JP2016113705A - Liquid softener composition - Google Patents

Abstract

Disclosed is a liquid softening agent composition having little dispersion in viscosity immediately after production and excellent in microcapsule dispersion stability. (A) An amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms which may be separated by an ester group and / or an amide group in the molecule, a salt thereof, and a quaternized product thereof. Containing at least one compound selected from the group consisting of: (B) a nonionic glucan having a weight average molecular weight of 10,000 to 2 million, (C) an inorganic salt, and (D) a microcapsule; The liquid softening agent composition whose mass ratio of content of (B) component with respect to quantity is 8 or more. [Selection figure] None

Description

  The present invention relates to a liquid softener composition. Specifically, the present invention relates to a liquid softener composition having little dispersion in viscosity immediately after production and excellent in microcapsule dispersion stability, particularly, microcapsule dispersion stability after high-temperature storage.

In recent years, an increasing number of consumers are demanding the sustainability of fragrance as a function of a softening agent, and various measures have been taken. For example, a technique using microcapsules containing a fragrance composition is known. For example, Patent Document 1 discloses a liquid finish composition for a textile product that includes a perfume composition as a core material, a microcapsule whose wall material is composed of a polymer material, and a silicone compound. .
In a liquid softening agent composition containing a microcapsule containing a fragrance composition as a core substance, if the component contained in the microcapsule and the specific gravity of the liquid preparation are different, the microcapsule floats in the preparation when stored for a long period of time. It is known that the microcapsules themselves will settle and cause problems such as aggregation, solidification, and film formation. In order to solve such a problem, Patent Document 2 forms a liquid crystal that is a large aggregate by applying a much gentler shear compared to the conventional manufacturing method, and then appropriately sets the size of the aggregate by high shear. It is disclosed that a composition excellent in dispersion stability can be obtained by exerting thixotropy and finally adding a microcapsule containing a fragrance composition.
However, it has been found that the method described in Patent Document 2 has a large variation in viscosity immediately after production, and it is difficult to perform fine viscosity control. A microcapsule having a fragrance composition as a core material requires fine viscosity control because the appropriate viscosity and TI value differ depending on the encapsulated fragrance. Moreover, it turned out that the microcapsule floats on the composition prepared by the method of patent document 2 on 40 degreeC high temperature conditions.

Patent Documents 3 to 5 disclose a composition containing microcapsules containing a core substance and a method for producing the composition. Patent Documents 3 to 5 describe that the permeability characteristics of microcapsules containing a core substance are improved in a composition produced by the method described in the document.
However, Patent Documents 3 to 5 do not mention anything about the dispersion stability of microcapsules containing a core substance. Patent Documents 3 to 5 do not mention at all the viscosity of the composition containing microcapsules containing a core substance.
Patent Document 6 discloses a fiber product treating agent composition having excellent storage stability.
However, Patent Document 6 does not mention any problems when using microcapsules containing a core substance.

JP 2008-7872 A JP2013-129922A Special table 2013-525565 gazette Special table 2013-531079 gazette Special table 2013-53694 gazette JP 2000-129570 A

As described above, the conventional technology can provide a liquid softening agent composition that has little dispersion in viscosity immediately after production and that is excellent in microcapsule dispersion stability, in particular, microcapsule dispersion stability after high-temperature storage. There wasn't. This was not limited to a composition containing microcapsules containing a fragrance composition as a core substance, but was also the same for compositions containing microcapsules containing a component other than the fragrance composition as a core substance.
Accordingly, an object of the present invention is to provide a liquid softening agent composition having little dispersion in viscosity immediately after production and excellent in microcapsule dispersion stability, particularly, microcapsule dispersion stability after high-temperature storage. .

As a result of intensive studies to solve the above-mentioned problems, the present inventors have formulated a liquid softening agent composition containing a cationic surfactant with an inorganic salt and a glucan having a specific average molecular weight in a specific ratio. As a result, it has been found that the variation in viscosity immediately after production can be reduced, and that the microcapsules can be dispersed and stabilized under high temperature storage conditions, and the present invention has been completed.
The present invention has been completed based on such novel findings.

In one embodiment of the present invention,
(A) Selected from the group consisting of an amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms which may be separated by an ester group and / or an amide group, a salt thereof and a quaternized product thereof At least one compound,
(B) a nonionic glucan having a weight average molecular weight of 10,000 to 2 million,
There is provided a liquid softener composition comprising (C) an inorganic salt, and (D) microcapsules, wherein the mass ratio of the content of the component (B) to the content of the component (C) is 8 or more.

  As shown in the examples below, in one embodiment of the present invention, there is little variation in viscosity immediately after production, and the liquid has excellent dispersion stability of the microcapsules, in particular, excellent dispersion stability of the microcapsules after high-temperature storage. A softener composition is provided. Furthermore, in one embodiment of the present invention, a liquid softener composition imparted with good thixotropy is provided.

[(A) component]
The component (A) contained in the softener composition of the present invention is a hydrocarbon group having 10 to 26 carbon atoms (hereinafter referred to as “long chain carbonization”) which may be separated by an ester group and / or an amide group. It is at least one compound selected from the group consisting of an amine compound having 1 to 3 hydrogen groups in the molecule, a salt thereof and a quaternized product thereof.
The carbon number of the long chain hydrocarbon group is 10 to 26, preferably 17 to 26, and more preferably 19 to 24. When the number of carbon atoms is 10 or more, flexibility is good, and when it is 26 or less, handling properties are good. The long chain hydrocarbon group may be saturated or unsaturated. When the long chain hydrocarbon group is unsaturated, the position of the double bond may be anywhere, but when there is one double bond, the position of the double bond is the long chain carbonization. It is preferably at the center of the hydrogen group or around the center.
The long chain hydrocarbon group may be a chain hydrocarbon group or a hydrocarbon group containing a ring in the structure, and is preferably a chain hydrocarbon group. The chain hydrocarbon group may be linear or branched. As the chain hydrocarbon group, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable.

The long chain hydrocarbon group may be separated by an ester group (—COO—) and / or an amide group (—NHCO—). That is, the long-chain hydrocarbon group has at least one kind of splitting group selected from the group consisting of an ester group and an amide group in the carbon chain, and the carbon chain is split by the splitting group. May be. Having the splitting group is preferable from the viewpoint of improving biodegradability.
When it has this dividing group, the number of the dividing groups which one long-chain hydrocarbon group has may be one, or may be two or more. That is, the long chain hydrocarbon group may be divided at one place by a dividing group, or may be divided at two or more places. When having two or more splitting groups, each splitting group may be the same or different.
In addition, when it has a splitting group in a carbon chain, the carbon atom which a splitting group shall count to carbon number of a long-chain hydrocarbon group. The long-chain hydrocarbon group is usually an unhydrogenated fatty acid derived from beef tallow, which is used industrially, a fatty acid obtained by hydrogenation or partial hydrogenation of an unsaturated part, palm-derived palm oil, oil palm-derived It is introduced by using a hydrogenated fatty acid or fatty acid ester, or a fatty acid or fatty acid ester obtained by hydrogenation or partial hydrogenation of an unsaturated portion.
The amine compound as the component (A) contained in the softener composition of the present invention is preferably a secondary amine compound or a tertiary amine compound, and more preferably a tertiary amine compound.

〔式中、Ｒ¹〜Ｒ³はそれぞれ独立に、炭素数１０〜２６の炭化水素基、−ＣＨ₂ＣＨ（Ｙ）ＯＣＯＲ⁴（Ｙは水素原子又はＣＨ₃であり、Ｒ⁴は炭素数７〜２１の炭化水素基である。）若しくは−（ＣＨ₂）_nＮＨＣＯＲ⁵（ｎは２又は３であり、Ｒ⁵は炭素数７〜２１の炭化水素基である。）、水素原子、炭素数１〜４のアルキル基、−ＣＨ₂ＣＨ（Ｙ）ＯＨ、又は−（ＣＨ₂）_nＮＨ₂であり、Ｒ¹〜Ｒ³のうちの少なくとも１つは、炭素数１０〜２６の炭化水素基、−ＣＨ₂ＣＨ（Ｙ）ＯＣＯＲ⁴又は−（ＣＨ₂）_nＮＨＣＯＲ⁵である。〕 More specifically, examples of the amine compound as the component (A) contained in the softener composition of the present invention include compounds represented by the following general formula (A1).

[Wherein, R ^{1 to} R ³ are each independently a hydrocarbon group having 10 to 26 carbon atoms, —CH ₂ CH (Y) OCOR ⁴ (Y is a hydrogen atom or CH ₃ , and R ⁴ is 7 carbon atoms. . ~ 21 is a hydrocarbon group) or _{-. (CH 2) n NHCOR} 5 (n is 2 or 3, R ⁵ is a hydrocarbon group having 7 to 21 carbon atoms), a hydrogen atom, the number of carbon atoms 1 to 4 alkyl group, —CH ₂ CH (Y) OH, or — (CH ₂ ) _n NH ₂ , and at least one of R ^{1 to} R ³ is a hydrocarbon group having 10 to 26 carbon atoms. _{, -CH 2 CH (Y) OCOR} 4 or - (CH _{2) n} NHCOR ^5. ]

In formula (A1), the carbon number of the hydrocarbon group having 10 to 26 carbon atoms in R ^{1 to} R ³ is preferably 17 to 26, and 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 , 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 R ⁴ is more present in the compounds represented by formula (A1), may be R ⁴ of said plurality of mutually identical, may be different.

