JP2023094910A - Liquid softener composition - Google Patents

Abstract

To provide a liquid softener composition excellent in perfume retention to a laundry.SOLUTION: An emulsion-type liquid softener composition comprises components (A) and (B) below: (A) one or more cationic surfactants selected from (A-1) and (A-2) below; (A-1) at least one compound selected from the group consisting of amine compounds having one to three hydrocarbon groups of 10 to 26 carbons in a molecule fragmented by an ester group (-COO-) and/or an amide group (-NHCO-), salts thereof and quaternized products thereof, (A-2) a quaternary ammonium salt represented by the (B) below, wherein a content of component (A) is less than 5 mass %, the content of component (B) is 0.01 to 2 mass%, and the mass ratio A/B of component (A) to component (B) is 1 to 200.SELECTED DRAWING: None

Description

The present invention relates to liquid softener compositions. The invention also relates to a method of treating textiles.

In recent years, due to the growing interest in scents, softeners are required to have strong scents and lingering scents for laundry products.
However, the function of the softening agent may be reduced by detergent components (anionic surfactants) such as alkylbenzenesulfonic acid (LAS), and there are known techniques for dealing with this point from the viewpoint of the function of imparting the softening agent ( Patent Documents 1 and 2), it cannot be said that the softening agents are sufficient in terms of imparting softness and lingering fragrance to laundry products.
For example, in Southeast Asia, while the demand for fragrance is particularly high, the use of powdered detergent is the mainstream, and the amount of anionic surfactant used is large. In Southeast Asia, the concentration of cationic surfactants, which are softening bases in softeners, is low. Therefore, in washing conditions where the amount of anionic surfactant used is large and the concentration of the cationic surfactant, which is the softening base in the softener, is low, as in Southeast Asia, the function of the softener tends to decrease due to the anionic surfactant. is strong. In order to meet the needs under such washing conditions, consumers' needs have been met by increasing the amount of perfume blended in softeners, but this is inefficient and uneconomical.

Japanese Patent Publication No. 2004-525271 Japanese Patent Publication No. 2008-538393

In view of the above background, it is an object of the present invention to provide a liquid softener composition that is excellent in imparting lingering fragrance to laundry products. In particular, it is an object of the present invention to provide a liquid softener composition containing a small amount of a cationic surfactant as a softening base, which is suitable for use under washing conditions in which a large amount of anionic surfactant is used.

（式中、Ｒ₁及びＲ₂は、独立して、エステル基（－ＣＯＯ－）でもアミド基（－ＮＨＣＯ－）でも分断されていない、炭素数８～２４のアルキル基またはアルケニル基であり、Ｒ₃及びＲ₄は、独立して、メチル基、エチル基、ヒドロキシエチル基、ヒドロキシプロピル基、ポリオキシエチレン基またはポリオキシプロピレン基であり、Ｘ^-は陰イオンを表す。）
及び
（Ｂ）下式（Ｂ）で表される４級アンモニウム塩

（式中、Ｒ¹は、エステル基（－ＣＯＯ－）でもアミド基（－ＮＨＣＯ－）でも分断されていない、炭素数８～２４の炭化水素基であり、Ｒ²及びＲ³は、独立して、炭素数１～３のアルキル基であり、Ｘ^-は陰イオンを表す。）
を含有する、乳濁型液体柔軟剤組成物であって、
（Ａ）成分の含量が、５質量％未満であり、
（Ｂ）成分の含量が、０．０１～２質量％であり、
（Ｂ）成分に対する（Ａ）成分の質量比Ａ／Ｂが、１～２００である、乳濁型液体柔軟剤組成物。
〔２〕１ppm以上の直鎖アルキルベンゼンスルホン酸又はその塩を含む水中において、前記〔１〕に記載の乳濁型液体柔軟剤組成物を繊維製品と接触させることを含む、繊維製品を処理する方法。 As a result of intensive studies by the present inventors, in a liquid softener containing a specific amount of cationic surfactant as a softening base, by blending a quaternary ammonium salt having a specific carbon chain length, only the softening effect can be obtained. In addition, it was found that the effect of imparting lingering fragrance can also be improved.
The present invention relates to the following [1] to [2].
[1] The following components (A) and (B):
(A) one or more cationic surfactants selected from (A-1) and (A-2) below;
(A-1) an amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms in the molecule separated by an ester group (-COO-) and/or an amide group (-NHCO-); At least one compound selected from the group consisting of salts and quaternary compounds thereof (A-2) a quaternary ammonium salt represented by the following formula (A2)

(Wherein, R ₁ and R ₂ are independently an alkyl or alkenyl group having 8 to 24 carbon atoms that is not divided by an ester group (-COO-) or an amide group (-NHCO-), R ₃ and R ₄ are independently a methyl group, ethyl group, hydroxyethyl group, hydroxypropyl group, polyoxyethylene group or polyoxypropylene group, and X ^- represents an anion.)
and (B) a quaternary ammonium salt represented by the following formula (B)

(In the formula, R ¹ is a hydrocarbon group having 8 to 24 carbon atoms that is not separated by an ester group (--COO--) or an amide group (--NHCO--), and R ² and R ³ are independently is an alkyl group having 1 to 3 carbon atoms, and X ^- represents an anion.)
An emulsion-type liquid softener composition containing
The content of component (A) is less than 5% by mass,
The content of component (B) is 0.01 to 2% by mass,
An emulsion-type liquid softener composition, wherein the mass ratio A/B of component (A) to component (B) is 1-200.
[2] A method of treating a textile product, comprising bringing the emulsion-type liquid softener composition of [1] into contact with the textile product in water containing 1 ppm or more of linear alkylbenzene sulfonic acid or a salt thereof. .

ADVANTAGE OF THE INVENTION According to one aspect of the present invention, it is possible to provide a liquid softener composition that is excellent in imparting a lingering fragrance to laundry.
ADVANTAGE OF THE INVENTION According to one aspect of the present invention, it is possible to provide a liquid softener composition that is excellent in retaining fragrance and imparting softness to laundry.
ADVANTAGE OF THE INVENTION According to one aspect of the present invention, it is possible to provide a liquid softening agent composition which is excellent in lingering fragrance and imparting softness to laundry products and which has good stability.
According to one aspect of the present invention, it is possible to provide a liquid softener composition containing a small amount of a cationic surfactant as a softening base, which is suitable for use under washing conditions in which a large amount of anionic surfactant is used. can.

Although the composition of the present invention is an emulsion-type liquid softener composition, the composition of the present invention may be simply referred to as the liquid softener composition in this specification.

[(A) component]
In the liquid softener composition of the present invention, the component (A) is blended in order to impart to the liquid softener composition the effect of imparting softness (texture) to textile products (that is, the original function of the softener). be.
Component (A) is one or more cationic surfactants selected from components (A-1) and (A-2).

<(A-1) Component>
Component (A-1) is a hydrocarbon group having 10 to 26 carbon atoms (hereinafter referred to as "long-chain It is at least one compound selected from the group consisting of amine compounds having 1 to 3 "hydrocarbon groups" in the molecule, salts thereof, and quaternary compounds thereof.
The carbon number of the long-chain hydrocarbon group is 10-26, preferably 17-26, more preferably 19-24. When the carbon number is 10 or more, the flexibility is good, and when it is 26 or less, the handleability is good.
Long chain hydrocarbon groups may be saturated or unsaturated. When the long-chain hydrocarbon group is unsaturated, the position of the double bond may be anywhere. It is preferably present at or around the center of the hydrogen group.
The long-chain hydrocarbon group may be a chain hydrocarbon group or a hydrocarbon group containing a ring in its structure, preferably a chain hydrocarbon group. The chain hydrocarbon group may be linear or branched. The chain hydrocarbon group is preferably an alkyl group or an alkenyl group, more preferably an alkyl group.

