JP6018523B2 - Liquid softener composition - Google Patents

Description

  The present invention relates to a liquid softener composition for textiles such as clothing.

In a liquid softener composition for clothing, a quaternary ammonium salt type softener having two long-chain alkyl groups or long-chain alkenyl groups having about 12 to 24 carbon atoms is generally used as a main base. ing. In recent years, in order to consider the influence of chemical substances on the environment, those having higher biodegradability have been required, and esters between long-chain alkyl groups and long-chain alkenyl groups have been required. A flexible base having various structures including an alkyl group or an alkenyl group derived from a fatty acid having a bond or an amide bond has been developed.
For example, Patent Document 1 discloses a compound obtained by quaternizing an esterified product of methyldiethanolamine and a long chain fatty acid with an alkylating agent.
Patent Documents 2 and 3 disclose quaternary ammonium composed of a mixture of a monoester, a diester and a triester obtained by quaternizing an esterified product of triethanolamine and a long chain fatty acid with an alkylating agent. Techniques using compounds as softeners are disclosed.

Japanese National Patent Publication No. 11-507419 JP 2002-284747 A JP 2002-266242 A

As described above, flexible base materials containing an alkyl group or an alkenyl group derived from a fatty acid having an ester bond or an amide bond are known, but an esterified product of methyldiethanolamine and a long chain fatty acid is quaternized with an alkylating agent. In such a compound, since there is a problem that the same flexible effect as that of a conventional dilong chain alkyl or dilong chain alkenyldimethylammonium salt type cation compound is hardly exhibited, improvement is desired.
This invention makes it a subject to provide the liquid softening agent composition excellent in a softening effect.

The gist of the present invention is as follows.
5% by mass or more and 20% by mass or less of the following component (A), 1% by mass or more and 10% by mass or less of the following component (B), and the mass ratio of the component (A) to the component (B) [(A) / (B)] is a liquid softener composition of 1-9.
Component (A): A quaternary ammonium salt mixture composed of a compound represented by the following general formula (1), wherein 1% by mass or more and 40% by mass or less of compound (a1) and 60% of compound (a2) are contained in the mixture. A quaternary ammonium salt mixture containing from mass% to 99 mass%.

(In the formula (1), R ¹ represents an acyl group having 16 to 22 carbon atoms, R ² represents an acyl group having 16 to 22 carbon atoms or a hydrogen atom, and R ³ and R ⁴ represent 1 or more carbon atoms. Represents an alkyl group of 3 or less, and Z ⁻ represents an organic or inorganic anion.)
Compound (a1): A compound wherein R ¹ is the acyl group and R ² is a hydrogen atom.
Compound (a2): A compound wherein R ¹ and R ² are the acyl group.
Component (B): A quaternary ammonium salt mixture comprising a compound represented by the following general formula (2), wherein 1% by mass or more and 10% by mass or less of compound (b1), and 4 of compound (b2) in the mixture. A quaternary ammonium salt mixture containing 50% by mass or more and 50% by mass or less and 50% by mass or more and 95% by mass or less of compound (b3).

(In formula (2), R ⁵ represents an acyl group having 16 to 22 carbon atoms, R ⁶ and R ⁷ represent an acyl group or hydrogen atom having 16 to 22 carbon atoms, and R ⁸ represents 1 or more carbon atoms. Represents an alkyl group of 3 or less, and Z ⁻ represents an organic or inorganic anion.)
Compound (b1): A compound in which R ⁵ is the acyl group and R ⁶ and R ⁷ are hydrogen atoms.
Compound (b2): A compound in which R ⁵ and R ⁶ are the acyl group, and R ⁷ is a hydrogen atom.
Compound (b3): A compound wherein R ⁵ , R ⁶ and R ⁷ are the acyl group.

  ADVANTAGE OF THE INVENTION According to this invention, the liquid softening agent composition excellent in a softening effect can be provided.

The liquid softener composition of the present invention contains 5% by mass or more and 20% by mass or less of the following component (A), 1% by mass or more and 10% by mass or less of component (B), and (A) component and (B) component. Is a liquid softener composition having a mass ratio [(A) / (B)] of 1 to 9.
As a liquid softening agent composition of this invention, from a viewpoint of improving a softening effect, (A) component is 5 mass% or more, Preferably it is 8 mass% or more, and contains 20 mass% or less, Preferably it is 15 mass% or less. And (B) component is contained in an amount of 1% by mass or more, preferably 2% by mass or more, and 10% by mass or less, preferably 5% by mass or less.
Moreover, mass ratio [(A) / (B)] of (A) component and (B) component is 1-9, Preferably it is 1.5-5, More preferably, it is 1.5-4. Further, the mass ratio [(A) / (B)] is 1.5 to 4, and the component (A) is more preferably 8% by mass or more, and more preferably 15% by mass or less.

<(A) component>
The component (A) is a quaternary ammonium salt mixture composed of a compound represented by the following general formula (1), and the compound (a1) is contained in an amount of 1% by mass to 40% by mass, and the compound (a2) is contained in the mixture. A quaternary ammonium salt mixture containing 60% by mass or more and 99% by mass or less.

(In the formula (1), R ¹ represents an acyl group having 16 to 22 carbon atoms, R ² represents an acyl group having 16 to 22 carbon atoms or a hydrogen atom, and R ³ and R ⁴ represent 1 or more carbon atoms. Represents an alkyl group of 3 or less, and Z ⁻ represents an organic or inorganic anion.)

The compound (a1) is a compound in which R ¹ is the acyl group and R ² is a hydrogen atom, and is 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass in the component (A). % Or more and 40% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less.
The compound (a2) is a compound in which R ¹ and R ² are the acyl group, and is 60% by mass or more, preferably 70% by mass or more, more preferably 75% by mass or more in the component (A), and 99 mass% or less, Preferably it is 95 mass% or less, More preferably, it is contained 90 mass% or less.

