JP5961872B2 - Liquid softener composition - Google Patents

Description

  The present invention relates to a liquid softener composition. Specifically, the present invention is a liquid softness that is less susceptible to the detergent even when used under the condition that the detergent remains in the wash water, and can impart excellent flexibility and deodorization to an object to be washed. The agent composition.

In recent years, the amount of water used for washing has been decreasing due to increasing environmental awareness. On the other hand, the amount of items to be washed per wash is increasing due to the increase in size of washing machines. As a result, the bath ratio (mass of water / mass of the object to be washed) at the time of washing is decreasing. As a result, the detergent used in the cleaning process may be brought into the rinsing process.
When a detergent containing an anionic surfactant is brought into the rinsing process, the anionic surfactant reduces the softening effect of the softener.
Also, under washing conditions where the amount of water used is low, dirt such as sebum tends to remain on the object to be washed, so if the object to be washed is dried under high temperature and humidity (for example, room drying), it will propagate on the remaining part of the dirt. An unpleasant odor may be generated from the bacteria.
The technique of patent document 1 is known as an attempt to solve the above problems.
Patent Documents 2 and 3 are known as attempts to solve the problem of unpleasant odor.
Moreover, the technique of patent document 4 is known as a softening agent composition.

JP 2001-336065 A JP 2004-211230 A JP 2004-211115 A JP 2012-202000 A

  A liquid softener composition that can impart a high level of flexibility and deodorization to a wash even when used under conditions where the bath ratio is low and the detergent remains in the washing water However, the provision of such a liquid softening agent composition has been a problem.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have combined the amino-modified silicone with a specific type of antibacterial agent, so that flexibility and deodorization can be achieved even when used under low bath ratio conditions. It has been found that it can be applied to the object to be washed at a high level, and the present invention has been completed. That is, the present invention relates to the following 1 to 8.

1. A liquid softener composition comprising:
(A) amino-modified silicone, and (B) biguanide antibacterial agent and the following general formula (3):
_{^{R 12 -N [(CH 2)}} n -NH 2] 2 (3)
(In the formula, R ¹² represents an alkyl group having 8 to 18 carbon atoms, and n is a number of 1 to 4.) containing one or more antibacterial agents selected from the group consisting of compounds represented by: A liquid softener composition characterized by the above.

2. 2. The liquid softener composition according to 1, wherein the mass of (A) / mass of (B) is 1/1 to 100/1.

3. Further, (C) the quaternized product of an amine having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms in the molecule, which may be separated by an ester group or an amide group, according to 1 or 2 above Liquid softener composition.

4). (C) The liquid softening agent composition of any one of said 1-3 whose mass of a component / (A) component is 40/1-2/1.

5. {The mass of the component (C) + the mass of the component (A)} / The mass of the component (B) is 10/1 to 200/1, and the liquid softener composition according to any one of 1 to 4 above. object.

6). Further, (D) one or more perfume ingredients selected from the group consisting of β ionone, jabanol, methyl dihydrojasmonate, hexyl salicylate , δ damascone, geraniol, dihydromyrsenol and benzaldehyde, The liquid softening agent composition of any one of Claims.

7). (B) The liquid softening agent composition of any one of said 1-6 whose component is a compound represented by General formula (3).

8). (B) The liquid softening agent composition of any one of said 1-7 whose component is N, N-bis (3-aminopropyl) dodecylamine.

  As shown in the examples described later, the liquid softener composition of the present invention can impart a high level of flexibility and deodorization to an object to be washed even when used under low bath ratio conditions. . Therefore, the present invention is useful as a liquid softener composition having added value not found in conventional liquid softener compositions.

(A) Component The amino-modified silicone that is the (A) component contained in the liquid softening agent composition of the present invention is a component that is blended in order to impart flexibility to the article to be washed.
Amino-modified silicone is a compound formed by introducing amino groups into both ends and / or side chains of a dimethyl silicone skeleton.
Preferred amino-modified silicones have the following general formula (I):

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 It is a compound formed by introducing an amino group into the side chain X.

  The amino-modified silicone is used in the form of an oil or an emulsion.

The amino-modified silicone is preferably a kinematic viscosity at 25 ° C. in a state of the silicone oil is 50~20000mm ² / s, and more preferably 500~10000mm ² / s. When the kinematic viscosity is within this range, a high flexibility-imparting effect is obtained, and the manufacturability and handleability of the liquid softening agent composition are facilitated. The kinematic viscosity can be measured with an Ostwald viscometer.
Further, the amino equivalent of the silicone oil is preferably 100 to 10,000 g / mol, more preferably 1200 to 4000 g / mol. When the amino equivalent is in this range, the flexibility imparting effect is good, which is preferable. 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.

  In addition, when an emulsion in which these amino-modified silicone oils are pre-emulsified with an emulsifier such as a cationic surfactant or a nonionic surfactant or an amino-modified silicone emulsion obtained by an emulsion polymerization method is used, a liquid softener composition is used. This is preferable since the manufacturability of the product is enhanced.

  Both the amino-modified silicone oils and amino-modified silicone emulsions described above are readily available on the market or can be synthesized.

Examples of amino-modified silicone oils are those sold by Toray Dow Corning Co., Ltd. under the trade names: SF-8417, BY16-203, BY16-849, BY16-889, FZ-3785, or BY16-890, Sold by Shin-Etsu Chemical Co., Ltd. under the trade name: KF-864, KF-860, KF-880, KF-8004, KF-8002, KF-8005, KF-867 or KF-869, KF-861, KF-8610 What is being done.
Examples of amino-modified silicone emulsions are those sold by Toray Dow Corning Co., Ltd. under the trade names: SM8904, BY22-079, FZ-4671, or FZ-4672, and Shin-Etsu Chemical Co., Ltd. as the Polon series. Polon MF-14, Polon MF-29, Polon MF-14D, Polon MF-44, Polon MF-14EC and Polon MF-52 are sold as WACKER FC201 and WACKER FC218 from Asahi Kasei Wacker Silicone Co., Ltd. What is being done.