Hydrocarbon group R ⁴ is a residue obtained by removing a carboxy group from a fatty acid having 8 to 22 carbon atoms (R ⁴ COOH) (fatty acid residues), R ⁴ Nomoto become fatty (R ⁴ COOH) is Saturated fatty acids or unsaturated fatty acids may be used, and straight-chain fatty acids or branched fatty acids may be used. Of these, saturated or unsaturated linear fatty acids are preferred. In order to impart good water absorption to the soft-treated garment, the saturated / unsaturated ratio (mass ratio) of the fatty acid serving as R ⁴ is preferably 90/10 to 0/100, and 80/20 to 0 / 100 is more preferable.
When R ⁴ is an unsaturated fatty acid residue, a cis isomer and a trans isomer are present, and the mass ratio of the cis isomer / trans isomer is preferably 40/60 to 100/0, and 70/30 to 90/10. Particularly preferred.

Specific examples of fatty acids used as R ⁴ include stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, elaidic acid, linoleic acid, partially hydrogenated palm oil fatty acid (iodine value 10 to 60), partial Examples include hydrogenated beef tallow fatty acid (iodine value of 10 to 60). Among them, a fatty acid prepared by combining two or more selected from stearic acid, palmitic acid, myristic acid, oleic acid, elaidic acid, and linoleic acid in predetermined amounts to satisfy the following conditions (a) to (c) It is preferable to use a composition.
(A) The ratio (mass ratio) of saturated fatty acid / unsaturated fatty acid is 90/10 to 0/100, more preferably 80/20 to 0/100. (B) The ratio (mass ratio) of cis isomer / trans isomer is 40/60 to 100/0, more preferably 70/30 to 90/10. (C) The fatty acid having 18 carbon atoms is 60 mass% or more, preferably 80 mass% or more, the fatty acid having 20 carbon atoms is less than 2 mass%, and the fatty acid having 21 to 22 carbon atoms is less than 1 mass%. .

In — (CH ₂ ) _n NHCOR ⁵ , n is 2 or 3, and 3 is particularly preferable. R ⁵ is a hydrocarbon group having 7 to 21 carbon atoms, preferably 15 to 19 carbon atoms. When R ⁵ is more present in the compounds represented by formula (A1), may be R ⁵ of said plurality of mutually identical, may be different. Examples of R ⁵ include the same as R ⁴ .

At least one of R ^{1 to} R ³ is a long-chain hydrocarbon group (a hydrocarbon group having 10 to 26 carbon atoms, —CH ₂ CH (Y) OCOR ⁴ , or — (CH ₂ ) _n NHCOR ⁵ ). Two are preferably long-chain hydrocarbon groups. When one or two of R ^{1 to} R ³ are long-chain hydrocarbon groups, the remaining two or one is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, —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, as a C1-C4 alkyl group, a methyl group or an ethyl group is preferable, and a methyl group is especially preferable. 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 .

〔式中、Ｒ⁷及びＲ⁸はそれぞれ独立に、炭素数１０〜２６の炭化水素基である。Ｒ⁹及びＲ¹⁰はそれぞれ独立に、炭素数７〜２１の炭化水素基である。〕 Preferable examples of the compound represented by the general formula (A1) include compounds represented by the following general formulas (A1-1) to (A1-8).

[Wherein, R ⁷ and R ⁸ are each independently a hydrocarbon group having 10 to 26 carbon atoms. R ⁹ and R ¹⁰ are each independently a hydrocarbon group having 7 to 21 carbon atoms. ]

Examples of the hydrocarbon group for R ⁷ and R ⁸ include the same hydrocarbon groups as those having 10 to 26 carbon atoms for R ^{1 to} R ³ .
Examples of the hydrocarbon group having 7 to 21 carbon atoms in R ⁹ and R ¹⁰ include those similar to the hydrocarbon group having 7 to 21 carbon atoms in R ⁴ . When R ⁹ is more present in the formula, R ⁹ of the plurality of may be the same as each other, it may be different.
The component (A) in the softener composition of the present invention may be a salt of an amine compound.

The salt of an amine compound is obtained by neutralizing an amine compound with an acid. The acid used for neutralization of the amine compound may be an organic acid or an inorganic acid, and examples thereof include hydrochloric acid, sulfuric acid, and methyl sulfuric acid. Neutralization of the amine compound can be performed 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 the quaternization of 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, the alkyl group of the quaternizing agent is introduced into the nitrogen atom of the amine compound, and a salt of a 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 performed by a known method.

The component (A) contained in the softener composition of the present invention is preferably at least one selected from the group consisting of the compound represented by the general formula (A1), a salt thereof, and a quaternized product thereof. At least one selected from the group consisting of formulas (A1-1) to (A1-8), a salt thereof, and a quaternized product thereof is more preferable, and (A1-4) to (A1-6), a salt thereof, and a salt thereof 4 More preferred is at least one selected from the group consisting of graded products.
As the compound represented by the formula (A1), a salt thereof, and a quaternized product thereof, commercially available products may be used, or those produced by a known method may be used.

For example, a compound represented by the general formula (A1-2) (hereinafter “compound (A1-2)”) and a compound represented by the general formula (A1-3) (hereinafter “compound (A1-3)”) are: The fatty acid composition, or a fatty acid methyl ester composition obtained by replacing the fatty acid in the fatty acid composition with a methyl ester of the fatty acid, and methyldiethanolamine can be synthesized. At that time, from the viewpoint of improving flexibility, the abundance ratio represented by “compound (A1-2) / compound (A1-3)” is synthesized such that the mass ratio is 99/1 to 50/50. It is preferable to do.
Furthermore, when the quaternized product is used, it is more preferable to use dimethyl sulfate as a quaternizing agent. At that time, from the viewpoint of flexibility, the abundance ratio represented by “a quaternized compound (A1-2) / a quaternized compound (A1-3)” is 99/1 to 50/50 in mass ratio. It is preferable to synthesize.

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

  The compound represented by general formula (A1-7) (hereinafter “compound (A1-7)”) and the compound represented by general formula (A1-8) (hereinafter “compound (A1-8)”) are as described above. From an adduct of a fatty acid composition, N-methylethanolamine and acrylonitrile, J. Org. Org. Chem. , 26, 3409 (1960), by a condensation reaction with N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine synthesized by a known method. In that case, it is preferable to synthesize | combine so that the abundance ratio represented by "compound (A1-7) / compound (A1-8)" may be 99 / 1-50 / 50 by mass ratio. When the quaternized product is used, it is preferable to use methyl chloride as a quaternizing agent, which is represented by “a quaternized compound (A1-7) / a quaternized compound (A1-8)”. It is preferable to synthesize the abundance ratio such that the mass ratio is 99/1 to 50/50.

  In the softener composition of the present invention, the amount of component (A) is not particularly limited, but is preferably 5 to 50% by weight, more preferably 8 to 30% by weight, based on the total weight of the softener composition. More preferably, it is 10-20 mass%. When the amount of component (A) is large, the viscosity and TI value increase, but when the amount is too large, the composition may be separated. On the other hand, if the amount of the component (A) is too small, the viscosity and the TI value are not increased and the component (D) may not be dispersed and stabilized.

[Component (B)]
Component (B) contained in the softener composition of the present invention is a nonionic glucan having a weight average molecular weight in the range of 10,000 to 2,000,000. Glucan is a condensation polymer of D-glucopyranose, and includes starch, glycogen, dextrin, cellulose and the like. It is divided into α-glucan and β-glucan by 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 as the component (B) contained in the softener composition of the present invention may be linear or branched as long as the weight average molecular weight is in the range of 10,000 to 2,000,000. . In addition, the nonionic glucan as the component (B) contained in the softener composition of the present invention may have a chain structure or a cyclic structure. Specifically, as component (B), polymer dextrin (Sanwa Starch Co., Ltd., trade name: Sandeck # 30) or a nonionic glucan having a cyclic structure and a branched structure, for example, a cyclic structure Retained branched glucan (described in JP 2012-120471 A), highly branched cyclic dextrin (trade name: cluster dextrin manufactured by Glico Nutrition Foods Co., Ltd.) and the like can be used. (B) A component may be used individually by 1 type and may combine 2 or more types suitably.
In addition, the glucan as the component (B) contained in the softening agent composition of the present invention is a nonionic compound, and a cationic cationized starch, a cationized cellulose, etc. having a cationic property in which a part of the glucan is modified. (B) Does not fall under component.

  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, etc. However, the present invention is not limited to these.

