JP2021179070A - Liquid softener composition - Google Patents

Abstract

To provide a liquid softener that contains a softening base and a flavor in high concentrations and resists an increase in viscosity.SOLUTION: A liquid softener composition contains (A) at least one compound selected from the group consisting of an amine compound intramolecularly having one to three C10-26 hydrocarbon groups, divided by an ester group and/or an amide group, a salt thereof and a quaternarized product thereof; (B) a quaternary ammonium salt represented by general formula (B1) (where R1 is a C16-26 saturated or unsaturated hydrocarbon group, optionally divided by an ester group and/or an amide group, R2 and R3 independently represent a C1-3 alkyl, X is an anion group); and (C) a flavor. The content of components (A) (B), and (C) are set, respectively, at 15-30 mass%, 1.0-3.0 mass%, and 1.0-5.0 mass% relative to the total mass of the liquid softener composition, and furthermore, the mass ratio between the components (A) and (B), (A/B), is set at 6-30.SELECTED DRAWING: None

Description

The present invention relates to a concentrated type liquid softener composition.

Reducing the mass of the liquid softener by enrichment has advantages such as improvement of consumer convenience and reduction of environmental load by reducing the amount of plastic container material used.
As a technique for concentrating a liquid softener, it is known to blend a softening base at a high concentration (Patent Documents 1 to 7).
In the field of liquid softeners, technology for blending quaternary ammonium salts for the purpose of improving freeze restoration, improving dispersibility of encapsulated fragrances, suppressing solid deposits due to exposure to sunlight, and maintaining a transparent appearance. Is known (Patent Documents 1, 2, 4, 5 and 7).

JP-A-2015-4145 Japanese Unexamined Patent Publication No. 2015-34371 Japanese Unexamined Patent Publication No. 2014-15687 Japanese Unexamined Patent Publication No. 2013-133547 Japanese Unexamined Patent Publication No. 2014-125692 Japanese Unexamined Patent Publication No. 2016-216864 JP-A-2019-94581

In order to develop a concentrated liquid softener with "fragrance", which is one of the important performances of softeners, a thickening phenomenon (a phenomenon in which the viscosity increases) when a softening base and a fragrance are mixed at a high concentration. The present inventor has found for the first time that this occurs. The thickened concentrated liquid softener has problems as a commercial product, such as a handling property at the time of charging into a washing machine and a decrease in efficiency of discharging from the loading port of the washing machine.

As a result of diligent studies on the above-mentioned problems, the present inventor found that when a quaternary ammonium salt having a specific carbon chain length was blended in a specific amount, the softening base and the fragrance were both thickened even in the presence of high concentrations. It was found that it can suppress. The present invention has been made based on this finding.

（式中、Ｒ¹は、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１６〜２６の飽和又は不飽和の炭化水素基であり、Ｒ²及びＲ³は独立して炭素数１〜３のアルキルであり、Ｘは陰イオン基である。）；及び
（Ｃ）香料を含み、
（Ａ）成分の含量が、液体柔軟剤組成物の総質量に対し１５〜３０質量％であり、
（Ｂ）成分の含量が、液体柔軟剤組成物の総質量に対し１．０〜３．０質量％であり、
（Ｃ）成分の含量が、液体柔軟剤組成物の総質量に対し１．０〜５．０質量％であり、
（Ａ）成分と（Ｂ）成分との質量比（Ａ／Ｂ）が６〜３０であり、
液体柔軟剤組成物が乳濁型であることを特徴とする、液体柔軟剤組成物。
〔２〕（Ｂ）成分が、オクタデシルトリメチルアンモニウムクロライド、ヘキサデシルトリメチルアンモニウムクロライド、オクタデシルトリメチルアンモニウムブロマイド及びヘキサデシルトリメチルアンモニウムブロマイドからなる群より選ばれる、前記〔１〕に記載の液体柔軟剤組成物。
〔３〕（Ａ）成分の含量が、液体柔軟剤組成物の総質量に対し１８〜２５質量％である、前記〔１〕又は〔２〕に記載の液体柔軟剤組成物。
〔４〕（Ｂ）成分の含量が、液体柔軟剤組成物の総質量に対し１．０〜２．０質量％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〕（Ｃ）成分の含量が、液体柔軟剤組成物の総質量に対し１．５〜２．５質量％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〕（Ａ）成分と（Ｂ）成分との質量比（Ａ／Ｂ）が１０〜２０である、前記〔１〕〜〔５〕のいずれか１項に記載の液体柔軟剤組成物。
〔７〕（Ａ）成分と（Ｃ）成分との質量比（Ａ／Ｃ）が５〜３０である、前記〔１〕〜〔６〕のいずれか１項に記載の液体柔軟剤組成物。 That is, the present invention relates to the following [1] to [7].
[1] A liquid softener composition comprising the following components (A) to (C):
(A) Amine compounds having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms in the molecule, which are separated by an ester group (-COO-) and / or an amide group (-NHCO-), salts thereof, and salts thereof. At least one compound selected from the group consisting of the quaternary compounds;
(B) Quaternary ammonium salt represented by the general formula (B1):

(In the formula, R ¹ is a saturated or unsaturated hydrocarbon group having 16 to 26 carbon atoms, which may be partitioned by an ester group (-COO-) and / or an amide group (-NHCO-). R ² and R ³ are independently alkyls with 1-3 carbon atoms and X is an anion group.); And (C) Containing fragrances.
The content of the component (A) is 15 to 30% by mass with respect to the total mass of the liquid softener composition.
The content of the component (B) is 1.0 to 3.0% by mass with respect to the total mass of the liquid softener composition.
The content of the component (C) is 1.0 to 5.0% by mass with respect to the total mass of the liquid softener composition.
The mass ratio (A / B) of the component (A) to the component (B) is 6 to 30, and the mass ratio is 6 to 30.
A liquid softener composition, characterized in that the liquid softener composition is an emulsion type.
[2] The liquid softener composition according to the above [1], wherein the component (B) is selected from the group consisting of octadecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide and hexadecyltrimethylammonium bromide.
[3] The liquid softener composition according to the above [1] or [2], wherein the content of the component (A) is 18 to 25% by mass with respect to the total mass of the liquid softener composition.
[4] The liquid according to any one of [1] to [3] above, wherein the content of the component (B) is 1.0 to 2.0% by mass with respect to the total mass of the liquid softener composition. Softener composition.
[5] The liquid according to any one of [1] to [4] above, wherein the content of the component (C) is 1.5 to 2.5% by mass with respect to the total mass of the liquid softener composition. Softener composition.
[6] The liquid softener composition according to any one of [1] to [5] above, wherein the mass ratio (A / B) of the component (A) to the component (B) is 10 to 20.
[7] The liquid softener composition according to any one of [1] to [6] above, wherein the mass ratio (A / C) of the component (A) to the component (C) is 5 to 30.