As particularly preferred component (A), in general formula (I),
X is — (CH ₂ ) _a —NH ₂ ;
The kinematic viscosity (25 ° C.) is 90 to 20,000 mm ² / s, preferably 500 to 10,000 mm ² / s, particularly preferably 1,000 to 5,000 mm ² / s, and
Amino-modified silicones having an amino equivalent of 400 to 8,000 g / mol, preferably 800 to 6,000 g / mol, particularly preferably 1,000 to 4,000 g / mol are preferred. Specific examples include KF-864 (kinematic viscosity: 1,700 mm ² / s (25 ° C.), amino equivalent: 3,800 g / mol) and BY16-203 (kinematic viscosity: 2,000 mm ² / s (25 ° C), amino equivalents: 1,900 g / mol) and the like.

  When the component (A) is used in the form of an emulsion, the average particle size of the emulsified particles is preferably 0.01 to 10 μm, more preferably 0.01 to 5 μm, particularly preferably from the viewpoint of dispersion stability of the silicone emulsion. 0.01 to 1 μm. The average particle diameter can be measured by a light scattering method using a laser diffraction / scattering particle size distribution analyzer (LA-920 manufactured by Horiba, Ltd.).

  The amino-modified silicone emulsion may be obtained by dispersing the above oily silicone in water using various emulsifiers (homomixer, high-pressure homogenizer, colloid mill, etc.) using an emulsifier such as a surfactant. Although an emulsion containing the desired amino-modified silicone is prepared by conducting a polymerization reaction in water using organoalkoxysilane and dimethylcyclopolysiloxane, this can be used as it is as the silicone emulsion of component (A). good.

  (A) 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 (A) is not particularly limited as long as the blending effect of the component (A) can be sufficiently obtained, but preferably 0.5 to 8 as an active ingredient with respect to the total mass of the liquid softener composition. It is 1 mass%, More preferably, it is 1-5 mass%. When it is 0.5% by mass or more, the blending effect of the component (A) can be sufficiently exhibited. It can suppress the raw material cost rise of a composition, suppressing yellowing at the time of the preservation | save of a liquid softening agent composition as it is 5 mass% or less.
Regarding the above description of “active ingredient”, when a silicone emulsion is used, “amino-modified silicone contained in silicone emulsion = active ingredient”. When silicone oil is used, “silicone oil = active ingredient”.
In this specification, the compounding quantity and mass of (A) component say the compounding quantity and mass as an active ingredient, respectively.

(B) Component The antibacterial agent which is the (B) component contained in the liquid softener composition of the present invention is intended to impart deodorant properties (inhibition of breeding of unpleasant odor-producing bacteria in the washed product) to the washed product. It is a component to be blended.
The component (B) is one or more antibacterial agents selected from the group consisting of biguanide antibacterial agents and N, N-bis (3-aminoalkyl) alkylamines.

を有するビグアニド又はビグアニドから誘導される化合物であって、抗菌作用を有するものをいう。 The biguanide antibacterial agent has the following structure:

Or a compound derived from a biguanide having antibacterial action.

As a biguanide antibacterial agent, the following general formula (2):

^{- [R 11 -NH-C (} NH) -NH-C (NH) -NH] n -n · HY (2)

(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.

As the component (B), a compound in which R ¹¹ is a hexamethylene group in the general formula (2), n is 10 to 14, and HY is hydrochloric acid is preferable. In the general formula (2), R ¹¹ is Particularly preferred are compounds that are hexamethylene groups, n is 11 to 13, and HY is hydrochloric acid.
As a specific example, a compound (poly (hexamethylene biguanide) hydrochloride, 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 (2) ) (Lonza).

を有する塩酸クロロヘキシジン（1,1'-Hexamethylene bis [5-(4-chlorophenyl)biguanide] dihydrochloride）が挙げられる。
ビグアニド系抗菌剤は、１種類を単独で用いてもよく、２種類以上からなる混合物として用いてもよい。 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 (B), the following general formula (3):

_{^{R 12 -N [(CH 2)}} n -NH 2] 2 (3)

(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 (3), 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 (3), n is 1-4, Preferably it is 2-4, More preferably, it is 3. When n is 1 to 4, an excellent antibacterial action can be exhibited.

As the compound represented by the general formula (3),
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 Aminomethyl) alkylamine;
N, N-bis (3-amino) such as N, N-bis (3-aminoethyl) octylamine, N, N-bis (3-aminoethyl) decylamine, N, N-bis (3-aminoethyl) dodecylamine Aminoethyl) alkylamine;
N, N-bis (3- (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) such as N, N-bis (3-aminobutyl) 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.
The compound represented by the general formula (3) may be used alone or as a mixture of two or more.

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

  As the component (B), one kind selected from the group consisting of the biguanide antibacterial agent and the compound represented by the general formula (3) may be used alone, or a mixture of two or more kinds may be used. .

  The blending amount of the component (B) is not particularly limited as long as the blending effect of the component (B) can be sufficiently obtained. However, the liquid softener composition can be further improved in the deodorizing property of the article to be washed. Preferably it is 0.01-3 mass% with respect to the total mass, More preferably, it is 0.05-2 mass%, More preferably, it is 0.1-1 mass%.

    In the liquid softening agent composition of the present invention, the mass ratio of the component (A) to the component (B) (the mass of (A) / the mass of (B)) is 1/1 to 100/1, preferably 2/1. -50/1, more preferably 3/1 to 20/1. When the mass of (A) / (B) is 1/1 to 100/1, flexibility and deodorization can be imparted to the article to be washed at a higher level.

(C) Component In the liquid softener composition of the present invention, as an optional component, “(C) a hydrocarbon group having 10 to 26 carbon atoms which may be separated by an ester group or an amide group” is 1 to 3 in the molecule. A cationic surfactant that is a “quaternized product of amines” can be blended. When (C) component is mix | blended, the softness | flexibility of a to-be-washed object can be improved more.