A long-chain hydrocarbon group is interrupted by an ester group (--COO--) or an amide group (--NHCO--). That is, the long-chain hydrocarbon group has, in the carbon chain, at least one splitting group selected from the group consisting of an ester group and an amide group, and the carbon chain is split by the splitting group. . By having the splitting group, biodegradability is improved.
One long-chain hydrocarbon group may have one or two or more splitting groups. That is, the long-chain hydrocarbon group may be cleaved at one site or may be cleaved at two or more sites. When having two or more splitting groups, each splitting group may be the same or different.
When the carbon chain has a splitting group, the carbon atoms of the splitting group are counted as the number of carbon atoms in the long-chain hydrocarbon group.
The long-chain hydrocarbon groups are usually industrially used unhydrogenated fatty acids derived from beef tallow, fatty acids obtained by hydrogenating or partially hydrogenating the unsaturated portion, and unhydrogenated fatty acids derived from plants such as palm 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.

［式中、Ｒ¹～Ｒ³は、それぞれ独立に、炭素数１０～２６の炭化水素基、－ＣＨ₂ＣＨ（Ｙ）ＯＣＯＲ⁴（Ｙは水素原子又はＣＨ₃であり、Ｒ⁴は炭素数７～２１の炭化水素基である。）、－（ＣＨ₂）_nＮＨＣＯＲ⁵（ｎは２又は３であり、Ｒ⁵は炭素数７～２１の炭化水素基である。）、水素原子、炭素数１～４のアルキル基、－ＣＨ₂ＣＨ（Ｙ）ＯＨ（Ｙは水素原子又はＣＨ₃である。）、又は－（ＣＨ₂）_nＮＨ₂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。］ The amine compound as the component (A) contained in the liquid softener composition of the present invention is preferably a secondary amine compound or a tertiary amine compound, more preferably a tertiary amine compound.
More specifically, the amine compound as the component (A) contained in the liquid softener composition of the present invention includes compounds represented by the following general formula (A1).

[In the formula, R ¹ to R ³ are each independently a hydrocarbon group having 10 to 26 carbon atoms, —CH ₂ CH(Y)OCOR ⁴ (Y is a hydrogen atom or CH ₃ , R ⁴ is a carbon number 7 to 21 hydrocarbon groups), —(CH ₂ ) _n NHCOR ⁵ (n is 2 or 3 and R ⁵ is a hydrocarbon group having 7 to 21 carbon atoms.), hydrogen atom, carbon an alkyl group having a number of 1 to 4, —CH ₂ CH(Y)OH (Y is a hydrogen atom or CH ₃ ), or —(CH ₂ ) _n NH ₂ , and at least R ¹ to R ³ One is a hydrocarbon group having 10 to 26 carbon atoms, --CH ₂ CH(Y)OCOR ⁴ or --(CH ₂ ) _n NHCOR ⁵ . ]

In formula (A1), the number of carbon atoms in 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. The hydrocarbon group is preferably an alkyl group or an alkenyl group.
In --CH ₂ CH(Y)OCOR ⁴ , Y is a hydrogen atom or CH ₃ , with a hydrogen atom being particularly preferred.
R ⁴ is a hydrocarbon group having 7 to 21 carbon atoms, preferably a hydrocarbon group having 15 to 19 carbon atoms. When a plurality of R ⁴ are present in the compound represented by formula (A1), the plurality of R ⁴ may be the same or different.
The hydrocarbon group of R ⁴ is ^{a residue (fatty acid residue) obtained by removing the carboxyl group from a fatty acid (R 4 COOH} ) having 8 to 22 carbon atoms ^. , saturated fatty acids or unsaturated fatty acids, straight chain fatty acids or branched fatty acids. Among them, saturated or unsaturated straight chain fatty acids are preferred. In order to impart good water absorbency to the softened clothes, the saturated/unsaturated ratio (mass ratio) of the fatty acid that is the basis of R ⁴ is preferably 90/10 to 0/100, and 80/20 to 0. /100 is more preferred.
When R ⁴ is an unsaturated fatty acid residue, there are cis and trans isomers, and the cis/trans isomer mass ratio is preferably 40/60 to 100/0, more preferably 70/30 to 90/10. Especially preferred.

Specific examples of fatty acids from which R ⁴ is derived 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), partial Hydrogenated beef tallow fatty acid (iodine value 10-60) and the like. Among them, two or more selected from stearic acid, palmitic acid, myristic acid, oleic acid, elaidic acid, and linoleic acid are combined in predetermined amounts and adjusted to satisfy the following conditions (a) to (c). It is preferred to use a composition.
(a) The saturated fatty acid/unsaturated fatty acid ratio (mass ratio) is 90/10 to 0/100, more preferably 80/20 to 0/100.
(b) The cis/trans isomer ratio (mass ratio) is 40/60 to 100/0, more preferably 70/30 to 90/10.
(c) C18 fatty acid is 60% by mass or more, preferably 80% by mass or more, C20 fatty acid is less than 2% by mass, and C21-22 fatty acid is less than 1% by mass. .

In —(CH ₂ ) _n NHCOR ⁵ , n is 2 or 3, with 3 being particularly preferred.
R ⁵ is a hydrocarbon group having 7 to 21 carbon atoms, preferably a hydrocarbon group having 15 to 19 carbon atoms. When multiple R ⁵ are present in the compound represented by formula (A1), the multiple R ⁵ may be the same or different.
Specific examples of R ⁵ include those similar to those of 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 of which are long-chain hydrocarbon groups.
When one or two of R ¹ to R ³ are a long-chain hydrocarbon group, the remaining two or one are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or —CH ₂ CH(Y) OH or --(CH ₂ ) _n NH ₂ , preferably an alkyl group having 1 to 4 carbon atoms, --CH ₂ CH(Y)OH or --(CH ₂ ) _n NH ₂ . Among these, the alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group, and particularly preferably a methyl group. Y in -CH ₂ CH(Y)OH is the same as Y in -CH ₂ CH(Y)OCOR ⁴ . n in —(CH ₂ ) _n NH ₂ is the same as n in —(CH ₂ ) _n NHCOR ⁵ .

A salt of an amine compound is obtained by neutralizing an amine compound with an acid. The acid used for neutralizing the amine compound may be either an organic acid or an inorganic acid, and examples thereof include hydrochloric acid, sulfuric acid, methylsulfuric acid and the like. 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 quaternizing the amine compound include alkyl halides such as methyl chloride and dialkyl sulfates such as dimethyl sulfate. When these quaternizing agents are reacted with an amine compound, an alkyl group of the quaternizing agent is introduced into the nitrogen atom of the amine compound to form a salt of a quaternary ammonium ion and a halogen ion or a monoalkyl sulfate ion. . 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, particularly preferably a methyl group. Quaternization of the amine compound can be carried out by a known method.