As an acyl group in General formula (1), the residue remove | excluding OH from a C16-C18 fatty acid is preferable.
Examples of the fatty acids include stearic acid, palmitic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, palm oil fatty acid, sunflower oil fatty acid, soybean oil fatty acid, rapeseed oil fatty acid, safflower oil fatty acid, cottonseed oil fatty acid, corn oil fatty acid 1 type, or 2 or more types chosen from olive oil fatty acid, hydrogenated palm oil fatty acid, beef tallow fatty acid, and hardened beef tallow fatty acid can be used.
R ³ and R ⁴ are each an alkyl group having 1 to 3 carbon atoms, preferably a methyl group or an ethyl group.
Z ⁻ is an organic or inorganic anion, preferably a halogen ion, more preferably a chloro ion, an alkyl sulfate ion having 1 to 3 carbon atoms, a fatty acid ion having 12 to 18 carbon atoms, or a carbon number of 1 or more. It is a benzenesulfonic acid ion that may be substituted by 1 or more and 3 or less alkyl groups, and among these, a chloro ion is preferred.

Component (A) is a method of subjecting fatty acid and methyldiethanolamine to dehydration esterification (referred to as dehydration esterification method), or transesterification of fatty acid lower alkyl ester (lower alkyl is methyl group, ethyl group, propyl group) and methyldiethanolamine. The esterified product obtained by the reaction method (referred to as transesterification method) can be obtained by quaternization with an alkylating agent.
The molar ratio of fatty acid or fatty acid lower alkyl ester to methyldiethanolamine in the reaction for obtaining an esterified product is preferably 1.2 / 1 to 1.85 / 1, more preferably 1.3 / 1 to 1.8 / 1, Preferably it is 1.4 / 1-1.7 / 1.

The fatty acid or fatty acid lower alkyl ester preferably has a fatty acid composition obtained by saponifying oil selected from beef tallow, palm oil, sunflower oil, soybean oil, rapeseed oil, safflower oil, cottonseed oil, corn oil, and olive oil. From the viewpoint of softness, those obtained from beef tallow, palm oil and sunflower oil are more preferred.
Since these contain a large amount of alkenyl groups having two or more carbon-carbon unsaturated bonds, for example, crystallization as described in JP-A-4-306296 or JP-A-6-41578 The ratio of fatty acids containing two or more carbon-carbon unsaturated bonds is controlled by distillation under reduced pressure of the methyl ester or by the selective hydrogenation reaction described in JP-A-8-99036. It can be manufactured by a method or the like.
When a selective hydrogenation reaction is performed, a mixture of geometric isomers of unsaturated bonds is obtained, and the cis / trans ratio (molar ratio) of the fatty acid geometric isomers is preferably 25/75 to 100 / 0, more preferably 50/50 to 95/5.

[Method for preparing component (A)]
First, the dehydration esterification method will be described. In the dehydration esterification method, the esterification reaction temperature is preferably 140 ° C. or higher and 230 ° C. or lower, and the reaction is preferably performed while removing condensed water.
From the viewpoint of promoting the reaction, a normal esterification catalyst may be used. For example, an inorganic acid such as sulfuric acid or phosphoric acid, an inorganic oxide such as tin oxide or zinc oxide, or an alcoholate such as tetrapropoxy titanium is selected. Can do.
The progress of the reaction can be confirmed by measuring the acid value (AV) and saponification value (SV) by the method described in JIS K 0070-1992, and AV is preferably 10 mgKOH / g or less, more preferably 6 mgKOH. The esterification reaction is terminated when it becomes less than / g.

Next, the transesterification method will be described. The reaction in the transesterification method is preferably carried out while removing lower alcohol produced at a temperature of 50 ° C. or higher and 150 ° C. or lower, more preferably 100 ° C. or higher and 150 ° C. or lower.
From the viewpoint of promoting the reaction, it is also possible to use an inorganic alkali such as sodium hydroxide or potassium hydroxide, or an alkoxy catalyst such as methylate or ethylate.
The progress of the reaction can be judged by directly quantifying the amount of fatty acid lower alkyl ester using gas chromatography or the like, and gas chromatography is performed on the fatty acid lower alkyl ester charged with unreacted fatty acid lower alkyl ester. On the chart, it is preferably terminated when it is 10 area% or less, more preferably 6 area% or less.
SV of the obtained ester compound is preferably 120 mgKOH / g or more and 200 mgKOH / g or less, more preferably 140 mgKOH / g or more and 190 mgKOH / g or less.

  By the dehydration esterification method and transesterification method, a mixture of tertiary amine compounds which are fatty acid methyldiethanolamine esters is obtained. A quaternary ammonium salt mixture (component (A)) can be obtained by quaternizing the mixture of the tertiary amine compounds with an alkylating agent shown below.

Hereinafter, the quaternization method of the ester compound obtained by the said method is demonstrated. Examples of the alkylating agent that can be used for the quaternization include methyl chloride, methyl bromide, methyl iodide, dimethyl sulfate, diethyl sulfate, and the like. Among these, methyl chloride is preferable.
When methyl chloride is used as the alkylating agent, it is not necessary to use a solvent, but when using a solvent, ethanol, isopropanol, or the like can be used. The amount of the solvent used is preferably 10% by mass or more and 50% by mass or less based on the ester compound.
The reaction is preferably carried out by charging the reaction solution into a pressure reactor such as a titanium autoclave and injecting methyl chloride at a reaction temperature of 30 ° C. or higher and 120 ° C. or lower under sealing. At this time, since a part of methyl chloride may be decomposed to generate hydrochloric acid, it is preferable to add a small amount of an alkaline agent from the viewpoint of efficiently proceeding the reaction.
The amount of methyl chloride with respect to 1 equivalent of the amino group of the ester compound is preferably 0.95 equivalents or more and 1.5 equivalents or less.

When dimethyl sulfuric acid or diethyl sulfuric acid is used as the alkylating agent, it is not necessary to use a solvent, but when using a solvent, ethanol, isopropanol, or the like can be used. The amount of the solvent used is preferably 10% by mass or more and 50% by mass or less based on the ester compound.
The reaction can be carried out by heating and mixing the reaction solution at 40 ° C. or higher and 100 ° C. or lower and adding at least one of dimethyl sulfate and diethyl sulfate dropwise.
The amount of at least one of dimethyl sulfate and diethyl sulfate with respect to 1 equivalent of amino group of the ester compound is preferably 0.9 equivalent to 1.1 equivalent, more preferably 0.95 equivalent to 0.99 equivalent.
The total amine value after the reaction is preferably 1 mgKOH / g or more and 5 mgKOH / g or less.
As a quaternization method for preparing the component (A), a method using methyl chloride as an alkylating agent is preferable.

