mixed with the obtained emulsion.
The component (B), the component (C), and the component (D) are not limited to the above-mentioned addition method.

[How to use liquid softener composition]
The method for treating the textile product using the liquid softener composition is not particularly limited, and can be used in the same manner as the conventional liquid softener. For example, in the rinsing stage of washing, the liquid softener composition is dissolved in rinsing water for treatment, or the liquid softener composition is dissolved in water in a container such as a tub, and a textile product is further added and immersed. There is a way to handle it. In each case, the solution is diluted to an appropriate concentration before use, but the bath ratio (weight ratio of the treatment liquid to the textile product) is preferably 3 to 100 times, particularly 5 to 50 times. Specifically, 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.
The type of textile product that can be treated with the liquid softener composition is not particularly limited, and examples thereof include clothing, curtains, sofas, carpets, towels, handkerchiefs, sheets, pillow covers and the like. The material may be a natural fiber such as cotton, silk or wool, or a chemical fiber such as polyester.

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

[Component (A): Cationic surfactant]
The following A-1 was used.

A-1: The cationic surfactant described in Example (Synthesis Example 1) of JP-A-2019-163559. 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.

[Component (B): divalent water-soluble metal salt]
The following B-1 was used.

B-1: Zinc sulfate (Supplier: Mitsui Mining & Smelting Co., Ltd. Product name: Zinc sulfate heptahydrate)

[Component (C): aminocarboxylic acid compound and ricinoleic acid]
The following C-1 to C-3 were used.

C-1: Methylglycin diacetate trisodium "MGDA" (manufactured by BASF)
C-1 is in the general formula (I), sodium A ^I is CH _3, M ^I is, m ^I is 0, n ^I is a compound which is 0.

C-2: Ricinoleic acid (Supplier: Tokyo Chemical Industry Co., Ltd. Product name: Ricinoleic acid)

C-3: Citric acid (Supplier: Lion Corporation. Product name: Citric acid)
C-3 did not correspond to either the aminocarboxylic acid compound or ricinoleic acid, and was used in the comparative example.

[Component (D): Nonionic surfactant]
The following D-1 was used.

D-1: 60 mol of polyoxyethylene isotridecyl ether EO (corresponding to an average 60 mol adduct of primary isotridecyl alcohol (C13)) (Supplier: Lion Corporation, trade name: TA600)

[(E) component: unencapsulated fragrance]
Free fragrance compositions E-1 to E-2 having the compositions shown in the table below were used. The value of the fragrance component in the table is the content (mass%) with respect to the total mass of the fragrance composition.

E-1

E-2

[(F) component: highly branched cyclic dextrin]
The following F-1 was used.

F-1: Highly branched cyclic dextrin (manufactured by Glico Foods Co., Ltd., trade name: cluster dextrin)

[(G) component: preservative]
The following G-1 was used.

G-1: Isothiazolone solution (Dow Chemical Japan Co., Ltd. Product name: Caisson CG-ICP)

[(H) component: functional capsule]
The following H-1 to H-2 were used.

H-1: Encapsulated fragrance (Supplier: Givaudan Co., Ltd. Product name: GREENBREEZE DeoB)

H-2: Encapsulated fragrance (Supplier: Givaudan Co., Ltd. Product name: VELVET UP)

[Method for preparing liquid softener composition]
A liquid softener composition having the composition shown in Table 1 below was prepared. In Table 1, the numerical unit of each component is mass% with respect to the total mass of the liquid softener composition.
“(B + C) / A” in Table 1 indicates the mass ratio of the total (B + C) of the component (B) and the component (C) to the component (A).
“(B + C) / D” indicates the mass ratio of the total (B + C) of the component (B) and the component (C) to the component (D).