（式中、Ｒ₁及びＲ₂は、独立して、エステル基（－ＣＯＯ－）でもアミド基（－ＮＨＣＯ－）でも分断されていない、炭素数８～２４のアルキル基またはアルケニル基であり、Ｒ₃及びＲ₄は、独立して、メチル基、エチル基、ヒドロキシエチル基、ヒドロキシプロピル基、ポリオキシエチレン基またはポリオキシプロピレン基であり、Ｘ^-は陰イオンを表す。）
Ｒ₁及びＲ₂における炭化水素基の炭素数は、８～２４であり、好ましくは１０～２０であり、より好ましくは１４～１８である。
Ｒ₁及びＲ₂は、同じであっても異なっていてもよい。
また、Ｒ₃及びＲ₄は、同じであっても異なっていてもよい。
Ｒ₃及びＲ₄において、ポリオキシエチレン基及びポリオキシプロピレン基は、特に限定されないが、平均重合度が１～５のものであり得る。
Ｒ₃及びＲ₄は、好ましくは、メチル基、エチル基、ヒドロキシエチル基であり、より好ましくは、メチル基、エチル基である。
Ｘとしては、ハロゲン原子又はＲ₅ＳＯ₄で示される基が挙げられる。このハロゲン原子としては、塩素、臭素及びヨウ素が挙げられ、好ましくは塩素である。また、Ｒ₅は、炭素数１～３のアルキル基であり、メチル基、エチル基もしくはプロピル基である。 <(A-2) Component>
Component (A-2) is a quaternary ammonium salt represented by the following formula (A2).

(Wherein, R ₁ and R ₂ are independently an alkyl or alkenyl group having 8 to 24 carbon atoms that is not divided by an ester group (-COO-) or an amide group (-NHCO-), R ₃ and R ₄ are independently a methyl group, ethyl group, hydroxyethyl group, hydroxypropyl group, polyoxyethylene group or polyoxypropylene group, and X ^- represents an anion.)
The hydrocarbon group in R ₁ and R ₂ has 8 to 24 carbon atoms, preferably 10 to 20 carbon atoms, more preferably 14 to 18 carbon atoms.
R ₁ and R ₂ may be the same or different.
Also, R ₃ and R ₄ may be the same or different.
The polyoxyethylene group and polyoxypropylene group in R ₃ and R ₄ are not particularly limited, but may have an average degree of polymerization of 1-5.
R ₃ and R ₄ are preferably methyl group, ethyl group or hydroxyethyl group, more preferably methyl group or ethyl group.
X includes a halogen atom or a group represented by R ₅ SO ₄ . The halogen atoms include chlorine, bromine and iodine, preferably chlorine. R ₅ is an alkyl group having 1 to 3 carbon atoms, and is a methyl group, an ethyl group or a propyl group.

The (A-2) component is a known substance and is readily available on the market or can be prepared.
Component (A-2) is, for example, unsaturated higher fatty acids such as oleic acid, linoleic acid and linolenic acid, or natural fatty acids such as palm oil fatty acid, soybean oil fatty acid, safflower oil fatty acid and tall oil fatty acid, or mixtures thereof or A mixture of these and beef tallow fatty acids may be used as a starting material. Among these, oleic acid, a mixture of oleic acid and beef tallow fatty acid, and palm oil fatty acid are particularly preferred.
Commercially available products of component (A-2) include, for example, Lipocard 2HT-75 manufactured by Lion Specialty Chemicals Co., Ltd., Arcard 2HT-75 manufactured by Akzo Nobel, and 2HT manufactured by hana resources. It is not limited to these.
A single type of component (A-2) may be used, or multiple types may be used in combination.

The amount of component (A) contained in the liquid softener composition of the present invention is less than 5% by mass, preferably less than 1% by mass to less than 4.5% by mass, relative to the total mass of the liquid softener composition. Yes, more preferably 1.5% by mass to less than 4% by mass. When the blending amount of component (A) is 1% by mass or more, the effect of imparting flexibility to textile products can be further improved, and the amount of the softener composition used can be reduced. When the amount of component (A) to be blended is less than 5% by mass, the amount of the softener composition to be used becomes appropriate, and satisfaction in use can be improved.

（式中、Ｒ¹は、エステル基（－ＣＯＯ－）でもアミド基（－ＮＨＣＯ－）でも分断されていない、炭素数８～２４の炭化水素基であり、Ｒ²及びＲ³は、独立して、炭素数１～３のアルキル基であり、Ｘ^-は陰イオンを表す。）
Ｒ¹における炭化水素基の炭素数は、８～２４であり、好ましくは１２～２０であり、より好ましくは１４～１８である。
Ｒ¹は飽和でも不飽和でもよいが、飽和炭化水素基であることが好ましい。
Ｒ²及びＲ³は独立して炭素数１～３のアルキルであり、好ましくはメチル基である。
Ｘとしては、メチル硫酸、臭素や塩素等が挙げられ、塩素が好ましい。 [(B) component]
In the liquid softener composition of the present invention, the component (B) improves the effect of the liquid softener composition on imparting flexibility to textile products and/or improves the effect of imparting lingering fragrance, particularly an anionic surfactant. It is blended in order to improve the effect of the liquid softener composition on imparting softness to textiles and/or the effect of imparting lingering fragrance to textiles under conditions of washing with a large amount of use.
(B) component is a quaternary ammonium salt represented by the following formula (B).

(In the formula, R ¹ is a hydrocarbon group having 8 to 24 carbon atoms that is not separated by an ester group (--COO--) or an amide group (--NHCO--), and R ² and R ³ are independently is an alkyl group having 1 to 3 carbon atoms, and X ^- represents an anion.)
The hydrocarbon group in R ¹ has 8 to 24 carbon atoms, preferably 12 to 20 carbon atoms, more preferably 14 to 18 carbon atoms.
R ¹ may be saturated or unsaturated, but is preferably a saturated hydrocarbon group.
R ² and R ³ are independently alkyl having 1 to 3 carbon atoms, preferably methyl.
Examples of X include methylsulfuric acid, bromine and chlorine, and chlorine is preferred.

Component (B) is a known substance and is readily available on the market or can be prepared.
Specific examples of component (B) include octyltrimethylammonium chloride, decyltrimethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, and stearyltrimethylammonium chloride, but are limited to these. not to be

The amount of component (B) contained in the liquid softener composition of the present invention is 0.01 to 2% by mass, preferably 0.1 to 2% by mass, relative to the total mass of the liquid softener composition. Yes, more preferably 0.2 to 1.5% by mass. When the blending amount of the component (B) is 0.01% by mass or more, the effect of imparting softness to textile products and/or the effect of imparting lingering fragrance is improved. (B) Storage stability is favorable in the compounding quantity of a component being 2 mass % or less.
The mass ratio A/B of component (A) to component (B) in the liquid softener composition of the present invention is 1-200, preferably 2-100, more preferably 3-20. When A/B is 1 or more, the fragrance strength, persistence, and deodorant effect required for the softener are good. Storage stability is favorable in A/B being 200 or less.

[(C) component]
In the liquid softener composition of the present invention, the component (C) is a perfume, and is blended to impart fragrance to the liquid softener composition and further to impart fragrance to textile products after treatment with the composition. obtain.
As component (C), perfumes commonly used in the field of softeners can be used, and there is no particular limitation. Lists of usable perfume raw materials are found in various literatures, for example, "Perfume and Flavor Chemicals", Vol. I and II, Steffen Arctander, Allured Pub. Co. (1994) and "Synthetic Perfume Chemistry and Product Knowledge", Genichi Indo, Chemical Daily (1996) and "Perfume and Flavor Materials of Natural Origin", Steffen Arctander, Allured Pub. Co. (1994) and "Encyclopedia of Aroma", edited by Japan Perfume Association, Asakura Shoten (1989) and "Perfumery Material Performance V.3.3", Boelens Aroma Chemical Information Service (1996) and "Flower oils and Floral Compou nds In Perfumery" , Danute Lajaujis Anonis, Allured Pub. Co. (1993) and others.