As shown in the examples below, according to the present invention, a concentrated liquid softener containing a softening base and a fragrance in a high concentration but having suppressed thickening can be obtained. The concentrated liquid softener with suppressed thickening has a viscosity that improves its usability (particularly, handleability at the time of loading into the washing machine and efficiency of discharging from the loading port of the washing machine). .. Therefore, the present invention can provide a concentrated liquid softener having added value not found in conventional products.

[Component (A): Cationic surfactant]
The component (A) is an amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms in the molecule, which are separated by an ester group (-COO-) and / or an amide group (-NHCO-). It is a cationic surfactant which is "at least one compound selected from the group consisting of the salt and the quaternary compound thereof".
The component (A) is a flexible base material, and is blended to impart the effect of imparting flexibility (texture) to the textile product to the liquid softener composition.

The hydrocarbon group having 10 to 26 carbon atoms (hereinafter, also referred to as “long-chain hydrocarbon group”) preferably has 17 to 26 carbon atoms, and more preferably 18 to 24 carbon atoms. When the number of carbon atoms is 10 or more, the softening effect is good, and when it is 26 or less, the handling property of the liquid softener composition is good.
The long-chain hydrocarbon group may be saturated or unsaturated. 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 containing a ring in the structure, and is preferably a chain hydrocarbon group. The chain hydrocarbon group may be either linear or branched. As the chain hydrocarbon group, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable.
The long-chain hydrocarbon group is fragmented by a fragmenting group. The division may be at one place or at two or more places. It is preferably one place.
The fusing group is an ester group (-COO-) or an amide group (-NHCO-). When the long-chain hydrocarbon group has two or more dividing groups, each dividing group may be the same or different.
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.
"An amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms in the molecule, which is separated by an ester group (-COO-) or an amide group (-NHCO-) (hereinafter," in the present specification ". The number of long-chain hydrocarbon groups in "amine compounds") is 1 to 3. It is preferably 2 (secondary amine compound) or 3 (tertiary amine compound), and more preferably 3 pieces.

（式中、Ｒ¹〜Ｒ³はそれぞれ独立に、−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、−ＣＨ₂ＣＨ（Ｙ）ＯＣＯＲ⁴及び／又は−（ＣＨ₂）_nＮＨＣＯＲ⁵である。）
一般式（Ａ１）における基「−ＣＨ₂ＣＨ（Ｙ）ＯＣＯＲ⁴」中、Ｙとしては水素原子が好ましい。
Ｒ⁴としては、炭素数１５〜１９の炭化水素基が好ましい。一般式（Ａ１）で表される化合物中にＲ⁴が複数存在するとき、該複数のＲ⁴は互いに同一であってもよく、それぞれ異なっていても構わない。
Ｒ⁴の炭化水素基は、炭素数８〜２２の脂肪酸（Ｒ⁴ＣＯＯＨ）からカルボキシ基を除いた残基（脂肪酸残基）であり、Ｒ⁴のもととなる脂肪酸（Ｒ⁴ＣＯＯＨ）は、飽和脂肪酸でも不飽和脂肪酸でもよく、また、直鎖脂肪酸でも分岐脂肪酸でもよい。なかでも、飽和又は不飽和の直鎖脂肪酸が好ましい。柔軟処理した衣類に良好な吸水性を付与するために、Ｒ⁴のもととなる脂肪酸の飽和／不飽和比率（質量比）は、９０／１０〜０／１００が好ましく、９０／１０〜４０／６０より好ましく、９０／１０〜７０／３０が特に好ましい。
Ｒ⁴が不飽和脂肪酸残基である場合、シス体とトランス体が存在するが、シス体／トランス体の質量比率は、４０／６０〜１００／０が好ましく、７０／３０〜９０／１０が特に好ましい。
Ｒ⁴の素となる脂肪酸として具体的には、ステアリン酸、パルミチン酸、ミリスチン酸、ラウリン酸、オレイン酸、エライジン酸、リノール酸、部分水添パーム油脂肪酸（ヨウ素価１０〜６０）や、部分水添牛脂脂肪酸（ヨウ素価１０〜６０）などが挙げられる。
中でも、ステアリン酸、パルミチン酸、ミリスチン酸、オレイン酸、エライジン酸、およびリノール酸から選ばれる２種以上を所定量ずつ組み合わせて、以下の条件（ａ）〜（ｃ）を満たすように調整した脂肪酸組成物を用いることが好ましい。
（ａ）飽和脂肪酸／不飽和脂肪酸の比率（質量比）が９０／１０〜０／１００、より好ましくは９０／１０〜４０／６０、特に好ましくは９０／１０〜７０／３０である。
（ｂ）シス体／トランス体の比率（質量比）が４０／６０〜１００／０、より好ましくは７０／３０〜９０／１０である。
（ｃ）炭素数１８の脂肪酸が６０質量％以上、好ましくは８０質量％以上であり、炭素数２０の脂肪酸が２質量％未満であり、炭素数２１〜２２の脂肪酸が１質量％未満である。
一般式（Ａ１）における、基「−（ＣＨ₂）_nＮＨＣＯＲ⁵」中、ｎとしては３が好ましい。
Ｒ⁵としては、炭素数１５〜１９の炭化水素基が好ましい。一般式（Ａ１）で表される化合物中にＲ⁵が複数存在するとき、該複数のＲ⁵は互いに同一であってもよく、それぞれ異なっていても構わない。
Ｒ⁵としては、Ｒ⁴と同様のものが具体的に挙げられる。 Examples of the amine compound include compounds represented by the following general formula (A1).

(In the formula, R ^{1 to} R ³ are independently −CH ₂ CH (Y) OCOR ⁴ (Y is a hydrogen atom or CH ₃ and R ⁴ is a hydrocarbon group having 7 to 21 carbon atoms), -(CH ₂ ) _n NHCOR ⁵ (n is 2 or 3, R ⁵ is a hydrocarbon group with 7 to 21 carbon atoms), hydrogen atom, alkyl group with 1 to 4 carbon atoms, -CH ₂ CH (CH 2) 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 −CH 2} CH (Y) OCOR ⁴ and / or − (CH ₂ ) _n NHCOR ⁵ . )
_{In the group "-CH 2} CH (Y) OCOR ⁴ " in the general formula (A1), a hydrogen atom is preferable as Y.
As R ⁴ , a hydrocarbon group having 15 to 19 carbon atoms is preferable. 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 90/10 to 40, in order to impart good water absorption to the soft-treated clothing. It is more preferable than / 60, and 90/10 to 70/30 is particularly preferable.
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 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 90/10 to 40/60, and particularly preferably 90/10 to 70/30.
(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), 3 is preferable as n.
As R ⁵ , a hydrocarbon group having 15 to 19 carbon atoms is preferable. When the compound represented by the general formula (A1) R ⁵ there are a plurality, may be R ⁵ of said plurality of mutually identical, may be different.
Specific examples of R ⁵ are the same as those of ^{R 4.}