The number of carbon atoms of the “C 10-26 hydrocarbon group (hereinafter sometimes referred to as“ long-chain hydrocarbon group ””) of the amine constituting the quaternized product of component (C) is 10- 26, 17 to 26 are preferable, and 19 to 24 are more preferable. When the carbon number is 10 or more, the flexibility of the article to be washed can be further increased, and when it is 26 or less, the handling property of the liquid softening agent composition can be improved.
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. The center of the hydrogen group is preferably distributed around the median.
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—) 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 two or more split groups are present, the type of each split 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.
Long-chain hydrocarbon groups are usually unhydrogenated fatty acids derived from beef tallow which are used industrially, fatty acids obtained by hydrogenation or partial hydrogenation of unsaturated parts, and underived from plants such as palm palm and oil palm. It is introduced by using a hydrogenated fatty acid or fatty acid ester, or a fatty acid or fatty acid ester obtained by hydrogenation or partial hydrogenation of an unsaturated portion.

  (C) The amine constituting the quaternized product of component is a secondary amine compound (having two long-chain hydrocarbon groups in the molecule) or a tertiary amine (having three long-chain hydrocarbon groups in the molecule) ) Is preferred, and tertiary amine compounds are more preferred.

（式中、
Ｒ¹〜Ｒ³はそれぞれ独立に、炭素数１０〜２６の炭化水素基、−ＣＨ₂ＣＨ（Ｙ）ＯＣＯＲ⁴（Ｙは水素原子又はＣＨ₃であり、Ｒ⁴は炭素数７〜２１の炭化水素基である。）、−（ＣＨ₂）_nＮＨＣＯＲ⁵（ｎは２又は３であり、Ｒ⁵は炭素数７〜２１の炭化水素基である。）、水素原子、炭素数１〜４のアルキル基、−ＣＨ₂ＣＨ（Ｙ）ＯＨ、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 constituting the quaternized product of the component (C) include compounds represented by the following general formula (C1).

(Where
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 a carbon atom having 7 to 21 carbon atoms. A hydrogen group), — (CH ₂ ) _n NHCOR ⁵ (n is 2 or 3, and R ⁵ is a hydrocarbon group having 7 to 21 carbon atoms), a hydrogen atom, or a carbon atom having 1 to 4 carbon atoms. An alkyl group, —CH ₂ CH (Y) OH, or — (CH ₂ ) _n NH ₂ ;
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 . )

Wherein (C1), the carbon number of the hydrocarbon group having 10 to 26 carbon atoms in R ¹ to R ³ is preferably 17 to 26, 19 to 24 is more preferable. 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 (C1), 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 softly treated article, the saturated / unsaturated ratio (mass ratio) of the fatty acid serving as R ⁴ is preferably 90/10 to 0/100, and 80/20. More preferable to 0/100.
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 preferably 70/30 to 100/0. 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 100/0.
(C) (i) the fatty acid having 18 carbon atoms is 60% by mass or more, preferably 80% by mass or more, (ii) the fatty acid having 20 carbon atoms is less than 2% by mass, and (iii) 21-22 carbon atoms. The fatty acid is less than 1% by mass and (iv) linoleic acid is less than 5%. In addition, in order to improve the odor of the synthesized quaternized product and the odor of the liquid softener composition containing the quaternized product, linoleic acid is more preferably less than 2%, and even more preferably less than 1%.

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 a hydrocarbon group having 15 to 19 carbon atoms. When R ⁵ is more present in the compounds represented by formula (C1), may be R ⁵ of said plurality of mutually identical, may be different.
Specific 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 ). And preferably two are 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 amine compound represented by the general formula (C1) include compounds represented by the following general formulas (C1-1) to (C1-8).

(In the formula, 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 the same groups as 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.

  Component (C) 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.

  As the component (C), at least one selected from quaternized compounds of the compound represented by the general formula (C1) is preferable, and from the quaternized compounds of the general formulas (C1-1) to (C1-8). At least one selected from the group consisting of: (C1-4) to (C1-6) quaternized compounds is more preferable.

As the quaternized product of the compound represented by the formula (C1), a commercially available product may be used, or a product produced by a known method may be used.
For example, a compound represented by the general formula (C1-2) (hereinafter referred to as “compound (C1-2)”) and a compound represented by the general formula (C1-3) (hereinafter referred to as “compound (C1-3)”). Can be synthesized by a condensation reaction of 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. At that time, from the viewpoint of improving flexibility, the abundance ratio represented by “compound (C1-2) / compound (C1-3)” is synthesized such that the mass ratio is 99/1 to 50/50. After that, the compound can be quaternized with methyl chloride as a quaternizing agent to prepare the target compound. At that time, from the viewpoint of flexibility, the abundance ratio represented by “a quaternized compound (C1-2) / a quaternized compound (C1-3)” is 99/1 to 50/50 in mass ratio. It is preferable to synthesize.

  A compound represented by the general formula (C1-4) (hereinafter referred to as “compound (C1-4)”), a compound represented by the general formula (C1-5) (hereinafter referred to as “compound (C1-5)”). ) And a compound represented by the general formula (C1-6) (hereinafter referred to as “compound (C1-6)”) is a fatty acid composition or a fatty acid methyl ester composition and triethanolamine. It can be synthesized by a condensation reaction. At that time, the content ratio of each component to the total mass of the compounds (C1-4), (C1-5), and (C1-6) is 1 for the compound (C1-4) from the viewpoint of improving the flexibility-imparting effect. It is preferable that it is -60 mass%, a compound (C1-5) is 5-98 mass%, a compound (C1-6) is 0.1-40 mass%, and a compound (C1-4) is 30-60 mass%. More preferably, the compound (C1-5) is 10 to 55% by mass and the compound (C1-6) is 5 to 35% by mass, and then the compound is quaternized with a quaternizing agent dimethyl sulfate, The target compound can be prepared. From the viewpoint of flexibility, the abundance ratio of each of the quaternized compounds (C1-4), (C1-5), and (C1-6) is (C1-4), (C1-5), and (C1-6). ), The quaternized compound (C1-4) is 1 to 60% by mass, the quaternized compound (C1-5) is 5 to 98% by mass, and the compound (C1-6) 4 It is preferable that the graded product is 0.1 to 40% by mass, the quaternized product of the compound (C1-4) is 30 to 60% by mass, the quaternized product of the compound (C1-5) is 10 to 55% by mass, The quaternized compound (C1-6) is more preferably 5 to 35% by mass. Moreover, when quaternizing the compounds (C1-4), (C1-5), and (C1-6), an amine compound that is not quaternized generally remains after the quaternization reaction. In that case, it is preferable that the ratio of “quaternized product / non-quaternized amine compound” is within the range of the mass ratio of 70/30 to 99/1.