(C) A single type may be used for the component, or multiple types may be used in combination (perfume composition is used).
The amount of component (C) contained in the liquid softener composition of the present invention is not particularly limited, but is preferably 0.1 to 3.0% by mass, more preferably 0.1 to 3.0% by mass, based on the total mass of the liquid softener composition. is 0.2 to 2.0% by mass, more preferably 0.2 to 1.5% by mass. When the blending amount of component (C) is 0.1% by mass or more, the fragrance intensity, persistence, and deodorant effect required for the softener are better, and when it is 3.0% by mass or less, the fragrance It is possible to better prevent the dispersion of the oil from becoming unstable and the oil from floating.

[Other optional ingredients]
The liquid softener composition of the present invention may optionally contain the following components in addition to the components (A) to (C) as long as the effects of the present invention are not impaired. For example, water, nonionic surfactants, water-soluble solvents, sugar compounds, silicone compounds, dyes and/or pigments, preservatives, UV absorbers, antibacterial agents, highly branched cyclic dextrin, functional capsules, viscosity modifiers, structure Agents and the like can be added.

<Water>
The liquid softener composition of the present invention is preferably an aqueous composition containing water.
As water, any of tap water, ion-exchanged water, pure water, distilled water, and the like can be used. Among them, ion-exchanged water is preferable.
Although the amount of water to be blended is not particularly limited, it is preferably 50% by mass or more, more preferably 60% by mass or more, relative to the total mass of the liquid softener composition. When the blending amount is 50% by mass or more, the handleability becomes better.

<Nonionic surfactant>
A nonionic surfactant may be blended in order to further improve the stability of the liquid softener composition, particularly to further improve the freeze reconstitution property.
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 alcohols, amines and fatty acids can be branched or straight chain and can be unsaturated. Moreover, there may be a distribution in the carbon chain. The number of carbon atoms in the carbon chain is preferably 6-20, more preferably 8-18. When the carbon chain is straight, it preferably has 6-14 carbon atoms, more preferably 8-12 carbon atoms, and most preferably 8-10 carbon atoms. When the carbon chain is branched, it preferably has 6-18 carbon atoms, more preferably 9-18 carbon atoms, and most preferably 13 carbon atoms.
As raw materials for nonionic surfactants, Exxon Chemical's Exal, BASF's LUTENSOL series, Kyowa Hakko Kogyo's Oxocol, Hoechst AG's GENAPOL series, and Shell's DOBANOL series can be used. Both primary and secondary alcohols can be used when the nonionic surfactant is an alkylene oxide adduct of an alcohol. The alcohol having 13 carbon atoms is produced from, for example, dodecene, but the starting material may be butylene or propylene.
If the carbon chain contains unsaturated groups, those with 18 carbon atoms are particularly preferred. The stereoisomeric structure of the unsaturated group may be cis or trans, or a mixture of both. is preferred.
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 added moles of EO is preferably 10 to 100 moles, more preferably 20 to 80 moles, particularly preferably 40 to 70 moles. Also, the average number of moles of PO or BO added together with EO is preferably 1 to 5, more preferably 1 to 3 moles. At this time, PO or BO may be added after adding EO, or EO may be added after adding PO or BO.
Specific examples of nonionic surfactants include average EO9PO1 adducts of nonyl alcohol, average EO40 mol adducts of primary isononyl alcohol, average EO20 mol adducts of primary isodecyl alcohol, average EO20 mol adducts of lauryl alcohol, primary Average EO60 mol adduct of isohexadecyl alcohol, average EO60 mol adduct of primary isotridecyl alcohol, average EO50 mol adduct of tridecyl alcohol, average EO60 adduct of tallow alkylamine, average EO60 adduct of tallow alkylamine average EO50 adduct of oleylamine and average EO20 mol adduct of lauric acid. Commercially available products include the Emalex series manufactured by Nippon Emulsion, the Emalmin series manufactured by Sanyo Chemical, the TDA series manufactured by Lion Chemical, the Esomin series, the Softanol series manufactured by Nippon Shokubai, and the LUTESOL series manufactured by BASF.

The amount of the nonionic surfactant to be blended is not particularly limited as long as it is an amount that can achieve the purpose of blending. More preferably, it is 1 to 4% by mass.

<Water-soluble solvent>
A water-soluble solvent can be blended in order to further improve the stability of the liquid softener composition, particularly to further improve the freeze recovery property.
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 are preferred. 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 preferred to incorporate a solvent component.
R ⁶ —O—(C ₂ H ₄ O) _y —(C ₃ H ₆ O) _Z —H (X)
(In the formula, R ⁶ is an alkyl or alkenyl group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms, y and z are the average number of added moles, and y is 1 to 10, preferably 2 to 5 and z is 0-5, preferably 0-2.)
Among those listed above, ethanol, ethylene glycol, butyl carbitol, propylene glycol, dipropylene glycol monomethyl ether, and diethylene glycol monobutyl ether are preferred.
Although the amount of the water-soluble solvent is not particularly limited, it is preferably 0 to 30% by mass, more preferably 0.01 to 25% by mass, still more preferably 0.1 to 20% by mass, based on the total mass of the liquid softener composition. % by mass.

<Sugar compound>
A sugar-based compound may be blended to further improve the stability of the liquid softener composition, particularly to further improve the freeze reconstitution property.
As the sugar compound, the number of repeating units in the sugar skeleton (degree of polymerization) is preferably 1 to 40, more preferably 1 to 20, and 1 to 5 (that is, monosaccharides and oligos having a degree of polymerization of more than 1 and 5 or less). sugar) are particularly preferred. Preferred sugar compounds include monosaccharides, disaccharides, oligosaccharides and sugar alcohols.
Specific examples of sugars include glucose, fructose, galactose, arabinose, ribose, maltose, isomaltose, cellobiose, lactose, sucrose, trehalose, talose, maltotriose, isomalttriose, and from partial hydrolysis of natural polysaccharides. Examples include the obtained oligosaccharides and compounds (sugar derivatives) in which substituents are introduced into these sugars. Examples of substituents that can be introduced include alkyl groups, alkenyl groups, alkoxy groups, hydroxyalkyl groups, amine groups, quaternary ammonium groups, and carboxyl groups. Among these, particularly alkyl groups, alkenyl groups, and alkoxy groups is mentioned. The substituent is preferably an alkyl group, alkenyl group or alkoxy group having 1 to 18 carbon atoms, more preferably an alkyl group, alkenyl group or alkoxy group having 1 to 12 carbon atoms, and further an alkyl group having 1 to 6 carbon atoms. Preferred are alkyl groups having 1 to 3 carbon atoms.
The sugar is selected from monosaccharides and oligosaccharides with a degree of polymerization of 1 to 5, and compounds in which at least one hydrogen atom of a hydroxyl group in the monosaccharides and oligosaccharides with a degree of polymerization of 1 to 5 is substituted with an alkyl group. One or more are preferred. Among those mentioned above, trehalose is preferable from the viewpoint of freeze recovery.
Sugar alcohols include erythritol, threitol, pentitol, hexitol, dulcitol, sorbitol, mannitol, boremitol, perseilletol, xylitol, maltitol, lactitol and the like.
The sugar compounds may be used singly or as a mixture of two or more.
The amount of the sugar-based compound to be blended is not particularly limited as long as the blending purpose can be achieved. , more preferably 0.1 to 5% by mass.