In the general formula (A1), at least one of ^{R 1 to} R ³ _{is −CH 2} CH (Y) OCOR ⁴ and / or − (CH ₂ ) _n NHCOR ⁵ ). It is preferable that two of R ^{1 to} R ³ _{are −CH 2} CH (Y) OCOR ⁴ and / or − (CH ₂ ) _n NHCOR ^5).
If one or two of ^{R 1 to} R ³ _{are −CH 2} CH (Y) OCOR ⁴ and / or − (CH ₂ ) _n NHCOR ⁵ ), the remaining two or one are hydrogen atoms. An alkyl group having 1 to 4 carbon atoms, −CH ₂ CH (Y) OH (Y is a hydrogen atom or CH ₃ ), or − (CH ₂ ) _n NH ₂ (n is 2 or 3). , Alkyl group having 1 to 4 carbon atoms, −CH ₂ CH (Y) OH, or − (CH ₂ ) _n NH ₂ . Here, as the alkyl group having 1 to 4 carbon atoms, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable. Y in −CH ₂ CH (Y) OH is the same as Y in −CH ₂ CH (Y) OCOR ⁴ . − (CH ₂ ) _{n n in} NH ₂ is similar to _{n in} − (CH ₂ ) n NHCOR ^5.

（（Ａ１−１）〜（Ａ１−７）の各式中、Ｒ⁹はそれぞれ独立に、炭素数７〜２１の炭化水素基であり、（Ａ１−６）〜（Ａ１−７）の各式中、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 tertiary amine compounds represented by the following general formulas (A1-1) to (A1-7).

(In each of the formulas (A1-1) to (A1-7), R ⁹ is a hydrocarbon group having 7 to 21 carbon atoms independently, and each formula of (A1-6) to (A1-7). Middle and R ¹⁰ are each independently a hydrocarbon group having 7 to 21 carbon atoms.)

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), and the hydrocarbon group having 7 to 21 carbon atoms is preferable. 15 to 17 alkyl and alkenyl groups. Note that when in the general formula R ⁹ there are a plurality, 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.
The salt of the amine compound is obtained by neutralizing the amine compound with an acid. The acid used for neutralization may be an organic acid or an inorganic acid, and examples thereof include hydrochloric acid, sulfuric acid, and methyl sulfuric acid. Neutralization of the amine compound can be carried out by a known method.
The quaternizing product of the amine compound is obtained by reacting the amine compound with a quaternizing agent. Examples of the quaternizing agent 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.

As the compounds represented by the general formulas (A1) and (A1-1) to (A1-7), salts thereof and quaternized products thereof, commercially available ones may be used, and those produced by a known method are used. You may.
For example, a compound represented by the general formula (A1-1) (hereinafter referred to as “compound (A1-1)”) and a compound represented by the general formula (A1-2) (hereinafter referred to as “compound (A1-2)”). ), the fatty acid composition described in the column of R ⁴ in the general formula (1), or a fatty acid methyl ester composition obtained by replacing the methyl ester of the fatty acids fatty acids in the fatty acid composition, by condensation reaction with methyldiethanolamine Can be synthesized. At that time, from the viewpoint of improving the flexibility imparting, the abundance ratio represented by "compound (A1-1) / compound (A1-2)" shall be 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 "quaternized compound (A1-1) / quaternized compound (A1-2)" is 99/1 to 50/50 in terms of mass ratio. It is preferable to synthesize so as to be.

Compounds represented by the general formula (A1-3) (hereinafter referred to as "compound (A1-3)"), compounds represented by the general formula (A1-4) (hereinafter referred to as "compound (A1-4)") and The compound represented by the general formula (A1-5) (hereinafter referred to as “compound (A1-5)”) is a fatty acid composition or a fatty acid methyl ester composition described in the column ^{of R 4 of the general formula (1).} It can be synthesized by a condensation reaction with ethanolamine. At that time, the content ratio of each component to the total mass of the compounds (A1-3), (A1-4) and (A1-5) is 1 to 60 for the compound (A1-3) from the viewpoint of imparting flexibility. It is preferable that the content is% by mass, 5 to 98% by mass of the compound (A1-4), 0.1 to 40% by mass of the compound (A1-5), and 30 to 60% by mass of the compound (A1-3). It is more preferable that (A1-4) is 10 to 55% by mass and the compound (A1-5) 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 quaternized product of the compound (A1-3), (A1-4), and (A1-5) is a mass ratio from the viewpoint of imparting flexibility, and the quaternized product of the compound (A1-3) is 1. It is preferable that the content is ~ 60% by mass, the quaternized product of the compound (A1-4) is 5 to 98% by mass, and the quaternized product of the compound (A1-5) is 0.1 to 40% by mass, preferably the compound (A1-). The quaternized product of 3) is 30 to 60% by mass, the quaternized product of the compound (A1-4) is 10 to 55% by mass, and the quaternized product of the compound (A1-5) is 5 to 35% by mass. More preferred.
When the compounds (A1-3), (A1-4), and (A1-5) 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 (A1-6) (hereinafter referred to as "compound (A1-6)") and the compound represented by the general formula (A1-7) (hereinafter referred to as "compound (A1-7)") are , a fatty acid composition as described in the column of R ⁴ in the general formula (1), from the adduct of N- methylethanolamine with 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 (A1-6) / compound (A1-7)" 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 (A1-6) / quaternized product of compound (A1-7)". It is preferable to synthesize the compound so that the abundance ratio is 99/1 to 50/50 in terms of mass ratio.

(A) As a component,
At least one selected from the group consisting of the compound represented by the general formula (A1), a salt thereof and a quaternary compound thereof is preferable.
More preferably, at least one selected from the group consisting of the compounds represented by the general formulas (A1-1) to (A1-7), 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 (A1-3) to (A1-5), salts thereof and quaternized compounds thereof is more preferable.

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 (for example, a mixture of compounds represented by the general formulas (A1-3) to (A1-5)).

The content of the component (A) is 15 to 30% by mass, preferably 15 to 25% by mass, and more preferably 18 to 25% by mass with respect to the total mass of the liquid softener composition. When the content of the component (A) is 15% by mass or more, the compounding purpose can be achieved, and when it is 30% by mass or less, the thickening of the liquid softener composition can be suppressed.

