JP2021107590A - Liquid softener composition - Google Patents

Abstract

To provide a liquid softener having separation stability while suppressing an odor of clothes dried indoors.SOLUTION: The present invention provides a liquid softener composition characterized by comprising the following compositions (A) to (C): (A) at least one compound selected from the group consisting of an amine compound that has one to three C10-26 hydrocarbon group(s) in a molecule thereof, and may be interrupted by an ester group (-COO-), a salt thereof, and a quaternary compound thereof; (B) an antibacterial compound having a phenol structure, and (C) a nonionic surfactant, the ratio of the content of the component (A) to the total mass of the liquid softener composition being 3 mass% or more and less than 12 mass%, the ratio of the content of the component (B) to the total mass of the liquid softener composition being 0.02-1 mass%, and the mass ratio of the component (B) to the component (A): (B/A) being 0.005-0.1.SELECTED DRAWING: None

Description

The present invention relates to a liquid softener composition.

In recent years, the market size of fabric softeners in Japan has been expanding, and the share of fabric softeners having a deodorant function is increasing year by year.
The sensory deodorization by masking the scent is effective against various odors, but the biological deodorization by antibacterial agents is effective against the odor generated when the laundry is dried in the room (room drying odor). It is used in combination (Patent Documents 1 and 2).
Diclosans are known to exert a high antibacterial effect against Gram-negative bacteria involved in room drying odor (Patent Document 3). In addition, diclosans are blended as preservatives for enhancing the storage stability of the softener itself (Patent Documents 4 to 5).
In addition, a softener in which diclosans and fragrances are used in combination is also known (Patent Document 3).

Japanese Unexamined Patent Publication No. 2001-192967 Japanese Unexamined Patent Publication No. 2001-192966 International Publication No. 2013/156371 JP-A-2019-163559 Japanese Unexamined Patent Publication No. 2002-327375

Since diclosans are water-insoluble, they need to be incorporated into vesicle particles formed by the cationic surfactant, which is the main base material, when blended into fabric softeners. The present inventor has found a problem that the softener separates at around room temperature when an effective amount of diclosans is blended.

As a result of diligent studies on the above problems, the present inventor obtained a combination of (A) a specific type of cationic surfactant, (B) an antibacterial agent having a specific structure, and (C) a nonionic surfactant in a specific ratio. It was found that the separation of the softener can be suppressed while suppressing the dry odor. The present invention has been made based on this finding.

That is, the present invention relates to the following [1] to [7].
[1] A liquid softener composition, wherein the following components (A) to (C):
(A) From the group consisting of an amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms in the molecule, a salt thereof, and a quaternary compound thereof, which may be separated by an ester group (-COO-). At least one compound of choice,
(B) Antibacterial compounds having a phenolic structure and
(C) Containing a nonionic surfactant,
The content of the component (A) is 3% by mass or more and less than 12% by mass with respect to the total mass of the liquid softener composition.
The content of the component (B) is 0.02 to 1% by mass with respect to the total mass of the liquid softener composition.
A liquid softener composition, wherein the mass ratio (B / A) of the component (B) to the component (A) is 0.005 to 0.1.
[2] The liquid softener composition according to the above [1], wherein the unsaturated ratio of the hydrocarbon group of the component (A) is 20% by mass or more.
[3] The liquid softener composition according to the above [1] or [2], wherein the tri-form ratio of the component (A) determined from the following formula is 10% or more and less than 50%.
Tri-body ratio = {mass of tri-body / (mass of tri-body + mass of di-body + mass of mono-body + mass of zero-body)} x 100
Tri-form: Amine compound having 3 hydrocarbon groups with 10-26 carbon atoms Di-form: Amine compound with 2 hydrocarbon groups with 10-26 carbon atoms Mono-form: Carbide with 10-26 carbon atoms Amine compound with one hydrogen group Zero compound: Amine compound with 0 hydrocarbon groups with 10 to 26 carbon atoms [4] Mass ratio (C / B) of component (C) to component (B) The liquid softener composition according to any one of the above [1] to [3], wherein the amount is 1 to 80.
[5] Further containing (D) an inorganic salt,
The liquid softener composition according to any one of [1] to [4] above, wherein the content of the component (D) is 0.001 to 1% by mass with respect to the total mass of the liquid softener composition. ..
[6] The liquid softener composition according to the above [5], wherein the mass ratio (D / B) of the component (D) to the component (B) is 0.001 to 1.
[7] Further (E) containing an unencapsulated fragrance composition.
The perfume composition comprises a perfume with a ClogP value of 2-4.
The liquid softener composition according to any one of [1] to [4] above, wherein the content of the fragrance having a ClogP value of 2 to 4 is 10 to 50% by mass with respect to the total mass of the fragrance composition. ..

As shown in Examples described later, the liquid softener composition of the present invention has a separation stability while exhibiting an effect of suppressing (deodorizing) the odor of drying in a room. Therefore, the present invention is useful as a softener having added value not found in conventional products.

[Component (A): Cationic surfactant]
The component (A) is composed of "an amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms in the molecule, which may be separated by an ester group (-COO-), a salt thereof, and a quaternized product thereof. At least one compound selected from the group consisting of ".
The component (A) is a cationic surfactant, and is blended to impart the effect of imparting flexibility (texture) to the textile product (that is, the original function of the softener) to the liquid softener composition.

The hydrocarbon group which may be partitioned by the ester group (-COO-) has 10 to 26 carbon atoms, preferably 17 to 26, and more preferably 19 to 24. When the number of carbon atoms is 10 or more, the effect of imparting flexibility is good, and when the number of carbon atoms is 26 or less, the handleability of the liquid softener composition is good.
The hydrocarbon group which may be separated by an ester group (-COO-) may be a chain hydrocarbon group or a hydrocarbon group containing a ring in the structure, and is preferably a chain hydrocarbon group. It is a hydrocarbon group. The chain hydrocarbon group may be either linear or branched.
If the hydrocarbon group is separated by an ester group (-COO-), the biodegradability is improved.
The number of ester groups contained in one hydrocarbon group may be one or two or more. That is, the hydrocarbon group may be divided at one place by the ester group or at two or more places.
The carbon atom of the ester group shall be counted as the number of carbon atoms of the hydrocarbon group.
The hydrocarbon group is usually industrially used unhydrogenated beef fat-derived fatty acid, fatty acid obtained by hydrogenating or partially hydrogenating an unsaturated portion, and unhydrogenated plant-derived such as palm palm and oil palm. It is introduced by using a fatty acid or a fatty acid ester, or a fatty acid or a fatty acid ester obtained by hydrogenating or partially hydrogenating an unsaturated portion.

The "unsaturation rate of hydrocarbon groups" is defined as the proportion (mass%) of alkenyl groups in the hydrocarbon groups that make up the amine compound.
The unsaturated rate can be calculated from the amount of the raw material that brings about the hydrocarbon group of the amine compound. For example, as raw materials, 25% by mass of methyl stearate (including saturated hydrocarbon groups), 40% by mass of methyl oleate (including unsaturated hydrocarbon groups), and 35% by mass of methyl palmitate (including saturated hydrocarbon groups). When a mixture of lower fatty acid alkyl esters containing% is used, the unsaturated ratio of hydrocarbon groups in the obtained amine compound is 40% by mass (= 40 / (25 + 40 + 35) × 100).
The unsaturated rate of the hydrocarbon group is not particularly limited, but is preferably 20% by mass or more, more preferably 30% by mass or more. The upper limit of the unsaturated rate is preferably 80% by mass, more preferably 60% by mass. When the unsaturated rate is 20% by mass or more, better separation stability and excellent viscosity stability after storage can be obtained. When the unsaturated rate is 80% by mass or less (upper limit or less), good emulsion dispersion stability can be obtained.