<(B) component>
The component (B) is a quaternary ammonium salt mixture composed of a compound represented by the following general formula (2), wherein the compound (b1) is contained in an amount of 1% by mass to 10% by mass, and the compound (b2) is added. It is a quaternary ammonium salt mixture containing 4% by mass to 50% by mass and 50% by mass to 95% by mass of the compound (b3).

(In formula (2), R ⁵ represents an acyl group having 16 to 22 carbon atoms, R ⁶ and R ⁷ represent an acyl group or hydrogen atom having 16 to 22 carbon atoms, and R ⁸ represents 1 or more carbon atoms. Represents an alkyl group of 3 or less, and Z ⁻ represents an organic or inorganic anion.)

Compound (b1) is a compound in which R ⁵ is the acyl group, R ⁶ and R ⁷ are hydrogen atoms, and is 1% by mass or more and 10% by mass or less, preferably in component (B) 8 mass% or less, More preferably, 7 mass% or less is contained.
The compound (b2) is a compound in which R ⁵ and R ⁶ are the acyl groups and R ⁷ is a hydrogen atom, and is 4% by mass or more, preferably 5% by mass or more, more preferably in the component (B). Is 8% by mass or more and 50% by mass or less, preferably 45% by mass or less, more preferably 40% by mass or less.
The compound (b3) is a compound in which R ⁵ , R ⁶ and R ⁷ are the acyl group, and is 50% by mass or more, preferably 55% by mass or more, more preferably 60% by mass or more in the component (B). And 95% by mass or less, preferably 94% by mass or less, more preferably 93% by mass or less.

The acyl group in the general formula (2) is preferably a residue obtained by removing OH from a fatty acid having 16 to 18 carbon atoms.
Examples of the fatty acids include stearic acid, palmitic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, palm oil fatty acid, sunflower oil fatty acid, soybean oil fatty acid, rapeseed oil fatty acid, safflower oil fatty acid, cottonseed oil fatty acid, corn oil fatty acid 1 type, or 2 or more types chosen from olive oil fatty acid, hydrogenated palm oil fatty acid, beef tallow fatty acid, and hardened beef tallow fatty acid can be used.
R ⁸ is an alkyl group having 1 to 3 carbon atoms, preferably a methyl group or an ethyl group.
Z ⁻ is an organic or inorganic anion, preferably a halogen ion, more preferably a chloro ion, an alkyl sulfate ion having 1 to 3 carbon atoms, a fatty acid ion having 12 to 18 carbon atoms, or a carbon number of 1 or more. A benzenesulfonic acid ion which may be substituted with 1 to 3 alkyl groups having 3 or less alkyl groups. Among them, an alkyl sulfate ion having 1 to 3 carbon atoms is preferred, and a methyl sulfate ion, ethyl A sulfate ester ion is more preferred.

Component (B) is a method in which a fatty acid and triethanolamine are subjected to a dehydration esterification reaction (referred to as a dehydration esterification method), or a fatty acid lower alkyl ester (lower alkyl is a methyl group, ethyl group, propyl group) and triethanolamine. The esterified product obtained by the transesterification method (referred to as transesterification method) can be obtained by quaternizing with an alkylating agent.
The molar ratio of the fatty acid or fatty acid lower alkyl ester to triethanolamine in the reaction for obtaining the esterified product is 2.2 / 1 to 3.2 / 1, preferably 2.5 / 1 to 3.0 / 1.

The fatty acid or fatty acid lower alkyl ester preferably has a fatty acid composition obtained by saponifying oil selected from beef tallow, palm oil, sunflower oil, soybean oil, rapeseed oil, safflower oil, cottonseed oil, corn oil, and olive oil. From the viewpoint of softness, those obtained from beef tallow, palm oil and sunflower oil are more preferred.
Since these contain a large amount of alkenyl groups having two or more carbon-carbon unsaturated bonds, for example, crystallization as described in JP-A-4-306296 or JP-A-6-41578 The ratio of fatty acids containing two or more carbon-carbon unsaturated bonds can be obtained by performing distillation under reduced pressure as described above, or by performing a selective hydrogenation reaction described in JP-A-8-99036. It can be manufactured by a controlling method or the like.
When a selective hydrogenation reaction is performed, a mixture of geometric isomers of unsaturated bonds is obtained, and the cis / trans ratio (molar ratio) of the fatty acid geometric isomers is preferably 25/75 to 100 / 0, more preferably 50/50 to 95/5.

[Method for preparing component (B)]
First, the dehydration esterification method will be described. In the dehydration esterification method, the esterification reaction temperature is preferably 140 ° C. or higher and 230 ° C. or lower, and the reaction is preferably performed while removing condensed water.
From the viewpoint of promoting the reaction, a normal esterification catalyst may be used. For example, an inorganic acid such as sulfuric acid or phosphoric acid, an inorganic oxide such as tin oxide or zinc oxide, or an alcoholate such as tetrapropoxy titanium is selected. Can do.
The progress of the reaction can be confirmed by measuring the acid value (AV) and saponification value (SV) by the method described in JIS K 0070-1992, and AV is preferably 15 mgKOH / g or less, more preferably 10 mgKOH. The esterification reaction is terminated when it becomes less than / g.

Next, the transesterification method will be described. The reaction in the transesterification method is preferably carried out while removing lower alcohol produced at a temperature of 50 ° C. or higher and 150 ° C. or lower, more preferably 100 ° C. or higher and 150 ° C. or lower.
From the viewpoint of promoting the reaction, it is also possible to use an inorganic alkali such as sodium hydroxide or potassium hydroxide, or an alkoxy catalyst such as methylate or ethylate.
The progress of the reaction can be judged by directly quantifying the amount of fatty acid lower alkyl ester using gas chromatography or the like, and gas chromatography is performed on the fatty acid lower alkyl ester charged with unreacted fatty acid lower alkyl ester. The reaction is terminated when it is preferably 15 area% or less, more preferably 10 area% or less on the chart.

