WO2014003180A1

WO2014003180A1 - Liquid fabric softener composition

Info

Publication number: WO2014003180A1
Application number: PCT/JP2013/067887
Authority: WO
Inventors: 恵美子橋本; 亮橋本; 麻優美新倉; 理恵安達; 直行江川; 英史小倉; 友彦天谷
Original assignee: ライオン株式会社
Priority date: 2012-06-29
Filing date: 2013-06-28
Publication date: 2014-01-03
Also published as: KR101988072B1; MY171472A; JPWO2014003180A1; KR20150027052A; JP5995294B2

Abstract

The present invention is related to a liquid fabric softener composition which has improved storage stability, while maintaining the functions as a fabric softener. The present invention is specifically related to a liquid fabric softener composition which contains: (A) a cationic surfactant which is composed of one or more cationic surfactants selected from the group consisting of amine compounds that contain one or more hydrocarbon groups having 10-24 carbon atoms in each molecule, neutralized products of the amine compounds, and quaternized forms of the amine compounds, and in which the hydrocarbon group may be interrupted by one or more groups selected from the group consisting of an ester group, an ether group and an amide group; (B) an amino-modified silicone; and (C) one or more compounds selected from the group consisting of urea, double salts thereof and urea derivatives represented by general formula (C) (wherein R^a represents a methyl group, an ethyl group or a hydroxyalkyl group having 1 or 2 carbon atoms; and each of R^b, R^c and R^d independently represents a hydrogen atom, a methyl group or an ethyl group). In this liquid fabric softener composition, the value of [mass of component (A) + mass of component (B)]/mass of component (C) is 1-40.

Description

Liquid softener composition

The present invention relates to a liquid softener composition. Specifically, the present invention relates to a liquid softener composition having excellent storage stability.

Cationic surfactants are known to be useful as softeners because they have the effect of imparting a texture to the fibers. It is also known that when silicone is combined with a cationic surfactant, the texture-imparting effect is further improved. Among silicones, amino-modified silicones are known to act on wet articles after dehydration during washing and to provide excellent texture imparting effects (Patent Documents 1 to 3). .
On the other hand, softeners containing silicone are known to have insufficient storage stability. Techniques for improving storage stability include blending urea (Patent Document 3), blending a compound capable of generating hydrogen peroxide (Patent Document 4), nonionic surfactant and carboxylic acid type amphoteric surfactant A blend of the above (Patent Document 5) is known.
Moreover, about the softening agent containing ester quaternary ammonium, it is known to mix | blend urea in order to improve the instability (patent document 6).

In recent years, the amount of water used for washing has been decreasing due to increasing environmental awareness. Under washing conditions where the amount of water used is low, dirt such as sebum is likely to remain on the washed object, so when the washed object is dried under high temperature and humidity (for example, room drying), the bacteria that have propagated on the remaining part of the dirt May cause an unpleasant odor.
As an attempt to solve the problem of unpleasant odor, the techniques of Patent Documents 7 and 8 are known.
Moreover, the technique of patent document 9 is known as a softening agent composition.
In addition, if washing of clothes and other items to be washed is performed at a low bath ratio and then dried using a drier or the like, the texture of the items to be washed is deteriorated or the washing power is reduced. It is also known that an odor derived from sebum stains is generated.
With respect to the reduction in the texture of an object to be washed, there has heretofore been the suppression of the decrease with a cationic surfactant and a softening agent in combination with a silicone compound such as an amino-modified silicone (Patent Document 10). ).
For odor generation, attempts have been made to reduce malodors by sensory deodorization, physical deodorization, chemical deodorization, biological deodorization, and the like. For example, as a method for deodorizing and preventing odors of clothing, conventionally, there is a method of preventing generation of odor by incorporating malodorous molecules into pores existing in molecules or base materials using silica or cyclodextrin. However, some offensive odor components cannot be taken into the holes.

JP 2008-150756 A JP 2000-110077 A Japanese Patent Laid-Open No. 4-50373 JP 2007-284843 A Japanese Patent Laid-Open No. 2003-3378 JP 2002-515551 A JP 2004-211230 A Japanese Patent Laid-Open No. 2004-21112 JP 2012-202000 A JP 2007-284843 A

So far, in the softener composition using a combination of cationic surfactant and amino-modified silicone, the storage stability (especially suppression of changes in fragrance, fragrance quality, yellowing, viscosity and fluidity during storage) There has been no excellent liquid softener composition, and the provision of such a liquid softener composition has been a problem.
Moreover, (1) While having the above-mentioned storage stability, (2) Deterioration of texture and odor of washing objects that occur when washing is performed at a low bath ratio (particularly when drying using a dryer is used in combination). There was also no liquid softener composition that could suppress the occurrence.

As a result of intensive studies to solve the above-mentioned problems, the inventors combined amino-modified silicone, a specific type of cationic surfactant, and urea at a specific ratio, and preserved the function as a softening agent. It has been found that stability can be improved (especially, changes in scent formation, scent quality, yellowing, viscosity and fluidity during storage) can be suppressed, and the present invention has been completed.
That is, the present invention relates to the following 1 to 7.

1. (A) one or more cationic surfactants selected from the group consisting of an amine compound containing at least one hydrocarbon group having 10 to 24 carbon atoms in the molecule, a neutralized product thereof, and a quaternized product thereof. The hydrocarbon group may be separated by one or more groups selected from the group consisting of an ester group, an ether group and an amide group,
(B) amino-modified silicone, and (C) urea, its double salt, and general formula (C):

(Wherein R ^a is a methyl group, an ethyl group or a hydroxyalkyl group having 1 to 2 carbon atoms, and R ^b , R ^c and R ^d are each independently a hydrogen atom, a methyl group or an ethyl group. A liquid softener composition comprising at least one compound selected from the group consisting of urea derivatives represented by:
[Mass of (A) + Mass of (B)] / Mass of (C) = 1-40.

2. (A) is represented by the following general formulas (A-III), (A-IV) and (A-V):

(In each of the general formulas, R ¹ is a hydrocarbon group having 15 to 17 carbon atoms which may be the same or different.) Agent composition.

3. 3. The liquid softener composition according to the above 1 or 2, wherein [mass of (A) + mass of (B) / mass of (C) = 1-5.

4). 4. The liquid softener composition as described in any one of 1 to 3 above, wherein (B) is an emulsion obtained by emulsion polymerization of an amino-modified silicone having a —H group and / or —OH group at a terminal with a surfactant. .

5. 5. The liquid softener composition as described in any one of 1 to 4 above, wherein (C) is urea or dimethylurea.

6). 6. The liquid softener composition as described in any one of 1 to 5 above, further comprising (L) trehalose.

7). 7. The liquid softener composition as described in any one of 1 to 6 above, further comprising (N) a highly branched cyclic dextrin.

8). Further, (M) biguanide antibacterial agent and the following general formula (M-2):
R ¹² —N [(CH ₂ ) _n —NH ₂ ] ₂ (M-2)
(Wherein R ¹² represents an alkyl group having 8 to 18 carbon atoms, and n is a number of 1 to 4), and contains at least one antibacterial agent selected from the group consisting of compounds represented by: 8. The liquid softener composition as described in any one of 1 to 7 above.

As shown in the examples described later, the liquid softener composition of the present invention improves the storage stability while maintaining the function as a softener (especially the fragrance during storage, the quality of the fragrance, the yellowing, The change in viscosity and fluidity can be sufficiently suppressed).
Furthermore, as shown in the examples described later, the liquid softener composition of the present invention has the above-mentioned storage stability and is washed at a low bath ratio (particularly, drying using a dryer is used in combination). In this case, it is possible to suppress the deterioration of the texture of the object to be washed and the generation of odor.
Therefore, the present invention is useful as a softener having an added value not found in conventional liquid softener compositions.

The component (A) contained in the liquid softener composition of the present invention, together with the component (B) described later, has an effect of imparting a texture (including smoothness) to the fibers (that is, the original function of the softener). Is added to the liquid softener composition.
The component (A) is selected from the group consisting of an amine compound containing one or more hydrocarbon groups having 10 to 24 carbon atoms in the molecule, a neutralized product thereof, and a quaternized product thereof, and as a cationic surfactant. It functions.
In the amine compound, the hydrocarbon group is bonded to a nitrogen atom, and the number of hydrocarbon groups bonded to the nitrogen atom is 1 to 3.
The hydrocarbon group has 10 to 24 carbon atoms, preferably 12 to 22 carbon atoms, and particularly preferably 14 to 18 carbon atoms.
Further, the hydrocarbon group may be separated by one or more groups selected from the group consisting of an ester group, an ether group and an amide group. Among ester groups, ether groups and amide groups, ester groups are particularly preferred. When the group to be split is an ester group or an amide group, the number of groups to be split is one for each hydrocarbon group. In the case where the group to be split is an ether group, the number is one per hydrocarbon group.
The neutralized product is a compound obtained by neutralizing the above amine compound with an acid. Examples of the acid used for neutralization include hydrochloric acid, sulfuric acid, methyl sulfuric acid, and paratoluenesulfonic acid. The neutralized product is preferably in the form of an amine salt.
The neutralized product is produced by dispersing an amine compound that has been neutralized with an acid in advance, adding a liquid or solid amine compound into an aqueous acid solution, or simultaneously adding an amine compound and an acid into water, etc. Can be performed.