  The above-mentioned component (C) is easily available in the market or can be synthesized. For example, a composition containing the compound (C1-4), the compound (C1-5) and the compound (C1-6) is synthesized by the method described in Example 4 of JP-A-2003-12471. Can do.

  (C) The compounding quantity of a component is 5-30 mass% with respect to the total mass of a liquid softening agent composition, Preferably it is 5-20 mass%, More preferably, it is 10-20 mass%. When it is 5 to 30% by mass, the softening effect can be enhanced while avoiding an increase in the viscosity of the liquid softening agent composition.

  When the component (C) is blended, the mass ratio of the component (C) to the component (A) (mass of (C) / mass of (A)) is preferably 40/1 to 2/1, more preferably The softness | flexibility provision effect of a liquid softening agent composition can be improved more as it is 20/1-2/1, Most preferably 10/1-3/1.

  The total amount of the component (C) and the component (A) is 5.5 to 35% by mass, preferably 6 to 25% by mass, and most preferably 15 to 25% by mass with respect to the total mass of the liquid softening agent composition. %, The softening effect of the liquid softening agent composition can be further enhanced.

  Further, the ratio of the total mass of the component (C) and the component (A) to the mass of the component (B), that is, {mass of (C) + mass of (A)} / mass of (B) is 10/1. ~ 200/1, preferably 10/1 to 100/1, most preferably 20/1 to 50/1, the effect of component (B) (improving deodorizing properties to the object to be washed) can be further enhanced. it can.

(D) Component The liquid softener composition of the present invention is selected from the group consisting of “(D) β ionone, methyl dihydrojasmonate, hexyl salicylate , δ damascone, geraniol, dihydromyrsenol and benzaldehyde as an optional component. One or more perfume ingredients "can be blended. When (D) component is mix | blended, the deodorizing property of a to-be-washed object can be improved more.
In these fragrance | flavor components, methyl dihydrojasmonate, dihydromyrsenol, and (beta) ionone are preferable at the point of deodorizing provision.
(D) A component may be used individually by 1 type among said fragrance | flavor components, and may be used as a mixture which consists of 2 or more types.
(D) Each fragrance | flavor component of a component is a well-known substance, can be obtained easily in a market, or can be prepared.

  The blending amount of the component (D) is preferably 0.001 to 1% by mass, more preferably 0.005 to 0%, based on the total mass of the liquid softening agent composition, in that the deodorizing property of the washing object is further increased. 0.5% by mass, particularly preferably 0.01 to 0.1% by mass.

Other Optional Components The liquid softener composition of the present invention may contain other components other than the above components as necessary, as long as the effects of the present invention are not impaired. Other optional components are shown below.

Liquid softener composition of the water present invention are preferably aqueous compositions, 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.
The amount of water is preferably 50% by mass or more, more preferably 60% by mass or more, based on the total mass of the liquid softening agent composition. The handling property of a liquid softening agent composition becomes it more favorable that it is 50 mass% or more.

Nonionic surfactant Nonionic surfactant can be mix | blended in order to improve the storage stability of a liquid softening agent composition.
A nonionic surfactant is a compound obtained by adding an alkylene oxide to a primary or secondary alcohol. Specifically, it is a compound obtained by adding an average of 5 to 100 moles of alkylene oxide to a primary or secondary alcohol having a linear or branched alkyl group having 8 to 20, preferably 10 to 14 carbon atoms.
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.
When ethylene oxide is used as the alkylene oxide, the average added mole number of ethylene oxide is preferably 20 to 80 mol, particularly preferably 20 to 60 mol. Moreover, when adding propylene oxide with ethylene oxide, the average addition mole number of propylene oxide can be 1-5 mol, Preferably it is 1-3 mol.
Specific examples of nonionic surfactants include an average of 60 mol of ethylene oxide (EO) added to primary isotridecyl alcohol, an average of 40 mol of ethylene oxide (EO) added to primary isotridecyl alcohol, and an alkyl group carbon. Examples include those obtained by adding 50 mol of EO to an average of 10 to 14 linear secondary alcohols, or adding 40 mol of ethylene oxide to natural alcohol (trade name: CO-1214 manufactured by P & G). It is done.
The nonionic surfactant may be prepared, for example, using the above natural alcohol as it is, or using propylene or butylene as a raw material, and an n-mer (3 to 6-mer in the case of propylene, 2 in the case of butylene). ˜tetramer etc.) are prepared, then converted into an aldehyde by oxo reaction and hydrogenated to a primary or secondary alcohol obtained by adding an alkylene oxide by a conventional method known to those skilled in the art. be able to.

  Nonionic surfactants are readily available on the market or can be synthesized. As a commercially available product, trade name: Leocol TDA400-75 (EO 40 mol adduct of primary isotridecyl alcohol) sold by Lion Chemical Co., Ltd. can be mentioned.

  The compounding amount of the nonionic surfactant is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 7% by mass, and most preferably 1% with respect to the total mass of the liquid softening agent composition. 0.0 mass% to 5 mass%. The storage stability of a liquid softening agent composition can be improved more as it is 0.1 mass%-10 mass%.