The highly branched cyclic dextrin is a glucan having an inner branched cyclic structure portion and an outer branched structure portion and having a polymerization degree in the range of 50 to 10,000, where the inner branched cyclic structure portion is α-1 , 4-glucoside bond and α-1,6-glucoside bond, and the outer branched structure part is a non-cyclic structure part bonded to the inner branched cyclic structure part. is there.
The highly branched cyclic dextrin as the component (B) contained in the softener composition of the present invention has a weight average molecular weight of about 30,000 to 1,000,000, has one cyclic structure in the molecule, and further has a cyclic portion. Mainly contains dextrin having a weight average degree of polymerization of about 2500 and a large number of glucan chains bound thereto.
The inner branched cyclic structure portion of the highly branched cyclic dextrin as the component (B) contained in the softener composition of the present invention is composed of about 10 to 100 glucose, and the inner branched cyclic structure portion is acyclic. The outer branched structure portion consisting of a large number of branched glucan chains is bound.

For example, the degree of polymerization of the highly branched cyclic dextrin as the component (B) contained in the softener composition of the present invention is in the range of 50 to 5000.
For example, the polymerization degree of the inner branched cyclic structure portion of the highly branched cyclic dextrin as the component (B) contained in the softening agent composition of the present invention is in the range of 10-100.
For example, the degree of polymerization of the outer branched structure portion of the highly branched cyclic dextrin as the component (B) contained in the softener composition of the present invention is 40 or more.
For example, the degree of polymerization of each unit chain of the outer branched structure portion of the highly branched cyclic dextrin as the component (B) contained in the softener composition of the present invention is 10 to 20 on average.

The highly branched cyclic dextrin as the component (B) contained in the softener composition of the present invention is produced, for example, by using starch as a raw material and an enzyme called a branching enzyme. Starch, which is a raw material, is composed of amylose in which glucose is linearly bound by α-1,4-glucoside bonds and amylopectin having a structure that is complicatedly branched by α-1,6-glucoside bonds. It is a macromolecule with many connected structures. Branching enzyme, an enzyme used, is a glucan chain transferase widely distributed in animals, plants, and microorganisms. It acts on the seam portion of the cluster structure of amylopectin and catalyzes the reaction of cyclizing it.
More specifically, the highly branched cyclic dextrin as the component (B) contained in the softener composition of the present invention has an inner branched cyclic structure portion and an outer branched structure portion described in JP-A-8-134104. It is a glucan having a polymerization degree in the range of 50 to 10,000. In the present specification, the highly branched cyclic dextrin can be understood in consideration of the description in JP-A-8-134104.

The cyclic structure-containing branched glucan has a cyclic structure and at least one branched structure based on an α-1,6 bond and an α-1,4 bond, and at least in a sugar chain constituting the cyclic structure. It is a glucan having a structure in which one α-1,6 bond exists.
In the branched structure-containing branched glucan as the component (B) contained in the softener composition of the present invention, the branching frequency is, for example, 8% or more.
The branching frequency of the cyclic structure-containing branched glucan as the component (B) contained in the softener composition of the present invention is indicated by the ratio of α-1,6 branches. The proportion of α-1,6 branches is, 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. Although there is no upper limit to the proportion of α-1,6 branches, 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.
Note that the branching frequency is calculated by the following formula:
Branching frequency (%) = {(number of branches) / (number of glucose units in the whole molecule)} × 100

The weight average molecular weight of the cyclic structure-containing branched glucan as the component (B) contained in the softener composition of the present invention is preferably about 30,000 or more, more preferably about 50,000 or more, particularly preferably. It is about 100,000 or more, preferably about 500,000 or less, 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-containing branched glucan as the component (B) contained in the softener composition of the present invention is preferably about 10 or more, more preferably about 15 or more, More preferably, it is about 20 or more, preferably about 500 or less, more preferably about 300 or less, and further preferably about 100 or less.
The average degree of polymerization of the branched structure portion in the cyclic structure-containing branched glucan as the component (B) contained in the softener composition of the present invention is preferably about 40 or more, more preferably about 100 or more, More preferably about 300 or more, still more preferably about 500 or more, preferably about 4 × 10 ³ or less, more preferably about 3 × 10 ³ or less, and further preferably about 2 × 10 ³ or less, and even more preferably about 1 × 10 ³ or less.

The cyclic structure-containing branched glucan as the component (B) contained in the softener composition of the present invention may have at least one α-1,6-glucoside bond, for example, 1 or more, 5 The number may be 10 or more, for example, about 200 or less, about 50 or less, about 30 or less, about 15 or less, or about 10 or less.
As the cyclic structure-containing branched glucan as the component (B) contained in the softener composition of the present invention, those having one degree of polymerization may be used alone or as a mixture of those having various degrees of polymerization. Also good. Preferably, the degree of polymerization of the cyclic structure-carrying branched glucan is such that the ratio of the degree of polymerization between the maximum degree of polymerization and the minimum degree of polymerization is about 100 or less, more preferably about 50 or less, even more preferably about 10 or less.
The cyclic structure-containing branched glucan as the component (B) contained in the softener composition of the present invention preferably has a part of the branched glucan structure forming 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 an acyclic 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, still more preferably about 6 or more, and preferably about 20 or less, more Preferably it is 18 or less, More preferably, it is 15 or less.

The average degree of polymerization of the cyclic structure-containing branched glucan as the component (B) contained in the softener composition of the present invention is preferably about 50 or more, more preferably about 70 or more, and further preferably about 100. Or more, most preferably about 150 or more, preferably about 5 × 10 ³ or less, more preferably about 4 × 10 ³ or less, further preferably about 3 × 10 ³ or less, Most preferably, it is about 2 × 10 ³ or less.
The number of branches of the cyclic structure-containing branched glucan (that is, the number of α-1,6-glucoside bonds) as the component (B) contained in the softener composition of the present invention is preferably about 10 or more. More preferably about 15 or more, further preferably about 20 or more, preferably about 1000 or less, more preferably about 800 or less, and further preferably about 500 or less. is there.
In the branched structure-containing branched glucan as the component (B) contained in the softener composition of the present invention, the ratio of the number of α-1,4-glucoside bonds to the number of α-1,6-glucoside bonds (“ The number of α-1,6-glucoside bonds ”:“ the number of α-1,4-glucoside bonds ”) is preferably 1: 3 to 1:13, more preferably 1: 4 to 1:12. Yes, more preferably 1: 5 to 1:10, and still more preferably 1: 5 to 1: 9.
The cyclic structure-retaining branched glucan as the component (B) contained in the softener composition of the present invention,
i) A branching enzyme is allowed to act on a branched glucan as a substrate, and then a 4-α-glucanotransferase is allowed to act;
ii) causing 4-α-glucanotransferase to act on the substrate branched glucan and then allowing the branching enzyme to act; or
iii) It is produced by simultaneously acting a branching enzyme and 4-α-glucanotransferase on a branched glucan as a substrate.
More specifically, the cyclic structure-retaining branched glucan as the component (B) contained in the softener composition of the present invention is described in JP2012-120471A. In the present specification, the cyclic structure-carrying branched glucan can be understood with reference to the description in JP2012-120471A.

In the softener composition of the present invention, the blending amount of the component (B) is not particularly limited, but is preferably 0.01 to 5% by mass, more preferably 0.05 to the total mass of the softener composition. It is 3 mass%, More preferably, it is 0.2-2 mass%. When the blending amount of the component (B) is more than 0.01% by mass, an excellent microcapsule dispersion stabilization effect can be exhibited. Even if the blending amount of the component (B) is more than 5% by mass, the dispersion stabilizing effect of the microcapsules may not be improved and the usability may be deteriorated.
Moreover, the weight average molecular weight of the glucan of (B) component is 10,000-2 million, Preferably it is 50,000-1 million, More preferably, it is 100,000-500,000. When the average molecular weight of the component (B) is larger than 10,000, an excellent microcapsule dispersion stabilizing effect can be exhibited. On the other hand, when the weight average molecular weight of the component (B) is larger than 2 million, the composition may be separated after long-term storage.
In place of the nonionic glucan having a weight average molecular weight in the range of 10,000 to 2,000,000 as component (B) contained in the softener composition of the present invention, α-cyclodextrin (n = 6), β-cyclo General cyclodextrins and low molecular weight dextrins with 6-8 glucoses, such as dextrin (n = 7) and γ-cyclodextrin (n = 8) (for example, Sanwa Starch Co., Ltd., trade name: Sandeck # 185N ) In the softener composition, an excellent microcapsule dispersion stabilizing effect equivalent to that of the softener composition of the present invention cannot be obtained.

[Component (C)]
(C) component contained in the softening agent composition of this invention is an inorganic salt. For example, as the inorganic salt that is component (C), alkali metal or alkaline earth metal chlorides, sulfates, phosphates, nitrates, ammonium salts, and the like can be given. Specifically, sodium chloride, sodium sulfate, calcium chloride, and magnesium chloride are preferable as the inorganic salt as the component (C), and calcium chloride and magnesium chloride are particularly preferable from the viewpoint of suppressing viscosity variation.
(C) The inorganic salt which is a component may be used individually by 1 type, and may combine 2 or more types suitably.
In the softener composition of the present invention, the blending amount of the component (C) is not particularly limited, but is preferably 0.002 to 0.4% by mass, more preferably 0.00%, based on the total mass of the softener composition. It is 01-0.15 mass%, More preferably, it is 0.02-0.1%. However, surfactants such as fatty acid salts include sodium salts and potassium salts, but inorganic salts that are mixed into the composition by using such surfactants are not considered in the above preferred amounts. To do.