（式中、Ｒ¹は、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１６〜２６の飽和又は不飽和の炭化水素基であり、Ｒ²及びＲ³は独立して炭素数１〜３のアルキルであり、Ｘは陰イオン基である。）
（Ｂ）成分は、液体柔軟剤組成物の増粘を抑制するために配合する。 [(B) component: quaternary ammonium salt]
The component (B) is a quaternary ammonium salt represented by the general formula (B1).

(In the formula, R ¹ is a saturated or unsaturated hydrocarbon group having 16 to 26 carbon atoms, which may be partitioned by an ester group (-COO-) and / or an amide group (-NHCO-). R ² and R ³ are independently alkyl having 1 to 3 carbon atoms, and X is an anion group.)
The component (B) is blended in order to suppress the thickening of the liquid softener composition.

The hydrocarbon group of R ¹ has 16 to 26 carbon atoms, preferably 16 to 24 carbon atoms, and more preferably 16 to 20 carbon atoms. R ¹ may be saturated or unsaturated, but is preferably a saturated hydrocarbon group.
The hydrocarbon group may contain a fusing group, but preferably does not contain a fusing group.
The fusing group is an ester group (-COO-) or an amide group (-NHCO-). The division may be at one place or at two or more places. It is preferably one place. When the hydrocarbon group has two or more dividing groups, each dividing group may be the same or different.
The carbon atom contained in the dividing group shall be counted as the number of carbon atoms of the hydrocarbon group. ^{Specific examples of R 1} include octadecyl group, hexadecyl group, eikosyl and the like, and octadecyl group and hexadecyl group are preferable.
R ² and R ³ are independently alkyl having 1 to 3 carbon atoms, and are preferably methyl groups.
Examples of X include methyl sulfuric acid, bromine, chlorine and the like, and chlorine is preferable.

Specific examples of the component (B) include octadecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide and the like, and octadecyltrimethylammonium chloride and hexadecyltrimethylammonium chloride are preferable.

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

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

The content of the component (B) is 1.0 to 3.0% by mass, preferably 1.0 to 2.5% by mass, and more preferably 1.0 to 2.0% by mass with respect to the total mass of the liquid softener composition. It is mass%. When the content of the component (B) is 1.0 to 3.0% by mass, the compounding purpose can be achieved.

[(C) ingredient: fragrance]
The component (C) is added to the liquid softener composition for scenting, and further for scenting clothing after treatment with the same composition.
The component (C) is a fragrance that is not contained in the capsule, which is different from the fragrance contained as the core substance in the encapsulated fragrance (functional capsule) described later.
As the component (C), a fragrance widely used in the field of softeners can be used 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 Chemical Performance V.3.3", Boelens Aroma Chemical Information Service (1996) and "Flower , Danute Lajaujis Anonis, Allured Pub. Co. (1993) and the like.

A single type of the component (C) may be used, or a plurality of types may be used in combination (fragrance composition).
The fragrance composition may contain a solvent commonly used in liquid softener compositions. Examples of the fragrance solvent include dipropylene glycol (DPG) and isopropyl myrysterate (IPM).

The content of the component (C) is 1.0 to 5.0% by mass, preferably 1.0 to 3.0% by mass, and more preferably 1.5 to 2.5% by mass with respect to the total mass of the liquid softener composition. It is mass%. When the content of the component (C) is 1.0% by mass or more, the compounding purpose can be achieved, and when it is 5.0% by mass or less, the thickening of the liquid softener composition can be suppressed.

[Mixing ratio of each component]
The mass ratio (A / B) of the component (A) to the component (B) is 6 to 30, preferably 10 to 25, and more preferably 10 to 20. When blended in these mass ratios, thickening of the liquid softener composition can be suppressed while achieving the blending purpose of each component.
The mass ratio (A / C) of the component (A) to the component (C) is preferably 5 to 30, more preferably 8 to 25, and particularly preferably 10 to 20. Within this mass ratio range, thickening of the liquid softener composition can be suppressed.

[Emulsified liquid softener composition]
The liquid softener composition is an emulsion type. “Emulsion” means that a glass cell having an optical path length of 10 mm is used as a measurement cell, and when ion-exchanged water is put into the control cell, the visible light transmittance (wavelength 660 nm) of the sample is less than 30%, preferably 20. % Or less, more preferably 15% or less.

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

〔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.

[Nonion surfactant]
Nonionic surfactants are added to improve the stability (particularly freeze-restorability) of the liquid softener composition.
As the nonionic surfactant, components known in the field of liquid softener compositions can be used without particular limitation. For example, alkylene oxide adducts of alcohols, amines or fatty acids can be used.
Each carbon chain moiety of the alcohol, amine and fatty acid may be branched or linear and may be unsaturated. Further, the carbon chain may have a distribution. The carbon number of the carbon chain is preferably 6 to 20, more preferably 8 to 18. When the carbon chain is linear, the number of carbon atoms is preferably 6 to 14, more preferably 8 to 12, and most preferably 8 to 10. When the carbon chain is a branched chain, the number of carbon atoms is preferably 6 to 18, more preferably 9 to 18, and most preferably 13.
As a raw material for the nonionic surfactant, Exxon manufactured by Exxon Chemical, LUTENSOL series manufactured by BASF, Oxocol manufactured by Kyowa Hakko Kogyo, GENAPOL series manufactured by Hoechst AG, DOBANOL series manufactured by Shell, and the like can be used. When the nonionic surfactant is an alkylene oxide adduct of an alcohol, either a primary alcohol or a secondary alcohol can be used. The alcohol having 13 carbon atoms is produced from, for example, dodecene, and the starting material thereof may be butylene or propylene.
When the carbon chain contains an unsaturated group, it is particularly preferable that the carbon number is 18. The stereoisomeric structure of the unsaturated group may be a cis-form or a trans-form, or a mixture of both, but in particular, the ratio of the cis-form / trans-form is 25/75 to 100/0 (mass ratio). Is preferable.
As the alkylene oxide, ethylene oxide (EO) is preferable, but propylene oxide (PO) or butylene oxide (BO) may be added together with EO. The average number of moles of EO added is preferably 5 to 100 mol, more preferably 10 to 80 mol, and particularly preferably 15 to 70 mol. The average number of moles of PO or BO added together with EO is preferably 1 to 5, and more preferably 1 to 3 mol. At this time, EO may be added and then PO or BO may be added, or PO or BO may be added and then EO may be added.
Specific examples of the nonionic surfactant include an average EO9PO1 adduct of nonyl alcohol, an average EO 40 mol adduct of primary isononyl alcohol, an average EO 20 mol adduct of primary isodecyl alcohol, an average EO 20 mol adduct of lauryl alcohol, and a first grade. An average EO60 mol adduct of isohexadecyl alcohol, an average EO 20 mol adduct of primary isotridecyl alcohol, an average EO 60 mol adduct of primary isotridecyl alcohol, an average EO 50 mol adduct of tridecyl alcohol, beef alkylamine Examples thereof include an average EO60 adduct, an average EO60 adduct of beef fat alkylamine, an average EO50 adduct of oleylamine, and an average EO20 mol adduct of lauric acid. As commercially available products, Emarex series manufactured by Nippon Emulsion, Emalmin series manufactured by Sanyo Kasei, TDA series, Esomin series manufactured by Lion Chemical, Softanol series manufactured by Nippon Shokubai, LUTESOL series manufactured by BASF, and the like can be used.