A quaternized product is a compound obtained by treating a compound having 3 hydrocarbon groups bonded to a nitrogen atom (tertiary amine) with a quaternizing agent among the above amine compounds. . Examples of the quaternizing agent include methyl chloride and dimethyl sulfate.

Examples of the amine compound of component (A) include compounds represented by any one of the following general formulas (AI) to (A-VII), neutralized products thereof, or quaternized products thereof.

In each of the above formulas (AI) to (A-VII), R ¹ may be the same or different from a hydrocarbon group having 15 to 17 carbon atoms (in other words, from a fatty acid having 16 to 18 carbon atoms). Residue derived by removing the carboxyl group). Examples of fatty acids from which R ¹ is derived include saturated fatty acids, unsaturated fatty acids, linear fatty acids and branched fatty acids. In the case of an unsaturated fatty acid, a cis isomer and a trans isomer are present, and the mass ratio is preferably cis isomer / trans isomer = 25/75 to 100/0, and preferably 40/60 to 80/20. Is particularly preferred.
Preferred fatty acids for inducing R ¹ include stearic acid, palmitic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, partially hydrogenated palm oil fatty acid (iodine value 10-60), and partially hydrogenated beef tallow fatty acid (iodine). Valence 10-60) and the like. More preferably, it is a mixture of stearic acid, palmitic acid, oleic acid, elaidic acid, linoleic acid and linolenic acid, and the mass ratio of saturated fatty acid / unsaturated fatty acid is 95/5 to 50/50, cis isomer / trans isomer Is 40/60 to 80/20, iodine value is 10 to 50, and the fatty acid content of 18 carbon atoms is 80% by mass or more based on the total mass of the mixture, and the total amount of linoleic acid and linolenic acid is the total amount of the mixture The mixture is 2% by mass or less based on the mass.

(A) When using the composition containing the compound represented by general formula (AI) and the compound represented by general formula (A-II) as a component, the said composition is said fatty acid mixture or The methyl esterified product can be synthesized by a condensation reaction of methyldiethanolamine. At that time, from the viewpoint of improving the dispersion stability in the liquid softening agent composition, the compound is synthesized so that the mass ratio of each compound is (A-II) / (AI) = 99/1 to 50/50. It is preferable to do.
When using a composition containing a quaternized product of the compound represented by the general formula (AI) and a quaternized product of the compound represented by the general formula (A-II), methyl chloride or the like is used as the quaternizing agent. Although dimethyl sulfate can be used, methyl chloride is preferred because it has a low molecular weight and can reduce the amount required for quaternization. At that time, from the viewpoint of improving the dispersion stability in the liquid softening agent composition, the quaternized product in which the mass ratio of each quaternized product is (A-II) / quaternary product in (AI) = 99 / It is preferable to synthesize so as to be 1 to 50/50.
In the above quaternization reaction, unreacted substances (that is, the compound represented by (AI) and the compound represented by (A-II)) remain. At that time, from the viewpoint of stability against hydrolysis of the ester group contained in the quaternized product, the quaternized product (quaternized product of (AI) + quaternized product of (A-II)) and unreacted product ( It is preferable to synthesize so that the mass ratio of (compound represented by (AI) + compound represented by (A-II)) is quaternized product / unreacted product = 99/1 to 70/30. .

As the component (A), a composition comprising a compound represented by the general formula (A-III), a compound represented by the general formula (A-IV), and a compound represented by the general formula (A-V) When using a product, the composition can be synthesized by subjecting the fatty acid composition or its methyl esterified product to a condensation reaction with triethanolamine. At that time, from the viewpoint of improving the dispersion stability in the liquid softening agent composition, the mass ratio of each compound is [(A-IV) + (A-V)] / (A-III) = 99/1 to It is preferable to synthesize so as to be 50/50.
A quaternized product of the compound represented by the general formula (A-III), a quaternized product of the compound represented by the general formula (A-IV), and a quaternized product of the compound represented by the general formula (A-V). In the case of using a composition containing dimethylsulfate, methyl chloride, dimethyl sulfate, or the like can be used as the quaternizing agent, but dimethyl sulfate is preferred from the viewpoint of the reactivity of the quaternization reaction. At that time, from the viewpoint of improving the dispersion stability in the liquid softening agent composition, the mass ratio of each quaternized product is [(A-IV) + (A-V)] / (A-III) = 99 / It is preferable to synthesize so as to be 1 to 50/50.
In the quaternization reaction, an unreacted product (that is, a compound represented by the general formula (A-III), a compound represented by the general formula (A-IV), and a general formula (A-V) The compound represented) remains. At that time, from the viewpoint of stability against hydrolysis of the ester group contained in the quaternized product, the quaternized product (quaternized product of (A-III) + quaternized product of (A-IV) + (A-V) Quaternized product) and unreacted material (compound represented by (A-III) + compound represented by (A-IV) + compound represented by (A-V)) are quaternized. It is preferable to synthesize so that / unreacted material = 99/1 to 70/30.

(A) When using the composition containing the compound represented by general formula (A-VI) and the compound represented by general formula (A-VII) as a component, the said composition is the said fatty acid composition, N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine (Adduct of N-methylethanolamine and acrylonitrile according to the method described in J. Org. Chem., 26, 3409 (1960)) Can be synthesized by a condensation reaction. From the viewpoint of improving the texture-imparting effect, the compounds are preferably synthesized such that the mass ratio of each compound is (A-VII) / (A-VI) = 99/1 to 50/50.
When a composition containing a quaternized product of the compound represented by the general formula (A-VI) and a quaternized product of the compound represented by the general formula (A-VII) is used, methyl chloride is used as a quaternizing agent. Can be used. At that time, from the viewpoint of improving the texture-imparting effect, the mass ratio of each quaternized product is (A-VII) quaternized product (A-VI) quaternized product = 99/1 to 50/50. It is preferable to synthesize.
In the quaternization reaction, unreacted substances (that is, the compound represented by (A-VI) and the compound represented by (A-VII)) remain. At that time, from the viewpoint of stability against hydrolysis of the ester group contained in the quaternized product, the quaternized product (quaternized product of (A-VI) + quaternized product of (A-VII)) and unreacted product ( It is preferable to synthesize so that the mass ratio of the compound represented by (A-VI) + the compound represented by (A-VII) is quaternized product / unreacted product = 99/1 to 70/30. .

Among the above-mentioned compositions, a quaternized product of the compound represented by the general formula (A-III), a quaternized product of the compound represented by the general formula (A-IV), and the general formula (A-V). And a composition containing a quaternized product of the compound represented by
In this case, from the viewpoint of further enhancing the function as a softener, the content of each quaternized product in the composition is such that the quaternized product of the compound represented by (A-III) is based on the total mass of the composition. 5 to 98% by mass, 1 to 60% by mass of the quaternized product of the compound represented by (A-IV), 0.1 to 40% by mass of the quaternized product of the compound represented by (A-V) Preferably there is. More preferably, the quaternized product of the compound represented by (A-III) is 10 to 55% by mass with respect to the total mass of the composition, and the quaternized product of the compound represented by (A-IV) is 30%. The quaternized product of the compound represented by (A-V) is 5 to 35% by mass.

(A) A component may be used individually by 1 type and may be used as a mixture which consists of 2 or more types. When used as a mixture, if the content of the amine compound having 2 or 3 hydrocarbon groups bonded to the nitrogen atom is 50% by mass or more based on the total mass of the mixture, the function as a softener is further enhanced. This is preferable.

The blending amount of the component (A) is not particularly limited, but is preferably 10 to 30% by mass, more preferably 10 to 25% by mass with respect to the total mass of the liquid softening agent composition. The handling property fall by the liquid viscosity of a softening agent becoming it high that it is 30 mass% or less can be suppressed. When it is 10% by mass or more, it is possible to suppress an increase in the amount used for exerting the function as a softening agent.

(B) component contained in the liquid softening composition of this invention is mix | blended in order to provide the liquid softening composition with the effect which provides the texture to a fiber with the above-mentioned (A) component.
The amino-modified silicone as component (B) is a compound formed by introducing amino groups at both ends or side chains of the dimethyl silicone skeleton.
Preferred amino-modified silicones have the following general formula (B):

Wherein R is independently selected from the group consisting of —H, —OH, —CH ₃ and —Si (CH ₃ ) ₃ , and X is — (CH ₂ ) _a —NH ₂ , or , — (CH ₂ ) _a —NH (CH ₂ ) _b NH ₂ (a is an integer from 0 to 3, b is an integer from 1 to 3), n is from 1 to 1500, and m is 1 to 20, and a compound obtained by introducing an amino group into the side chain X.
The amino-modified silicone may be in the form of oil (silicone oil), or may be in the form of an emulsion (silicone emulsion) emulsified by using a nonionic surfactant or a cationic surfactant as an emulsifier.