  The mass ratio B / C of the (B) component and the (C) component in the softening agent composition of this invention is 8 or more, Preferably it is 10-100, More preferably, it is 16-50. When the mass ratio B / C is less than 8, the dispersion stabilizing effect is small, and problems such as floating and sedimentation of the component (D) such as capsule flavor may occur. On the other hand, when the mass ratio B / C is larger than 100, the viscosity of the composition may remarkably increase and the usability may deteriorate.

[(D) component]
The component (D) contained in the softener composition of the present invention is a microcapsule. The microcapsule includes a core material and a wall material that covers the core material. Microcapsules are used for the purpose of imparting various functions, and as core materials, 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 and the like may be included. As the component of the core substance, a component well known in the technical field of the present invention can be used.
(D) The microcapsule which is a component may be used individually by 1 type, and may combine 2 or more types suitably. The microcapsule as component (D) can be appropriately selected from commercially available products depending on the purpose, and specific examples thereof include the following.

Specific examples of microcapsules containing a fragrance as a core material, that is, capsule fragrances include BLUEFLOWERPOP “FFMHN2814” manufactured by Firmenich, GREEN BREEZE CAPS, ORCHARD GARDEN CAPS, RAINBOW CAPS, AULVET CAPS, AUROET CAPS, AUROET CAPS, AUVSM Examples include UNICAP 101 and UNICAP 503 manufactured by IFF.
Specific examples of microcapsules containing a cooling agent as a core material, i.e., cooling capsules, include MultiSal SalCool, HydroSal FreshCool, SalSphere SalCool manufactured by SALVONA Technologies, Neosphere AROMA-C, manufactured by Nikka Chemical Co., Ltd. Examples include Multis Fresh Cool manufactured by Ellis.
Specific examples of microcapsules containing a warming agent as a core substance, that is, warming capsules, include Riken Resin RMC-TO manufactured by Miki Riken Co., Ltd., Hydrostatic Heat manufactured by SALVONA Technologies, and the like.
Specific examples of the functional capsule include RIKEN RESIN NFHO-W (antibacterial effect), RIKEN RESIN, RMC-HBP (insect repellent effect), and RMC-PT (insect repellent effect) manufactured by Miki Riken Co., Ltd.

  The wall material of the microcapsule which is the component (D) is composed of a polymer substance, and materials generally used for capsules contained in softeners for clothes, detergents for clothes, and the like can be used. Examples of wall materials include natural polymers such as gelatin and agar, oily film forming materials such as fats and waxes, and synthetic polymer materials such as polyacrylic acid, polyvinyl, polymethacrylic acid, melamine, and urethane. These can be used alone, or one of them can be used alone or two or more of them can be used together as appropriate. In the case of a microcapsule containing a fragrance as the core material, the wall material is an aminoplast polymer, polyacrylic acid-based or polyacrylic polymer composed of melamine-formaldehyde resin or urea-formaldehyde resin, from the viewpoint of fragrance when the capsule is broken. A methacrylic acid polymer is preferred. In particular, aminoplast polymers such as those described in JP2010-520928 are preferred. Specifically, a terpolymer comprising a polyamine-derived moiety / aromatic polyphenol-derived moiety / methylene unit, an alkylene having dimethoxymethylene and dimethoxymethylene and an alkyleneoxy moiety is preferred.

  In the softener composition of the present invention, the blending amount of the component (D) is not particularly limited, but is preferably 0.05 to 5% by mass with respect to the total mass of the softener composition. In addition, in this specification, the compounding quantity of (D) component is the quantity (mass%) as a component contained as a core substance with respect to the total mass of the softening agent composition of this invention.

[Optional ingredients]
The softener composition of the present invention may contain other components other than the above components (A) to (D) as necessary, as long as the effects of the present invention are not impaired.
As this other component, the well-known component which can be mix | blended in a softening agent composition can be mix | blended suitably. For example, water, a water-soluble solvent, a nonionic surfactant, a fragrance composition, silicone, a dye and / or pigment, an antiseptic, an ultraviolet absorber, an antibacterial agent, and the like can be contained.

<Water>
The softener composition of the present invention is preferably an aqueous composition and preferably contains water.
As water, any of tap water, ion exchange water, pure water, distilled water, and the like can be used. Of these, ion-exchanged water is preferred.

<Nonionic surfactant (component (E))>
The nonionic surfactant can be preferably used mainly for the purpose of improving the emulsion dispersion stability of the oil-soluble component in the emulsion when the softener composition of the present invention is an emulsion. In particular, when a nonionic surfactant is blended, a sufficient level of freeze / restoration stability is easily secured in terms of commercial value.
As the nonionic surfactant, for example, those derived from polyhydric alcohols, higher alcohols, higher amines or higher fatty acids can be used. More specifically, it has a glycerin fatty acid ester or pentaerythritol in which glycerin or pentaerythritol is ester-bonded with a C10-22 fatty acid, an alkyl group or an alkenyl group having 10-22 carbon atoms, and the average added mole number of ethylene oxide is 10 to 100 mol polyoxyethylene alkyl ether, polyoxyethylene fatty acid alkyl (1 to 3 carbon atoms of the alkyl) ester; polyoxyethylene alkylamine having an average addition mole number of ethylene oxide of 10 to 100 mol, carbon number Examples include alkyl polyglucosides having 8 to 18 alkyl groups or alkenyl groups, and hydrogenated castor oil having an average addition mole number of ethylene oxide of 10 to 100 mol. Among these, a polyoxyethylene alkyl ether having an alkyl group having 10 to 18 carbon atoms and an average added mole number of ethylene oxide of 20 to 80 mol is preferable.
The content of the nonionic surfactant in the softener composition of the present invention can be determined according to the desired function, for example, preferably 0.01 to 10% by mass, more preferably 0.1 to 8% by mass. More preferably, it is 0.5 to 5% by mass. When the content of the nonionic surfactant is equal to or higher than the lower limit, the emulsion dispersion stability of the oil-soluble component in the emulsion and the freeze recovery stability of the emulsion are further improved. If it is below an upper limit, the raise of the viscosity of a liquid softening agent composition can be suppressed, and it can be made favorable in terms of usability.

<Water-soluble solvent (component (F))>
The softener composition of the present invention preferably contains a water-soluble solvent in addition to water. The water-soluble solvent is preferably one or more selected from the group consisting of lower (C1-4) alcohols, glycol ether solvents and polyhydric alcohols. Specifically, a solvent selected from ethanol, isopropanol, glycerin, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, hexylene glycol, polyoxyethylene phenyl ether, and a water-soluble solvent represented by the following general formula (X) It is preferable to blend the components.
^{_{R 11 -O- (C 2 H 4}} O) y - (C 3 H 6 O) z -H ··· (X)
[Wherein, R ¹¹ represents an alkyl group or an alkenyl group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms. y and z are average addition mole numbers, y is 1-10, Preferably it is 2-5, z shows the number of 0-5, Preferably it is 0-2. ]
Examples of the water-soluble solvent represented by the general formula (X) include butyl carbitol and diethylene glycol monopropylene glycol monobutyl ether.
Among the above-mentioned water-soluble solvents, ethanol, ethylene glycol, butyl carbitol, propylene glycol, diethylene glycol monopropylene glycol monobutyl ether, and glycerin are preferable.
The water-soluble solvent is preferably added to the softener composition of the present invention in an amount of 0 to 30% by mass, more preferably 0.01 to 25% by mass, and still more preferably 0.1 to 20% by mass.

<Perfume composition (component (G))>
In the softener composition of the present invention, a free fragrance composition can be blended separately from the fragrance composition that can be included as the core material of the component (D). In the softener composition of the present invention, the perfume composition that can be used as a free perfume composition is generally used as a textile product treatment composition, a textile product finish composition, or a softener composition. It may be a fragrance composition containing one or more fragrance ingredients.
Specific examples of the perfume component are not particularly limited and may be appropriately selected depending on the purpose. For example, aldehydes, phenols, alcohols, ethers, esters, hydrocarbons, ketones, lactones , Musks, fragrances having a terpene skeleton, natural fragrances, animal fragrances, and the like.
The aldehydes are not particularly limited and may be appropriately selected depending on the intended purpose. For example, undecylenaldehyde, lauryl aldehyde, aldehyde C-12MNA, miracaldehyde, α-amylcinnamic aldehyde, cyclamenaldehyde, citral Citronellal, ethyl vanillin, heliotropin, anisaldehyde, α-hexylcinnamic aldehyde, octanal, ligustral, lyial, rilal, tripral, vanillin, helional and the like.
There is no restriction | limiting in particular as said phenols, According to the objective, it can select suitably, For example, eugenol, isoeugenol, etc. are mentioned.
The alcohol is not particularly limited and may be appropriately selected depending on the intended purpose.For example, bacdanol, citronellol, dihydromyrcenol, dihydrolinalool, geraniol, linalool, nerol, sandalol, santarex, Examples include terpineol, tetrahydrolinalol, and phenylethyl alcohol.
There is no restriction | limiting in particular as said ether, According to the objective, it can select suitably, For example, cedula bar, glycalva, methyl eugenol, methyl isoeugenol etc. are mentioned.
The esters are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include cis-3-hexenyl acetate, cis-3-hexenyl propionate, cis-3-hexenyl salicylate, p-cresate. Dil acetate, pt-butyl cyclohexyl acetate, amyl acetate, methyl dihydrojasmonate, amyl salicylate, benzyl salicylate, benzyl benzoate, benzyl acetate, cedryl acetate, citronellyl acetate, decahydro-β-naphthyl acetate, dimethylbenzyl Carvinyl acetate, Ericapropionate, ethyl acetoacetate, Erica acetate, geranyl acetate, geranyl formate, hedion, linalyl acetate, β-phenylethyl acetate Hexyl salicylate, styryl acetate, terpinyl acetate, tiviberyl acetate, ot-butylcyclohexyl acetate, manzanate, allyl heptanoate, and the like.