The content of the nonionic surfactant is not particularly limited as long as the compounding purpose can be achieved, but is 0.1 to 10% by mass, preferably 0.5 to 5.0% by mass, more preferably 0.5 to 5.0% by mass, based on the total mass of the liquid softener composition. It is preferably 1.0 to 3.0% by mass.
The mass ratio (A / nonionic surfactant) of the component (A) to the nonionic surfactant is preferably 5 to 30, more preferably 8 to 25, and particularly preferably 10 to 20. Within this mass ratio range, it is possible to achieve the purpose of blending the nonionic surfactant while suppressing the thickening of the liquid softener composition.
The total content of the component (A) and the nonionic surfactant is preferably 35% by mass or less, more preferably 30% by mass or less, and particularly preferably 25% by mass or less, based on the total mass of the liquid softener composition. .. When the total content is 30% by mass or less, the purpose of blending the nonionic surfactant can be achieved while suppressing the thickening of the liquid softener composition.

[Water-soluble solvent]
The water-soluble solvent is added to improve the stability (particularly freeze-restorability) of the liquid softener composition.
As the water-soluble solvent, one or more selected from the group consisting of alcohols having 1 to 4 carbon atoms, glycol ether solvents, and polyhydric alcohols is preferable. Specifically, it is selected from ethanol, isopropanol, glycerin, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, hexylene glycol, polyoxyethylene phenyl ether, and a water-soluble solvent represented by the following general formula (X). It is preferable to add a solvent component.
R ^4- O- (C ₂ H ₄ O) _y- (C ₃ H ₆ O) _Z- H ... (X)
(In the formula, R ⁴ 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, respectively, and y is 1 to 10, preferably 2 to 10. 5 and z is 0-5, preferably 0-2.)
Among the above, ethanol, ethylene glycol, butyl carbitol, propylene glycol, dipropylene glycol monomethyl ether and diethylene glycol monobutyl ether are preferable.
A single type of water-soluble solvent may be used, or a plurality of types may be used in combination.
The content of the water-soluble solvent is not particularly limited as long as the compounding purpose can be achieved, but is 0.001 to 30% by mass, preferably 0.01 to 25% by mass, more preferably more preferably, based on the total mass of the liquid softener composition. 0.1 to 20% by mass.

[Silicone compound]
The silicone compound is blended mainly for the purpose of further improving the scent persistence.
As the silicone compound, a component known in the field of liquid softener composition can be used without particular limitation.
The molecular structure of the silicone compound may be linear, branched, or crosslinked. Further, the silicone compound may be a modified silicone compound. The modified silicone compound may be modified with one or more organic functional groups.
The silicone compound can be used in the oil state or in the emulsion state 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.
Among these, polyether-modified silicone, amino-modified silicone, and dimethyl silicone are preferable from the viewpoint of improving versatility and fragrance persistence. From the viewpoint of further improving the fragrance persistence and handling at the time of manufacture, polyether-modified silicone and amino-modified silicone are preferable.

For dimethylsilicone, There is no particular restriction on the kinematic viscosity is preferably 1~100,000,000mm ² / s, more preferably 10~10,000,000mm ² / s, 100~1,000,000mm ² / s is more preferable. Further, the dimethyl silicone may be an oil or an emulsion.

（式中、Ｍ、Ｎ、ａ及びｂは、それぞれ独立して平均重合度であり、Ｒは水素又はアルキル基である）
一般式（Ｉ）中、Ｍは、１０〜１０，０００、好ましくは１００〜３００である。
Ｎは、１〜１，０００、好ましくは１〜１００である。更に、Ｍ＞Ｎであることが好ましい。
ａは、２〜１００であり、好ましくは２〜５０である。
ｂは、０〜５０であり、好ましくは０〜１０である。
Ｒは、水素又は炭素数１〜４のアルキル基であることが好ましい。
一般式（Ｉ）で表されるポリエーテル変性シリコーンは、一般に、Ｓｉ−Ｈ基を有するオルガノハイドロジェンポリシロキサンと、例えば、ポリオキシアルキレンアリルエーテル等の炭素−炭素二重結合を末端に有するポリオキシアルキレンアルキルエーテルとを、白金触媒下、付加反応させることにより製造することができる。この場合、生成物中に未反応のポリオキシアルキレンアルキルエーテルやＳｉ−Ｈ基を有するオルガノハイドロジェンポリシロキサンがわずかに含まれる場合がある。Ｓｉ−Ｈ基を有するオルガノハイドロジェンポリシロキサンは反応性が高いため、前記ポリエーテル変性シリコーン中での存在量としては、３０ｐｐｍ以下（Ｓｉ−Ｈの量として）であることが好ましい。 Specific examples of the polyether-modified silicone include a copolymer of an alkylsiloxane and a polyoxyalkylene. The alkyl group of the alkylsiloxane preferably has 1 to 3 carbon atoms. The alkylene group of the polyoxyalkylene preferably has 2 to 5 carbon atoms.
Preferred polyether-modified silicones include copolymers of dimethylsiloxane and polyoxyalkylene (polyoxyethylene, polyoxypropylene, random or block copolymers of ethylene oxide and propylene oxide, etc.). Specific examples include, for example, a compound represented by the following general formula (I).

(In the formula, M, N, a and b are each independently having an average degree of polymerization, and R is a hydrogen or an alkyl group).
In the general formula (I), M is 10 to 10,000, preferably 100 to 300.
N is 1 to 1,000, preferably 1 to 100. Further, it is preferable that M> N.
a is 2 to 100, preferably 2 to 50.
b is 0 to 50, preferably 0 to 10.
R is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms.
The polyether-modified silicone represented by the general formula (I) is generally an organohydrogenpolysiloxane having a Si—H group and a poly having a carbon-carbon double bond at the end, for example, a polyoxyalkyleneallyl ether. It can be produced by subjecting it to an addition reaction with an oxyalkylene alkyl ether under a platinum catalyst. In this case, the product may contain a small amount of unreacted polyoxyalkylene alkyl ether or organohydrogen polysiloxane having a Si—H group. Since the organohydrogenpolysiloxane having a Si—H group has high reactivity, the abundance in the polyether-modified silicone is preferably 30 ppm or less (as the amount of Si—H).