Inorganic or organic water-soluble salts Inorganic or organic water-soluble salts can be used for the purpose of controlling the viscosity of the liquid softener composition.
Examples of inorganic or organic water-soluble salts include sodium chloride, potassium chloride, calcium chloride, magnesium chloride, 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, it is calcium chloride or sodium chloride.
The compounding amount of the inorganic or organic water-soluble salt is 0 to 3% by mass, preferably 0.01 to 2% by mass, and more preferably 0.05 to 1% by mass with respect to the total amount of the liquid softener composition. The addition of the inorganic or organic water-soluble salt may be performed at any step of producing the liquid softening agent composition.

Antiseptic | preservative A preservative can be mix | blended in order to improve the antiseptic property in the long-term preservation | save of a liquid softening agent composition.
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. As a specific example, trade name: Caisson CG-ICP sold by Dow Chemical may be mentioned.
Examples of benzisothiazoline-based organic sulfur compounds include 1,2-benzisothiazolin-3-one and 2-methyl-4,5-trimethylene-4-isothiazolin-3-one. -2,2-bis (benzmethylamide) and the like can also be used. When a plurality of types of benzisothiazoline-based organic sulfur compounds are used, they can be used in any mixing ratio.
An example of the iodine compound is 3-iodo-2-propynyl N-butylcarbamate.
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, and benzyl paraoxybenzoate. Can do.
The blending 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.

Antioxidant Antioxidant can be 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 (dibutylhydroxytoluene), BHA (butylated hydroxyanisole), a mixture of propyl gallate and citric acid, hydroquinone, tertiary butylhydroquinone, disaccharide Trehalose, 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, Examples include 4,5-dihydroxy-m-benzenesulfonic acid / sodium salt, dimethoxyphenol, catechol, methoxyphenol, carotenoid, furans, amino acids and the like.
As a method of blending the antioxidant into the liquid softener composition, it may be dispersed in water together with an oil-soluble component such as a cationic surfactant or a fragrance, or a cation is dispersed in water together with a fragrance. You may add to the dispersion liquid of the cationic surfactant made into the temperature below the phase transition temperature of surfactant.
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.

Additional perfume component In addition to the above-mentioned component (D), an additional perfume component can be appropriately blended in the liquid softener composition of the present invention. When an additional fragrance component is further blended in addition to the component (D), the deodorizing property of the article to be washed can be further improved.
As the additional fragrance component, a fragrance generally used in the art can be used and is not particularly limited. However, a list of fragrance 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, Chemical Industry Daily (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).
The amount of the additional fragrance component is preferably 0.1 to 2% by mass with respect to the total mass of the liquid softening agent composition.

Aliphatic alcohols Aliphatic alcohols can be blended to improve the viscosity of the liquid softener composition.
The aliphatic alcohol is represented by the formula: R ^b OH (R ^b represents an alkyl or alkenyl group having 8 to 35 carbon atoms, preferably an alkyl group or alkenyl group having 16 to 28 carbon atoms, more preferably 18 to 24 carbon atoms. It is a compound represented by.
Specific examples of the aliphatic alcohol include, for example, myristyl alcohol, cetyl alcohol, 2-hexadecanol, stearyl alcohol, 2-octadecanol, oleyl alcohol, elaidyl alcohol, petrocerinyl alcohol, eleostearyl alcohol, and arachi. Examples include gil alcohol, 2-icosanol, behenyl alcohol, erucyl alcohol, and brassyl alcohol.

Dye and / or pigment dye and / or pigment can be mix | blended in order to improve the external appearance of a liquid softening agent composition.
As the dye and pigment, general-purpose dyes and pigments can be used in the technical field and are not particularly limited, but are preferably selected from acid dyes, direct dyes, basic dyes, reactive dyes, and mordant / acid mordant dyes. , One or more of red, blue, yellow or purple water-soluble 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.). Further, JP-A-6-123081, JP-A-6-123082, JP-A-7-18573, JP-A-8-27669, JP-A-9-250085, JP-A-10-77576, The dyes described in JP-A-11-43865, JP-A-2001-181972, or JP-A-2001-348784 can also be used.
From the viewpoint of the storage stability of the liquid softener composition and the dyeing property to the fiber, an acid dye or a direct 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 A reactive dye is preferred, and its blending amount is preferably 1 to 50 ppm, more preferably 1 to 30 ppm, based on the entire composition.

  In addition to the above-mentioned optional components, reducing agents, emulsions (for example, polystyrene emulsion), opacifiers, anti-shrinking agents, and anti-wrinkle agents for improving the stability of the fragrance and color tone of the liquid softener composition , Shape retainer, drape retainer, iron improver, oxygen bleach inhibitor, whitening agent, whitening agent, fabric softening clay, antistatic agent, dye transfer inhibitor (eg, polyvinylpyrrolidone), polymer dispersion Agent, stain remover, scum dispersant, fluorescent whitening agent (for example, 4,4-bis (2-sulfostyryl) biphenyl disodium (Cinopearl CBS-X manufactured by Ciba Specialty Chemicals)), dye fixing agent, anti-fading agent (Eg, 1,4-bis (3-aminopropyl) piperazine), stain removers, enzymes as fiber surface modifiers (eg, cellulase, amylase, protease, lipase) , Keratinase), foam suppressor, silk protein powder imparting silk texture / function such as moisture absorption and release, surface modified products and emulsified dispersions (for example, 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)), antifouling agent (for example, alkylene terephthalate and / or alkylene) A nonionic polymer compound composed of an isophthalate unit and a polyoxyalkylene unit (for example, FR627 manufactured by Kyoyo Chemical Industry Co., Ltd., SRC-1 manufactured by Clariant Japan) and the like can be appropriately blended.