There is no restriction | limiting in particular as said hydrocarbons, According to the objective, it can select suitably, For example, limonene (especially d-limonene), alpha-pinene, beta-pinene, myrcene, camphene, terpinolene, etc. Can be mentioned.
The ketones are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include α-ionone, β-ionone, methyl-β-naphthyl ketone, α-damascon, β-damascon, and δ-damascon. Cis-jasmon, methylionone, allylionone, cashmerelan, dihydrojasmon, iso-Esuper, belt fix, isolone diforanone, coabon, rosephenone, raspberry ketone, dynascon and the like.
The lactone is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include γ-decalactone, γ-undecalactone, γ-nonalactone, γ-dodecalactone, coumarin, and ambroxan. It is done.
There is no restriction | limiting in particular as said musk, According to the objective, it can select suitably, For example, cyclopentadecanolide, ethylene brush rate, galaxolide, musk ketone, tonalid, nitromusk etc. are mentioned.
The fragrance having the terpene skeleton is not particularly limited and may be appropriately selected depending on the intended purpose.For example, geraniol (gelaniol), nerol, linalool, citral, citronellol, menthol, mint, citronellal, myrcene, pinene, Examples include limonene, terpineol, carvone, yonon, camphor, and borneol.
The natural perfume is not particularly limited and may be appropriately selected depending on the intended purpose. For example, orange oil, lemon oil, lime oil, petitgren oil, yuzu oil, neroli oil, bergamot oil, lavender oil, lavandin oil , Abies oil, anise oil, bay oil, bored rose oil, ylang ylang oil, citronella oil, geranium oil, peppermint oil, peppermint oil, spearmint oil, eucalyptus oil, lemongrass oil, patchouli oil, jasmine oil, rose oil, cedar oil , Essential oils such as vetiver oil, galvanum oil, oak moss oil, pine oil, camphor oil, sandalwood oil, mellow oil, turpentine oil, clove oil, clove leaf oil, cassia oil, nutmeg oil, cananga oil, thyme oil, etc. .
There is no restriction | limiting in particular as said animal fragrance | flavor, According to the objective, it can select suitably, For example, a scent, a ghost cat scent, a sea scent incense, a dragon scent etc. are mentioned.

You may mix | blend the solvent used normally with a fragrance | flavor. Examples of the fragrance solvent include acetin (triacetin), MMB acetate (3-methoxy-3-methylbutyl acetate), sucrose diacetate hexaisobutyrate, ethylene glycol dibutyrate, hexylene glycol, dibutyl sebacate, deltil extra ( Isopropyl myristate), methyl carbitol (diethylene glycol monomethyl ether), carbitol (diethylene glycol monoethyl ether), TEG (triethylene glycol), benzyl benzoate (BB), propylene glycol, diethyl phthalate, tripropylene glycol, aborin ( Dimethyl phthalate), deltyl prime (isopropyl palmitate), dipropylene glycol (DPG), farnesene, dioctyl adipate Tributyrin (glyceryl tributanoate), hydrolite-5 (1,2-pentanediol), propylene glycol diacetate, cetyl acetate (hexadecyl acetate), ethyl abiate, avaline (methyl abietate), citroflex A-2 (Acetyl triethyl citrate), citroflex A-4 (tributyl acetyl citrate), citroflex no. 2 (triethyl citrate), Citroflex No. 4 (tributyl citrate), Durafix (methyl dihydroabietate), MITD (isotridecyl myristate), polylimonene (limonene polymer), 1,3-butylene glycol and the like.
The amount of these solvents used is, for example, 0.1 to 30% by mass, preferably 1 to 20% by mass in the fragrance composition.

In the free fragrance composition used in the softener composition of the present invention, a fragrance component having a ClogP value of 1.0 or more and 8.0 or less is used as a free fragrance composition from the viewpoint of freshness of fragrance and palatability. The total mass is preferably 30% by mass or more, more preferably 45% by mass or more, further preferably 50% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% or more. desirable.
The ClogP value is a value representing a 1-octanol / water partition coefficient P representing a ratio of equilibrium concentrations in 1-octanol and in water in the form of logarithmic logP with respect to the base 10 for a chemical substance. The ClogP value can be obtained by f-method (hydrophobic fragment constant method) by decomposing the chemical structure of a compound into its components and integrating the hydrophobic fragment constants / f values possessed by each fragment (for example, , Clog 3 Reference Manual DaylightSoftware 4.34, Albert Leo, David Weininger, Version 1, March 1994).
Generally, since a fragrance | flavor is so hydrophobic that a ClogP value is large, the fragrance | flavor composition containing many fragrance components with a small ClogP value is more hydrophilic than the fragrance | flavor composition containing many fragrance components with a large ClogP value. You can say that.

In the softener composition of the present invention, as a fragrance component in a free fragrance composition preferably used, specifically, as aldehydes, undecylene aldehyde, lauryl aldehyde, aldehyde C-12MNA, mirac aldehyde, α -Amylcinnamic aldehyde, cyclamenaldehyde, citral, citronellal, heliotropin, anisaldehyde, α-hexylcinnamic aldehyde, octanal, ligustral, lyral, rilal, tripral, vanillin, ethyl vanillin, helional, ketones, α-ionone , Β-ionone, methyl-β-naphthylketone, α-damascone, β-damascone, δ-damascone, cis-jasmon, methylyonone, allylyonone, cashamelan, dihydrojasmon, isoey Examples of super, belt fix, isolone diforanone, coabon, rosephenone, raspberry ketone, dinascon, maltol, and hydrocarbons include limonene, α-pinene, β-pinene, myrcene, terpinolene, etc., but are used in the present invention. The perfume ingredients to be used are not limited to these.
In the softener composition of the present invention, the amount of the free fragrance composition is not particularly limited, but is 0.01 to 5% by mass, preferably 0.3 to 5%, based on the total mass of the softener composition. It is 0.5 mass%, More preferably, it is 0.5-3 mass%. When the blending amount of the free fragrance composition is less than 0.01% by mass, the fragrance is weak and the scent sustaining effect is difficult to understand. If the amount of the free fragrance composition is more than 5% by mass, the storage stability at high temperature may be lowered.

<Silicone compound>
A silicone compound can be further blended for the purpose of improving scent sustainability (fragrance) and flexibility. In the softening agent composition of the present invention, a free silicone compound can be blended separately from the silicone compound that can be contained as the core substance of the component (D). There is no restriction | limiting in particular in the kind of a silicone compound, According to the objective, it can select suitably. The molecular structure of the silicone compound may be linear, branched, or cross-linked. The silicone compound may be a modified silicone compound, and the modified silicone compound may be modified with one organic functional group or modified with two or more organic functional groups. It may be.
The silicone compound can be used in the state of oil, and can also be used in the state of an emulsion dispersed by any emulsifier.
Specific examples of the silicone compound include, for example, dimethyl silicone, polyether modified silicone, methylphenyl silicone, alkyl modified silicone, higher fatty acid modified silicone, methyl hydrogen silicone, fluorine modified silicone, epoxy modified silicone, carboxy modified silicone, carbinol. Examples thereof include modified silicone and amino-modified silicone.

前記一般式（Ｉ）中、Ｍ、Ｎ、ａ、及びｂは、平均重合度を表し、Ｒは、水素又はアルキル基を表す。ここで、Ｍは、１０〜１０，０００であることが好ましく、１００〜３００がより好ましい。Ｎは、１〜１，０００であることが好ましく、１〜１００がより好ましい。更に、Ｍ＞Ｎであることが好ましい。ａは、２〜１００であることが好ましく、２〜５０がより好ましい。ｂは、０〜５０であることが好ましく、０〜１０がより好ましい。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。
前記一般式（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。したがって、前記ポリエーテル変性シリコーン中には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。 Among these, polyether-modified silicone, amino-modified silicone, dimethyl silicone and the like are preferable from the viewpoint of versatility and deodorizing and deodorizing effect, and polyether-modified silicone and amino are particularly preferable from the viewpoint of effect and handling during production. Modified silicone is preferred.
Specific examples of the polyether-modified silicone include, for example, a copolymer of alkylsiloxane and polyoxyalkylene. In addition, as carbon number of the alkyl group of the said alkylsiloxane, 1-3 are preferable, and as carbon number of the alkylene group of the said polyoxyalkylene, 2-5 are preferable. Among these, the polyether-modified silicone is preferably a copolymer of dimethylsiloxane and polyoxyalkylene (polyoxyethylene, polyoxypropylene, a random or block copolymer of ethylene oxide and propylene oxide, etc.). Specific examples of such a polyether-modified silicone include, for example, a compound represented by the following general formula (I), a compound represented by the following general formula (II), and the like.