As the amine compound, a secondary amine compound (the number of hydrocarbon groups is 2) or a tertiary amine compound (the number of hydrocarbon groups is 3) is preferable, and a tertiary amine compound is more preferable.
The proportion of the component (A) determined from the following formula is preferably 10% or more and less than 50%, more preferably 12% or more and less than 40%, and more preferably 15% or more and less than 30%. Especially preferable. When the proportion of the bird is 10% or more and less than 50%, better separation stability and excellent viscosity stability after storage can be obtained.

Tri-body ratio = {mass of tri-body / (mass of tri-body + mass of di-body + mass of mono-body + mass of zero-body)} x 100

Tri-form: Amine compound with 3 hydrocarbon groups Di-form: Amine compound with 2 hydrocarbon groups Mono-form: Amine compound with 1 hydrocarbon group Zero-form: Number of hydrocarbon groups Amine compound with 0

Examples of the amine compound include compounds represented by the following general formula (A1).

[In the formula, R ^{1 to} R ³ are independently hydrogen atoms, hydrocarbon groups having 10 to 26 carbon atoms, -CH ₂ CH (Y) OCOR ⁴ (Y is a hydrogen atom or CH ₃ ), and carbon. Alkyl groups of numbers 1 to 4, -CH ₂ CH (Y) OH (Y is a hydrogen atom or CH ₃ ), and at least one of ^{R 1 to} R ³ _{is -CH 2} CH (Y). It is OCOR ⁴ , and R ⁴ is a hydrocarbon group having 7 to 21 carbon atoms. ]

In the general formula (A1), the number of carbon atoms of the hydrocarbon group having 10 to 26 carbon atoms in ^{R 1 to} R ^{3 is preferably 17 to 26, more preferably 19 to 24.} The hydrocarbon group has an unsaturated rate of 38% or more.
-CH _{2 In} CH (Y) OCOR ⁴ , Y is a hydrogen atom or CH ₃ , and a hydrogen atom is particularly preferable. R ⁴ is a hydrocarbon group having 7 to 21 carbon atoms, preferably a hydrocarbon group having 15 to 19 carbon atoms. When the compound represented by the general formula (A1) R ⁴ there are a plurality, may be R ⁴ of said plurality of mutually identical, may be different.
The hydrocarbon group of R ⁴ is a fatty acid or fatty acid methyl ester (R ⁴ COOME) having 8 to 22 carbon atoms minus a carboxy group (fatty acid residue), and is a fatty acid or fatty acid ^{that is the source of R 4.} The methyl ester (R ⁴ COOME) may be a saturated fatty acid or a saturated fatty acid methyl ester, an unsaturated fatty acid or an unsaturated fatty acid methyl ester, or a linear fatty acid or a linear fatty acid methyl ester, or a branched fatty acid or a branched fatty acid methyl ester. But it may be. Of these, saturated or unsaturated linear fatty acids are preferable. The higher the unsaturated ratio of the fatty acid or fatty acid methyl ester ^{that is the source of R 4} , the more preferable it is, in order to impart good water absorption to the soft-treated garment.
Specific examples of fatty acids that form the basis of R ⁴ include stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, elaidic acid, linoleic acid, partially hydrogenated palm oil fatty acids (iodine value 10 to 60), and Examples thereof include partially hydrogenated beef fatty acid (iodine value 10 to 60). Among them, it is preferable to use two or more kinds selected from stearic acid, palmitic acid, myristic acid, oleic acid, elaidic acid, and linoleic acid in combination of predetermined amounts. In this case, the proportion of those having 16 to 18 carbon atoms is 80% by mass or more from the viewpoint of imparting flexibility to fibers and clothing, the fatty acid having 20 carbon atoms is less than 2% by mass, and the fatty acid having 21 to 22 carbon atoms is 1 mass%. It is preferably less than%.

In the general formula (A1), at least one, preferably two of ^{R 1 to} R ³ _{, is −CH 2} CH (Y) OCOR ⁴ .
When one or two of ^{R 1 to} R ³ _{are -CH 2} CH (Y) OCOR ⁴ , the remaining two or one are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and -CH ₂ It is CH (Y) OH, and is preferably an alkyl group having 1 to 4 carbon atoms and −CH ₂ CH (Y) OH. 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 .

Preferred examples of the compound represented by the general formula (A1) include compounds represented by the following general formulas (A1-2) to (A1-6).

[In each of the formulas ((A1-2) to (A1-6), R ⁹ is independently a hydrocarbon group having 7 to 21 carbon atoms, preferably 15 to 17 carbon atoms.]
Examples of the hydrocarbon group having 7 to 21 carbon atoms in R ⁹ include the same hydrocarbon groups having 7 to 21 carbon atoms ^{in R 4 of the general formula (A1).} Incidentally, when the R ⁹ there are a plurality in the formula, R ⁹ of the plurality of may be the same as each other, may be different.

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

As an ingredient (A)
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 (A1-2) to (A1-6), salts thereof and quaternized compounds thereof is more preferable.
At least one selected from the group consisting of the compounds represented by the general formulas (A1-4) to (A1-6), salts thereof and quaternized compounds thereof is particularly preferable.
In particular, a quaternized compound represented by the general formula (A1-4), a quaternized compound represented by (A1-5), and a quaternized compound represented by (A1-6). It is preferable to use in combination with.
The compounds represented by the general formulas (A1) and (A1-2) to (A1-6), salts thereof and quaternized products thereof may be commercially available products or may be produced by a known method.
For example, a compound represented by the general formula (A1-2) (hereinafter referred to as “compound (A1-2)”) and a compound represented by the general formula (A1-3) (hereinafter referred to as “compound (A1-3)”). The composition containing (referred to as) is, for example, stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, ellagic acid, linoleic acid, partially hydrogenated palm oil fatty acid (iodine value 10 to 60), and partially hydrogenated beef fat. It can be synthesized by a condensation reaction of a fatty acid composition such as a fatty acid (iodine value 10 to 60) or a fatty acid methyl ester composition in which the fatty acid in the fatty acid composition is replaced with a methyl ester of the fatty acid and methyl diethanolamine. At that time, from the viewpoint of improving the flexibility imparting, the abundance ratio represented by "Compound (A1-2) / Compound (A1-3)" is set to 99/1 to 50/50 in terms of mass ratio. It is preferable to synthesize.
Further, when the quaternized product is used, it is more preferable to use dimethyl sulfate as the quaternizing agent. At that time, from the viewpoint of imparting flexibility, the abundance ratio represented by "quaternized compound (A1-2) / quaternized compound (A1-3)" is 99/1 to 50/50 in terms of mass ratio. It is preferable to synthesize so as to be.