  By the dehydration esterification method and transesterification method, a mixture of tertiary amine compounds which are fatty acid triethanolamine esters is obtained. A quaternary ammonium salt mixture (component (B)) can be obtained by quaternizing the mixture of tertiary amine compounds with an alkylating agent shown below.

Hereinafter, the quaternization method of the ester compound obtained by the said method is demonstrated. Examples of the alkylating agent that can be used for the quaternization include methyl chloride, dimethyl sulfate, and diethyl sulfate. Among these, dimethyl sulfate is preferable.
When methyl chloride is used as the alkylating agent, it is not necessary to use a solvent, but when using a solvent, a solvent such as ethanol or isopropanol is used in an amount of 10% by mass or more and 50% by mass with respect to the ester compound. The mixed solution is charged into a pressure reactor such as a titanium autoclave, and reacted by injecting methyl chloride at a reaction temperature of 30 ° C. or higher and 120 ° C. or lower under sealing. At this time, since a part of methyl chloride may be decomposed and hydrochloric acid may be generated, it is preferable to add a small amount of an alkali agent from the viewpoint of allowing the reaction to proceed efficiently.
The amount of methyl chloride with respect to 1 equivalent of the amino group of the ester compound is preferably 1 equivalent to 1.5 equivalents.

When dimethyl sulfuric acid or diethyl sulfuric acid is used as the alkylating agent, it is not necessary to use a solvent, but when using a solvent, ethanol, isopropanol, or the like can be used. The amount of the solvent used is preferably 10% by mass or more and 50% by mass or less based on the ester compound.
The reaction can be carried out by heating and mixing the reaction solution at 40 ° C. or higher and 100 ° C. or lower and adding at least one of dimethyl sulfate and diethyl sulfate dropwise.
The amount of at least one of dimethyl sulfate and diethyl sulfate with respect to 1 equivalent of amino group of the ester compound is preferably 0.9 equivalent to 1.1 equivalent, more preferably 0.95 equivalent to 0.99 equivalent.
The total amine value after the reaction is preferably 1 mgKOH / g or more and 5 mgKOH / g or less.
As the quaternization method for preparing the component (B), a method using one or more alkylating agents selected from dimethyl sulfate and diethyl sulfate is preferable.
In addition, although (A) component and (B) component contain the amine derived from a raw material, a fatty acid, a by-product derived from these, and the amine compound which is not quaternized slightly in relation to the said manufacturing method. Even if these are contained in a small amount, there is no problem because the effects of the present invention are not impaired.

The liquid softener composition of the present invention is preferably composed of (A) component, (B) component and water, and as water, sterilized water obtained by treating deionized water with a small amount of hypochlorite is used. More preferred. The deionized water can be appropriately used so that the balance, that is, the softener composition has a predetermined concentration.
In addition, in the preparation process of the component (A) and the component (B), unreacted alkanolamine and its quaternized product, various tertiary amine compounds having different degrees of esterification with fatty acids, fatty acids, solvents and the like are mixed. As long as this effect is not affected, it may be contained in the liquid softening agent composition of the present invention.

<PH and viscosity>
The pH of the liquid softener composition is preferably 2.0 or more, more preferably 2.5 or more, and preferably 4.0 or less, more preferably 3.5 or less.
When the pH is within the above range, the fragrance and the remaining fragrance of the treated fiber product are improved, and the storage stability is also improved.
The pH value is a value measured at 30 ° C. in accordance with “JIS K 3362; Item 8.3 of 2008”.
The pH can be adjusted with an alkali agent and an acid agent, and organic acids such as citric acid and succinic acid described later may be used as the acid agent.

The viscosity of the liquid softening agent composition is preferably 5 mPa · s or more, more preferably 10 mPa · s or more, and preferably 200 mPa · s or less, more preferably 150 mPa, from the viewpoint of improving handleability during use. -S or less.
The viscosity was measured using a B-type viscometer, No. 1-No. Using one of the three rotors suitable for the viscosity of the solution to be measured, the indicated value is 1 minute after the start of measurement at 60 r / min, and the temperature of the liquid softener composition is adjusted to 30 ± 1 ° C. It is a measured value.

<Other active ingredients>
It is preferable that the liquid softening agent composition of this invention contains the component shown below.
[(C) Nonionic surfactant]
The liquid softener composition of the present invention preferably contains a nonionic surfactant as the component (C).
The component (C) preferably has an alkyl group or alkenyl group hydrophobic group having 8 to 20 carbon atoms, and has an alkyleneoxy group, more preferably an organic group selected from an ethyleneoxy group and a hydroxy group. Nonionic surfactants, more preferably, nonionic surfactants represented by the following general formula (3) are exemplified.

R ^3a -A-[(R ^3b O) _p -R ^3c ] _q (3)
(In the formula, R ^3a is preferably an alkyl group or alkenyl group having 8 to 18 carbon atoms, more preferably 10 to 16 carbon atoms, and R ^3b is preferably an alkylene group having 2 or 3 carbon atoms, More preferably, it represents an ethylene group, R ^3c represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom, and p is the average number of added moles of an alkyleneoxy group, preferably 2 to 100, more preferably Represents a number of 5 to 80, more preferably 5 to 60, still more preferably 10 to 60, A represents —O—, —COO—, —CONH—, or —NH—, and A represents — When O-, -COO-, -CONH- or -NH-, q is 1, and when A is -CON <or -N <, q is 2.]

  Specific examples of the compound of the general formula (3) include compounds represented by the following formulas (3-1) to (3-3).

R ^3a —O— (C ₂ H ₄ O) _r —H (3-1)
(In formula (3-1), R ^3a has the same ^{meaning as} in formula (3). R is the average number of moles added of the ethyleneoxy group, preferably 8 or more and 100 or less, more preferably 10 or more and 60 or less. Number.)