When used as a silicone oil, the kinematic viscosity at 25 ° C. is preferably 50 to 20000 mm ² / s, and more preferably 500 to 10,000 mm ² / s. When the kinematic viscosity is within this range, a high texture-imparting effect can be obtained, and the manufacturability and handleability of the liquid softener composition can be facilitated. The kinematic viscosity can be measured with an Ostwald viscometer. The amino equivalent of the silicone oil is preferably 100 to 10,000 g / mol, more preferably 1200 to 4000 g / mol. An amino equivalent within this range is preferable because the function as a softening agent is good. The amino equivalent can be determined by dividing the weight average molecular weight of the amino-modified silicone by the number of nitrogen atoms contained in the amino-modified silicone. The number of nitrogen atoms can be determined by elemental analysis.

When used as a silicone emulsion, the viscosity of the base silicone oil is 1,000 mm ² / s or more, more preferably 10,000 mm ² / s or more. Examples of the emulsifier in the emulsion include a cationic surfactant and a nonionic surfactant, and a cationic surfactant is preferable.

A particularly preferred component (B) is an emulsion obtained by emulsion polymerization of an amino-modified silicone having a —H group and / or —OH group at the terminal with a surfactant. Use of this emulsion is preferable because the degree of yellowing during storage of the liquid softening agent composition is the smallest and the effect of improving the texture is excellent. This emulsion preferably has a kinematic viscosity at 25 ° C. of 100 to 20,000 mm ² / s and an amino equivalent of 400 to 8000 g / mol.

A commercially available amino-modified silicone can be used.
Examples of silicone oils are those sold under the trade names: SF-8417, BY16-849, BY16-892, FZ-3785, or BY16-890 from Toray Dow Corning Co., Ltd., or from Shin-Etsu Chemical Co., Ltd. Product names: KF-864, KF-860, KF-880, KF-8004, KF-8002, KF-8005, KF-867 or those sold under KF-869, KF-861, KF-8010, etc. can give.
Silicone emulsions sold by Toray Dow Corning Co., Ltd. under the trade name: SM8904, BY22-079, FZ-4671 or FZ-4672, or the Polon series from Shin-Etsu Chemical Co., Ltd. under the trade name: PolonMF- 14, Polon MF-29, Polon MF-14D, Polon MF-44, Polon MF-14EC and Polon MF-52, and those sold by Asahi Kasei Wacker Silicone Co., Ltd. on WACKER FC201.

(B) A component may be used individually by 1 type and may be used as a mixture which consists of 2 or more types.

The blending amount of the component (B) is 0.1 to 15% by mass, preferably 0.5 to 15% by mass with respect to the total mass of the liquid softening agent composition. When it is 0.1% by mass or more, the blending effect of the component (B) can be sufficiently exhibited. When it is 15% by mass or less, yellowing during storage of the liquid softening agent composition can be sufficiently suppressed, and an increase in production cost can be suppressed.

The component (C) contained in the liquid softening composition of the present invention is yellowing, fragrance and fragrance quality during storage of the liquid softening composition resulting from the blending of the components (A) and (B). It is blended in order to suppress the deterioration.
Urea is a compound represented by the chemical formula: (NH ₂ ) ₂ C═O.
The double salts of _{_{urea, HNO 3 · CO (NH 2}} ) 2, H 3 PO 4 · CO (NH 2) 2, H 2 C 2 O 4 · 2 CO (NH 2) 2, Ca (NO 3) 2 _{_{· 4CO (NH 2) 2,}} CaSO 4 · 4CO (NH 2) 2, Mg (NO 3) 2 · CO (NH 2) 2 · 2H 2 O, CaSO 4 · (5 ~ 6) 4CO (NH 2) 2 -2H ₂ O and the like. Of these, urea is particularly preferred.
The urea derivative is the following general formula (C):

(Wherein R ^a is a methyl group, an ethyl group or a hydroxyalkyl group having 1 to 2 carbon atoms, and R ^b , R ^c and R ^d are each independently a hydrogen atom, a methyl group or an ethyl group. .)
It is a compound represented by these. Specific examples include 1,3-dimethylurea and N- (2-hydroxyethyl) urea. Of these, 1,3-dimethylurea is preferred.
As the component (C), urea is particularly preferable.

The urea, the double salt of urea and the urea derivative of the general formula (C) are all readily available on the market or can be synthesized.

(C) A component may be used individually by 1 type, and may be used as a mixture which consists of 2 or more types.

The blending amount of the component (C) is 0.5 to 10% by mass, preferably 1 to 10% by mass, and more preferably 1 to 5% by mass with respect to the total mass of the liquid softening agent composition. When it is 0.5% by mass or more, yellowing, storage of fragrance, and deterioration of fragrance quality during storage of the liquid softening agent composition can be sufficiently suppressed. When it is 10% by mass or less, deterioration in usability due to an increase in viscosity during storage of the liquid softening agent composition can be suppressed.

Here, the yellowing that occurs during storage of the liquid softening agent composition occurs because the amine group and amino group contained in the component (A) and the component (B) are thermally oxidized to form an azo bond and turn yellow. It is considered a phenomenon. Although yellowing involves both the component (A) and the component (B), it is thought that the component (B) is more involved.
The fragrance standing and the deterioration of the scent quality that occur during storage of the liquid softener composition are phenomena that occur because the (A) component and the (B) component decompose at a high temperature, and the (A) component and the (B) component. All of these are considered to be involved. Although both the component (A) and the component (B) are involved in the fragrance standing and the deterioration of the quality of the scent, it is considered that the component (A) is more involved.

In the present invention, the blending amounts of the components (A) to (C) are [mass of (A) + mass of (B)] / mass of (C) = 1 to 40 in mass ratio. Within such a range, yellowing, scenting, and deterioration of scent quality that occur during storage of the liquid softening agent composition can be sufficiently suppressed. The mass ratio is preferably 1 to 20, and more preferably 1 to 5.

In the present invention, the blending amount of the components (B) and (C) is (B) mass / (C) mass = 50 or less in mass ratio. Within this range, yellowing of the component (B) can be suppressed. The mass ratio is preferably 20 or less, and more preferably 0.2 to 5.

(L) component which is a trehalose can be mix | blended with the liquid softening agent composition of this invention as an arbitrary component.
Component (L) is for improving the decrease in texture and odor generation (especially the decrease in texture and generation of odor that occurs when a dryer is used after washing at a low bath ratio). Blended. In addition to the above-described improvement effect, the component (L) can be added to further suppress an increase in viscosity after storage of the liquid softening agent composition and increase usability.
Trehalose used in the present invention is a non-reducing disaccharide in which two molecules of glucose are linked by 1,1. There are three isomers, trehalose having an α, α structure (α-D-glucopyranosyl α-D-glucopyranoside), α, β type (neotrehalose), and β, β type (isotrehalose). In the present invention, any type may be used, and one type may be used alone, or two or more types may be used in appropriate combination, and α and α types are particularly preferable. Trehalose may be a commercially available product, and examples of the commercially available product include Treha (manufactured by Hayashibara Co., Ltd.).

The blending amount of the component (L) is not particularly limited as long as the blending effect of the component (L) can be sufficiently obtained, but is 0.01 to 10.0 with respect to the total mass of the liquid softener composition of the present invention. % By mass is preferable, 0.1 to 5% by mass is more preferable, and 1 to 5% by mass is still more preferable. When the blending amount is 0.01% by mass or more, it is possible to sufficiently obtain an effect of suppressing the odor generated in the clothes when the clothes that are repeatedly worn and washed are dried with a dryer of a drum type washing machine. Furthermore, a sufficient inhibitory effect on viscosity increase after storage of the liquid softening agent composition can also be obtained. When the blending amount is 10% by mass or less, an increase in viscosity immediately after preparation of the liquid softening agent can be suppressed.
In the liquid softener composition of the present invention, the mass ratio of the (L) component to the sum of the (A) component and the (B) component is not particularly limited, but (L) / ((A) + (B)) = 0.002 to 0.50 is preferable, and 0.03 to 0.25 is more preferable. When the mass ratio of the (L) component to the sum of the (A) component and the (B) component is within such a range, in addition to the above blending effect, the viscosity stability of the liquid softener composition after storage is increased. It can be improved further.