A compound represented by the general formula (A1-4) (hereinafter referred to as "compound (A1-4)") and a compound represented by the general formula (A1-5) (hereinafter referred to as "compound (A1-5)"). And the composition containing the compound represented by the general formula (A1-6) (hereinafter referred to as "compound (A1-6)"), for example, stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, ellaidin. Condensation of triethanolamine with fatty acid compositions or fatty acid methyl ester compositions such as acids, linoleic acids, partially hydrogenated palm oil fatty acids (iodine values 10-60) and partially hydrogenated beef fatty acids (iodine values 10-60). It can be synthesized by the reaction. At that time, the content ratio of each component to the total mass of the compounds (A1-4), (A1-5) and (A1-6) was 1 to 60 for the compound (A1-4) from the viewpoint of imparting flexibility. It is preferably 5 to 98% by mass of the compound (A1-5) and 0.1 to 40% by mass of the compound (A1-6), and 30 to 60% by mass of the compound (A1-4) and the compound. It is more preferable that (A1-5) is 10 to 55% by mass and compound (A1-6) is 5 to 35% by mass.
Further, when the quaternized product is used, it is more preferable to use dimethyl sulfate as the quaternizing agent from the viewpoint of sufficiently advancing the quaternization reaction. The abundance ratio of each quaternized compound (A1-4), (A1-5) and (A1-6) is a mass ratio from the viewpoint of imparting flexibility, and the quaternized product of compound (A1-4) is 1. It is preferable that the content is ~ 60% by mass, the quaternized product of compound (A1-5) is 5 to 98% by mass, and the quaternized product of compound (A1-6) is 0.1 to 40% by mass. The quaternized product of 4) is 30 to 60% by mass, the quaternized product of compound (A1-5) is 10 to 55% by mass, and the quaternized product of compound (A1-6) is 5 to 35% by mass. More preferred.
When the compounds (A1-4), (A1-5) and (A1-6) are quaternized, generally, the esteramine that has not been quaternized remains even after the quaternization reaction. At that time, the ratio of "quaternized / non-quaternized esteramine" is preferably in the range of 70/30 to 99/1.

The component (A) may have a hydroxyl group in the acyl group. The presence of an acyl group having a hydroxyl group can reduce the viscosity of the liquid softener. When reducing the viscosity, the proportion of the acyl group having a hydroxyl group in the acyl group is preferably in the range of 0.1 to 5%.
As the component (A), one kind of amine compound, a salt thereof or a quaternary compound thereof may be used alone, or a mixture consisting of two or more kinds, for example, in the general formulas (A1-4) to (A1-6). It may be used as a mixture of the represented compounds.

The blending amount of the component (A) is 3% by mass or more and less than 12% by mass, preferably 8% by mass or more and 11.5% by mass with respect to the total mass of the liquid softener composition. When it is 3% by mass or more, a sufficient softening effect can be obtained, and when it is less than 12% by mass, a softener viscosity that enables good usability can be obtained.

[Component (B): Antibacterial compound having a phenolic structure]
The component (B) is blended in order to impart antibacterial properties to the textile product after washing and suppress offensive odors (particularly, room drying odors) derived from microorganisms.
The "phenol structure" refers to a structure in which one or more hydrogen atoms of an aromatic hydrocarbon nucleus are substituted with a hydroxy group.

Examples of the component (B) include phenol derivatives and hydroxydiphenyl compounds known as antibacterial agents. Specific examples include 5-chloro-2- (2,4-dichlorophenoxy) phenol (common name: triclosan), 4,4'-dichloro-2-hydroxydiphenyl ether (common name: diclosan), o-benzyl-. Examples thereof include p-chlorophenol (chlorophenol), isopropylmethylphenol, and parachloromethaxylenol. Among these, hydroxydiphenyl compounds are preferable, and specifically, triclosan, diclosan and chlorophen are preferable.

As the component (B), a 2-hydroxydiphenyl compound represented by the following general formula (3) (hereinafter, also referred to as “compound (3)”) is used because it has a high adsorption amount to the fiber and a high compounding effect. preferable.

(In general formula (3),
X is an oxygen atom or an alkylene group having 1 to 4 carbon atoms.
Y is an independent chlorine atom or bromine atom, respectively.
Z is SO ₂ H, NO ₂ , or an alkyl group having 1 to 4 carbon atoms.
a, b, and c are independently integers of 0 or 1-3, respectively.
d is 0 or 1 and
m is 0 or 1 and
n is 0 or 1. )
In addition,-(Y) _b means that b of hydrogen atoms of a benzene ring are substituted with Y. The same applies to − (Y) _c , − (Z) _d , − (OH) _m and − (OH) _n.

As the compound (3), X is an oxygen atom or a methylene group, Y is a chlorine atom or a bromine atom, m is 0, n is 0 or 1, a is 1, and b is 0. More preferably, the compound is 1 or 2, c is 0, 1 or 2, and d is 0.

Specific examples of the preferred compound (3) include
Monochlorohydroxydiphenyl ether (X is an oxygen atom, a is 1, Y is a chlorine atom, one of b or c is 1, the other is 0, d is 0, m is 0, and so on. Compounds where n is 0),
Dichlorohydroxydiphenyl ether (X is an oxygen atom, a is 1, Y is a chlorine atom, b is 1, c is 1, d is 0, m is 0, n is Compounds that are 0),
Trichlorohydroxydiphenyl ether (X is an oxygen atom, a is 1, Y is a chlorine atom, one of b or c is 1 and the other is 2, d is 0, m is 0, and so on. Compounds where n is 0) and
Benzylchlorophenol (X is a methylene group, a is 1, Y is a chlorine atom, b is 0, c is 1, d is 0, m is 0, n is Compounds that are 0).

Examples of the compound (3) include 5-chloro-2- (2,4-dichlorophenoxy) phenol (common name: triclosan), 4,4'-dichloro-2-hydroxydiphenyl ether (common name: diclosan), o-. It is benzyl-p-chlorophenol (trivial name: chlorophen), and 4,4'-dichloro-2-hydroxydiphenyl ether (trivial name: diclosan) is particularly 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 blending amount of the component (B) is 0.02 to 1% by mass, preferably 0.03 to 0.8% by mass, and more preferably 0.05 to 0.5% by mass with respect to the total mass of the liquid softener composition. %. When it is 0.02% by mass or more, a sufficient antibacterial property-imparting effect can be obtained, and when it is less than 1% by mass, good separation stability can be obtained.

[Component (C): Nonionic surfactant]
The component (C) is blended in order to improve the separation stability, freeze restoration property, and dispersion stability of the capsule fragrance (arbitrary component) of the liquid softener composition.
As the component (C), for example, a component derived from a polyhydric alcohol, a higher alcohol, a higher amine or a higher fatty acid can be used.
As a specific example of the component (C),
Glycerin fatty acid ester or pentaerythritol in which a fatty acid having 10 to 22 carbon atoms is ester-bonded to glycerin or pentaerythritol;
A polyoxyethylene alkyl ether having an alkyl group or an alkenyl group having 10 to 22 carbon atoms and having an average addition mole number of ethylene oxide (EO) of 10 to 100 moles;
Polyoxyethylene fatty acid alkyl (1 to 3 carbon atoms of the alkyl) ester;
Polyoxyethylene alkylamines with an average addition of 10-100 moles of ethylene oxide;
Examples thereof include alkyl polyglucosides having an alkyl group or an alkenyl group having 8 to 18 carbon atoms; and hardened castor oil having an average addition mole number of ethylene oxide of 10 to 100 moles.
Among them, a polyoxyethylene alkyl ether having an alkyl group having 10 to 18 carbon atoms and having an average addition molar number of EO of 20 to 100 mol (preferably 30 to 80 mol, more preferably 40 to 60 mol) is preferable. When the average number of moles of EO added is 20 to 100 moles, better separation stability and a softener viscosity that enables good usability can be obtained.