In the general formula (I), M, N, a, and b represent the average degree of polymerization, and R represents hydrogen or an alkyl group. Here, M is preferably 10 to 10,000, and more preferably 100 to 300. N is preferably 1 to 1,000, and more preferably 1 to 100. Furthermore, it is preferable that M> N. a is preferably 2 to 100, and more preferably 2 to 50. b is preferably 0 to 50, and more preferably 0 to 10. R is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms.
The polyether-modified silicone represented by the general formula (I) generally has an organohydrogenpolysiloxane having a Si-H group and a carbon-carbon double bond such as polyoxyalkylene allyl ether at the terminal. It can be produced by addition reaction of polyoxyalkylene alkyl ether with a platinum catalyst. Therefore, the polyether-modified silicone may contain a slight amount of unreacted polyoxyalkylene alkyl ether or organohydrogenpolysiloxane having a Si—H group. Since the organohydrogenpolysiloxane having a Si—H group has high reactivity, the abundance in the polyether-modified silicone is preferably 30 ppm or less (as the amount of Si—H).

前記一般式（ＩＩ）中、Ａ、Ｂ、ｈ、及びｉは、平均重合度であり、Ｒは、アルキル基を表し、Ｒ’は、水素又はアルキル基を表す。ここで、Ａは、５〜１０，０００であることが好ましく、Ｂは、２〜１０，０００であることが好ましい。ｈは、２〜１００であることが好ましく、ｉは、０〜５０であることが好ましい。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。
前記一般式（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。該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。
前記ポリエーテル変性シリコーンとしては、より具体的には、例えば、東レ・ダウコーニング（株）製の、ＳＨ３７７２Ｍ、ＳＨ３７７５Ｍ、ＦＺ−２１６６、ＦＺ−２１２０、Ｌ−７２０、ＳＨ８７００、Ｌ−７００２、Ｌ−７００１、ＳＦ８４１０、ＦＺ−２１６４、ＦＺ−２２０３、ＦＺ−２２０８、信越化学工業（株）製の、ＫＦ３５２Ａ、ＫＦ６１５Ａ、Ｘ−２２−６１９１、Ｘ−２２−４５１５、ＫＦ−６０１２、ＫＦ−６００４等、モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製のＴＳＦ４４４０、ＴＳＦ４４４１、ＴＳＦ４４４５、ＴＳＦ４４５０、ＴＳＦ４４４６、ＴＳＦ４４５２、ＴＳＦ４４６０等が挙げられる。

In the general formula (II), A, B, h, and i are average polymerization degrees, R represents an alkyl group, and R ′ represents hydrogen or an alkyl group. Here, A is preferably 5 to 10,000, and B is preferably 2 to 10,000. h is preferably 2 to 100, and i is preferably 0 to 50. R is preferably an alkyl group having 1 to 5 carbon atoms. R ′ is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms.
The linear polysiloxane-polyoxyalkylene block copolymer represented by the general formula (II) has a polyoxyalkylene compound having a reactive terminal group and a terminal group that reacts with the reactive terminal group of the compound. It can be produced by reacting with dihydrocarbylsiloxane. Such polyether-modified silicone has a longer side chain polyoxyalkylene chain, and the higher the degree of polymerization of the polysiloxane chain, the higher the viscosity. Therefore, it is easy to improve workability during production and blend into aqueous compositions. Therefore, it is preferable to use it in the form of a premix with a water-soluble organic solvent. Examples of the water-soluble organic solvent include ethanol, dipropylene glycol, butyl carbitol and the like.
More specifically, examples of the polyether-modified silicone include SH3772M, SH3775M, FZ-2166, FZ-2120, L-720, SH8700, L-7002, and L-, manufactured by Toray Dow Corning Co., Ltd. 7001, SF8410, FZ-2164, FZ-2203, FZ-2208, manufactured by Shin-Etsu Chemical Co., Ltd., KF352A, KF615A, X-22-6191, X-22-4515, KF-6012, KF-6004, etc. Examples include TSF4440, TSF4441, TSF4445, TSF4450, TSF4446, TSF4452, and TSF4460 manufactured by Momentive Performance Materials Japan GK.

前記一般式（ＩＩＩ）中、Ｒ₁、Ｒ₆は互いに同一でも、異なっていてもよく、メチル基、水酸基、水素のいずれかを表す。Ｒ₂は、−（ＣＨ₂）_n−Ａ₁、及び−（ＣＨ₂）_n−ＮＨＣＯ−（ＣＨ₂）_m−Ａ₁のいずれかを表す。Ａ₁は、−Ｎ（Ｒ₃）（Ｒ₄）、及び−Ｎ⁺（Ｒ₃）（Ｒ₄）（Ｒ₅）・Ｘ^-のいずれかを表す。Ｒ₃〜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、及び−（ＣＨ₂）_n−ＮＨ₂のいずれかを表す。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、及び硫酸エチルイオンのうちのいずれかを表す。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の整数を表す。ｐ及びｑの値は、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、ｑは１〜５００、好ましくは１〜１００を表す。 The amino-modified silicone is a silicone oil in which an amino group is introduced into the terminal or side chain of the dimethyl silicone skeleton, and a substituent such as a hydroxyl group, an alkyl group, or a phenyl group may be substituted in addition to the amino group. Moreover, the form of oil may be sufficient, and the form of the amino modified silicone emulsion which emulsified the nonionic surfactant and the cationic surfactant as an emulsifier may be sufficient. A preferred amino-modified silicone oil or base oil in the case of an emulsion is represented by the following general formula (III).

In the general formula (III), R ₁ and R ₆ may be the same as or different from each other and each represents a methyl group, a hydroxyl group, or hydrogen. R ₂ represents any _one of — (CH ₂ ) _n —A ₁ and — (CH ₂ ) _n —NHCO— (CH ₂ ) _m —A ₁ . A ₁ represents any _one of —N (R ₃ ) (R ₄ ) and —N ⁺ (R ₃ ) (R ₄ ) (R ₅ ) · X ⁻ . R _{3 to} R ₅ may be the same or different from each other, and are any one of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, and — (CH ₂ ) _n —NH ₂ . Represents. X ⁻ represents any one of fluorine ion, chlorine ion, bromine ion, iodine ion, methyl sulfate ion, and ethyl sulfate ion. The values of m and n may be the same as or different from each other, and represent an integer of 0 to 12. The values of p and q represent the degree of polymerization of the polysiloxane and may be the same or different from each other. p is 0 to 20000, preferably 10 to 10000, q is 1 to 500, preferably 1-100 are represented.

For amino-modified silicone oil used in the softener composition of the present invention preferably has a kinematic viscosity at 25 ° C. is 50~20000mm ² / s, more preferably 100~10000mm ² / s. When the kinematic viscosity is in this range, a high texture imparting effect is exhibited, manufacturability is good, and the composition is easy to handle, which is preferable.
Commercially available amino-modified silicones can be used. For example, amino-modified silicone oils sold by Toray Dow Corning Co., Ltd. as SF-8417, BY16-892, BY16-890. From Shin-Etsu Chemical Co., Ltd., KF-864, KF-860, KF-8004, KF-8002, KF-8005, KF-867, KF-861, KF-880, KF-867S and the like can be mentioned.
The amino-modified silicone emulsion type is sold by Toray Dow Corning Co., Ltd. as SM8904, BY22-079, FZ-4671, FZ-4672, and sold by Shin-Etsu Chemical Co., Ltd. in the Polon series. Polon MF-14, Polon MF-29, Polon MF-14D, Polon MF-44, Polon MF-14EC, Polon MF-52 sold by Asahi Kasei Wacker Silicone Co., Ltd., WACKER FC201, WACKER FC218 Is given.
The kinematic viscosity of the dimethyl silicone is not particularly limited but is preferably 1~100,000,000mm ² / s, more preferably ^{10~10,000,000mm 2 / s, 100~1,000,000mm 2 /} s Is more preferable. Further, it may be an oil or an emulsion.

<Dye and / or pigment>
For the purpose of improving the appearance of the softener composition of the present invention, a dye and / or a pigment can be blended. In the softener composition of the present invention, free dyes and / or pigments can be blended separately from the dyes and / or pigments that can be included as the core material of the component (D). 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.
Specific examples of the dyes that can be added are described in the Dye Handbook (edited by the Society of Synthetic Organic Chemistry, published on July 20, 1970, Maruzen Co., Ltd.).
From the viewpoint of the storage stability of the softener composition of the present invention and the dyeing property to fibers, an acidic dye 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, Direct dyes and reactive dyes are preferred, and the blending amount thereof is preferably 1 to 50 ppm, more preferably 1 to 30 ppm, based on the entire composition.
As dyes used in the softener composition of the present invention, JP-A-6-123081, JP-A-6-123082, JP-A-7-18573, JP-A-8-27669, JP-A-9- The dyes described in Japanese Patent No. 250085, Japanese Patent Application Laid-Open No. 10-77576, Japanese Patent Application Laid-Open No. 11-43865, Japanese Patent Application Laid-Open No. 2001-181972, or Japanese Patent Application Laid-Open No. 2001-348784 can also be used.