<Silicone compound>
A silicone compound may be blended for the main purpose of further improving fragrance persistence.
As the silicone compound, components known in the field of liquid softener compositions can be used without particular limitation.
The molecular structure of the silicone compound may be linear, branched, or crosslinked. Also, 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 form of an oil or in the form of an emulsion dispersed with any emulsifier.
Specific examples of silicone compounds include dimethylsilicone, polyether-modified silicone, methylphenylsilicone, alkyl-modified silicone, higher fatty acid-modified silicone, methylhydrogensilicone, fluorine-modified silicone, epoxy-modified silicone, carboxy-modified silicone, and carbinol. Examples 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. Polyether-modified silicones and amino-modified silicones are preferable from the viewpoint of further improving the fragrance persistence and handling during production.

The dynamic viscosity of dimethyl silicone is not particularly limited, but is preferably 1 to 100,000,000 mm ² /s, more preferably 10 to 10,000,000 mm ² /s, and more preferably 100 to 1,000,000 mm ² /s. s is more preferred. Moreover, 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 polyether-modified silicones include copolymers of alkylsiloxanes and polyoxyalkylenes. The number of carbon atoms in the alkyl group of the alkylsiloxane is preferably 1-3. The number of carbon atoms in the alkylene group of the polyoxyalkylene is preferably 2-5.
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 compounds represented by the following general formula (I).

(wherein M, N, a and b are each independently the average degree of polymerization, and R is hydrogen or an alkyl group)
In general formula (I), M is 10-10,000, preferably 100-300.
N is 1-1,000, preferably 1-100. Furthermore, it is preferred that M>N.
a is 2-100, preferably 2-50.
b is 0-50, preferably 0-10.
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 composed of an organohydrogenpolysiloxane having a Si—H group and a carbon-carbon double bond-terminated poly, such as polyoxyalkylene allyl ether. It can be produced by an addition reaction with an oxyalkylene alkyl ether in the presence of a platinum catalyst. In this case, the product may contain a small amount of unreacted polyoxyalkylene alkyl ether or organohydrogenpolysiloxane having Si—H groups. Since the organohydrogenpolysiloxane having Si—H groups is highly reactive, the amount present 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 also include linear polysiloxane-polyoxyalkylene block copolymers represented by the following general formula (II).

(Wherein, A, B, h and i are average degrees of polymerization, R is an alkyl group, and R' is hydrogen or an alkyl group.)
In general formula (II), A is 5 to 10,000,
B is 2 to 10,000;
h is 2 to 100,
i is 0-50.
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 general formula (II) comprises a polyoxyalkylene compound having a reactive terminal group and a di It can be produced by reacting with hydrocarbylsiloxane. Such a polyether-modified silicone has a longer polyoxyalkylene chain in the side chain, and the higher the degree of polymerization of the polysiloxane chain, the higher the viscosity. In order to make it possible, it is preferable to use it in the form of a premix with a water-soluble organic solvent. Examples of water-soluble organic solvents include ethanol, dipropylene glycol, butyl carbitol and the like.

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

（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 obtained by introducing an amino group to the terminal or side chain of a dimethylsilicone skeleton. A substituent such as a hydroxyl group, an alkyl group, or a phenyl group may be introduced in addition to the amino group.
The amino-modified silicone may be in the form of an oil, or in the form of an amino-modified silicone emulsion emulsified using a nonionic surfactant or cationic surfactant as an emulsifier.
Preferred amino-modified silicone oils or base oils in emulsions are compounds represented by the following general formula (III).

(Wherein, R ¹ and R ⁶ are a methyl group, a hydroxyl group, or hydrogen, which may be the same or different,
R ² is —(CH ₂ ) _n —A ¹ or —(CH ₂ ) _n —NHCO—(CH ₂ ) _m —A ¹ (wherein A ¹ is —N(R ³ )(R ⁴ ), -N ⁺ (R ³ )(R ⁴ )(R ⁵ )·X ⁻ (wherein R ³ , R ⁴ and R ⁵ may be the same or different , a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group or —(CH ₂ ) _n —NH ₂ (wherein n is 0 to 12), X ⁻ is a fluorine ion, a chloride ion, bromide ion, iodine ion, methyl sulfate ion, or ethyl sulfate ion), and the values of m and n may be the same or different, and are integers from 0 to 12). can be,
p and q each represent the degree of polymerization of polysiloxane, may be the same or different, p is 0 to 20000, preferably 10 to 10000, q is 1 to 500, preferably 1 to 100. )

The amino-modified silicone oil preferably has a kinematic viscosity at 25° C. of 50 to 20,000 mm ² /s, more preferably 100 to 10,000 mm ² /s. When the kinematic viscosity is within this range, a high fragrance persistence effect is exhibited, the manufacturability is improved, and the handling of the product is facilitated.

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

One silicone compound may be used alone, or two or more silicone compounds may be used as a mixture.
The amount of the silicone compound to be blended is not particularly limited as long as it is an amount that can achieve the purpose of blending. More preferably, it is 0.1 to 5% by mass.

<Dyes and/or pigments>
Dyes and pigments may each be incorporated to enhance the appearance of the liquid softener composition.
For both dyes and pigments, ingredients known in the field of liquid softener compositions can be used without particular limitations. Specific examples of dyes that can be added are described in Dye Handbook (edited by the Society of Organic Synthetic Chemistry, published on July 20, 1970, Maruzen Co., Ltd.). In addition, JP-A-6-123081, JP-A-6-123082, JP-A-7-18573, JP-A-8-27669, JP-A-9-250085, JP-A-10-77576, Dyes described in JP-A-11-43865, JP-A-2001-181972 and JP-A-2001-348784 can also be used.
Preferably, it is one or more of red, blue, yellow or purple water-soluble dyes selected from acid dyes, direct dyes, basic dyes, reactive dyes and mordant/acid mordant dyes.
From the viewpoint of the storage stability of the liquid softener composition and the dyeing property to fibers, acid dyes and direct dyes having at least one functional group selected from a hydroxyl group, a sulfonic acid group, an amino group and an amide group in the molecule. Alternatively, reactive dyes are preferred.
For each of the dyes and pigments, one type may be used alone, or two or more types may be used as a mixture. Also, a dye and a pigment may be used in combination.
The amounts of the dyes and pigments to be added are not particularly limited as long as the purpose of the addition can be achieved.

<Preservative>
A preservative can be added mainly to enhance the antiseptic power and bactericidal power of the liquid softener composition and to maintain the antiseptic properties during long-term storage.
As the preservative, components known in the field of liquid softener compositions can be used without particular limitation. Specific examples include isothiazolone-based organic sulfur compounds, benzisothiazolone-based organic sulfur compounds, benzoic acids, and 2-bromo-2-nitro-1,3-propanediol.
Examples of isothiazolone organic sulfur compounds include 5-chloro-2-methyl-4-isothiazolin-3-one, 2-n-butyl-3-isothiazolone, 2-benzyl-3-isothiazolone, and 2-phenyl-3-isothiazolone. , 2-methyl-4,5-dichloroisothiazolone, 5-chloro-2-methyl-3-isothiazolone, 2-methyl-4-isothiazolin-3-one, and mixtures thereof. Among them, 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one are preferred, and 5-chloro-2-methyl-4-isothiazolin-3-one and 2 -methyl-4-isothiazolin-3-one is more preferred, and a mixture of about 77% by weight of the former and about 23% by weight of the latter or a diluted solution thereof (eg, isothiazolone solution) is particularly preferred.
Examples of benzisothiazolone organic sulfur compounds include 1,2-benzisothiazolin-3-one, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, and analogous compounds such as dithio-2,2-bis ( benzmethylamide) and mixtures thereof. Among them, 1,2-benzisothiazolin-3-one is particularly preferred.
Examples of benzoic acids include benzoic acid or salts thereof, parahydroxybenzoic acid or salts thereof, methyl parahydroxybenzoate, ethyl parahydroxybenzoate, propyl parahydroxybenzoate, butyl parahydroxybenzoate, and benzyl parahydroxybenzoate.
The amount of the preservative to be added is not particularly limited as long as it is an amount that can achieve the purpose of the addition, but is preferably 0.0001 to 1% by mass relative to the total mass of the liquid softener composition. When the amount is 0.0001% by mass or more, a sufficient effect of the preservative can be obtained, and when the amount is 1% by mass or less, the high storage stability of the liquid softener composition can be sufficiently maintained.