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

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

The content of the component (C) is not particularly limited as long as the compounding purpose can be achieved, but is, for example, 0.5 to 5% by mass, preferably 1 to 4% by mass, more preferably, with respect to the total mass of the liquid softener composition. It is 1.5 to 3% by mass. When the content of the component (C) is 0.5% by mass or more, high temperature stability is obtained in addition to improved freeze stability, and when it is 5% by mass or less, better separation stability is obtained. ..

[Mixing ratio of each component]
The mass ratio (B / A) of the component (B) to the component (A) is 0.005 to 0.1, preferably 0.005 to 0.05, and more preferably 0.005 to 0.03. When blended in this mass ratio, excellent separation stability of the liquid softener composition can be obtained. This is because when the B / A exceeds 0.1, the vesicle particle size becomes excessively large due to an increase in the amount of the component (B) taken into the vesicle composed of the component (A) and the component (C). The liquid softener composition becomes easy to separate, while when the B / A is less than 0.005, the volume fraction of the vesicle becomes smaller due to the decrease in the amount of the component (B) taken into the vesicle, and the volume fraction of the vesicle. It is considered that this is because the liquid softener composition is easily separated due to the decrease in the amount of the liquid softener, and the excessive increase in the vesicle particle size and the decrease in the volume fraction of the vesicle are suppressed by blending in the above mass ratio. However, the present invention is not limited to the above theory.

The mass ratio (C / B) of the component (C) to the component (B) is preferably 1 to 80, more preferably 2 to 50. When blended in this mass ratio, excellent separation stability of the liquid softener composition can be obtained. This is because "the uptake of the component (B) into the vesicle composed of the component (A) and the component (C) is excessively increased, the excluded volume of the vesicle is increased, and the liquid softener composition is aggregated and separated. It is considered that this is because "easy to do" is suppressed by the mass ratio. However, the present invention is not limited to the above theory.

[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.
[(D) component: inorganic salt]

The component (D) is blended in order to further improve the usability of the liquid softener composition.
Specific examples of the component (D) include calcium chloride, magnesium chloride, sodium citrate and the like. Among these, calcium chloride, magnesium chloride and sodium citrate, which are excellent in compounding effect, are preferable, and calcium chloride is more preferable.

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

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

The content of the component (D) is not particularly limited as long as the compounding purpose can be achieved, but is, for example, 0.001 to 1% by mass, preferably 0.01 to 0.1% by mass, based on the total mass of the liquid softener composition. Is. When the content of the component (D) is 0.001% by mass or more, a high compounding effect can be obtained, and when it is 1% by mass or less, better separation stability can be obtained.

The mass ratio (D / B) of the component (D) to the component (B) is preferably 0.001 to 1, more preferably 0.005 to 0.5. When blended at this mass ratio, better separation stability of the liquid softener composition can be obtained. This is because "the excluded volume of the vesicle composed of the component (A) and the component (C) is excessively reduced, the amount of water separated from the vesicle (bulk water content) is increased, and the liquid softener composition is aggregated. It is considered that this is because "easy to separate" is suppressed by the mass ratio. However, the present invention is not limited to the above theory.

[(E) component: unencapsulated fragrance composition (free fragrance composition)]
The component (E) is a fragrance composition not contained in a capsule, which is different from the fragrance composition contained as a core substance in the encapsulated fragrance (component (G)) described later (hereinafter, also referred to as “free fragrance composition”). ).
The component (E) is blended in order to improve the deodorizing effect of the liquid softener composition by the masking effect of the aroma.
The free fragrance composition contains fragrances having a ClogP value of 2-4.
The ClogP value is a value obtained by expressing the 1-octanol / water partition coefficient P representing the ratio of equilibrium concentrations in 1-octanol and water for a chemical substance in the form of a logarithmic logP with respect to the base 10.
The ClogP value can be obtained by decomposing the chemical structure of a compound into its constituent elements by the f-number method (hydrophobic fragment constant method) and integrating the hydrophobic fragment constant and f-number of each fragment (for example). See Clog 3 Reference Manual Daylight Software 4.34, Albert Leo, David Weininger, Version 1, March 1994).
In general, the larger the ClogP value, the more hydrophobic the fragrance. Therefore, the fragrance composition containing a large amount of the fragrance component having a small ClogP value is more hydrophilic than the fragrance composition containing a large amount of the fragrance component having a large ClogP value. You can say that.
A list of fragrances with a ClogP value of 2-4 is shown below.

The content of the fragrance having a ClogP value of 2 to 4 is preferably 10 to 50% by mass with respect to the total mass of the free fragrance composition. When the content of the fragrance having a ClogP value of 2 to 4 is 10 to 50% by mass, the separation stability of the liquid softener composition is further improved.
The fragrance having a ClogP value of 2 to 4 may be one type or two or more types, but preferably two or more types.

The chemical structure of the fragrance having a ClogP value of 2 to 4 is not particularly limited. The reason why the ClogP value of the fragrance is considered to affect the separation stability of the liquid softener composition will be described below.
The fragrance, which is a hydrophobic substance, is incorporated into the hydrophobic field in the vesicle formed from the cationic surfactant (component (A)) and the nonionic surfactant (component (C)) in the liquid softener composition. There is. As the amount of fragrance taken up increases and the vesicle particle size increases, the viscosity increases and the volume fraction of the vesicles also increases, so that the liquid softener composition becomes difficult to separate. However, as the diameter of the vesicle particles further increases and the distance between the vesicle particles becomes shorter, the cohesiveness of the vesicle particles becomes higher, and the liquid softener composition becomes easier to separate. The present inventor has confirmed based on a plurality of verification experiments that this phenomenon does not depend on the chemical structure of the fragrance but largely depends on the physical characteristic of ClogP. Further, according to the study of the present inventor, a fragrance having a ClogP value of 2 to 4 is likely to be incorporated into the vesicle particles, and the separation stability of the liquid softener composition is likely to be deteriorated due to the above phenomenon.
From the above, it is considered that the separation stability of the liquid softener composition is influenced by the ClogP value of the fragrance, but the present invention is not limited by the above theory.

One or more fragrances having a ClogP value of not 2 to 4 contained in the free fragrance composition can be appropriately selected from the fragrance components generally used in liquid softeners. Specific examples include aldehydes, phenols, alcohols, ethers, esters, hydrocarbons, ketones, lactones, musks, fragrances having a terpene skeleton, natural fragrances, animal fragrances and the like. ..

The average ClogP value calculated from the ClogP values of all the fragrances contained in the free fragrance composition is preferably 1 to 6, more preferably 2 to 5. When the average ClogP value is in the above range, the storage stability of the softener composition becomes better.