The pH of the liquid softening agent composition of the present invention is not particularly limited, but the pH at 25 ° C. is in the range of 1.0 to 6.0 from the viewpoint of suppressing hydrolysis of the component (C) accompanying storage aging. Preferably, it is within the range of 2.0 to 4.0.
When adjusting pH, hydrochloric acid, sulfuric acid, phosphoric acid, alkyl sulfuric acid, benzoic acid, p-toluenesulfonic acid, citric acid, malic acid, succinic acid, lactic acid, glycolic acid, hydroxyethane diphosphonic acid, phytin PH adjusting agents such as acids, short-chain amine compounds such as ethylenediaminetetraacetic acid and dimethylamine, alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates and alkali metal silicates 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).

Method for Producing Liquid Softener Composition The liquid softener composition of the present invention can be produced using various methods generally used for producing liquid softener compositions. For example, (C) When producing a liquid softener composition containing a component (cationic surfactant), the method described in JP-A-10-237762 is preferred.
In particular,
An aqueous mixture containing (A) component, (B) component, (C) component (arbitrary), (D) component (arbitrary) and other oil-soluble components, and containing the water-soluble component in this oil-based mixture How to add,
(C) An oily mixture containing component (optional), (D) component (optional) and other oil-soluble components is prepared, and an aqueous mixture containing water-soluble components is added to and mixed with this oily mixture. (A) It can manufacture by the method of adding a component and (B) component.
As for other optional components, those having high water solubility are preferably added to an aqueous mixture, and those having low water solubility are preferably added to an oily mixture.

Method of Using Liquid Softener Composition 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, the liquid softener composition of the present invention is added to the wash water at the stage of rinsing and the object to be washed is softened, or the water in a container such as a tub is used for the liquid softener composition of the present invention. In addition, there is a method of adding an object to be washed and dipping treatment.
The liquid softener composition of the present invention has a low bath ratio of detergent containing an anionic surfactant (for example, mass of water / mass of article to be washed = 10/1 to 4/1, particularly 5/1 to 6/1). It can be suitably used when an anionic surfactant remains in the washing water used in the subsequent rinsing step.
The use amount (volume) of the liquid softening agent composition is preferably 0.1 to 5 (v / w)%, and 0.3 to 2 (v / w)% with respect to the mass of the object to be washed. More preferably.

  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).

Amino-modified silicone (component (A))
The following (A-1) to (A-3) were used as the component (A).

(A-1)
Side chain-modified amino-modified silicone oil obtained from Shin-Etsu Chemical Co., Ltd. under the trade name: KF-864 (a compound in which X is — (CH ₂ ) ₃ —NH ₂ in general formula (I)). Kinematic viscosity at 25 ° C .: 1700 mm ² / s, amino equivalent: 3800 g / mol).

(A-2)
Amino-modified silicone emulsion obtained from Asahi Kasei Wacker Silicone Co., Ltd. under the trade name WACKER FC201

(A-3)
An emulsion obtained from Toray Dow Corning Co., Ltd. under the trade name: SM8904, which is obtained by emulsion polymerization of an amino-modified silicone having a —H group and / or —OH group at its terminal with a surfactant.

In Comparative Examples, the following (A-4) and (A-5) that do not correspond to the component (A) of the present invention (the structure does not contain an amino group) were used.

(A-4)
Polyether-modified silicone oil obtained from Toray Dow Corning Co., Ltd. as trade name: SH3775

(A-5)
Dimethyl silicone emulsion obtained from Toray Dow Corning Co., Ltd. as trade name: SM7036EX

Antibacterial agent (component (B))
As the component (B), the following (B-1) to (B-2) were used.

(B-1)
A compound obtained from Lonza Corporation under the trade name: Proxel IB (registered trademark), wherein R ¹¹ is a hexamethylene group, n is 12, and HY is hydrochloric acid.

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

In the comparative example, the following (B-3) and (B-4) not corresponding to the component (B) of the present invention were used.
(B-3)
Triclosan obtained as trade name: 2,4,4′-trichloro-2′-hydroxydiphenyl ether from Mikami Co., Ltd.

(B-4)
Stearyltrimethylammonium chloride obtained from Lion Akzo Co., Ltd. under the trade name: ARCARD T-800

Quaternized product of amine having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms which may be separated by ester group or amide group in the molecule (component (C))
The following (C) was used as the component (C).

(C)
A cationic surfactant synthesized according to the procedure described in Example 4 of JP-A-2003-12471. (C) is each compound represented by the general formula (C1-5), (C1-4) and (C1-6) (in each formula, R ⁹ is an alkyl group or an 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. Based on the total mass of (C1-5), (C1-4) and (C1-6), (C1-5) is 25%, (C1-4) is 55%, and (C1-6) is 20%. Abundance ratio (mass ratio). The ratio of “quaternized product / amine compound not quaternized” was 90/10 (mass ratio).

Fragrance ingredient (component (D))
As the component (D), the following (D-1) to (D-7) were used.

(D-1)
βYonon (Wako Pure Chemical Industries, Ltd.)

(D-2)
Methyl dihydrojasmonate (Tokyo Chemical Industry Co., Ltd.)

(D-3)
Dihydromilsenol (Wako Pure Chemical Industries, Ltd.)

(D-4)
Geraniol (Wako Pure Chemical Industries, Ltd.)

(D-5)
Hexyl salicylate (Sigma Aldrich Japan Co., Ltd.)

(D-6)
δ Damascon (Sigma Aldrich Japan Co., Ltd.)

(D-7)
Benzaldehyde (Wako Pure Chemical Industries, Ltd.)

EO 40 mol adduct of primary isotridecyl alcohol obtained from Nonionic Surfactant Lion Chemical Co., Ltd. under the trade name: Leocol TDA400-75

Inorganic water-soluble salts Calcium chloride obtained from Tokuyama Corporation

An isothiazolone solution (an aqueous solution of a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one obtained as a trade name: Caisson CG-ICP from the preservative Dow Chemical (Mass ratio is 75:25)

Dibutylhydroxytoluene obtained from Mikami, an antioxidant, as trade name: dibutylhydroxytoluene

(D) Perfume component other than component A perfume composition having the following composition was used.