The liquid softening agent composition of the present invention can contain an (M) component that is an antibacterial agent as an optional component.
Component (M) imparts a good deodorizing property to the object to be washed (inhibition of the growth of unpleasant odor-producing bacteria in the object to be washed. In particular, the washing that occurs when a dryer is used after washing at a low bath ratio. For the purpose of suppressing the generation of odors.
Component (M) is one or more antibacterial agents selected from the group consisting of biguanide antibacterial agents and N, N-bis (3-aminoalkyl) alkylamines.

The biguanide antibacterial agent has the following structure:

Or a compound derived from a biguanide having antibacterial action.

The biguanide antibacterial agent includes the following general formula (M-1):

-[R ¹¹ -NH-C (NH) -NH-C (NH) -NH] _n -n.HY (M-1)

(Wherein R ¹¹ is an alkylene group having 2 to 8 carbon atoms, n is 2 to 14, and HY is an organic acid or an inorganic acid).
R ¹¹ is preferably an alkylene group having 4 to 8 carbon atoms, and particularly preferably a hexamethylene group.
n is preferably 10 to 14, more preferably 11 to 13, and particularly preferably 12.
HY is preferably hydrochloric acid, gluconic acid or acetic acid, and particularly preferably hydrochloric acid.

The component (M) is preferably a compound in which R ¹¹ is a hexamethylene group in the general formula (M-1), n is 10 to 14, and HY is hydrochloric acid. Particularly preferred are compounds in which R ¹¹ is a hexamethylene group, n is 11 to 13, and HY is hydrochloric acid.
As a specific example, a compound (poly (hexamethylene biguanide) hydrochloride in which R ¹¹ is a hexamethylene group in the general formula (M-1), n is 12, and HY is hydrochloric acid, trade name: Proxel IB ( Registered trademark) (Lonza).

Other specific examples of biguanide antibacterial agents include the following structures:

And chlorohexidine hydrochloride (1,1′-Hexamethylene bis [5- (4-chlorophenyl) biguanide] dihydrochloride).
A biguanide antibacterial agent may be used alone or as a mixture of two or more.

As the component (M), the following general formula (M-2):
R ¹² —N [(CH ₂ ) _n —NH ₂ ] ₂ (M-2)
(Wherein R ¹² represents an alkyl group having 8 to 18 carbon atoms and n is a number of 1 to 4) (N, N-bis (3-aminoalkyl) alkylamine) Can also be used.
In general formula (M-2), R ¹² may be linear or branched, but is preferably linear. When R ¹² is a straight chain, the deodorizing property of the article to be washed can be further improved.
R ¹² has 8 to 18 carbon atoms, preferably 8 to 14 carbon atoms, and more preferably ¹² carbon atoms. When R ¹² has 8 or more carbon atoms, an excellent antibacterial action can be exhibited. When the number of carbon atoms in R ¹² is 14 or less, it is possible to avoid a decrease in compoundability in the softener composition due to a decrease in water solubility.
In general formula (M-2), n is 1 to 4, preferably 2 to 4, and more preferably 3. When n is 1 to 4, an excellent antibacterial action can be exhibited.

As the compound represented by the general formula (M-2),
N, N-bis (3-amino) such as N, N-bis (3-aminomethyl) octylamine, N, N-bis (3-aminomethyl) decylamine, N, N-bis (3-aminomethyl) dodecylamine, etc. Aminomethyl) alkylamine;
N, N-bis (3-aminoethyl) octylamine, N, N-bis (3-aminoethyl) decylamine, N, N-bis (3-aminoethyl) dodecylamine, etc. Aminoethyl) alkylamine;
N, N-bis (3-amino) such as N, N-bis (3-aminopropyl) octylamine, N, N-bis (3-aminopropyl) decylamine, N, N-bis (3-aminopropyl) dodecylamine, etc. Aminopropyl) alkylamines;
N, N-bis (3-amino (butylamino) octylamine, N, N-bis (3-aminobutyl) decylamine, N, N-bis (3-aminobutyl) dodecylamine, etc. Aminobutyl) alkylamine and the like.
Of these, N, N-bis (3-aminopropyl) alkylamine is preferable, and N, N-bis (3-aminopropyl) dodecylamine is more preferable.
As the compound represented by the general formula (M-2), one type may be used alone, or a mixture of two or more types may be used.

The above component (M) is easily available on the market or can be synthesized.

As the component (M), one kind selected from the group consisting of a biguanide antibacterial agent and a compound represented by the above general formula (M-2) may be used alone, or a mixture of two or more kinds may be used. Also good.

The blending amount of the component (M) is not particularly limited as long as the blending effect of the component (M) can be sufficiently obtained. However, the liquid softening agent composition can be further improved in the deodorizing property of the washing object. The amount is preferably 0.01 to 3% by mass, more preferably 0.05 to 2% by mass, and still more preferably 0.1 to 1% by mass with respect to the total mass.

In the liquid softener composition of the present invention, the mass ratio of the component (B) to the component (M) (mass of (B) / mass of (M)) is 1/1 to 100/1, preferably 2/1. ~ 50/1. When the mass of (B) / (M) is 1/1 to 100/1, the deodorizing property can be imparted to the article to be washed at a higher level.

(N) component which is a highly branched cyclic dextrin can further be mix | blended with the liquid softening agent composition of this invention as an arbitrary component. Highly branched cyclic dextrin is a substance also called cluster dextrin.
The component (N) includes the odor that could not be suppressed by the component (L) (trehalose), thereby further enhancing the deodorizing and deodorizing effects of the liquid softening agent composition, It is blended to further improve odor and deodorization properties (particularly, deodorization and deodorization of sebum oxidation odor).
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. Here, the inner branched cyclic structure portion refers to a cyclic structure portion formed by an α-1,4-glucoside bond and an α-1,6-glucoside bond. The outer branched structure portion means an acyclic structure portion bonded to the inner branched cyclic structure portion.
The highly branched cyclic dextrin has a specific structure as described above and has a high degree of polymerization (molecular weight). Α-cyclodextrin (n = 6), β-cyclodextrin (n = 7), γ- It is a substance different from general cyclodextrins in which 6 to 8 glucoses are bound, such as cyclodextrin (n = 8).
Specific examples of the highly branched cyclic dextrin of component (N) include an inner branched cyclic structure portion and an outer branched structure portion described in JP-A-8-134104, and the degree of polymerization is in the range of 50 to 10,000. Glucan is mentioned. In the present specification, the highly branched cyclic dextrin can be understood in consideration of the description in JP-A-8-134104.
More specifically, the molecular weight is about 30,000 to 1,000,000 and the molecule has one cyclic structure (inner branched cyclic structure portion) composed of about 10 to 100 glucoses, and the cyclic structure. A dextrin having a weight average degree of polymerization of about 2500, in which a large number of acyclic glucan chains (external branching structure portions) are bonded to the portion.
The degree of polymerization of glucose in the highly branched cyclic dextrin is, for example, in the range of 50 to 5000.
The degree of polymerization of glucose in the inner branched cyclic structure portion of the highly branched cyclic dextrin is, for example, in the range of 10-100.
The degree of polymerization of glucose in the outer branched structure portion of the highly branched cyclic dextrin is, for example, 40 or more. The average polymerization degree of glucose in each unit chain constituting the outer branched structure portion is 10 to 20.

The highly branched cyclic dextrin of component (N) is produced, for example, using starch as a raw material and an enzyme called branching enzyme. Starch, which is a raw material, is composed of amylose in which glucose is linearly linked 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 and plants and microorganisms, and acts on the seam portion of the cluster structure of amylopectin to catalyze the reaction of cyclizing it.

(N) component is easily available in the market or can be synthesized. Specific examples include “Cluster Dextrin” (registered trademark) of Glico Nutrition Foods, Inc.

As the component (N), one highly branched cyclic dextrin may be used alone, or a mixture of two or more may be used.

The blending amount of the component (N) is not particularly limited as long as the blending effect of the component (N) can be sufficiently obtained, but is preferably 0.01 to 10% by mass with respect to the total mass of the liquid softening agent composition, More preferably, it is 0.05 to 5% by mass, and still more preferably 0.1 to 2% by mass. When the blending amount of the component (N) is 0.01% by mass or more, an excellent deodorizing effect and deodorizing effect can be exhibited. When the blending amount of the component (N) is 10% by mass or less, while suppressing the increase in the viscosity of the liquid softening agent composition while obtaining the blending effect, the dischargeability from the container and the insertion into the inlet of the washing machine Usability such as ease can be maintained.

The pH of the liquid softening agent composition of the present invention is not particularly limited, but the pH is set in the range of 1 to 6 for the purpose of suppressing hydrolysis of the ester group contained in the molecule of the component (A) accompanying storage aging. It is preferable to adjust, and more preferably in the range of 2 to 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 of short chain amine compounds such as triethanolamine, diethanolamine, dimethylamine, N-methylethanolamine, N-methyldiethanolamine, alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates, alkali metal silicates, etc. A regulator can be used.