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

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

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

[(F) component: preservative]
The component (F) is mainly blended to enhance the antiseptic and bactericidal activity of the liquid softener composition itself and to maintain the antiseptic property during long-term storage.
As the component (F), a preservative known in the field of liquid softener can be used without particular limitation. Specific examples 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 isothiazolin-based organic sulfur compounds include 5-chloro-2-methyl-4-isothiazolin-3-one, 2-n-butyl-3-isothiazolinone, 2-benzyl-3-isothiazolinone, and 2-phenyl-3. Examples thereof include -isothiazolinone, 2-methyl-4,5-dichloroisothiazolinone, 5-chloro-2-methyl-3-isothiazolinone, 2-methyl-4-isothiazolin-3-one, and mixtures thereof. Preferably, it is 5-chloro-2-methyl-4-isothiazolin-3-one and / or 2-methyl-4-isothiazolin-3-one, and more preferably 5-chloro-2-methyl-4-isothiazolin-. A mixture of 3-one and 2-methyl-4-isothiazolin-3-one, particularly preferably about 77% 5-chloro-2-methyl-4-isothiazolin-3-one and about 23% 2-. A water-soluble mixture with methyl-4-isothiazolin-3-one (for example, isothiazolinone solution, specifically, Kason CG-ICP manufactured by Dow Chemical Co., Ltd.).
Examples of benzisothiazolinone-based organic sulfur compounds include 1,2-benzisothiazolin-3-one, 2-methyl-4,5-trimethylen-4-isothiazolin-3-one, and dithio- as related compounds. 2,2-Bis (benzmethylamide) and the like can also be used. Of these, 1,2-benzisothiazolin-3-one is particularly preferable, and specifically, Nipperside manufactured by Clariant AG, Proxel BDN, Proxel GXL, Proxel XL, Proxel LV, and Proxel CRL manufactured by Lonza Co., Ltd. , Proxel NBZ, Proxel AM, Proxel B20 and the like.
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. ..

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

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

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

[(G) component: encapsulated fragrance]
The component (G) is blended in order to improve the deodorizing effect of the liquid softener composition by the masking effect of the aroma.
The encapsulated fragrance is composed of a core substance and a wall substance that covers the core substance.

The core material contains a fragrance composition.
As the fragrance composition, those used in the field of liquid softeners can be used without particular limitation, and can be appropriately selected depending on the intended purpose. For example, essential oils and absolutes commonly used in fabric softeners and detergents for clothing, as well as hydrocarbons, alcohols, aldehydes, ketones, ethers, acetals, ketals, nitriles, etc. Synthetic perfume components and the like.
Examples of preferable fragrance components to be incorporated into the fragrance composition are described in JP-A-2010-520928, for example, Agrumex, Aldron, Ambrettolide, Ambroxan, benzyl silicate, benzyl salicylate, Boisambrene, sedrol, acetic acid. Cedrill, Celestolid / Crysolide, Cetalox, Citroneryl etoxalate, Fixal, Fixolide, Galaxoride, Guaiacwood Acetate, cis-3-hexenyl salicylate, hexyl silicate aldehyde, hexyl salicylate, IsoE Super, linaryl benzoate, phenyl silicate Linaryl acetate, Javanol, methylsedrill ketone, Moskene, Musk, Musk Ketone, Musk Tibetine, Musk Xylol, Myraldyl Acetate, nerolidyl acetate, Novalide, Okoumal, paracresyl caprylate, paracresyl phenylacetate, Phantolid, phenylethyl silicate, salicylate Phenylethyl, Rose Crystals, Rosene, Sandela, Tetradecanitrile, Thibetolide, Traseolide, Trimofix O, 2-methylpyrazine, acetaldehyde phenylethylpropylacetal, acetphenone, alcohol C6 (Hereinafter, the notation Cn is n carbon atoms. And all substances with one hydroxyl function), alcohol C8, aldehyde C6 (hereinafter, notation Cn includes n carbon atoms and all isomers with one aldehyde function), aldehyde. C7, aldehyde C8, aldehyde C9, nonenylic aldehyde, allyl amyl glycolate, allyl caproate, amyl butyrate, anisique, benzaldehyde, benzyl acetate, benzylacetone, benzyl alcohol, benzyl butyrate, benzyl formate , Benzyl isovalerate, benzylmethyl ether, benzyl propionate, Bergamyl Acetate, butyl acetate, cypress, 3-methyl-5-propyl-2-cyclohexenone, silicate aldehyde, cis-3-hexenol, cis-3-acetate Hexenyl, cis-giate-3-hexenyl, isobutyric acid Sis-3-hexenyl, cis-3-hexenyl propionate, cis-3-hexenyl thyglycane, citronellal, citronellol, citronellylnitrile, 2-hydroxy-3-methyl-2-cyclopenten-1-one, cuminaldehyde, cyclal C, acetic acid (cyclohexyloxy) -2-propenyl ester, damasenone, alpha-damascon, beta-damascon, decahydrobeta-naphthyl formate, diethyl malate, dihydrojasmon, dihydrolinalol, dihydromilsenol, dihydroterpineol, anthranyl acid Dimethyl, dimethylbenzylcarbinol, dimethylbenzylcarbinol acetate, dimethyloctenone, Dimetol, dimyrcetol, estragor, ethyl acetate, ethyl acetoacetate, ethyl benzoate, ethyl heptate, ethyllinalol, ethyl salicylate, ethyl butyrate 2-Methyl, Eucalyptor, Eugenol, Fenquil acetate, Fenquil alcohol, 4-Phenyl-2,4,6-trimethyl1,3-dioxane, Methyl 2-octanoate, 4-Isopropylcyclohexanol, 2-sec-Butylcyclohexanone , Stilllyl acetate, geranylnitrile, hexyl acetate, alpha-ionone, isoamyl acetate, isobutyl acetate, iso-cyclocitral, dihydroisojasmon, isomentone, iso-pentylate, iso-pregol, cisjasmon, left-handed carboxylic acid, phenyl Acetaldehyde glyceryl acetal, 3-hexenylmethyl ether carbinic acid, 1-methyl-cyclohexa-1,3-diene, linalol, linalol oxide, 2-ethylethyl ester of pentanoic acid, 2,6-dimethyl-5-heptenal, Mentor, Menton, Methylacetophenone, Methylamylketone, Methyl benzoate, Alpha-Methylsilicate aldehyde, Methylheptenone, Methylhexylketone, Methylparacresol, Methylphenylacetate, Methyl salicylate, Neral, Nerol, 4-tert-Pentyl-cyclohexanone, Para-cresol, para-crecil acetate, para-t-butylcyclohexanone, para-toluylaldehyde, phenylacetaldehyde, phenylethyl acetate, phenylethyl alcohol, phenylethyl butyrate, phenylethyl formate, phenylethyl isobutyrate, fepionate Nylethyl, phenylpropyl acetate, phenylpropyl aldehyde, tetrahydro-2,4-dimethyl-4-pentyl-furan, 4-methyl-2- (2-methyl-1-propenyl) tetrahydropyran, 5-methyl-3-heptanone Examples thereof include oxime, stillaryl propionate, styrene, 4-methylphenylacetaldehyde, terpineol, terpinolene, tetrahydro-linalol, tetrahydro-milsenol, trans-2-hexenal, berzyl acetate and Viridine.
The fragrance composition may contain one kind of fragrance component or two or more kinds of fragrance components.
The fragrance composition of the component (G) and the fragrance composition of the component (E) may be the same or different. When a highly volatile fragrance component is used as the component (G) and a fragrance component having a low volatility is used as the component (E), the fragrance lasting effect can be further enhanced.