<Ultraviolet absorber>
A UV absorber may be included to protect the liquid softener composition from UV light.
An ultraviolet absorber is a component that exerts an ultraviolet protection effect by absorbing ultraviolet rays, converting them into infrared rays, visible rays, or the like and emitting them.
As the ultraviolet absorber, components known in the field of liquid softener compositions can be used without particular limitation. Specific examples include aminobenzoic acid derivatives such as p-aminobenzoic acid, ethyl p-aminobenzoate, glyceryl p-aminobenzoate, and amyl p-dimethylaminobenzoate; ethylene glycol salicylate and dipropylene glycol salicylate. , octyl salicylate and salicylic acid derivatives such as myristyl salicylate; Cinnamic acid derivatives such as butyl acetate; Benzophenone derivatives such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and 2,2'-dihydroxy-4-methoxybenzophenone; Azole compounds such as urocanic acid and ethyl urocanate; 4-t-butyl-4'-methoxybenzoylmethane and the like.
The blending amount of the ultraviolet absorber is not particularly limited as long as the blending purpose can be achieved, but it is preferably 0.001 to 5% by mass based on the total mass of the liquid softener composition.

<Antibacterial agent>
An antimicrobial agent may be included to enhance the shelf life of the liquid softener composition.
As the antibacterial agent, components known in the field of liquid softener compositions can be used without particular limitation. Specific examples include diclosan, triclosan, benzalkonium chloride, bis-(2-pyridylthio-1-oxide)zinc, 8-oxyquinoline, biguanide compounds (e.g., polyhexamethylenebiguanide), chlorhexidine hydrochloride, and , polylysine, and the like. Among these, benzalkonium chloride, biguanide compounds, and chlorhexidine hydrochloride are preferred.
The amount of the antibacterial agent to be added is not particularly limited as long as the purpose of the addition can be achieved, but it is preferably 0.001 to 5% by mass based on the total mass of the liquid softener composition.

<Highly branched cyclic dextrin>
The highly branched cyclic dextrin can be blended in order to further improve the stability (particularly freeze-restoring property) of the liquid softener composition, and to impart deodorizing and deodorizing properties to textile products.
A highly branched cyclic dextrin is a glucan having an inner branched cyclic structure portion and an outer branched cyclic structure portion and having a weight average degree of polymerization in the range of 50 to 10,000.
A glucan having an inner branched cyclic structure portion and an outer branched structure portion is a substance called highly branched cyclic dextrin or cluster dextrin.
A highly branched cyclic dextrin has a structure in which a plurality of (for example, 100) non-cyclic glucose chains (outer branched structural portions) are bound to one inner branched cyclic structural portion.
The term “internally branched cyclic structure portion” refers to a cyclic structure portion formed by α-1,4-glucosidic bonds and α-1,6-glucosidic bonds. The inner branched cyclic structural portion of the highly branched cyclic dextrin is composed of about 10 to 100 glucoses. That is, the degree of polymerization of the inner branched cyclic structure portion is in the range of 10-100.
The outer branched structure portion refers to a non-cyclic structure portion bonded to the inner branched cyclic structure portion. The average degree of polymerization in the acyclic glucose chains constituting the outer branched structure portion of the highly branched cyclic dextrin is 10-20. However, the degree of polymerization in one acyclic glucose chain may be 40 or more.
The weight average polymerization degree of glucose in the highly branched cyclic dextrin is 50 to 10,000, specifically in the range of 50 to 5,000, more specifically about 2,500.
Further, 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 degree of polymerization (molecular weight) include α-cyclodextrin (degree of polymerization 6), β-cyclodextrin (degree of polymerization 7 ) and γ-cyclodextrin (degree of polymerization 8).

A highly branched cyclic dextrin can be produced, for example, by using starch as a raw material and allowing an enzyme called a branching enzyme to act on it.
Starch, which is a raw material, consists of amylose, in which glucose is linearly linked by α-1,4-glucosidic bonds, and amylopectin, which has a complex branched structure by α-1,6-glucosidic bonds. Amylopectin is a macromolecule with many linked cluster structures.
The branching enzyme used is a glucan chain transferase widely found in animals, plants and microorganisms. The branching enzyme acts on the joints of the amylopectin cluster structure and catalyzes the reaction to cyclize it.

Specific examples of highly branched cyclic dextrins include glucans 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, as described in JP-A-8-134104. In the present invention, the highly branched cyclic dextrin can be understood with reference to the description of JP-A-8-134104.
Highly branched cyclic dextrins can be produced as described above and are readily available commercially. Commercial products of highly branched cyclic dextrin include "Cluster Dextrin" (registered trademark) from Glico Nutrient Foods Co., Ltd.
A single kind of highly branched cyclic dextrin may be used, or a plurality of kinds thereof may be used in combination.

The content of highly branched cyclic dextrin is not particularly limited as long as the purpose of blending can be achieved, but it 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 blending effect (in particular, the effect of imparting deodorizing and deodorizing properties to fibers) can be fully exhibited. When the content is 10% by mass or less, the increase in viscosity of the liquid softening agent composition is suppressed, and usability such as ease of discharge from a container and ease of insertion into a washing machine can be maintained satisfactorily. can.

<Functional Capsule>
Functional capsules can be blended to impart various functions to the liquid softener composition due to the core substance encapsulated in the capsule.
A functional capsule is composed of a core substance and a wall substance covering the core substance.

As the core substance, those generally used as encapsulation substances in the field of liquid softeners can be used without particular limitation. Specific examples include fragrances, essential oils, whitening agents, insect repellents, silicones, waxes, flavoring agents, vitamins, skin care agents, enzymes, probiotics, dyes, pigments, fragrance precursors, cooling agents, warming agents, Attractants such as pheromones, antibacterial agents, bleaching agents, flavoring agents, sweeteners, waxes, drugs, fertilizers, herbicides, and the like.
The core substance may be used singly or in combination of two or more.

As the wall material, those commonly used as encapsulating 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 having a fragrance as a core material include BLUEFLOWERPOP "FFMHN2814" manufactured by Firmenich, GREEN BREEZE CAPS, GREENBREEZE DeoB, ORCHARD GARDEN CAPS, RAINBOW CAPS, VELVET CAPS, VELVET UP, and AURO manufactured by Givaudan. RACAPS, and COSMICCAPS, and UNICAP101 and UNICAP503 manufactured by IFF.
Specific examples of cooling capsules having a cooling agent as a core material include MultiSal SalCool, HydroSal FreshCool, and SalSphere SalCool manufactured by SALVONA Technologies, and Neoage AROMA-C manufactured by Nicca Chemical Co., Ltd., and the like.
Specific examples of the warming capsule containing a warming agent as a core material include Riken Resin RMC-TO manufactured by Miki Riken Co., Ltd., and Hydrosal Heat manufactured by SALVONA Technologies.
Other specific examples include Riken resin NFHO-W (antibacterial effect) manufactured by Miki Riken Co., Ltd., and Riken resin RMC-HBP (insect repellent effect) and RMC-PT (insect repellent effect).