R ^3a —O (C ₂ H ₄ O) _s (C ₃ H ₆ O) _t —H (3-2)
(In formula (3-2), R ^3a has the same ^{meaning as} in formula (3). S is the average number of moles of ethyleneoxy group represented by “C ₂ H ₄ O”, and t is “C ₃ H _6. The average number of moles of propyleneoxy group represented by “O”, each independently, preferably more than 0 and 50 or less, more preferably 2 or more and 40 or less, and even more preferably 5 or more and 40 or less. More preferably, s is 5 or more and 40 or less, and t is more than 0 and 3 or less, and (C ₂ H ₄ O) and (C ₃ H ₆ O) are not limited in order and are random It may be an adduct or a block adduct.)

(In formula (3-3), R ^3a has the same ^{meaning as} in formula (3), A represents —N <or —CON <, u and w represent the average number of moles of ethyleneoxy group added, and v and z represents the average number of moles added of propyleneoxy groups, and the ethyleneoxy group and propyleneoxy group may be random addition or block addition, and the ethyleneoxy groups are each independently a number of 0 to 40; The group is a number of 0 to 5, and u + v + w + z preferably represents a number of 5 to 60, more preferably 5 to 40. R ^3d and R ^3e are each independently a hydrogen atom or a carbon number of 1 to 3 Represents an alkyl group of

As a nonionic surfactant (C), the nonionic surfactant shown by the said General formula (3) is preferable, and the polyoxyethylene alkyl ether shown by General formula (3-1) is more preferable.
By using the component (C), the viscosity of the liquid softening agent composition is lowered, so that the handling from the mixing step to the filling step becomes easy.
The content of the component (C) in the liquid softening agent composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and preferably 5% by mass or less, more preferably 3%. It is below mass%.

[(D) Water-soluble organic solvent]
The liquid softener composition of the present invention preferably contains a water-soluble organic solvent (D) from the viewpoints of stability and viscosity. In addition, the water-soluble organic solvent in this specification means what melt | dissolves 20g or more with respect to 100g of deionized water of 20 degreeC.
Examples of the water-soluble organic solvent include one or more selected from propylene glycol, ethylene glycol, glycerin, diethylene glycol, monoethylene glycol monophenyl ether, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, isopropanol, and ethanol. Can be used. Among these, propylene glycol, ethylene glycol, glycerin and ethanol are preferable.
The amount of the water-soluble organic solvent (D) in the liquid softener composition is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, and preferably 10% by mass or less, more preferably Is 8% by mass.

[(E) inorganic salt]
The liquid softening agent composition of the present invention preferably contains an inorganic salt as the component (E) from the viewpoint of improving storage stability.
As the inorganic salt, one or more selected from sodium chloride, calcium chloride, and magnesium chloride can be used from the viewpoint of storage stability. Of these, calcium chloride is preferred.
The amount of the inorganic salt (E) in the liquid softening agent composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and preferably 2.0% by mass or less, more preferably Is 1.5% by mass or less, more preferably 1.0% by mass or less.

[(F) Other surfactants]
The liquid softener composition of the present invention preferably contains a surfactant (F) other than the component (A) and the component (B) from the viewpoint of storage stability, and the component (F) is a cationic interface. The activator (F-1) is more preferable.
The component (F-1) has 1 or 2 alkyl groups or alkenyl groups having 10 to 22 carbon atoms, and the remaining organic group may have a hydroxy group. Examples thereof include tertiary amine compounds having 4 or less alkyl groups or benzyl groups, preferably methyl groups, their acid salts, and quaternary ammonium salt compounds. In addition, when preparing the quaternary ammonium salt compound as (F-1) component, the alkylating agent used for preparation of (A) component can be used.
When it aims at providing a bactericidal effect to a softening agent, it is preferable to use the (F-1) component which has one benzyl group.

As specific (F-1) component, at least 1 sort (s) as described in the following (i)-(iii) is preferable, and (ii) is more preferable.
(I) a dilong chain alkyl or dilong chain alkenyldimethylammonium salt having an alkyl group or an alkenyl group having 10 to 22 carbon atoms,
(Ii) a mono long chain alkyl or mono long chain alkenyl trimethylammonium salt having an alkyl group or an alkenyl group having 10 to 22 carbon atoms,
(Iii) Mono long chain alkyldimethyl monobenzylammonium salt having an alkyl group or an alkenyl group having 10 to 22 carbon atoms

More specific examples of the component (F-1) include lauryltrimethylammonium chloride salt, didecyldimethylammonium chloride salt, and lauryldimethylbenzylammonium chloride salt.
The content of (F-1) in the liquid softening agent composition is preferably 0.01% by mass or more from the viewpoint of reducing the viscosity and improving the bactericidal property, and the stability and the softening effect are reduced. From the viewpoint of preventing this, it is preferably 2.0% by mass or less.

Moreover, as other surfactant, surfactant (F-2) other than the said surfactant which can generally be mix | blended with a softening agent can also be used.
Examples of (F-2) include amphoteric surfactants, such as C12-22 alkylamidopropylcarbobetaine, C12-22 alkylamidopropylsulfobetaine, C12-22 alkylcarbobetaine, C12-22 alkylsulfobetaine, C10-18 alkyl dimethylamine oxide etc. are mentioned.
Here, C12-22 indicates that the carbon number is 12-22, and other notations have the same meaning. (F-2) The density | concentration of a component can be suitably adjusted as needed.

[(G) Silicone]
The liquid softener composition of the present invention preferably contains a water-insoluble silicone compound as the component (G). In the present specification, the water-insoluble silicone compound refers to a silicone compound having an amount of 1 g or less dissolved in 1 L of ion-exchanged water at 20 ° C.
Examples of water-insoluble silicone compounds include dimethylpolysiloxane, quaternary ammonium-modified dimethylpolysiloxane, amino-modified dimethylpolysiloxane, amide-modified dimethylpolysiloxane, epoxy-modified dimethylpolysiloxane, carboxy-modified dimethylpolysiloxane, and polyoxyalkylene-modified dimethylpolysiloxane. And silicone compounds such as fluorine-modified dimethylpolysiloxane.

The molecular weight of silicone is preferably 1,000 or more, more preferably 3,000 or more, still more preferably 5,000 or more, and preferably 1,000,000 or less.
The viscosity at 25 ° C. of the silicone is preferably 2 mm ² / s or more, more preferably 500 mm ² / s or more, still more preferably 1,000 mm ² / s or more, and preferably 1,000,000 mm ² / s or less. is there.