The liquid softener composition was prepared by the following procedure using a glass container (inner diameter 100 mm, height 150 mm) and a stirrer (Agitator SJ type, manufactured by Shimadzu Corporation).
First, a component (A), a part of the component (D), and the component (E) were mixed and stirred to obtain an oil phase mixture.
On the other hand, the component (G) was dissolved in ion-exchanged water for balance to obtain an aqueous phase mixture. The mass of the ion-exchanged water for balance is the total amount of the oil phase mixture, the component (B), the component (C), the balance of the component (D), the component (F), and the component (H) from 980 g. It corresponded to the deducted balance.
Next, while storing the oil phase mixture heated above the melting point of the component (A) in a glass container and stirring, the aqueous phase mixture heated above the melting point of the component (A) is added in two portions. , Stirred. The division ratio of the aqueous phase mixture was 30:70 (mass ratio), and the stirring was performed at a rotation speed of 1,000 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.
After that, the component (B), the component (C), the rest of the component (D), the component (F), and the component (H) are added, and if necessary, hydrochloric acid (reagent 1 mol / L, Kanto Chemical Co., Ltd.) or sodium hydroxide (reagent 1 mol / L, Kanto Chemical Co., Inc.) was added in an appropriate amount to adjust the pH to 3.0 (25 ° C.), and ion-exchanged water was added so that the total mass was 1,000 g. , The desired liquid softener composition was obtained.

[Evaluation of liquid softener composition]
The "deodorant effect", "usability" and "freeze stability" of the prepared liquid softener composition were evaluated.

[Suppression (deodorant) effect of room drying odor]
Used towels, which are worrisome of dry odor, were collected from ordinary households and used as evaluation cloth.
The evaluation cloth was treated with a liquid softener composition, dehydrated, and then dried indoors (25 ° C., relative humidity 100% RH) for 6 hours (room drying). Evaluation after drying the room The odor of the cloth was sensory evaluated according to the following evaluation criteria. The evaluation was carried out by 6 specialized panelists.
<Evaluation criteria>
0 points: No offensive odor.
1 point: The offensive odor is barely perceptible.
2 points: The offensive odor is felt weak.
3 points: A strange odor is felt a little strongly.
4 points: A strong offensive odor is felt.
5 points: A strong offensive odor is felt.

The deodorant effect of the liquid softener composition was judged according to the following criteria based on the average score of 6 specialized panelists (calculated to the first decimal place). The results are shown in the "Deodorant effect" column of Table 1. ○ or ◎ was judged to be acceptable in terms of commercial value.

<Criteria>
⊚: less than 2.0 points ○: 2.0 points or more and less than 2.5 points Δ: 2.5 points or more and less than 3.0 points ×: 3.0 points or more

[Usability]
400 mL of the liquid softener composition was filled in a container of a commercially available fiber treatment agent (a container of "Soflan Premium Deodorant" manufactured by Lion Corporation). The usability of the liquid softener composition after filling was evaluated according to the following evaluation criteria from the viewpoints of "easiness of pouring when measuring viscosity increase or measuring cap" and "easiness of refilling from pouch to bottle". .. The evaluation was carried out by five specialized panelists.

<Evaluation criteria>
3 points: Can be weighed without problems and can be refilled.
2 points: Although the viscosity increases, it can be weighed and refilled without any problem.
1 point: Significant increase in viscosity is observed, and it is difficult or impossible to measure, or it is difficult to refill or cannot be refilled.

The usability of the liquid softener composition was judged according to the following criteria based on the average score (calculated to the first decimal place) of five specialized panelists. The results are shown in the "Usability" column of Table 1. ○ or ◎ was judged to be acceptable in terms of commercial value.

<Criteria>
⊚: 2.5 points or more 〇: 2.0 points or more and less than 2.5 points Δ: 1.5 points or more and less than 2.0 points ×: less than 1.5 points

[Freeze stability]
80 mL of the liquid softener composition was placed in a lightweight glass bottle (PS-No. 11, manufactured by Tanuma Glass Industry Co., Ltd.) and sealed tightly, and used as an evaluation sample.
The evaluation sample was subjected to a durability test in which a cycle of holding (freezing) at −15 ° C. for 40 hours and then holding (melting) at 25 ° C. for 8 hours was repeated three times.
The liquid state of the evaluation sample after the durability test at 25 ° C. was visually observed and evaluated according to the following evaluation criteria. The evaluation was carried out by eight specialized panelists.