The average particle size of the functional capsule is preferably 10 μm to 30 μm. The functional capsules having the above particle size are highly adsorbable to clothes and can be stably dispersed in the liquid softener composition.
Functional capsules are known substances and are readily available on the market or can be prepared.
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 purpose of formulation can be achieved, but it is preferably 0.0001 to 1% by mass based on the total mass of the liquid softener composition.

<Viscosity modifier>
Inorganic or organic water-soluble salts can be used for the purpose of controlling the viscosity of the liquid softener composition of the present invention. Specifically, calcium chloride, magnesium chloride, sodium chloride, sodium p-toluenesulfonate, sodium citrate, and the like can be used, and among them, calcium chloride, magnesium chloride, and sodium citrate are preferred.
The blending amount is 0 to 1.5% by mass, preferably 0.01 to 1.0% by mass, more preferably 0.01 to 0.8% by mass. The viscosity modifier may be blended in any step.

<Structuring agent>
As a structuring agent, polyethyleneimine or a derivative thereof, or a cationic (meth)acrylic polymer may be blended into the liquid softener composition.
Examples of polyethyleneimine or derivatives thereof include Lupasol SK (manufactured by BASF), which is an amide derivative of polyethyleneimine, and LupasolPS (manufactured by BASF), which is polyethyleneimine.
Examples of cationic (meth)acrylic polymers include Rheovis FRC (manufactured by BASF) and Rheovis CDE (manufactured by BASF).
The content of the structuring agent is not particularly limited as long as the purpose of blending can be achieved, but it is preferably 0.01 to 5.0% by mass based on the total mass of the liquid softener composition.

<Other optional ingredients>
In addition to the above optional components, antioxidants, reducing agents, emulsifying agents (such as polystyrene emulsions), opacifying agents, anti-shrinking agents, and laundry detergents are used to improve the stability of the aroma and color tone of the liquid softener composition. anti-wrinkle agent, shape retention agent, drape retention agent, ironing agent, oxygen bleaching inhibitor, whitening agent, whitening agent, fabric softening clay, antistatic agent, anti-dye transfer agent (polyvinylpyrrolidone, etc.), high Molecular dispersant, stain remover, scum dispersant, fluorescent brightening agent (4,4-bis(2-sulfostyryl)biphenyl disodium (Ciba Specialty Chemicals Tinopal CBS-X), etc.), dye fixing agent, anti-fading agent agents (1,4-bis(3-aminopropyl) piperazine, etc.), stain removers, fiber surface modifiers (enzymes such as cellulase, amylase, protease, lipase, and keratinase), foam inhibitors, moisture absorption and release, etc. Ingredients that impart the texture and function of silk (silk protein powder, their surface modified products, emulsified dispersions, specifically K-50, K-30, K-10, A-705, S-702, L- 710, FP series (Idemitsu Petrochemical), hydrolyzed silk liquid (Jomo), Silkgen G Solble S (Ichimaru Falcos)) and antifouling agents (from alkylene terephthalate and/or alkylene isophthalate units and polyoxyalkylene units Nonionic polymer compounds such as FR627 manufactured by GOO CHEMICAL INDUSTRY CO., LTD., SRC-1 manufactured by Clariant Japan Co., Ltd., etc.) can be appropriately blended.

[Viscosity of Liquid Softener Composition]
The viscosity of the liquid softener composition is not particularly limited as long as it does not impair its usability, but it is preferably less than 500 mPa·s, more preferably less than 300 mPa·s. Within such a range, the usability such as the handling property at the time of throwing into the washing machine is good.
The viscosity is a value measured at 25° C. using a Brookfield viscometer (for example, Brookfield Analog Viscometer T).

[pH of Liquid Softener Composition]
Although the pH of the liquid softener composition is not particularly limited, it is preferable that the pH at 25°C is within the range of 1 to 6 from the viewpoint of suppressing hydrolysis of the component (A) due to aging of storage. It is more preferably in the range of 2-4, and even more preferably in the range of 2-3.
For pH adjustment, hydrochloric acid, sulfuric acid, phosphoric acid, alkyl sulfuric acid, benzoic acid, p-toluenesulfonic acid, citric acid, malic acid, succinic acid, lactic acid, glycolic acid, hydroxyethanediphosphonic acid, phytic acid, ethylenediaminetetraacetic acid, Short-chain amine compounds such as dimethylamine, alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates, and pH adjusters such as alkali metal silicates can be used.

[Method for preparing liquid softener composition]
The method for preparing the liquid softener composition of the present invention is not particularly limited. The liquid softener composition can be produced by a known method, for example, a method similar to the production method of a conventional liquid softener composition using a cationic surfactant as a main ingredient.
For example, an oil phase containing components (A), (B) and (C), and optionally other components, and an aqueous phase are mixed at a temperature above the melting point of component (A). A liquid softener composition can be produced by preparing an emulsion using the above steps, and optionally adding and mixing other components to the obtained emulsion.

[How to use the liquid softener composition]
The method for using the liquid softener composition of the present invention is not particularly limited, and it can be used in the same manner as for general softener compositions. For example, a method of dissolving the liquid softener composition of the present invention in rinsing water in the rinsing stage of washing to soften the laundry, or a method of dissolving the liquid softener composition of the present invention in water in a container such as a basin. There is also a method of dissolving in , and then immersing the items to be washed.
One aspect of the invention also relates to a method of treating textiles. Specifically, one aspect of the present invention relates to a method of treating a textile product, which comprises contacting the textile product with a liquid softener composition in water containing 1 ppm or more of linear alkylbenzene sulfonic acid or a salt thereof. . The liquid softener composition in this method is as described herein.
The water containing 1 ppm or more of linear alkylbenzene sulfonic acid or its salt is, for example, rinsing water when a softening agent is added in laundry. The concentration of linear alkylbenzene sulfonic acid or its salt in such water may be 3 ppm or more, or may be 5 ppm or more.
Linear alkyl benzene sulfonic acids or salts thereof, also called LAS, for example, have alkyl groups in the range of 8 to 16 carbon atoms.

Bringing the liquid softener composition into contact with textile products in water containing 1 ppm or more of linear alkylbenzene sulfonic acid or a salt thereof is not particularly limited, but means that the textile product and 1 ppm or more of linear alkylbenzene sulfonic acid or its salt are brought into contact with each other. adding a liquid softener composition to water containing salt, or immersing a textile product in water containing a liquid softener composition and 1 ppm or more of linear alkylbenzene sulfonic acid or a salt thereof. obtain.
Textile products to be treated are not particularly limited, but examples thereof include clothing, curtains, sofas, carpets, towels, handkerchiefs, sheets, and pillow covers. The material may be natural fibers such as cotton, silk and wool, or chemical fibers such as polyester.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the scope of the present invention is not limited thereto. In the examples, all of the compounding amounts of components are shown in mass % (converted to pure content, unless otherwise specified).