Preparation method of liquid softening agent composition The softening agent composition of Examples 1-21 and Comparative Examples 1-5 which have a composition shown to the below-mentioned Tables 1-1 to 1-3 was prepared according to the following procedures. In each table, the unit of the numerical values of the components (A) to (D) is mass% with respect to the total mass of the liquid softening agent composition.
In addition, the compounding quantity (mass% with respect to the total mass of a liquid softening agent composition) of the following component mix | blended in common with all the Examples and the comparative examples was as follows.

Preparation method 1 of liquid softening agent composition (preparation methods of Examples 6, 12, and 14 and Comparative Examples 1, 2, 4, and 5)
The component (C) was heated above its melting point, and a predetermined amount was weighed into a glass container having an inner diameter of 100 mm and a height of 150 mm according to the composition in each table. Add the components (A) and (B) to this, and add a predetermined amount of “fragrance components other than the component (D)”, “antioxidant” and “nonionic surfactant”, which are common components, to make it uniform. And an oily mixture was prepared.
In addition, the “preservative”, which is a common component, was dissolved in a predetermined amount of ion-exchanged water and heated to 50 ° C. to prepare an aqueous mixture.
Next, the warmed aqueous mixture was added to the oily mixture in two portions. The split ratio of the first addition / second addition of the aqueous mixture was 30/70 (mass ratio), and the stirring was performed using a three-one motor (manufactured by Shinto Kagaku Co., Ltd.) at a rotation speed of 1,000 rpm. Thereafter, the mixture was stirred for 3 minutes after the second aqueous mixture was added for 3 minutes. Finally, “inorganic water-soluble salts” as common components were added, and stirred for 1 minute to obtain a liquid softening agent composition. As the stirring blade, a paddle blade having three blades having a length of 100 mm at intervals of 30 mm was used.
The pH of each liquid softener composition obtained (25 ° C., stock solution) is a value of 2.0 to 4.0, and the viscosity at 25 degrees (Analog Viscometer T manufactured by Brookfield) is 100 mPa · s or less. there were.

Preparation method 2 of liquid softening agent composition (preparation methods of Examples 4 and 5 and Comparative Example 3)
The component (C) was heated above its melting point, and a predetermined amount was weighed into a glass container having an inner diameter of 100 mm and a height of 150 mm according to the composition in each table. Furthermore, a predetermined amount of “fragrance component other than component (D)”, “antioxidant” and “nonionic surfactant” which are common components was added and stirred uniformly to prepare an oily mixture.
In addition, the “preservative”, which is a common component, was dissolved in a predetermined amount of ion-exchanged water and heated to 50 ° C. to prepare an aqueous mixture.
Next, the warmed aqueous mixture was added to the oily mixture in two portions. The split ratio of the first addition / second addition of the aqueous mixture was 30/70 (mass ratio), and the stirring was performed using a three-one motor (manufactured by Shinto Kagaku Co., Ltd.) at a rotation speed of 1,000 rpm. After 3 minutes, the mixture was stirred for 3 minutes after the second aqueous mixture was added. Finally, “inorganic water-soluble salts” as common components were added and stirred for 1 minute. As the stirring blade, a paddle blade having three blades having a length of 100 mm at intervals of 30 mm was used.
Thereafter, the component (A) and the component (B) were mixed while stirring the product at a rotation speed of 200 rpm to obtain a liquid softening agent composition. The pH of each liquid softener composition obtained (25 ° C., stock solution) is a value of 2.0 to 4.0, and the viscosity at 25 degrees (Analog Viscometer T manufactured by Brookfield) is 100 mPa · s or less. there were.

Preparation method 3 of liquid softening agent composition (preparation methods of Examples 3, 7, 8, 9, 10, 11, 13, and 15 to 21)
The component (C) was heated above its melting point, and a predetermined amount was weighed into a glass container having an inner diameter of 100 mm and a height of 150 mm according to the composition in each table. Add (A) component here, and if necessary, add (D) component, and also a predetermined amount of “perfume components other than (D) component”, “antioxidant” and “nonionic surfactant” which are common components. The mixture was stirred uniformly to prepare an oily mixture.
In addition, the “preservative”, which is a common component, was dissolved in a predetermined amount of ion-exchanged water and heated to 50 ° C. to prepare an aqueous mixture.
Next, the warmed aqueous mixture was added to the oily mixture in two portions. The split ratio of the first addition / second addition of the aqueous mixture was 30/70 (mass ratio), and the stirring was performed using a three-one motor (manufactured by Shinto Kagaku Co., Ltd.) at a rotation speed of 1,000 rpm. After 3 minutes, the mixture was stirred for 3 minutes after the second aqueous mixture was added. Finally, “inorganic water-soluble salts” as common components were added and stirred for 1 minute. As the stirring blade, a paddle blade having three blades having a length of 100 mm at intervals of 30 mm was used.
Thereafter, the component (B) was mixed while stirring the product at a rotation speed of 200 rpm to obtain a liquid softening agent composition. The pH of each liquid softener composition obtained (25 ° C., stock solution) is a value of 2.0 to 4.0, and the viscosity at 25 degrees (Analog Viscometer T manufactured by Brookfield) is 100 mPa · s or less. there were.

Method 4 for preparing liquid softener composition (Method for preparing Examples 1 and 2)
Dissolve “fragrance ingredients other than (D) ingredient”, “antioxidant”, “nonionic surfactant”, “preservative” and “inorganic water-soluble salts” which are common ingredients in a predetermined amount of ion-exchanged water. , Dispersed.
Next, the component (A) and the component (B) were mixed while stirring the solution at a rotation speed of 200 rpm to obtain a liquid softening agent composition. The pH of each liquid softener composition obtained (25 ° C., stock solution) is a value of 2.0 to 4.0, and the viscosity at 25 degrees (Analog Viscometer T manufactured by Brookfield) is 100 mPa · s or less. there were.