  The amino equivalent (amino equivalent is the molecular weight per nitrogen atom) of the amino-modified dimethylpolysiloxane is preferably 1,500 g / mol or more, more preferably 2,500 g / mol or more, and still more preferably 3,000 g / mol. It is above, and is preferably 40,000 g / mol or less, more preferably 20,000 g / mol or less, still more preferably 10,000 g / mol or less.

  The content of the component (G) in the liquid softening agent composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, from the viewpoint of giving a refreshing feeling to the finish of the textile product. From the viewpoint of improving dispersibility, it is preferably 5% by mass or less.

[(H) acid agent]
The liquid softener composition of the present invention preferably contains an acid agent. From the viewpoint of suppressing decomposition due to hydrolysis of the quaternary ammonium compound, the pH of the liquid softener composition at 30 ° C. is 2. It is preferable to mix an acid agent so that it may be 0 or more and 4.0 or less.
Examples of the acid include inorganic acids and organic acids. Specific examples of the inorganic acid include hydrochloric acid and sulfuric acid.
Specific examples of the organic acid include a monovalent or polyvalent carboxylic acid having 1 to 10 carbon atoms, or a monovalent or polyvalent sulfonic acid having 1 to 20 carbon atoms. More specifically, methylsulfuric acid, ethylsulfuric acid, p-toluenesulfonic acid, (o-, m-, p-) xylenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, glycolic acid, ethylenediaminetetraacetic acid, citric acid, Examples include benzoic acid, salicylic acid, and succinic acid.
In addition, what is necessary is just to mix | blend an acid agent in the grade which does not impair stability in the range which pH becomes the said range. Moreover, a compounding quantity can be suitably adjusted with the kind and quantity of (A) component.

[(I) Fatty acid]
The liquid softener composition of the present invention contains an unreacted product during the synthesis of the component (A), a fatty acid as a decomposition product of the component (A) and the component (B), but from the viewpoint of improving the softening effect, Furthermore, you may mix | blend a fatty acid.
The fatty acid is preferably a saturated or unsaturated fatty acid having 12 to 22 carbon atoms, such as lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, erucic acid, and behenic acid, and palmitic acid. , Stearic acid, oleic acid, and linoleic acid are more preferable.

[(J) Fragrance]
From the viewpoint of realizing a feeling of use, the liquid softener composition of the present invention is preferably blended with a fragrance, and various natural or synthetic fragrances generally used in softener compositions can be used.
Examples of the fragrances include ethers such as fatty acid ethers and aromatic ethers, oxides such as fatty acid oxides and terpene oxides, acetals, ketals, phenols, phenol ethers, fatty acids, terpene carboxylic acids, hydrogen Synthetic fragrances such as acid-containing aromatic carboxylic acids, acids such as aromatic carboxylic acids, acid amides, nitromusks, nitriles, amines, pyridines, quinolines, pyrroles, indoles, and the like, and animals and plants A blended fragrance containing at least one of a natural fragrance, a natural fragrance, and a synthetic fragrance can be used.
Specifically, the fragrances described in 1969, Chemical Industries Daily, published by Motoichi Into, “Synthetic Fragrance Chemistry and Product Knowledge”, 1969 MONTCLAIR, published by STEFFEN ARCTANDER, published by NJ, “Perfume and Flavor Chemicals” can be used.

From the viewpoint of improving the fragrance sustainability and the remaining fragrance, the fragrance may be blended in microcapsules. The fragrance microcapsule is a spherical substance that is made by wrapping the fragrance of the core material with a wall material. Its role is to protect the fragrance of the core material, and when the capsule is subjected to physical force, the capsule wall breaks and the core It releases the fragrance of the substance.
Regarding the manufacturing method of the microcapsule, “Making and using microcapsules” (Masumi Koishi et al., Industrial Research Committee, published in October 2005), JP-A-2008-63575, JP-A-2006-249326, The methods described in Kaihei 11-216354, JP-A-5-222672, etc. can be employed.
Further, from the viewpoint of improving scent sustainability and residual fragrance, for example, a silicate ester of an alcohol fragrance described in JP-A-2009-256818 can be used in combination.

[Other ingredients]
Examples of other optional components include the following.
A known antioxidant such as BHT can be used from the viewpoint of suppressing deterioration of the substrate and the generation of odor due to decomposition.
From the aesthetic point of view, it is possible to blend dyes and pigments that are generally blended in softeners, to eliminate concerns about coloring during long-term storage.
Moreover, antibacterial / antifungal agents such as proxel can be blended. Furthermore, from the viewpoint of preventing hue change and fragrance alteration during long-term storage and adjusting pH, chelating agents such as ethylenediaminetetraacetic acid, citric acid and salts thereof can be blended.

In addition to the embodiment described above, the present invention discloses the following liquid softener composition.
<1> 5% by mass or more and 20% by mass or less of the following (A) component, 1% by mass or more and 10% by mass or less of the following (B) component, and the mass ratio of the (A) component and the (B) component [( A) / (B)] is a liquid softener composition of 1-9.
Component (A): A quaternary ammonium salt mixture composed of a compound represented by the following general formula (1), wherein 1% by mass or more and 40% by mass or less of compound (a1) and 60% of compound (a2) are contained in the mixture. A quaternary ammonium salt mixture containing from mass% to 99 mass%.

(In the formula (1), R ¹ represents an acyl group having 16 to 22 carbon atoms, R ² represents an acyl group having 16 to 22 carbon atoms or a hydrogen atom, and R ³ and R ⁴ represent 1 or more carbon atoms. Represents an alkyl group of 3 or less, and Z ⁻ represents an organic or inorganic anion.)
Compound (a1): A compound wherein R ¹ is the acyl group and R ² is a hydrogen atom.
Compound (a2): A compound wherein R ¹ and R ² are the acyl group.
Component (B): A quaternary ammonium salt mixture comprising a compound represented by the following general formula (2), wherein 1% by mass or more and 10% by mass or less of compound (b1), and 4 of compound (b2) in the mixture. A quaternary ammonium salt mixture containing 50% by mass or more and 50% by mass or less and 50% by mass or more and 95% by mass or less of compound (b3).