（式中、Ａ、Ｂ、ｈ及びｉは、それぞれ平均重合度であり、Ｒはアルキル基であり、Ｒ’は水素又はアルキル基である。）
一般式（ＩＩ）中、Ａは５〜１０，０００であり、
Ｂは、２〜１０，０００であり、
ｈは、２〜１００であり、
ｉは、０〜５０である。
Ｒは、炭素数１〜５のアルキル基であることが好ましい。
Ｒ’は、水素又は炭素数１〜４のアルキル基であることが好ましい。
一般式（ＩＩ）で表される線状ポリシロキサン−ポリオキシアルキレンブロック共重合体は、反応性末端基を有するポリオキシアルキレン化合物と、該化合物の反応性末端基と反応する末端基を有するジヒドロカルビルシロキサンとを反応させることにより製造することができる。このようなポリエーテル変性シリコーンは、側鎖のポリオキシアルキレン鎖が長く、ポリシロキサン鎖の重合度が大きいものほど粘度が高くなるので、製造時の作業性改善及び水性組成物への配合を容易にするために、水溶性有機溶剤とのプレミックスの形で配合に供することが好ましい。水溶性有機溶剤としては、例えば、エタノール、ジプロピレングリコール、ブチルカルビトール等が挙げられる。 Preferred polyether-modified silicones include linear polysiloxane-polyoxyalkylene block copolymers represented by the following general formula (II).

(In the formula, A, B, h and i are the average degrees of polymerization, respectively, R is an alkyl group, and R'is a hydrogen or an alkyl group.)
In the general formula (II), A is 5 to 10,000,
B is 2 to 10,000,
h is 2 to 100,
i is 0 to 50.
R is preferably an alkyl group having 1 to 5 carbon atoms.
R'is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms.
The linear polysiloxane-polyoxyalkylene block copolymer represented by the general formula (II) has a polyoxyalkylene compound having a reactive end group and a di group having a terminal group that reacts with the reactive end group of the compound. It can be produced by reacting with hydrocarbylsiloxane. Such a polyether-modified silicone has a longer side chain polyoxyalkylene chain and a higher degree of polymerization of the polysiloxane chain, the higher the viscosity. Therefore, it is easy to improve workability during production and to incorporate it into an aqueous composition. It is preferable to prepare the mixture in the form of a premix with a water-soluble organic solvent. Examples of the water-soluble organic solvent include ethanol, dipropylene glycol, butyl carbitol and the like.

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

（式中、Ｒ¹及びＲ⁶は互いに同一でも、異なっていてもよい、メチル基、水酸基又は水素であり、
Ｒ²は、−（ＣＨ₂）_n−Ａ¹、又は、−（ＣＨ₂）_n−ＮＨＣＯ−（ＣＨ₂）_m−Ａ¹（各式中、Ａ¹は、−Ｎ（Ｒ³）（Ｒ⁴）、−Ｎ⁺（Ｒ³）（Ｒ⁴）（Ｒ⁵）・Ｘ^-（各式中、Ｒ³、Ｒ⁴及びＲ⁵は、互いに同一であってもよいし、異なっていてもよく、水素原子、炭素数１〜１２のアルキル基、フェニル基又は−（ＣＨ₂）_n−ＮＨ₂（式中、ｎは０〜１２である）であり、Ｘ^-は、フッ素イオン、塩素イオン、臭素イオン、ヨウ素イオン、硫酸メチルイオン又は硫酸エチルイオンである）であり、ｍ及びｎの値は、互いに同一であってもよいし、異なっていてもよく、０〜１２の整数である）であり、
ｐ及びｑはそれぞれポリシロキサンの重合度を表し、互いに同一であってもよいし、異なっていてもよく、ｐは０〜２００００、好ましくは１０〜１００００であり、ｑは１〜５００、好ましくは１〜１００である。） Amino-modified silicone is a dimethyl silicone skeleton in which an amino group is introduced into the terminal or side chain. In addition to the amino group, a substituent such as a hydroxyl group, an alkyl group or a phenyl group may be introduced.
The amino-modified silicone may be in the form of an oil, or may be in the form of an amino-modified silicone emulsion emulsified using a nonionic surfactant or a cationic surfactant as an emulsifier.
The preferred amino-modified silicone oil, or base oil in an emulsion, is a compound represented by the following general formula (III).

(In the formula, R ¹ and R ⁶ are methyl groups, hydroxyl groups or hydrogens, which may be the same or different from each other.
R ² is − (CH ₂ ) _n −A ¹ or − (CH ₂ ) _n −NHCO− (CH ₂ ) _m −A ¹ (In each equation, A ¹ is −N (R ³ ) (R). ^{4), - N + (R} 3) (R 4) (R 5) · X - ( in each formula, R ^3, R ⁴ and R ⁵ may be the same as each other or different , Hydrogen atom, alkyl group with 1 to 12 carbon atoms, phenyl group _{or-(CH 2} ) _n- NH ₂ (in the formula, n is 0 to 12), and X ^- is fluorine ion, chlorine ion, Bromine ion, iodine ion, methyl sulfate ion or ethyl sulfate ion), and the values of m and n may be the same or different from each other, and are integers of 0 to 12). can be,
p and q each represent the degree of polymerization of the polysiloxane and may be the same or different from each other, p is 0 to 20000, preferably 10 to 10000, and q is 1 to 500, preferably 1 to 500. It is 1 to 100. )

Oil amino-modified silicone preferably has a kinematic viscosity at 25 ° C. is 50~20000mm ² / s, more preferably 100~10000mm ² / s. When the kinematic viscosity is in this range, a high fragrance-sustaining effect is exhibited, the manufacturability is improved, and the handling of the adult product becomes easy.

Commercially available amino-modified silicones can be used.
Examples of amino-modified silicone oils include those sold by Toray Dow Corning Co., Ltd. on SF-8417 and BY16-892 and BY16-890, and Shin-Etsu Chemical Co., Ltd. on KF-864, KF-860 and KF. Examples thereof include those sold by -8004, KF-8002, KF-8005, KF-867, KF-861, KF-880, and KF-867S.
As the amino-modified silicone emulsion type, for example, those sold by Toray Dow Corning Co., Ltd. in SM8904, BY22-079, FZ-4671, and FZ-4672, and those sold by Shin-Etsu Chemical Co., Ltd. in the Polon series. Examples thereof include Polon MF-14, Polon MF-29, Polon MF-14D, Polon MF-44, Polon MF-14EC, Polon MF-52, and those sold by Asahi Kasei Wacker Silicone Co., Ltd. under WACKER FC201.

A single type of silicone compound may be used, or a plurality of types may be used in combination.
The content of the silicone compound is not particularly limited as long as the compounding purpose can be achieved, but is 0.01 to 10% by mass, preferably 0.05 to 8% by mass, and more preferably 0. It is 1 to 5% by mass.