As the wall material, those generally used as a fragrance encapsulating material in the field of liquid softeners can be used without particular limitation. For example, the wall material is composed of a polymer substance, specifically, a natural polymer such as gelatin and agar, an oily film-forming substance such as oil and wax, a polyacrylic acid type, a polyvinyl type, and a polymethacrylic acid type. Examples thereof include synthetic polymer substances such as melamine-based and urethane-based substances, and one of them can be used alone or two or more of them can be used in combination as appropriate.
From the viewpoint of fragrance when the encapsulated fragrance is destroyed, the wall material is preferably an aminoplast polymer composed of a melamine-formaldehyde resin or a urea-formaldehyde resin, a polyacrylic acid-based polymer, or a polymethacrylic acid-based polymer. .. Aminoplast polymers as described in JP-A-2010-520928 are particularly preferred. Specifically, it is preferably a terpolymer composed of a polyamine-derived moiety / aromatic polyphenol-derived moiety / methylene unit, dimethoxymethylene and an alkylene and alkyleneoxy moiety having dimethoxymethylene.

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

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

The content of the component (G) (content as the amount of the fragrance in the component (G)) is not particularly limited as long as the compounding purpose can be achieved, but is preferable as the amount of the fragrance with respect to the total mass of the liquid softener composition. Is 0.01 to 3% by mass, more preferably 0.05 to 2% by mass, still more preferably 0.1 to 1% by mass.

[(H) component: nonionic glucan]
The component (H) is a nonionic glucan having a weight average molecular weight in the range of 10,000 to 2 million. The component (H) is blended in order to further improve the stability of the liquid softener composition and to impart deodorant property and deodorant property to the textile product.
Glucan is a condensed polymer of D-glucopyranose and contains starch, glycogen, dextrin, cellulose and the like. It is divided into α-glucan and β-glucan according to the configuration at the C1 position, and 1 → 3, 1 → 4, 1 → 6 bonds are distinguished by the position of the glycosidic bond.
The nonionic glucan may be straight chain or branched chain. Further, the nonionic glucan may have a chain structure or a cyclic structure.
Specific examples of the component (H) include high molecular weight dextrin (Sanwa Cornstarch Co., Ltd., trade name: Sandec # 30) and nonionic glucan having a cyclic structure and a branched structure (for example, cyclic structure). Examples thereof include retained branched glucan (described in JP-A-2012-120471), highly branched cyclic dextrin (manufactured by Glyco-Nutrition Foods Co., Ltd., trade name: cluster dextrin), and the like.

Glucan as the component (H) is a nonionic compound, and cationized starch, cationized cellulose, and the like having cationism in which a part of the glucan is modified does not correspond to the component (H).
Nonionic glucan having a cyclic structure and a branched structure is produced by the method described in JP-A-8-134104, the method described in Takata et al., Carbohydrate Research, 295, 91-101, 1996, and the like. However, it is not limited to these.

The highly branched cyclic dextrin is a glucan having an inwardly branched cyclic structure portion and an outerly branched cyclic structure portion and having a degree of polymerization in the range of 50 to 10,000. Here, the internally branched cyclic structure portion is α-1. , 4-Glucoside bond and α-1,6-glucoside bond form a cyclic structure portion, and the outer branch structure portion is a non-cyclic structure portion bonded to the inner branch cyclic structure portion, which is a glucan. be.
Highly branched cyclic dextrin has a weight average molecular weight of about 30,000 to 1,000,000, has one cyclic structure in the molecule, and has a weight average degree of polymerization of about 2500 in which a large number of glucan chains are bonded to the cyclic portion. Mainly includes.
The inner branched cyclic structure portion of the highly branched cyclic dextrin is composed of about 10 to 100 glucoses, and the outer branched structural portion composed of a large number of acyclic branched glucan chains is bonded to the inner branched cyclic structure portion. There is.

The degree of polymerization of highly branched cyclic dextrin is, for example, in the range of 50 to 5000.
The degree of polymerization of the internally branched cyclic structure portion of the highly branched cyclic dextrin is, for example, in the range of 10 to 100.
The degree of polymerization of the outer branch structure portion of the highly branched cyclic dextrin is, for example, 40 or more.
The degree of polymerization of each unit chain of the outer branch structure portion of the highly branched cyclic dextrin is, for example, 10 to 20 on average.

Highly branched cyclic dextrin is produced, for example, from starch as a raw material by the action of an enzyme called blanching enzyme. Starch, which is a raw material, consists of amylose, in which glucose is linearly bound by α-1,4-glucosidic bonds, and amylopectin, which has a complex branched structure by α-1,6-glucosidic bonds. Amylopectin is a cluster. It is a macromolecule in which many structures are linked. The enzyme used, blanching enzyme, is a glucan chain transferase that is widely distributed in animals, plants and microorganisms, and acts on the seams of the cluster structure of amylopectin to catalyze the reaction of cyclizing it.
More specifically, the highly branched cyclic dextrin is a glucan described in JP-A-8-134104, which has an inner branched cyclic structure portion and an outer branched structural portion and has a degree of polymerization in the range of 50 to 10,000. In the present specification, the highly branched cyclic dextrin can be understood with reference to the description of JP-A-8-134104.

The cyclic structure-bearing branched glucan has a cyclic structure and at least one branched structure based on α-1,6 bond and α-1,4 bond, and at least in the sugar chain constituting the cyclic structure. It is a glucan having a structure in which one α-1,6 bond is present.
The branching frequency of the cyclic structure-bearing branched glucan is, for example, 8% or more. The branching frequency of the cyclic structure-bearing branched glucan is indicated by the ratio of α-1,6 branches. The proportions of α-1,6 branches are, for example, about 10% or more, about 11% or more, about 12% or more, about 13% or more, about 14% or more, about 15% or more, about 16% or more, about 17% or more, It can be about 20% or more. There is no upper limit to the ratio of α-1,6 branches, but it can be, for example, about 50% or less, about 40% or less, about 30% or less, about 25% or less, about 20% or less, and the like.
The branch frequency is calculated by the following formula:
Branching frequency (%) = {(number of branches) / (number of glucose units in the entire molecule)} x 100

The weight average molecular weight of the cyclic structure-bearing branched glucan is preferably about 30,000 or more, more preferably about 50,000 or more, particularly preferably about 100,000 or more, and preferably about 500,000 or less. Yes, more preferably about 300,000 or less, and particularly preferably about 200,000 or less.
The average degree of polymerization of the cyclic structure portion in the cyclic structure-bearing branched glucan is preferably about 10 or more, more preferably about 15 or more, further preferably about 20 or more, and preferably about 500 or less. It is more preferably about 300 or less, and even more preferably about 100 or less.
The average degree of polymerization of the branched structure portion in the cyclic structure-bearing branched glucan is preferably about 40 or more, more preferably about 100 or more, still more preferably about 300 or more, and even more preferably about 500 or more. It is preferably about 4 × 10 ³ or less, more preferably about 3 × 10 ³ or less, still more preferably about 2 × 10 ³ or less, and even more preferably about 1 × 10 ³ or less. Is.