The viscosity of the liquid softening agent composition of the present invention is preferably less than 1000 mPa · s. Considering the increase in viscosity due to storage aging, the viscosity immediately after blending is more preferably less than 800 mPa · s, and even more preferably less than 500 mPa · s. When it is in such a range, it is preferable because the usability such as handling property when being put into a washing machine is good.
From the viewpoint of usability, the lower limit of the viscosity is not particularly limited.
The viscosity of the liquid softening agent composition in the present invention refers to a value measured at 25 ° C. using a B-type viscometer (for example, an analog viscometer T manufactured by Brookfield).

In the liquid softener composition of the present invention, in addition to the component (A), the component (B) and the component (C), and the optional components (L), (M) and (N), As needed, the component normally used for a liquid softening agent composition can be arbitrarily mix | blended in the range which does not impair the effect of this invention. Examples of the optional component include those shown below.

(D) component: nonionic active agent (D) component is mix | blended in order to improve the storage stability of the liquid softening agent composition of this invention more.
The component (D) is a nonionic surfactant obtained by adding an alkylene oxide to a primary or secondary alcohol. Specifically, a nonionic interface obtained by adding an average of 5 to 100 moles of alkylene oxide to a primary or secondary alcohol having a branched alkyl group or branched alkenyl group having 8 to 20, preferably 10 to 14 carbon atoms. It is an activator.
As the alkylene oxide, ethylene oxide is preferably used alone, but propylene oxide may be added together with ethylene oxide. When both are added, any order may be added first.
The average number of moles of alkylene oxide added is preferably 10 to 80 moles, particularly preferably 20 to 60 moles. When propylene oxide is added together with ethylene oxide, the average number of moles of propylene oxide added can be 1 to 5 moles, preferably 1 to 3 moles.
Specific examples of the component (D) include those obtained by adding an average of 60 mol of ethylene oxide (EO) to primary isotridecyl alcohol, those obtained by adding an average of 40 mol of ethylene oxide (EO) to primary isotridecyl alcohol, and alkyl group carbon. Examples include those obtained by adding 50 moles of EO to an average of 10 to 14 linear secondary alcohols.
The component (D) is prepared, for example, by using propylene or butylene as a raw material and preparing an n-mer thereof (3 to 6-mer in the case of propylene, 2 to 4-mer in the case of butylene, etc.) Then, it can be prepared by adding alkylene oxide to a primary or secondary alcohol obtained by hydrogenation by a conventional method known to those skilled in the art.
The blending amount of the component (D) is preferably 0.1% by mass to 15% by mass, more preferably 0.5% by mass to 10% by mass, and most preferably 1% with respect to the total mass of the liquid softening agent composition. 0.0 mass% to 7 mass%. The stability with respect to freezing of a liquid softening agent composition can be improved as it is 0.1 mass% or more. When it is 15% by mass or less, the stability of the liquid softening agent composition during high-temperature storage can be improved.

(E) component: fragrance | flavor (E) A component is mix | blended for the fragrance to the liquid softening agent composition, and also the fragrance to the clothing after a process by the same composition.
As the component (E), a general perfume can be used in the technical field and is not particularly limited. However, a list of perfume raw materials that can be used is various documents such as “Perfume and Flavor Chemicals”, Vol. Iand II, Steffen Arctander, Allured Pub. Co. (1994) and "Synthetic fragrance chemistry and commercial knowledge", Motoichi Into, Kagaku Kogyo Nipposha (1996) and "Perfume and Flavor Materials of Natural Origin", Stephen Arctander, Allred Pub. Co. (1994) and "Encyclopedia of Scents", edited by Japan Fragrance Association, Asakura Shoten (1989) and "Performer Material Performance V.3.3", Boelens Aroma Chemical Information Service (1996) and "Flower oil". , Danute Lajaujis Anonis, Allured Pub. Co. (1993).
In the present invention, the blending of the component (C) sufficiently suppresses fragrance formation and deterioration of the fragrance quality during storage of the liquid softening agent composition, so that the scenting effect by the component (E) is higher. It becomes.
The amount of component (E) is preferably 0.1 to 5% by mass relative to the total mass of the liquid softening agent composition.

Other optional components include the following.
(F) component: A solvent (F) component is mix | blended in order to stabilize the viscosity at the time of storing a liquid softening agent composition for a long term.
The component (F) is one or more aqueous solvents selected from the group consisting of alcohols having 1 to 4 carbon atoms, glycol ether solvents and polyhydric alcohols. Specific examples include ethanol, isopropanol, glycerin, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, hexylene glycol, polyoxyethylene phenyl ether, and the following general formula (X):
R—O— (C ₂ H ₄ O) _y — (C ₃ H ₆ O) _z —H (X)
(Wherein R is an alkyl or alkenyl group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms, y and z are average added mole numbers, and y is 1 to 10, preferably 2 to 5, z represents a number of 0 to 5, preferably 0 to 2.)
The solvent component chosen from the water-soluble solvent represented by these is mention | raise | lifted.
Preferable examples include ethylene glycol, butyl carbitol, propylene glycol, glycerin and the like, and glycerin is particularly preferable from the viewpoint of viscosity stabilization at a low temperature.
The amount of component (F) is 0 to 10% by mass, preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total mass of the liquid softening agent composition. The function as a solvent can be effectively exhibited as the mass is 0.1% or more. When it is 10% by mass or less, stability can be secured effectively and efficiently.

(G) component: antiseptic | preservative Preservatives other than the above-mentioned (M) component (antibacterial agent) can be mix | blended as (G) component.
The preservative is blended in order to maintain the antiseptic property of the liquid softener composition during long-term storage.
As the preservative, those known in the art can be used and are not particularly limited. Specific examples include isothiazolone-based organic sulfur compounds, benzisothiazolone-based organic sulfur compounds, benzoic acids, alcohol-based 2-bromo-2-nitropropane-1,3-diol, and iodine-based compounds.
Examples of isothiazolone-based organic sulfur compounds include 5-chloro-2-methyl-4-isothiazolin-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-isothiazoline-3-one, and mixtures thereof. A more preferred preservative is a water-soluble mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, more preferably about 77% by weight of 5 A water-soluble mixture of chloro-2-methyl-4-isothiazolin-3-one and about 23% by weight of 2-methyl-4-isothiazolin-3-one.
Examples of benzisothiazoline-based organic sulfur compounds include 1,2-benzisothiazolin-3-one, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, and dithio- 2,2-bis (benzmethylamide) and the like can also be used. Of these, 1,2-benzisothiazolin-3-one is particularly preferred. When a plurality of types of benzisothiazoline-based organic sulfur compounds are used, they can be used in any mixing ratio.
An example of an iodine compound is 3-iodo-2-propynyl N-butylcarbamate.
Examples of the 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. it can.
The compounding amount of the preservative is preferably 0.0001 to 1% by mass with respect to the total mass of the liquid softening agent composition. The function as a preservative can be exhibited as it is 0.0001 mass% or more. When the content is 1% by mass or less, it is possible to suppress a decrease in storage stability of the liquid softening agent composition due to excessive blending.

Component (H): Inorganic or organic water-soluble salts Inorganic or organic water-soluble salts can be used for the purpose of controlling the viscosity of the composition. Examples of inorganic or organic water-soluble salts include sodium chloride, potassium chloride, calcium chloride, magnesium chloride, etc., alkali metal salts or alkaline earth metal salts of sulfuric acid or nitric acid, p-toluenesulfonic acid, glycolic acid, lactic acid, etc. And alkali metal salts of organic acids. Preferably, they are calcium chloride, magnesium chloride, and sodium chloride. The amount of the inorganic or organic water-soluble salt is 0 to 3% by mass, preferably 0.01 to 2% by mass, more preferably 0.05 to 1% by mass, based on the total amount of the composition. The addition of inorganic or organic water-soluble salts may be added at any step in the production of the composition.

(I) Component: Antioxidant An antioxidant other than the aforementioned component (L) (trehalose) can be blended as the component (I).
Antioxidant is mix | blended in order to improve the fragrance stability and color tone stability of a liquid softening agent composition.
As the antioxidant, both natural antioxidants and synthetic antioxidants known in the art can be used. Specifically, ascorbic acid, ascorbyl palmitate, propyl gallate, BHT (butylated hydroxytoluene), particularly dibutylhydroxytoluene, BHA (butylated hydroxyanisole), a mixture of propyl gallate and citric acid, hydroquinone, three Grade butyl hydroquinone, natural tocopherol compounds, long chain esters of gallic acid (C8 to C22) such as dodecyl gallate, irganox compounds available from Ciba Specialty Chemicals, citric acid and / or isopropyl citrate 4,5-dihydroxy-m-benzenesulfonic acid / sodium salt, dimethoxyphenol, catechol, methoxyphenol, carotenoid, furans, amino acids and the like. Of these, BHT, methoxyphenol, and tocopherol compounds are preferred from the viewpoint of improving the storage stability of the liquid softening agent composition.
The blending amount of the antioxidant is preferably 0.01 to 1% by mass with respect to the total mass of the liquid softening agent composition. The function as an antioxidant can be exhibited as it is 0.01 mass% or more. When the content is 1% by mass or less, it is possible to suppress a decrease in storage stability of the liquid softening agent composition due to excessive blending.