  About each prepared liquid softening agent composition, the effect which provides a softness | flexibility and deodorizing property to a to-be-washed object was evaluated.

Flexibility-improving effect Preparation of evaluation cloth Commercially available cotton towel (manufactured by Toshin Co., Ltd.) was washed with a two-tank washing machine (Mitsubishi Electric) using a commercial detergent "Top Platinum Clear" (manufactured by Lion Corporation) containing an anionic surfactant as the main cleaning substrate. CW-C30A1-H) was used for pretreatment twice (detergent standard usage: 30 times the bath ratio. 45 ° C. tap water. After 10 minutes of washing, 10 minutes of water rinsing twice). What was dried for 20 hours under constant temperature and humidity conditions of 20 ° C. and 45% RH after the pretreatment was used as an evaluation fabric.

2. Treatment with a softening agent in the rinsing step during washing The evaluation fabric was treated with each liquid softening agent composition of Examples and Comparative Examples. The treatment is performed using a drum-type washing machine (HITACHI BD-V1, standard course), a commercially available detergent “Top Platinum Clear” (manufactured by Lion Corporation, standard use amount) and a liquid softener composition (cloth 1.5 Kg). 10 mL) was added. Under the present circumstances, the bath ratio (ratio of the mass of water to the mass of evaluation cloth) at the time of washing-rinsing was 5 to 6 times. After the treatment, after drying for 20 hours under constant temperature and humidity conditions of 20 ° C. and 45% RH, the flexibility of the evaluation fabric was evaluated by the following method.

3. Evaluation of the softener-treated cloth Using the evaluation cloth treated with the liquid softener composition of Comparative Example 1 as a control, a sensory pair comparison was performed by 10 professional panelists, and the evaluation criteria shown below were evaluated.

<Evaluation criteria>
+2: clearly softer than the control +1: slightly softer than the control 0: almost the same as the control -1: slightly softer than the control -2: clearly softer than the control

  The average score of 10 professional panelists was taken. The obtained average points are shown in the “flexibility” column of Tables 1-1 to 1-3.

Deodorant imparting effect 20 men in their 20s to 40s wiped sweat with an evaluation cloth prepared by the procedure described in column 1 of the above-mentioned “flexibility imparting effect” after running for 15 minutes. Then, using a standard amount of commercially available detergent (trade name “Top Platinum Clear”, manufactured by Lion Corporation), it was washed in a drum-type washing machine (HITACHI BD-V1, standard course) and indoors (20 ° C., relative humidity). 45%). The cycle of use (sweat wiping) / washing / drying was repeated 10 times, and then each evaluation cloth was divided into four equal parts and mixed randomly so that the amount of dirt was average. Four of these were used as a set for the deodorization evaluation test.

2. Immerse the above-mentioned evaluation cloth (a set of 4 sheets) in tap water, dehydrate it so that the water content becomes 100% ± 10%, put it in a plastic bag and leave it at 30 ° C. for 12 hours for evaluation of deodorization. An evaluation cloth was used.
Take out this evaluation cloth from the plastic bag, and nine new commercial cotton towels (one towel weighed about 70 g), as well as a standard amount of commercial detergent (trade name "Top Platinum Clear", Lion Corporation ), Using a drum-type washing machine (HITACHI BD-V1, standard course), and at the second rinse, each liquid softener composition of the examples and comparative examples is 10 mL for 1.5 kg of cloth. In addition, flexible processing was performed. After the softening treatment, it was dehydrated for 1 minute.
From the dehydrated evaluation cloth, the above-mentioned evaluation cloth (1 set of 4 sheets) was collected, placed in a plastic bag, and left at 30 ° C. for 12 hours.

3. Using the odor of the evaluation fabric treated with the softening agent of Comparative Example 1 as a control, the odor of the evaluation fabric treated with each liquid softening agent composition was evaluated according to the following evaluation criteria. The evaluation was performed by 10 expert panelists.

<Evaluation criteria>
+2: The unpleasant odor is suppressed much more than the control +1: The unpleasant odor is suppressed slightly compared to the control 0: The unpleasant odor equivalent to the control is −1: The unpleasant odor is suppressed slightly in the control -2: The control has much less unpleasant odor

The average score of 10 professional panelists was taken. The obtained average score is shown in the column of “Deodorization” in Tables 1-1 to 1-3.

  The present invention can be used in the field of liquid softening agents.

Claims (7)

A liquid softener composition comprising:
(A) amino-modified silicone, and (B) biguanide antibacterial agent and the following general formula (3):
_{^{R 12 -N [(CH 2)}} n -NH 2] 2 (3)
(Wherein, R ¹² represents an alkyl group having 8 to 18 carbon atoms, n is the number of 1-4.) Look contains one or more antimicrobial agents selected from the group consisting of compounds represented by ,
The mass of (A) / the mass of (B) is 1/1 to 100/1.
A liquid softener composition characterized by the above. 2. The liquid according to claim 1, further comprising (C) a quaternized product of an amine having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms which may be separated by an ester group or an amide group in the molecule. Softener composition. The liquid softening agent composition of Claim 2 whose mass of (C) component / (A) component is 40/1-2/1. The liquid softener according to any one of claims 2 and 3 , wherein {mass of component (C) + mass of component (A)} / mass of component (B) is 10/1 to 200/1. Composition. Further, (D) beta-ionone, including Jabanoru, methyl dihydro jasmonate, hexyl salicylate, [delta] -damascone, geraniol, one or more flavoring components selected from the group consisting of dihydromyrcenol and benzaldehyde, claim 1-4 The liquid softening agent composition of any one of these. (B) The liquid softening agent composition of any one of Claims 1-5 whose component is a compound represented by General formula (3). The liquid softener composition according to any one of claims 1 to 6 , wherein the component (B) is N, N-bis (3-aminopropyl) dodecylamine.