The cyclic structure portion of the cyclic structure-bearing branched glucan may have at least one α-1,6-glucoside bond, for example, one or more, five or more, ten or more, for example, about 200 or less. It can be about 50 or less, about 30 or less, about 15 or less, about 10 or less, and so on.
As the branched glucan having a cyclic structure, one having one kind of degree of polymerization may be used alone, or one having various degrees of polymerization may be used as a mixture. Preferably, the degree of polymerization of the cyclic structure-bearing branched glucan is such that the ratio of the degree of polymerization of the one having the highest degree of polymerization to the one having the lowest degree of polymerization is about 100 or less, more preferably about 50 or less, and even more preferably about. It is 10 or less.
In the branched glucan having a cyclic structure, a part of the branched glucan structure preferably forms a ring. Here, the cyclic structure portion is a cyclic structure portion formed by an α-1,4-glucoside bond and an α-1,6-glucoside bond, and the branched structure portion is bonded to the cyclic structure portion. It is a non-annular structure part. The degree of polymerization of each unit chain of the branched structure portion is preferably about 2 or more, more preferably about 4 or more, further preferably about 6 or more, and preferably about 20 or less. It is preferably 18 or less, and more preferably 15 or less.

The average degree of polymerization of the cyclic structure-bearing branched glucan is preferably about 50 or more, more preferably about 70 or more, further preferably about 100 or more, most preferably about 150 or more, and preferably about 150 or more. Is about 5 × 10 ³ or less, more preferably about 4 × 10 ³ or less, still more preferably about 3 × 10 ³ or less, and most preferably about 2 × 10 ³ or less.
The number of branches of the cyclic structure-bearing branched glucan (that is, the number of α-1,6-glucoside bonds) is preferably about 10 or more, more preferably about 15 or more, still more preferably about 20. The number is more than, preferably about 1000 or less, more preferably about 800 or less, still more preferably about 500 or less.
In the cyclic structure-bearing branched glucan, the ratio of the number of α-1,4-glucosidic bonds to the number of α-1,6-glucosidic bonds (“number of α-1,6-glucosidic bonds”: “α-1”. , 4-Glycosidic bond number ") is preferably 1: 3 to 1:13, more preferably 1: 4 to 1:12, still more preferably 1: 5 to 1:10, and further. It is preferably 1: 5 to 1: 9.
Bifurcated glucan with a ring structure
i) Whether the substrate, branched glucan, is allowed to act on the blanching enzyme and then 4-α-glucanotransferase;
ii) Whether the substrate, branched glucan, is allowed to act on 4-α-glucanotransferase and then blanched enzyme;
iii) It is produced by simultaneously acting a blanching enzyme and 4-α-glucanotransferase on a branched glucan which is a substrate.
More specifically, the cyclic structure-bearing branched glucan is described in JP2012-120471. In the present specification, the cyclic structure-bearing branched glucan can be understood with reference to the description of JP2012-120471.

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

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

The content of the component (H) is not particularly limited as long as the compounding purpose can be achieved, but is 0.01 to 5% by mass, preferably 0.05 to 3% by mass, more preferably, with respect to the total mass of the liquid softener composition. Is 0.2 to 2% by mass.

[Component (I): Antibacterial compound other than component (B)]
The component (I) is blended to enhance the storage stability of the liquid softener composition.
As the component (I), a component known in the field of liquid softener can be used without particular limitation. Specific examples include, for example, benzalkonium chloride, bis- (2-pyridylthio-1-oxide) zinc, 8-oxyquinoline, biguanide compounds (for example, polyhexamethylene biguanide), chlorohexidine hydrochloride, polylysine and the like. Be done. Among these, benzalkonium chloride, biguanide compounds, and chlorohexidine hydrochloride are preferable.

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

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

The content of the component (I) 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.

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

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

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

〔Production method〕
The liquid softener composition can be produced by a known method, for example, the same method as the conventional method for producing a liquid softener composition using a cationic surfactant as a main agent.
For example, an oil phase containing a component (A), a component (B), a component (C) and a component (E) and an aqueous phase containing a component (F) are placed under temperature conditions equal to or higher than the melting point of the component (A). Mix to prepare an emulsion, and then add and mix other components ((D) component, (G) component, (H) component, (I) component, etc.) to the obtained emulsion as needed. It can be manufactured by doing so.
The addition of the component (B), the component (C), the component (D), the component (E), the component (F), the component (G) and the component (I) is not limited to the above-mentioned addition method.

[How to use liquid softener composition]
The method for treating the textile product using the liquid softener composition is not particularly limited, and can be used in the same manner as the conventional liquid softener. For example, in the rinsing stage of washing, the liquid softener composition is dissolved in rinsing water for treatment, or the liquid softener composition is dissolved in water in a container such as a tub, and a textile product is further added and immersed. There is a way to handle it. In each case, the solution is diluted to an appropriate concentration before use, but the bath ratio (weight ratio of the treatment liquid to the textile product) is preferably 3 to 100 times, particularly 5 to 50 times. Specifically, the concentration of the component (A) is preferably 0.01 ppm to 1000 ppm, more preferably 0.1 ppm to 300 ppm, based on the total amount of water used.
The type of textile product that can be treated with the liquid softener composition is not particularly limited, and examples thereof include clothing, curtains, sofas, carpets, towels, handkerchiefs, sheets, pillow covers and the like. The material may be a natural fiber such as cotton, silk or wool, or a chemical fiber such as polyester.

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

[Component (A): Cationic surfactant]
The following A-1 or A-3 was used.

A-1: Cationic surfactant (quaternary ammonium salt composition (A-3) used in Examples of JP-A-2018-59242). A-1 is a compound represented by the general formulas (A1-4), (A1-5) and (A1-6) (in each formula, R ⁹ is an alkyl group and an alkenyl group having 15 to 17 carbon atoms. ) Is quaternized with dimethyl sulfate. The unsaturated rate of the hydrocarbon group of A-1 was 40% by mass. The proportion of A-1 to birds was 20%.

A-3: Cationic surfactant (compound according to Example I of JP-A-2013-525617). The avian body of A-3 was 0%.

[Component (B): Antibacterial compound having a phenolic structure]
The following B-1 to B-2 were used.

B-1: Dichlorosan (TINOSAN HP100 (aqueous solution of 4,4'-dichloro-2-hydroxydiphenyl ether), manufactured by BASF). B-1 is the general formula (3) (in the formula, X is an oxygen atom, a is 1, Y is a chlorine atom, b is 1, c is 1, and d is 0. Yes, m is 0, and n is 0).

B-2: Triclosan (IRGASAN DP300 (aqueous solution of 5-chloro-2- (2,4-dichlorophenoxy) phenol), manufactured by BASF). B-2 is the general formula (3) (in the formula, X is an oxygen atom, a is 1, Y is a chlorine atom, b is 2, c is 1, and d is 0. Yes, m is 0, and n is 0).

[Component (C): Nonionic surfactant]
The following C-1 to C-2 were used.

C-1: 60 mol of polyoxyethylene isotridecyl ether EO (corresponding to an average 60 mol adduct of primary isotridecyl alcohol (C13))

C-2: 20 mol of polyoxyethylene lauryl ether EO (corresponding to an average 20 mol adduct of lauryl alcohol (C12))

[(D) component: inorganic salt]
The following D-1 was used.
D-1: Calcium chloride (supplier: Tokuyama. Trade name: granular calcium chloride).

[Ingredient (E): unencapsulated fragrance composition]
The following E-1 to E-4 were used.

[(F) component: preservative]
The following F-1 to F-2 were used.