(In formula (2), R ⁵ represents an acyl group having 16 to 22 carbon atoms, R ⁶ and R ⁷ represent an acyl group or hydrogen atom having 16 to 22 carbon atoms, and R ⁸ represents 1 or more carbon atoms. Represents an alkyl group of 3 or less, and Z ⁻ represents an organic or inorganic anion.)
Compound (b1): A compound in which R ⁵ is the acyl group and R ⁶ and R ⁷ are hydrogen atoms.
Compound (b2): A compound in which R ⁵ and R ⁶ are the acyl group, and R ⁷ is a hydrogen atom.
Compound (b3): A compound wherein R ⁵ , R ⁶ and R ⁷ are the acyl group.

<2> The component (A) is preferably contained in an amount of 8% by mass or more, and preferably 15% by mass or less, and the component (B) is preferably contained in an amount of 2% by mass or more, and preferably 5% by mass or less. The liquid softening agent composition as described in <1>.
<3> The mass ratio [(A) / (B)] of the component (A) and the component (B) is preferably 1.5 to 5.0, more preferably 1.5 to 4.0. The liquid softening agent composition as described in <1> or <2>.

<4> The compound (a1) is preferably contained in the component (A) in an amount of 5% by mass or more, more preferably 10% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less. (A2) is preferably contained in the component (A) in an amount of 70% by mass or more, more preferably 75% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less. 3> Liquid softening agent composition in any one of.
<5> The compound (b1) is contained in the component (B) in an amount of 1% by mass or more, and preferably 8% by mass or less, more preferably 7% by mass or less, and the compound (b2) is contained in the component (B). Is preferably 5% by mass or more, more preferably 8% by mass or more, and preferably 45% by mass or less, more preferably 40% by mass or less, and the compound (b3) is preferably 55% in the component (B). The liquid softening agent composition according to any one of <1> to <4>, which is contained by mass% or more, more preferably 60% by mass or more, and preferably 94% by mass or less, more preferably 93% by mass or less.

<6> The liquid softener composition according to any one of <1> to <5>, further containing a nonionic surfactant (C) in an amount of 0.1% by mass to 5% by mass.
<7> Component (C) is preferably an organic group selected from an alkyleneoxy group, more preferably an ethyleneoxy group and a hydroxy group, having a hydrophobic group of an alkyl group or an alkenyl group having 8 to 20 carbon atoms The liquid softener composition as described in <6> which has.

<8> The liquid softener composition according to any one of <1> to <7>, further containing 1.0% by mass or more and 10% by mass or less of the water-soluble organic solvent (D).
<9> The liquid softener composition according to <8>, wherein the water-soluble organic solvent (D) is one or more selected from propylene glycol, ethylene glycol, glycerin, and ethanol.

<10> The liquid softener composition according to any one of <1> to <9>, further containing 0.01% by mass or more and 2.0% by mass or less of the inorganic salt (E).
<11> The liquid softener composition according to <10>, wherein the inorganic salt (E) is one or more selected from sodium chloride, calcium chloride, and magnesium chloride.

<12> The pH of the liquid softening agent composition is preferably 2.0 or more, more preferably 2.5 or more, and preferably 4.0 or less, more preferably 3.5 or less, <1 >-<11> The liquid softening agent composition in any one of.
<13> The viscosity of the liquid softening agent composition is preferably 5 mPa · s or more, more preferably 10 mPa · s or more, and 200 mPa · s or less, more preferably 150 mPa · s or less, <1> to <12> The liquid softening agent composition according to any one of the above.

The components used in Examples and Comparative Examples are as follows.
<(A) component>
After esterifying a fatty acid (palmitic acid / stearic acid / oleic acid / others = 11% by mass / 66% by mass / 20% by mass / 3% by mass) with respect to 1 mol of methyldiethanolamine with 1.7 mol, methyl chloride 0 A quaternary ammonium salt compound quaternized with 97 equivalents (a1 / a2 = 21% by mass / 79% by mass).

<(B) component>
(B-1): Ester of fatty acid (palmitic acid / stearic acid / oleic acid / others = 28% by mass / 32% by mass / 32% by mass / 8% by mass) with respect to 1 mol of triethanolamine by 3.0 mol And then quaternized with 0.97 equivalents of dimethyl sulfate (b1 / b2 / b3 = 1 mass% / 6 mass% / 93 mass%).

  (B-2): Fatty acid (palmitic acid / stearic acid / oleic acid / others = 43% by mass / 25% by mass / 26% by mass / 6% by mass) is ester by 2.7 mol with respect to 1 mol of triethanolamine. And then quaternized with 0.95 equivalent of dimethyl sulfate (b1 / b2 / b3 = 1.5 mass% / 19 mass% / 79.5 mass%).

  (B-3): Ester of fatty acid (palmitic acid / stearic acid / oleic acid / others = 28% by mass / 32% by mass / 32% by mass / 8% by mass) with respect to 1 mol of triethanolamine at 2.5 mol And then quaternized with 0.97 equivalents of dimethyl sulfate (b1 / b2 / b3 = 5% by mass / 45% by mass / 50% by mass).

<(B ′) Component: Comparative Component of (B) Component>
(B′-1): 1.7 mol of fatty acid (palmitic acid / stearic acid / oleic acid / others = 43% by mass / 25% by mass / 26% by mass / 6% by mass) with respect to 1 mol of triethanolamine. After esterification, a quaternary ammonium salt compound (b1 / b2 / b3 = 22 mass% / 48 mass% / 30 mass%) quaternized with 0.95 equivalent of dimethyl sulfate.

<(C) component>
(C-1): Addition of ethylene oxide to linear primary alcohol having 12 to 14 carbon atoms
Nonionic surfactant (average added moles of ethylene oxide: 50 moles)
(C-2): Addition of ethylene oxide to a linear secondary alcohol having 12 to 14 carbon atoms
Nonionic surfactant (average added moles of ethylene oxide: 40 moles)

<(D) component>
Ethylene glycol <(E) component>
Calcium chloride

Examples 1-8 and Comparative Examples 1-4
According to the composition shown in Table 1, a liquid softener composition was prepared by the following method. Moreover, about the obtained liquid softening agent composition, the softness | flexibility was evaluated in the following way. The results are shown in Table 1.