〔Preservative〕
The preservative is mainly added to enhance the antiseptic and bactericidal activity of the liquid softener composition and to maintain the antiseptic property during long-term storage.
As the preservative, ingredients known in the field of liquid softener compositions can be used without particular limitation. Specific examples thereof include isothiazolone-based organic sulfur compounds, benzisothiazolone-based organic sulfur compounds, benzoic acids, 2-bromo-2-nitro-1,3-propanediol and the like.
Examples of the isothiazolin-based organic sulfur compound include 5-chloro-2-methyl-4-isothiazolin-3-one, 2-n-butyl-3-isothiazolinone, 2-benzyl-3-isothiazolinone, and 2-phenyl-3-isothiazolinone. , 2-Methyl-4,5-dichloroisothiazolinone, 5-chloro-2-methyl-3-isothiazolinone, 2-methyl-4-isothiazolin-3-one, and mixtures thereof. Of these, 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one are preferable, and 5-chloro-2-methyl-4-isothiazolin-3-one and 2 A mixture with −methyl-4-isothiazolin-3-one is more preferable, and a mixture of about 77% by mass with the former and about 23% by mass with the latter and a diluted solution thereof (for example, isothiazolinone solution) are particularly preferable.
Benzisothiazolinone-based organic sulfur compounds include 1,2-benzisothiazolin-3-one and 2-methyl-4,5-trimethylethylene-4-isothiazolin-3-one, and related compounds include dithio-2,2-bis (). Benzmethylamide) and mixtures thereof. 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.
A single type of preservative may be used, or a plurality of types may be used in combination.
The content of the preservative 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. When it is 0.0001% by mass or more, the effect of blending the preservative is sufficiently obtained, and when it is 1% by mass or less, high storage stability of the liquid softener composition can be sufficiently maintained.

[Antibacterial agent]
The antibacterial agent is added to enhance the storage stability of the liquid softener composition.
As the antibacterial agent, ingredients known in the field of liquid softener compositions can be used without particular limitation. Specific examples include, for example, diclosan, triclosan, benzalkonium chloride, bis- (2-pyridylthio-1-oxide) zinc, 8-oxyquinoline, biguanide compounds (eg, polyhexamethylene biguanide), chlorohexidine hydrochloride, and the like. , Polylysine and the like. Among these, benzalkonium chloride, biguanide compounds, and chlorohexidine hydrochloride are preferable.
A single type of antibacterial agent may be used, or a plurality of types may be used in combination.
The content of the antibacterial agent is not particularly limited as long as the compounding purpose can be achieved, but is preferably 0.001 to 5% by mass with respect to the total mass of the liquid softener composition.

[Viscosity regulator]
The viscosity modifier is added to further improve the usability of the liquid softener composition.
Specific examples of the viscosity modifier include calcium chloride, magnesium chloride, sodium chloride, sodium p-toluenesulfonate, sodium citrate and the like. Of these, calcium chloride, magnesium chloride and sodium citrate are preferable.
The content of the viscosity modifier is 0.01 to 1.5% by mass, preferably 0.1 to 1.0% by mass, and more preferably 0.3 to 0.8% by mass with respect to the total mass of the liquid softener composition. %.
A single type of viscosity modifier may be used, or a plurality of types may be used in combination.
The viscosity modifier can be added at any step in the production of the liquid softener composition.

[Functional capsule]
The functional capsule is formulated to impart various functions due to the core substance contained 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 encapsulation substance in the field of liquid softener can be used without particular limitation. Specific examples include fragrances, essential oils, whitening agents, 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, bleaching agents, flavoring agents, sweetening agents, waxes, chemicals, fertilizers, herbicides and the like.
As the core substance, a single type may be used, or a plurality of types may be used in combination.

As the wall material, those generally used as encapsulation materials in the field of liquid softener compositions can be used without particular limitation. Specific examples include natural polymers such as gelatin and agar, oily 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 fragrance as a core material include BLUEFLOWERPOP "FFMHN2814" manufactured by Firmenich; GREEN BREEZE CAPS, ORCHARD GARDEN CAPS, RAINBOW CAPS, VELVET CAPS, and AUROCAPS manufactured by Givaudan. UNICAP 101 and UNICAP 503 and the like.
Specific examples of the cooling sensation capsule having a cooling sensation agent as a core substance include MultiSal SalCol, HydroSal FreshCool, SalSphereSalCol manufactured by SALVONA Technologies, and Neoage AROMA-C manufactured by NICCA CHEMICAL CO., LTD.
Specific examples of the warming capsule having 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) manufactured by Miki Riken Co., Ltd., Riken Resin RMC-HBP (insect repellent effect), RMC-PT (insect repellent effect) and the like.

The average particle size of the functional capsule is preferably 10 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.

A single type of functional capsule may be used, or a plurality of types may be used in combination.
The content of the functional capsule 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.

[Structuring agent]
The structuring agent is added to uniformly and stably disperse insoluble particles such as functional capsules in the liquid softener composition.
Examples of the structuring agent include polyethyleneimine or a derivative thereof, a cationic (meth) acrylic polymer, dextrins, and a nonionic polymer having a urethane skeleton.
Examples of polyethyleneimine or a derivative thereof include Lupasol SK (manufactured by BASF), which is an amide derivative of polyethyleneimine, and LupasolPS (manufactured by BASF), which is polyethyleneimine.
Examples of the cationic (meth) acrylic polymer include Rheovis FRC (manufactured by BASF) and Rheovis CDE (manufactured by BASF).
Examples of dextrins include cyclodextrin, highly branched cyclic dextrin and the like. The highly branched cyclic dextrin is a glucan having an inner branched cyclic structure portion and an outer branched structure portion and having a degree of polymerization in the range of 50 to 10,000, and the inner branched cyclic structure portion has an α-1,4-glucosidic bond. A cyclic glucan chain formed by an α-1,6-glucoside bond, and the outer branch structure portion includes dextrin, which is an acyclic glucan chain bonded to the inner branch ring structure portion. Examples of the highly branched cyclic dextrin include cluster dextrin (manufactured by Glico Foods Co., Ltd.).
Examples of the nonionic polymer having a urethane skeleton include OPTIFLO-H 7625 VF, OPTIFLO-H 7500 VF, OPTIFLO-H 6500 VF, OPTIFLO-H 3300 VF, OPTIFLO 2600 VF (manufactured by BYK-Chemie), and Acculin (Acul). ) 44 (manufactured by DOW) and the like.
A single type of structuring agent may be used, or a plurality of types may be used in combination.
The content of the structuring agent is not particularly limited as long as the compounding purpose can be achieved, but is preferably 0.01 to 5% by mass with respect to the total mass of the liquid softener composition.