F-1: 1,2-Benzisothiazolin-3-one (BIT) (Product name: Nipponide BIT 20 (Clariant Japan Co., Ltd.)

F-2: Isothiazolone solution (Dow Chemical Japan Co., Ltd. Product name: Caisson CG-ICP)

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

G-1: Encapsulated fragrance (Supplier: Givaudan Co., Ltd. Product name: GreenBreeze)

[(H) component: nonionic glucan]
The following H-1 was used.

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

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

The liquid softener composition was prepared by the following procedure using a glass container (inner diameter 100 mm, height 150 mm) and a stirrer (Agitator SJ type, manufactured by Shimadzu Corporation).
First, the component (A), the component (B), a part of the component (C) and the component (E) were mixed and stirred to obtain an oil phase mixture.
On the other hand, the component (F) 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, the component (C) and the component (G) from 980 g.
Next, while storing the oil phase mixture heated above the melting point of the component (A) in a glass container and stirring, the aqueous phase mixture heated above the melting point of the component (A) is added in two portions. , Stirred. The division ratio of the aqueous phase mixture was 30:70 (mass ratio), and the stirring was performed at a rotation speed of 1,000 rpm for 3 minutes after the first addition of the aqueous phase mixture and 2 minutes after the second addition of the aqueous phase mixture.
After that, the balance of the component (C), the component (D), the component (G) and the component (H) are added, and if necessary, hydrochloric acid (reagent 1 mol / L, Kanto Chemical Co., Inc.) or sodium hydroxide (reagent 1 mol) is added. / L, Kanto Chemical Co., Inc.) was added in an appropriate amount to adjust the pH to 3.0 (25 ° C.), and ion-exchanged water was further added so that the total mass was 1,000 g to obtain the desired liquid softener composition. rice field. The viscosity (25 ° C.) of each liquid softener composition immediately after production was in the range of 10 to 500 mPa · s.

[Evaluation of liquid softener composition]
The "effect of suppressing room-drying odor" and "separation stability" of the prepared liquid softener composition were evaluated.

[Effect of suppressing room drying odor]
1. 1. Pretreatment of evaluation cloth Use a two-tank washing machine (Mitsubishi Electric CW-C30A1-H) to use the evaluation cloth (commercially available cotton towel) with the commercially available detergent "Top Platinum Clear" (manufactured by Lion). Pretreatment was performed (standard amount of detergent used, bath ratio 30 times, tap water at 45 ° C., washing for 10 minutes → water injection and rinsing for 10 minutes twice).

2. Cleaning and softening treatment The evaluation cloth after the pretreatment was used by a man in his thirties for one day as a test cloth. The test cloth is washed with a commercially available detergent "Top Platinum Clear" (manufactured by Lion) for 10 minutes using a two-tank washing machine (CW-C30A1-H manufactured by Mitsubishi Electric) (standard usage amount, standard course, bath ratio). 20 times, using tap water at 25 ° C), perform the first rinse (3 minutes), and then soften the liquid softener composition for 3 minutes during the second rinse (liquid softening for 1 kg of test cloth). The agent composition was 5 mL, the bath ratio was 20 times, and tap water at 25 ° C. was used). Those without flexible treatment were used as controls. Dehydration was performed for 1 minute after the washing treatment and after each rinsing treatment. After the softening treatment, the wet test cloth was left indoors (30 ° C., 100% RH) for 6 hours (room drying).

3. 3. Evaluation of inhibitory effect The odor of the test cloth after drying in the room was evaluated according to the following evaluation criteria by sensory paired comparison. The evaluation was carried out by 10 specialized panelists.

<Evaluation criteria>
+2: Clearly better than the control.
+1: Slightly better than the control.
0: Almost the same as the control.
-1: The control is slightly better.
-2: The control is clearly better.

The effect of suppressing the room-drying odor of the liquid softener composition was determined based on the average score of 10 specialized panelists (calculated to the first decimal place) according to the following criteria. The results are shown in the "Room dry odor" column of Table 1. ○ or ◎ was judged to be acceptable in terms of commercial value.

<Criteria>
⊚: 1.5 points or more and 2.0 points or less ○: 1.0 points or more and less than 1.5 points Δ: 0.5 points or more and less than 1.0 points ×: 0 points or more and less than 0.5 points

[Evaluation of separation stability]
80 mL of the liquid softener composition was placed in a lightweight PS glass bottle (PS-No. 11, manufactured by Tanuma Glass Industry Co., Ltd.) and sealed, and used as an evaluation sample. The evaluation sample was stored at 25 ° C. for 6 months. The state of the evaluation sample after storage was visually evaluated according to the following evaluation criteria. The evaluation was carried out by eight specialized panelists. The results are shown in the "Separation Stability" column of Table 1. ○, ◎ or ◎◎ was evaluated as passing in terms of commercial value.

<Evaluation criteria>
◎ ◎: Equivalent to the sample before storage ◎: Very slightly semi-transparent layer can be confirmed in the upper layer ○: Slightly semi-transparent layer can be confirmed in the upper layer △: Semi-transparent layer can be clearly confirmed in the upper layer ×: A transparent layer can be clearly seen in the upper layer.

The present invention is available in the field of softeners.

Claims (7)

A liquid softener composition, wherein the following components (A) to (C):
(A) From the group consisting of an amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms in the molecule, a salt thereof, and a quaternary compound thereof, which may be separated by an ester group (-COO-). At least one compound of choice,
(B) Antibacterial compounds having a phenolic structure and
(C) Containing a nonionic surfactant,
The content of the component (A) is 3% by mass or more and less than 12% by mass with respect to the total mass of the liquid softener composition.
The content of the component (B) is 0.02 to 1% by mass with respect to the total mass of the liquid softener composition.
A liquid softener composition, wherein the mass ratio (B / A) of the component (B) to the component (A) is 0.005 to 0.1. The liquid softener composition according to claim 1, wherein the unsaturated rate of the hydrocarbon group of the component (A) is 20% by mass or more. The liquid softener composition according to claim 1 or 2, wherein the tri-form ratio of the component (A) obtained from the following formula is 10% or more and less than 50%.
Tri-body ratio = {mass of tri-body / (mass of tri-body + mass of di-body + mass of mono-body + mass of zero-body)} x 100
Tri-form: an amine compound having 3 hydrocarbon groups having 10 to 26 carbon atoms Di-form: an amine compound having 2 hydrocarbon groups having 10 to 26 carbon atoms Mono-form: hydrocarbon compound having 10 to 26 carbon atoms Amine compound with one hydrogen group Zero form: Amine compound with 0 hydrocarbon groups with 10 to 26 carbon atoms The liquid softener composition according to any one of claims 1 to 3, wherein the mass ratio (C / B) of the component (C) to the component (B) is 1 to 80. Further (D) contains an inorganic salt,
The liquid softener composition according to any one of claims 1 to 4, wherein the content of the component (D) is 0.001 to 1% by mass with respect to the total mass of the liquid softener composition. The liquid softener composition according to claim 5, wherein the mass ratio (D / B) of the component (D) to the component (B) is 0.001 to 1. Further contains (E) an unencapsulated fragrance composition.
The perfume composition comprises a perfume with a ClogP value of 2-4.
The liquid softener composition according to any one of claims 1 to 4, wherein the content of the fragrance having a ClogP value of 2 to 4 is 10 to 50% by mass with respect to the total mass of the fragrance composition.