(J) Component: Dye As the dye, those known in the technical field can be used and are not particularly limited. A water-soluble dye is preferable from the viewpoint of ease of blending, and among these, one or more water-soluble dyes selected from acidic dyes and direct dyes are more preferable. Specific examples of dyes that can be added include, for example, the Dye Handbook (edited by the Society of Synthetic Organic Chemistry, issued July 20, 1970, Maruzen Co., Ltd.), Dye Note 22nd Edition (Color Dye Co., Ltd.), Legal Dye Handbook (Edited by the Japan Cosmetic Industry Association, published on November 28, 1988, Yakuho Nippo Co., Ltd.).
The compounding amount of the dye is preferably 0.01 to 50 ppm, more preferably 0.1 to 30 ppm, based on the mass, with respect to the liquid softening agent composition. By setting it as such a compounding quantity, it can prevent that the color colored by the liquid softening agent composition becomes very thin, and can make a coloring effect sufficient, On the other hand, in a liquid softening agent composition It is possible to prevent the colored color from becoming too dark.

Component (K): Other additives As other additives, in addition to the above-mentioned compounds, hydrocarbons, nonionic cellulose derivatives, ultraviolet absorbers, emulsions such as polystyrene emulsions, opaque agents, anti-shrink agents, laundry Anti-wrinkle agent, shape retention agent, drape retention agent, ironability improver, oxygen bleach inhibitor, whitening agent, whitening agent, antibacterial agent, fabric softening clay, antistatic agent, 4,4-bis (2 -Sulfostyryl) Biphenyl disodium (Chino Specialty Chemicals Chino Pearl CBS-X) and other brightening agents, dye fixing agents, 1,4-bis (3-aminopropyl) piperazine and other fading inhibitors, stain removers, fibers As a surface modifier, enzymes such as cellulase, amylase, protease, lipase, keratinase, foam suppressor, and the like can be blended.

The liquid softener composition of the present invention is preferably an aqueous composition. In this case, water is mix | blended with a liquid softening agent composition. As water to be mixed, tap water, ion exchange water, pure water, distilled water, etc. can be used. In view of cost, ion exchange water is most preferable.

Method for Producing Liquid Softener Composition The liquid softener composition of the present invention can be produced using various methods generally used for the production of liquid softener compositions. The methods described in JP-A-68137, JP-A-10-237762, JP-A-5-310660, JP-A-5-310661, and JP-A-5-310661 are preferred.
In particular,
1) After premixing the oil-soluble components (A), (B) (in the case of oil), (D), and (E) of the present invention, an oil phase is prepared. (C) component dissolved in water, add a part of the mixture consisting of other aqueous phase components, or add the oil phase to a part of the aqueous phase to form a liquid crystal phase of a cationic surfactant, Next, the liquid crystal phase and the remaining aqueous phase are mixed to invert the liquid crystal phase, or 2) The oil phase and the aqueous phase of 1) above are mixed together and emulsified and dispersed. be able to.
Moreover, when (B) component is an emulsion, you may mix | blend (B) component at the end of a manufacturing process.
As for other optional components, those having high water solubility are preferably added to the aqueous phase, and those having low water solubility are preferably added to the oil phase. You may mix | blend a viscosity control agent ((H) component) in multiple steps at the arbitrary timings of a manufacture process.
When the component (M) is used, the water-soluble (M) component is preferably blended in the aqueous phase or at the end of production, and the oil-soluble (M) component is blended in the oil phase.
Component (N) may be blended at the end of production.
During the production, the stirring force and shearing force of the mixing apparatus are such that the average particle size of the oil phase of the obtained liquid softening agent composition is preferably 0.01 μm to 10 μm, more preferably 0.05 to 5 μm, still more preferably. The thickness is preferably set to 0.1 to 1 μm. When in such a range, the dispersion stability of the oil phase becomes good.

Method of Use There is no particular limitation on the method of using the liquid softener composition of the present invention, and the liquid softener composition can be used in the same manner as a general liquid softener composition. For example, a method of softening a washing object by dissolving the liquid softener composition of the present invention in rinse water at the stage of rinsing or water in a container such as a tub with the liquid softener composition of the present invention. There is a method in which the product is dissolved, and further, an article to be cleaned is put in and immersed.
When the liquid softener composition of the present invention is used after being diluted, the bath ratio (mass ratio of the liquid softener composition to the article to be washed) is preferably 3 to 100 times, particularly preferably 5 to 50 times. Specifically, it is preferably used in such an amount that the concentration of the component (A) is 5 ppm to 1000 ppm, more preferably 10 ppm to 300 ppm, with respect to the total amount of water used.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

Experimental example A
Cationic surfactant (component (A))
The following (A-1) and (A-2) were synthesized as cationic surfactants.
(A-1)
A cationic surfactant synthesized according to the procedure described in Example 4 of JP-A-2003-12471.
(A-1) is a compound represented by the general formulas (A-III), (A-IV) and (AV) (wherein R ¹ is an alkyl group and alkenyl having 15 or 17 carbon atoms) It was a composition containing a quaternary cis-trans body of an unsaturated part = 75/25 (mass ratio) with dimethyl sulfate.

(A-2)
A cationic surfactant synthesized according to the procedure described in Example 1 of JP-A-2002-167366.
(A-2) is each compound represented by (A-III), (A-IV) and (AV) (wherein R ¹ is an alkyl group or alkenyl group having 15 or 17 carbon atoms) Yes, the composition was obtained by quaternizing unsaturated cis isomer / trans isomer = 75/25 (mass ratio) with dimethyl sulfate.

Amino-modified silicone (component (B))
The following (B-1) to (B-6) were obtained as amino-modified silicones.
(B-1)
An emulsion obtained by emulsion polymerization of an amino-modified silicone having a —H group and / or —OH group at its terminal, obtained from Toray Dow Corning Co., Ltd. under the trade name: SM8904.

(B-2)
An amino-modified silicone emulsion obtained from Shin-Etsu Chemical Co., Ltd. under the trade name PlonMF-52.

(B-3)
An amino-modified silicone emulsion obtained from Asahi Kasei Wacker Silicone Co., Ltd. under the trade name WACKER FC201.

(B-4)
Side chain modified type amino modified silicone oil obtained from Shin-Etsu Chemical Co., Ltd. under the trade name KF-880. (Kinematic viscosity at 25 ° C. 650 mm ² / s, amino equivalent 1800 g / mol)

(B-5)
Side chain modified type amino modified silicone oil obtained from Shin-Etsu Chemical Co., Ltd. under the trade name KF-864. (Kinematic viscosity at 25 ° C. 1700 mm ² / s, amino equivalent 1800 g / mol)

(B-6)
A double-end modified amino-modified silicone oil obtained from Shin-Etsu Chemical Co., Ltd. under the trade name KF-8010. (Kinematic viscosity at 25 ° C. 12 mm ² / s, amino equivalent 430 g / mol)

The following (B-7) was obtained as a component to be blended into the comparative example not containing amino-modified silicone.
(B-7)
A polyether-modified silicone described as (B-2) in Example 2 of JP-A-2005-187987.

(Where α = 210 and β = 9)

Urea and urea derivatives (component (C))
The following (C-1) and (C-2) were obtained as urea and urea derivatives.

(C-1)
Urea obtained as a product name: urea (special grade) manufactured by Pure Chemical Co., Ltd. Urea is a compound represented by the chemical formula: (NH ₂ ) ₂ C═O, and corresponds to urea which is the component (C) of the present invention.

(C-2)
Trade name: 1,3-dimethylurea manufactured by Tokyo Chemical Industry Co., Ltd. Dimethylurea obtained. Dimethylurea is a compound represented by the general formula (C) (wherein R ^a is a methyl group, R ^b and R ^c are hydrogen atoms, and R ^d is a methyl group), and the present invention This corresponds to the urea derivative which is the component (C).

Nonionic activator (component (D))
The following (D-1) and (D-2) were obtained as nonionic active agents.

(D-1)
60 mol of ethylene oxide (hereinafter referred to as EO) adduct of primary isotridecyl alcohol (carbon number: 13) obtained from Lion Corporation under the trade name: TA600-75

(D-2)
Primary isotridecyl alcohol ethylene oxide (hereinafter referred to as EO) 40 mol adduct obtained from Lion Corporation under the trade name: Leocol TDA-400-75

Fragrance ((E) component)
Perfumes E-1 and E-2 having the following compositions were prepared. The numerical value of each fragrance in the table is part by mass.