<Preparation of liquid softener composition>
In a 300 mL glass beaker (inner diameter: 7 cm, height: 11 cm), deionized amount equivalent to 95% by mass of water necessary for the mass of the liquid softener composition to be finally prepared to be 200 g. Stirring blades (turbine-type stirring blades, three blades, blade length 2 cm) attached to a three-one motor (manufactured by Shinto Kagaku Co., Ltd., “TYPE HEIDON 1200G”) with water (60 ° C.) and component (D) It was set at a height of 1 cm from the bottom of the glass beaker and stirred and mixed until a uniform solution was obtained at a rotation speed of 150 r / min.
Next, after the (A) component, the (B) component, and the (C) component, which were uniformly mixed in advance at 60 ° C., were added, the (E) component was immediately added, and the rotation speed was 150 r / min. Stir for minutes. Then, it heated until the temperature of the content became 70 degreeC with the water bath, and stirred for 15 minutes at the rotation speed of 400 r / min.
Finally, after cooling in a water bath containing ice water until the temperature of the contents reaches 25 ° C., add the fragrance and ion exchange water necessary for the concentration of each component to be the concentration shown in Table 1. The mixture was stirred at 25 ° C. and a rotation speed of 200 r / min for 15 minutes to obtain a liquid softener composition.

<Method for evaluating flexibility effect>
(1) Pre-treatment method of evaluation towel Using a commercially available powder detergent (manufactured by Kao Corporation, “Attack” manufactured in May 2012), a commercially available cotton towel (manufactured by Takei Towel, “TW-220”) 24 A series of washing steps were repeated 5 times using a Hitachi fully automatic washing machine NW-6CY (attack usage amount 34 g, standard course, water volume 45 L, water temperature 20 ° C., washing time 10 minutes, twice for rinsing). Then, it dried on 20 degreeC and 45% RH conditions.

(2) Softening method of evaluation towel Cotton which was pretreated by the method of (1) above was poured 4.5L of water at 20 ° C into a National electric bucket washing machine (MiniMini, model number "NA-35"). Two towels were added and stirred for 1 minute. After stirring, the liquid softener composition shown in Table 1 was added in an amount of 10 ml per 1.5 kg of cotton towel, and treated for 5 minutes while stirring. After the treatment, it was dehydrated in a dehydration tank for 2 minutes and dried under the conditions of 20 ° C. and 45% RH.

(3) Method for evaluating flexibility For dry cotton towels, a pair of Scheffe's comparison method by 10 panelists was used, and a towel treated with the fiber treatment composition shown in Comparative Example 1 was used as a control. Flexibility was evaluated based on the following criteria.
Evaluation criteria:
◎: Feels softer at the significance level of less than 5% than the control (Comparative Example 1) ○: Feels softer at the significance level of 5% to 10% than the control (Comparative Example 1) △: Same as the control (Comparative Example 1) X: The control (Comparative Example 1) feels softer at a significance level of 5% or less

  According to the liquid softener composition of the present invention, a liquid softener composition having an excellent softening effect can be provided.

Claims (6)

5% by mass or more and 20% by mass or less of the following component (A), 1% by mass or more and 10% by mass or less of the following component (B), and the mass ratio of the component (A) to the component (B) [(A) / (B)] is a liquid softener composition of 1-9.
Component (A): A quaternary ammonium salt mixture composed of a compound represented by the following general formula (1), wherein 1% by mass or more and 40% by mass or less of compound (a1) and 60% of compound (a2) are contained in the mixture. A quaternary ammonium salt mixture containing from mass% to 99 mass%.

(In the formula (1), R ¹ represents an acyl group having 16 to 22 carbon atoms, R ² represents an acyl group having 16 to 22 carbon atoms or a hydrogen atom, and R ³ and R ⁴ represent 1 or more carbon atoms. Represents an alkyl group of 3 or less, and Z ⁻ represents an organic or inorganic anion.)
Compound (a1): A compound wherein R ¹ is the acyl group and R ² is a hydrogen atom.
Compound (a2): A compound wherein R ¹ and R ² are the acyl group.
Component (B): A quaternary ammonium salt mixture comprising a compound represented by the following general formula (2), wherein 1% by mass or more and 10% by mass or less of compound (b1), and 4 of compound (b2) in the mixture. A quaternary ammonium salt mixture containing 50% by mass or more and 50% by mass or less and 50% by mass or more and 95% by mass or less of compound (b3).

(In formula (2), R ⁵ represents an acyl group having 16 to 22 carbon atoms, R ⁶ and R ⁷ represent an acyl group or hydrogen atom having 16 to 22 carbon atoms, and R ⁸ represents 1 or more carbon atoms. Represents an alkyl group of 3 or less, and Z ⁻ represents an organic or inorganic anion.)
Compound (b1): A compound in which R ⁵ is the acyl group and R ⁶ and R ⁷ are hydrogen atoms.
Compound (b2): A compound in which R ⁵ and R ⁶ are the acyl group, and R ⁷ is a hydrogen atom.
Compound (b3): A compound wherein R ⁵ , R ⁶ and R ⁷ are the acyl group.   Furthermore, the liquid softening agent composition of Claim 1 containing 0.1 mass% or more and 5 mass% or less of nonionic surfactant (C).   Furthermore, the liquid softening agent composition of Claim 1 or 2 containing 1.0 mass% or more and 10 mass% or less of water-soluble organic solvents (D).   The liquid softening agent composition according to claim 3, wherein the water-soluble organic solvent (D) is one or more selected from propylene glycol, ethylene glycol, glycerin, and ethanol.   Furthermore, the liquid softening agent composition in any one of Claims 1-4 which contains 0.01 mass% or more and 2.0 mass% or less of inorganic salt (E).   The liquid softening agent composition according to claim 5, wherein the inorganic salt (E) is one or more selected from sodium chloride, calcium chloride, and magnesium chloride.