[(A) component]
A-1 and A-2 below were used.
A-1: Cationic surfactant of ester type Cationic surfactant synthesized according to the procedure described in Example 4 of JP-A-2003-12471 A-2: Dimethyl dialkyl cation (trade name "Lipocard 2HT-75", manufactured by Lion Specialty Chemicals Co., Ltd.)
In A-2, each dialkyl is an alkyl group having 18 carbon atoms.

[(B) component]
B-1 to B-3 below were used.
B-1: Hexadecyltrimethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.)
B-2: Dodecyltrimethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.)
B-3: Octyltrimethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.)

[(C) Component]
C-1: Perfume containing perfume ingredients with the composition shown in Table 1 below

[Common component]
D-1: Components shown in Table 2 below

D-2: Components shown in Table 3 below

[Method for preparing emulsion-type liquid softener composition]
Using a glass container with an inner diameter of 100 mm and a height of 150 mm and a stirrer (Agitor SJ type, manufactured by Shimadzu Corporation), the blending amount of each component was adjusted as shown in Table 4 below, and the emulsion type liquid was prepared by the following procedure. A softener composition was prepared. First, the components (A), (B), (C) and nonionic surfactant were mixed and stirred to obtain an oil phase mixture. On the other hand, a preservative was dissolved in ion-exchanged water for balance to obtain an aqueous phase mixture. The mass of ion-exchanged water for balance (including preservatives) corresponds to the balance after subtracting the total amount of the oil phase mixture from 980 g.
Next, the oil phase mixture heated to the melting point or higher of the component (A) is placed in a glass container and stirred while the aqueous phase mixture heated to the melting point or higher of the component (A) is added in two portions. and stirred. Here, 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 for 2 minutes after the second addition of the aqueous phase mixture. rice field. After that, calcium chloride and capsule perfume were added to the obtained emulsion and stirred. If necessary, add an appropriate amount of hydrochloric acid (reagent 1 mol/L, Kanto Kagaku) or sodium hydroxide (reagent 1 mol/L, Kanto Kagaku) to adjust the pH, and further adjust the total mass to 1,000 g. By adding ion-exchanged water to the above, the desired emulsion-type liquid softener compositions (Examples 1 to 13, Comparative Examples 1 to 3) were obtained.

[Evaluation method for liquid softener composition]
The "fragrance intensity", "softness" and "storage stability" of each obtained liquid softener composition were evaluated according to the following procedures.

<1. Treatment of cotton towels with a liquid softener composition>
(Pretreatment of cloth for evaluation)
A commercially available cotton towel (manufactured by Toshin Co., Ltd.) was subjected to the following pretreatment three times with a commercially available detergent "Top Platinum Clear" (manufactured by Lion Corporation) using a two-tank washing machine (Toshiba VH-30S). .
Pretreatment: 2 cycles of washing with tap water at 45° C. for 10 minutes, followed by rinsing with water for 10 minutes, using standard amount of detergent, bath ratio of 30 times.

(Treatment with liquid softener composition in rinsing process during washing)
A cotton towel (manufactured by Toshin Co., Ltd.) that has been pretreated and washed is used in a two-tank washing machine (Toshiba VH-30S), assuming the second rinse. Specialty Chemicals Co., Ltd.) was added to adjust to 15 ppm, each liquid softener composition obtained as described above was added, and softening treatment was performed for 3 minutes (amount of softener used: 25 ml/amount of cloth 1.5 kg, bath ratio 20 times, 25° C. tap water was used). After the softening treatment, dehydration was performed for 1 minute.
After the treatment, the cotton towel was removed from the two-tank washing machine, dried for 18 hours under constant temperature and humidity conditions of 20° C. and 40% RH, and subjected to the following evaluations.

<2. Fragrance intensity evaluation>
The odor intensity of the cotton towel after drying for 18 hours was subjected to sensory evaluation according to the following 6-step odor intensity indication method. Based on the average score (calculated to the first decimal place) of 8 expert panelists, the fragrance intensity was determined according to the following criteria. The results are shown in the section of "fragrance intensity" in Table 4 below. In terms of commercial value, ◯ or better was determined as acceptable.
(Evaluation criteria)
0: Odorless 1: Smell barely detectable 2: Smell recognizable 3: Smell easily perceivable 4: Strong scent 5: Strong scent (judgment criteria)
◎: 2.5 points to 3.5 points ○: 2 points to less than 2.5 points,
×: Less than 2 points

<3. Flexibility Evaluation>
The softness imparted to the cotton towel towels after drying for 18 hours was evaluated according to the following criteria: control (same as "Treatment with liquid softener composition in wash rinse step" above, except LAS was not present) A sensory evaluation was performed with a paired comparison with a softly treated product). Evaluation was performed by six expert panelists according to the following evaluation criteria. The results are shown in the "Flexibility" section of Table 4 below. In terms of commercial value, △ or more was regarded as a pass.
(Evaluation criteria)
◎: 5 to 6 out of 6 people evaluated that there was almost no difference in flexibility compared to the condition without LAS ○: Flexibility compared to the condition without LAS 3-4 out of 6 people evaluated that there was almost no difference △: 1-2 out of 6 people evaluated that there was little difference in flexibility compared to the flexibility in the condition without LAS × : 0 out of 6 people evaluated that there was little difference in flexibility compared to the flexibility of the condition without LAS

<4. Storage stability (separation) evaluation>
80 mL of each liquid softener composition obtained as described above was placed in a lightweight glass bottle (PS-No. 11, manufactured by Tanuma Glass Industry Co., Ltd.), sealed, and used as a sample for evaluation. The liquid state after the test was visually observed, and the average score of 8 expert panelists was evaluated according to the following evaluation criteria, and the separation was evaluated according to the following criteria. The results are shown in the "storage stability" section of Table 4 below. From the point of view of commercial value, 0 or more was regarded as a pass.
<Judgment Criteria>
⊚: Absolutely no change from before the endurance test.
◯: Almost no change compared to before the durability test, but slight separation is observed.
Δ: Separation of 1 to 10% is observed compared to before the durability test.
x: Separation of 10% or more is observed compared to before the endurance test.

Claims (2)

The following components (A) and (B):
(A) one or more cationic surfactants selected from (A-1) and (A-2) below;
(A-1) an amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms in the molecule separated by an ester group (-COO-) and/or an amide group (-NHCO-); At least one compound selected from the group consisting of salts and quaternary compounds thereof (A-2) a quaternary ammonium salt represented by the following formula (A2)

(Wherein, R ₁ and R ₂ are independently an alkyl or alkenyl group having 8 to 24 carbon atoms that is not divided by an ester group (-COO-) or an amide group (-NHCO-), R ₃ and R ₄ are independently a methyl group, ethyl group, hydroxyethyl group, hydroxypropyl group, polyoxyethylene group or polyoxypropylene group, and X ^- represents an anion.)
and (B) a quaternary ammonium salt represented by the following formula (B)

(In the formula, R ¹ is a hydrocarbon group having 8 to 24 carbon atoms that is not separated by an ester group (--COO--) or an amide group (--NHCO--), and R ² and R ³ are independently is an alkyl group having 1 to 3 carbon atoms, and X ^- represents an anion.)
An emulsion-type liquid softener composition containing
The content of component (A) is less than 5% by mass,
The content of component (B) is 0.01 to 2% by mass,
An emulsion-type liquid softener composition, wherein the mass ratio A/B of component (A) to component (B) is 1-200. A method of treating textiles, comprising contacting textiles with the emulsion-type liquid softener composition according to claim 1 in water containing 1 ppm or more of linear alkylbenzenesulfonic acid or a salt thereof.