Other optional ingredients

Preparation Method of Liquid Softener Composition The liquid softener compositions of Examples 1 to 25 and Comparative Examples 1 to 4 having the compositions shown in Table 2 below were prepared according to the following procedure. In Table 2, the units of the numerical values of the components (A) to (I) are mass% relative to the total mass of the liquid softener composition, and the numerical unit of the component (J) is ppm (based on the liquid softener composition). Mass basis).

When component B is an emulsion (use (B-1), (B-2), (B-3) as component (B))
The liquid softening agent composition was prepared by the following procedure 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). First, (A) component, (D) component, (E) component, (G) component, and (I) component were mixed and stirred, and the oil phase mixture was obtained. On the other hand, component (C) and component (J) were dissolved in ion-exchange water for balance to obtain an aqueous phase mixture. Here, the mass of ion-exchange water for balance corresponded to the balance obtained by subtracting the total mass of the oil phase mixture, the components (B), (F), (H), and hydrochloric acid from 980 g. 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 (H) is added, and thereafter component (B) and component (F) are added, and hydrochloric acid (reagent 1 mol / L, Kanto Chemical) or sodium hydroxide (reagent 1 mol / L) as necessary. , Kanto Chemical) was added in an appropriate amount to adjust the pH to 2.5, and ion exchange water was added so that the total mass became 1,000 g to obtain a target liquid softener composition.

When component B is oil (use component (B-4), (B-5), (B-6) or (B-7) as component (B))
The liquid softening agent composition was prepared by the following procedure 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). First, (A) component, (B) component, (D) component, (E) component, (G) component, and (I) component were mixed and stirred, and the oil phase mixture was obtained. On the other hand, component (C) and component (J) were dissolved in ion-exchange water for balance to obtain an aqueous phase mixture. Here, the mass of ion-exchange water for balance corresponded to the balance obtained by subtracting the total mass of the oil phase mixture, the component (F) and the component (H) from 980 g. 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. Then, the (F) component and the (H) component are added, and then an appropriate amount of hydrochloric acid (reagent 1 mol / L, Kanto Chemical) or sodium hydroxide (reagent 1 mol / L, Kanto Chemical) is added as necessary. Then, the pH was adjusted to 2.5, and ion-exchanged water was further added so that the total mass became 1,000 g to obtain a target liquid softener composition.

About each prepared liquid softening agent composition, the function (softness | flexibility) as a softening agent, the change of fragrance formation and fragrance quality by preservation | save, the appearance change by preservation | save (the presence or absence of yellowing, change of a viscosity and fluidity | liquidity Existence) was evaluated.

Flexibility Pre-treatment method for evaluation cloth Commercial cotton shirt (BVD) was pre-treated three times with a commercial detergent “Top” (manufactured by Lion) using a two-tank washing machine (CW-C30A1-H manufactured by Mitsubishi Electric). (Standard amount of detergent used: 30 times the bath ratio. Tap water at 45 ° C. After washing for 10 minutes, rinsing twice for 10 minutes).

2. Treatment with a softener in the rinsing process during washing Using a two-tank washing machine (Mitsubishi Electric CW-C30A1-H) 1.5 kg of pre-washed cotton skin shirt, a commercial detergent “Top” (manufactured by Lion) (Standard amount used: bath ratio 20 times, standard course, using 25 ° C. tap water). After the washing step, dehydration was performed for 1 minute. After the dehydration step, first, rinsing was performed for 3 minutes, and at the time of the second rinsing, the liquid softening agent composition was added and softening treatment was performed for 3 minutes (amount of liquid softening agent composition: 10 mL. Bath). 20 times the ratio (using tap water at 25 ° C). After the softening treatment, the cotton shirt was dried for 20 hours under constant temperature and humidity conditions of 20 ° C. and 45% RH, and subjected to the evaluation test shown below.

3. Evaluation of flexibility The flexibility of the softener composition was evaluated using the smoothness of the article to be washed after the treatment as an index. Specifically, cotton treated with the same softener composition was treated under the same conditions as above except that the softener “Fluffy Soflan” (manufactured by Lion) was used. A sensory pair comparison was performed using a skin shirt as a control.
Evaluation was performed by 10 professional panelists in accordance with the following evaluation criteria.

<Evaluation criteria>
5: much smoother than control 4: much smoother than control 3: slightly smoother than control 2: equivalent to control 1: less smooth than control

The average score of 10 panelists was taken, and an average score of 3.0 or more was determined to be acceptable in terms of commercial value as a softener. The average score of each liquid softener composition is shown in the “smoothness” column of Table 2.

After storage, the fragrance and quality of the scent 100 mL of each liquid softener composition was placed in a lightweight PS glass bottle (PS-No. 11, manufactured by Tanuma Glass Industrial Co., Ltd.), sealed, and stored at 50 ° C. for 4 weeks. The scent was evaluated. As a control, those stored under the same conditions except that the temperature during storage was 5 ° C. were used. In addition, the scent of the control and the quality of the scent after storage were the same as the scent and quality of the scent before storage (immediately after preparation).
Evaluation was performed by 10 professional panelists in accordance with the following evaluation criteria.

<Evaluation criteria>
5: Good fragrance and fragrance quality is equivalent to the control 4: Good fragrance and fragrance quality is slightly different from the control, but no odor is felt 3: No odor Good, slightly off-flavor is felt compared to the control 2: Scent is slightly worse, the quality of the scent is quite different compared to the control, and off-flavor is felt 1: Smell is poor, scent compared to the control There are very different quality

The average score of 10 panelists was taken, and an average score of 3.0 or more was determined to be acceptable in terms of commercial value as a softener. The average score of each liquid softening agent composition is shown in the column of “scent after storage” in Table 2.

Appearance after storage 100 mL of each liquid softening agent composition is put into a lightweight PS glass bottle (PS-No. 11, manufactured by Tanuma Glass Industrial Co., Ltd.), sealed and stored at 50 ° C. for 2 weeks, and then the degree of yellowing is evaluated. did. As a control, those stored under the same conditions except that the temperature during storage was 5 ° C. were used. The appearance of the control after storage was the same (unchanged) as that before storage (immediately after preparation).
Evaluation was performed by 10 professional panelists in accordance with the following evaluation criteria.

<Evaluation criteria>
5: Equivalent to the control 4: Very slightly yellow compared to the control 3: Slightly yellow compared to the control 2: Very yellow compared to the control 1: Very yellow compared to the control

The average score of 10 panelists was taken, and an average score of 3.0 or more was determined to be acceptable in terms of commercial value as a softener. The average score of each liquid softening agent composition is shown in the column “Appearance after storage” in Table 2.

Viscosity and flowability after storage 100 mL of each liquid softener composition was put into a lightweight PS glass bottle (PS-No. 11, manufactured by Tanuma Glass Industrial Co., Ltd.), sealed, and stored at 40 ° C. for 6 months. The fluidity was evaluated from the appearance. As a control, those stored under the same conditions except that the temperature during storage was room temperature were used. In addition, the viscosity and fluidity of the control after storage were the same (invariable) as the viscosity and fluidity before storage (immediately after preparation).
Evaluation was carried out by five expert panelists in accordance with the following evaluation criteria.

<Evaluation criteria>
3: Almost no change in both viscosity and fluidity compared to the control 2: Increase in viscosity is observed compared to the control, but fluidity is sufficient 1: Viscosity compared to the control Markedly up and not very fluid

The average of the scores of five panelists was taken, and those with an evaluation of 2.0 or more were judged to be acceptable in terms of commercial value as a softener. The average score of each liquid softening agent composition is shown in the “viscosity after storage” column of Table 2.

Experimental example B
Cationic surfactant (component (A))
The following (A-1) and (A-2) were synthesized as cationic surfactants.
(A-1)
A cationic surfactant synthesized according to the procedure described in Example 4 of JP-A-2003-12471.
(A-1) is a compound represented by the general formulas (A-III), (A-IV) and (AV) (wherein R ¹ is an alkyl group and alkenyl having 15 or 17 carbon atoms) It was a composition containing a quaternary cis-trans body of an unsaturated part = 75/25 (mass ratio) with dimethyl sulfate.

(Where α = 210 and β = 9)

Other optional ingredients

Trehalose ((L) component)
(L) Trehalose (manufactured by Hayashibara Co., Ltd.)

Antibacterial agent (component (M))
(M-1)
A compound obtained from Lonza Corporation under the trade name: Proxel IB (registered trademark), in which R ¹¹ is a hexamethylene group, n is 12, and HY is hydrochloric acid in the general formula (M-1).