<Evaluation criteria>
5: Sufficient fluidity and almost no change compared to before the durability test.
4: Increase in viscosity is observed compared to before the durability test, but the fluidity is sufficient.
3: Increase in viscosity is observed compared to before the durability test, but fluidity is observed.
2: Viscosity increases compared to before the durability test, and there is not much fluidity.
1: Viscosity increases remarkably compared to before the durability test, and there is almost no fluidity.
0: Viscosity is significantly increased compared to before the durability test, and there is no fluidity at all.

The freeze-restorability of the liquid softener composition was determined by the average score of eight specialized panelists (calculated to the first decimal place) according to the following criteria. The results are shown in the "Freeze Stability" column of Table 1. ○ or ◎ was judged to be acceptable in terms of commercial value.

<Criteria>
⊚: 4.0 points or more ○: 3.0 points or more to less than 4.0 points Δ: 2.0 points or more to less than 3.0 points ×: less than 2.0 points

The present invention is available in the field of softeners.

Claims (6)

A liquid softener composition, wherein the following components (A) to (D):
(A) From the group consisting of an amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms in the molecule, a salt thereof, and a quaternary compound thereof, which may be separated by an ester group and / or an amide group. Compound of choice,
(B) Water-soluble salt of divalent metal,
Compounds selected from the group consisting of aminocarboxylic acid compounds represented by formulas (I) to (IV), ricinoleic acid and salts thereof, (C).

(During the ceremony,
A ^I is a linear or branched alkyl group having 8 to 22 carbon atoms, a sulfo group, an amino group, a hydroxyl group, a hydrogen atom or a COOM ^I,
M ^I may be the same or different from each other, a hydrogen atom, an alkali metal, alkaline earth metal, a cationic ammonium group, and selected from the group consisting of alkanolamine,
m ^I and n ^I are integers of 0 to 2, respectively. )

(During the ceremony,
X ^{II-1 to} X ^II-4 may be the same or different and are selected from the group consisting of hydrogen atoms, alkali metals, alkaline earth metals, cationic ammonium groups, and alkanolamines.
Q ^II is a hydrogen atom or a linear or branched alkyl group having 8 to 22 carbon atoms.
R ^II is a hydrogen atom or a hydroxyl group,
n ^II is 0 or 1. )

(During the ceremony,
R ^III is a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms.
A ^III is an H, methyl group or (CH ₂ ) m ^III- COOX ^III .
m ^III is 1-3
X ^III is H, alkali metal, alkaline earth metal, alkanolamine or NH ₄ .
n ^III is 1-3. )

(During the ceremony,
X ^IV is a hydrogen atom, alkali metal or alkaline earth metal,
n ^IV is 1 or 2. ), And (D) nonionic surfactant,
The mass ratio ([B + C] / A) of the total of the components (B) and (C) to the component (A) is 0.01 to 0.5, and the total of the components (B) and (C) (D) A liquid softener composition, wherein the mass ratio ([B + C] / D) to the component is 0.1 to 4. The liquid softener composition according to claim 1, wherein the component (B) is a water-soluble zinc salt or a water-soluble copper salt. The liquid softener composition according to claim 1 or 2, wherein the component (C) is a compound represented by the formula (I) or a salt thereof, or ricinoleic acid or a salt thereof. The method according to any one of claims 1 to 3, wherein the mass ratio ([B + C] / A) of the total of the component (B) and the component (C) to the component (A) is 0.25 to 0.45. Liquid softener composition. The liquid softener composition according to any one of claims 1 to 4, wherein the mass ratio ([B + C] / D) of the total of the component (B) and the component (C) to the component (D) is 1 to 2. thing. The invention according to any one of claims 1 to 5, wherein the component (D) is a polyoxyethylene alkyl ether having an alkyl group having 10 to 18 carbon atoms and having an average addition mole number of ethylene oxide of 20 to 80 moles. Liquid softener composition.