[Viscosity of liquid softener composition]
Since the liquid softener composition according to the present invention is suppressed from thickening, its usability (particularly, handleability at the time of loading into a washing machine and efficiency of discharging from the loading port of the washing machine) is good. Has a viscosity that makes it. Specifically, the viscosity (25 ° C.) is preferably less than 500 mPa · s, more preferably less than 300 mPa · s. The viscosity can be measured using a B-type viscometer (manufactured by TOKIMEC).

[PH of liquid softener composition]
The pH of the liquid softener composition is not particularly limited, but the pH at 25 ° C. is preferably 1 to 6, more preferably 2 to 6 from the viewpoint of suppressing the hydrolysis of the component (A) with the aging of storage. Adjust to the range of 4.
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 dimethylamine, alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates, alkali metal silicates and the like can be used.

〔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 (B) and a component (C) and an aqueous phase are mixed under temperature conditions equal to or higher than the melting point of the component (A) to prepare an emulsion, and then an emulsion is prepared. A liquid softener composition can be produced by adding and mixing other components to the obtained emulsion and, if necessary, other components.

[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 basin, 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 preferably 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 with respect to the total amount of water used.
The types of textile products that can be treated with the liquid softener composition are 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 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).

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

A-1: A cationic surfactant synthesized according to the procedure described in Example 4 of JP-A-2003-12471. A-1 is a compound represented by the general formulas (A1-3), (A1-4) and (A1-5) (in each formula, R ⁹ is an alkyl group or an alkenyl group having 15 to 17 carbon atoms. ) Is quaternized with dimethyl sulfate.

[(B) component: quaternary ammonium salt]
The following B-1 to B-3 were used.

B-1: Octadecyltrimethylammonium chloride (manufactured by Tokyo Chemical Industry). In the general formula (B1), B-1 is a compound in which R ¹ is a saturated hydrocarbon group having 18 carbon atoms, R ² is a methyl group, R ³ is a methyl group, and X is chlorine. ..


B-2: Hexadecyltrimethylammonium chloride (manufactured by Tokyo Chemical Industry). In the general formula (B1), B-2 is a compound in which R ¹ is a saturated hydrocarbon group having 16 carbon atoms, R ² is a methyl group, R ³ is a methyl group, and X is chlorine. ..

B-3: Dodecyltrimethylammonium chloride (manufactured by Tokyo Chemical Industry). In the general formula (B1), B-3 is a compound in which R ¹ is a saturated hydrocarbon group having 12 carbon atoms, R ² is a methyl group, R ³ is a methyl group, and X is chlorine. .. B-3 was used as a comparative example in that it did not satisfy the requirement ^{of R 1} (carbon number 16 to 26) in the general formula (B1).

[(C) ingredient: fragrance]
A fragrance composition C-1 having the composition shown in the table below was used. The numerical value of each fragrance component in the table is mass% with respect to the total mass of the fragrance composition C-1.

Ｄ−２

Ｄ−３

Ｄ−４

[Other ingredients]
The following common components D-1 to D-4 were used. The content in the table is a value with respect to the total mass of the liquid softener composition.

D-1

D-2

D-3

D-4

[Preparation method of 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.
“A / B” in Table 1 indicates the mass ratio of the component (A) and the component (B). "A / C" indicates the mass ratio of the component (A) and the component (C).

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).
The component (A), the component (B), the component (C) and the nonionic surfactant were mixed and stirred to obtain an oil phase mixture.
The preservative was dissolved in ion-exchanged water for balance to obtain an aqueous phase mixture. The mass of the ion-exchanged water for balance corresponded to the balance obtained by subtracting the total amount of the oil phase mixture and the preservative 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. , 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, a viscosity modifier, a structuring agent and a functional capsule were added and stirred. If necessary, add an appropriate amount of hydrochloric acid (reagent 1 mol / L, Kanto Chemical) or sodium hydroxide (reagent 1 mol / L, Kanto Chemical) to adjust the pH to 3.0 (25 ° C), and the total mass is 1,. Ion-exchanged water was added so as to be 000 g, and the desired liquid softener composition was obtained.

[Evaluation of liquid softener composition]
The viscosity (mPa · s) of the liquid softener composition at 25 ° C. was measured using a B-type viscometer (manufactured by TOKIMEC). The results are shown in the "Viscosity" column of Table 1.
When the appearance was visually evaluated, each of the liquid softener compositions of Examples and Comparative Examples was not transparent but turbid, and was an emulsion type. Further, a glass cell having an optical path length of 10 mm was used as the measurement cell, and the visible light transmittance (wavelength 660 nm) of each liquid softener composition when ion-exchanged water was put into the control cell was measured and found to be 1%. It was as follows.

The present invention is available in the field of softeners.

Claims (7)

A liquid softener composition, wherein the following components (A) to (C):
(A) Amine compounds having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms in the molecule, which are separated by an ester group (-COO-) and / or an amide group (-NHCO-), salts thereof, and salts thereof. At least one compound selected from the group consisting of the quaternary compounds;
(B) Quaternary ammonium salt represented by the general formula (B1):

(In the formula, R ¹ is a saturated or unsaturated hydrocarbon group having 16 to 26 carbon atoms, which may be partitioned by an ester group (-COO-) and / or an amide group (-NHCO-). R ² and R ³ are independently alkyls with 1-3 carbon atoms and X is an anion group.); And (C) Containing fragrances.
The content of the component (A) is 15 to 30% by mass with respect to the total mass of the liquid softener composition.
The content of the component (B) is 1.0 to 3.0% by mass with respect to the total mass of the liquid softener composition.
The content of the component (C) is 1.0 to 5.0% by mass with respect to the total mass of the liquid softener composition.
The mass ratio (A / B) of the component (A) to the component (B) is 6 to 30, and the mass ratio is 6 to 30.
A liquid softener composition, characterized in that the liquid softener composition is an emulsion type. The liquid softener composition according to claim 1, wherein the component (B) is selected from the group consisting of octadecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide and hexadecyltrimethylammonium bromide. The liquid softener composition according to claim 1 or 2, wherein the content of the component (A) is 18 to 25% by mass with respect to the total mass of the liquid softener composition. The liquid softener composition according to any one of claims 1 to 3, wherein the content of the component (B) is 1.0 to 2.0% by mass with respect to the total mass of the liquid softener composition. The liquid softener composition according to any one of claims 1 to 4, wherein the content of the component (C) is 1.5 to 2.5% by mass with respect to the total mass of the liquid softener composition. The liquid softener composition according to any one of claims 1 to 5, wherein the mass ratio (A / B) of the component (A) to the component (B) is 10 to 20. The liquid softener composition according to any one of claims 1 to 6, wherein the mass ratio (A / C) of the component (A) to the component (C) is 5 to 30.