(M-2)
N, N-bis (3-aminopropyl) dodecylamine obtained from Lion Akzo under the trade name: Triamine Y12D (in the general formula (M-2), R ¹² is a dodecyl group (carbon number 12), and n is 3)

Highly branched cyclic dextrin ((N) component)
(N-1)
Cluster dextrin (registered trademark) (manufactured by Glico Nutrition Foods Co., Ltd.)
The main component of Cluster Dextrin (Registered Trademark) has a molecular weight of about 30,000 to 1,000,000, and has one cyclic structure (inner branched cyclic structure) composed of about 10 to 100 glucose in the molecule. Furthermore, it was a dextrin having a weight average degree of polymerization of about 2500, in which a large number of acyclic glucan chains (outer branched structure portions) were bonded to the cyclic structure portion.

Preparation Method of Liquid Softener Composition Liquid softener compositions of Examples 26 to 55 and Comparative Examples 5 to 8 having the compositions shown in Table 4 to be described later were prepared according to the following procedure. In Table 4, the numerical units of the components (A) to (N) are mass% with respect to the total mass of the liquid softener composition, and the numerical unit of the component (J) is ppm (based on the liquid softener composition). Mass basis).

When component B is an emulsion (use (B-1), (B-2), (B-3) as component (B))
The liquid softening agent composition was prepared by the following procedure 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). First, (A) component, (D) component, (E) component, (G) component, and (I) component were mixed and stirred, and the oil phase mixture was obtained. On the other hand, the component (C), the component (J) and, if necessary, the component (L) were dissolved in ion-exchange water for balance to obtain an aqueous phase mixture. Here, the mass of ion-exchange water for balance was obtained by subtracting the total mass of the oil phase mixture, the component (B) and the component (F), the component (H), the component (M), the component (N) and hydrochloric acid from 900 g. It was equivalent to the rest. 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, the component (H) is added, and then the components (B) and (F) are added. If necessary, the components (M) and (N) are added, and hydrochloric acid (reagent 1 mol / L, Kanto Chemical) or sodium hydroxide (reagent 1 mol / L, Kanto Chemical) is added to adjust the pH to 2.5, and ion exchange water is added so that the total mass becomes 1,000 g. A liquid softener composition was obtained.

When component B is oil (use component (B-4), (B-5), (B-6) or (B-7) as component (B))
The liquid softening agent composition was prepared by the following procedure 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). First, (A) component, (B) component, (D) component, (E) component, (G) component, and (I) component were mixed and stirred, and the oil phase mixture was obtained. On the other hand, the component (C), the component (J) and, if necessary, the component (L) were dissolved in balance ion-exchanged water to obtain an aqueous phase mixture. Here, the mass of ion-exchange water for balance corresponded to the balance obtained by subtracting the total mass of the oil phase mixture, the component (F) and the component (H) from 950 g. 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. Then, (F) component and (H) component are added, and then (M) component and (N) component are added as necessary, hydrochloric acid (reagent 1 mol / L, Kanto Chemical), or sodium hydroxide. (Reagent 1 mol / L, Kanto Chemical) was added in an appropriate amount to adjust the pH to 2.5, and ion-exchanged water was further added so that the total mass became 1,000 g to obtain the target liquid softener composition. .

The average score of 10 panelists was taken, and an average score of 3.0 or more was determined to be acceptable in terms of commercial value as a softener. The average score of each liquid softener composition is shown in the “Smoothness” column of Table 4.

The average score of 10 panelists was taken, and an average score of 3.0 or more was determined to be acceptable in terms of commercial value as a softener. The average score of each liquid softening agent composition is shown in the column of “scent after storage” in Table 4.

The average score of 10 panelists was taken, and an average score of 3.0 or more was determined to be acceptable in terms of commercial value as a softener. The average score of each liquid softener composition is shown in the column “Appearance after storage” in Table 4.

Viscosity and fluidity after storage 100 mL of each liquid softening agent composition was put into a lightweight PS glass bottle (PS-No. 11, manufactured by Tanuma Glass Industrial Co., Ltd.), sealed, and stored at 40 ° C. for 4 months. The viscosity increase of the agent composition and the ease of pouring of the liquid softener composition when weighed into the measuring cap were evaluated.
Evaluation was performed by 10 professional panelists in accordance with the following evaluation criteria.

<Evaluation criteria>
3: Can be measured without problems 2: Increased viscosity is observed, but can be measured without problems 1: Increased viscosity is observed, difficult to measure or cannot be measured

The average of the scores of 10 panelists was taken, and those with an evaluation of 2.0 or more were determined to be acceptable in terms of commercial value as a softener. The average score of each liquid softening agent composition is shown in the “viscosity after storage” column of Table 4.

The average of the scores of five panelists was taken, and those with an evaluation of 2.0 or more were judged to be acceptable in terms of commercial value as a softener. The average score of each liquid softening agent composition is shown in the “viscosity after storage” column of Table 4.

Deodorant evaluation 1 of sebum odor of skin shirts worn repeatedly
1. Washing treatment after wearing After wearing a commercially available cotton shirt (BVD) for 9 hours, it was washed using a drum-type washing machine (Toshiba TW-4000VFL) at the course / setting (use detergent “Top NANOX” (Lion Corporation), 15 minutes of washing, 1 rinse, 5 minutes of dehydration, 1.5 kg of items to be washed). At the time of rinsing, each liquid softener composition was charged from an automatic charging port. The amount of detergent used was 10 mL, and the amount of liquid softener composition used was 5.0 mL. After washing, the cotton-skin shirt was dried at the left setting.
This cycle of wearing, washing (softener treatment) and drying was repeated 5 times under the same conditions. A cotton skin shirt after the fifth cycle was used as a test cloth.

2. Smell Evaluation Method The odor of the sebum on the chest of the test cloth was evaluated by 10 professional panelists according to the following 6-step odor intensity standard.

<6-level odor intensity>
5 points: Strong odor 4 points: Strong odor 3 points: Easy to understand odor 2 points: Weak odor 1 point: Weak odor not knowing what odor is (threshold)
0 points: odorless

The average of the scores of 10 panelists was taken, and it was evaluated that a value lower by 0.25 points or more compared with the average score of the target (Comparative Example 5) exhibited preferable deodorizing properties. The average score of each liquid softener composition is shown in the column of “Deodorization After Wear 1” in Table 4.

Deodorant evaluation of sebum odor of skin shirts worn repeatedly 2
1. Washing treatment after wearing The cotton shirt after completion of the above-mentioned deodorant evaluation 1 was further subjected to each step of wearing and washing described in the column of deodorant evaluation 1. After the washing process, a cotton skin shirt was put in a plastic bag and left at 30 ° C. for 12 hours to obtain a test cloth for evaluating deodorization.

An average of the scores of 10 panelists was taken, and it was evaluated that a value lower by 0.25 points or more compared with the average score of the subject (Comparative Example 5) exhibited preferable deodorizing properties. The average score of each liquid softening agent composition is shown in the column of “Deodorizing After Wear 2” in Table 4.

The present invention can be used in the field of liquid softeners for clothing.

Claims

(A) one or more cationic surfactants selected from the group consisting of an amine compound containing at least one hydrocarbon group having 10 to 24 carbon atoms in the molecule, a neutralized product thereof, and a quaternized product thereof. The hydrocarbon group may be separated by one or more groups selected from the group consisting of an ester group, an ether group and an amide group,
(B) amino-modified silicone, and (C) urea, its double salt, and general formula (C):

(Wherein R a is a methyl group, an ethyl group or a hydroxyalkyl group having 1 to 2 carbon atoms, and R b , R c and R d are each independently a hydrogen atom, a methyl group or an ethyl group. A liquid softener composition comprising at least one compound selected from the group consisting of urea derivatives represented by:
[Mass of (A) + Mass of (B)] / Mass of (C) = 1-40.
(A) is represented by the following general formulas (A-III), (A-IV) and (A-V):

2. The liquid according to claim 1, which is a mixture of quaternized compounds of the compounds represented by the formula (wherein R 1 is a hydrocarbon group having 15 to 17 carbon atoms, which may be the same or different). Softener composition.
The liquid softener composition according to claim 1 or 2, wherein [mass of (A) + mass of (B) / mass of (C) = 1-5.
The liquid softener composition according to any one of claims 1 to 3, wherein (B) is an emulsion obtained by emulsion polymerization of an amino-modified silicone having a -H group and / or -OH group at a terminal with a surfactant. object.
The liquid softener composition according to any one of claims 1 to 4, wherein (C) is urea or dimethylurea.
The liquid softener composition according to any one of claims 1 to 5, further comprising (L) trehalose.
The liquid softener composition according to any one of claims 1 to 6, further comprising (N) a highly branched cyclic dextrin.
Further, (M) biguanide antibacterial agent and the following general formula (M-2):
R 12 —N [(CH 2 ) n —NH 2 ] 2 (M-2)
(Wherein R 12 represents an alkyl group having 8 to 18 carbon atoms, and n is a number of 1 to 4), and contains at least one antibacterial agent selected from the group consisting of compounds represented by: The liquid softener composition according to any one of claims 1 to 7, wherein the composition is a liquid softener composition.