<Preservative>
The preservative can be used mainly in the softener composition of the present invention in order to enhance the antiseptic and sterilizing power and maintain the antiseptic property during long-term storage. In the softener composition of the present invention, a free preservative can be blended in addition to the preservative that can be included as the core material of the component (D).
Examples of the preservative 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 isothiazolone organic sulfur compounds include 5-chloro-2-methyl-4-isothiazoline-3-one, 2-n-butyl-3-isothiazolone, 2-benzyl-3-isothiazolone, 2-phenyl-3-isothiazolone. 2-methyl-4,5-dichloroisothiazolone, 5-chloro-2-methyl-3-isothiazolone, 2-methyl-4-isothiazolin-3-one, or a mixture thereof. Among them, 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one are preferable, and 5-chloro-2-methyl-4-isothiazolin-3-one and 2- A mixture of 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 is particularly preferred.
Examples of benzisothiazolone-based organic sulfur compounds include 1,2-benzisothiazoline-3-one, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, and dithio-2,2-bis ( Benzmethylamide) or a mixture thereof. Among these, 1,2-benzisothiazolin-3-one is particularly preferable.
Examples of benzoic acids include benzoic acid or a salt thereof, parahydroxybenzoic acid or a salt thereof, methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, butyl paraoxybenzoate, benzyl paraoxybenzoate, and the like.
In the softener composition of the present invention, the blending amount of the preservative is preferably 0.0001 to 1% by mass with respect to the total amount of the softener composition. When the blending amount of the preservative is less than the lower limit, it is difficult to obtain the effect of adding the preservative, and when it exceeds the upper limit, the storage stability may be lowered.

<Ultraviolet absorber>
An ultraviolet absorber is a chemical | medical agent with the effect which protects an ultraviolet-ray, it is a component which absorbs an ultraviolet-ray, converts into infrared rays, visible light, etc., and discharge | releases.
Examples of the ultraviolet absorber include aminobenzoic acid derivatives such as p-aminobenzoic acid, ethyl p-aminobenzoate, glyceryl p-aminobenzoate, and amyl p-dimethylaminobenzoate; ethylene glycol salicylate, dipropylene glycol salicylate , Salicylic acid derivatives such as octyl salicylate, myristyl salicylate; methyl diisopropylcinnamate, ethyl p-methoxycinnamate, isopropyl p-methoxycinnamate, p-methoxycinnamate-2-ethylhexyl, p-methoxycinnamic acid Cinnamic acid derivatives such as butyl; benzophenone derivatives such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and 2,2′-dihydroxy-4-methoxybenzophenone; urocanic acid, Ouro Examples include azole compounds such as ethyl kanate; 4-t-butyl-4′-methoxybenzoylmethane.

<Antimicrobial agent>
The antibacterial agent is a component having an effect of suppressing the growth of bacteria on the fiber and further suppressing the generation of an unpleasant odor derived from the degradation product of the microorganism. In the softener composition of the present invention, a free antibacterial agent can be blended separately from the antibacterial agent that can be included as the core substance of the component (D).
As an antibacterial agent, for example, a cation fungicide such as a quaternary ammonium salt (benzalkonium chloride), diclosan, triclosan, bis- (2-pyridylthio-1-oxide) zinc, polyhexamethylene biguanidine hydrochloride, Examples include 8-oxyquinoline and polylysine.

In addition to the above-mentioned optional components, as a function improver that can be blended in the softener composition of the present invention, an anti-shrink agent, an anti-wrinkle agent, a shape retainer, a drape retainer, an iron improver, an oxygen bleach Inhibitor, brightener, whitening agent, fabric softening clay, antistatic agent, dye transfer inhibitor such as polyvinylpyrrolidone, polymer dispersant, soil release agent, scum dispersant, 4,4-bis (2-sulfo) Styryl) biphenyl disodium (Chino Specialty Chemicals' Chino Pearl CBS-X) and other brightening agents, dye fixing agents, 1,4-bis (3-aminopropyl) piperazine and other anti-fading agents, stain removers, and fiber surface modification Silk that can give the texture and function of silk, such as cellulase, amylase, protease, lipase, keratinase, etc. B Tain powder, their surface reformate, emulsified dispersion, and the like. Specifically, K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk solution (upper hair), Silken G Solvel S (Ichimaru Falcos), a nonionic polymer compound composed of alkylene terephthalate and / or alkylene isophthalate unit and polyoxyalkylene unit, for example, FR627 manufactured by Kyoyo Chemical Industry, SRC-1 manufactured by Clariant Japan, etc. Can do.
These optional components can be blended separately from those that can be included as the core material of the component (D) in the softener composition of the present invention.

[PH of composition]
The pH of the softener composition of the present invention is not particularly limited, but the pH is adjusted to a range of 1 to 6 for the purpose of suppressing hydrolysis of the ester group contained in the molecule of the component (A) accompanying the storage aging date. It is preferable to do it, and it is more preferable that it is the range of 2-4. 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, PH adjustment of short chain amine compounds such as triethanolamine, diethanolamine, dimethylamine, N-methylethanolamine, N-methyldiethanolamine, alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates, and alkali metal silicates An agent can be used.

[Viscosity of composition]
The viscosity of the softener composition of the present invention is not particularly limited, but has a TI (thixotropic index) value measured as described below of 2.0 or more, and further has a viscosity at 25 ° C. of 50 to 300 mpa · s. Is preferred.
Here, the TI value is the following for each composition adjusted to 25 ° C. from the viscosity value after 10 rotations at a rotation speed of 6 rpm and 60 rpm with a B-type viscometer (manufactured by TOKIMEC, rotor No. 2). This is a calculated value based on the formula.
TI value = (6 rpm viscosity value) / (60 rpm viscosity value)
The viscosity at 25 ° C. is the viscosity at the rotation speed of 30 rpm. This TI value is used as an index representing the thixotropy by measuring the dependency of the shear rate (rotational speed of the viscometer) and the viscosity.

The TI value is TI value = 1 in the case of a Newtonian fluid such as water that does not change in viscosity even when the shear rate changes. When the TI value is greater than 1, it indicates that a smaller shear force has a higher viscosity than a larger shear force, and the liquid has thixotropic properties.
In the liquid softening agent composition of the present invention, the range of the TI value indicating thixotropy is preferably 2.0 or more, more preferably 2.0 to less than 5.0, and still more preferably 2.5 to 4.0. is there. When the TI value is 2.0 or more, excellent thixotropy is obtained, and the dispersion stability of the component (D) is further improved. On the other hand, if it exceeds 5.0, thixotropy is enhanced and the dispersion stability of the component (D) is improved, but there may be a problem that it is difficult to take out the composition into the cap when measuring the liquid softener composition. .
Further, the liquid softener composition of the present invention has a dispersion stability of the component (D) when the viscosity at the above 25 ° C. when the rotational speed of the viscometer is 30 rpm is in the range of 50 to 300 mpa · s. It becomes good and the handling ease as a liquid softening agent also becomes good.

[Production method]
The softener composition of the present invention can be produced by a known method, for example, a method similar to the conventional method for producing a liquid softener composition using a cationic surfactant as a main agent.
For example, an oil phase containing the component (A) and the component (E) and an aqueous phase containing the component (B) are mixed under a temperature condition equal to or higher than the melting point of the component (A) to prepare an emulsion, The resulting emulsion can be produced by adding and mixing the (C) component, the (D) component and other components as necessary.
The oil phase can be prepared by mixing the component (A), the component (E) and an optional component as necessary at a temperature equal to or higher than the melting point of the component (A).
An aqueous phase can be prepared by mixing water, (B) component, and an arbitrary component as needed.
In addition, the addition method of (B) component, (C) component, (D) component, and (E) component is not limited to the addition method of the said description. That is, (B) component can be manufactured by adding and mixing as aqueous solution, after an emulsion is obtained. (C) component and (D) component can also be added to an aqueous phase. Moreover, (E) component can also be divided | segmented and added to an oil phase and a water phase, and it is also possible to add to the water phase whole quantity.

[Usage and usage]
The processing method of textiles, such as clothing, by the softening agent composition of the present invention is not particularly limited, and can be used in the same manner as conventional usage methods. For example, in the rinsing stage of washing, the softener composition of the present invention is dissolved in water for treatment, or the softener composition of the present invention is dissolved in water using a container such as a tub, and further, clothing is added. In such a case, it is used after being diluted to an appropriate concentration. In that case, the bath ratio (weight ratio of the treatment liquid to the textile product) is preferably 3 to 100 times, particularly preferably 5 to 50 times. Specifically, when performing the flexible treatment, it is preferably used in such an amount that the concentration of the component (A) is 0.01 ppm to 1000 ppm, more preferably 0.1 ppm to 300 ppm, with respect to the total amount of water used. Is used in such an amount.
The textile product that can be treated with the softener composition of the present invention is not particularly limited, and examples thereof include clothing, curtains, sofas, carpets, towels, handkerchiefs, sheets, and macula covers. The material may also be natural fibers such as cotton, silk, and wool, or chemical fibers such as polyester.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. In the examples, the component blending amounts are all expressed in mass% (in terms of pure content, unless otherwise specified).

[(A) component]
The following A-1 to A-4 were used.
A-1: cationic surfactant (compound described in Example 4 of JP2003-12471)
A-2: Cationic surfactant (made by Tonan Gosei Co., Ltd., trade name: HITEX RO16E)
A-3: cationic surfactant (manufactured by Stepan, trade name: Stepantex SE-88)
A-4: Cationic surfactant (N, N-bis (stearoyl-oxy-ethyl obtained by quaternization of reaction product of fatty acid and methyldiethanolamine in a molar ratio of 1.5: 1 with methyl chloride) ) A 1: 1 molar mixture of N, N-dimethylammonium chloride and N- (stearoyl-oxy-ethyl) N-hydroxyethyl N, N dimethylammonium chloride.)

[Component (B)]
The following B-1 to B-5 were used.
B-1: highly branched cyclic dextrin (Glyco Nutrition Foods, Inc., trade name: cluster dextrin, weight average molecular weight: 400,000)
B-2: Polymer dextrin (Sanwa Starch Co., Ltd., trade name: Sandeck # 30, weight average molecular weight: 100,000)
B-3 (comparative example): low molecular dextrin (Sanwa Starch Co., Ltd. trade name: Sandeck # 185N, weight average molecular weight: 3000)
B-4 (comparative example): β cyclodextrin (Tokyo Chemical Industry Co., Ltd.)
B-5 (comparative example): cationized starch (Nippon Lubrizol Corporation, trade name: SENSOMER CI-50)

[Component (C)]
The following C-1 and C-2 were used.
・ C-1: Calcium chloride (Product name: Granular calcium chloride, manufactured by Tokuyama Corporation)
C-2: Magnesium chloride (trade name: Magnesium chloride anhydride 99%)

[(D) component]
The following D-1 and D-2 were used.
-D-1: Capsule flavor (trade name: GREEN BREEZE CAPS manufactured by Givaudan)
D-2: Capsule cooling agent (trade name: Multis Fresh Refresh Cool, manufactured by Wilber Ellis)

[Optional ingredients]
The following optional ingredients were used.
<(E) component>
E-1: Nonionic surfactant (primary isotridecyl alcohol ethylene oxide 60 mol adduct, a product obtained by adding ethylene oxide to BASF Rutensol TO3)
E-2: Nonionic surfactant (glyceryl monostearate, trade name: Rheidol MS-50, manufactured by Kao Corporation)
E-3: Nonionic surfactant (pentaerythritol tetrapalmitate, trade name: EXCEPARL PE-TP manufactured by Kao Corporation)

<(F) component>
・ F-1: Ethylene glycol (Sankyo Chemical Co., Ltd.)
・ F-2: Glycerin (Sakamoto Pharmaceutical Co., Ltd.)

<(G) component>
G-1: Perfume composition described in Table 1

各成分の配合量の表記は、調製される液体柔軟剤組成物の総質量に対する各成分の質量％である。 <Common ingredients>
・ Common ingredient 1:

The notation of the amount of each component is mass% of each component with respect to the total mass of the prepared liquid softening agent composition.

[Method for Preparing Liquid Softener Composition]
Using a glass container having an inner diameter of 100 mm and a height of 150 mm and a stirrer (Agitator SJ type, manufactured by Shimadzu Corporation), the blending amount of each component is adjusted as described in Tables 3 and 4 below. An agent composition and a base composition were prepared. First, (A) component, (E) component, and (G) component were mixed and stirred to obtain an oil phase mixture. On the other hand, common component 1 was dissolved in ion-exchange water for balance to obtain an aqueous phase mixture. Here, the mass of ion-exchange water for balance is from 980 g to the sum of the oil phase mixture, component (B) (including ion-exchange water necessary for dissolving component B), component (C), and component (D) It corresponds to the balance after subtracting the amount. Next, the oil phase mixture heated above the melting point of component (A) is placed in a glass container and stirred, and the aqueous phase mixture heated above the melting point of 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 rotational speed of 1,000 rpm for 3 minutes after the first aqueous phase mixture addition and for 2 minutes after the second aqueous phase mixture addition. It was. Thereafter, component (C), component (B), component (D), and component (F) were added. In addition, (B) component melt | dissolved in ion-exchange water before addition, and used as 30% wt aqueous solution. If necessary, add a suitable amount of hydrochloric acid (reagent 1 mol / L, Kanto Chemical) or sodium hydroxide (reagent 1 mol / L, Kanto Chemical) to adjust the pH to 2.5, and further adjust the total mass to 1,000 g. Ion exchange water was added so that the intended softener composition (Examples 1-11, 13-16, and Comparative Examples 1-6) was obtained.
In Example 12, a softener composition was prepared in the same manner as described above except that calcium chloride as component (C) was added to the aqueous phase mixture.

[Measurement of viscosity and TI value]
About each liquid softening agent composition prepared as mentioned above, it adjusts to 25 degreeC and it uses the B-type viscometer (the product made by TOKIMEC, rotor No. 2) from the viscosity value after 10 rotations of each of rotational speed 6rpm and 60rpm. The TI value was calculated based on the following formula.
TI value = (6 rpm viscosity value) / (60 rpm viscosity value)
Further, the viscosity at 25 ° C. was measured as a viscosity value after 10 rotations at a rotation speed of 30 rpm using a B-type viscometer (manufactured by TOKIMEC, rotor No. 2).
In addition, the viscosity and TI value calculated the average value of the value which measured the same composition 3 times and prepared, respectively. The results are shown in Tables 3 and 4.

[Viscosity variation evaluation]
About each liquid softening agent composition, as above-mentioned, it prepared repeatedly 3 times, calculated | required the difference of the minimum and the maximum viscosity value, and evaluated by the following evaluation criteria.
<Evaluation criteria>
4: The difference in viscosity is less than 20 mPa · s 3: The difference in viscosity is 20 mPa · s or more and less than 50 mPa · s 2: The difference in viscosity is 50 mPa · s or more and less than 100 mPa · s 1: The difference in viscosity is 100 mPa · s or more <Judgment criteria>
Three or more points were accepted.

[Evaluation of dispersion stability of component (D) (microcapsule)]
100 mL of each liquid softening agent composition prepared as described above was put in a lightweight PS glass bottle (PS-No. 11, manufactured by Tanuma Glass Industrial Co., Ltd.) and sealed, and the dispersibility of component (D) (microcapsule) is shown below. Evaluation was performed by a five-step evaluation method. Similarly, the sealed sample was stored for one month under the condition of 40 ° C., and visually evaluated by 10 professional panels based on the following criteria. The dispersion stability was evaluated by the average value of 10 people. The results are shown in Tables 3 and 4.
<Evaluation criteria>
4: Capsule floating / sedimentation and composition separation are not observed 3: Extremely slight capsule floating / sedimentation and composition separation are observed 2: Capsule floating / sedimentation and composition separation slightly Slightly recognized 1: Capsule floating / sedimentation and separation of composition are observed <Criteria>
Three or more points were accepted.

組成表中の数字は質量％を表す。尚、（Ｄ）成分の数値は、液体柔軟剤組成物の総質量に対する、芯物質として含まれる成分としての量（質量％）である。

The numbers in the composition table represent mass%. In addition, the numerical value of (D) component is the quantity (mass%) as a component contained as a core substance with respect to the total mass of a liquid softening agent composition.

組成表中の数字は質量％を表す。尚、（Ｄ）成分の数値は、液体柔軟剤組成物の総質量に対する、芯物質として含まれる成分としての量（質量％）である。

The numbers in the composition table represent mass%. In addition, the numerical value of (D) component is the quantity (mass%) as a component contained as a core substance with respect to the total mass of a liquid softening agent composition.

Claims (3)

(A) Selected from the group consisting of an amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms which may be separated by an ester group and / or an amide group, a salt thereof and a quaternized product thereof At least one compound,
(B) a nonionic glucan having a weight average molecular weight of 10,000 to 2 million,
A liquid softener composition comprising (C) an inorganic salt, and (D) a microcapsule, wherein the mass ratio of the content of the component (B) to the content of the component (C) is 8 or more.   The liquid softening agent composition according to claim 1, wherein the nonionic glucan has a cyclic structure and a branched structure.   The nonionic glucan is a glucan having an inner branched ring structure portion and an outer branch structure portion and having a polymerization degree in the range of 50 to 10,000, wherein the inner branch ring structure portion is α-1 , 4-glucoside bond and α-1,6-glucoside bond, and the outer branched structure part is a non-cyclic structure part bonded to the inner branched cyclic structure part. The liquid softening agent composition according to claim 1 or 2.